MATERIALS PERSPECTIVE

A review of advances in processing and

metallurgy of titanium alloys
M. Jackson*1 and K. Dring2
Titanium and its alloys exhibit excellent mechanical properties, unrivalled corrosion resistance
and outstanding biocompatibility; however, annual global titanium production is dwarfed by
commodity metals. This is in part due to the current primary production method (Kroll process),
which requires a complex and discontinuous reduction route in addition to several costly
downstream processing steps to convert titanium sponge to usable product forms. Alternative
extraction processes are reviewed in the present paper with emphasis on the electrochemical
reduction routes, such as the FrayFarthingChen (FFC) Cambridge process. Improvements in
thermomechanical processing including the use of modelling are briefly examined. Alloy
development is also discussed with particular regard to superelastic and shape memory alloys.
Keywords: Titanium, Review, Extractive metallurgy, Electrochemical reduction

Professor Harvey Flower

The review is dedicated to the memory of Harvey
Flower (Fig. 1) who was Professor of Materials Science
at Imperial College London and a world leading expert
on titanium and aluminium aerospace alloys. His
research on microstructure evolution in alloy systems
and its effect on the resultant properties were highly
influential to the international scientific community.
Among his numerous achievements was the first
observation and explanation of V phase in many
titanium alloys, as well as the development of new high
strength, high toughness b alloys. Harvey Flowers
materials science and technology review paper of 1990
(Ref. 1) on the microstructural development in relation
to hot working in titanium alloys is still referred to as a
primary source. Before his untimely death, Professor
Flower was a major driving force behind many of the
developments discussed in this review.

Introduction 1 Professor Harvey Flower at 10th World Conference on

Over 60 years has passed since Wilhelm Kroll developed
a viable method for the conversion of titanium oxide ore
into useable metal. Unfortunately, titanium has not
made the breakthrough into mainstream engineering
applications accomplished by aluminium. This is not
due to inferior properties; titanium alloys exhibit out-
standing structural efficiency and corrosion resistance.
For example, 15% (by weight) of titanium will be used in
the 787 Dreamliner compared with 8% on the Boeing
747 on account of the better corrosion compatibility of
titanium with carbon composites (relative to aluminium
1
Department of Materials, Imperial College London, South Kensington
campus, London SW7 2AZ, UK
2
Norsk Titanium AS, Bankplassen 1a, 0151, Oslo, Norway
*Corresponding author, email martin.jackson@imperial.ac.uk
Titanium in Hamburg, 2003
and steel) as well as selection of high strength titanium
forgings in the internal structures.2 Furthermore, strong
demand from aerospace, owing to a robust aircraft
order market following the sharp downturns caused by
9/11 and SARS, and the steel industry, which consumes
scrap for use in products such as interstitial free (IF)
steels, has led to a situation where sponge prices are
y10/kg. Although there is a current strong demand for
sponge, overall suppliers are globally running at 85
90% full capacity: in 2005, y95 000 t of sponge was
produced and it is estimated that the total global
capacity is 110 000 t globally.3 However, both these
cyclical industries must accommodate the high prices for
titanium and the boom bust cycle appears to be
presently atop a crest.

2006 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 31 March 2006; accepted 26 April 2006
DOI 10.1179/174328406X111147 Materials Science and Technology 2006 VOL 22 NO 8 881
Jackson and Dring A review of advances in processing and metallurgy of titanium alloys
2 Breakdown of cost to produce 10 plate: from Kraft5
What is needed is a high volume consumer of titanium
with a steady demand for titanium that will stabilise the
industry. The automotive market has long been hailed as
such a market, however, the price of titanium will need
to fall substantially to compete with the established steel
and aluminium products. Although the daily global
production of steel greatly exceeds the annual produc-
tion of titanium, economies of scale will not lead to
significantly lower titanium prices. The Kroll process
has already been optimised to a high degree and only
step change technologies will enable broader titanium
usage. Figure 2 depicts the contributions to the overall
cost of producing 10 titanium plate.4
A three pronged approach to reducing the cost of
titanium mill products is currently being pursued. First,
improvements in the utilisation of titanium have been
accomplished via predictive models of the processes used
to create titanium products, essentially making more
efficient use of this high cost material. Second, advances
in melting technology and certification have provided
significant cost savings, particularly for non-aerospace
grade materials, and have been recently reviewed by
Fox5 and Kraft.4 One example of such an improvement
is the development of electron beam single melt (EBSM)
alloys for non-aerospace applications (Timetal XT).6 The
third development, which has received the most interest
both within and outside the industry, is the emergence
of several low cost extraction methods as alternatives to
the Kroll process. A successful scale up of a low cost
extraction process coupled with non-melt downstream
processing routes could produce titanium at a price
suitable to high volume applications. Such an accom-
plishment would have a similar effect to the discovery of
the Hall-Heroult process for the aluminium industry.
Titanium reduction processes
The Kroll process depicted in its original laboratory
configuration in Fig. 3 has been the dominant commer-
cial production route for titanium since the 1940s.7,8
Previous attempts to reduce titanium dioxide (TiO2)
directly to metallic titanium have been largely unsuc-
cessful owing to the highly negative free energy of
formation for TiO2 (Ref. 9) and titaniums ability to
dissolve a substantial amount of oxygen in solid
solution.10 Any possible reducing agent must not only
surmount this free energy barrier, but also overcome the
increasing chemical affinity titanium exhibits for oxygen
as the latter concentration decreases.11 Consequently, a
discontinuous metallothermic reduction process has
been the dominant means of titanium production.
The Kroll process first involves the carbochlorination
of the oxide ores in a fluidised bed at 1300 K via
reaction 1 to produce an oxygen free tetrachloride.
Subsequent fractional distillation at 400 K removes
882 Materials Science and Technology 2006 VOL 22
3 Original laboratory set-up of Kroll process
most of the remaining ore impurities and the TiCl4 is
slowly fed into a large steel retort containing liquid
magnesium between 1073 and 1173 K. Titanium sponge
is formed via reaction 2, which requires an excess of
magnesium to drive the equilibrium to the right and
avoid residual TiCl2. Slow reduction of TiCl4 is
necessary as reaction 2 is highly exothermic and heat
extraction from the retort is rate determining, hence the
long reduction times. Magnesium and chlorine are
regenerated in a separate electrolysis cell.
TiO2 z2Cl2 zC?TiCl4 zCO2 (1)
TiCl4 z2Mg?Tiz2MgCl2 (2)
The porous sponge product is crushed, alloyed and
either consolidated into a welded electrode for vacuum
arc remelting (VAR) or fed directly into an electron
beam cold hearth melting (EBCHM) furnace, depending
on the final product applications. The cast ingot from
then undergoes extensive thermomechanical processing
to achieve the final product shape, size and micro-
structure. Although a significant proportion of the total
cost of titanium products is due to these downstream
processes, the high cost of producing titanium sponge is
nonetheless seen as an area for significant gains in
productivity. Minor savings in the reduction process
could be obtained using a lower purity TiCl4 feedstock
than that required for high purity pigment grade TiO2
production. Improvements to the already high efficiency
of magnesium electrolysis and changes to the reduction
retort design to maximise heat extraction are only
evolutionary changes. To achieve the production costs
and consequent volumes associated with commodity
metals, a step change in the extractive metallurgy
process is necessary.
Over the past decade, several novel reduction tech-
nologies have emerged as low cost challengers to the
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 Jackson and Dring
Kroll process. Clear cost savings are also to be realised
by eliminating the multiple melting operations and
possibly some ingot homogenisation/breakdown hot
working stages, as many of these processes strive to
do. Many of these processes employ TiCl4 with the
economics associated with conventional carbochlorina-
tion. Those using titanium oxide feedstock must incur
additional costs to obtain high grade TiO2 from TiCl4 or
develop alternate purification methods that ideally
retain the impurities in titanium ore that are currently
removed from pigment grade TiO2, but are common
alloying additions to titanium alloys, e.g. V. Alter-
natively, forgoing carbochlorination or using an alter-
nate technology would eliminate the dioxin issue that is
a major environmental regulation concern.
A survey by EHK Technologies4 of emerging reduc-
tion technologies was conducted shortly after the 10th
World Conference on Titanium, and several companies
have intensified their efforts including Information
Technology Partners (ITP), Materials and Electro-
chemical Research (MER) Corporation and BHP
Billiton, to name a few.1214 Other processes, such as
the molten oxide research at MIT and the mechan-
icothermal processing at the University of Idaho remain
at the laboratory scale.15,16 Of the reviewed technolo-
gies, many share technical similarities, especially in the
proposed cell designs and reduction principles. Only a
select few will be discussed further. Those processes
involving plasma or the production of liquid titanium
metal face significant issues regarding cost and heat
balances, while the hydrogen reduction of TiCl4 has not
experienced a successful past. A Defense Advanced
Research Projects Agency (DARPA) initiative on
titanium was started in 2003 to accelerate the develop-
ment of a few select processes and established defined
chemistry and production targets (see the DARPA
website for further details: www.darpa.mil/dso/thrust/
matdev/titanium.htm).
The ITP/Armstrong process is a continuous version of
the Hunter reduction route, where gaseous TiCl4 is
reduced and cooled as it is injected into a flowing stream
of molten sodium (reaction 3). This suggests an
economic improvement over the Hunter process, which
is no longer used to produce titanium at present. The
ability to produce alloy powders by mixing the requisite
chlorides is promising, although some chlorides are
particularly corrosive (AlCl3). The control of the powder
size distribution via nozzle design is critical because the
titanium product must be of sufficient size to avoid high
oxygen contamination upon exposure to the atmo-
sphere. Additional powder processing is necessary to
densify a very porous and fine particle size powder
product.12 Furthermore, the boiling point of sodium
(1156 K) is only slightly higher than the melting point of
the product sodium chloride (1074 K), which necessi-
tates fine control of the reduction rate. Nevertheless,
this process has reportedly been scaled up to the
2 Mlb year21 production level, and according to the
company website, small quantities of powder are
available for analysis.
In the MER process17 TiO2 is carbothermically
reduced to produce a lower oxide approaching TiO in
composition. A composite anode is manufactured by
blending carbon and this oxide, which is then immersed
in a molten salt electrolyte. The anodic reaction
A review of advances in processing and metallurgy of titanium alloys
(reaction 3) is the generation of CO and CO2 coupled
with formation of predominantly Ti2z ions that are
transported to the cathode, where they are reduced to
metal (reaction 4). A similar process has been developed
by Zhu,18 using a TiCzTiO anode instead, leading to an
equivalent anode reaction (reaction 5).
xTiOzC~COx zxTi2z z2xe (3)
xTi2z z2xe ~xTi (4)
xTiOzTiC~COx z(xz1)Ti2z z2xe (5)
The advantages of this process are that the titanium is
formed at a separate physical location to any sources of
oxygen and high mass flow rates because both dissolu-
tion and deposition process are limited by mass transfer
in the molten electrolyte. Consequently, smaller cells
may be employed for a given throughput and oxygen
contamination in the as deposited product should be
extremely low. Disadvantages include the problems of
redox cycling, where higher valence state titanium ions,
e.g. Ti3z and Ti4z, are reduced to a lower valence, e.g.
Ti2z, but not deposited. The soluble lower valence
species may then diffuse back to the anode and be
oxidised back to their original valence state, thus
wasting electrolysis currents. Additionally, the electro-
deposited metal tends to form in dendrites that have a
high surface area, leading to high electrolyte drag-out
and increased oxygen contamination upon exposure to
ambient atmospheres.
Another competing electrochemical process features a
titanium oxide cathode that is progressively reduced and
deoxidised to form a low oxygen titanium product.
Several industrial players have been involved with
commercialising this technology including BHP
Billiton, Metalysis, British Titanium, Timet and
QinetiQ. These processes, which include the Fray
FarthingChen (FFC) Cambridge and OS processes,
are referred to as electrochemical deoxidation (EDO)
processes. Two reportedly different reduction mechan-
isms, oxygen ionisation (primary) and calciothermic
(secondary) are postulated to defend the intellectual
property claims of the various companies involved.
Figure 4 depicts the two proposed reaction pathways for
the electrochemical technologies.
Although the calciothermic and ionisation processes
are typically described as separate entities, they both
share several key features. The reaction of the dissolved
CaO with graphitic anodes produces CO and CO2 gases.
The electrolysis voltages of both processes are similar
(2.83.5 V) and the TiO2 cathode feedstock, in either
pellet or powder form, is suspended or contained at the
cathode. Molten CaCl2 is selected as the electrolyte
for its high oxide solubility19 and low melting point
(1055 K), in addition to low cost. The reduction of TiO2
proceeds via the lower oxides and during the concluding
stages of deoxidation, diffusion of oxygen in metallic
titanium is rate determining.14,2022 The disadvantages
of these EDO processes include the precipitation of CaO
and CaTiO3 in the pellet pores and the slow diffusion of
oxygen in metallic titanium at feasible reduction
temperatures leading to long reduction times. Excess
calcium formation in either embodiment leads to a
decrease in current efficiency and a mechanism for
Materials Science and Technology 2006 VOL 22 NO 8 883
Jackson and Dring A review of advances in processing and metallurgy of titanium alloys
4 Schematic representation of EDO process mechanisms
carbon contamination as the elemental calcium reacts
with the graphite anode. However, by careful control of
the operating parameters the process is capable of
producing not only low oxygen titanium,23,24 but also
alloys of both conventional and novel compositions.24,25
Furthermore, fine grain sizes (1020 mm) are observed
post-reduction despite a slow cooling from 1173 K and
without any thermomechanical processing (Fig. 5).26
This is due to the fine oxide particle size of the ceramic
precursor and reduction that occurs entirely in the solid
state without liquid melt processing.
Thermomechanical processing
Currently, titanium is cast as ingots of several tonnes
weight that must be forged to a slab or billet. The
primary processing stage involves the breakdown of a
microstructure that consists of coarse b grains with grain
boundary a and intragranular a lamellar plates. An
initial cogging process which is a combination of
incremental open forging ram passes and reheats breaks
down this inhomogeneous microstructure. The work-
piece is normally cogged at temperatures above the b
transus where lower working energies are required, with
final cogging passes carried out at subtransus tempera-
tures to generate a fine ab microstructure. One of the
major advances in the primary processing stage has been
5 Backscattered electron micrograph of Ti10V2Fe3Al
material produced by EDO process under as-reduced
condition
884 Materials Science and Technology 2006 VOL 22
to use four die radial presses instead of conventional
open die forging presses to reduce processing costs
and to improve the final microstructural refinement.
Figure 6 shows the RUMX radial forging machine
employed by Timet UK to produce forged bars.27 The
machine has four simultaneously acting forging rams,
each opposing ram pair delivering an 8 MN forging
force. Side spread is restricted owing to the high degree
of material enclosure, thus the number of passes
required, and hence forging time is reduced. The
Rumx is capable of forging a large range of cross-
sections without tool changes.28
In recent years, work led by Semiatin29,30 and
Brooks31 with support from the major titanium produ-
cers has contributed significantly to the understanding
of both microstructural and textural evolution during
the cogging and secondary hot and/or isothermal
forging processes, which has led to significant cost
reductions. One approach has been to develop empirical
relationships that predict the evolution of microstruc-
tural constituents such as a phase volume fraction,
morphology and b grain size for a range of processing
variables, i.e. temperature, strain and strain rate.32,33
Such empirical relationships coupled with finite element
simulation have provided engineers with the tools to
reduce scrap and improve final forging properties.5
However, the development of such models is complex,
primarily owing to the allotropic nature of titanium, and
is not fully understood. To emphasise the complexity of
6 Forging from initially large cross-section to final billet
size using RUMX press: sideways movement of tools
at end of forging pass (inset) allows smaller cross-
sections to be forged;27 courtesy of Timet UK
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 Jackson and Dring A review of advances in processing and metallurgy of titanium alloys

a at 1023 K dynamic recovery processes are clearly inactive, owing to observation of dynamically recrystallised b grains;
b at 1033 K, dynamic recovery processes are clearly active owing to development of equiaxed subgrain structure; c
above 1033 K, dissolution of a phase contributes to instability of b phase and at 1048 K, mixed microstructure of meta-
stable b and martensite is observed in b phase; d however, at 1063 K, entire specimen transforms to martensite owing
to low level of b stability, as consequence of large volume fraction of b containing dilute quantities of b stabilisers
7 Backscattered electron micrograph of Ti10V2Fe3Al material isothermally forged at strain rate of 0.01 s21 at sub-
transus temperatures

microstructural prediction during isothermal forging,
Fig. 7 illustrates the range of microstructures obtained
over a narrow subtransus temperature range (1023
1063 K) for near b alloy Ti1023 (Ti10V2Fe3Al)
which is currently used for landing gear bogie beam
forgings on the Boeing 777. Such variation in micro-
structure and thus, properties, clearly emphasise the
need for good temperature control during forging. The
same testing methodology34 used to exploit such micro-
structural sensitivity in Ti1023 is currently being
applied to the near b alloy Ti 555 (Ti5Al5Mo5V
3Cr0.6Fe), similarly to understand the microstructural
evolution during isothermal forging. Timet has been
manufacturing and evaluating Ti 555 for a variety of
aerospace applications35,36 and Boeing announced their
intention to use the alloy for landing gear forgings on
the 787 Dreamliner.2
Alloy development
The American Society for Metals (ASM) Titanium
Handbook37 lists around fifty alloys and six commer-
cially pure grades of titanium, although only about half
this number are commonly available. Given the current
world market of only y70 000 t this is clearly excessive
and suppliers have sought to reduce the number of
alloys supplied to lower their costs. In contrast, China is
continually increasing its portfolio of alloys, merely
reflecting the rapid development and expansion of the
titanium industry in China;38 titanium producers, in

Materials Science and Technology 2006 VOL 22 NO 8 885

Jackson and Dring A review of advances in processing and metallurgy of titanium alloys
8 Relationship of tensile strength and Youngs modulus
for gum metal compared with conventional metal
alloys: after Ref. 44
general, have concentrated on improving the processing
of their conventional aerospace alloys. One of the most
significant alloy developments in the industry over the
last few years has been the production of leaner titanium
containing alloys, such as TiNi and gum metal39 which
have multifunctional properties that are opening up new
markets for the titanium industry.
Approximately equiatomic TiNi is the most widely
used superelastic and shape memory alloy. TiNi has
found numerous applications in high value applications
including actuators, electrical connectors and many
other demonstration devices40,41 and is getting much
attention for the biomedical applications such as stents
and catheters.42 Unfortunately, the material is expensive
owing to the required vacuum melting steps because of
the reactivity of TiNi. It is perceived that an electro-
chemical reduction process could overcome the pro-
blems of conventional processes, which include melt
segregation and containment, such as reaction and
contamination with mould materials and atmospheres,
and thus provides a cheaper product. Electrochemical
deoxidation processes could also produce ternary TiNi
X alloys, where X is niobium, tantalum, zirconium or
hafnium, which would control the important transfor-
mation temperatures and improve overall properties by
grain size refinement, for example.
A new near b-Ti alloy labelled as Gum Metal owing
to its super ductility and developed by Saito and
researchers39 has recently generated interest in the
titanium community. The alloy, which contains nio-
bium, tantalum and zirconium, is claimed to be super
multifunctional with ultra high strength and ultra low
elastic modulus (Fig. 8), as well as superelasticity at
room temperature. Such properties are:
(i) sensitive to composition, designed by theoretical
calculation43
(ii) the amount of cold work
(iii) the level of oxygen.
The statement by Saito et al. that such properties are a
result of dislocation free plastic deformation mechanism
has been a minor cause of contention within the
academic community for the last couple of years.
However, recent measurements show that the ideal
886 Materials Science and Technology 2006 VOL 22
9 Backscattered electron micrograph of Ti10W alloy
shear strength of gum metal is so small (y1 GPa) that it
is almost equal to its actual shear strength, thus implying
that plastic deformation can occur by ideal shear.44
Gum Metal is currently being used for spectacle frames
and precision screws,44 but compositions that constitute
Gum Metal have significant potential for biomedical
applications owing to their good biocompatibility,
excellent corrosion resistance and the absence of
cytotoxic constituents such as aluminium and vana-
dium.42 In the future, Gum Metal could also supersede
TiNi in medical and dental components to avoid the
metal allergies associated with nickel.
Although conventional titanium alloys are of signifi-
cant interest for biomedical applications, alloying with
tungsten improves both wear resistance and strength, as
well as lowering the elastic modulus, which is advanta-
geous for stress sharing.45 However, in Kroll production
facilities, tungsten is rigorously prohibited from reach-
ing the titanium during all stages of processing because
of the consequent high density inclusions that would
result. TiW implants, much less cytotoxic than Al, V,
or Ni containing alloys,46 have higher radio-opacity, and
unlike cobaltous or ferrous materials, are compatible
with magnetic resonance imaging (MRI) techniques.
Conventional powder metallurgy approaches require
fine metallic particles in order to ensure homogenisation
of slow diffusing tungsten during consolidation.45
Oxygen pickup and tungsten rich regions both degrade
the fatigue properties and fracture toughness. By
electrochemical deoxidation of a sintered blend of
micrometre scale WO3 and TiO2 particles, a low oxygen
Ti10W alloy was obtained.32 The stepwise reduction of
WO3 to WO2 led to a TiO2WO2 oxide solid solution
that enhanced the distribution of the refractory element.
As metallic tungsten formed before titanium, the slow
diffusion of the former was advantageous in producing a
fine grained microstructure corresponding to a slow
cooled hypoeutectoid alloy (Fig. 9). The advantages of
solid state reduction of metal compounds are being
exploited to produce novel alloys and powders by
researchers at the University of Cambridge, Metalysis
and Imperial College London.26,47,48
Conclusions
A commercialised low cost extraction process coupled
with non-melt downstream processing routes would
provide a dramatic step change in the price of titanium,
which would then become an economical alternative to
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 Jackson and Dring
steel and aluminium. This would pave the way for an
expansion of the overall market into a range of high
volume applications, in particular the holy grail of the
automotive industry. For this expansion to be successful,
a cultural shift from directly comparing an alloy that has
been processed from an electrochemical reduction route to
aerospace grade triple vacuum arc remelt (VAR) material
is needed. Industry must consider material from these
emerging reduction processes as a separate entity to that
associated with compressor disks and high strength
forgings, otherwise the potential for expansion will be
restrained by a pointless need to achieve a certain
microstructure, property or defect level.
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