Smart Materials

MM 496 Advanced Materials

Spring 2019
 Smart Materials
• Smart Materials are designed materials that have one or
more properties that can be significantly changed in a
controlled fashion by external stimuli, such as:

• Stress
• Temperature
• Moisture
• pH
• Electric or magnetic fields
 Shape Memory Alloys
Shape-memory alloys and shape-memory
polymers are materials in which large
deformation can be induced and recovered
through:

o Temperature changes (shape memory effect)

o Stress changes (pseudoelasticity)

The large deformation results due to martensitic

phase change.
 Shape Memory Alloys
Shape memory alloys (SMA) are a group of metallic materials, which are
able to return to a given, pre-defined shape or size after they were
submitted to thermal treatment. This is known as shape memory effect
 Shape Memory Alloys
Martensite transformation in the shape memory alloys exhibits the following basic
characteristics

• The transformation is accompanied by a non-elastic

deformation of crystalline lattice and a non-
diffusive process.

• The transformation of the elementary cell causes a

volume and shear deformation along the defined
planes. This transformation is crystallographically
reversible.

• The transformation takes place if the difference of

the free energies of both phases reaches a critical
point. Temperature
 Shape Memory Alloys

Crystalline lattices B2, (CsCl), D03 (Fe3Al) or L21 (Cu2AlMn)

Structural Changes During SME

[www.fitec.co.jp/ftm/nt-e/appli/appli.htm]
Shape Memory Alloys
Shape Memory Alloys

Twinning in B19- orthorhombic Martensite

 Two Phases Responsible for SME in NiTi

Austenite
– Hard,
– Parent Phase(ß) with B2 Structure

Martensite

– Soft,
– Daughter Phase with a Monoclinic
or Orthorhombic
structure

http://mrsec.wisc.edu
Shape Memory Alloys
 SHAPE MEMORY MATERIALS

SHAPE MEMORY ALLOY (NITINOL)

Inactive

Active - Bending Active - Twist

 Medical Applications of NiTi
Shape Memory Alloys

Medical tools and devices Self-expanding Nitinol stent Non-kinking microsurgical instrument

Stone retrieval basket flexible biopsy forceps used in Dental Braces for teeth adjustments
laparoscopic and gastroscopic
surgery
http://mrsec.wisc.edu
Air-craft, Space Technology Robotics and
Joining Applications

Deformation resistant Aircraft Maneuverability

Dust Measurement on Mars
eyeglass frames

Water Mixer Couplings

Robotic Muscles
 Applications of Shape Memory Alloys

Total and cut-away view of the SMA torque tube

Boeing variable geometry chevron

Aerospace applications of shape memory alloys, D. Hartl, D. C. Lagoudas, Aerospace Engineering Department Texas A&M University
 Applications of Shape Memory Alloys

detail of hinges, folded and deployed configurations

Aerospace applications of shape memory alloys, D. Hartl, D. C. Lagoudas, Aerospace Engineering Department Texas A&M University
Ni-Ti Binary Phase Diagram
Transformation temperatures of the TiNi and other
Shape memory Alloys

SMA
Sample
Stress Dependence of Martensitic Transformation temperatures
 Effects of Alloying Additions on NiTi

Alloying additions to TiNi provide a powerful tool for controlling the

properties and can be used to:

1. Control Transformation Temperatures

2. Control the hysteresis width
3. Increase austenitic strength
4. Increase or decrease the martensitic strength
5. Improve corrosion resistance
6. Introduction or suppression of R-phase
7. Increase two-way memory ability
 Effects of Alloying Additions on NiTi

Property Cu Co Cr Fe Nb V Pd Pt Hf Zr C O N H

Transformation Temperatures

Strength

Ductility
 Fabrication of TiNi alloys

• Ti is very reactive to oxygen

• Ti-Ni alloys are melted in high vacuum or an
inert gas atmosphere.
– Induction Melting
– Electron beam melting
– Argon arc melting
– Plasma arc melting
 Induction Melting
Induction melting (mixing effect, recommended crucible
materials are graphite and CaO)

• Alumina or magnesia crucibles are not ok?

• Graphite crucible (not good at temperatures exceeding 1723K)

• The melting point of a Ti50Ni50 is about 1510K.

• By Induction melting the transformation temperatures can be

adjusted +5K.

• To achieve more precise control an in-situ composition control

furnace is useful.
 Electron Beam Melting
• EBM utilizes a high-voltage electron beam as the heating
source.
• Molten alloy/metal is melted by EB and put into a water
cooled Cu mold.
• The alloy start to solidify from the bottom.
• Because of the purifying effect of high vacuum and high
heating temperatures purity is high
• Composition homogeneity is not good.
• Evaporation of metals complicates the composition control.
• It is used to prepare the TiNi alloys which do not require
precise control of transformation temperatures
 Electric Arc Melting
• Consumable and non-consumable electrode systems
• Applicable to many kinds of alloys
• Molten alloy is solidified in the form of a button
• Buttons are remelted for several times to improve the
homogeneity
• Buttons are remelted and cast into
cylindrical/rectangular rods.
Electric Arc Furnace
 Plasma Melting

• Compared to the hard irradiation from a high

voltage electron beam or an argon arc, this
method is relatively milder.

• It results in low loss of the alloy elements.

• Composition distribution is relatively uniform

 Hot and Cold working of TiNi shape memory alloys

• After melting scale is removed and ingot

is forged and rolled into bars or slabs.
• The optimum heating temperature for hot
working is around 1073 K.
• Compared to hot working, cold working
of TiNi alloys is far more difficult.

• Difficulty arises because of the strong

work hardening.
• The workability strongly depends on the
alloy composition.
• It becomes harder with increasing Ni
contents (becomes worse Ni >51at%).
 Mechanical Properties

• Yield strength of TiNi alloy is lower than 100MPa.

• Cold worked TiNi alloy can achieve strength up to 1000MPa.

• In case of cold drawing the strength surpasses 1500MPa.

• During cold working proper lubrication is essential.

• Machining of TiNi alloys is hard (WC tools are used for

machining).
Forming and Shape Memory Treatment

• The specific shape is formed

• It is fixed using special fixtures and heat treated at

623-723 K temperature to memorize the shape.

• The holding time is between 10 -100 min.

• Virtually any shape can be memorized.

• If tensile strength of shape memory alloy is less than

1000 MPa sufficient shape memory effect is not
possible.
Improvement in Cyclic Stability by Training/Cycling
Improvement in Cyclic Stability by Training/Cycling

A typical martensite NbRu microstructure,

with coarse and fine twinning.
 Change in transformation temperatures by
changing the composition

Ti50Ni15Pd25-Cu10

Ti50Ni20Pd25-Cu5

Ti50Ni25Pd25

Ti50Ni50
TiNiPd Alloys
(Orthorhombic)

(Cubic) B19 (Orthorhombic)

B19’(M)

Dependence of the Ms temperature on the Pd contents.

(Monoclinic)

Dependence of the Ms temperature on the Ti/(Ni + Pd)

ratio.

Y.Watanabe, T.Saburi, Y.Nakagawa, S.Nenno, JIM meeting .54 (1990) 861. S. Shimizu et al. /Materials Letters 34(1998)23-29
 High Temperature Shape Memory Systems
Base System System Transformation temperature range (K)
Ti50-Ni50-x-Pdx
(x = up to 50at%) 373-800
Ti50-Ni50-x-Ptx
(x = up to 50at%) 373-1300
Ti50-Ni50-x-Aux
Ti-Ni-X
(x = up to 50at%) 373-800
Ti50-y-Ni50-Hfx
(x = up to 30at%) 373-673+
Ti50-y-Ni50-Zrx
(x = up to 30at%) 373-523+
Cu-Al-Ni (Al< 16 wt%) 373-673
Cu-base Cu-Zn-Al (Zn< 24 wt%) 70-470
Cu-Al-Nb/Ag 373-673
Co-Al 373-673
Co base
Co-Ni-Al/Ga 373-673
Co-Si Ms = 861
Ni-Al ( Al < 37at%) 373-573
Ni base
Ni-Mn (Al> 37at%) 373-943
 High Temperature Shape memory Systems

Base System System Transformation temperature range (K)

Ti-Nb 373-473
Ti-Au 373-903
βTi base Ti-Pd 373-883
Ti-Pt-Ir 1263-1457
Ti-Ta (Ta < 35at%) 373-500
Pt-Ga Ms = 1373
Pt base
Pt-Al Ms = 593
(Ta or Nb)-Ru Ta-Ru 1173-1423
base Nb-Ru 698-1173
Zr50-Cu50 Ms = 413
Zr base
Zr50-Rh50 Ms = 723
U-Nb base U-Nb Ms = 450
 Shape Memory Alloys
Comparison of the martensite transformation in the alloys based on Fe
and SMA
Non-Thermoelastic Transformation
• Large shape strain associated that can
only be accommodated through plastic
deformation of the lattice
• Immobile interface between austenite
and martensite.
• Nucleation of the plates is favored
instead of the growth of the existing
ones.
• Formation required larger driving force
and therefore hysteresis is greater.
Thermoelastic Transformation
• Small shape strain that matrix can
accommodate within limits
• Glissile interface allowing reversibility
of the transformation
• Upon decrease of temperature or
application of stress amount of
martensite increases due to glissile
interface.
• Requires less driving force and results
in smaller hysteresis.
 Shape Memory Alloys
Precipitation Mechanism
Annealing causes the formation
Cold deformation Induced of TiPdCu precipitates on
Defects i.e. dislocations defects
Defects
Solution Treated
Ti50Ni15Pd25Cu10

Annealing at Intermediate
Cold Deformation Temperatures

TiPdCu

Ti rich region
Formation of Ti rich Ti2Pd type Formation of TiPdCu results in a
precipitates around TiPdCu Ti rich region around these
precipitates precipitates
 Shape Memory Alloys
Evidence of precipitation by back-scattered SEM images

Fig: Back scattered SEM images showing distribution and morphologies of precipitates in 10Cu alloy annealed for
3.6ks after 40% cold deformation (a) 673 K (b) 773K (c) 823K (d) 873K (e) 923 K (f) 973 K.
 Shape Memory Alloys

0 at%Cu Alloy 10 at% Cu Alloy

XRD scans of the 0at%Cu and 10at%Cu alloys in cold rolled, annealed, aged and solution
treated conditions.
 Shape Memory Alloys

Stress (MPa)

% Strain

I - Elastic deformation of the martensitic state, it is an initial deformation with the elastic modulus EI
II - Non-elastic deformation associated with the reorientation of the martensite variants while creating a
certain plateau.
III - Reorientation takes place as well as the plastic deformation (with the ES module) of the oriented
martensite M up until the yield strength σY.
IV - Plastic deformation of the oriented martensitic structure leading to fracture (fracture strength σY.
Shape Memory Alloys
 Ferromagnetic Shape Memory Alloys

Shape memory alloys are a subset smart materials

Materials responding to external stimuli (applied stress, temperature,
acoustics, electric and magnetic field) producing induced
strain/signal.
Shape memory alloy
A material that has been deformed at a certain low temperature (twinned
thermoelastic martensitic phase) regains its original or initial shape upon
heating through the transformation range. e.g., NiTi, CuZn, TiNb, FeMnSi
etc.

Ferromagnetic shape memory alloy

In FSMAs shape changes take place by the application of magnetic field in
the thermoelastic martensitic state by the motion of twin boundaries. e.g.,
NiMnGa, FePd, FePt, CoNiAl, NiFeGa etc.

47
 Ferromagnetic Shape Memory Alloys

Martensitic
Transformation

Shape memory effect

a: Cubic phase b: Internal strain by lattice deformation

c: Strain accomodation by twinning
d: Strain accomodation through slip
Magnetic field induced strain

48
 Ferromagnetic Shape Memory Alloys

Requirements for magnetic shape memory effect

Ferromagnetic materials exhibiting diffusionless reversible martensitic

transition

1. Transformation to thermoelastic martensite

2. High magnetocrystalline anisotropy ( > 105 J/m3 )

3. High curie temperature

4. Low critical stress for twin boundary motion ( < 10 MPa )

49
 Ferromagnetic Shape Memory Alloys

Limiting factors for magnetic shape memory effect

• Critical stress for twin boundary motion exceeds the magnetic stress.

• Transition temperatures (TM & TC).

• Saturation magnetization (MS).

• Intermartensitic transformation.

• Low magnetocrystalline anisotropy.

• Operating temperature.

50
 Ferromagnetic Shape Memory Alloys

Magnetic field induced strain

51
 Ferromagnetic Shape Memory Alloys

Ferromagnetic Alloy Systems

Fe-Pt
Expensive raw material
Fe-Pd

Ni-Mn-Al Low MFIS (0.1%)

Co-Ni-Ga Inferior repeatability

Co-Ni-Al
Low MFIS
Fe-Ni-Ga

Co-Ni TM below 0oC

Large MFIS at & above RT

Ni-Mn-Ga Good repeatibility,
moderate magnetic field required
52
 Ferromagnetic Shape Memory Alloys
Applications in aerospace, robotics, MEMS.

A proportional fluid valve MSM Linear motor

MSM pump MSM actuator 53

 Ni-Mn-Ga FSMAs
1050 – 1150oC 1050 – 1150oC 700-800oC 50-100oC
Liquid <=========> Liquid + B2 <=========> B2 <=========> L21 <=======> Martensite

B2(cubic)
Austenite Martensite Martensite
(cubic) (tetragonal) (Orthorhombic)

Non-modulated Modulated

I. I. Aaltio, O. Söderberg, Y. Ge, O. Heczko and S.-P. Hannula, Lab. of MaterialsScience, HUT, Finland. 54
II. Y. Ge, PhD Thesis, Department of Materials Science and Engineering, HUT, Finland.
III. D.L. Schlagel, Y.L. Wu, W. Zhang, T.A. Lograsso, Journal of Alloys and Compounds 312 (2000) 77–85
Ni-Mn-Ga FSMAs
 Ni-Mn-Ga FSMAs

4.1

4.0
Heat Flow (mW/mg)

3.9
340.1
3.8 360

3.7

3.6

3.5 331.9

320 340 360 380 400

50 um
Temperature (K)

Ni48Mn31Ga21 Homogenized Condition

Ni-Mn-Ga FSMAs
 Ni-Mn-Ga FSMAs

The stress-strain curves in compression of the alloy Ni50.6Mn28.5Ga20.9 at

different temperatures.
 Ni-Mn-Ga FSMAs

MSM element (1) in the constant unidirectional and (2) in the rotating magnetic field
and (3) in the actuator. a, b and c are crystallographic axes of martensite (c < a,b). The
short c-axis is the easy axis of magnetization.
Ni-Mn-Ga FSMAs
 Ni-Mn-Ga FSMAs

Simultaneous measurement of strain and magnetization of Ni48.6Mn26.3Ga25.1 single variant

specimen (5M martensite) in a typical experiment with a quasistatic magnetic field.
Vickers hardness of Ni-Mn-Ga alloys

320

300
Vickers Hardness (Hv)
280
Austenite
Alloy 3
260

240

220

200 Martensite
Alloy 2

180

160
Cast Homogenized Annealed
Heat treatment

62
Ni-Mn-Ga FSMAs
Ni-Mn-Ga FSMAs
 Ni-Mn-Ga FSMAs
Effect of heatreatment on M-H curves of the Ni-Mn-Ga alloys
Ni48.0Mn 30.6Ga2
Alloy 21.1

Magnetization (emu/g)
100

80 Annealed
60

40 Cast
20

0
-20000 -10000 0 10000 20000
-20
Magnetic Field (Oe)
-40

-60

-80

-100

65
 Fracture behaviour of Ni-Mn-Ga alloys

-90 deg
eg
2d
deg 23.
83
22.

-90 deg
-90 deg
.26
123 30 g
de
deg 120
deg

-90 deg
g
de
33

Thermal cycling between austenitic & martensitic states

Formation & propagation of cracks

Low fatigue life

66
 Ni-Mn-Ga FSMAs

FSMA alloys have martensite tranformation temperature – 400°K (max)

• Alloy modification to enhance the MT Temperature above 400°K

• Aging effect on transformation temperature
• Modification of magnetic properties

Ni-Mn-Ga HT-FSMAs

Ni-rich Ni2MnGa developed as HTSM alloys with

 Good SME

 High thermo-cycling stability

 Good super-elasticity
 Ni-Mn-Ga FSMAs

Elements (at. %)
Alloy Composition
Ni Mn Ga
A-1 54.11 23.53 22.36 Ni54 Mn 23.5 Ga 22.5

A-2 58.20 23.59 18.21 Ni 58 Mn 23.5 Ga 18.5

800.0 K 786.7 K
Martensitic Transformation Temperatures

Temperature Mp
750.0 K
Temperature Ap
735.5 K
700.0 K

650.0 K

600.0 K

550.0 K

500.0 K
441.8 K
450.0 K
425.8 K

400.0 K
54% 58%
Ni at%
 Ni-Mn-Ga FSMAs
A1 - Ni54 Mn 23.5 Ga 22.5
1400
M(222)
1300 M(400)
1200
1100
A-1(Homogenization)
1000
900 M(440)
Intensity (CPS)

M(004)
800
700
A-1(As-Cast)
600 M(400)
500 M(440) M(404)

400 M(004)
M(002)
300
200
M = Martensitic Tetragonal Structure
100
0
20 40 60 80 100

2

Single Phase
Lamellar Twin
Martensite

A-1 As-Cast A-1 Homogenized

 Ni-Mn-Ga FSMAs
A2 - Ni 58 Mn 23.5 Ga 18.5
1400

M(222)
1200 (111)
A-2 Homogenized

M(004)
M(400)

M(440)
1000

M(321)

M(402)
(200)
M(002)
Intensity (CPS)

(202)

M(202)
M(112)
800

600
(220)
M(400) A-2(As-Cast)
400

M(002)
200
M = Martensitic Tetragonal Structure
 = FCC Structure
0
20 30 40 50 60 70 80 90 100

2

Dual Phase

Lamellar Twin
Martensite
(matrix)

γ (fcc) Phase

A-2 As-Cast A-2 Homogenized

 Ferromagnetic Shape Memory Effect

Fixture support Rubber pad

Strain gage

Electromagnets
N S

Sample

Fixture support