Engineering Alloys (307) Lecture 7

Titanium Alloys I

David Dye

Department of Materials, Imperial College

Royal School of Mines, Prince Consort Road, London SW7 2BP, UK
+44 (207) 594-6811, david.dye@imperial.ac.uk
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 Outline Page 2

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• Ti primary production
• CP Ti and applications
• α-Ti alloying, alloy design
• near-α alloy microstructures, forging and heat treatment
• α/β alloys, Ti-6Al-4V
• defects
Ti Primary Production – Kroll Process Page 3

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• Ti common in Earth’s crust

• Energy to separate ~125 MWhr/tonne (£4/kg just in power)
• Batch process over 5 days:
– Produce TiCl4 from TiO2 and Cl2
– TiCl4 + 2 Mg → 2 MgCl2 + Ti
– chip out Ti sponge (5-8t) from reactor
– cost £5/kg
– Chlorides corrosive, nasty
• World annual capacity ~100,000 t, demand ~60,000t ($500m - small)

• Need a cheaper process that is direct

– FFC (Cambridge) and others
Subsequent Processing Page 4

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harvey fig p11

Casting Page 5

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• Use skull melting (EBHCR) instead of VIM/VAR/ESR for final

melting stage in triple melting process
Ti Allotropes, Phase Diagram Page 6

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• Pure Ti:
– L→β (bcc) @ 1660 C
– β→α (hcp) @ 883 C
• ρ=4.7 g/cc
• highly protective TiO2
film
• Diffusion in α 100x
slower than in β
– origin of better α
creep resistance
 Alloying: Pure α alloys Page 7

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• α stabilisers: O, Al (N,C)
• β stabilisers: V,Mo,Nb,Si,Fe
• neutral: Sn, Zr harvey fig p13
Table of CP Ti
• Strengthen pure α alloys by
– solid solution – O, Al, Sn
– Hall-Petch – σ = 231 + 10.5
d
– cold work
– martensite reaction exists, of little
benefit (not heat-treatable)

• Uses: chiefly corrosion resistance

– chemical plant
– heat exchangers
– cladding
Microstructures – near α alloys Page 8

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• α stabilisers – raise α/β

transus
• β stabilisers to widen α/β
field and allow hot working
• heat – treatable
– ~10% primary (grain
boundary) α during h.t. @
>900C
– oil quench – intragranular α’
plates + retained β
– age at ~625C to form α,
spheroidise β and stress
relieve
– Then >>90% α

Lightly deformed (~5%) Ti-834

 Properties –
near-α alloys
Page 9

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• Refined grain size

– stronger
– better fatigue resistance
• Predominantly α – few good slip systems
– good creep resistance
• Si segregates to dislocation cores – inhibit glide/climb further
Ti Creep Rates Page 10

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 α+β alloys: Microstructures Page 11

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• Contain significant β stabilisers to enable β to be retained to RT

• Classic Ti alloy: Ti-6Al-4V
– >50% of all Ti used
• Classically
– 1065 C all β
– forge @ 955C – acicular α
on grain boundaries to
inhibit β coarsening
– Air cool – produce α
lamellae colonies formed
in prior β grains (minimise
strain), w/ β in between
(think pearlite)
Ti-6-4: heat treat Page 12

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Ti-6-4: properties Page 13

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• N.B. Must avoid Ti3Al formation

– via Al equivalent: Al+0.33 Sn + 0.16 Zr + 10 (O+C+2N) < 9 wt%

ppt hardening
+ grain size
 Defects Page 14

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• Major α-related problem is the production of α-rich regions due to

oxygen (+N) embrittlement – the entrapment of O-rich particles
during melting

• Called α case

• Also a problem in welding – often Ti is welded in an Ar-filled cavity

to avoid this

• β alloys suffer from β-rich regions from solute segregation (β

flecks), and/or from embrittling ω phase, a diffusionless way to
transform from β-bcc to a hexagonal phase.
– more in lecture on β alloys
Review: Titanium I (L7) Page 15

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near-α
microstructure

α/β microstructure α-Ti Alloys

Casting Phase
Diagram