Light Metals

Lecture 18: Titanium

MMAT 380

Topics to be covered

• Production of Ti
• Ti in context with other metals
• Introduction to crystallography of Ti
• 4 alloy groups
– chemistry,
– phase diagrams
– heat treatments and microstructures
– mechanical properties
– applications

1
 Production of Ti

• Obtained from minerals:

– rutile (TiO2)
– ilmenite (FeO-TiO2) approx 97-98% TiO2
• Chemically converted to pure TiCl4
• Kroll Process:
– TiCl4 reacted with liquid Mg at ~773-873°C in a closed
stainless-steel vessel (retort)
– 4TiCl4 (gas) + 2Mg (liquid) → Ti (solid) + 2MgCl2 (liquid)

Ti sponge

Preparation of Ti Ingots

• Molten Ti reacts with oxygen & nitrogen

• Ti sponge crushed & compacted into electrode
compacts
– these welded together
– form consumable electrode
– for vacuum arc melting
• For alloy ingots the alloying materials are mixed
with the crushed Ti sponge before compacting

2
 Production of
Titanium

Titanium Alloys
• Relatively new engineering metals
• Been in use as structural materials only since 1952
• Ti alloys attractive because:
– High strength/weight ratio
– High elevated temperature properties (i.e., ~550°C)
– Excellent corrosion resistance (particularly in oxidizing acids and
chloride media and in most natural environments)
• Disadvantage is cost i.e., Ti ~6x cost of aluminum and
10x cost of stainless steel
• However they do compete effectively in areas where
strength/weight and high-elevated temperature properties
are of prime importance (i.e. aerospace)

3
 Ti Pourbaix
Diagram:
good corrosion
resistance

Susceptibility to crevice corrosion

Crevice corrosion
of Ti-0.3Mo-0.8Ni
and grade 2
unalloyed Ti in
saturated NaCl
solution. Shaded
band represents
transition zone
between active
and passive
behavior.

4
 High temperature properties as
compared to steels

Table 10-1 Selected physical properties of

titanium as compared to those of aluminum and iron

5
 Commercially attractive properties
and applications
• resistance to corrosion:
– chemical processing, the pulp and paper industry,
marine applications, and energy production and storage
• inertness in the human body:
– biomedical, surgical implants and prosthetic devices
• high specific strength:
– automotive industry
– Cameras, jewellery, frames for glasses musical
instruments, and sports equipment

Consider “pure” Ti
• Purity ranges from 99.5-99.0%Ti
• Main alloying elements: Fe, C, O, N (interstitials)
• Can be considered an α−phase alloy in which oxygen
content determines the grade and strength
%O equivalent = %O + 2%N + 0.67%C
– Each 0.1%O equivalent of interstitial elements in pure Ti
increases strength by ~120 Mpa
– Although interstitials increase strength they decrease toughness
• Therefore if high toughness desired (especially at low
temperatures) alloy will be produced with extra-low-
interstitials (ELI)

6
 Allotropic forms of pure titanium

Beta: β
Body Centered
Temperature oC

Cubic

Beta Transus Temperature: 883oC

Alpha: α
Hexagonal
Close Packed

Miller indices of hexagonal crystal

planes

(c) Pyramidal
(a) Basal planes (b) Prism planes planes

7
 Deformation properties of “pure” Ti
– Can be cold-rolled at room temp to >90% without
cracking
– Unusual for HCP metals due to low c/a ratio
• Relatively high ductility of HCP Ti is attributed to
the many operative slip systems and available
twinning planes in the crystal lattice
– i.e. slip occurs on the {1010} prism planes and the
{1011} pyramidal plans as well as on the basal planes
• Twinning in plastic deformation more important in
Ti than in Mg, Zn and Cd

Lattice parameters of HCP metals

Metal a c c/a*
Beryllium 2.2840 3.5841 1.5692
Cadmium 2.9787 5.6170 1.8857
Cobalt 2.5070 4.0690 1.6230
Hafnium 3.2060 5.0870 1.5867
Magnesium 3.2092 5.2103 1.6235
Titanium 2.9504 4.6833 1.5873
Zinc 2.6640 4.9450 1.8562
Zirconium 3.2300 5.1330 1.5892
*High c/a ratio leads to primary slip system on basal planes
Note: c/a affects tendency towards 2 secondary slip systems:
•Pyramidal
•Prismatic (primary is Basal plane)

8
 Effects of alloying elements
Alloying Range Effect on structure
element (approx) wt %
Aluminum 2-7 α stabilizer
Tin 2-6 α stabilizer
Vanadium 2-20 β stabilizer
Molybdenum 2-20 β stabilizer
Chromium 2-12 β stabilizer
Copper 2-6 β stabilizer
Zirconium 2-8 α and β strengtheners
Silicon 0.05 to 1 Improves creep resistance
gallium, germanium, carbon, oxygen, and nitrogen also α
stabilizers

4 alloys to be considered

Grades 1-4 increase in O-C-N

Usage

1. “Pure” Ti (99.0 + %Ti) 35%

α- phase stabiliser
2. α alloy (Ti-5Al-2.5Sn) Grade 5 10%
HCP
3. β alloy (Ti-13V-11Cr-3Al) ~1%
BCC β- phase stabiliser
4. α + β alloy Ti-6Al-4V 55%
α- phase stabiliser β- phase stabiliser

9
 Mechanical properties
UTS %
Grade Y.S. (MPa)
(MPa) Elongation
1. “Pure” Ti 241-585 331-661 30-20
2. Ti-5Al-2.5Sn (α) 806 861 16
3. Ti-13V-11Cr-3Al (β ) 1205 (H.T.) 1275 8
4. Ti-6Al-4V (α+β) 1102 (H.T.) 1171 10

(H.T.) = Solution anneal – quench and aged

Characteristics of Ti alloy families

10
 Table 10-14: Approximate %’s of Ti alloys
used in the US in 1989
Extra Low Interstitial: O, C, N

Effect of interstitial content on impact

toughness of pure titanium
O N C

11
Effect of interstitial content on yield
strength and % elongation of Ti
O N C

Interstitials effects

12
Table 10-4 Mechanical properties of commercially
pure titanium and low-alloyed titanium

1
2
3
4

Grades 1-4 Extreme temperatures: TH>0.4 -0.5

Table 10-3 Chemical compositions (max values)

and typical applications of unalloyed titanium

13
 α−Titanium Alloys
Al - most important alloying element in Ti
1. Extensive solid solubility ~8% at room
temperature
2. Strong solid solution hardening effect
3. Raises transition temperature therefore good for
elevated temperature properties to 1000°C α→β
4. Lower density
5. Moderate strength
6. Weldable
7. Good stability & oxidation resistance @ elevated
temperatures
i.e., Ti-5%Al-2.5%Sn Most important α−alloy

Alpha-stabilised system

• α-phase field extended

883
• β transus raised

8%

14
 Unalloyed Ti sheet microstructure

• Annealed 1hr @ 700oC

• Air-cooled
• Equiaxed α grains
• β spheroids

α−Titanium Alloys
• Sn – stabilizes α−phase
– Contributes to solid solution strengthening
• Limit to how much Al can be added to Ti
because of α 2 formation
– α 2 is a Ti3Al coherent ordered phase – leads to
embrittlement
• Therefore Al limited to ~5-6% in Ti
– Aleq = Al + Sn/3 + Zr/6 + 10(O) ≤ 9 wt%
– To avoid excessive α 2 formation
• Therefore low O Grade 6 for good ductility at
low temperatures Ti, 5%Al, 2.5%Sn

15
 Ti-Al phase
diagram
β

883oC

100% Ti

Effect of Al content on embrittlement

of Ti-Al alloys

16
Titanium-rich end of Ti-Al phase diagram

883oC

α 2: Ti3Al

α 1: Ti

Table 10-5
Chemical compositions and typical applications
of α titanium alloys

17
 Table 10-6
Mechanical properties of α titanium alloys

α + β Alloys

• Most important is:

– Ti-6%Al-4%V (Al α-stabilizer; V - β-stabilizer)
• 60% of all Ti usage
• Modifications of 6-4 used for increased
“hardenability”
• Heat-treat larger section sizes
• Ti-6Al-2Sn-4Zr-6-Mo

18
 Table 10-9:
Chemical compositions and typical applications α−β Ti

Table 10-10
Mechanical properties of α−β titanium alloys

19
Schematic pseudo-binary phase diagram

For Ti-6%Al alloy

with additions of
Vanadium

Heat treatments of α+β Ti

Cooling from 1066°C

Fast
Slow
(water quench)
(furnace cool)

β β+α β α1 (Ti martensite

HCP)
tempering

α+ fine β

20
 Heat treatments of α+β Ti

Cooling from
1066°C:
a) Furnace cool
b) Air cool
c) Water quench

Furnace cooling

Equilibrium α+β structures

• Coarse plate-like α is formed by nucleation and growth
• Some β phase retained and occurs intergranularly
– Furnace cool UTS = 1034 MPa
– Ti martensite (α 1) UTS = 1102 MPa
– Therefore increase 70 MPa before tempering

21
Microstructure for Ti-6%Al-4%V

Solution treated at
1066oC for 30 min
Furnace cooled
Nucleation & growth α

Plate-like α
(light-HCP)
Intergranular β
(dark-BCC)

Microstructure for Ti-6%Al-4%V

Solution treated at
1066oC for 30 min
Air cooled
Nucleation & growth of
α

Acicular α
(prior β g.b’s visible)

22
Microstructure for Ti-6%Al-4%V
Solution treated at 1066oC for
30 min and water quenched
α 1 titanium martensite (HCP)
platelets which are heavily
twinned and have an HCP
structure
Soft compared to steel
martensite
Tempering produces
strengthening when fine β starts
to ppt

Heat treatments of α+β Ti

Cooling from
954°C:

Primary α + enriched β
- Ti martensite α ’
(fast cooling)

α+β (slow cooling)

23
 Heat treatments of α+β Ti
Cooling from 954°C

Fast
Slow
(water quench)
(furnace cool)

α+β α + (α + β) α+β α + α1
tempering

α+ fine β

Microstructure for Ti-6%Al-4%V

o
Solution treated at 945 C for 5hr
3a) FAST COOL 3b) SLOW (AIR) COOL

β transformed
α – α1
5.0µm

24
 Heat treatments of α+β Ti

Cooling from
843°C:

Primary α+β
On fast cooling:
α +retained β

On aging: α+β

Heat treatments of α+β Ti

Cooling from 843°C

Fast
Slow
(water quench)
(furnace cool)

α+β α+β α+β α+β

25
 Microstructure for Ti-6%Al-4%V

Solution treated at
843oC for 1hr
4a) Water quenched

α titanium
(HCP)

β titanium
(BCC)

Schematic pseudo-binary phase diagram

For Ti-6%Al alloy

with additions of
Vanadium

26
 β-Alloys
– Highest strength Ti alloys – used in specialized
applications
– Higher density because of Mo, V, Fe additions
– Add Al to lower density and give solid solution strength
and high temperature oxidation resistance
– Easy to cold work (BCC) in solution treated and
quenched condition
– Can be subsequently aged to very high strengths
strength

1hr 10hrs 100hrs

β1 β 1+ ω β+ ω +α β+ α
metastable

β-Alloys
• ω - omega – transition phase is brittle
• Ti-13%V-11%Cr-3%Al – only β−alloy
produced in large quantities
• Limited use because of:
– Relatively high density because of V, Mo
– Low ductility in high strength condition
– In thick sections – chemical segregation;
large grain size therefore low tensile
ductility and poor fatigue performance

27
 Two groups of beta stabilisers
Beta eutectoid Beta isomorphous
• eutectoid mixture of alpha • metastable beta
and a compound form decomposes to
• active eutectoid formers isomorphous (same crystal)
(eg, Ni, Cu) promote rapid alpha phase
decomposition, • elements are completely
• sluggish eutectoid formers miscible in the beta phase;
(eg Fe, Mn) induce a • molybdenum, vanadium,
slower reaction tantalum, and niobium

Ti-Cr Phase Diagram

28
 Ti-V Phase Diagram

Microstructure for Ti-13%V-11%Cr-3%Al

Solution treated at
788oC for 30min
5a) Water quenched

Metastable β
phase (BCC)

29
 Table 10-12
Mechanical Properties of β Ti alloys

Table 10-11
Chemical composition and typical applications
of β Ti alloys

30
 Summary

Alpha Alpha-Beta Beta

• Non-heat • Heat treatable • Heat treatable
treatable • Most are weldable • Generally
• Weldable • Strength levels weldable
• Low to medium medium to high. • High strengths
strength • High temperature • Good creep
• Good notch creep strength is resistance to
toughness. not as good as intermediate
• High temp. creep most alpha alloys. temperatures
strength, • Excellent
oxidation formability in the
resistance solution treated
condition

31