• low thermal neutron absorption cross-section (0.

185 barn);
• allotropy, the high temperature b.c.c. β phase transforming into
the h.c.p α phase at 1135 K;
• anisotropic thermal and mechanical properties leading to unequal
thermal expansions along different crystallographic directions
and formation of strong crystallographic texture during mechanical
working;
• h.c.p. structure of the a phase with a c/a ratio of 1.593, which is
less than ideal, making the prismatic slip on {101̄0} planes
most predominant;
• high reactivity with oxygen, nitrogen, and carbon and high
solubility of these interstitial elements in the α phase, necessitating
special care during melting and fabrication processes;
• low solubility, 0.034 ppm at 293 K, of hydrogen in the α phase;
excess hydrogen, if present, causing hydride precipitation
which may result in serious embrittlement.
 Design of zirconium alloys for meeting the service requirements
takes into account the consideration of neutron absorption
cross-section
 Only niobium, tin, and oxygen, having low neutron absorption
cross-sections, are added to a limited extent in zirconium alloys
for applications in nuclear reactors.
 Alloying elements in zirconium alloys can be grouped into α-
stabilizers and β-stabilizers
 Tin, oxygen, and aluminum are α-stabilizers; Generally,
peritectoid reactions are exhibited in the zirconium-rich end of
the binary phase diagrams of alloys with α-stabilizers
 iron, chromium, nickel, niobium, molybdenum, and hydrogen are
β-stabilizers; corresponding binary diagrams usually show
eutectoid or monotectoid in the zirconium-rich end.
 The different phase transformations present makes these alloys
amenable to microstructural control through suitable thermo-
mechanical treatments
 Two types of athermal transformations can be induced in
zirconium alloys, namely, the β-α'martensitic transformation and
the β-ω displacive transformation.
Upto 7% α'martensite, 7-20% β+ω and beyond β metastable
 Phase separation of the β phase in Zr–Nb alloys is
reflected in the presence of the miscibility gap (β1 + β2)
 Occurrence of the monotectoid reaction β1– α+ β2 at
610C
 In nuclear reactors, the metastable β-phase is usually
present along with the predominant α –phase
 β-stabilizing elements,iron, nickel, chromium, and
molybdenum, have little solubility in the α phase, they
form ordered intermetallic phases which are
precipitated even in very dilute zirconium alloys
resulting in precipitation hardening.
 Chemical ordering reaction in the Zr–Al system can
produce the ordered intermetallic Zr3Al phase(LI2)
 low self-diffusion rate in ordered phases is exploited
in the design of alloys with good creep resistance
under irradiation.
 A number of zirconium-based binary phase diagrams exhibit
eutectoid reactions, with the eutectoid composition very lean in
alloying element. This offers the opportunity of producing a fine
lamellar α+ intermetallic structure in systems like Zr–Cu and
Zr–Fe.
 Presence of fine and brittle ω particles influences mechanical
properties of Zr–Nb alloys for use as nuclear material.
 Four different ω variants are known to grow in
thermomechanically processed Zr–8% Nb alloy as ellipsoidal
shaped particles based on the conditions of microstructural
evolution, which may be athermal transformation or
transformation under uniaxial/biaxial state of stress.
 Athermal phase transformation occurs more
readily under plastic strain state and evolution
of ω -phase depends upon the different stress
states and hence different mechanical
properties .
 Excel alloy (Zr–Sn–Nb–Mo) superior to Zr2.5Nb alloy; Sn is
concentrated in alpha grains while Nb and Mo are present in the
beta grains.
 β -Zr phase is metastable and decomposes during the stress-
relief treatment at 400C, forming ω -particles that are depleted
in beta-stabilizing elements surrounded by a matrix rich in these
elements
 Zircaloys contain tin, iron, chromium, and in some cases nickel
are most widely used in nuclear reactors. They are essentially α
Zr–Sn solid solution containing fine intermetallic precipitates
 Two distinct types of intermetallic particles are observed in
zircaloy-Zr2(Fe,Ni) with BCT structure and Zr(Cr,Fe)2 , the Laves
phase of HCP structure.
 precipitate particles formed at the grain boundaries of zircaloy-
2 are larger (typical size ~3 μm) and are of the Zr2(Fe,Ni) type
while intragranular precipitates (typical size ˂1 μm) are of both
Zr2(Fe,Ni) and Zr(Cr,Fe)2 types.
• Zr(Cr,Fe)2 type precipitate is characterized by stacking
faults

• Size and distribution of ordered intermetallics

determine corrosion and mechanical properties

• High strength is needed for use of Zr alloys as nuclear

materials. For this purpose, Zr–5Al–xSn (x¼2–6) alloys
with improved strength and ductility have been
developed

• Zr–5Al–xSn alloy consists of martensite

• Heat treatment of the alloys results in the formation of

ZrAl in the Zr–5Al–xSn alloys
martensitic
 The axial ratio (c/a) of the α phase being less than ideal, alpha-
zirconium alloys can be classified as hard h.c.p. material with the
{1010}〈1012〉 slip system most predominant. The high ductility of α
-Zr alloys cannot be accounted for solely by this prismatic slip which
provides only two independent slip systems.

Apart from slip, twinning plays an important role in the plastic

deformation of zirconium and its alloys. A number of twinning
systems are operative in zirconium alloys depending on the
type of loading and the temperature and strain rate of
deformation.
Under a tensile stress along the c-axis, {1012}〈1011〉 twins are
activated at the ambient temperature, while {112̄1}〈1126〉 at
higher temperature.
Though the critical resolved shear stress is higher for {1012}
〈1011〉 twinning than for prismatic slip at ambient
temperature, twinning is activated before slip in some
favorably oriented grains.
The solute strengthening contribution due to oxygen comes down with increase
in temperature, Such a strong temperature dependence of the strengthening
contribution of the interstitial oxygen suggests that the barriers introduced by
oxygen atoms can be overcome by thermally activated dislocation motion at
about 300 C. In contrast, solution
strengthening by most of the substitutional solutes contributes toward the
athermal component of the flow stress and is, therefore, retained at service
temperatures heavy water reactors (PHWR).
Aluminum and tin are two alloying elements which have good solubility in
alpha-Zr and also possess low thermal neutron absorption cross sections.
While aluminum in Zr lattice is not acceptable because of its deleterious effect
on the corrosion properties, tin is extensively used in nuclear grade zirconium
alloys for improving both corrosion resistance and strength.
Precipitation hardening is employed in zirconium alloys which can be
supersaturated with solutes by a solution treatment either in the alpha or in the
beta field. The solubility of the majority of alloy additions such as niobium, iron,
chromium, and nickel being very small in the alpha phase, solutionizing treatment
followed byquenching is required for bringing all these elements into solid solution.
In zircaloys, alloying elements except tin are precipitated out. In order to restrain the
growth of intermetallic particles a control must be exercised on the cumulative
annealing operations.
 The beta quenching operation also introduces a martensitic structure which is
associated with both solid solution andsubstructure strengthening. In general,
martensites in dilute zirconium alloys possess adequate ductility and are
amenable to further ductilization by subsequent tempering .
In fact, the Zr–2.5Nb alloy in the tempered martensitic condition has tensile
strength about 30% higher than that in the cold worked condition. In spite of
the higher strength associated with the tempered martensitic condition, the
alloy is used in the cold worked state for pressure tube applications in PHWRs
because of better in-reactor creep properties of the latter.
Order hardening of zirconium alloys was considered to combat the in-reactor creep
process. Since movement of point defects in ordered structures is much slower,
there is a higher probability of mutual recombination of vacancies and interstitials
produced in a radiation environment. The ordered Zr3Al alloy (L12 structure) has
high strength, good corrosion resistance, and very low in-reactor creep rate.

Due to the inherently anisotropic behavior of the h.c.p. alpha-phase in used in

nuclear reactors, preferred orientations develop in these alloys during fabrication
processing and recrystallization steps. The presence of such crystallographic
texture is important ; as this influences the ease with which the next
deformation process can be imparted. Second, the texture of the fabricated
material controls properties such as the yield strength, thermal and in-reactor
MONOTECTOID α 2 = α1 +β
MONOTECTIC REACTION

L1 -α + L2
At 882.5 °C, titanium undergoes an allotropic transformation from a low
temperature, hexagonal close-packed structure α to a body-centred cubic phase β

Titanium is a transition metal with an incomplete shell in its electronic structure

which enables it to form solid solutions with substitutional elements

Titanium may form solid solutions and compounds with metallic, covalent or ionic
bonding

Alloying elements with electron/atom ratios of less than 4 stabilize the α -phase,
elements with a ratio of 4 are neutral, and elements with ratios greater than 4 are
β stabilizing.

α –alloys have higher resistance to plastic deformation, lower ductility, significant

anisotropy of physical and mechanical properties, diffusion rates that are lower by
at least two orders of magnitude, higher creep resistance

β stabilisers are classified in two groups: those which form binary systems of the β
isomorphous type , and those which favor formation of a β -eutectoid .
Eutectoid reactions are very sluggish so alloys like Ti–Fe and Ti–Mn behave as if
they conformed to the β -isomorphous phase diagram

Oxygen, nitrogen and carbon favor α phase and hydrogen promotes β –phase

Molybdenum and tungsten are strong β stabilizers; W is little used due to its
high density and problems of segregation. Vanadium is another common β
stabilizer but less effective than molybdenum at higher temperature ranges

Properties of titanium alloys are determined by the morphology, volume fraction

and individual properties of the two phases.

Strength of annealed α- alloys increases gradually and linearly with alloy content,

When quenched from β -phase field, the transformation of β to the martensitic

form of the α -phase, designated α’ .

For low concentrations of solute, some strengthening occurs, but the effect is
much less than that traditional martensitic reactions in ferrous materials
Little change occurs after martensitic is tempered or aged. Strength of quenched
alloys to minimum value when composition is such that Ms temperature reaches
room temperature, i.e. 100% metastable β
αβ
Small amounts of other elements can be present and α -alloys are divided into
three subgroups: single phase , containing up to 2% of β -stabilizing elements
(near- α alloys) or respond to age-hardening reaction (Ti–Cu alloys with 2.5%Cu)

Too much addition of α -stabilizers embrittles the alloy because of an ordering

reaction that occurs if aluminium equivalent’ exceeds about 9%.

Al +1/3 Sn+ 1/6 Zr + 10(O+C +2N) :- is Al-equivalent.

5–6% Al addition lead to the formation of a finely dispersed, ordered phase α2

coherent with the lattice of the -phase over a wide temperature range. This
has the general formula Ti3X and has the DO19 (hexagonal) crystal structure
noted for precipitates formed in several magnesium alloys

The only element to improve the ductility of α2 in titanium alloys is gallium which
is cost prohibitive.
Fully α alloys are Ti–O alloys, and the ternary Ti–5Al–2.5Sn alloys

Alloys being single phase, tensile strengths are low but high thermal stability leads
to reasonable creep strengths in the upper temperature

It is necessary to hot-work the alloys at temperatures below α/ β transus to avoid

grain growth, formability is limited because of hexagonal crystal structure and that
they exhibit a high rate of strain hardening.

Ti–5Al–2.5Sn is replaced by the age-hardenable Ti–Cu alloy which can be easily

fabricated after solution treatment, but prior to ageing when it is soft.

Applications are skin panels ,fire walls in aircraft and tubing in heat exchangers

One continuing application of Ti–5Al–2.5Sn alloys however, has been cryogenic

storage tanks for which the relatively high strength of titanium alloys at low
temperatures is attractive; suitable for liquid hydrogen storage ; Titanium alloy
pressure vessels have become standard for fuel storage in space vehicles as specific
strengths are double of aluminium alloys and stainless steel at such temperatures.
Near α-alloys meet demands for higher operating temperatures in the compressor
section of aircraft gas turbine engines; the greatest creep resistance of all titanium
alloys at temperatures above approximately 400 °C.

IMI 679 alloy : Ti–11Sn–2.25Al–5Zr–1Mo–0.2Si; forged and heat treated in α +β

region; alloy like Ti–11Sn–2.25Al is used without causing α’ embrittling phase and
to avoid hydrogen embrittlement

Keep maximum α, add some β stabilizer to enhance forgeability, amenable to heat

treatment without sacrificing creep, i.e addition of 1%Mo; silicon is added then to
Increase strength and creep by going in solution in α

Forge in α +β and 50: 50 α and β kept in microstructure, i.e at 900C for IMI 679
Different microstructures with properties evolve with different treatment
These α/ β alloys have the greatest commercial importance with composition,
Ti–6Al–4V
α phase forms as Widmanstätten laths in a β -matrix, although β may itself
transform to martensitic α ‘. The size of laths depends on the rate of cooling
and the basket weave structure is obtained when cooling rates are slow.

The α / β titanium alloys are most often used in the annealed condition for
good Fatigue properties

Relatively dilute α / β alloys form hexagonal α’ martensite or two orthorhombic

martensites α’’ and α’’’ on quenching, and in more concentrated alloys β
-phase may be partly or completely retained in a metastable condition
Transmission electron micrographs showing martensites:
(a) hexagonal (lath) martensite in a dilute alloy (Ti–1.8Cu)quenched from 900 °C;
(b) hexagonal (lenticular) martensite containing twins in a concentrated alloy (Ti–12V)
quenched from 900 °C(c) orthorhombic martensite in Ti–8.5Mo–0.5Si quenched from 950 °C
The orientation relationship of the β -phase and α’ martensite is (110)//(0001);
[111]//[1120 ] and the habit planes for the untwinned and twinned planes are
{334} and {344} respectively

The second type of titanium martensite (α’’) has an orthorhombic structure

and a similar lattice correspondence with the β –phase; it is probably face-
centred and its lattice dimensions are a = 0.298 nm,b = 0.494 nm, c = 0.464 nm.
It is also internally twinned .

Formation of α’’ is thought to be strongly composition dependent; it occurs in

Ti–Mo but not in Ti–V alloys although it may form in Ti-Al-V alloy

α’’ martensite can be formed in the following three ways.

1. Decomposition of metastable during quenching, β  α’’ (β)

2. Decomposition of retained by intermediate (bainitic) transformation during

isothermal ageing, , β  β (lean) + β(rich)  α’’ + β(rich)

3. Stress-induced transformation of retained, β  α’’ + twinned β

Two other martensites (face-centred orthorhombic and face-centred cubic)
have been reported in electron microscope studies; One has been termed α’’’
(or β’) and has lattice parameters quite distinct from α’’ martensite, i.e. a=
0.356 nm, b = 0.439 nm and c= 0.447 nm. The existence of the second phase has
not been confirmed and it may well arise as an artefact

If the Ms and Mf fall above and below room temperature respectively, then a
mixed microstructure containing lenticular α’ or α’’ (or perhaps α’’’ ) martensite
may be formed together with retained β .
In the β–isomorphous alloys, α’ decomposes directly to equilibrium α at the
tempering temperature and β precipitates heterogeneously at martensite plate
boundaries or at internal twins. Significant increase in strength

In β -eutectoid alloys, α’ may decompose directly into the α -phase and an

intermetallic compound, which forms in several stages

Tempering of α’’ martensite may occur by two mechanisms; In alloy with Ms(α’’ )
at a relatively high temperature, α’’ decomposes first by the formation of a fine
and uniformly dispersed α -phase in the α’’ -matrix.

Further ageing causes coarsening of these particles and nucleation of a cellular

reaction at the prior β -grain boundaries leading to formation of a lamellar
structure of α + β.

In alloys of Ms(α’’ ) near room temperature, the α’’ reverts to the β -phase,
which decomposes by mechanism characteristic of tempering temperature.
β alloys of various compositions; high strength, formability with applications in aerospace
Nickel–copper alloys, nickel–chromium alloys, nickel–iron alloys, nickel–
chromium molybdenum alloys, nickel–iron–chromium alloys
Alloying elements such as Al, Si, Ti, Nb, and others are added in very small
concentrations either singly or in combination to make nickel and its alloys
susceptible to precipitation hardening.
Nickel-base superalloys have an austenitic matrix structure; In nickel-base
superalloys, γ’ and γ’’ lead to precipitation strengthening;

The γ’ phase, is identified as Ni3(Al,Ti) with its L12 ordered f.c.c structure
Solutionising followed by ageing; APB hardening

The γ’’ phase is ordered Ni3Nb phase and of body-centered tetragonal

structure; while γ’ is the predominant matrix strengthening phase in nickel-base
superalloys, the γ’’ serves as the major strengthening precipitate and it can be
stabilized by addition of iron.

η phase in nickel–iron-base superalloys containing Ti and Al is primarily Ni3Ti

and here aluminum does not play any direct role in the precipitation
strengthening.
Long-time exposure at about 650–750 1C leads to transformation of the γ’ and
γ’’ phases to η and δ phases

TiC, TiN, Ti(C, N), M6C, and M23C6 have also been identified in the structure of
many nickel-base alloys. Ni–Cr–Fe-based (e.g., Inconels), Ni–Mo–Fe-based (e.g.,
Hastelloy A and B), and Ni–Cr– Mo–Fe-based (e.g., Hastelloy C and Hastelloy X).
Microstructure of Monel K-500 solution treated at 1200C and aged at 700 C for 4 h.