MATERIAL

SCIENCES
 CLASSIFICATION OF MATERIALS
 Materials used in the design and
manufacture of products

 Plastics
 Wood
 Composites
 Ceramics
 Metals
 Fabrics
 Wood can be further categorised as;
Hardwood
Softwood
Manufactured board

Hardwood Softwood Manufactured

Board
Oak Pine Plywood
Ash Cedar Blockboard
Beech Fir MDF
Sycamore Spruce Melamine board
 Fabrics can be further classified as natural
and synthetic

Natural Synthetic

Cotton Nylon

Canvas Polyester
 Classes and Properties:
Metals
Applications
• Electrical wiring
• Structures: buildings, bridges, etc.
• Automobiles: body, chassis, springs, engine block, etc.
• Airplanes: engine components, fuselage, landing gear
assembly, etc.
• Trains: rails, engine components, body, wheels
• Machine tools: drill bits, hammers, screwdrivers, saw
blades, etc.
• Shape memory materials: eye glasses
• Magnets
• Catalysts
Examples
• Pure metal elements (Cu, Fe, Zn, Ag, etc.)
• Alloys (Cu-Sn=bronze, Cu-Zn=brass, Fe-C=steel, Pb-
Sn=solder, NiTinol)
• Intermetallic compounds (e.g. Ni3Al)
 CRYSTAL
STRUCTURE
CLASSIFICATION OF
MATTER
 SOLIDS
Solids are again classified in to two
types
 Crystalline
 Non-Crystalline (Amorphous)
WHAT IS A CRYSTALLINE
SOLID?
 A crystal or crystalline solid is a solid
material, whose constituent atoms,
molecules, or ions are arranged in an
orderly repeating pattern extending in
all three spatial dimensions.

 So a crystal is characterized by regular

arrangement of atoms or molecules
 EXAMPLES !

Non-Metallic crystals:
 Ice, Carbon, Diamond, Nacl, Kcl etc…

Metallic Crystals:
 Copper, Silver, Aluminium, Tungsten,
Magnesium etc…
CRYSTALLINE SOLID
SINGLE CRYSTAL

Single Crystal example

 AMORPHOUS SOLID
 Amorphous (Non-crystalline) Solid is
composed of randomly orientated atoms
, ions, or molecules that do not form
defined patterns or lattice structures.

 Amorphous materials have order only within

a few atomic or moleculardimensions(within
the particular grains).
 Amorphous materials do not have any
long-range order, but they have varying
degrees of short-range order.

 Examples to amorphous materials

include amorphous silicon, plastics, and
glasses.

 Amorphous silicon can be used in solar

cells and thin film transistors.
Non-crystalline
 WHAT ARE THE CRYSTAL
PROPERTIES?

 Crystals have sharp melting points

 They have long range positional order
 Crystals are anisotropic (Properties change
depending on the direction)
 Crystals exhibit Bi-refringence
 Some crystals exhibit piezoelectric
effect & Ferroelectric effect etc…also
 What is Space lattice ?
 An infinite array of
points in space, y

B C D E
α
 Each point has identical b
surroundings to all O a A x
others.

 Arrays are arranged

exactly in a periodic
manner.
Translational Lattice Vectors – 2D
A space lattice is a set of
points such that a translation
from any point in the lattice by
a vector;
R=la+mb
locates an exactly equivalent
point, i.e. a point with the
same environment as P . This
is translational symmetry. The
vectors a, b are known as
lattice vectors and (l,m) is a
pair of integers whose values
depend on the lattice point.
 For a three dimensional lattice
 R = la + mb +nc
 Here a, b and c are non co-planar vectors

 The choice of lattice vectors is not

unique. Thus one could equally well take
the vectors a, b and c as a lattice vectors.
 BASIS & UNIT CELL

 A group of atoms or molecules identical

in composition is called the basis
or
 A group of atoms which describe crystal
structure
 UNIT CELL

 The smallest component of the crystal

(group of atoms, ions or molecules),
which when stacked together with pure
translational repetition reproduces the
whole crystal.
 S
S

S S

a
2D Unit Cell example -(NaCl)
Choice of origin is arbitrary - lattice points need
not be atoms - but unit cell size should always
be the same.
 This is also a unit cell -
it doesn’t matter if you start from Na or Cl
This is NOT a unit cell even though they are all
the same - empty space is not allowed!
In 2Dimensional space this is a unit cell
but in 3 dimensional space it is NOT
 Now Crystal structure !!
 Crystal structure can be obtained by attaching atoms, groups of
atoms or molecules which are called basis (motif) to the lattice
sides of the lattice point.

Crystal lattice + basis = Crystal structure

The unit cell and,
consequently, the
entire lattice, is
uniquely
determined by the
six lattice
constants: a, b, c,
α, β and γ. These
six parameters are
also called as basic
lattice parameters.
 Primitive cell
 The unit cell formed by the primitives
a,b and c is called primitive cell. A
primitive cell will have only one lattice
point. If there are two are more lattice
points it is not considered as a primitive
cell.

 As most of the unit cells of various

crystal lattice contains two are more
lattice points, its not necessary that
every unit cell is primitive.
 CRYSTAL SYSTEMS

 We know that a three dimensional space

lattice is generated by repeated
translation of three non-coplanar vectors
a, b, c. Based on the lattice parameters
we can have 7 popular crystal systems
shown in the table
 Table-1
Crystal system Unit vector Angles

Cubic a= b=c α =β =√=90

Tetragonal a = b≠ c α =β =√=90
Orthorhombic a≠b≠c α =β =√=90
Monoclinic a≠b≠c α =β =90 ≠√
Triclinic a≠b≠c α ≠ β ≠√ ≠90
Trigonal a= b=c α =β =√≠90
Hexagonal a= b ≠ c α =β=90
√=120
 BRAVAIS LATTICES

 In 1850, M. A. Bravais showed that

identical points can be arranged spatially
to produce 14 types of regular pattern.
These 14 space lattices are known as
‘Bravais lattices’.
 14 Bravais lattices
S.No Crystal Type Bravais lattices Symbol

1 Cubic Simple P
2 Body centred I
3 Face centred F
4 Tetragonal Simple P
5 Body centred I
6 Orthorhombic Simple P
7 Base centred C
8 Body I
centred
9 Face F
centred
10 Monoclinic Simple P

11 Base C
centred
12 Triclinic Simple P

13 Trigonal Simple P

14 Hexgonal Simple P
 COORDINATION NUMBER
 Coordination Number (CN) : The Bravais
lattice points closest to a given point are
the nearest neighbours.
 Because the Bravais lattice is periodic, all
points have the same number of nearest
neighbours or coordination number. It is a
property of the lattice.
 A simple cubic has coordination number 6;
a body-centered cubic lattice, 8; and a face-
centered cubic lattice,12.
 Primitive cubic Body centered cubic Face centered cubic

Coordination
6 8 12
number
 Theoretical density (mass/ volume) can
then be calculated using the
 crystal structure of metallic solid material.
 CRYSTALLOGRAPHİC DİRECTİONS

The direction is a line between two points or a vector as shown below:

 Steps for defining a direction in a crystal system:
 A vector is positioned such that it passes through the origin of the
coordinate system. Then you can move the vector if you keep the
parallelism.
 The length of the vector projection on each of the three axes is
determined in terms of the unit cell dimensions (a, b, c).
 The three numbers are multiplied or divided by a common factor to
reduce them to the smallest integer values.
 Three indices are enclosed in square brackets as [uvw]
 Remember to count for positive and negative coordinates based on
the origin. When there is a negative index value, then show that by a
bar over it, as

This vector has a component in –y direction.

In cubic crystals, all directions showed by the
indices of

are equivalent. Therefore they can be grouped as a family, which is shown

as

Hexagonal Crystals: There is a four-axis (Miller-Bravais) coordinate system

used for this type of structures.
 CRYSTALLOGRAPHIC PLANE

 Except hexagonal crystal system, crytallographic planes are

specified using three Miller indices (hkl). Any two planes parallel
to each other are equivalent and have same indices.
 The determination of the h,k, and l index numbers are as follows:
 If the plane passes through the selected origin, then construct a
new parallel plane or change the originto a corner of another unit
cell.
 Plane intersects or parallels each of the axes: the length of each
axis is determined by using lattice parameters; a,b, and c.
 Take the reciprocals of the lattice parameters. Therefore a plane
that parallels an axis has a ZERO index. (1/infinity=zero)
 You may then change these three numbers to the set of smallest
integers using a common factor.
 Report the indices as (hkl).
 An intercept on the negative side of the origin is indicated by a
bar over that index.
 THREE IMPORTANT CRYSTAL
PLANES

( 1 0 0) (1 1 0) (1 1 1)
For cubic crystals: Planes and directions having the same indices are
perpendicular to one another.
We are interested in specification fo planes
because atomic arrangement depends on the
crystal structure.
 Close packed crystals

A plane
B plane

C plane

A plane

…ABCABCABC… packing …ABABAB… packing

[Face Centered Cubic (FCC)] [Hexagonal Close Packing (HCP)]
Characteristics of Selected Elements at 20C
At. Weight Density Atomic radius
Element Symbol (amu) (g/cm3) (nm)
Aluminum Al 26.98 2.71 0.143
Argon Ar 39.95 ------ ------
Barium Ba 137.33 3.5 0.217
Beryllium Be 9.012 1.85 0.114
Boron B 10.81 2.34 ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ teristics of
Cadmium Cd 112.41 8.65 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 0.197 inside front
Carbon C 12.011 2.25 0.071 cover,
Cesium Cs 132.91 1.87 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------
Chromium Cr 52.00 7.19 0.125
Cobalt Co 58.93 8.9 0.125
Copper Cu 63.55 8.94 0.128
Flourine F 19.00 ------ ------
Gallium Ga 69.72 5.90 0.122
Germanium Ge 72.59 5.32 0.122
Gold Au 196.97 19.32 0.144
Helium He 4.003 ------ ------
Hydrogen H 1.008 ------ ------
 THEORETICAL DENSITY, 

Example: Copper
Data from Table inside front cover of Callister (see previous slide):
• crystal structure = FCC: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10 -7cm)

Result: theoretical Cu = 8.89 g/cm3

Compare to actual: Cu = 8.94 g/cm3
 DENSITIES OF MATERIAL CLASSES
metals> ceramics> polymers
Why?
Metals have...
• close-packing
(metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing
(often amorphous)
• lighter elements (C,H,O)
Composites have...
• intermediate values Data from Table B1, Callister 6e.
ATOMIC PACKING FACTOR

 Atomic Packing Factor (APF) is defined

as the volume of atoms within the unit
cell divided by the volume of the unit
cell.
 SİMPLE CUBİC (SC)
 Simple Cubic has one lattice point so its
primitive cell.
 In the unit cell on the left, the atoms at
the corners are cut because only a portion
(in this case 1/8) belongs to that cell. The
rest of the atom belongs to neighboring
cells.
 Coordinatination number of simple cubic
is 6.
b
c

a
 ATOMIC PACKING FACTOR OF SC
VOLUME OF ATOM PER UNIT CELL
APF=
VOLUME OF UNIT CELL

V=n*4/3 п r3
where n is the number of atoms per unit cell
a=2 r,R=a/2

APF=4/3п(a/2)3/a3 = п/6= 0.52

APF=0.52
 BODY CENTERED CUBIC
(BCC)
 As shown, BCC has two lattice
points so BCC is a non-primitive
cell.

 BCC has eight nearest neighbors.

Each atom is in contact with its
neighbors only along the body-
diagonal directions.

 Many metals (Fe, Li, Na.. etc),

including the alkalis and several
transition elements choose the
BCC structure.
 ATOMİC PACKİNG FACTOR OF BCC

AB2=BC2+CA2
B
(4r)2=(a2+a2)2+a2

A (4r)2=3a2
C

a=4/31/2 *r

APF=2*4/3 п(a*31/2/4)3/a3=0.68

APF=0.68
FACE CENTERED CUBIC (FCC)
 There are atoms at the corners of the unit
cell and at the center of each face.
 Face centered cubic has 4 atoms so its
non primitive cell.
 Many of common metals (Cu, Ni, Pb ..etc)
crystallize in FCC structure.
Face Centered Cubic (FCC)
ATOMİC PACKİNG FACTOR OF FCC

AB2=BC2+CA2
A
(4r)2=a2+a2
n= 4

C r=a*21/2/4
B

APF=4*(a*21/2/4)3 * 4/3 п
a3

APF=0.74
 HEXAGONAL SYSTEM
 A crystal system in which three equal coplanar axes
intersect at an angle of 60, and a perpendicular to the
others, is of a different length.
 TRICLINIC & MONOCLINIC
CRYSTAL SYSTEM
Triclinic minerals are the least symmetrical. Their three axes are all
different lengths and none of them are perpendicular to each
other. These minerals are the most difficult to recognize.

Triclinic (Simple) Monoclinic (Simple) Monoclinic (Base Centered)

aß g 90 a = g = 90o, ß 90o a = g = 90o, ß 90o
oa b c
a b c a b c,
 ORTHORHOMBIC SYSTEM

Orthorhombic (Simple) Orthorhombic (Base- Orthorhombic (BC) Orthorhombic (FC)

a = ß = g = 90o centred) a = ß = g = 90o a = ß = g = 90o
a b c a = ß = g = 90o a b c a b c
a b c
 TETRAGONAL SYSTEM

Tetragonal (P) Tetragonal (BC)

a = ß = g = 90o a = ß = g = 90o
a = b c a = b c
Rhombohedral (R) or
Trigonal

Rhombohedral (R) or Trigonal (S)

a = b = c, a = ß = g90o
 CRYSTAL DIRECTIONS
 We choose one lattice point on the line as an
origin, say the point O. Choice of origin is
completely arbitrary, since every lattice point is
identical.
 Then we choose the lattice vector joining O to
any point on the line, say point T. This vector can
be written as;
 R = la + mb + nc
 To distinguish a lattice direction from a lattice
point, the triple is enclosed in square brackets [
... ] is used. [l, m, n]
 [l, m, n] is the smallest integer of the same
relative ratios.
210

X=1,Y=½,Z=0
[1 ½ 0] [2 1 0]
 Negative directions
 When we write the
direction [n1n2n3]
depend on the origin,
negative directions
can be written as

 R=la+mb+nc

 Direction must be
smallest integers.
Examples of crystal
directions

X = 1 , Y = 0 , Z = 0 ► [1 0 0]
 CRYSTAL PLANES
 Within a crystal lattice it is possible to identify sets of
equally spaced parallel planes. These are called
lattice planes.
 In the figure density of lattice points on each plane of
a set is the same and all lattice points are contained
on each set of planes.

b b
a a
 MILLER INDICES FOR
CRYSTALLOGRAPHIC PLANES
 William HallowesMiller in 1839 was able to give
each face a unique label of three small integers,
the Miller Indices

 Definition: Miller Indices are the reciprocals of

the fractional intercepts (with fractions cleared)
which the plane makes with the crystallographic
x,y,z axes of the three nonparallel edges of the
cubic unit cell.
 Miller Indices
 Miller Indices are a symbolic vector representation for
the orientation of an atomic plane in a crystal lattice and
are defined as the reciprocals of the fractional intercepts
which the plane makes with the crystallographic axes.

 To determine Miller indices of a plane, we use the

following steps

 1) Determine the intercepts of the plane along each

 of the three crystallographic directions

 2) Take the reciprocals of the intercepts

 3) If fractions result, multiply each by the

 denominator of the smallest fraction
 IMPORTANT HINTS:
 When a plane is parallel to any axis,the
intercept of the plane on that axis is
infinity.So,the Miller index for that axis
is Zero
 A bar is put on the Miller index when
the intercept of a plane on any axis is
negative
 The normal drawn to a plane (h,k,l)
gives the direction [h,k,l]
 Example-1

(1,0,0)
 Example-2

(0,1,0)

(1,0,0)
 Example-3

(0,0,1)

(0,1,0)

(1,0,0)
 Example-4

(0,1,0)
(1/2, 0, 0)
Miller Indices
 Spacing between planes in a
cubic crystal is

a
d hkl = 2 2 2
h +k +l
Where dhkl = inter-planar spacing between planes with Miller
indices h, k and l.
a = lattice constant (edge of the cube)
h, k, l = Miller indices of cubic planes being considered.
 DISLOCATIONS
• How do metals plastically deform?
• Plastic deformation due to motion of large number of dislocations.

Plastic deformation under shear stress

 Dislocation is a boundary
between the slipped and the
unslipped parts of the crystal
lying over a slip plane

Slipped Unslipped
part part
of the of the
crystal crystal
 Dislocations allow deformation at much
lower stress than in a perfect crystal

Top of crystal slipping one plane at a time.

Only a small of fraction of bonds are broken at any time.

Propagation of dislocation causes top half of crystal to slip

with respect to the bottom.

The slip plane – crystallographic plane of dislocation motion.

 Direction of Dislocation Motion

Edge dislocation line moves parallel to applied stress

Screw dislocation line moves perpendicular to applied stress

Mixed dislocations: direction is in between parallel

and perpendicular to applied shear stress
 Edge Climb

Positive climb Negative climb

Removal of a row of atoms Addition of a row of atoms
 Motion of a mixed dislocation

[1]

We are looking at the plane of the cut (sort of a semicircle centered in the lower left
corner). Blue circles denote atoms just below, red circles atoms just above the cut. Up on
the right the dislocation is a pure edge dislocation on the lower left it is pure screw. In
between it is mixed. In the link this dislocation is shown moving in an
animated illustration.

[1] http://www.tf.uni-kiel.de/matwis/amat/def_en/kap_5/backbone/r5_1_2.html
 Strain Field around Dislocations

Strain fields from distortions at dislocations: Drops radially with

distance.

Edge dislocations  compressive, tensile, and shear lattice strains.

Screw dislocations  shear strain only.

Interactions between Dislocations

Strain fields around dislocations cause them to exert force on

each other.
Direction of Burgers vector  Sign
Same signs  Repel
Opposite signs  Attract (annihilate)
Compressive stress
field

Tensile stress
field
Positive edge dislocation
Negative edge dislocation

ATTRACTION Can come together and cancel

one another

REPULSION
Where do Dislocations Come From ?
Dislocation density 
dislocation length/ volume OR number of dislocations
intersecting a unit area.
105 cm-2 in carefully solidified metal crystals to 1012 cm-2 in
heavily deformed metals.

Most crystalline materials have dislocations due to stresses

associated with the forming process.
Number increases during plastic
deformation. Spawn from dislocations,
grain boundaries, surfaces.
Picture is snapshot from simulation of plastic
deformation in a fcc single crystal (Cu).
 SLIP SYSTEM
Preferred planes for dislocation movement (slip planes)
Preferred crystallographic directions (slip directions)
Slip planes + directions (slip systems)
highest packing density.

Distance between atoms shorter than average; distance perpendicular to plane longer
than average. Far apart planes can slip more easily. BCC and FCC have more slip
systems compared to HCP: more ways for dislocation to propagate  FCC and BCC
are more ductile than HCP.
Slip in a Single Crystal

Zn
Each step (shear band) results from the
generation of a large number of
dislocations and their propagation in the
slip system
 Plastic Deformation of Polycrystalline Materials

Grain orientations with respect to applied stress are typically random.

Dislocation motion occurs along slip systems with favorable orientation
(i.e. highest resolved shear stress).
Plastic Deformation of Polycrystalline Materials
Larger plastic deformation corresponds to elongation of grains along direction
of applied stress.

Before After
 Plastic Deformation of Polycrystalline Materials

 Polycrystalline metals are typically stronger than single

crystals. WHY?

 Slip directions vary from crystal to crystal  Some grains

are unfavorably oriented with respect to the applied stress
(i.e. cos cos low)

 Even those grains for which cos cos is high may be

limited in deformation by adjacent grains which cannot
deform so easily

 Dislocations cannot easily cross grain boundaries because

of changes in direction of slip plane and disorder at grain
boundary
 CRYSTAL STRUCTURE
NUMBER OF SLIP SYSTEMS

Body-centred cubic - 12
Face-centred cubic- 12
Hexagonal close-packed- 03
FCC metals are soft at all temperatures

BCC metals brittle at low T (slip planes not close packed)

HCP metals tend to be brittle (few slip planes)

 Strengthening

The ability of a metal to deform depends on the ability of dislocations to move

Restricting dislocation motion can make material stronger

Mechanisms of strengthening in single-

phase metals:
 grain-size reduction
 solid-solution alloying
 strain hardening
Ordinarily, strengthening reduces ductility
 Strengthening by grain-size reduction (I)

Grain boundaries are barriers to dislocation motion: slip plane discontinues or

change orientation.
Small angle grain boundaries are not very effective.
High-angle grain boundaries block slip and increase
strength of the material.
 Strengthening by grain-size reduction (II)
Finer grains  larger area of grain boundaries to impede dislocation motion:
also improves toughness.
Hall-Petch equation:

 y  0  k y d
o and ky constants for particular material
d is the average grain diameter.

70 Cu - 30 Zn
brass alloy

d determined by rate of solidification, by plastic

deformation and by heat treatment.
 SOLID-SOLUTION STRENGTHENING (I)

Alloys usually stronger than pure metals

Interstitial or substitutional impurities cause lattice strain and interact with

dislocation strain fields
 hinder dislocation motion.

Impurities diffuse and segregate around dislocation to find atomic sites more
suited to their radii:
Reduces strain energy + anchors dislocation

Motion of dislocation away from impurities moves it to region where atomic

strains are greater
 SOLID-SOLUTION
STRENGTHENING (II)

Smaller and larger substitutional impurities diffuse into strained

regions around dislocations leading to partial cancellation of
impurity-dislocation lattice strains.
 DIFFUSION IN SOLIDS
WHY STUDY DIFFUSION?
• Materials often heat treated to improve properties

• Atomic diffusion occurs during heat treatment

• Depending on situation higher or lower diffusion

rates desired
• Heat treating temperatures and times, and heating or
cooling rates can be determined using the
mathematics/physics of diffusion
Example: steel gears are “case-hardened” by
diffusing C or N to outer surface
 Diffusion: Material transport by atomic or particle transport
from region of high to low concentration (???)

 What forces the particles to go from left to right?

 Does each particle “know” its local concentration?
 Every particle is equally likely to go left or right!
 At the interfaces in the above picture, there are more particles going
right than left  this causes an average “flux” of particles to the right!
 Largely determined by probability & statistics
• Interdiffusion: In an alloy or “diffusion couple”, atoms tend
to migrate from regions of large to lower concentration.

Initially (diffusion couple)

After some time

Adapted from
Figs. 5.1 and
5.2, Callister
6e.

100%

0
Concentration Profiles
Correct Definition of Diffusion

Fig. 2.1 Free energy and chemical potential changes during

diffusion. (a) and (b) ‘down-hill’ diffusion. (c) and (d) ‘up-hill’
diffusion. (e)  A   A therefore A atoms move from (2) to (1),
2 1

 1B   B2 therefore B atoms move from (1) to (2). (f)  1A   A2

therefore A atoms move from (1) to (2),  B2   1B therefore B
atoms move from (2) to (1).
 SUBSTITUTIONAL DIFFUSION

• Self-diffusion: In an elemental solid, atoms

also migrate.

Label some atoms After some time

C
A
D
B
 SUBSTITUTIONAL DIFFUSION
VACANCY DIFFUSION

Fig. 2.17 (a) before, (b) after: a vacancy is absorbed at a jog on an edge dislocation
(positive climb). (b) before, (a) after: a vacancy is created by negative climb of an
edge dislocation. (c) Perspective drawing of a jogged edge dislocation.

Fig. 2.16 The jumping of atoms in one direction

can be considered as the jumping of vacancies in
the other direction.

Fig. 2.18 A flux of vacancies causes the atomic planes to move through
the specimen.
SUBSTITUTIONAL DIFFUSION
Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
-- number of vacancies
-- temperature
-- activation energy to exchange.
 SUBSTITUTIONAL DIFFUSION
Initial state Intermediate state Final state

Energy Activation energy

 Also called energy barrier for diffusion

Solutions to the Diffusion Equations
• Copper diffuses into a bar of aluminum.

C(x,t)
Cs

t3 Adapted from
t2 Fig. 5.5,

t t1 Callister 6e.

Co o
position, x
• General solution:

"error function"
 TWINNING
A shear force which causes atomic displacements
such that the atoms on one side of a plane (twin
boundary) mirror the atoms on the other side.
Displacement magnitude in the twin region is
proportional to the atom’s distance from the twin
plane takes place along defined planes and
directions depending upon the system.

Ex: BCC twinning occurs on the (112)[111]

system
Slip Twinning

orientation of atoms reorientation of atomic

remains the same direction across twin plane

displacements take place atomic displacement is less

in exact atomic spacings than interatomic spacing
 PROPERTIES OF TWINNING

– occurs in metals with BCC or HCP crystal

structure
 occurs at low temperatures and high
rates of shear loading (shock loading)
 conditions in which there are few
present slip systems (restricting the
possibility of slip)
– small amount of deformation when compared
with slip.
 PHASE DIAGRAMS
Equilibrium phase diagram
or
Equilibrium diagram
or
Phase diagram

A diagram in the space of relevant

thermodynamic variables (e.g., T
and x) indicating phases in
equilibrium is called a phase
diagram.
PHASE DIAGRAM IS A PLOT OF THE STABLE PHASES PRESENT AS A FUNCTION
OF TEMPERATURE AND COMPOSITION.
PHASE IS A HOMOGENEOUS PORTION OF THE SYSTEM THAT HAS UNIFORM
PHYSIACL AND CHEMICAL CHARACTERISTICS.

WHAT IS THE DIFFERENCE BETWEEN COMPONENET AND PHASE?

COMPONENTS:
ELEMENTS OR COMPOUNDS MIXED INITIALLY
EX:AL&CU
PHASES:
PHYSICALLY AND CHEMICALLY DISTINCT MATERIALS REGIONS THAT
RESULTS
EX: a
PHASES OF EACH REGION ARE DETERMINED BY PHASES OF THE REGIONS
LEFT AND RIGHT
PHASE DIAGRAM TELLS US ABOUT THE MICROSTRUCTURE BASED ON
WHAT FORMS UPON COOLING.
IN SUMMARY PHASE DIAGRAMS CAN BE USED TO TELL ABOUT
FRACTION OF EACH PHASE AND MICROSTRUCTURE.
A EUTECTIC PHASE DIAGRAM CONTAINS A POINT WHERE LIQUID
TRANSFORMS DIRECTLY TO TWO SOLIDS,A EUTECTIC PHASE
DIAGRAM HAS ONE INVARIANT(REACTION).
A EUTECTOID PHASE DIAGRAM CONTAINS A POINT WHERE A SOLID
TRANSFORMS DIRECTLY TO TWO SOLIDS, SOLIDS,A EUTECTOID
PHASE DIAGRAM HAS ONE INVARIANT(REACTION).
TIE LINE IS USED TO DETERMINE THE COMPOSITION OF PHASES IN
A TWO PHASE REGION.
TIE LINE CAL ALSO BE USED TO DETERMINE THE RELATIVE
FRACTION OF EACH PHASE.
LEVER RULE CALCULATES THE FRACTION OF EACH PHASE PRESENT.
Solid solutions: ONE ELEMENT DISSOLVED IN ANOTHER TO FORM
SINGLE-PHASE SOLUTION.
SOLID SOLUTION ALLOY STRUCTURE STRONGER AND HARDER
Carbon dissolved in Iron to form STEEL
Metals – Phase diagram
Fig. 1.3 is a copper-nickel alloy system

Fig.1
Metals – Phase diagram
The following things are known from Fig.1.3

(1) Pure copper melts at 1981 F

(2) Pure nickel melts at 2651 F
(3) The system is a solid solution throughout
(4) Below solidus line – solid
(5) Above liquidus line – liquid
(6) Between, two phases: solid and liquid
Metals – Phase diagram
- The overall composition of the alloy (i.e., amount of
copper and amount of nickel) is given by its position
along the horizontal axis.
-The compositions of the liquid and solid phases are
not the same (Cu-Ni ratio in Solid phase NOT
EQUAL to Cu-Ni ratio in Liquid phase)
- Ex 1. 50 % copper-nickel and at 1260 deg C, see
Fig.1.3. Find the compositions of the solid and liquid.
Solution: draw a horizontal line, which intersects the
liquidus and solidus lines, respectively, see Fig.1
Metals – Phase Diagram for Iron and Carbon

1. Iron – Ferrous Metals, Fe

Iron + Carbon = Alloys: Steel and Cast iron
BCC structure
2. Iron – Carbon phase diagram (Fig.2.1)

• Pure iron, melting point 2802 F

• From room temp. to melting, several solid phases
transforms: α -> γ -> δ
 Metals – Phase diagram for Iron and Carbon

FCC
Eutectic
BCC

Eutectoid

Fe3C

2.1%
0.022%
Metals – Phase diagram for Iron and Carbon

• Iron: pure iron (99.99 %),

ingot iron (some carbon, 0.1 % impurities),
wrought iron (3% slug with low carbon).
• Solubility of carbon in iron will depend on solid phases
of iron: Ferrite 0.02%; Austenite 2.1 %;
• Steel: 0.02 – 2.1 %; Cast iron: 2.1-4 %
• Cementite, Fe3C: hard and brittle
• Carbon: an element increasing strength; Fe is soft.
Metals – Phase diagram for Iron and Carbon

3. Steel
- Steel is an alloy of iron that contains carbon ranging
by weight between 0.02% and 2.11%
-It often includes other alloying ingredients as well:
manganese, chromium, nickel, molybdenum
- classification of steels:
plain carbon, low-alloy, stainless, tool
Metals – Phase diagram for Iron and Carbon

3. Steel
plain carbon steel: low-carbon (<0.2%), medium-
carbon (0.2%< and <0.5%), high-carbon (>0.5%).

Low-alloy steel: Cr, Mn, Mo, Ni, V

Stainless steels: highly alloyed steels, Cr 15%, Ni

Tool steel: highly alloyed steels designed for use as

industrial cutting tools, dies, and molds.
 Features
Phases present
L
a ferrite
d Bcc structure
Bcc structure Ferromagnetic
Paramagnetic Fairly ductile

g austenite Fe3C cementite

Fcc structure Orthorhombic
Reactions Non-magnetic Hard
ductile brittle
Peritectic L + d = g
Max. solubility of C in ferrite=0.022%
Eutectic L = g+ Fe3C
Max. solubility of C in austenite=2.11%
Eutectoid g = a + Fe3C
 Steels
Steel is an interstitial solid solution of carbon in iron.

Theoretically steel has a maximum of 2.11% carbon.

In practice, the amount of carbon rarely exceeds 0.8%

Classification/Nomenclature
Low carbon steels up to 0.2%C AISI 1020:
Last two numbers indicate
Medium carbon steels 0.2-0.4%C Amount of carbon :0.2%C
10 indicates plain carbon steel
High carbon steels >0.4% C AISI 4340: 0.4%C
43 indicates alloy steel
 MELTING POINT OF AN ALLOY

Liquid, L 1453ºC
L+a

1085ºC

Solid solution, a

Cu Ni
Wt% Ni
 Components
The independent chemical species (element or
compound) in terms of which the composition of
the system is described are called components.

System components phases

Water H 2O liquid

Water +ice H 2O Liquid+solid

shikanji nimbu, chini and pani liquid solution

Mild steel Fe + C a + Fe3C

A single component phase diagram:
Unary diagram

A two-component phase diagram:

Binary diagram

A three-component phase diagram:

Ternary diagram
Cu-Ni binary
phase diagram Any given point (x,T) on the
phase diagram represents
an alloy of composition x
held at equilibrium at
temperature T

Point A:
60 wt% Ni at 1100ºC

a Point B:
35 wt% Ni at 1250ºC
Phase Diagrams

For any given point (x,T) the phase

diagram can answer the following:
1. What phases are present?
2. What are the phase compositions?
3. What are the relative amounts of
the phases (phase proportions or
phase fractions)?
 Point A:
60 wt% Ni at 1100ºC

Q: Phase present?

Ans: a

Q: Phase composition ?

Ans: 60 wt%Ni
a
Q: Phase amount ?

Ans: 100%
 Point B:
35 wt% Ni at 1250ºC

Q: Phases present?

Ans: a + L

Q: Phase compositions ?

Tie Line Rule

a
Q: Phase amounts ?

Lever Rule
Composition of phases in the two-phase region
Tie Line Rule
a
L

Tie Line

CL= 31.5 wt% Ni

Ca= 42.5 wt% Ni
 Amount of phases in the two-phase region
a Tie-Line: A lever
L Alloy composition C0: Fulcrum
fL: weight at liquidus point
fa: weight at solidus point

The lever is balanced

fa
fL f L (C0  CL )  fa (Ca  C0 )

f L  fa  1
Ca  C0 opposite lever arm
Tie Lever Rule fL  
Ca  C L total lever arm
The Lever Rule: A Mass balance Proof Prob. 7.6
Wt of alloy = W
a
L Wt of a in alloy = faW
Wt of L in alloy = f LW

Wt of Ni in alloy = W C0/100

Wt of Ni in a = faWCa/100

Wt of Ni in L = fL WCL/100

Wt of Ni in alloy = Wt of Ni in a + Wt of Ni in L
Ca fa + CL fL = C0 Ca  C0 opposite lever arm
fL  
Ca  C L total lever arm
f a + fL = 1
Development of Microstructure during
solidification

35  32 3
fa    0.273
43  32 11
f L  1  fa  0.727

Single phase
polycrystalline a
Solder alloy?

An alloy of Pb and Sn

What is best composition of the

solder alloy?

Requirements:
1. should melt easily
2. should give a strong joint
 Solder alloy 1-2-1 rule Eutectic diagram

327
L
232
aL
L
183 a 
Eutectic horizontal

Eutectic
a point

Pb Sn
62
Eutectic Eutectic
temperature Wt % Sn composition
Pb: monatomic fcc
Sn: monatomic bct

a: Pb rich substitutional solid

solution of Pb and Sn
crystal structure: monatomic FCC

: Sn rich substitutional solid

solution of Pb and Sn
crystal structure: monatomic BCT
 Woods metal tea
party
Bi 50.0 wt%
Pb 25.0 wt%
Cd 12.5 wt%
Sn 12.5 wt%

An eutectic alloy with m.p. of 70ºC

100 g US$ 181
Anti-Fire Sprinklers
Eutectic
reaction

Invariant
reaction
cool
L a  
183ºC
62 18 97
wt%Sn wt%Sn wt%Sn

Eutectic mixture

Callister Figs. 9.11, 12 375 X

 L
(40 wt% Sn)

a
L

a
18 wt% Sn

L+

a
L (62 wt% Sn) Eutectic mixture a

a+
Primary a
18 wt% Sn

Eutectic a Eutectic  (97 wt %

(18 wt % Sn) Sn)

Hypoeutectic alloy

Microstructure of hypoeutectic alloy

 Eutectc mixture a

Proeutectic
or Primary a

18 62 97

Amount of total a and total  at a temperature just below 183ºC

Tie line just below 183ºC (red)

97  40 57 f total  1  0.72  0.28

f totala    0.72
97  18 79
 Eutectc mixture a

Proeutectic
or Primary a

18 62 97

Amount of proeutectic a at a temperature just below 183ºC

= Amount of a at a temperature just above 183ºC

Tie line just above 183ºC (green)

62  40 22 f euta    1  0.5  0.5
f pro a    0.5
62  18 44
 Eutectc mixture a EXPERIMENT 5

Proeutectic
or Primary a

18 62 97

Let the fraction of proeutectic a in micrograph fpro a= 0.25

Let the composition (wt% Sn) of the alloy be C0

Tie line just above 183ºC (green)

62  C0 C0  51 wt % Sn
f pro a   0.25
62  18
Optimum composition for solders

For electronic application

Eutectic solder
62 wt% Sn
18 62 97

Minimum heating

For general application

Hypoeutectic solder
Cheaper Allows adjustment of joint during
solidification in the aL range
Modern Trend

Lead-free solders

Phase diagrams can help in

identification of such solders

Sn-Ag-Cu
 Gibbs Phase Rule

Thermodynamic variables:
P, T, Phase Compositions
(overall composition is not considered)

If there are C components then C-1 compositions

have to be specified for each phase

Therefore total number of composition variables:

P (C-1)

With Pressure and Temperature, total number of

variables = P (C-1) + 2
Gibbs phase rule states that one
cannot specify all of the above
P (C-1) + 2 variables independently in
a system at equilibrium

Degrees of Freedom F:
No. of thermodynamic variables
that can be specified independently
 Gibbs Phase Rule

F = Degrees of freedom
C = No. of components in the system
P = No. of phases in equlibrium

F=C–P+2
If pressure and temp both are variables

F=C–P+1
If pressure is held constant
 F=C–P+1

C=2

F=3-P
F =2
At eutectic
reaction P=3
(L, a, )

F =1 F=0

Invariant
reaction
 Mild steel
The Iron-carbon system
0-0.3 wt% C

Bicycle frame
Ship hull
1410
Car body
1150
Medium C steel
0.4-0.7 wt% C
910
steel Cast iron Rail wheel
725
rail axle
0.8
rails
0.02
High C steel
0.8-1.4 wt% C
Razor blades
scissors, knives
Phases in Fe-C system
Phase Symbol Description
Liquid L Liquid solution of Fe and C
d-Ferrite d Interstitial solid solution of C in
d-Fe (high temperature bcc phase)
Austenite g Interstitial solid solution of C in
g-Fe (FCC phase of Fe)
Ferrite a Interstitial solid solution of C in
a-Fe (room temperature bcc phase)
Soft and Ductile
Cementite Fe3C Intermetallic compound of Fe and C
(orthorhombic system)
Hard and Brittle
Ferrite Austenite
 Invariant Reactions in Fe-C system
A horizontal line always indicates an invariant reaction
in binary phase diagrams

Peritectic Reaction

a (0.1 wt % C)  L (0.5 wt % C) d (0.18 wt % C)

1493o C

Eutectic Reaction

L (4.3 wt % C )  g (2.1 wt % C )  Fe3C (6.67 wt % C )

1150o C

Eutectoid Reaction

g (0.8 wt % C ) a (0.02 wt % C )  Fe3C (6.67 wt % C )

725o C
 Eutectoid Reaction

g a  Fe3C
725o C
cool
0.8 0.02 6.67

Pearlite
 Eutectoid Reaction

g a  Fe3C
725o C
cool
0.8 0.02 6.67

Pearlite

Ammount of Fe3C in Pearlite

Red Tie Line below eutectoid temp
0.8  0.02 0.78
f pearlite
   0.117
6.67  0.02 6.65
F3C
Development of
Microstructure
in a
hypoeutectoid
steel
Proeutectoid
Ferrite EXPERIMENT 5

Pearlite

Microsructure of a hypoeutectoid steel, 0.38 wt% C

 0.8  0.38 0.42
f pearlite    0.54
0.8  0.02 0.78

fpearlite below TE = faustenite above TE

Tie-Line above the eutectoid temperature TE

0.8  0.38 0.42
f pearlite    0.54
0.8  0.2 0.78
Development of
Microstructure
in a
hypereutectoid
steel
 Pearlite

Proeutectoid
cementite on
prior
austenite
grain
boundaries

Microsructure of a hypereutectoid steel, 1.4 wt% C

Fproeutectoid cementite=fcementite above TE

1.4  0.8 0.6

f proeutectoid cementite    0.10
6.67  0.8 5.87
 Phase vs. microconstituents

A phase or a mixture of phases which has a distinct

identity in a microstructure is called a
microconstituent

Pearlite is not a phase.

It is microconstituent which is a mixture of
two phases a and Fe3C.
Eutectoid Hypoutectoid Hypereutectoid
steel steel steel
a+Fe3C a+Fe3C a+Fe3C
Pearlite Pearlite + Pearlite +
proeutectoid ferrite proeutectoid
cementite
How to calculate the total amount of a phase (both eutectic and primary)?
Fraction of a phase determined by application of the lever rule
across the entire a +  phase field:

Wa = (Q+R) / (P+Q+R) (a phase)

W = P / (P+Q+R) ( phase)
 Intermediate Phases
So far only two solid phases (a and ) Terminal solid solutions

Some binary systems have intermediate

solid solution phases.
Cu-Zn: a and h are terminal solid solutions,
, ’, g, d, e are intermediate solid solutions.
 Intermetallic Compounds
Intermetallic compounds 
precise chemical compositions exist in some systems.
Using the lever rules, intermetallic compounds are treated like any
other phase, They appear as a vertical line.

intermetallic
compound

Two eutectic diagrams: Mg-Mg2Pb and Mg2Pb-Pb.

Intermetallic compound Mg2Pb is considered a
component.
 Eutectoid Reactions (I)
Eutectoid (eutectic-like in Greek) reaction similar to eutectic reaction
One solid phase to two new solid phases
Invariant point (the eutectoid) 
Three solid phases in equilibrium
Upon cooling, a solid phase transforms into two other solid phases (d
 g + e below)

Cu-Zn

Eutectoid
 Eutectoid Reactions (II)

Contains an eutectic reaction

and an eutectoid reaction
 Peritectic Reactions
Peritectic  solid phase + liquid phase will together form a second solid
phase at a particular temperature and composition upon cooling
L+ a  
Reactions are slow as product phase will form at boundary between two
reacting phases separating them

Peritectics are not as common as eutectics

and eutectiods. There is one in Fe-C system
 Congruent Phase Transformations
Congruent transformation  no change in composition
(e.g, allotropic transformation such as a-Fe to g-Fe or melting transitions in pure solids)
Incongruent transformation, at least one phase changes composition (eutectic, eutectoid, peritectic).

Ni-Ti
Congruent
melting of g
 Eutectic and eutectoid reactions in Fe–Fe3C
Eutectic: 4.30 wt% C, 1147 C
L  g + Fe3C

Eutectoid: 0.76 wt%C, 727 C

g(0.76 wt% C)  a (0.022 wt% C) + Fe3C
 Summary
Make sure you understand language and concepts:
 Austenite  Microconstituent
 Cementite  Pearlite
 Component  Peritectic reaction
 Congruent transformation  Phase
 Equilibrium  Phase diagram
 Eutectic phase  Phase equilibrium
 Eutectic reaction  Primary phase
 Eutectic structure  Proeutectoid cementite
 Eutectoid reaction  Proeutectoid ferrite
 Ferrite  Solidus line
 Hypereutectoid alloy  Solubility limit
 Hypoeutectoid alloy  Solvus line
 Intermediate solid solution  System
 Intermetallic compound  Terminal solid solution
 Invariant point
 Tie line
 Isomorphous
 Lever rule
 Liquidus line
 Metastable
 SMART
MATERIALS
Smart materials are 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.
 DIFFERENCE BETWEEN CONVENTIONAL AND
SMART MATERIALS
 In comparison to conventional materials, smart materials
are functional, that is, they are required to undergo
purposeful and reversible changes, playing an active part
in the way the structure or device works.

 Their degree of smartness is measured in terms of their

“responsiveness” to environmental stimuli and their
“agility”.

 Responsiveness implies a large amplitude change while

agility implies a fast response
 CLASSIFICATION OF SMART MATERIALS

 PIEZOELECTRIC
 ELECTROSTRICTIVE
 MAGNETOSTRICTIVE
 SHAPE MEMORY ALLOYS
 OPTIC FIBRE
APPLICATION OF SMART MATERIALS:

• Aerospace
• Mass transit
• Marine
• Automotive
• Computers and other electronic devices
• Consumer goods applications
• Civil engineering
• Medical equipment applications
• Rotating machinery applications
SHAPE MEMORY
ALLOYS
Shape Memory Alloys (SMAs) are a unique class of
metal alloys that can recover apparent (noticeable)
permanent strains when they are heated above a
certain temperature. The SMAs have two stable
phases - THE HIGH-TEMPERATURE PHASE,
CALLED AUSTENITE AND THE LOW-
TEMPERATURE PHASE, CALLED MARTENSITE.
In addition, the martensite can be in one of two
forms: twinned and detwinned. A phase
transformation which occurs between these two
phases upon heating/cooling is the basis for the
unique properties of the SMAs. The key effects of
SMAs associated with the phase transformation are
PSEUDOELASTICITY and SHAPE MEMORY
EFFECT.
Shape memory alloys (SMAs) are metals that
"remember" their original shapes.

SMAs are useful for such things as actuators

which are materials that "change shape,
stiffness, position, natural frequency, and
other mechanical characteristics in response
to temperature or electromagnetic fields“.
TYPES OF SHAPE MEMORY ALLOYS:

COPPER-ZINC-ALUMINIUM.

COPPER-ALUMINIUM-NICKEL.

NICKEL-TITANIUM (NITI) ALLOYS.

FERROMAGNETIC SHAPE MEMORY ALLOY.

Besides the phenomenal Shape Memory behavior of NiTi alloys, two other favorable
properties are their excellent corrosion resistance and stable Configuration.
These alloys have chemical compositions in the range of 53 to 57 weight percent
nickel (= 48 to 52 atom percent, i.e. near-equiatomic alloys).

Nitinol (NiTi) has long fatigue life, relatively high ductility and corrosion resistance in
addition to displaying two unusual phenomena: the pseudoelastic effect and the shape
memory effect due to reversible martensitic transformation. For example, if NiTi
encounters a constraint during reverse transformation, it can generate extremely large
recovery stresses which provide a unique mechanism for the actuation.

The transition from the martensite phase to the austenite phase is only dependent on
temperature and stress, not time, as most phase changes are, as there is no diffusion
involved. Similarly, the austenite structure gets its name from steel alloys of a similar
structure. It is the reversible diffusionless transition between these two phases that
allow the special properties to arise.

While martensite can be formed from austenite by rapidly cooling carbon-steel, this
process is not reversible, so steel does not have shape memory properties.
COMPARION OF NITI AND NI50TI50-XMX (where
M=Hf, Pt, Pd) AND COPPER BASED ALLOYS:

– Greater shape memory strain (8% vs. 4 to 5% for

Cu-based Alloys), More Thermally Stable, Excellent
Corrosion Resistance, Higher Ductility
– Processing procedures are important to get
desired properties.

Cu-Zn-Al and Cu-Al-Ni

– Less expensive, easier to process, wider

transformation temperature range
– Moderate corrosion resistance and susceptible to
stress corrosion cracking
ONE WAY MEMORY EFFECT:

When a shape memory alloy is in its cold state (below As),

the metal can be bent or stretched and will hold those
shapes until heated above the transition temperature.
Upon heating, the shape changes to its original. When the
metal cools again it will remain in the hot shape, until
deformed again.

With the one-way effect, cooling from high temperatures

does not cause a macroscopic shape change. A
deformation is necessary to create the low-temperature
shape. On heating, transformation starts at As and is
completed at Af (typically 2 to 20 C or hotter, depending
on the alloy or the loading conditions). As is determined by
the alloy type and composition. It can be varied between
150 C and 200 C.
Two way memory effect

The two-way shape memory effect is the effect that the material
remembers two different shapes: one at low temperatures, and one
at the high temperature shape. A material that shows a shape
memory effect during both heating and cooling is called two-way
shape memory. This can also be obtained without the application of
an external force (intrinsic two-way effect). The reason the
material behaves so differently in these situations lies in training.
Training implies that a shape memory can “learn” to behave in a
certain way. Under normal circumstances, a shape memory alloy
“remembers” its high-temperature shape, but upon heating to
recover the high-temperature shape, immediately “forgets” the
low-temperature shape. However, it can be “trained” to
“remember” to leave some reminders of the deformed low-
temperature condition in the high-temperature phases. There are
several ways of doing this. A shaped, trained object heated beyond
a certain point will lose the two way memory effect, this is known
as “amnesia”.
 CRYSTAL
STRUCTURES
Many metals have several different crystal structures at the
same composition, but most metals do not show this shape
memory effect. The special property that allows shape
memory alloys to revert to their original shape after heating
is that their crystal transformation is fully reversible. In
most crystal transformations, the atoms in the structure will
travel through the metal by diffusion, changing the
composition locally, even though the metal as a whole is
made of the same atoms. A reversible transformation does
not involve this diffusion of atoms, instead all the atoms
shift at the same time to form a new structure, much in the
way a parallelogram can be made out of a square by
pushing on two opposing sides. At different temperatures,
different structures are preferred and when the structure is
cooled through the transition temperature, the martensitic
structure forms from the austenitic phase.
MANUFACTURE
Shape memory alloys are typically made by casting, using
vacuum arc melting or induction melting. These are specialist
techniques used to keep impurities in the alloy to a minimum
and ensure the metals are well mixed. The ingot is then hot
rolled into longer sections and then drawn to turn it into wire.

The way in which the alloys are “trained” depends on the

properties wanted. The “training” dictates the shape that the
alloy will remember when it is heated. This occurs by heating
the alloy so that the dislocations re-order into stable positions,
but not so hot that the material recrystallizes. They are
heated to between 400 C and 500 C for 30 minutes. Typical
variables for some alloys are 500 C and for more than 5
minutes.

They are then shaped while hot and are cooled rapidly by
quenching in water or by cooling with air.
PROPERTIES
The copper-based and Ni Ti (nickel and titanium)-based shape
memory alloys are considered to be engineering materials.
These compositions can be manufactured to almost any shape
and size.The yield strength of shape memory alloys is lower
than that of conventional steel, but some compositions have a
higher yield strength than plastic or aluminum. The yield stress
for Ni Ti can reach 500 MPa. The high cost of the metal itself
and the processing requirements make it difficult and expensive
to implement SMAs into a design. As a result, these materials
are used in applications where the super elastic properties or
the shape memory effect can be exploited. The most common
application is in actuation.One of the advantages to using shape
memory alloys is the high level of recoverable plastic strain that
can be induced. The maximum recoverable strain these
materials can hold without permanent damage is up to 8% for
some alloys. This compares with a maximum strain 0.5% for
conventional steels.
APPLICATIONS
AIRCRAFT:
Boeing, General Electric Aircraft Engines, Goodrich Corporation,
NASA, and All Nippon Airways developed the Variable Geometry
Chevron using shape memory alloy that reduces aircraft’s
engine noise. All of Boeing’s new aircraft will be equipped with
this new technology.
PIPING:
The first consumer commercial application for the material was
as a shape memory coupling for piping, e.g. oil line pipes for
industrial applications, water pipes and similar types of piping
for consumer/commercial applications. The late 1980s saw the
commercial introduction of Nitinol as an enabling technology in
a number of minimally invasive endovascular medical
applications. While more costly than stainless steel, the self
expanding properties of Nitinol alloys manufactured to BTR
(Body Temperature Response), have provided an attractive
alternative to balloon expandable devices. On average, 50% of
all peripheral vascular stents currently available on the
worldwide market are manufactured with Nitinol.
ROBOTICS:
There have also been limited studies on using these materials in robotics (such as
“Roboterfrau Lara”), as they make it possible to create very light robots. Weak
points of the technology are energy inefficiency, slow response times, and large
hysteresis.Nitinol wire is also used in robotics (e.g. the hobbyist robot Stiquito) and
in a few magic tricks, particularly those involving heat and shapeshifting.

MEDICINE:
Optometry
Eyeglass frames made from titanium-containing SMAs are marketed under the
trademarks Flexon and TITANflex. These frames are usually made out of shape
memory alloys that have their transition temperature set below the expected room
temperature. This allows the frames to undergo large deformation under stress,
yet regain their intended shape once the metal is unloaded again. The very large
apparently elastic strains are due to the stress-induced martensitic effect, where
the crystal structure can transform under loading, allowing the shape to change
temporarily under load. This means that eyeglasses made of shape memory alloys
are more robust against being accidentally damaged.
ORTHOPAEDIC SURGERY:

This section is in need of attention from an expert on the subject.

WikiProject Medicine or the Medicine Portal may be able to help recruit one.
(February 2009)Memory metal has been utilised in orthopaedic surgery as a
fixation device for osteotomies, typically around the foot and ankle. The
device, usually a staple, is stored in a refrigerator in its malleable form and is
implanted into pre-drilled holes in the bone across an osteotomy. As the
staple warms it returns to its non-malleable state and compresses the bony
surfaces together to promote union of the osteotomy.

DENTISTRY:

The range of applications for SMAs has grown over the years, a major area of
development being medicine. One example is the prevalence of dental braces
using SMA technology to exert constant tooth-moving forces on the teeth; the
nitinol archwire was developed in 1972 by orthodontist George Andreasen. This
revolutionized clinical orthodontics and has also had an effect on fiber optic
development. Andreasen’s alloy has a patterned shape memory, expanding and
contracting within given temperature ranges because of its geometric
programming.
Harmeet D. Walia later utilized the alloy in the manufacture of root canal files
for endodontics
Alloys of metals having the memory effect at different temperatures and at
different percentages of its solid solution contents.

Ag-Cd 44/49 at.% Cd

Au-Cd 46.5/50 at.% Cd

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

Cu-Sn approx. 15 at.% Sn

Cu-Zn 38.5/41.5 wt.% Zn

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

Fe-Pt approx. 25 at.% Pt

Mn-Cu 5/35 at.% Cu

Fe-Mn-Si

Pt alloys
Pt alloys

Co-Ni-Al

Co-Ni-Ga

Ni-Fe-Ga

Ti-Pd in various concentrations

Ni-Ti (~55% Ni)

Ni-Mn-Ga
PHYSICAL PROPERTIES OF NITINOL

• Density: 6.45gms/cc
• Melting Temperature: 1240-1310° C
• Resistivity (hi-temp state): 82 uohm-cm
• Resistivity (lo-temp state): 76 uohm-cm
• Thermal Conductivity: 0.1 W/cm-° C
• Heat Capacity: 0.077 cal/gm-° C
• Latent Heat: 5.78 cal/gm; 24.2 J/gm
• Magnetic Susceptibility (hi-temp): 3.8 uemu/gm
• Magnetic Susceptibility (lo-temp): 2.5 uemu/gm
MECHANICAL PROPERTIES OF NITINOL

•Ultimate Tensile Strength: 754 - 960 MPa or 110 - 140 ksi

• Typical Elongation to Fracture: 15.5 percent
• Typical Yield Strength (hi-temp): 560 MPa, 80 ksi
• Typical Yield Strength (lo-temp): 100 MPa, 15 ksi
• Approximate Elastic Modulus (hi-tem): 75 GPa, 11 Mpsi
• Approximate Elastic Modulus (lo-temp): 28 GPa, 4 Mpsi
• Approximate Poisson's Ratio: 0.3

ACTUATION

• Energy Conversion Efficiency: 5%

• Work Output: ~1 Joule/gram
• Available Transformation Temperatures: -100 to +100° C
 PSEUDOELASTICITY
AND
SHAPE MEMORY EFFECT
THE THERMAL MEMORY-EFFECT (ONE WAY- OR TWO WAY EFFECT):

Even more spectacular than the mechanical memory effect is the „thermal
memory effect“: after an obvious „plastic“ deformation of e.g. a paper clamp
or a spring made of memory metal wire the alloy recovers the initial shape
upon heating with a hot tea, a lighter or an electrical current. In contrast to
the competing Bi-metal the deformation is not limited to just pure bending:
tensional and torsional deformations are also possible and even mixtures of
all kinds of deformation are useable. Furthermore, the materials generate
very high forces if the shape recovery is hindered by an external mechanical
component. Thus, a 4 mm diameter actuator wire made of „NiTiNOL“
memory alloys is able to lift up to 1 ton of load for at least one time. In order
to prevent „amnesia“ of being the limiting factor for the life cycle of the
actuator, the actuator load in this example should be reduced to about 150
kg, which is still a very high force output. However, the generation of very
high forces is not the strength of shape memory actuators, as most
applications of memory metal make use of max. 10 N force. The “thermal”
Memory Effect occurs upon heating of a Memory metal, which has been previously
deformed „plastically“. A high specific mechanical work is generated.
A shape memory alloy is capable of remembering a previously memorized shape. It
has to be deformed in its low temperature phase Martensite and subsequently
heated to the high temperature phase Austenite, e.g. in hot water or with
anelectrical current. The alloy generates a high force during the phase
transformation. Thus, it can be used as an actuator in a multitude of different
applications. The shape change is not restricted to just pure bending. The most
suitable actuation mode has proved to be the linear contraction of a straight wire
actuator.In contradiction to the mechanical shape memory effect, the thermal shape
memory effect is related to a heat stimulus, with which the Memory-Metal is capable
of delivering a high amount of work output per material volume.

The martensitic low temperature phase can be deformed similar to pure Tin: it can
be bent back and forth without strain hardening. Thus, the risk of breakage of a
component made from martensitic NiTinol is significantly lower as for instance in
stainless steel. And finally when heated into the austenitic phase, the alloy recovers
its initial shape.

The metallurgical reason for the martensite deformability is the twinned structure of
the low temperature phase: the twin boundaries can be moved without much force
and without formation of dislocations, which can be considered as being the initiator
of fracture.
 LOAD INDUCED PHASE TRANSITION OF 85 ATOMS OF TWO TYPES

Screenshot 1 : 85 particle body at initial

configuration.

In this simulation 85 atoms of type "yellow" and "red" are initially placed in a
square (austenitic) lattice as shown in screenshot 1.
The process is performed at a low and constant temperature level. Thus the
Lennard-Jones parameters are chosen such as to provide a stable austenitic
lattice even at low temperatures. Therefore this experiment investigates the
mechanic properties of the body, rather than its thermodynamics.
 Screenshot 2 : Setup of the load-controlled
experiment. Positive Loading.

We will apply an increasing load in the horizontal direction to the uppermost

row of atoms and record the displacement of this row from its initial position
as calculated by the dynamic simulation algorithm. Screenshot 2 illustrates
this setup.
 Screenshot 3 : Opposite shearing under
negative loading

The load increases up to a maximum, and this increase is followed by

unloading. After the zero load is passed, the process is repeated for a load
in the opposite direction as shown in screenshot 3:
The applied loads may be plotted versus the calculated displacements so
as to give the following load-displacement-plot:
1: Initially the block exists in the rectangular, austenitic lattice. In this
configuration, the uppermost row has zero displacement. The loading starts.

With increasing load the block is sheared elastically. The load-displacement

curve shows a nearly linear progress, superposed by small oscillations of
the block as such. If we idealize this part of the curve as a straight line, its
slope provides the Young modulus of the austenite.
2: At a certain critical load -- the yield load -- the phase transition occurs.
3: While the phase transition occurs, the load remains constant. The crystal
lattice is sheared into the martensitic configuration. A large displacement at
the yield load is observable; this horizontal part of the load-displacement-
plot is called the yield line. In order to keep the temperature constant we
must cool.
4: At the end of the yield-line the load increases again. The displacement is
proportional to the load. Thus a second linearly-elastic line is found, whose
slope provides the Young modulus of the martensite. Afterwards the load is
reduced.
 6 At constant recovery load (still positive), the displacement is recovered:
- Under this load, we observe a shearing motion of the martensite back
> into the austenite. This process is dynamic and we must cool so as to
7 prevent the lattice to break through to the left. A significant, large
: hysteresis has occured during the loading/unloading process.
7 The body is in the austenitic configuration again, slightly sheared. Thus
: this point is located on the austenitic elastic line. Further unloading to
zero load leads back to the original shape.

Afterwards the body may be loaded in the opposite direction, and a

symmetric load-displacement plot is shown: Linearly-elastic loading of the
austenite (8), the occurrence of a critical yield load (9), the large
displacement along the yield-line (10) and the linearly-elastic shear of the
martensite (11). Upon unloading: Unloading along the martensitic elastic line
(11-12), the occurrance of the recovery load (12), the recovery line into the
austenitc state (13).
Temperature induced phase transition of 230 atoms of two types:

Screenshot 1 : 230
particle body under
adiabatic condition.
Austenitic Phase.

230 atoms of type "red" and "yellow" are placed into a rectangular square lattice. The
Lennard Jones parameters are chosen in an appropriate manner: At low temperatures,
the square lattice is not a stable configuration. However, if a higher initial temperature
is applied to the body, this square lattice becomes stable! The initial temperature is
chosen by fixing the initial velocities. Calculation under adiabatic conditions for an
extended lapse of time proves that the austinitic lattice is stable at this temperature
level, although significant thermal fluctuations can be observed. The bottom row of
atoms (marked blue) is fixed over time so as to avoid the movement of the block as a
whole. Screenshot 1 shows the 230 atom body under adibatic conditions in the
austenitic phase:
After some time, the cooling process starts. We observe the decay of the
mean kinetic energy over the time in the small upper window on the right-
hand side of screenshot 2:

Screenshot 2 : 230 particle body under temperature control. Cooling the body.
After some time the critical transformation temperature is reached. From this
time on we observe a martensitic transformation in progress: The whole
block does not transform at once. Rather we observe that some rows
transform as one layer, followed by some further rows, which act as a second
layer and so forth. Screenshots 3 and 4 illustrate this process.

Screenshot 3 : Transformation in progress: First layer starts to transform.

Screenshot 4 : Transformation in progress: Transforamtion of first and
second layer is finished. We observe how the transformation wave rushes
over the body. At the end the whole body has been transformed from the
austenitic lattice into the martensitic lattice.
We observe that not all layers possess the same shear-direction: Some are
tilted to the right, others to the left. This phenomenon is well known in
material science and it is called "twinning". Screenshot 5 shows the body,
when the transformation has ended.

Screenshot 5 : 230 particle body, transformed into the martensitic phase.

Shape Memory Alloys (SMA's) are all alloys exhibiting the Shape Memory
Effect (SME),i.e. if a specimen of these alloys is deformed "plastically"
(under well defined conditions),the resulting apparently permanent
deformation can easily be reversed by simply heating the specimen up
above a specific temperature, returning the specimen to its original shape;
Shape Memory Alloys are capable to 'remember' their high temperature
shape. A Shape Memory Alloy can be in two phases, i.e. a high temperature,
'austenite', or 'parent' phase and a low temperature, 'martensite' or
'product' phase. The terms parent phase and martensite phase will mostly
be used. If a specimen at a high temperature, being fully parent phase, is
cooled, then at a specific temperature M, (M of Martensite, s of start)
martensite starts to form. This transformation proceeds on further cooling
until at a temperature Mf (f of finish) the specimen is wholly martensite. On
heating again, the reverse transformation takes place, starting at a
temperature As (A of Austenite), which may only be the same as Mf by
coincidence, and ending at Af . Both the P(arent) + M and M -+ P
transformations are normally not attended by a macroscopic shape change:
nothing seems to happen from the outside. As will be seen, a lot does
happen on the inside.In order to show the Shape Memory Effect, the
martensite has to be deformed 'plastically'; the resulting permanent
macroscopic deformation disappears on heating the specimen above Af. In
this way strains of 6-8% allow for full shape recovery. (The maximum value
of elastic strain in steel or aluminium is about l%!)
The Shape Memory behaviour is basically a consequence of a martensitic
transformation, which in his turn is a change of crystal structure.

The two unique properties described above are made possible through a
solid state phase change, that is a molecular rearrangement, which
occurs in the shape memory alloy. Typically when one thinks of a phase
change a solid to liquid or liquid to gas change is the first idea that comes
to mind. A solid state phase change is similar in that a molecular
rearrangement is occurring, but the molecules remain closely packed so
that the substance remains a solid. In most shape memory alloys, a
temperature change of only about 10°C is necessary to initiate this phase
change. The two phases, which occur in shape memory alloys, are
Martensite, and Austenite.

Martensite, is the relatively soft and easily deformed phase of shape

memory alloys, which exists at lower temperatures. The molecular
structure in this phase is twinned which is the configuration shown in the
middle of Figure 2. Upon deformation this phase takes on the second
form shown in Figure 2, on the right. Austenite, the stronger phase of
shape memory alloys, occurs at higher temperatures. The shape of the
Austenite structure is cubic, the structure shown on the left side of Figure
2. The un-deformed Martensite phase is the same size and shape as the
cubic Austenite phase on a macroscopic scale, so that no change in size or
shape is visible in shape memory alloys until the Martensite is deformed.
Figure:2
The temperatures at which each of these phases begin and finish forming are
represented by the following variables: Ms, Mf, As, Af. The amount of loading placed
on a piece of shape memory alloy increases the values of these four variables as
shown in Figure 3. The initial values of these four variables are also dramatically
affected by the composition of the wire (i.e. what amounts of each element are
present).

The Dependency of Phase Change Temperature on Loading

Microscopic Diagram of the Shape Memory Effect
The shape memory effect is observed when the temperature of a piece
of shape memory alloy is cooled to below the temperature Mf. At this
stage the alloy is completely composed of Martensite which can be
easily deformed. After distorting the SMA the original shape can be
recovered simply by heating the wire above the temperature Af. The
heat transferred to the wire is the power driving the molecular
rearrangement of the alloy, similar to heat melting ice into water, but
the alloy remains solid. The deformed Martensite is now transformed to
the cubic Austenite phase, which is configured in the original shape of
the wire.
PSEUDOELASTICITY
THE SUPERELASTICITY OR MECHANICAL MEMORY:

The superelastic effect of memory alloys is characterized by the impressive

amount of possible „elastic“ strain, which is more than 20x higher compared
to conventional materials. It is beyond elasticity,therefore called
„Superelasticity“. The effect is based on a internal transformation of the
crystal structure, which is called „Austenite“ in the initial condition and which
transform to the „Martensite“ (this phase is well-known from steel hardening)
if external stresses affect the material. The phase transformation is related to
the appearance of a pseudo-elastic strain, giving the effect its name
superelasticity. After releasing the stress the material recovers the initial
shape and temperature changes are not necessary for the occurance of the
effect. The presently most interesting applications of the superelastic effect
can be found in medical implants and instruments, where e.g. the availabilty
of thin-walled tubing the market of stents has opened for the Memory Alloys.
Due to the high elasticity the stents can be folded into of catheter sheeth and
pushed into the vessel, where they expand and provide a force to keep the
vessel open.
Pseudo-elasticity occurs in shape memory alloys when the alloy is completely
composed of Austenite (temperature is greater than Af). Unlike the shape
memory effect, pseudo-elasticity occurs without a change in temperature. The
load on the shape memory alloy is increased until the Austenite becomes
transformed into Martensite simply due to the loading; this process is shown
in Figure below. The loading is absorbed by the softer Martensite, but as soon
as the loading is decreased the Martensite begins to transform back to
Austenite since the temperature of the wire is still above Af, and the wire
springs back to its original shape.

Load Diagram of the pseudo-elastic effect Occurring

NiTiCr: Superelastic alloys containing up to 1% chromium to improve
strength.

NiTi-6.0% Cu: Shape memory alloys containing copper to reduce the

transformation temperature range and mechanical hysteresis.

NiTi-1.6% Fe: Superelastic NiTi with Fe to improve cold workability and

stabilize R-phase transformation.

NiTi-3.4% Fe: Superelastic NiTi with Fe to reduce transformation

temperature to the cryogenic temperature range; alloy also has higher cold
workability.
DSC
DSC
 HEAT TREATING AND SHAPING

Nitinol and other shape memory alloy mill products - bar, wire, ribbon and sheet are
normally finished by cold working to achieve dimensional control and enhance surface
quality. Cold working suppresses the shape memory response of these alloys. It also
raises the strength and decreases the ductility. However, cold work does not raise the
stiffness of the material. Heat treating after cold working diminishes the effects of cold
working and restores the shape memory response of these alloys. Therefore, in order to
optimize the physical and mechanical properties of a Nitinol product and achieve shape
memory and /or superelasticity, the material is cold worked and heat treated. The mill
product supplier normally provides the material in the cold worked condition. The
maximum practical level of cold work will be limited by the alloy and by the product
section size. Binary superelastic NiTi alloy fine wires with As in the range of –25 to
+95°C are typically supplied with cold reduction after the final anneal in the range of 30
to 50%. Higher reductions are sometimes used for very fine wires. These same alloys
will be limited to about 30% maximum cold reduction in larger diameter bar sizes.
Binary NiTi alloys with very low As in the range of –50 to –60 °C will not sustain the
higher levels of cold work without cracking. Both superelastic and shape memory
properties are optimized by cold work and heat treatment. This thermo-mechanical
process is applied to all Nitinol alloys although different amounts of cold work and
different heat treatments may be used for different alloys and property requirements.
Shape setting is accomplished by deforming the Nitinol to the shape of a desired
component, constraining the Nitinol by clamping and then heat treating. This is
normally done with material in the cold worked condition, for example cold drawn
wire. However, annealed wire may be shape set with a subsequent lower temperature
heat treatment. In shape setting cold worked material, care must be taken to limit
deformation strain to prevent cracking of the material. Another approach is to partially
anneal the wire prior to shape setting. Yet another option is to shape set in
incremental steps. Smith et al. reviewed the types of furnaces and fixturing hardware
or mandrels that have been used in heat treatment. Many types of furnaces have been
used including box furnaces, continuous belt hearth furnaces, tube furnaces, heated
platen presses, vacuum furnaces, induction heaters, salt baths and fluidized bed
furnaces. The electrical resistance of Nitinol makes it a good candidate for self heating
by electric current. Nitinol will be oxidized when heat treated in air. Therefore, surface
requirements and atmosphere control are important considerations. Shape setting can
be done over a wide temperature range from 300 °C to 900°C. However, heat treating
temperatures for binary NiTi alloys are usually chosen in the narrower range of 325 to
525°C in order to optimize a combination of physical and mechanical properties. Heat
treating times are typically 5 minutes to 30 minutes. Consideration must be given to
the mass of the heat treating fixture as well as the mass of the product. Sufficient time
must be allowed in the furnace to get the entire mass to the desired temperature.
The shape setting heat treatment changes the physical and mechanical properties of
Nitinol. Morgan and Broadly mapped the effect of temperature and time at temperature
on shape set wire properties. Their response curves illustrate that physical and
mechanical property do not always change in the same direction. Also, some properties
are not monotonic functions of time at temperature. For example, upper plateau stress
goes through a minimum as a function of time at temperature when heat treating a
superelastic alloy in the range of 450°C to 550°C. This can be understood in terms of
the complex precipitation response of the nickel rich Ni – Ti alloys. Precipitation
processes in nickel rich NiTi were studied in detail by Nishida et al. Their TTT diagram
shows that in a Ti – 52 atomic % Ni alloy heat treated below 820oC, precipitation starts
as fine Ti11Ni14 transitions over time to Ti2Ni3 and terminates after long time as TiNi3
in equilibrium with the NiTi matrix. All the while, the NiTi ratio in the matrix is being
shifted towards higher Ti content and higher transformation temperature. Pelton et al.
reported on the combined effects of non-isothermal and isothermal heat treatment on
the physical and mechanical properties of Nitinol wire. This work suggests that for a
50.8 atomic % Ni alloy Ti11Ni14 dissolves at about 500oC and Ti2Ni3 will start to
precipitate at 550oC. This results a minimum or maximum in properties as NiTi ratio in
the matrix goes through a peak. Furthermore, this analysis suggests that the
temperature for transition from Ti11Ni14 precipitation to Ti2Ni3 precipitation occurs at
higher temperatures for higher Ni content alloys. Brailovski used measurement of latent
heat measured by DSC and Vickers hardness to map mechanical and physical properties
as a function of heat treatment. He obtained maximum fatigue performance when the
combination of transformation temperature and hardness were optimized.
Shape memory effect: Shape memory alloys in martensite, if thermally
stimulated by external heat or internal electrical current flow (Joule effect),
exhibit a reversible thermoelastic martensitic transformation with a macroscopic
shape change.

Super elastic effect:When mechanically loaded, a shape memory alloy in

austenite deforms reversibly to very high strains - up to 10% - by the creation of
a stress induced martensitic phase. When the load is removed the material
regains its original shape.

Small changes in the composition can change the transition temperature

of the alloy significantly. For this reason, SMA may be in austenite or in
martensite at room temperature, showing either superelastic or shape
memory properties.

Histeresys cycle for Superelastic and shape memory material

WHY NITINOL
Af-Temperature: Temperature, above which the phase transformation from Martensite to
Austenite is fully completed during heating of the alloy.

Actuator: Device made out of a shape memory alloy, which is able to provide a
significant amount of mechanical work due to the occurrence of the phase
transformation during heating. Actuation force and displacement are functions of the
actuator geometry and design.

Apeak- or Ap-Temperature: Temperature, at which the phase transformation from

Martensite to Austenite shows the maximum of heat flow during heating. The alloy
needs a certain amount of energy (heat flow) to initiate the phase transformation and to
move the phase boundary through the alloy.

The maximum is a value which can be accurately measured in a DSC equipment,

whereas the As and Af-temperature measurements are sometimes lacking reproduce
ability.

As-Temperature: Temperature, at which the phase transformation from Martensite to

Austenite is initiated during heating of the alloy.

Austenite: Crystallographic description of the high temperature phase of a shape

memory alloy, which starts to form during heating of the low temperature phase
Martensite when the As-temperature is passed. The formation of Austenite is completed
above the Af-temperature.
DSC (Differential Scanning Calorimetry): Calorimetric method for the
characterization of a shape memory alloy with respect to its transformation
temperatures. The DSC measures the specific heat flow, which changes constantly
during the phase transformation. The overall accuracy and the ease of usage of the
DSC equipment together with the high reproduce ability makes it the most suitable
method for alloy characterization. The main disadvantage of the DSC is the fact, that
material deformation and external load cannot be simulated with this measurement.

Hysteresis:
a) thermal hysteresis:The thermal hysteresis means generally the difference between
the Apeak- and the Mpeak-temperatures.The hysteresis appears during passing of
the transformation temperatures and is affected by a number of parameters (alloy
composition, thermo-mechanical treatment, external load, etc.).
b) mechanial hysteresis:The mechanical hysteresis appears during loading and
unloading of a shape memory component in its high temperature phase above Af.
The NiTinol component shows a large amount of strain during loading, which
recovers during unloading. The necessary force to initiate the transformation during
loading is higher as the released force during unloading.

Martensite: Crystallographic description of the low temperature phase of a shape

memory alloy,which starts to form during cooling of the high temperature phase
Austenite when the Ms-temperature is passed. The formation of Martensite is
completed below the Mf-temperature. But the Martensite can also be induced during
loading of the Austenite above Mf. This is related to a large amount of recoverable
Phase transformation (here: martensitic phase transformation): Physical mechanism,
which is the metallurgical basis of the shape memory effect. The term martensitic phase
transformation describes the formation of Martensite during cooling OR during loading
with an external stress of the austenitic high temperature phase.
R-Phase: Phase, which appears under certain conditions in for instance NiTinol alloys
and which is still considered as being a ‚pre-martensitic‘. The R-phase is related to some
anomalies of certain functional properties. The R-phase transformation shows a very
narrow thermal hysteresis, but at the same time a very small amount of work output.
Applications of the R-phase transformation are very hard to find in the market.
Superelasticity: Sometimes compared to a rubber-like deformability of shape memory
alloys, which occurs during application of an external stress on the austenitic high
temperature phase above Af.Thus, the superelastic effect is related to about 8% of
recoverable elastic stress, for which temperature changes are not necessary. The
superelasticity occurs basically in the same alloys as the thermal shape memory (one
way effect).Thermomechanical treatment: Treatment of a shape memory alloy
consisting out of a combination between colk working steps and annealing processes.
The purpose of the thermomechanical treatment is the adjusting of a number of
functional properties, like e.g. the phase transformation temperatures. Usually the
annealing of the component or the semi-finished shape is the last step of the fabrication
process.
Transformation temperatures: Temperature values, at which start and finish of the
phase transformation can be measured (Ms-, Mf-, As-, Af-temperature).
Two way effect: Special form of the thermal shape memory effect, in which not just
the heating but also the cooling of the shape memory element are subject to shape
changes. This effect is induced either by a special thermomechanical treatment
(‚Training‘) or through external stresses during cooling.For design and industrial
application of actuators this latter option is highly preferred for as multitude of
reasons.
SHAPE SETTING OF NITINOL:The application of a NiTinol shape memory or
superelastic element for a particular purpose generally requires the setting of a custom
shape in a piece of NiTinol. The process required to set the shape is similar whether
beginning with NiTinol in the form of wire, ribbon, strip, sheet, tubing, or bar. Shape
setting is accomplished by constraining the NiTinol element on a mandrel or fixture of
the desired shape and applying an appropriate heat treatment. The heat treatment
methods used to set shapes in both shape memory and superelastic forms of NiTinol
are similar.The heat treatment parameters chosen to set both the shape and the
properties of the part are critical, and usually need to be determined experimentally
for each desired part's requirements. In general, temperatures as low as 400 deg.C
and times as short as 1-2 minutes can set the shape, but generally one uses a
temperature closer to 500 deg.C and times over 5 minutes. Rapid cooling of some
form is preferred via a water quench or rapid air cool (if both the parts and the fixture
are small). Higher heat treatment times and temperatures will increase the actuation
temperature of the part and often gives a sharper thermal response (in the case of
shape memory elements). However, there is usually a concurrent drop either in peak
force (for shape memory elements) or in plateau stresses (for superelastic
elements).There is also an accompanying decrease in the ability of the NiTinol element
A. Chemical Composition
NiTinol alloys are mainly use due to their specific functional properties. These
properties are related to the martensitic phase transformation, which is controlled by
two independent parameters: the mechanical stress and the temperature. This
means, that a NiTinol alloy can transform from the austenitic high temperature phase
into the martensitic low temperature phase due to the following reasons: S an
increasing mechanical stress exerted on the specimen S a decreasing temperature
below the martensitic transformation temperatures. or a combination of both. Usualy,
the transformation behavior of NiTinol is characterized at a stress level of zero by
measuring the characteristic transformation temperatures As, Af or Apeak. The
chemical composition of a intermetallic compound can certainly be measured, but it
has shown to be very critical to bring chemical composition and transformation
temperatures in relationship to each other. The reasons for this is: S The most
precise method to analyze composition of NiTinol is the wet chemical analysis.
This method shows the Ni and Ti composition with a tolerance of 0.2 wt-%.S The
whole range of commercially available alloys is covered by a composition range of
less than 2 wt-% of Ni content changes. With this composition window, the NiTinol
alloys cover as much as -100°C up to +100°C for the As temperatures. As a
consequence, we can derive that a small change in chemical composition (such as we
find in the tolerance window of the chemical analysis) leads to a wide window of
transformation temperatures. Therefore, this pure measurement of chemical
composition is considered to be unsuitable for the specification of NiTinol. Today, the
specification of the alloy types by transformation temperatures which are measured
in a well defined thermo-mechanical condition (annealing at 800 to 850 °C/15 min.)
is widely accepted.
B. CLASSIFICATION OF ALLOY TYPES:

As a consequence of the said, NiTinol alloys are classified Austenite transformation

temperatures in the so-called ‚fully annealed condition‘ at zeron stress rather than by
chemical composition. We basically distinguish between 6 different alloys and a seventh
alloy that is derived from the others:

S Alloy N (superelastic standard alloy) with an Af temperature around -10 to -15°C.

This alloy is used widely e.g. in guidewires, medical instruments and implants. The
measured compositional average is around 51.0 at-% Ni. The alloy is very sensitive
to effects of so-called thermo-mechanical treatments.
S Alloy S (superelastic standard alloy) with an Af temperature around 0°C (slightly
‚warmer‘than alloy N). This alloy is used widely medical instruments and implants. The
measured compositional average is around 50.8 at-% Ni.

S Alloy C (Cr-doped superelastic alloy) with an Af temperature around -10 to -20°C.

This alloy is used for applications where a slightly higher stiffness or torqueability is
required, such as guidewires and other medical instruments or implants. The measured
Cr content is around 0,25 wt-%.

S Alloy B (standard alloy for body temperature shape memory applications) with an Af
temperature around +25 to +35°C. This alloy is used in applications, where a shape
change due to changes in temperatures around body temperature is required. The
measured compositional average is around 50.2 to 50.4 at-% Ni.
S Alloy M (standard alloy for intermediate temperature actuation) with an Af
temperature around +55 to +65°C. This alloy is used in applications, where a shape
change due to changes in temperatures is required. The measured compositional
average is around 50.0 to 49.8 at-% Ni.

S Alloy H (standard alloy for higher temperature actuation) with an Af temperature

around +95 to +110°C. This alloy is mainly used in actuator applications, where an
electrical current (or boiling water) are used as actuation energy. The measured
compositional average is around 49.6 to 49.4 at-% Ni.

S FlexinolTM wire: this is a special actuator alloy generated by a proprietary process

from either alloy M or alloy H exclusively for use in straight wire actuators with
maximum performance.
C. THERMOMECHANICAL CONDITIONS:

NiTinol materials are typically supplied in two different thermomechanical conditions:

S straight annealed: this is the standard condition, with which the alloy is annealed to a
well defined straight shape using a standard process with a certain furnace temperature
(around 500 °C), for a certain period of time under a defined tensile load. This
process leads to a good average of functional properties and is suitable for a multitude
of applications.

S shape annealed: the Nitinol alloy is shape-set by a certain heat treatment to a custom
specified shape (e.g. expanded to a stent or coiled to a spring). This is done
with steel fixtures or tools in different types of furnaces or salt baths.

S as cold worked: material is supplied in this condition is neither straight (or flat) nor
does it have good functional properties. Customers typically order this material when
they want to apply their own heat treatment to the wire. However, it is recommended
to order NiTinol in the shape annealed condition, which gives Memory-Metalle GmbH
the chance to carry out the heat treatment under tightly controlled conditions.

S actuator optimized: this process can only be applied to thin wire and is done by using
a proprietary process, which Memory-Metalle GmbH has exclusively licenced from
its partner company Dynalloy, Inc. The special trade name of this kind of material is
FlexinolTM.
PHASE DIAGRAMS FOR NITINOL