Acta Materialia 168 (2019) 261e274

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Acta Materialia
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Full length article

Promoting the columnar to equiaxed transition and grain refinement

of titanium alloys during additive manufacturing
M.J. Bermingham a, *, D.H. StJohn a, b, J. Krynen a, S. Tedman-Jones a, M.S. Dargusch a, b
a
Centre for Advanced Materials Processing and Manufacturing, School of Mechanical and Mining Engineering, The University of Queensland, St Lucia,
Queensland, 4072, Australia
b
Defence Materials Technology Centre, VIC, 3122, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Preventing columnar grain formation during additive manufacturing has become a significant challenge.
Received 23 August 2018 Columnar grains are generally regarded as unfavourable as their presence can impart solidification defects
Received in revised form and mechanical property anisotropy, however, the thermal conditions experienced during additive
10 February 2019
manufacturing make columnar grains difficult to avoid. In this work the thermal conditions during so-
Accepted 12 February 2019
Available online 16 February 2019
lidification (cooling rate, temperature gradients) are characterised during wire based additive
manufacturing. For the selection of deposition conditions that favour equiaxed grain formation, the role of
alloy constitution is explored in three classical alloy design regimes: an alloy containing no grain refiners
Keywords:
Deposition
(Tie6Ale4V); an alloy only containing grain refining solutes (Tie3Ale8Ve6Cre4Moe4Zr); and an alloy
Grain refinement containing both grain refining solute and nucleant particles (Tie3Ale8Ve6Cre4Moe4Zr þ La2O3). Sub-
Solidification microstructure stantial refinement and equiaxed grain formation is achieved in the latter case which is attributed to b-Ti
Titanium alloys nucleation on La2O3. However, the thermal environment is dynamic during additive manufacturing and
Columnar-to-equiaxed transition equiaxed grain formation is only achievable when temperature gradients decrease sufficiently to permit
constitutional supercooling.
© 2019 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction equiaxed transition (CET) is to manipulate the processing param-

The great deal of research into metal Additive Manufacturing
(AM) technologies over recent years has identified a clear need to
prevent the formation of columnar grains that are widely reported
when producing titanium and other metal alloy components. The
presence of textured grain structures causes mechanical property
anisotropy, which is often perceived to be undesirable and which
presents challenges in component design, build strategy and cer-
tification of products. Producing homogenous microstructures with
fine grained equiaxed structures during AM is often highly desir-
able. The ability to achieve equiaxed grains during AM is dependent
on the factors driving nucleation and growth such as the thermal
conditions and alloy constitution.
Columnar grains form during AM on account of the prevailing
solidification conditions that favour epitaxial growth (from prior
deposited layers) and a lack of nucleation events ahead of the solid/
liquid (S/L) interface. One approach to promote the columnar to
* Corresponding author.
E-mail address: m.bermingham@uq.edu.au (M.J. Bermingham).
eters during AM to affect the temperature gradient (G), growth rate
of the S/L interface (R) and cooling rate (product of G and R). In
general, it is understood that the CET is favoured when R increases
and G decreases [1]. Kobryn and Semiatin [2] studied the grain
morphology of Tie6Ale4V under a range of solidification condi-
tions from directionally solidified castings through to laser clad
deposition and established a G/R solidification map for the alloy.
Using this map, Bontha and co-workers [3] modelled the solidifi-
cation conditions for laser AM of Tie6Ale4V and predicted that
increasing the laser power (with other parameters constant) could
theoretically produce equiaxed grain morphologies during depo-
sition by reducing G, albeit acknowledging that R is also likely to
reduce on account of lower cooling rates. Although there has been
limited experimental evidence of forming equiaxed grains during
Tie6Ale4V laser AM methods, Xu et al. [4] reported the presence of
equiaxed grains in Selective Laser Melting (SLM) of Tie6Ale4V after
carefully manipulating the build parameters to affect a reduction in
the G. Wu et al. [5] also reported some large equiaxed grains could
be formed under high laser power during deposition of Tie6Ale4V
which was attributed to a reduction in G. Despite isolated cases, the

https://doi.org/10.1016/j.actamat.2019.02.020
1359-6454/© 2019 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
262 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274
majority of literature relating to AM of Tie6Ale4V does not report
the CET.
While G and R are undeniably important parameters influencing
the CET, other factors such as alloy constitution (which favours
nucleation) are also important in achieving equiaxed grain mor-
phologies [1]. During laser metal deposition of Tie6A-
le2Sne2Zre3Mo-1.5Cre2Nb, Zhang et al. [6] reported columnar
grains at higher laser energy densities and equiaxed grains at lower
energy densities. On first appearance this is at odds with the pre-
diction by Bontha et al. [3] (which expects the CET at higher laser
energy density), however, an important distinction is that the effect
of powder deposition rate or changing nucleation factors (such as
nucleation undercooling DTN, nuclei population etc.) were not
considered in the model presented in Ref. [3]. As a result Zhang and
co-workers [6,7] demonstrated that increasing the powder depo-
sition rate increased the tendency for the CET by providing het-
erogeneous nucleation on partially unmelted powder particles.
Conversely, it was found that increasing the laser energy density
reduced the survival rate of unmelted powders and therefore
reduced the nucleation rate. Wang et al. [8] also reported this same
observation during laser metal deposition of Ti-
6.5Ale3.5Moe1.5Zre0.3Si as did Wu et al. [9] who found columnar
grains when the energy density increased during laser deposition
of Tie25Ve15Cre2Ale0.2C (but otherwise reported equiaxed
grains at lower laser energy densities).
It is worth noting that of the handful of cases where the CET has
been achieved during AM, it mainly occurs in titanium alloys other
than Tie6Ale4V. For the CET to occur it is essential for supercooled
liquid to exist ahead of the columnar front in order for a large
proportion of equiaxed grains to nucleate or for detached solid
fragments or unmelted powders to survive and grow. It is well
known that alloy solute plays an important role in generating
constitutional supercooling (DTCS). The rate at which a solute
generates DTCS is determined by the growth restriction factor, Q,
whereby solutes with large Q values rapidly develop DTCS and are
considered as growth restricting solutes that can provide effective
grain refinement [10]. The Al and V solute in Tie6Ale4V provides
no DTCS (both Al and V solute have negligible Q values in Ti [11])
whereas the alloys mentioned above contain solutes that do (e.g. Cr
[12] and C [13]). This means that the CET is far harder to achieve in
Tie6Ale4V during AM. This point was clearly demonstrated by
Wang et al. [14] when fabricating a compositionally graded
Tie6Ale4V to Tie25Ve15Cre2Ale0.2C component by laser metal
deposition using a combined Tie6Ale4V wire feed source and
Tie25Ve15Cre2Ale0.2C powder. Initially, the 100% Tie6Ale4V
end of the component produced columnar grains but equiaxed
grains resulted as soon as composition grading began (i.e. resulting
in the Tie6Ale4V alloying with Cr and C).
The purpose of this study is to investigate the role of alloy
constitution on the CET during additive manufacturing of titanium
alloys. Existing literature provides evidence that it is possible to
achieve equiaxed grains and the purpose here is to understand how
alloy chemistry can be manipulated to achieve the CET during AM.
First the thermal conditions during AM that favour equiaxed grain
formation will be identified (through melt pool characterisation)
and then alloy design incorporating growth restricting solute and
nucleant grain refiners, is used to achieve substantial refinement.
2. Alloy selection
The base alloy selected for this study is Tie6Ale4V which con-
tains a total of 10 wt% Al and V solute that does not provide growth
restriction. Previous studies have shown that cast Tie6Ale4V has
similar grain size to cast ASTM Grade 2 commercially pure titanium
[11]. Oxygen (QO z 10.8C0 [15]) and iron (QFe z 3.8C0 [15]), present
in the alloy as trace elements, are known to be effective grain re-
finers in Ti castings [12,16] but their small concentrations in
Tie6Ale4V make negligible contributions to grain refinement. For
this reason a second commercial alloy containing sufficient growth
restricting solute was sourced. Tie3Ale8Ve6Cre4Moe4Zr
(commonly known as Beta C and ASTM Grade 19) is a metastable b-
titanium alloy used in aerospace applications and it contains
growth restricting solute that should provide the necessary DTCS to
activate available nucleant particles. Although containing a total of
25 wt% solute, it is the 6 wt% Cr (QCr z 1.5C0 [15]) in particular that
should provide DTCS (similar to Al and V, Zr has a negligible Q value
in titanium [11]). The present authors have confirmed that sub-
stantial grain refinement occurs in titanium castings with addition
of 6 wt% chromium solute [12]. Mo has a partition coefficient
greater than unity in the Ti system (k ¼ 1.41 [17]) and Samsonov
et al. [18] demonstrated that it offers negligible grain refinement in
titanium alloys. Even with 10 wt% Mo, Vrancken et al. [17] reported
only minor columnar grain narrowing in a b-Ti alloy produced by
SLM.
To date no stable and potent1 nucleant particles have been
conclusively identified for the b-phase in low concentrations. In the
1970s Crossley [19] achieved grain refinement with nitrogen, car-
bon and oxygen through the peritectic reaction. Qiu et al. [20]
recently confirmed that TiN particles can heterogeneously nucleate
b-Ti but require a nitrogen concentration of at least 0.4 wt% to
achieve in situ particles. Such a high interstitial content is expected
to cause embrittlement. Although stable nucleant particles for b-Ti
at low concentrations are yet to be identified, it is understood that
titanium alloys contain a naturally occurring population of ‘native’
particles that under favourable conditions are able to nucleate
equiaxed grains during solidification (demonstrable by the fact that
equiaxed grains are frequently observed in castings in a range of
alloys). While unknown in origin, it is reasonable to expect that the
native particles in titanium are not particularly potent because
there are numerous examples in the literature where equiaxed
grains fail to form in casting, welding and AM. Only when growth
restricting solutes are introduced does the nucleation rate increase
[21].
Although potent foreign nucleant particles for b-Ti are yet to be
conclusively identified, there are encouraging reports that several
rare earth elements refine the grain size of titanium alloys and
could be suitable nucleant catalysts. Yttrium, lanthanum and other
rare earth elements are reported to refine the central equiaxed
grains in the fusion zone of titanium welds [22e24] and castings
[18,25e27]. Although some rare earths theoretically should be
effective grain refining solutes (for example, QY ¼ 7.93 C0 and
QLa ¼ 3.3 C0 [15]), in reality if small levels of metallic rare earth are
alloyed with liquid titanium they should scavenge oxygen from the
melt and form oxide particles just as they do in steel melts [28], on
account that many rare earth oxides have lower free energy than
titanium oxides. Thus metallic rare earth solute should not be
available to generate DTCS unless there is a surplus of solute
compared to the available oxygen present in the system, in which
case not all solute is consumed by oxidation. It was first proposed
by Simpson [22] that yttrium scavenges oxygen to form Y2O3 which
heterogeneously nucleates titanium, although it has not been
supported by definitive evidence and alternative mechanisms for
refinement have also been proposed [24]. Nevertheless, the pres-
ence of a thermodynamically stable particle in liquid Ti is of interest
given the fact that very few compounds are stable in liquid titanium
at very small concentrations.
In this work we investigate La2O3 as one such potential particle.
1
‘potent’ particles are described here as those having small DTN.
 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274
Several researchers have reported that La2O3 forms by scavenging
oxygen if La is added to titanium alloys [29e31]. Recent work by the
present authors [32] suggests that La2O3 exists in the liquid
Tie6Ale4V prior to solidification in WAAM and small particles
several micrometres in diameter were dispersed throughout the
solidified microstructure. According to the Free-Growth model for
grain refinement [33], the presence of such particles may enhance
nucleation under the appropriate thermal environment and in al-
loys that produce DTCS.
To summarise, the grain size and morphology during WAAM is
explored in three alloy systems:
1) Tie6Ale4V e a commercial low Q alloy containing no growth
restricting solutes or added nucleant particles.
2) Tie3Ale8Ve6Cre4Moe4Zr e a commercial high Q alloy con-
taining growth restricting solute and no added nucleant
particles.
3) Tie3Ale8Ve6Cre4Moe4Zr þ La2O3 e a commercial high Q alloy
containing growth restricting solute plus added nucleant par-
ticles (La2O3).
To support the analysis of the macrostructures obtained quan-
tification of the thermal environment, in particular the temperature
gradient, is undertaken.
3. Experimental methods
The cooling rates during AM are high and collecting experi-
mental data is challenging, particularly in very small melt pools. In
this work, the wire þ arc additive manufacturing process (WAAM)
is explored because the melt pool is large enough for the cooling
rate to be reliably measured using pyrometers, from which the
solidification parameters G and R can be measured or calculated.
The WAAM equipment used for this research consists of a EWM
Tetrix 350 Gas Tungsten Arc Welding torch (GTAW) equipped with
a wire feed unit installed into a customised build chamber with a 3-
axis CNC controlled table. The build chamber is exposed to the open
atmosphere and localised shielding (Argon 99.999%) is employed to
protect the melt from oxidation. Shielding is provided through the
water cooled GTAW nozzle, and where necessary, a trailing shield is
also installed behind the GTAW nozzle which provides shielding to
the hot metal as it cools. Details of the trailing shield and other
equipment are available elsewhere [34]. This research first estab-
lishes the thermal environment during WAAM, then moves to
explore the role of alloy constitution on the columnar to equiaxed
transition. The experimental method for each activity is described
in the following sections.
3.1. Establishing the thermal environment in WAAM
The seminal empirical work by Kobryn and Semiatin [2] in
developing a solidification map for Tie6Ale4V has been universally
referenced to predict the solidification mode (i.e. columnar or
equiaxed) of Tie6Ale4V. This map will be used in this work to
determine if the inherent solidification conditions encountered
during WAAM promote dendritic equiaxed solidification. For a
given alloy the most important solidification parameters deter-
mining the extent of constitutional supercooling, and therefore the
growth mode (planar, cellular, dendritic) is the temperature
gradient G and the growth rate R. The temperature gradient is
particularly important since it determines whether or not a den-
dritic protuberance develops and can advance into a supercooled
liquid. Furthermore, the steep temperature gradients characterised
by AM reduce or eliminate constitutional supercooling which can
prevent nucleation events ahead of the main interface and favour
263
cellular or dendritic columnar grain morphologies.
Accurately measuring G and R during AM is challenging. While
the growth rate R can be approximated from the travel/scan speed
or a simple trigonometrical relationship therein [24], measuring
the temperature gradient can only be achieved experimentally.
Traditional measurement via thermocouples is challenging because
the Tie6Ale4V build layer must be deposited over the thermo-
couples and the heat source and liquid metal must not melt or
dissolve the thermocouples. Non-contact infrared pyrometers
overcome these problems but only the surface temperature can be
accurately measured, thus are limited in that they may not be
representative of changing thermal conditions below the surface.
To overcome these challenges a hybrid process was used to
approximate the average thermal gradient across the melt pool
using surface temperature data and post-mortem microstructural
analysis. This approach firstly involves measuring the temperature
of the liquid at the top surface during deposition using a pyrometer.
In this work a pyrometer with effective range of 800e2100  C was
used (Micro-Epsilon, spectral range 1 mm, ±7  C accuracy at
1680  C, 1 ms response time), with emissivity of 0.288 calibrated
against high purity titanium using the same technique outlined
elsewhere [32]. After deposition, the layer is cross-sectioned and
polished to reveal the extent of melting in order to measure the
depth of the layer. The cross-section naturally consists of a melted
region and an unmelted region from the previous layer or the base
plate if it is the first layer. The average thermal gradient across the
bulk liquid pool can then be determined given that the temperature
of this interface during deposition equals the freezing temperature
of the alloy and the distance between it and the top surface (where
the temperature is known) is measurable. However, the effective-
ness of this method requires distinguishing between the S/L
interface corresponding to the melted region and the unmelted
prior layer or baseplate, which becomes almost impossible if the
same alloy is used. To overcome this problem, single Tie3Ale8-
Ve6Cre4Moe4Zr layers were deposited onto Tie6Ale4V sub-
strates which allowed a very distinctive boundary to be observed
when examining the metallurgical cross-section, an example is
given in Fig. 1 (B). This technique was used on both flat Tie6Ale4V
substrates (representing layer 1) as well as previously deposited
Tie6Ale4V layers (at least 3 layers high) which are curved. Similar
results were obtained irrespective of the shape of the substrate
(curved vs flat).
The deposition parameters investigated are shown in Table 1.
The purpose of this activity was not to map all possible deposition
parameter combinations, but only focus on a select range of
deposition speeds that are frequently reported in the literature for
wire based AM processes. The other parameters such as wire feed
rate, arc power etc. have been used in other research to produce
quality components with minimum oxidation [34,35]. It was not
possible to use a trailing shield in this initial stage of experiments
because it obstructed temperature measurements. While the
absence of the trailing shield may slightly affect the solid state
cooling rate (through convective cooling associated with the argon
gas), it is not expected to significantly influence the cooling rate of
the melt pool (or the measured G) because this is protected by
argon from the GTAW nozzle and not by the trailing shield. Our
previous work in Tie6Ale4V WAAM with similar build parameters
to those studied here, found that complete solidification occurs
while still protected by the cover gas flowing from the GTAW nozzle
[34].
3.2. Experimental methods investigating the CET
As previously mentioned, the three alloys studied in this work
are: Tie6Ale4V, Tie3Ale8Ve6Cre4Moe4Zr, and Tie3Ale8Ve
264 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274
Fig. 1. (A) Diagram and photograph showing the experimental set up. A pyrometer
(fixed in relative position to the work piece) measures the real time cooling rate as the
torch passes by (depositing along the Y-axis). A video camera (synchronised with the
pyrometer) observes the process in the Y-Z plane. (B) Diagram with example optical
and Backscatter SEM images at deposition speed 400 mm/min showing how the
average temperature gradient G was determined. Similar results were obtained when
depositing on curved surfaces (i.e. on a pre-existing layer) and flat substrates (i.e. first
layer). T1 is measured by the pyrometer and T2 equals the melting point of Tie6Ale4V.
EDS maps show minimal mixing between the Tie3Ale8Ve6Cre4Moe4Zr and
Tie6Ale4V layers making the interface easily discernible.
6Cre4Moe4Zr þ La2O3. Both Tie6Ale4V and Tie3Ale8Ve6Cre4-
Moe4Zr were commercially sourced wires having 1 mm diameter.
Where it was necessary to add La2O3 particles, an alcohol based
Table 1
Deposition parameters used to build the components.
Deposition Parameters
Base Current: 113Amp
Wire feed: 1.5 m/min
Wire: Tie6Ale4V, Tie3Ale8Ve6Cre4Moe4Zr; both
ø ¼ 1.0 mm
Deposition speeds: 50 mm/min, 100 mm/min, 200 mm/min, 400 mm/min
Electrode-substrate 5 mm
gap:
Substrate: Tie6Ale4V
Electrode: ø ¼ 2.4 mm tungsten-rare earth
Argon: 99.999% purity, 20 L/min
paint containing La2O3 powder (with approximately 50% by weight
La2O3) was painted onto the surface before deposition, in the same
way as described in earlier work [32]. The La2O3 powder selected
for study contained a distribution of large particles (D50 4.362 mm;
D90 26.0 mm, Alfa Aesar, 99.9%).
Four layer high deposits were fabricated using the parameters
identified in Table 1 with the most appropriate travel speed iden-
tified in Section 3.1 (50 mm/min). The chemical composition of the
alloys after deposition is given in Table 2. Each deposit was
approximately 130 mm long. A trailing shield was used to minimise
contamination during deposition (details of this shield are available
in Ref. [34]). An unavoidable consequence of using the trailing
shield is that it makes thermal measurements during deposition
impossible (since it encloses the hot metal), however, it was still
possible to measure the stationary melt pool at the end of depo-
sition since this was not obstructed by the trailing shield. After each
layer the component was allowed to cool to room temperature
before the next layer was deposited.
A Tie6Ale4V baseplate was used for deposition. After deposi-
tion, several cross sectional samples were machined from the
components and prepared using conventional metallographic
methods (grinding on SiC paper followed by polishing with
0.05 mm colloidal Silica) followed by etching with Kroll's reagent
(5% HF, 30% HNO3, 65% H2O). The samples were characterised using
optical and electron microscopy techniques and the grain size was
measured using the linear intercept method [36].
4. Results
4.1. Thermal conditions during WAAM
The thermal conditions measured before, during and after so-
lidification are provided in Fig. 2 (A) for four deposition speeds. For
each deposition speed the liquid is superheated in excess of 2100  C
and the temperature rapidly fluctuates in the liquid under the
electric arc most likely due to rapid fluid flow generated by Mar-
angoni forces. Bai et al. [37] modelled the thermal environment
within the melt pool during plasma arc additive manufacturing of
Tie6Ale4V under comparable deposition conditions to that here.
The authors predicted that liquid temperatures under the arc can
exceed 2400  C and steep temperature gradients within the liquid
produce strong and complex Marangoni currents causing rapid
mixing. The cooling rates depend strongly on the travel speed and
from multiple tests the average cooling rates during solidification
ranged from 101  C/s at 50 mm/min deposition speed to 642  C/s at
400 mm/min. After solidification, a significant exothermic reaction
(latent heat release) is observed between 1400 and 1500  C and
corresponds to oxide formation in Fig. 2 (B). This occurred because
it was not possible to use a trailing shield to provide localised inert
gas shielding to the hot solid metal which would otherwise prevent
 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274 265

Table 2
Chemical analysis of each alloy determined by ICP-AES and Leco Combustion. Note that the accuracy range of the O, N, Fe and La detection is approximately ±0.005e0.016 wt%
and for all other elements the accuracy in the range of ±0.06e0.08 wt% (these ranges represent 1 standard deviation).

Alloy O N Al V Fe Mo Cr Zr La

wt% wt% wt% wt% wt% wt% wt% wt% wt%

Tie6Ale4V 0.08 0.012 5.91 3.74 0.11 e e e e

Tie3Ale8Ve6Cre4Moe4Zr 0.11 0.032 3.85 7.51 0.18 3.74 5.55 3.56 e
Tie3Ale8Ve6Cre4Moe4Zr þ La2O3 0.15 0.035 3.99 7.6 0.12 3.83 5.58 3.6 0.31

thermal measurements. Finally, Fig. 2 (C) shows the solidification

map for Tie6Ale4V at the four different WAAM deposition speeds.
The growth rate R is approximated by the deposition speed and the
average thermal gradients presented are calculated from the bot-
tom of the melt pool to the external surface being measured by the
pyrometer. The maximum temperature of the liquid exceeds the
pyrometer's effective range (i.e. 2100  C) and as such an upper
and lower range of G values are shown based on minimum surface
temperature of 2100  C to an upper temperature of 2400  C re-
ported by Bai et al. [37]. For comparison, the typical operating range
for LENS (blown powder-laser AM) is provided based on the work
of Bontha et al. [3].
The solidification map predicts a mixed equiaxed þ columnar
grain morphology during deposition at each travel speed. In light of
this, deposition at a speed of 50 mm/min was selected for the next
experimental section studying the composition effects on the alloys
because this speed had the lowest G of the conditions explored.
Fig. 3 shows the cooling curves for each individual alloy at the
end of deposition when the arc was terminated. Without interfer-
ence from the electric arc, this shows sensitive thermal events such
as recalescence and changing cooling rates associated with this
latent heat release. Initially the liquid in all alloys cools very rapidly
from above 1700  C (exceeding 5000  C/s) but dramatically slows
and eventually plateaus during solidification. This happens when
the rate of latent heat release balances the rate of heat extraction,
and occurs over a duration of about 1e2 s. The Tie6Ale4V and
Tie3Ale8Ve6Cre4Moe4Zr alloys also recalesce by 11e16  C,
however, the addition of La2O3 eliminates this phenomena.

4.2. Promoting the CET

Fig. 4 shows the microstructures and measured grain size for

Tie6Ale4V, Tie3Ale8Ve6Cre4Moe4Zr and
Tie3Ale8Ve6Cre4Moe4Zr þ La2O3 deposited under thermal
conditions that should be favourable to a mixed equiaxed-
columnar microstructure. The Tie6Ale4V build contains very
large grains which are mostly columnar but with some isolated
equiaxed grains which is consistent with the prediction from the
solidification map. The introduction of solute (Tie3Ale8Ve6-
Cre4Moe4Zr) substantially refines the grain size including the
width of the columnar grains, however, fails to prevent columnar
grain formation. This is a similar trend to that observed by Mereddy
Fig. 2. (A) Example cooling rates for Tie6Ale4V during WAAM at deposition speeds
et al. with the introduction of Si solute to CPeTi [38] or carbon between 50 and 400 mm/min (B) Shows photographs at three time intervals (I, II, III)
solute in Tie6Ale4V [13]. Although this is a significant refinement, during deposition at 100 mm/min as an example. It is clear that temperatures near the
the greatest change in the microstructure occurred with the arc exceed 2100  C and considerable thermal fluctuations occur within the melt pool.
After solidification and once the torch nozzle moves past there is no longer inert gas
introduction of La2O3 particles to the Tie3Ale8Ve6Cre4Moe4Zr
shielding and oxidation occurs which releases latent heat at time III. (C) Tie6Ale4V
which produced substantial refinement while increasing the pro- solidification map for WAAM (based on the original map by Kobryn and Semiatin [2]).
portion of equiaxed grains within the microstructure. A comparison to the laser þ powder AM process is also provided based on the work
Close examination of the microstructure reveals spherical La2O3 and map presented by Bontha et al. [3] in modelling a range of typical laser powers and
particles distributed throughout. Fig. 5 shows the size and shape of scanning speeds encountered during LENS that yield energy densities between 40 and
260 J/mm.
the La2O3 before and after deposition, as well as the measured size
distributions of La2O3 within the Tie3Ale8Ve6Cre4Moe4Zr
microstructure.
266 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274
Fig. 3. Example of typical cooling curves collected at the end of deposition during so-
lidification of Tie6Ale4V, Tie3Ale8Ve6Cre4Moe4Zr and Tie3Ale8Ve6Cre4Moe4Zr þ
La2O3. Both Tie6Ale4V and Tie3Ale8Ve6Cre4Moe4Zr recalesce by 11e16  C but this is
eliminated with the addition of La2O3. The cooling rate (DT/Dt) is averaged over a 20 ms
period.
5. Discussion
In this work we determined the approximate thermal condi-
tions (G, R and cooling rate) during WAAM of Tie6Ale4V and
confirm the accuracy of the solidification map [2] in predicting a
mixed columnar þ equiaxed growth morphology for the condi-
tions studied here. Compared to other directed energy deposition
processes such as LENS, the formation of some equiaxed grains is
possible in Tie6Ale4V WAAM due to the lower thermal gradients.
As a general rule, WAAM will have a higher linear energy density
(also known as heat input) than LENS and this creates larger melt
pools, slower cooling rates and lower thermal gradients at
comparable growth velocities (hence smaller G/R ratio). The linear
energy density (LED) for WAAM in this study was 1.49 kJ/mm at a
deposition speed of 50 mm/min (compared to 0.06e0.26 kJ/mm
for LENS conditions shown in Fig. 2). While this is favourable in
terms of lower average thermal gradients that permit the forma-
tion of some equiaxed grains, the undesirable consequence is a
large grain size. The average grain size in Tie6Ale4V determined
using the linear intercept method exceeded 1.5 mm, which is
three times larger than the equiaxed grain size in Tie6Ale4V
castings produced with similar cooling rates [11]. However, some
individual columnar grains can be much larger than the average
value as evident in Fig. 4. LENS, with its lower LED and higher
cooling rates typically forms much thinner columnar grains. For
example, Carroll et al. [39] reported an average columnar width of
0.375 mm during LENS of Tie6Ale4V with a LED of 0.189 kJ/mm.
The challenge, therefore, is to not only achieve equiaxed grain
formation (through a reduction in G), but also to refine the grain
size at the same time.
This is achievable with grain refiners. In the present example
for WAAM, the growth restricting solute (especially Cr) in
Tie3Ale8Ve6Cre4Moe4Zr generates a DTCS zone ahead of the S/
L interface and equiaxed grain initiation will occur when DTCS
equals or exceeds the potency of the nucleant particles (DTN)
present in this zone. However, for the CET to occur there must be
suitable particles present within the supercooled zone. Titanium
alloys naturally contain a large population of uncharacterised,
semi-potent nucleant particles [21]. From Fig. 4 (B) it is clear that
the introduction of growth restricting solute has not promoted a
complete CET but instead adopts a mixed mostly columnar with
isolated equiaxed grain structure similar to Tie6Ale4V. However,
the grain size, including the width of the columnar grains, is less
than half of that measured in the Tie6Ale4V build. The mecha-
nism for this columnar refinement has been previously discussed
for boron [40] and silicon [38] additions in WAAM but in sum-
mary manifests by lateral solute rejection and accumulation be-
tween columnar grains and the associated growth restriction.
Although some nucleation events occur ahead of the columnar
front which generate some equiaxed grains, there are also many
cases where this does not occur and instead very long and nar-
row columnar grains result. Achieving the CET during WAAM
requires the addition of extra nucleating particles that are more
potent or more numerous than the native population found in
titanium alloys.
The introduction of La2O3 into Tie3Ale8Ve6Cre4Moe4Zr
further refines the grain size while also increasing the fraction of
equiaxed grains, however, does not eliminate all columnar grains.
The average grain size of Tie3Ale8Ve6Cre4Moe4Zr reduced from
685 ± 222 mm to 252 ± 12 mm with La2O3 addition and was much
more consistent in comparison to the grain size of Tie6Ale4V and
Tie3Ale8Ve6Cre4Moe4Zr which had a large standard deviation
due to the presence of both small and very large columnar grains.
SEM examination reveals that the microstructure contains an
abundance of La2O3 particles and it is probable that some of these
have nucleated new equiaxed grains.
5.1. Refinement by La2O3
The presence of thermodynamically stable particles within the
melt is the first key requirement for heterogeneous nucleation.
Given the reactivity of liquid titanium, identifying a stable solid
particle has traditionally been problematic as most high melting
point compounds dissolve in liquid titanium. However, rare earth
metal oxides (including La2O3) have lower free energies than tita-
nium dioxide and should be stable in titanium melts. Metallic
erbium and yttrium additions to titanium have long been known to
 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274 267

Fig. 4. Microstructures of as-built Tie6Ale4V (A), Tie3Ale6Cre4Moe4Zr (B) and Tie3Ale6Cre4Moe4Zr þ La2O3 (C). (D) Shows the average grain size for each alloy (error bars ±1
standard deviation). Deposition speed 50 mm/min. Note that the grain boundaries have been enhanced in (A1), (B1) and (C1) for visibility. The large red box overlay marks the
approximate locations for all SEM images (all from top layer) except for (C4) which shows the interface between the Tie6Ale4V substrate and the Tie3Ale6Cre4Moe4Zr þ La2O3 at
the first layer and is approximately located by the small blue box in image (C1). The white ‘dots’ in images (C2), (C3) and (C4) are La2O3 particles which have strong contrast during
the backscatter imaging mode. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

scavenge oxygen and form oxide particles during melting and so-
 ..
lidification [41e44]. The same phenomena was recently observed 1011 ð1 0 0ÞbTi
with LaB6 which decomposes into La2O3 in Tie6Ale4V melts pro- La2O3

duced by WAAM [32]. Complete melting is not required and this h i ..

oxygen scavenging reaction (to form La2O3) also occurs during solid 1121 ½0 1 0bTi
state sintering [29]. Thus La2O3 belongs to a small group of com- La2O3

pounds that are thermodynamically stable at titanium's freezing
temperature and may be able to facilitate heterogeneous nucle-
ation under appropriate thermal conditions.
The traditional consideration for effective nucleation is that the
crystallography of the nucleating phase should be close to that of
the growing solid phase [45,46]. The edge-to-edge crystallographic
model developed by Zhang et al. [47] builds upon early plane-
matching theory with a focus on atom-row matching at the inter-
face and has been effective in predicting potent nucleating particles
in a number of systems including Mg [48] and Al [49]. Applied to
the current investigation, the following orientation relationship
between La2O3 and b-Ti was identified:
Using published crystallographic data of La2O3 [50] and b-Ti [51]
at elevated temperatures, the misfit of this orientation relationship
was evaluated to be ~5%, with lattice parameters of ~3.17 Å and
~3.33 Å along the ½1 1 0 1La2O3 and ½0 1 0bTi directions respec-
tively. Given that the lattice parameter of the b-Ti phase is likely
smaller in Tie3Ale8Ve6Cre4Moe4Zr due to the substitutional
content of Cr, Mo, V and Al, the actual lattice disregistry between
La2O3 and b-Ti is expected to be less than ~5%. It is therefore
plausible that La2O3 particles could act as favourable nucleation
substrates for the b-Ti phase during solidification.
While the orientation relationship between the nucleating
particle and the new solid phase is important, perhaps an even
more important consideration influencing the potency of a particle
268 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274

Fig. 5. Backscatter SEM images showing the size and morphology of the initial La2O3 powder (A) compared to the morphology of the La2O3 particles after deposition (B). The shape
of the particles becomes more spherical after the deposition process and the size decreases. (C) La2O3 particle size distribution after deposition and (D) area fraction of La2O3
particles distributed within the Tie3Ale8Ve6Cre4Moe4Zr at different layers (box plots showing 25th,50th & 75th percentiles; whiskers showing 5e95th percentiles). Note that
data for (C) and (D) was measured from 60 SEM images containing over 13,500 particles and calculated using ImageJ software assuming an average spherical shape.

is its size. Classical nucleation theory indicates that free growth of a
grain can only occur if the nuclei embryo exceeds the critical size
(r*) to overcome the interfacial energy barrier of formation. The
Free Growth theory proposed by Greer et al. [33,52] predicts that
the presence of large particles in the melt enables the liquid to wet
a larger surface and form a thin hemispherical cap, effectively
increasing its radius of curvature above r* and facilitating further
growth. In contrast, free growth on smaller particles can only occur
by growing the height of the hemispherical cap which effectively
reduces the radius and in some cases this may fall below r*.
Therefore, the potency of particles is inversely proportional to their
size, with larger particles having smaller DTN. An analysis of particle
size and potency of TiB2 nucleants for aluminium alloys found that
particles above 3 mm had high potency (DTN z 0.2  C) and that it
was the large particles that were responsible for most nucleation
events [52]. Particles less than 1 mm are generally ineffective
because DTN is large and this amount of supercooling is rarely
achieved, especially once latent heat and recalesence reduces
available supercooling (generated from the growing solid that may
have nucleated on larger particles). The La2O3 powder used in this
study had a distribution of large particles, with 50% exceeding
4.362 mm in diameter and 10% exceeded 26.0 mm in size. However,
close examination of the as-built microstructures (see Fig. 5)
revealed that the typical La2O3 particle size is much smaller.2 In
addition, it is clear that the particles have changed shape during
AM, which could indicate that the particles themselves melt/
decompose and reform or change shape through solid state
2
The particle size in the as-built microstructure is still quite large (up to
~3.5 mm). It is worth noting that particles sizes above ~0.5 mm might be considered
‘coarse’ and not helpful for dispersion strengthening and may even negatively in-
fluence some properties such as ductility.
diffusion driven by a surface area reduction. The melting temper-
ature of La2O3 is 2313  C [53] and Bai et al. [37] predict that this
temperature is exceeded during WAAM of Tie6Ale4V. Weng et al.
[54] also report that Y2O3, which has a melting temperature of over
2400  C, also decomposes into Y and O atoms in laser heated
Tie6Ale4V melt pools before reforming as spherical Y2O3 particles.
An undesirable consequence of La2O3 decomposition is that the
particle size is reduced which may reduce its potency. Like other
heterogeneous nucleant particles, it is expected that the potency of
La2O3 will be linked to its size and that only the largest particles will
be responsible for nucleation events, with many of the smaller
particles lacking the potency to activate under the available ther-
mal or constitutional supercooling.
The above factors are all important considerations affecting
nucleant potency but ultimately such particles can only seed new
grains if they are present at the right location in time. The Inter-
dependence model developed by StJohn et al. [55] predicts the
grain size (dgs ) by considering these important interrelated factors
including alloy chemistry (solute effects including concentration C0,
solute diffusion rate D, solute growth restriction factor Q, solute
partition coefficient k, and solute concentration at the interface C *l );
nucleant particle potency (DTN) and particle spacing (xSD ). Note that
due to the inherent distribution of particles sizes, DTN referred to in
this paper and in Equation (1) represents the undercooling required
to activate the largest particles that have the lowest value of DTN.
The Interdependence model is given by Equation (1) and is sepa-
rated into its three key terms in Equation (2):
!
D,z,DTn 4:6,D C *  C0
dgs ¼ þ , *l þ xSD (1)
R,Q R C l ð1  kÞ
dgs ¼ xCS þ xDL þ xSD (2)
 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274
In essence, the Interdependence model predicts that the grain
size is determined by the summation of three distinct length scales:
xCS , xDL , and xSD . The first term, xCS , represents the distance (or size)
that a grain must grow before it generates sufficient DTCS to activate
nearby nucleant particles (i.e. where DTN  DTCS). zDTN is the in-
cremental amount of undercooling required to achieve DTN  DTCS
for subsequent nucleation of equiaxed grains. The second term, xDL ,
relates to the diffusion dependent distance of the solute profile
(and therefore DTCS profile) from the S/L interface to the moment
sufficient DTCS is achieved for nucleation. The final term, xSD , relates
to the distance from xDL to the nearest nucleant particle where the
condition DTN  DTCS is satisfied. Considering that particle potency
is inversely related to its size, xSD is therefore influenced by both the
number of particles present in the melt, their size distribution and
the probability that sufficiently potent (large) particles will be
nearby the interface. It is worth noting that to achieve the CET
during casting, welding or AM, sufficient particles need to be pre-
sent along the entire growth front otherwise only a few new
equiaxed grains will grow where particles are available and areas
devoid of suitable particles will solidify into columnar grains.
5.2. Challenges in achieving fully equiaxed microstructures during
AM
Recalling the microstructures in Fig. 4, the addition of both
segregating solute and nucleant particles refine the columnar
grains and promote the formation of equiaxed grains. Each new
layer in Fig. 4 (C1) is a mixture of columnar grains and equiaxed
grains. It appears that the columnar grains form first with the
deposition of each layer followed by a region of equiaxed grains.
The question remains, why do columnar grains still form? The
Interdependence model provides two possibilities. The first is that
suitable nucleant particles are not present at the start (bottom) of
each layer (i.e. xSD is very large). However, this scenario is unlikely
given the abundance and homogenous distribution of particles
seen in Fig. 4 (C4) and Fig. 5 (D), which are much more closely
spaced than the columnar length scale (which can be hundreds or
even thousands of micrometres). The second and more likely sce-
nario is that thermal conditions at the bottom of the layer are not
yet ready for nucleation. It is important to recognise that the first
nucleation event occurs epitaxially where DTN is effectively zero.
Therefore, solidification of the columnar front begins instanta-
neously when the freezing temperature of the alloy is reached. Any
foreign nucleant particle within the melt (including La2O3 in the
present case) will require some amount of supercooling
(DTN > 0  C). This can occur once constitutional supercooling de-
velops ahead of the columnar front which in turn can only occur
once the thermal gradient G is sufficiently low.
Additive manufacturing processes are widely believed to form
columnar microstructures on account of steep thermal gradients.
Even for high energy density, large melt pool AM processes such as
WAAM, the conservative estimates of average bulk thermal gradi-
ents across the melt pool is of the order of 100  C/mm (presented in
Fig. 2), which is in stark contrast to that experienced in typical
castings which are almost flat. Under such steep thermal gradients
it is surprising that any equiaxed grains can form. Given the avail-
able evidence that equiaxed grains do indeed form, the most likely
scenario is that G is not constant across the melt pool, but rather,
dynamically reduces during different stages of solidification.
Eventually a reducing thermal gradient will allow constitutional
supercooling to develop.
Multiple factors could cause G to decrease throughout solidifi-
cation of a layer during AM. One important physical attribute of
solidification is the generation of latent heat. The effects of latent
heat release are evident on the solidification curves presented in
269
Fig. 3. The magnitude of latent heat release during solidification of
each titanium alloy3 is so significant that it can temporarily match
or exceed the rate of heat extraction. To put this into perspective,
the cooling rate of the liquid prior to solidification exceeded
5000  C/s but during solidification the heat release was so intense
that not only did the cooling rate decrease to zero, but latent heat
actually caused a net heating effect in Tie6Ale4V and Tie3Ale8-
Ve6Cre4Moe4Zr whereby the actual temperature increased by
11e16  C (recalesence). Such significant latent heat will cause a
lowering of G as solidification proceeds.3
Melt turbulence, and therefore thermal mixing will also cause G
to reduce before or during solidification. It is well known that
Marangoni forces are active during AM which will cause rapid fluid
flow and mixing within the melt pool. This mixing will continue as
long as the heat source is present but once the heat source passes
the melt may thermally equilibrate before complete solidification.
This could be similar to the situation in castings when the appli-
cation of external ultrasonic fields causes rapid mixing and
consequently thermal gradients flatten (approaching zero) prior to
solidification [57].
Not much is known about the temperature distribution within
molten titanium pools during AM, however, in Fig. 6 we present
new data from recently published research simulating the WAAM
process as well as new experimental data confirming that tem-
perature gradients are changing throughout the molten pool. Fig. 6
(A) is a reproduction of work presented by Bai et al. [37] in
modelling the heat transfer during WAAM of Tie6Ale4V using a
plasma heat source. The figure shows the local temperatures within
the melt pool which vary significantly and generate significant
Marangoni convection. Using Bai's data, we have calculated the
temperature gradient within the liquid at different positions along
the melt pool and presented this in Fig. 6 (B). The temperature
gradients are predicted to be very high initially (over 500  C/mm
directly underneath the heat source) but rapidly flatten out due to
efficient liquid mixing and decreases to approximately 50e60  C/
mm at the tail of the melt pool. In Fig. 6 (D) we present new
experimental data collected using tandem pyrometers to monitor
the melt pool at fixed distance apart (see Fig. 6 (C) for experimental
schematic). This data confirms that the temperature gradient
within the liquid at the rear of the melt pool is much smaller than
previously expected (fluctuating between 0 and 50  C/mm). Inter-
estingly, even under very high cooling rates approaching 105  C/s,
Zhao et al. [58] showed through in situ synchrotron imaging that
the growth rate (and by extension G) decreased during solidifica-
tion of very small melt pools in SLM of Tie6Ale4V. Thus, although
initial thermal conditions directly underneath the heat source may
preclude nucleation ahead of the interface, a reduction in G even-
tually generates DTCS which makes nucleation of equiaxed grains
possible.
Given that the whole solidification process takes only a few
seconds or fractions of a second with a very high cooling rate and
steep initial temperature gradient, it is surprising that a model
(Equation (2)) that was developed for quiescent, low G conditions
and potent particles can still shed light on the mechanisms occur-
ring. The application of the model to date has not specifically
considered high G environments although we know that a rela-
tionship between grain size and the inverse of Q applies in high
pressure die casting environments [59]. The most influential terms
affecting both the CET and equiaxed grain size in Equation (2) are
3
Latent heat of fusion for titanium is approximately 14,550 ± 500 J mol1 and
molten titanium has a specific heat of 46.29 ± 1.7 J mol1 [56], so as an example a
mass of solidifying titanium will release heat equivalent to it cooling from about
2000  C to 1680  C.
270 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274

Fig. 6. Temperature distribution within Tie6Ale4V melt pools during WAAM. (A) and (B) are based on the analysis of Bai et al. [37] who developed a model for heat transfer during
plasma arc additive manufacturing of Tie6Ale4V. (A) is a reproduction from the original research and shows a temperature profile within the melt pool. Note that the arc position is
at approximately Y ¼ 0 mm on this figure. Using this map the present authors have calculated local temperature gradients along the melt pool, presented in (B). (D) Shows new
experimental data for the dynamic temperature gradient between tandem pyrometers positioned a fixed distance apart (experimental schematic shown in (C). The result shows
that the temperature gradient fluctuates within the liquid at the back of the melt pool (T > 1700  C) and is less than 50  C/mm.

xCS and xSD . xCS is the amount of growth required to achieve suffi-
cient DTCS for nucleation. In the case of epitaxial nucleation
(DTN ¼ 0) DTCS equal to DTN of a suitable nucleant particle, needs to
be generated which is given by the first term in Eq. (2) when z ¼ 1.
This situation corresponds to the equation developed by Qian et al.
[60] for the case of nucleation without considering the effect of
casting conditions or the availability of nucleant particles. Simul-
taneously, latent heat is released during growth to xCS which lowers
the temperature gradient. Once nucleation on the first available
potent nucleant particle occurs, xCS for subsequent nucleation is
much smaller (i.e. z is a fraction of 1) promoting equiaxed nucle-
ation. The size of the initial xCS after epitaxial nucleation is
important as this represents the amount of unimpeded growth of
the columnar grains before CET becomes possible.
In alloys containing high Q solutes, (e.g. Tie3Ale8Ve6Cre4-
Moe4Zr) a concentration gradient may develop quickly ahead of
the interface but no DTCS occurs until G sufficiently reduces. How-
ever, in alloys absent of high Q solutes (e.g. Tie6Ale4V), no DTCS
occurs due to the lack of segregating solute, regardless of whether G
is low or even completely flat. Thus for the CET to occur a concur-
rent requirement is an abundance of potent particles (small DTN)
which will determine xSD . The addition of La2O3 particles to
Tie3Ale8Ve6Cre4Moe4Zr appears to substantially reduce xSD ,
although it remains unknown whether this occurs because the
particles have a smaller DTN than the native nucleants, or have
equal potency and are simply more numerous and therefore closely
packed, or even a combination of both. The microstructure reveals
that La2O3 particles are abundant and quite closely packed even in
areas at the base of the layers where columnar grains form so it is
clear that xCS is the dominant term here. This highlights a chal-
lenging reality for some AM processes with steep initial thermal
gradients in that xCS may exceed the depth of the melt pool and
thus make the CET impossible in alloys not containing potent
nucleant particles and sufficiently high Q solute.
Fig. 7 illustrates the principles of the Interdependence model
applied during AM solidification at different time intervals. As
previously mentioned, the first growth occurs epitaxially at
DTN ¼ 0  C under a steep thermal gradient (t1) where no DTCS or
solute diffusion into the liquid has occurred. After a small amount
of epitaxial growth (t2) solute rejection into the melt will begin
generating a constitutional profile ahead of the growing cellular/
columnar grains, however, G is still too steep to permit DTCS and
hence nearby particles (with DTN > 0  C) cannot activate. With
further growth of the columnar front, G continues to decrease and
after time t3 a small constitutionally supercooled zone exists,
however, this DTCS may be insufficient to activate nearby particles
(DTCS < DTN). With further growth eventually G decreases suffi-
ciently where DTCS  DTN and thus nucleation can occur if a suitable
particle is nearby, however, at t4 no such particle is nearby and thus
columnar growth continues by distance xSD1 until the next particle
is reached and an equiaxed grain can form (t5). Once nucleation on
the first available potent nucleant particle occurs, the first term of
Eq. (1) is then relevant where much less growth (i.e. z is a fraction of
1) is required to trigger subsequent equiaxed nucleation events (t6).
From this point on, the temperature gradient is low enough and
sufficient DTCS exists that new nucleation events are mostly
determined by particle spacing xSD .
Fig. 8 shows the relationship between the measured grain size
and the inverse of the growth restriction factor (1/Q) for the alloys
studied here and compared with the WAAM data presented by
Mereddy et al. [38] (TieSi alloys) and previous data reported by
Bermingham et al. [12,15,61,62] in casting for a range of TieBe,
 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274 271

Fig. 7. Diagram illustrating the key principles of the Interdependence model applied to AM at six time intervals, t1-t6 (refer to text for a detailed description of the event sequence).
272 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274

Fig. 8. Grain size plotted against the inverse Q for a range of titanium alloys produced by casting and WAAM. The presence of La2O3 to Tie3Ale8Ve6Cre4Mo-4Z reduced the grain
size beyond levels achievable with solute effects alone (more nucleation events) and as such was excluded from the line of best fit calculation for the WAAM series.

TieCr, TieFe, TieB and TieSi alloys. Presenting grain size data this particularly the presence of potent nucleant particles. For example,
way is a useful way to understand the relationship between the Shabestari and Malekan [65] investigated the effects of potent
nucleant and solute parameters of the Interdependence model. A titanium-boron grain refiners on the solidification of aluminium
considerable amount of empirical evidence has been generated alloys and found that recalescence disappeared completely in alloys
over recent decades suggesting a linear relationship occurs in alloys containing potent nucleant particles. It is believed that fewer grains
where only solutes are changed (Q term) in titanium, aluminium (larger grain size) result in melts that undergo large recalescence
and magnesium systems [55,63,64]. Assuming sufficiently low G because some smaller grains that may have initially nucleated are
where constitutional supercooling is achieved, the Interdepen- remelted by the temperature rise [33], so the absence of this
dence model predicts that only changing solute terms will decrease reheating effect enhances survivability of newly nucleated grains.
the grain size to a minimum theoretical value where the xCS and xDL The low undercooling also means a slower growth rate and a bal-
terms approach zero (1/Q / zero). This means that the grain size is ance is achieved between heat released and heat extracted. In this
controlled by the spacing of the particles (xSD ) which corresponds condition, G will begin to decrease due to thermal diffusion sooner
to the y-intercept on the grain size vs 1/Q plot. Further refinement than the case when recalesence occurs.
from here is only possible by reducing xSD (increasing the number
of activated particles so that they are closer together and smaller
5.3. Other considerations for refinement with La2O3
grains result). A clear trend emerges in that titanium alloys pro-
duced by WAAM (containing Si and Cr as the most powerful growth
Recently it was observed that the Heiple-Roper effect occurred
restricting solute) exhibit much larger grain size than the same
during WAAM of Tie6Ale4V alloyed with LaB6 [32], as did Yin et al.
alloys cast into copper moulds. The best fit lines through the
during WAAM of Tie6Ale4V alloyed with CaF2 [66]. The Heiple-
respective casting and WAAM data sets are similarly sloped, which
Roper effect occurs when surface active solutes reverse the sur-
from the Interdependence theory, suggests that the potency of the
face tension-temperature coefficient of the liquid metal solvent
native nucleant population is similar between these data sets. The
which, due to Marangoni forces, changes the direction of fluid flow
main difference, however, is that the y-intercept (xSD ) is much
and the melt pool shape [67]. The effect is exploited during steel
larger for WAAM than for the cast alloys, although it is recognised
welding using trace sulphur additions to enhance weld penetration
that the growth required to reduce G within xCS may also account
[68]. The effect was also observed here when La2O3 was added to
for this difference. The addition of La2O3 to Tie3Ale8Ve6Cre4-
Tie3Ale8Ve6Cre4Moe4Zr as evidenced by the deeper penetra-
Moe4Zr substantially reduced the grain size beyond the xSD value
tion along the centreline into the baseplate (Fig. 4 (C1)) in com-
for the WAAM data set. This implies that the nucleation events
parison to Tie3Ale8Ve6Cre4Moe4Zr (Fig. 4 (B1)) and the
within this alloy are more closely spaced than in alloys not con-
tendency for taller, narrower deposited layers. One consequence of
taining La2O3 and infers that some La2O3 particles are responsible
this is that localised temperature gradients within the melt pool
for the enhanced nucleation.
will change which could influence xCS . Another consequence is that
The cooling curves in Fig. 3 shows no evidence of recalescence
this effect could amplify other mechanisms for equiaxed grain
during solidification when La2O3 is alloyed with Tie3Ale8Ve6-
formation such those covered by the Dendrite Arm Remelting
Cre4Moe4Zr indicating that the added particles have sufficient
Theory [69], Free Chill Theory [70] or the Separation Theory [71].
potency to readily nucleate grains. Due to the nucleation of grains,
Readers interested in the details of these theories are referred to the
latent heat is released and as the grains grow the larger surface area
original works but the common theme to all is that growing den-
increases the rate of latent heat release. This was a repeatable
drites (which initiate at the mould wall in a casting or the previous
observation from multiple tests. This same observation was
layer in AM) become separated from the interface and are swept
apparent when LaB6 was alloyed with Tie6Ale4V and decomposed
into the interior of the melt pool where they grow into equiaxed
into La2O3 during WAAM [32]. In castings, the absence of recale-
grains. In addition to nucleation on La2O3 particles, a reversal of
sence has long been associated with grain refinement and
fluid flow direction with La2O3 addition may enhance the
 M.J. Bermingham et al. / Acta Materialia 168 (2019) 261e274
survivability of detached dendrites at the edges and top surface of
the melt while also accounting for coarser grain sizes along the
centreline of the component that is exposed to hotter liquid.
Another notable observation that requires further research is
the potential grain boundary Zener pinning with La2O3 particles.
The La2O3 particles were widely distributed throughout the
microstructure but occasionally some particles were observed at
the grain boundaries. If such particles pin the boundaries, then
grain growth in the existing solid would be reduced during AM as
new layers are being deposited. A number of rare earth oxides
(including La2O3) are known to pin b-grain boundaries during heat
treatment of titanium alloys at levels as low as 0.01 wt% [29,72] and
thus their potential exploitation for grain size control during AM
requires ongoing investigation.
This work has demonstrated the importance of nucleant parti-
cles in promoting equiaxed grain formation during AM. The La2O3
particles selected for this study are a good starting point but more
work is needed to identify better, more potent nucleant particles for
b-Ti. The initially large xCS at the start of each layer is underpinned
by the difference between epitaxial nucleation (DTN ¼ 0  C) and the
potency of nulceant particles (DTN > 0  C) which will always exist
unless perfect nucleant particles (i.e. DTN approximately equal to
zero) can be identified. The discovery of very potent particles with
smaller DTN than La2O3 would make the CET more achievable
during AM of titanium alloys.
6. Conclusions
This work explored the thermal and composition sensitive fac-
tors affecting the columnar to equiaxed transition (CET) during
wire based additive manufacturing of titanium alloys. Titanium
alloy melt pools were thermally characterised and average tem-
perature gradients varied from 100 to 500  C/mm across a range of
deposition rates. A solidification map for Tie6Ale4V was con-
structed which predicts a mixed columnar þ equiaxed grain
morphology. To promote the CET, classical solidification theory
indicates that segregating solute is required to provide constitu-
tional supercooling and potent nucleant particles are required to
facilitate heterogeneous nucleation of equiaxed grains. Three
representative alloys were selected to study the relevance of this
theory to additive manufacturing. The first alloy investigated was
Tie6Ale4V and represents the control containing no added grain
refiners. The second alloy was a commercial alloy containing only
growth restricting solutes (Tie3Ale8Ve6Cre4Moe4Zr). The third
alloy contained both growth restricting solute and added nucleant
particles (Tie3Ale8Ve6Cre4Moe4Zr þ La2O3 particles). As pre-
dicted by the solidification map the control alloy (Tie6Ale4V)
produced a mixed columnar-equiaxed grain morphology with a
very large grain size. The presence of grain refining solute in
Tie3Ale8Ve6Cre4Moe4Zr refined the grain size by over 55%
principally through a narrowing in columnar grain width but failed
to produce a substantial fraction of equiaxed grains. However, the
addition of La2O3 particles refined the grain size by 85% and pro-
duced an equiaxed zone at the top of the layer and columnar grains
at the base. The La2O3 particles are believed to act as heterogeneous
nucleation sites for b-Ti when present at the right location and
time. The Interdependence model for equiaxed grain formation
accounts for the columnar grains at the base of each layer given that
constitutional supercooling is not generated until the thermal
gradient locally reduces. In-situ melt temperature monitoring
confirmed that temperature gradients decrease during layer so-
lidification which permits constitutional supercooling and equi-
axed grain nucleation.
273
Acknowledgements
The authors would like to acknowledge the support of the
School of Mechanical and Mining Engineering and the Queensland
Centre for Advanced Materials Processing and Manufacturing. MJB
acknowledges the support of the Australian Research Council Dis-
covery Program and is in receipt of Discover Early Career
Researcher Award (DE160100260). All authors acknowledge the
support of the Australian Research Council Research Hub for
Advanced Manufacturing of Medical Devices (IH150100024). MSD
also acknowledges the Australian Research Council Research Hub to
Transform Australia's Manufacturing Industry through High Value
Additive Manufacturing (IH130100008). DHS and MSD also
acknowledge the support of the Defence Materials Technology
Centre (DMTC).
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