3 Titanium

Titanium
Dipartimento di Ingegneria «Enzo Ferrari» 1

Titanium
Turbojet
The turbojet is an airbreathing jet engine, usually used in aircraft. It consists of a gas
turbine with a propelling nozzle. The gas turbine has an air inlet, a compressor, a
combustion chamber, and a turbine (that drives the compressor). The compressed air
from the compressor is heated by the fuel in the combustion chamber and then
allowed to expand through the turbine. The turbine exhaust is then expanded in the
propelling nozzle where it is accelerated to high speed to provide thrust
Dipartimento di Ingegneria «Enzo Ferrari»
Titanio
Large dimensions and high rotational speed require turbine blades to be
lighweight. Can we use Titanium?

Titanium
Melting point1670°C
Density 4.51 g cm-3
80% of TI is used in aerospace applications
Max use temperature: T< 400°C

Titanium and its alloys

Titanium – corrosion resistance
Ti is initially (fast) corroded, then

it passivates
Pourbaix
Titanium
Structure BCC
890°C
Structure HCP

Titanium - anisotropy
It is clear that the due to the denser
atomic packing along the c-axis
(<0001> direction) a
maximum value of the Young’s
modulus occurs in this direction,
which shows a gradual
decrease with increasing angle made
with the c-axis. It is also apparent
that this variation
can account for differences of up to
40GPa, which significantly alters the
mechanical
response of the alloy. However, these
changes do not only affect elastic
deformation of these
alloys, but also the plastic
deformation, in terms of the
orientation of slip planes with
relatively low critical resolved shear
https://www.intechopen.com/books/advances-in-gas-turbine-
technology/titanium-in-the-gas-turbine-engine stress (CRSS) values.

RD= Rolling Direction
TD= Transverse Direction
Under strain control testing at R=0 (20°C, 1-1-1-1 second

trapezoid cycle) it can be seen that specimens
taken parallel to the rolling direction of the material show
longer fatigue lives than counterparts taken from the
transverse direction of the plate (TD), i.e. at 90° to the rolling
direction.
Initially this result may be considered counterintuitive; the
increased density of basal planes perpendicular to the TD
direction results in a higher modulus in the TD specimens,
and also higher yield stress and UTS values.
However, in order to understand

this effect, it is necessary to consider the behaviour of the
material under strain control, and the effect of the material
texture.
.
https://www.intechopen.com/books/advances-in-gas-turbine-technology/titanium-in-the-gas-turbine-engine

RD= Rolling Direction

TD= Transverse Direction
Figure illustrates the evolution of the maximum and minimum stress values achieved during a
strain control test with a peak strain of 1.4%. It can be seen that there is considerably more stress
relaxation in the early part of the test in the RD specimen. This is related to the availability of
prismatic planes (which have a low critical resolved shear stress in titanium at room temperature)
for slip in the early part of the test.
This leads to the TD specimen operating at a higher maximum stress. In combination with this, the
TD specimen also has a higher modulus, and consequently a lower minimum stress during the test.
The TD specimen therefore operates over a larger stress range for a given strain range and shows
a reduced fatigue life.
https://www.intechopen.com/books/advances-in-gas-turbine-technology/titanium-in-the-gas-turbine-engine

Titanium: plastic deformation
Structure HCP a Slip planes
basal
c/a = 1.587 prismatic
(th=1.633)
pyramidal
aTitanium: deformation
It can be cold rolled at RT with defomations higher than 90%

without breaking
Unusual behaviour for an EC, but the low c/a ratio allows slip
also on prismatic {1010} and pyramidal {1011} planes, ad not
only the basal plane is the one with maximum density
High ductility of Ti (EC) is due to the many existing slip

systems and to the formation of twins
Twinning during cold deformation is more pronounced than

in Mg, Zn and Cd
https://www.phase-trans.msm.cam.ac.uk/2000/C9/lecture3.pdf

Titanium: solid solutions
Hume-Rothery: H,B,C,N,O can originate interstitial S.S.; other elements

(atomic radii difference ±15%) enter as substitutional S.S. formers
Titanium: alloys

Titanium: alloys
“pure” Ti: 99.5-99.0%Ti
• main alloying gelements: Fe, C, O, N (interstitials)
• it can be considered a phase where the O content determines the

mechanical properties
%O equivalent = %O + 2%N + 0.67%C
– Each 0.1%O equivalent makes UTS grow of approx. 120 MPa

– However, this happens at the cost of toughness
• If a high toughness is required, then the ELI (Extra-Low

Interstitials) versions should be preferred

Titanium: interstitials

Titanium: alloys
Grade 1
Grade 1 titanium is the first of four commercially pure titanium

grades. It is the softest and most ductile of these grades. It possesses
the greatest formability, excellent corrosion resistance and high
impact toughness.
Because of all these qualities, Grade 1 is the material of choice for

any application where ease of formability is required and is
commonly available as titanium plate and tubing. These include:
Chemical processing, Desalination, Architecture, Medical industry

Marine industry, Automotive parts, Airframe structure

Titanium: alloys
Grade 2
Grade 2 titanium is called the “workhorse” of the commercially pure

titanium industry, thanks to its varied usability and wide availability.
It shares many of the same qualities as Grade 1 titanium, but it is
slightly stronger. Both are equally corrosion resistant.
This grade possesses good weldability, strength, ductility and

formability. This makes Grade 2 titanium bar and sheet are the prime
choice for many fields of applications:
Architecture, Power generation, Medical industry, Exhaust pipe

shrouds, Airframe skin, Desalination, Chemical processing

Titanium: alloys
Grade 3
This grade is least used of the commercially pure titanium grades,

but that does not make it any less valuable. Grade 3 is stronger than
Grades 1 and 2, similar in ductility and only slightly less formable -
but it possesses higher mechanicals than its predecessors.
Grade 3 is used in applications requiring moderate strength and

major corrosion resistance. These include:
Aerospace structures
Chemical processing
Medical industry
Marine industry
Titanium: alloys
Grade 4
Grade 4 is known as the strongest of the four grades of commercially

pure titanium. It is also known for its excellent corrosion resistance,
good formability and weldability.
Though it is normally used in the following industrial applications,

Grade 4 has recently found a niche as a medical grade titanium. It is
needed in applications in which high strength is required:
Airframe components, Cryogenic vessels, Heat exchangers

Condensor tubing, Surgical hardware

Stabilizers of a: enlarge the field of existence of EC

Stabilizers of b: reduce the EC and favour BCC
Eutectoids formers: in reality they stabilize b because at room temperature the
possibility of rearranging the alloy is slow
why??? perlite instead is formed also at low T!
In case of perlite, C moves as interstitial, while here they are substitutional elements
a stabilisers b stabilisers b stabilisers (eutectoid)

Al, Sn Mo, V, W Cu, Mn, Fe, Ni, Co, H


a stabilisers - Al b stabilisers - V

a-stabilized Ti
a-leghe
Al – main alloying elements
•Solid solubility up to ~8% at RT
•Solid solution stregnthening
•Usually not heat treatable
•Lower density
•Weldable
•Good thermal stability and ressitance to oxidation at high T

a-stabilized Ti
Usually divided into 3 groups:
1. Only α phase
2. Up to 2% of β phase (near α)
3. Age-hardenable (up to 2.5% of Cu) - Ti2Cu
Titanium α-Alloys and Near α-Alloys have good Fracture Toughness and creep
resistance combined with moderate mechanical strength, which is retained at
increased temperatures up to 600ºC.
The alloys are easily welded, but their workability in hot state is poor.
Due to the presence of β-phase in Near α-Alloys they may be heat-treated and are
forged in hot state.
Titanium α-Alloys and Near α-Alloys are used for manufacturing steam turbine
blades, autoclaves and other process equipment vessels operating up to 480ºC,
high pressure cryogenic vessels, aircraft engine compressor blades, missile fuel
tanks and structural parts, operating for short times up to 600ºC, airframe and jet-
engine parts, welded stator assemblies and hollow compressor blades.
a-stabilized Ti
Ti - 11Sn – 2.25Al - 5Zr - 1Mo - 0,2Si;

b-alloys
Titanium β-alloys are titanium alloys rich of β-phase due to the presence of substation
amount of β-phase stabilizers: molybdenum (Mo), vanadium (V), tungsten (W),
tantalum (Ta), silicon (Si). β-phase stabilizers prevent β-α transformation at high
cooling rates
Titanium β-alloys are heat-treatable. They may be significantly strengthened by

precipitation hardening. Solution treatment of β-alloys causes transformation of α-
phase, which is stable at room temperature, to β-phase, which is stable at temperatures
above the Beta Transus. Quenching suppresses β-α transformation. Titanium β-alloys
are normally supplied in solution-treated condition.
The metastable β-phase partially transforms to fine precipitation particles of α-phase

during aging. The precipitation treatment results in increase of mechanical strength
and decrease of ductility.
Titanium β-alloys are used for manufacturing aerospace components, high-strength fasteners, torsion bars,
high-strength aircraft sheets, burn-resistant aircraft engine parts. Titanium β-alloys, containing at least 10%
of chromium (Cr), possess increased burn resistance and are used in aircraft engines at temperatures up to
510ºC.
a/b alloys
Titanium α-β alloys are titanium alloys containing 4-6% of β-phase stabilizers: amount
of β-phase is proportional to the content of β-phase stabilizers.
Titanium α-β alloys are heat-treatable. They may be significantly strengthened by

precipitation hardening. Solution treatment of α-β alloys causes increase of β-phase
content in the alloy which is stable at temperatures above the Beta Transus. Quenching
suppresses β-α transformation. The metastable β-phase transforms to fine
precipitation particles of α-phase during aging.
Ti-6Al-4V is the most popular Titanium α-β Alloy - its total production is about half of
all titanium alloys.
Titanium α-β Alloys have high tensile strength and fatigue strength, good hot
formability and creep resistance up to 570ºF - 800ºF (300ºC - 425ºC).
Titanium α-β Alloys are used for manufacturing steam turbine blades, gas and chemical pumps, airframes and
jet engine parts,pressure vessels, blades and discs of aircraft turbines, aircraft hydraulic tubing, rocket motor
cases, cryogenic parts, marine components.
a/b alloys microstructure
Ti - 6Al - 4V slowly
cooled from β
state.Widmanstatten
structure
Ti - 6Al - 4V
Annealed at 700 C
(α and β grains)

Ti - 6Al - 4V slowly cooled from β .

α+β alloys with transition elements:

Ti Mn 7 (σT = 900 MPa, ε = 10%)
Ti Mn 8 (σT = 1000 MPa, ε = 15%)
Ti Cr 3 Fe 1.5 (σT = 1000 MPa, ε = 12%)
Ti Cr 2 Fe 2 Mo 2 (σT = 1050 MPa, ε = 12%)
Ti Mn 3 Fe 1 Cr 1 Mo 1 V 1 (σT = 900 MPa, ε = 20%)
α+β alloys containing Al+ transition elements:

Ti Al 1.5 Mn 3 (σT = 1000 MPa, ε = 17%)
Ti Al 4, Mn 4 (σT =1040 MPa, ε = 15%)
Ti Al 5, Cr 3, Fe 1 (σT =1060 MPa, ε = 8%)
Ti Al 3, Cr 5 (σT =1080 MPa, ε = 15%)

Heat treatment
Martensite a’ (HCP),disc
shaped, formed in proximity of
the maximum density planes

Heat treatment
As a consequence of rapid cooling,

Martensite a’ (HCP) can be frmed
It has a highly distorted lattice, where

c/a < 1
Mechanical properties are much

lower than steel martensite: a
quenched TI has an increased UTS of
only 70 MPa

Heat treatment
Slow cooling: s increases as b content increases
β is different depending whether it is heat

treated starting from α+β or β.
Maximum strength for quenched Ti occurs when

Mf is at RT, wile minimum is in case of Ms at RT
(100% β metastable).
However, if tehrses compositions are aged

(controlled formation of alfa and
decomposition of β, maximum strength can
be achieved.

Heat treatment
b -> w transformation
Sequence ABCABC typical of BCC, (111)
ω is a metastable phase which

forms from β in alloys based on
titanium, zirconium and hafnium.
It is important because its
formation generally leads to a
deterioration in the mechanical
properties.
It is not diffusive and it can not be

suppressed by rapid cooling
Heat resistant alloys
TiO2 has a high formation entaply, hence it orginates highly

exothermal reactions (Ti burns!)

Titanium fire
Spontaneous ignition of massive shapes of titanium can occur at room

temperature when a fresh, oxide-free metal surface is exposed to
oxygen under pressure.
Spontaneous ignition will occur only if the initial reaction is vigorous

enough to raise the surface temperature to the titanium melting point.
Due to the extreme sensitivity of the applications titanium is
used in, the engineers take into account several design
factors to minimize the occurrence of a titanium fire. Also
the specific composition of some titanium alloys also affects
the probability of ignition and combustion severity. Several
highly specialized titanium alloys have been developed for
this purpose. They all have in common increased contents of
vanadium and chromium.

Heat resistant alloys
Modifying alloys adding >10% Cr, in presence of V, it is possible to extend the

maximum continuos use temperature to 510°C
Le leghe binarie di TI-Cr non hanno questa proprietà
Ti - 35V - 15Cr

Summary: alloy type

Applications: heat exchngers

Applications: chemical reactors
reactor
roll-bonded,
explosion-clad

Applications: aerospace

Applications: biomedical

Applications: sport

Case study: exhaust
Collettori in titanio durante prova

al banco - Image courtesy of
Akrapovič d.d.
AKRAPOVIČ
Ducati Panigale
Full Titanium AFTM
system
AKRAPOVIČ
Porsche GT2
Porsche GT2 link pipes durante prova al banco – Full Titanium OEM
Image courtesy of DM Performance, France system
After 25 hours testing
AKRAPOVIČ
BMW M3
Impianto auto in titanio dopo prova al banco - Image courtesy of Full Titanium AFTM
Akrapovič d.d.
system
Ti alloys for exhaust system
Ti-Fe-Si-O Ti-Al-Si-Nb
(Timetal Exhaust XT) (Kobe Steel Ti 1,2 ASN-EX)

Ti alloys for exhaust system
Lega Ti-Fe-Si-O Lega Ti-Al-Si-Nb
(Timetal Exhaust XT) (Kobe Steel Ti 1,2 ASN-EX)
Oxidation test 24h @ 800 °C  mass gain + 0,41% Oxidation tests 24h @ 800 °C  mass + 0,36%
Comparison between Gr. 2 and Ti-Fe-Si-O

after @700 °C for 100 h Comparison between Gr. 2 and Ti-Al-Si-Nb
after 100 h exposure at different T
Automotive applications
The various applications fall into

one of three broad categories
driven by two key product
features: components
contributing to unsprung mass
for reduced momentum transfer
into the passenger compartment
and components subjected to
high temperatures and highly
cyclic loading for inertial mass
benefits.
http://www.nssmc.com/en/tech/report/nsc/pdf/8503.pdf
Automotive applications
Reciprocating components:
The application of Ti valves and connecting rods in
the Corvette Z06 V8 engine enabled the maximum
engine rpm to increase from 6,600 rpm to 7,100
rpm.8 The large 56-mm-diameter Ti intake valves
were 21 g lighter than the stainless steel valves
they replaced while providing 22% greater surface
area coverage, whereas the forged Ti-6Al- 4V
connecting rods weighed only 464 g each for an
approximate 30% weight reduction compared with
forged powder metal ferrous connecting rods. The
lighter connecting rods also resulted in decreased
loading on the rod end and main bearings, thereby
allowing the bearings to be designed for minimal
friction.
DOI: 10.1007/s11837-012-0310-8
Automotive applications (see aluminides)
Extreme temperatures and thermal gradients:
Turbochargers especially benefit from the low
mass of titanium. Turbochargers use the hot
exhaust gas to power the turbine wheel, which
drives the compressor to pressurize the inlet air
leading to more power and cleaner fuel burn,
which translates to improved fuel economy. For
the turbocharger to deliver the power boost, the
turbine wheel (and shaft) must operate at
extraordinarily high rotational speeds (depending
on size they can spin at speeds greater than
250,000 rpm) and at temperatures reaching
950C. To rapidly reach these high speeds,
the turbine wheel needs to be lightweight to
reduce rotational inertia and to reduce the
power boost time known as turbo lag.. A lighter
alloy, based on gamma titanium aluminide with a
density
DOI: of 3.8 g/cm3 , led to a perceptible 0.2 s
10.1007/s11837-012-0310-8
shaving off of the turbo lag. Dipartimento di Ingegneria «Enzo Ferrari»

Suspension components:
Springs, for example, exploit the combination of high
strength and low shear modulus that requires
approximately half as many turns for titanium
compared with steel. This along with the lower
density of titanium can provide a weight savings of
60–70%. In addition, the free height of the spring can
be reduced to 50– 80% that of a comparable steel
spring,10 which translates to styling opportunities.
Extending titanium to other suspension components
that are part of the mass below the springs and
dampers (unsprung mass as opposed to sprung
mass that includes the body and powertrain) reduces
momentum transfer into the passenger compartment
for a smoother ride; aka Maglev trains. Reducing
unsprung mass and inertia also improves
performance by increasing the ability of the tire to
closely
DOI: follow road inputs and contours, contributing
10.1007/s11837-012-0310-8
to a smooth ride as well. Dipartimento di Ingegneria «Enzo Ferrari»
Drawbacks
MAIN LIMITATIONS:
• The extraction process is currently not highly automated and is only performed
using low volume batch production.
• A strong affinity for oxygen requires a well controlled atmosphere during melting
and high temperature processing to minimize oxidation and oxygen pickup that
decreases ductility.
• Need for specialized mold materials because of its reactivity with conventional
mold materials.
• Excessive tool wear during machining caused by low thermal conductivity and
high work-hardening rate that result in large forces and high temperatures at the
tool work interface, leading to increased manufacturing cost.
• The excessive wear is generally a consequence of thermochemical wear
mechanisms present in the tool-chip contact and shear plane regions.
• Galvanic corrosion when joining to other materials.
• Special care required to avoid impurity contamination during recycling and the
need to segregate the various alloys.
DOI: 10.1007/s11837-012-0310-8
Intermetallics
Intermetallic compounds are generally brittle and have a high melting point. They often
offer a compromise between ceramic and metallic properties when hardness and/or
resistance to high temperatures is important enough to sacrifice some toughness and
ease of processing. They can also display desirable magnetic, superconducting and
chemical properties, due to their strong internal order and mixed (metallic and
covalent/ionic) bonding, respectively. Intermetallics have given rise to various novel
materials developments. Some examples include alnico and the hydrogen storage
materials in nickel metal hydride batteries.
Intermetallics for high T

Ni aluminides

Ni3Al
It can be made tougher than other intermetallics; B additioj further increase

toughness
Usually good oxidation resistance thanks to the formation of alumina on the
surface
Ni3Al
YS increases with temperature (see superalloys) , up to 600-800°C

NiAl
Advantages: high metling point, low density, good oxidation resistance,

high thermal conductivity, similar to metals, low cost of raw materials
Disadvantages: brittle, not excellent mechanical properties (UTS), low

creep resistance

Ti aluminides
Low density ,good mechanical properties even at high T, oxidation resistance,
low hydrogen absorption, resistant to creep

Ti aluminides
Ti3Al (a 2).
TiAl (g )

Ti aluminides
Monophasic alloys(g): Ti-(50 )Al-(1¸ 2)X1
X1=W,Nb,Ta
Biphasic alloys (g+a2): : Ti(44¸ 49)Al-(1¸ 3)X1-(1¸ 4)X2-(0.1¸ 1)X3
X1=V,Mn,Cr X2=Nb,W,Ta,Mo X3=Si,B,NP,ScTcNiFe
Density (g/cm3)
E , RT (GPa)
YS (MPa)
Creep limit (°C)
Oxidation (°C)
Ductility , RT (%)
Ductility (HT) (%)
Ti aluminides matrix composites

Comprison Ti-based materials
Property Ti-base Ti3 Al-base TiAl-base Superalloys

Structure A3/A2 D019/A2/B2 L10/D019 A1/L12
Density [g/cm3] 4.5 4.1 – 4.7 3.7 - 3.9 7.9 – 9.1
Young’s modulus (RT) [GN/m2] 95 - 115 100 - 145 160 - 180 195 – 220
Yield Strength (RT) [MN/m2] 380 - 1150 700 - 990 400 - 650 250 - 1310
Tensile Strength (RT) [MN/m2] 480 - 1200 800 - 1140 450 - 800 620 – 1620
Creep Temp. limit [°C] 600 760 1000 1090
Oxidation Temp. limit [°C] 600 650 900 1090
Tensile Strain / Fracture (RT) [%] 10 – 25 2 – 26 1–4 3 – 50
Tensile Strain / Fracture (high T) [%] 12 – 50 10 – 20 10 – 60 8 – 125
Fracture Toughness KIc (RT) [MN/m3/2] high 13 – 42 10 – 20 25

Aluminides

Ni-Al-Ti
Scratch test, 1N
Scratch test, 5N

3 Titanium

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Titanium

Dipartimento di Ingegneria «Enzo Ferrari» 1

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

Ti is initially (fast) corroded, then

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

Under strain control testing at R=0 (20°C, 1-1-1-1 second

However, in order to understand

Dipartimento di Ingegneria «Enzo Ferrari»

RD= Rolling Direction

Dipartimento di Ingegneria «Enzo Ferrari»

Structure HCP a Slip planes

It can be cold rolled at RT with defomations higher than 90%

High ductility of Ti (EC) is due to the many existing slip

Twinning during cold deformation is more pronounced than

Dipartimento di Ingegneria «Enzo Ferrari»

Hume-Rothery: H,B,C,N,O can originate interstitial S.S.; other elements

Dipartimento di Ingegneria «Enzo Ferrari»

• it can be considered a phase where the O content determines the

– Each 0.1%O equivalent makes UTS grow of approx. 120 MPa

• If a high toughness is required, then the ELI (Extra-Low

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

Grade 1 titanium is the first of four commercially pure titanium

Because of all these qualities, Grade 1 is the material of choice for

Chemical processing, Desalination, Architecture, Medical industry

Dipartimento di Ingegneria «Enzo Ferrari»

Grade 2 titanium is called the “workhorse” of the commercially pure

This grade possesses good weldability, strength, ductility and

Architecture, Power generation, Medical industry, Exhaust pipe

Dipartimento di Ingegneria «Enzo Ferrari»

This grade is least used of the commercially pure titanium grades,

Grade 3 is used in applications requiring moderate strength and

Grade 4 is known as the strongest of the four grades of commercially

Though it is normally used in the following industrial applications,

Airframe components, Cryogenic vessels, Heat exchangers

Dipartimento di Ingegneria «Enzo Ferrari»

Stabilizers of a: enlarge the field of existence of EC

a stabilisers b stabilisers b stabilisers (eutectoid)

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

Ti - 11Sn – 2.25Al - 5Zr - 1Mo - 0,2Si;

Dipartimento di Ingegneria «Enzo Ferrari»

Titanium β-alloys are heat-treatable. They may be significantly strengthened by

The metastable β-phase partially transforms to fine precipitation particles of α-phase

Titanium α-β alloys are heat-treatable. They may be significantly strengthened by

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

α+β alloys with transition elements:

α+β alloys containing Al+ transition elements:

Dipartimento di Ingegneria «Enzo Ferrari»

Dipartimento di Ingegneria «Enzo Ferrari»

As a consequence of rapid cooling,

It has a highly distorted lattice, where

Mechanical properties are much

Dipartimento di Ingegneria «Enzo Ferrari»

Slow cooling: s increases as b content increases

β is different depending whether it is heat

Maximum strength for quenched Ti occurs when