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Kroll process. Clear cost savings are also to be realised (reaction 3) is the generation of CO and CO2 coupled
by eliminating the multiple melting operations and with formation of predominantly Ti2z ions that are
possibly some ingot homogenisation/breakdown hot transported to the cathode, where they are reduced to
working stages, as many of these processes strive to metal (reaction 4). A similar process has been developed
do. Many of these processes employ TiCl4 with the by Zhu,18 using a TiCzTiO anode instead, leading to an
economics associated with conventional carbochlorina- equivalent anode reaction (reaction 5).
tion. Those using titanium oxide feedstock must incur
additional costs to obtain high grade TiO2 from TiCl4 or xTiOzC~COx zxTi2z z2xe (3)
develop alternate purification methods that ideally
retain the impurities in titanium ore that are currently xTi2z z2xe ~xTi (4)
removed from pigment grade TiO2, but are common
alloying additions to titanium alloys, e.g. V. Alter- xTiOzTiC~COx z(xz1)Ti2z z2xe (5)
natively, forgoing carbochlorination or using an alter-
nate technology would eliminate the dioxin issue that is The advantages of this process are that the titanium is
a major environmental regulation concern. formed at a separate physical location to any sources of
A survey by EHK Technologies4 of emerging reduc- oxygen and high mass flow rates because both dissolu-
tion technologies was conducted shortly after the 10th tion and deposition process are limited by mass transfer
World Conference on Titanium, and several companies in the molten electrolyte. Consequently, smaller cells
have intensified their efforts including Information may be employed for a given throughput and oxygen
Technology Partners (ITP), Materials and Electro- contamination in the as deposited product should be
chemical Research (MER) Corporation and BHP extremely low. Disadvantages include the problems of
Billiton, to name a few.1214 Other processes, such as redox cycling, where higher valence state titanium ions,
the molten oxide research at MIT and the mechan- e.g. Ti3z and Ti4z, are reduced to a lower valence, e.g.
icothermal processing at the University of Idaho remain Ti2z, but not deposited. The soluble lower valence
at the laboratory scale.15,16 Of the reviewed technolo- species may then diffuse back to the anode and be
gies, many share technical similarities, especially in the oxidised back to their original valence state, thus
proposed cell designs and reduction principles. Only a wasting electrolysis currents. Additionally, the electro-
select few will be discussed further. Those processes deposited metal tends to form in dendrites that have a
involving plasma or the production of liquid titanium high surface area, leading to high electrolyte drag-out
metal face significant issues regarding cost and heat and increased oxygen contamination upon exposure to
balances, while the hydrogen reduction of TiCl4 has not ambient atmospheres.
experienced a successful past. A Defense Advanced Another competing electrochemical process features a
Research Projects Agency (DARPA) initiative on titanium oxide cathode that is progressively reduced and
titanium was started in 2003 to accelerate the develop- deoxidised to form a low oxygen titanium product.
ment of a few select processes and established defined Several industrial players have been involved with
chemistry and production targets (see the DARPA commercialising this technology including BHP
website for further details: www.darpa.mil/dso/thrust/ Billiton, Metalysis, British Titanium, Timet and
matdev/titanium.htm). QinetiQ. These processes, which include the Fray
The ITP/Armstrong process is a continuous version of FarthingChen (FFC) Cambridge and OS processes,
the Hunter reduction route, where gaseous TiCl4 is are referred to as electrochemical deoxidation (EDO)
reduced and cooled as it is injected into a flowing stream processes. Two reportedly different reduction mechan-
of molten sodium (reaction 3). This suggests an isms, oxygen ionisation (primary) and calciothermic
economic improvement over the Hunter process, which (secondary) are postulated to defend the intellectual
is no longer used to produce titanium at present. The property claims of the various companies involved.
ability to produce alloy powders by mixing the requisite Figure 4 depicts the two proposed reaction pathways for
chlorides is promising, although some chlorides are the electrochemical technologies.
particularly corrosive (AlCl3). The control of the powder Although the calciothermic and ionisation processes
size distribution via nozzle design is critical because the are typically described as separate entities, they both
titanium product must be of sufficient size to avoid high share several key features. The reaction of the dissolved
oxygen contamination upon exposure to the atmo- CaO with graphitic anodes produces CO and CO2 gases.
sphere. Additional powder processing is necessary to The electrolysis voltages of both processes are similar
densify a very porous and fine particle size powder (2.83.5 V) and the TiO2 cathode feedstock, in either
product.12 Furthermore, the boiling point of sodium pellet or powder form, is suspended or contained at the
(1156 K) is only slightly higher than the melting point of cathode. Molten CaCl2 is selected as the electrolyte
the product sodium chloride (1074 K), which necessi- for its high oxide solubility19 and low melting point
tates fine control of the reduction rate. Nevertheless, (1055 K), in addition to low cost. The reduction of TiO2
this process has reportedly been scaled up to the proceeds via the lower oxides and during the concluding
2 Mlb year21 production level, and according to the stages of deoxidation, diffusion of oxygen in metallic
company website, small quantities of powder are titanium is rate determining.14,2022 The disadvantages
available for analysis. of these EDO processes include the precipitation of CaO
In the MER process17 TiO2 is carbothermically and CaTiO3 in the pellet pores and the slow diffusion of
reduced to produce a lower oxide approaching TiO in oxygen in metallic titanium at feasible reduction
composition. A composite anode is manufactured by temperatures leading to long reduction times. Excess
blending carbon and this oxide, which is then immersed calcium formation in either embodiment leads to a
in a molten salt electrolyte. The anodic reaction decrease in current efficiency and a mechanism for
carbon contamination as the elemental calcium reacts to use four die radial presses instead of conventional
with the graphite anode. However, by careful control of open die forging presses to reduce processing costs
the operating parameters the process is capable of and to improve the final microstructural refinement.
producing not only low oxygen titanium,23,24 but also Figure 6 shows the RUMX radial forging machine
alloys of both conventional and novel compositions.24,25 employed by Timet UK to produce forged bars.27 The
Furthermore, fine grain sizes (1020 mm) are observed machine has four simultaneously acting forging rams,
post-reduction despite a slow cooling from 1173 K and each opposing ram pair delivering an 8 MN forging
without any thermomechanical processing (Fig. 5).26 force. Side spread is restricted owing to the high degree
This is due to the fine oxide particle size of the ceramic of material enclosure, thus the number of passes
precursor and reduction that occurs entirely in the solid required, and hence forging time is reduced. The
state without liquid melt processing. Rumx is capable of forging a large range of cross-
sections without tool changes.28
In recent years, work led by Semiatin29,30 and
Thermomechanical processing Brooks31 with support from the major titanium produ-
Currently, titanium is cast as ingots of several tonnes cers has contributed significantly to the understanding
weight that must be forged to a slab or billet. The of both microstructural and textural evolution during
primary processing stage involves the breakdown of a the cogging and secondary hot and/or isothermal
microstructure that consists of coarse b grains with grain forging processes, which has led to significant cost
boundary a and intragranular a lamellar plates. An reductions. One approach has been to develop empirical
initial cogging process which is a combination of relationships that predict the evolution of microstruc-
incremental open forging ram passes and reheats breaks tural constituents such as a phase volume fraction,
down this inhomogeneous microstructure. The work- morphology and b grain size for a range of processing
piece is normally cogged at temperatures above the b variables, i.e. temperature, strain and strain rate.32,33
transus where lower working energies are required, with Such empirical relationships coupled with finite element
final cogging passes carried out at subtransus tempera- simulation have provided engineers with the tools to
tures to generate a fine ab microstructure. One of the reduce scrap and improve final forging properties.5
major advances in the primary processing stage has been 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
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, intention to use the alloy for landing gear forgings on
Fig. 7 illustrates the range of microstructures obtained the 787 Dreamliner.2
over a narrow subtransus temperature range (1023
1063 K) for near b alloy Ti1023 (Ti10V2Fe3Al)
which is currently used for landing gear bogie beam
Alloy development
forgings on the Boeing 777. Such variation in micro- The American Society for Metals (ASM) Titanium
structure and thus, properties, clearly emphasise the Handbook37 lists around fifty alloys and six commer-
need for good temperature control during forging. The cially pure grades of titanium, although only about half
same testing methodology34 used to exploit such micro- this number are commonly available. Given the current
structural sensitivity in Ti1023 is currently being world market of only y70 000 t this is clearly excessive
applied to the near b alloy Ti 555 (Ti5Al5Mo5V and suppliers have sought to reduce the number of
3Cr0.6Fe), similarly to understand the microstructural alloys supplied to lower their costs. In contrast, China is
evolution during isothermal forging. Timet has been continually increasing its portfolio of alloys, merely
manufacturing and evaluating Ti 555 for a variety of reflecting the rapid development and expansion of the
aerospace applications35,36 and Boeing announced their titanium industry in China;38 titanium producers, in
steel and aluminium. This would pave the way for an 24. R. Dashwood, M. Jackson and K. Dring: Electrolytic production
of near net shape titanium components, Contract N68171-01-C-
expansion of the overall market into a range of high
9018, Office of Naval Research, Arlington, VA, USA, 2005.
volume applications, in particular the holy grail of the 25. K. Dring, R. Bhagat, M. Jackson and R. Dashwood: Direct
automotive industry. For this expansion to be successful, electrochemical production of Ti-10W alloys from mixed oxide
a cultural shift from directly comparing an alloy that has precursors, J. Alloy. Compd, to be published.
been processed from an electrochemical reduction route to 26. Unpublished results, High Temperature Electrochemistry Group,
Department of Materials, Imperial College London, 2005.
aerospace grade triple vacuum arc remelt (VAR) material 27. P. J. Nieschwitz and C. Meybohm: Hydraulically driven radial
is needed. Industry must consider material from these forging machine for flexible forging of small batch sizes, Stahl un
emerging reduction processes as a separate entity to that Eisen, 1990, 11, 101108.
associated with compressor disks and high strength 28. A. F. Wilson: Personal communication, 2006.
forgings, otherwise the potential for expansion will be 29. S. L. Semiatin, V. Seetharaman and I. Weiss: Hot workability of
titanium and titanium aluminide alloys an overview, Mater. Sci.
restrained by a pointless need to achieve a certain Eng. A, 1998, 243A, 1.
microstructure, property or defect level. 30. S. L. Semiatin, V. Seetharaman and I. Weiss: The thermomecha-
nical processing of a/b titanium alloys, J. Metals, 1997, (6), 33.
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