Intermetallics, Refractory

metals and alloys, High

temperature ceramic
materials, Shape memory
alloys,

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MME 5122: MANUFACTURING MATERIALS
Content:
Inter-metallic like-Aluminides, Silicides,
Borides, Nitrides Carbides

Reference books:
Introduction to Physical Metallurgy - Avner S.H., (3e), McGraw
Hill, 2004.
Heat treatment, structure and properties of Nonferrous alloys-
Charlie R Brooks, Americal Society for Metals, Metals Park, Ohio.
Materials Science and Engg., - I P Singh, Rajesh K Prasad, Subhash
Chander, Jain Brothers, New Delhi.

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Intermediate alloy phase and Compounds

Exhibits definite melting or solidification

temperature.
Cooling curve is similar to that of pure metal.
These phases are said to be Congruent melting
phase.
The chemical composition is intermediate
between two pure metals and is generally
constant or changes in narrow margin w r t
temperatures.
Crystal structure is different from
solvent(atleast). 3
A3, Acm upper
critical
temperature
Fe3C
Phase diagram of Al Cu alloy

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Fig.: The Ti-Al phase diagram 6
(T.B. Massalski, 1990)
TiMn2

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 Ni-Al phase diagram

Ni3Al

Al
Ni
Solid solutions
A homogeneous mixture of atoms of two or more elements in
solid state. It is a single phase system.
Atoms of different elements in it cannot be either mechanically
separated or physically distinguished.
In a solid solution, the metal in the major portion is called the
solvent.
The metal in the minor portion is called the solute.
The amount of solute that can be dissolved by any solvent is
function of temperature with pressure as constant.
-Changes with temperature.

Types of solid solutions:

Interstitial Solid Solutions

Substitutional Solid Solutions
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 Interstitial Solid Solution
These are formed when atoms of small atomic radii fit
into the interstitial spaces of larger solvent atoms.
Atoms of elements such as carbon, nitrogen, boron,
hydrogen, etc. which have radii less than 1 Ao are likely
to form interstitial solid solutions.
Favorable conditions: Solvent atoms
Solute atoms

1. Solvent is metal (W, Fe, Mo, Co)

Solute is non metal (C, N, B)
2. The atomic radii differences is
very high ( > 15%)
3. Solubility of solute in solvent is
very less to get solid solution. Interstitial solid solution

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4. Solute occupies at interstitial space in solvent unit
cell.
E.g. In -Fe, C atoms having smaller size (C atoms radius
being 0.7 Ao) occupy the interstitial sites of Fe atoms (Fe
atoms radius being 1.4 Ao). The solubility of C atoms is very
low in -Fe, as low as 0.025% (weight percentage) at 724oC
and as low as 0.008% at room temp.

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 Substitutional Solid Solution

Solute atoms substitute the atoms of the solvent in the crystal

structure of the solvent.
For example, the Au-Ag solid solution, the Ag (silver) atoms
substitute for the Au (gold) atoms in the FCC structure of gold.
Solvent and solute atoms have almost the same size with a slight
difference. This results in only a slight distortion of the solvent
crystal lattice structure.
The crystal structure of the solute and the solvent are the same.
The solubility of the solute in solvent is usually much higher
when compared to that of interstitial solid solution.

There are 2 types of substitutional solid solutions:

Ordered Substitutional Solid Solutions
Disordered Substitutional Solid Solution
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 Ordered Substitutional Solid Solution: In this type, the solute
atoms occupy fixed positions in the solvent unit cell. Generally
obtained on very slow cooling & only particular composition
ranges. Ex.: Super lattices.

Disordered Substitutional Solid Solution: Atoms do not occupy

any fixed positions but are distributed randomly in the lattice
structure of the solvent. In this type, the concentration of solute atoms
may vary considerably throughout the lattice structure.

Subtitutional atom

Parent atom

Disordered Substitutional Solid Solution Ordered Substitutional Solid Solution

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Hume - Rothary Rules: Regarding the formation of substitutional solid
solutions. The following requirements are satisfied in the selection of
elements for alloy formation, substitutional solid solution with unlimited
solubility forms.
Crystal structure factor: For complete solid solubility of two elements, both
should have the same type of crystal structures. For example, in Au Ag, Cu Ni,
Sb-Bi both components forming the solid solutions have same crystal structures.
Relative Size Factor: The atoms of solute and solvent should have approximately
the same atomic size. This factor is satisfied if the difference in the atomic radii of
the two elements is less than 15%. Less than 8% higher solubility, 8 to 15% lesser
solubility and greater than 15% least or no solubility.

0.1%
Ag and Pb-----FCC, rd=20%, Sb and Bi----Rhombohedral, rd=20%
1.5% Complete solubility.

Sb - Al 0.1%, rd=2%
 Chemical Affinity Factor: For a substitutional solid solution to form, the two metals should
have very less chemical affinity. Higher electro negativity of two elements, greater is the
chance of forming a compound rather than a solid solution. Greater the chemical affinity
between the two metals, lesser is the chances of forming a solid solution. Generally, the
farther apart the elements are in the periodic table, the greater is their chemical affinity. Mg
Pb, Mg Sn, Cu-Al
The atomic no. of Mg is 12, Cu is 29, Al is 13, Pb is 82, Sn is 50, Zn is 30.
Ex. Mg3Zn3Al2, Mg2Pb, Mg2Sn, CuAl2 (Compounds )

Relative Valence Factor: Lower valence is favourable for solid solubility. Among two
metals, which have satisfied all the above rules, the metal with lower valency tends to
dissolve more amount of higher valence metal and vice-versa.
Cu-Zn system, solubility of Zn (valency 2) in Cu (valency 1) is about 40%, solubility of
Cu in Zn is negligible.
5%
Al-Ni (lower valence) ---system, rd=14%, Al valence 3, Ni valence 2, both has FCC.
0.04%, They do not have chemical affinity to each other.
 Intermediate Phases
Some metal alloy systems exhibit total or partial solubility and others are
insoluble in the solid state. Metals combine together to form an
intermediate phase (intermediate compounds) along with sold solutions.
An intermediate phase is nothing but a compound and is made up of two
or more elements of which at least one of them is a metal. Generally,
compound is a chemical combination of positive and negative
valence elements. These phases are expressed by chemical formulae
like Fe3C, Mg2Pb, Mg2Sn, CuAl2 etc. The atoms combine to form
molecules which are smallest units of a compound. The atoms are held
together by covalent or ionic bond. Most of the intermediate phases are
crystalline in nature, exhibit definite melting points and have the
same cooling curves as pure metals. Intermediate phases are having
definite compositions and possess crystal structure different from
those of solvent metals. Types of intermediate alloy phases are:
i) Intermetallic or Valence Compounds ii)Interstitial Compounds
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iii) Electron Compounds
 Intermetallic or Valence Compounds
These compounds are of definite chemical formula and arise if the two
alloying metals are of different crystal structures, valency, and if one
of these metals is highly electro- positive with the other being highly
electro- negative.
Exclusively metal-metal systems with fixed or a narrow range of
composition are called intermetallic compounds. These are formed
between chemically dissimilar metals and are combined by following
the rules of chemical valence. Hume Rothery rule states that greater
the chemical affinity of two metals, lesser is solid solubility. On the
other hand this condition supports for compound formation.
Many of these compounds are strengthening phases in alloys including
cemented carbide tools, super alloys and ceramics.

The atomic no. of Mg is 12, Cu is 29, Al is 13, Pb is 82, Sn is 50, Zn is

30.
Ex. Mg3Zn3Al2, Mg2Pb, Mg2Sn, CuAl2 (Compounds ) 17
 Intermetallic or Valence Compounds
An example of this type of electron compound is between
Magnesium and Tin which combine to form an intermetallic
compound Mg2Sn. The composition of the compound is
fixed and consists of two atoms of Magnesium combining
with one atom of Tin . Metallic compounds form a crystal
lattice with the solute atoms taking up specific positions
within the lattice. The property is usually non-metallic
and show poor ductility and poor electrical conductivity
and have complex crystal structure due to strong
bonding (ionic or covalent). These compounds are
usually hard and brittle. Other examples for intermetallic
compounds: Mg2Pb, CuAl2, Mg2Si, Mg3Zn3Al2.
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 ALUMINIDES
ALUMINIDES are intermetallic compounds considered as
emerging materials due to high specific mechanical
properties. Among other intermetallic compounds, with large
range of homogeneity, containing aluminium, those having the
highest potential for industrial applications are: CuAl2,
NiAl (thermal barriers), FeAl and TiAl (light weight structural
alloys). Borides
Borides are compounds formed between boron and metals
with varying composition. They have high temperature
resistance and hardness and often good thermal
conductivity. Their electrical conductivity makes them usable
from semiconductors to superconductors.
Boride can be produced directly from its elements through
melting or sintering.
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Example: TiB2, AlB2
 Titanium Diboride (TiB2)
Titanium Diboride is an extremely hard ceramic material
(33GPa) with excellent corrosion resistance at high
temperatures and excellent wear resistance which does not
occur naturally in earth.
Many TiB2 applications are inhibited by economic factors,
particularly the costs of densifying high melting point
material. The use is limited to specialized applications such as
cutting tools, crucibles and wear resistant coatings etc.
Thin layers of TiB2 have a wide range of potential
industrial applications due to the wear and corrosion
resistance properties that TiB2 can provide to a cheap
and/or tough substrate. The TiB2 layers electroplated possess
two main advantages : i) The growing rate of the layer is
200 times faster ii) Easy flowability (covering complex 20
shaped products).
 Interstitial Compounds
Similar to interstitial solid solutions except that they have
more or less a fixed composition. Formed between the
transition metal (Sc, Ti, Ta, W, Cr, V, Fe) with nonmetals
(H, O, C, N). In solid solution, when optimum number of
solute atoms exists in the interstitial space of the solvent,
these solute atoms have considerable mobility in the
interstitial spaces of the lattice structure. This is regarded
as saturation condition. Because of more chemical affinity,
increasing the amount of solute atoms beyond this limit
severely restricts the mobility of solute atoms in the void
space, hence favour the formation of interstitial compound
of fixed or a narrow range of composition. It is expressed by
a chemical formula.
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Ex., Cementite is an interstitial compound containing 3 iron
atoms for every 1 atom of Carbon and has got orthorhombic
crystal structure. It has 6.67% carbon by weight when it
solidifies and maintains same composition at all temp. These
smaller solute atoms fit into the space between the solvent
atoms. Example: TiC, TaC, CrN, TiH W2C, Fe3C, Fe4N .
The interstitial compounds are metallic in nature, have high
melting points and are extremely hard. Many of these
compounds are strengthening phases in alloys including
cemented carbide tools, super alloys and ceramics. This
type of compound differs from solid solution where the
number of nonmetallic atoms required to be dissolved
interstitially is greater than that of solid solution.

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 Boron nitride
Boron nitride (BN) is the most common nitride among hard
materials. Industrially boron nitride was introduced in the 80's. It is
usually hexagonal, but the most interesting structure is the cubic boron
nitride.
The synthesis of cubic crystal structure requires high temperature
and pressure, a process similar to the diamond synthesis. It is almost as
hard as diamond, but is resistant to much higher temperatures. A
composite material with metal or ceramic as binding material gives a
polycrystalline cubic boron nitride that is used in materials for tools.
Sintering with cobalt might give a more ductile material.

Titanium nitride
Titanium nitride is a hard material often combined with titanium
carbide in coatings for hard surfaces. TN are cubic closed packed
structure.
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 Carbides
Tungsten carbide
Silicon carbide
Titanium carbide
Tungsten carbide
Tungsten carbide together with cobalt is a commonly used hard
material from the 20's, and is often combined with diamond for
instance in grinding applications.
The tungsten carbide is usually produced by letting a powder of the
metal to react with carbon at a temperature of 1500 C. This is a
powder with a grain size of a few micrometers, which is being mixed
and grinded with a powder of cobalt as binder. This mix is then
pressed and sintered into a compact hard metal body at a
temperature around 1400 - 1500 C. (At this temperature the cobalt is
a liquid, so that the shrinkage is easier.
The sintered material consists of WC-grains surrounded by cobalt matrix.
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This kind of cementation of a extremely hard material with a ductile
binder metal is called a cemented carbide.
This hard metal has a density of between 10000 and 15000 kg/m3. Has
got excellent hot hardness and at room temperature is between 1000
and 2000 VHN.
Sandvik is an important producer of hard metal and started the
production during the Second World War.
The structure of WC is built up by trigonal prisms.
Silicon carbide
Silicon carbide is a hard crystalline material, which is thermally
stable up to 2700 C, because of a protecting silicon oxide layer is
formed at the surface. It has good chemical resistance, and the
hardness is close to diamond. Therefore it is widely used as an
abrasive, called karborundum. Silicon carbide might also be used as
high temperature semiconductor and also used for fire resistant
brick. The packing might be either cubic or hexagonal. Pure silicon
carbide is colourless, but technical products are coloured from
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impurities.
 Titanium carbide
Titanium carbide is extremely hard and is therefore used as a
protective layer on hard materials, such as WC and cobalt, to improve
the wear-resistance. This can be done by CVD-technology. Sometimes
it is combined with TiN. Titanium carbide as hard coating was
introduced by Sandvik in 1969. Today these kinds of coating is common
to cutting tools.
Replacing the binder cobalt with nickel in hard metals, tungsten carbide
with titanium carbide or titanium carbonitride (cermets) is being
developed. The structure of TiC is BCC.

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Electron Compounds: A number of alloy systems formed
between Cu, Au, Ag, Fe, Ni as one group of elements with
Cd, Mg, Sn, Zn, Al as another group of elements show
similarity and three different sets of compounds are formed
whose crystal structure depends on the ratio between total
number of free electrons to total number of atoms (e/a).
These compounds have properties resembling those of
solid solutions, including a wide range of composition, high
ductility and low hardness. They do not obey the valence
law.
If ratio is 3/2-BCC, 21/13-Complex cubic and 7/4- HCP
structure.

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 EXAMPLES OF ELECTRON COMPOUNDS
Note: Fe and Ni assumed to be zero valence

e/a=3/2 BCC e/a=21/13 complex e/a=7/4 HCP

cubic
AgCd Ag5Cd8 AgCd3

AgZn Au5Zn8 AuZn3

CuZn (Beta Brass) Cu5Zn8 (Gamma CuZn3 (Epsilon

Valence of Cu is 1& Brass) Brass)
Zn is 2, Al=3.
Cu3Al Cu9Al4 Cu3Sn

Cu3Si Cu31Sn8 Cu3Si 28

Shape Memory and
Superelasticity

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 SMAs
History:
Nickel-titanium alloys have been found to be the most useful of
all SMAs. The generic name for the family of nickel-titanium alloys
is Nitinol. In 1961, Nitinol, which stands for Nickel Titanium
Naval Ordnance Laboratory, was discovered to possess the
unique property of having shape memory. William J. Buehler,
a researcher at the Naval Ordnance Laboratory in White Oak,
Maryland, was the one to discover this shape memory alloy. The
actual discovery of the shape memory property of Nitinol came
about by accident. At a laboratory management meeting, a strip of
Nitinol was presented that was bent out of shape many times.
One of the people present, Dr. David S. Muzzey, heated it with his
pipe lighter, and surprisingly, the strip stretched back to its original
form.

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Dr. Frederick E. Wang, an expert in crystal physics, found that Nitinol
had phase changes while still a solid. These phase changes, known as
martensite and austenite, "involve the rearrangement of the position of
particles within the crystal structure of the solid". Under the transition
temperature, Nitinol is in the martensite phase. The transition
temperature varies for different compositions from about -50 to
166C. In the martensite phase, Nitinol can be bent into various
shapes. To fix the "parent shape" (as it is called), the metal must be
held in position and heated to about 500C. The high temperature
"causes the atoms to arrange themselves into the most compact and
regular pattern possible" resulting in a rigid cubic arrangement known as
the austenite phase. Above the transition temperature, Nitinol reverts
from the martensite to the austenite phase which changes it back into its
parent shape. This cycle can be repeated millions of times.

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Introduction:
Shape-Memory Alloys (SMAs) are metals that, after being
strained, at a certain temperature revert back to their original
shape. A change in crystal structure above transformation
temperature causes them to return to the original shape.
SMAs are also superelastic, namely they are able to sustain a
large deformation (Typically, elastic strain up to 10%) at a
constant temperature, and when the deforming force is released
they return to their original undeformed shape. 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".
The two unique properties described above are made possible
through a solid to solid state phase change that is a atomic
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rearrangement, which occurs in the shape memory alloy.
In most shape memory alloys, a temperature change of only about
10C 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
macroscopic and microscopic views of two phases are shown in
Figure 1. The atomic 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 alloys33 until
the Martensite is deformed.
 Phase transformation
Martensite Lower
strength, increased ductility
Austenite- Higher strength,
decreased ductility
HEATING

COOLING
STRESS

Macroscopic Views of the Two Phases of Shape Memory Alloys

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Shape Memory Effect Martensitic to Austenitic phase
Austenitic to Martensitic phase
Phase dependent on temperature

After the load

Easy to deform is removed,
deformation
remains

Microscopic Diagram of the Shape Memory Effect 35

Superelasticity
Superelasticity occurs in shape memory alloys when
the alloy is completely composed of Austenite
Unlike the shape memory effect, superelasticity 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.
Loading is absorbed by the softer Martensite, but as
soon as the loading is released the Martensite begins to
transform back to Austenite since the temperature of the
wire is above Af.

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 Superelasticity
When SMA is above Af Reversion to austenite at
stress deforms SMA to constant temperature
martensite and if load is
removed martensite is
Mf
unstable recovers its Ms
original structure and
shape in an elastic manner.
As
This is the basis for Af
Superelastic behavior. The
transformation occurs at Ref 2
constant temperature and
load, is called Stress-
induced martensite 37
formation
 Constant Load Method
Constant Load applied
Shape recovery and
deformation as
functions of temperature
Transformation
Temperature
extrapolation to zero
stress
Transformation during cooling and
heating do not overlap i.e., system
exhibits hysteresis
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The shape memory effect is observed when the temperature of
a piece of shape memory alloy is cooled to below the
temperature Mf. At this stage the alloy is completely
composed of Martensite, which can be easily deformed. After
distorting the SMA the original shape can be recovered simply
by heating the wire above the temperature Af. The heat
transferred to the wire is the power driving the atomic
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
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configured in the original shape of the wire.
 Ms (martensite starts),
Mf(martensite finishes),
As (austenite starts), Af
(austenite finishes)
Usually 20oC-40oC for
SMAs.

Figure 3: The Dependency of Phase Change Temperature on

Loading 40
Texas A&M SMART Lab - http://smart.tamu.edu/
Types of Shape Memory Alloys:

Example: NiTi and Ni50Ti50-xMx (where M=Hf, Pt,

Pd), Au-Cd, Cu-Zn-Al, Cu-Al-Ni, Fe-Mn-Si.
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.

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 Other shape memory alloy compositions.
Titanium-palladium-nickel Iron-manganese-silicon
Nickel-titanium-copper Nickel-titanium
Gold-cadmium Nickel-iron-zinc-aluminium
Iron-zinc-copper-aluminium Copper-aluminium-iron
Titanium-niobium-aluminium Titanium-niobium
Uranium-niobium Zirconium-copper-zinc
Hafnium-titanium-nickel Nickel-zirconium-titanium

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Current examples of applications of shape memory alloys
Aids for disabled Micro-actuators
Aircraft flap/slat adjusters Mobile phone antennas
Anti-scald devices Orthodontic archwires
Arterial clips
Penile implant
Automotive thermostats
Pipe couplings
Braille print punch
Catheter guide wires Robot actuators
Cold start vehicle Rock splitting
actuators Root canal drills
Contraceptive devices Satellite antenna
Electrical circuit breakers deployment
Fibre-optic coupling Scoliosis correction
Filter struts Solar actuators
Fire dampers
Spectacle frames
Fire sprinklers
Steam valves
Gas discharge
Graft stents Stents
Intraocular lens mount Switch vibration
Kettle switches damper
Keyhole instruments Thermostats
Key-hole surgery Underwired bras
instruments Vibration dampers 43
ZIF connectors
 Reference Sites
1. SMA/MEMS Research Group, 2001.
http://www.cs.ualberta.ca/~database/MEMS/sma_mems/sma.html

2. Shape Memory Applications Inc. http://www.sma-inc.com/

3. TiNi Aerospace Inc. http://www.tiniaerospace.com/

4. Berton, Jeffrey J. Advanced Engine Cycles Analyzed for Turbofans with Variable-Area
Fan Nozzles Actuated by a Shape Memory Alloy, 2001.
http://www.grc.nasa.gov/WWW/RT2001/2000/24000berton.html

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