Materials Science & Engineering A 719 (2018) 1–11

Contents lists available at ScienceDirect

Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Effect of trace lanthanum hexaboride and boron additions on T

microstructure, tensile properties and anisotropy of Ti-6Al-4V produced by
additive manufacturing
⁎
M.J. Bermingham , S.D. McDonald, M.S. Dargusch
Centre for Advanced Materials Processing and Manufacturing, School of Mechanical and Mining Engineering, The University of Queensland, St Lucia, Queensland 4072,
Australia

A R T I C L E I N F O A B S T R A C T

Keywords: In this work trace lanthanum hexaboride (LaB6) and elemental boron are alloyed with Ti-6Al-4V and their effects
Titanium alloys on the microstructure, tensile properties (including anisotropy) and melt pool shape during Additive
Characterization Manufacturing (AM) are investigated. During the melting process, the LaB6 scavenges oxygen and decomposes
Stress/strain measurements into La2O3 and TiB. The presence of the rare earth element drastically changes the apparent surface tension and
Grains and interfaces
shape of the deposited layers. This is attributed to the Heiple-Roper effect and could have benefits during AM in
producing components with unsupported overhangs. The formation of eutectic TiB during the final stages of
solidification results in highly directional TiB needles in between columnar grains that are aligned with the build
direction. The slow cooling rate during deposition of approximately 90–100 °C s−1 produces very large TiB
particles which can exceed 50 µm in length. Although improving strength by up to 10%, under tensile stress the
high aspect ratio TiB particles are sites for crack opening which leads to a decline in ductility in the longitudinal
test direction and a corresponding increase in anisotropy over unmodified Ti-6Al-4V.

1. Introduction direction and this can account for anisotropy [11,12]. It is therefore
important for future research efforts to find ways to prevent anisotropy.
Additive Manufacturing offers many advantages over conventional The most obvious way of achieving this is to produce homogeneous
manufacturing processes and research efforts to advance this tech- equiaxed microstructures during AM.
nology have grown considerably in recent years. Titanium alloys are There are two approaches that may improve the homogeneity in the
strong candidates for AM because of their high material cost and the microstructure of α + β titanium alloys produced during solidification.
high cost of traditional manufacturing processes. Ti-6Al-4V is by far the The first is to eliminate the highly textured columnar β-grains that re-
most studied of all titanium alloys in AM and now researchers have a sult from the prevailing solidification conditions and alloy constitution,
comprehensive understanding of the Ti-6Al-4V microstructure and i.e. promote the Columnar to Equiaxed Transition (CET). The second
properties inherent to AM. For instance, across multiple AM technolo- approach is to refine the α-phase and eliminate unfavourable variants
gies with different cooling rates it is now understood that the solidifi- such as grain boundary-α or large α-colonies that can be several mil-
cation conditions during AM of Ti-6Al-4V generally favour epitaxial limetres in size and adopt texture from the parent β-grain. Both of these
growth of textured columnar-β grains which can create material prop- approaches may be achievable through selective chemical alloying,
erty anisotropy [1–7]. While incomplete fusion (and therefore porosity) however, to date there has been limited progress made in developing
between layers can also contribute to anisotropy during AM of Ti-6Al- new titanium alloys for this purpose. Silicon is an effective growth re-
4V [8,9], Kobryn and Semiatin [8] and Qiu et al. [10] have shown that, stricting solute based grain refiner in titanium [13] and recently Mer-
even after the removal of porosity through Hot Isostatic Pressing, or in eddy et al. [14] investigated Ti-Si alloys during Wire Arc Additive
the absence of porosity in the case of Carroll et al. [11], anisotropy still Manufacturing (WAAM) in an attempt to achieve homogenous equiaxed
remains, on account of the microstructural texture. It has been pro- grains throughout the build. Although substantial refinement of the
posed that grain boundary-α (which delineates the columnar prior β- grain size occurred (including the presence of some fine grained
grains) is susceptible to failure under tensile loads normal to the build equiaxed crystals), ultimately the addition was unable to completely

⁎
Corresponding author.
E-mail address: [email protected] (M.J. Bermingham).

https://doi.org/10.1016/j.msea.2018.02.012
Received 9 December 2017; Received in revised form 2 February 2018; Accepted 3 February 2018
Available online 06 February 2018
0921-5093/ © 2018 Elsevier B.V. All rights reserved.
M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

Table 1 microstructure while the lanthanum lowers the dissolved oxygen con-
Average chemical analysis of the components determined by ICP AES and Leco tent. Therefore, this is a promising compound to explore as a trace alloy
Combustion (in wt%). The composition of all alloys is within the tolerance specified in
addition to Ti-6Al-4V for AM. For comparison, Ti-6Al-4V modified with
ASTM F2924.
trace boron is also investigated. Although the effect of trace boron
Alloy O N Al V B La additions on the microstructure and compressive strength of Ti-6Al-4V
has been reported [15], to date no research has investigated the po-
Ti-6Al-4V 0.07 0.02 6.09 3.86 – –
tential improvement in tensile anisotropy associated with the elimina-
Ti-6Al-4V+Boron 0.07 0.02 5.98 3.76 0.05 –
Ti-6Al-4V +LaB6 0.06 0.02 6.07 3.91 0.03 0.08 tion of grain boundary-α with the introduction of TiB during AM of Ti-
6Al-4V.

suppress epitaxial growth and some columnar grains still formed. Boron
has also been studied as a grain refiner in trace additions to Ti-6Al-4V 2. Experimental methods
during AM processes. Although the columnar grain structure remained,
Bermingham et al. [15] demonstrated substantial refinement of the α- The wire arc additive manufacturing technique was used for this
grain morphology, elimination of continuous segments of grain study (details about the equipment available in [15]). Ti-6Al-4V wire
boundary-α and an improvement in compressive strength with trace was used as the feedstock and a wrought Ti-6Al-4V base plate was used
boron additions during Ti-6Al-4V AM. In light of the work by Carroll as a substrate for the deposits. Three alloys were investigated in this
et al. [11], the elimination of grain boundary-α is another promising study, namely Ti-6Al-4V, Ti-6Al-4V + boron and Ti-6Al-4V + LaB6. As
approach that may eliminate anisotropy and warrants further in- previously mentioned, the level of addition of B and La was targeted to
vestigation. Additions of as little as 1000 ppm boron to cast Ti-6Al-4V be within the limits specified by ASTM F2924, i.e. < 0.10 wt% of each
are known to prevent the formation of grain boundary-α [16]. element. The boron and LaB6 containing alloys were prepared by
Recently the ASTM released a standard specification for additive coating the build surface with specially prepared alcohol based paints
manufacturing Ti-6Al-4V by powder bed fusion (ASTM F2924). The (each approximately 15 wt% of LaB6 or B) prior to each deposition
standard provides guidance on the acceptable chemistry tolerance of using a similar method as reported elsewhere [14,15]. The average
the base alloy, and interestingly, it indicates a provision for up to 0.1 wt LaB6 powder size used in the paint was 10 µm (Sigma Aldrich, 99%) and
% of any ‘other’ elements,1 up to a maximum of 0.4 wt% in total. Po- the average boron powder size was 1 µm (Strem Chemicals, 92–95%).
tentially, new alloys could be carefully developed based on Ti-6Al-4V The average alloy chemistry sampled from multiple locations within the
that contain trace additions capable of eliminating the microstructural built components is shown in Table 1. Each deposit was created by
directionality and the associated anisotropy of AM while still complying moving the welding torch in a linear direction and feeding wire into the
with this new standard. However, there are only a handful of known molten pool, which solidified to make a layer. A subsequent layer was
elements that are powerful enough to impart substantial refinement in then deposited over the first by increasing the height of the torch,
such small concentrations. Boron [17,18], Beryllium [19], Carbon [20] however, between layers the direction of torch travel was reversed so
and several Rare Earth elements including La and Y [21–24] have all that the component was built up in a zig-zag fashion. The temperature
been reported to refine the microstructure of titanium alloys in small at the end of each layer deposition2 was measured using a non-contact
concentrations during solidification. Rare Earth elements are also IR pyrometer, calibrated for emissivity against ultra high purity tita-
known to reduce the dissolved oxygen concentration in titanium nium (99.995% purity). Calibration was performed by melting a sta-
through a ‘scavenging’ phenomena [25] and this trait could be very tionary pool of the high purity titanium and experimentally de-
beneficial for AM. Not only could this permit the use of lower quality, termining the emissivity against the measured thermal arrests occurring
cheaper feedstock material (i.e. with higher oxygen contents), but it at known phase transformation temperatures as it cooled (L→S at
also provides a margin of safety for AM processes that are vulnerable to 1668°C and β→α at 882°C). The average emissivity from three cali-
atmospheric contamination. For example, there is growing interest in bration tests was 0.2907 at the solidification temperature and 0.2909 at
developing large scale ‘out of chamber’ AM technologies capable of the β→α transformation temperature for the high purity titanium. It
producing components several metres in size [26] outside of an inert was assumed that the emissivity would be comparable between Ti-6Al-
gas or vacuum chamber, and therefore, any trace alloy addition that can 4V and pure titanium. After each layer the build was allowed to cool to
reduce the dissolved oxygen content has clear potential in AM processes room temperature before the next layer was deposited. Approximately
susceptible to atmospheric contamination. halfway through the build (when the height was approximately
The purpose of this study is to investigate the effect of trace 20 mm), deposition was ceased and the components were subjected to a
Lanthanum hexaboride (LaB6) additions on the microstructure and stress-relief at 480 °C for 2 h. After this, deposition continued until the
tensile properties, including the effects of anisotropy, of Ti-6Al-4V approximate dimensions of the final build were
components produced by Wire Arc Additive Manufacturing (WAAM). 180 mm ×12 mm × 45 mm (not measuring the base plate). Details of
The level of addition is to be within the chemical tolerance specified by the deposition parameters are given in Table 2.
ASTM F2924, and thus considered to be present in ‘trace levels’. After deposition the components were subjected to Hot Isostatic
Although ASTM F2924 specifically relates to powder bed fusion AM, it Pressing (HIPing) in a 150 MPa argon atmosphere at 920 °C for 4 h.
is reasonable to expect that other AM processes including Directed Tensile bars complying with ASTM E8 (ø4mmx20mm gauge) were
Energy Deposition (such as WAAM, LENS etc.) would follow similar machined from the builds in both the longitudinal (horizontal) and
guidelines for acceptable alloy chemistry. Only a few researchers have transverse (vertical) build orientations and tested at 0.5 mm/min using
considered using LaB6 as a trace alloy element in titanium and these an Instron machine. Specimens were extracted from the builds for
have been exclusively in casting and powder metallurgy processes metallographic analysis and prepared using conventional techniques.
[27–29]. When mixed with titanium the LaB6 is reported to decompose Photographs and cross-sections of the specimens and the orientations of
into TiB and La2O3 (via the reaction 2LaB6 + 12Ti + 3O → 12TiB the tensile bars are shown in Fig. 1.
+ La2O3), and the subsequent TiB is reported to refine the

1 2
ASTM F2924 specifies maximum levels for Al, V, Fe, O, C, N, H and Y but all other The temperature was measured at the end of the layer after the arc was terminated. It
elements individually have a maximum allowance of 0.1 wt%, up to a combined limit of was not possible to measure during deposition as radiation from the arc interfered with
0.4 wt%. the pyrometer and the trailing shield prevented direct measurement.

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M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

Table 2 been reported to reduce the liquid surface tension in many alloys of
Deposition parameters used during fabrication of the components. aluminium [30,31], Co-Fe [32], silver [33] and tin based solders
[34–36]. Lanthanum has a much lower surface energy than titanium
Deposition Parameters
[37], and on this basis alone would be expected to wet the surface and
Peak Current: 150 Amp lower the bead aspect ratio, however, the chemical and physical in-
Base Current: 75 Amp teractions that occur in the melt are far more complex and these in-
Arc Pulse: 5 kHz
teractions may act to reverse the effect. For instance, in liquid steels the
Wire feed: 1.5 m/min
Wire: Ti−6Al-4V, ø=1.0 mm addition of cerium is known to initially cause a rapid decrease in sur-
Deposition speed: 50 mm/min face tension as it is being dissolved, however, surface tension quickly
electrode-substrate gap: ≈ 5 mm increases as the rare earth begins to react with dissolved oxygen to form
Vertical build interval: ≈ 3 mm oxides [38]. Furthermore, oxygen is also highly surface active and is
Substrate: Ti−6Al-4V
known to strongly decrease the surface tension in many metals [39], so
Electrode: ø = 2.4 mm tungsten-rare earth
Argon: 99.999% purity the removal of dissolved oxygen and the formation of La2O3 in the

Fig. 1. Cross sections of the built components. The addition of LaB6 (C) caused instability during deposition resulting in a highly undulated surface. The orientation of the tensile bars
machined from the builds are shown: T (Transverse/Vertical) and L (Longitudinal/Horizontal). The instability in the melt pool with the addition of LaB6 may be exploitable if it is desired
to produce unsupported overhangs (demonstrated by arrow in C).

3. Results and discussion present case could also act to increase the surface tension in Ti-6Al-4V.
There are also complex physical fluid flow processes that are likely
3.1. Effect of LaB6 and boron on liquid metal bead shape to have a strong effect on the shape of the molten bead. Several fluid
flow mechanisms are known to operate during Gas Tungsten Arc
The addition of LaB6 to Ti-6Al-4V had a marked effect on the molten Welding (and therefore WAAM) including thermocapillary
metal's apparent surface tension and the associated geometry of the (Marangoni), electromagnetic (Lorentz), aerodynamic plasma drag and
deposited bead produced during wire arc additive manufacturing. The buoyancy forces. However, under normal welding conditions it has
aspect ratio of the bead (ratio of width to height) substantially reduced been determined from multiple mathematical models that Marangoni
from approximately 4 (in Ti-6Al-4V and Ti-6Al-4V+B) to ~1.7 in the convection is the dominant fluid flow force influencing the molten pool
alloy containing LaB6. The narrowing of the bead width and the ex- shape [40]. Marangoni forces operate in the molten pool due to steep
tension of its height promoted unstable deposition and the resulting temperature gradients that exist across the pool which, firstly create a
build structure exhibited extreme undulations in topography, as shown surface tension gradient and then a surface flow from the low to high
in Fig. 1. This can be attributed to the presence of lanthanum as there surface tension regions [41]. Since the surface tension of most pure
was no discernible difference between surface tension and bead shape metals decreases with increasing temperature (i.e. the surface tension
when comparing the Ti-6Al-4V and the Ti-6Al-4V + boron build. temperature coefficient (dγ/dT) is negative) [42], the fluid flow during
The decrease in the deposited bead's aspect ratio may suggest that WAAM is expected to move from the centre of the weld pool outwards,
the surface tension (γ) of the melt has increased when LaB6 is in- as depicted in Fig. 2. However, extensive experimental testing in steel
troduced. However, this is at odds with conventional wisdom given that welds has revealed a powerful effect generated by the addition of sur-
rare earths are well known for their surface active properties and have face active elements to the melt. Heiple & Roper [43] found that the

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M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

exceeds 1700 °C (average cooling rate ≈ 1100 °C s−1). As the tem-

perature continues to fall the cooling rate decreases and a clear thermal
arrest with duration of around 1.5 s is apparent on the curves of each
alloy, representing the solidification of primary Ti. During this plateau,
the latent heat of fusion that is evolved, more or less balances with the
rate of heat extraction. During the final stages of solidification the rate
of heat extraction exceeds the rate of latent heat release, which again
leads to an increase in cooling rate. The average cooling rate im-
mediately preceding the thermal arrest was 93 °C s−1. This cooling rate
was averaged over a ΔT= 20 °C period before recalescence and pro-
vides an approximation for the cooling rate during initial solidification.
It is also worth noting that this cooling rate is far lower than typical
cooling rates reported during laser based additive manufacturing pro-
cesses (which are estimated to range between 103–108 °C s−1 [46]).
The presence of boron or LaB6 decreases the solidification tem-
perature of Ti-6Al-4V from around 1679 °C to approximately
1660–1662 °C and this is not unexpected as boron decreases the equi-
librium liquidus temperature. The cooling curves of both Ti-6Al-4V and
Ti-6Al-4V+B display a degree of recalescence prior to the primary
solidification plateau of ≈ 17 °C and 9 °C respectively but this is not
present when LaB6 is alloyed. It is noted that the absence of recales-
Fig. 2. Schematic diagram showing how the Heiple-Roper effect may influence the de- cence has been associated with grain refinement in the literature (see
posited bead shape in AM. Marangoni forces create fluid flow from regions of small Figure 9 in Shabestari et al. [47]) and this is the focus of ongoing re-
tension (γ) to regions of large surface tension. In most metals (A), hotter liquid will have search.
smaller γ than colder liquid. Consequently, fluid flows out from underneath the arc The derivatives of the cooling curves (cooling rate) for Ti-6Al-4V+B
(hottest region) to the cooler sides, producing wide melt pools with lower bead height. (B)
and Ti-6Al-4V+LaB6 also show clear evidence of a reaction occurring
- The Heiple-Roper effect associated with the introduction of surface active elements (La
in this case) causes hotter liquid to have a larger γ than colder liquid, and this causes a around 1465 °C in these alloys. This is likely to be the final stages of
reverse in fluid flow directions [42]. The diameter of the melt bead decreases and its eutectic TiB solidification given that TiB has a large exothermic heat of
height increases. formation [48]. The reaction is not observed in Ti-6Al-4V. These events
provide an indication of the total solidification time which was mea-
addition of trace surface active elements such as sulphur in steel reverse sured to be 1.6 s, 1.8 s and 1.9 s for Ti-6Al-4V, Ti-6Al-4V + B and Ti-
the surface tension temperature coefficient (dγ/dT) so that it becomes a 6Al-4V + LaB6, respectively. No other reactions that possibly corre-
positive value. In other words, the colder liquid now has a lower surface spond to La2O3 or La-containing intermetallics can be discerned during
tension than the hotter liquid. This has a dramatic effect on the weld the cooling of Ti-6Al-4V + LaB6.
penetration and pool shape because the direction of fluid flow reverses
and now moves towards the centre of the weld [42]. In the present case, 3.3. Tensile properties and microstructure
if lanthanum was to act in a similar way to how sulphur acts in steel,
then it is conceivable that marangoni forces could be responsible for the Fig. 4 shows the results of tensile testing. The addition of trace
taller and thinner beads observed in the Ti-6Al-4V+LaB6 deposits. Yin boron and LaB6 had a strong influence on the mechanical properties
et al. [44] recently reported the narrowing of build walls produced by and generally increased strength at the expense of ductility. The addi-
WAAM with the addition of CaF2 (believed to be a surface active ad- tion of LaB6 had the strongest effect: tensile strength increased by about
dition) to Ti-6Al-4V components built by WAAM and also attributed 10% but the ductility, expressed as elongation at failure (εf) and re-
this change to a reversal in the direction of fluid flow. With such a duction in area, both decreased significantly. The typical εf of Ti-6Al-4V
powerful effect on the shape of the component, further study is needed produced by wire arc additive manufacturing has been reported by
in this important area in order to understand the role of lanthanum and others to be between 7% and 10% in the longitudinal direction and
other surface active elements on the shape of titanium components 12–16% in the transverse build direction [2–5]. Thus the transverse
produced by AM. This phenomenon could be exploited, for example, it orientation is generally about 60% more ductile than the longitudinal
may be possible to fabricate components with unsupported overhangs orientation in these works. However, in the present study the HIPed Ti-
during AM (see arrow in Fig. 1C). Wu et al. [45] propose low heat input 6Al-4V components were much more isotropic in strength and ductility
arc pulsing during WAAM enables unsupported Ti6Al-4V overhangs (εf ≈ 20% in the longitudinal orientation and εf ≈ 23.5% in the
and after many progressive layers was able to produce a 90° un- transverse orientation). The initial intention of adding the boron was
supported overhang. With the addition of LaB6 is appears that similar that it may refine the α-phase and eliminate the α-phase that forms
overhangs could be possible with only 1 layer, however, more work is along β-grain boundaries (known as grain boundary-α) as was pre-
needed in this space. viously found [15]. However, instead of improving isotropy, the addi-
tions of boron and LaB6 actually had the reverse effect and increased
anisotropy. The longitudinal orientation was about 50% less ductile
3.2. Effect of LaB6 and boron on solidification process than the transverse orientation with either boron or Lab6 additions.
Ductility in the transverse orientation was satisfactory with both boron
Representative cooling curves from the liquid state for each alloy and LaB6 additions (εf ≈ 19.5% and 13.5% respectively, exceeding the
are given in Fig. 3. It is important to note that these measurements were 10% minimum required for wrought Ti-6Al-4V according to AMS4928)
collected at the end of a layer after the arc was terminated and may not but the ductility in the transverse orientation was considerably lower
exactly resemble the cooling rates during steady-state deposition. (εf < 8.5% in both cases).
Nevertheless, they provide useful insights into the effects of boron and Examination of the microstructure in Fig. 5 reveals the presence of
LaB6 additions on the solidification process of Ti-6Al-4V. From these highly orientated TiB ‘needles’ aligned with the build direction in both
curves it is clear that both additions have a noticeable effect. Initially, Ti-6Al-4V+B and Ti-6Al-4V+LaB6. Some of the borides were very
all alloys cool rapidly during the liquid state where the temperatures large and almost perfectly straight (> 50 µm long and ≈ 5 mm thick)

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M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

Fig. 3. Typical cooling curves and derivatives (over a 100 ms period) for each alloy. Left images show the cooling curve from liquid to approximately 800 °C, and the Right images show a
magnified view of the primary solidification event.

and were orientated in near perfect vertical directions (aligned with the effectively restricts growth in the lateral (horizontal) direction resulting
transverse direction) while other regions contained clusters of much in thinner columnar grains [15]. The concentration of the boron rich
smaller borides that, while still orientated in a general vertical direc- liquid (with low melting point) between the columnar grains continues
tion, took on a more dendritic appearance and outlined columnar grain to increase to the eutectic composition where borides are formed and
boundaries. solidification is complete. The solidification of the Ti-TiB eutectic is
The generalised preference for vertical TiB alignment parallel with exothermic [48] and is detected on the cooling curves presented in
the build direction is the likely microstructural feature accounting for Fig. 3, and is consistent with the temperatures corresponding to for-
the strong anisotropy measured. The alignment occurs because the mation of TiB according to the Ti-B phase diagram. The very small
eutectic TiB forms during the final stages of solidification which occurs concentration of boron solute in the alloys (≈ 0.05 wt%) essentially
at the edges of the columnar grains and/or within interdendritic creates a divorced TiB eutectic at the final stage of solidification, pre-
pockets. As the primary β-Ti dendrite (or cell) grows it rejects boron dominately in between the columnar grains. The nature of this solidi-
solute which accumulates between growing grains. The steep thermal fication process during AM is the subject of ongoing work.
gradients in AM ensure that the columnar β-Ti grain continues to ad- The microstructure of the HIPed Ti-6Al-4V is predominantly wid-
vance with the moving heat source but the presence of boron solute manstatten-α structure in a β-matix. The relatively low tensile strength
depresses the freezing range (by over 100 °C) and results in an accu- (around 800 MPa) is attributed to the coarse α-phase that results from
mulation of solute rich liquid between the columnar grains. This the slow cooling from the β-phase field into the α + β phase field

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M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

of these particles (0.08 wt% La was added) made detection using lab
XRD techniques difficult (results not shown) but it has been shown with
XRD that in higher concentrations (Ti-6Al-4V-1LaB6) the addition of
LaB6 decomposes into La2O3 [28]. It was noted that the TiB plates
adopted the same morphology as that observed in the Ti-6Al-4V+B
alloy. However, unlike the TiB, the La2O3 forms as very small round
particles up to ≈ 3 µm in diameter (but usually much smaller) which
are dispersed evenly throughout the microstructure. This could indicate
that they are not formed during solidification, but rather, are present
prior to the first β-titanium crystal nucleating. Yang et al. [53] proposed
that La2O3 does not form immediately during decomposition of LaB6
and suggested it forms during the β→α transformation (on account of
La having ≈ 8 wt% theoretical solubility in β-Ti but almost no solubi-
lity in α-Ti). However, this scenario is less likely than La2O3 sponta-
neously forming during decomposition of LaB6 on account of the low
Gibbs energy of the rare earth oxide. When metallic rare earths are
introduced to liquid steels the rare earths are known dissolve and im-
mediately scavenge oxygen (forming oxides) [38]. Furthermore, the
cooling curves presented in Fig. 3 do not reveal any evidence of other
reactions that could indicate the formation of La based compounds
during cooling, although the upper limit on the pyrometer is 1800 °C so
any reactions above this temperature are not detected. Lastly, the
uniform distribution of La2O3 throughout the alloy would not be ex-
pected if La2O3 precipitated during the β→α transformation because
the partition coefficient (determined from binary Ti-La phase diagram)
is 0.43 [19] which would result in segregation effects creating localised
regions richer in La solute and these regions would match the location
of the borides, which clearly does not occur. In any case, the homo-
genous distribution of small oxides is unlikely to contribute to the
tensile property anisotropy but they have been attributed to dispersion
strengthening mechanisms [53] which could account for the higher
strength (and loss of ductility) in alloys containing LaB6 compared to
boron only additions.

3.4. Sources of anisotropy

Examination of the fracture surfaces and the microstructure within

the broken tensile bars confirms microstructural factors that con-
tributed to fracture. Firstly, in standard Ti-6Al-4V free from boron or
LaB6 additions, it was identified that prior-β grain boundaries and the
Fig. 4. Tensile properties of each alloy in the Transverse and Longitudinal build or- associated grain boundary-α phase was prone to fracture. Grain
ientations. Error bars represent ± 1 standard deviation. boundary-α is known to nucleate cracks under fatigue loading [54] and
evidence of void coalescence and crack propagation along grain
boundary-α under tension is shown in Fig. 6. Carroll et al. [11] found
(cooling rates during deposition of 10–20 °Cs−1 in the present work). It
that the grain boundary-α is particularly important during AM pro-
is worth noting that this is a key difference compared to other AM
cesses because it provides a pathway for damage accumulation and
technologies such as SLM which can experience cooling rates exceeding
correlated the columnar grain texture to anisotropic ductility. There-
400 °C s−1 during the β→α transformation. The already relatively
fore, highly elongated columnar grains are susceptible to forming
coarse α-phase then further coarsens through grain growth during the
continuous grain boundary-α and ductility is lower in the transverse
high temperature HIPing that was performed post build. The α-colony
direction because these segments are unfavourably orientated with the
size (and α-lath size in highly Widmanstatten structures) is an im-
tensile loading axis and are prone to Mode I fracture. Wilson-Heid and
portant microstructural feature that determines the slip length in tita-
co-workers expanded upon this work and proposed that anisotropy in
nium alloys and has been shown to follow a Hall-Petch relationship
the ductility of Ti-6Al-4V can be predicted based on the grain aspect
with tensile strength [49]. A positive benefit of the coarse α-mor-
ratio (grain height/grain width) that develops during deposition and
phology is that very high ductility is achievable which exceeded 20% in
correlated lower anisotropy with lower β-grain aspect ratio [55].
the present study. This is high for Ti-6Al-4V and is actually twice the
Fig. 7 shows microstructures of failed tensile specimens in both
ductility requirement for wrought Ti-6Al-4V components according to
orientations and confirms that the highly orientated borides are re-
AMS4928. The effects of trace boron on the morphology of the α-phase
sponsible for increased anisotropy. In both Ti-6Al-4V + B and Ti-6Al-
of Ti-6Al-4V has been reported in detail elsewhere [15,16] and will not
4V + LaB6, TiB needles were found to contain severe cracking normal
be explored further here, however, the same refinement effect (decrease
to the direction of tensile loading. The tensile specimens tested in the
in α-lath aspect ratio) on the α-phase was observed in the present study
transverse (vertical) orientation (which contains the majority of borides
for both alloys containing boron. Similarly, the strengthening me-
aligned in this direction) resulted in the borides cracking multiple times
chanisms of TiB reinforcement in Ti-6Al-4V is covered in detail else-
throughout their length but due to the high aspect ratio of the TiB
where [50–52].
needles these cracks were limited to the width of the boride (about
The addition of trace LaB6 into Ti-6Al-4V during WAAM decom-
5 µm). However, when the tensile load was applied in the longitudinal
posed into TiB particles and La rich particles. The low volume fraction
orientation the cracking occurs along the length of the boride, which

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M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

Fig. 5. SEM images of the alloys – (A) Ti-6Al-4V, (B) Ti-6Al-4V + B, (C) Ti-6Al-4V + LaB6. These images were taken in the lower third section of the components (i.e. at build height
equivalent to approximately 15–17 mm) so have likely undergone remelting (and grain growth through reheating) as new layers are deposited on top. Due to atomic contrast the dark
phase indicates the presence of light atomic elements (e.g. boron) and the white phase indicates heavy elements (e.g. lanthanum).

can exceed 50 µm in large borides. The La2O3 particles were also found incompatibilities foster crack nucleation. However, Sen et al. [58] de-
to separate from the titanium matrix but because these particles were monstrated that an increasing fraction of TiB reinforcement in cast Ti-
very small the crack size was smaller than those found on TiB. The 6Al-4V-0.55B increased the high cycle fatigue strength3 by over 50%.
presence of large borides in the microstructure of AM parts is therefore The approximate length of the borides in the cast alloy was 20–50 µm
unfavourable due to these particles nucleating large cracks. Evidence of long and they were evenly dispersed. This is a surprising discovery and
the cracked borides (and La2O3) was also observed on the fracture it was suggested that the removal of grain boundary-α with increased
surface as seen in Fig. 8. Others have also reported cracking of TiB TiB volume fraction could have resulted in better fatigue performance.
under tension in cast Ti-6Al-4V-0.14B [56] and Ti-5Al-5Zr-0.5Mo- Improved fatigue endurance was also reported with boron additions (up
0.25Si-0.5B [57]. Although fatigue properties were not evaluated here
it would be reasonable to expect that the presence of large borides may
be detrimental to fatigue life because the internal strain 3
Fatigue strength was defined by Sen et al. as the maximum stress that at least 75% of
samples survived 106 cycles.

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M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

Fig. 6. Ti-6Al-4V fractured tensile test pieces showing that fracture has occurred along the grain boundary-α that forms along prior-β grain boundaries. The prior-β grain boundaries have
been enhanced (red) to more clearly show these in the top left figure. This particular test specimen failed at εf= 12%, which is significantly below the average Ti-6Al-4V( εf≈ 21%). (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.).

to 0.5 wt%) in Ti-6Al-4V produced by metal injection moulding The other notable difference between the present study and the
[59,60]. Nevertheless, the effect of such large and highly textured TiB prior literature is the size of the TiB that forms which is a function of
on the fatigue properties in the present study requires further in- cooling rate. The relatively slow cooling rate in the present study (of the
vestigation. order of 90–100 °C s−1) produced extremely coarse TiB that tended to
Several researchers have produced titanium-boron alloys (or metal- accumulate in a single region. Other AM processes experience higher
matrix composites) during additive manufacturing but the deleterious cooling rates which produces TiB that are orders of magnitude smaller
effect of large textured borides on anisotropy has not yet been reported. and more evenly dispersed. In their study Banerjee et al. [48] predicted
This in part is related to the variations in cooling rate during deposition cooling rates in their AM process range between 200 and 6000 °C s−1.
and the composition of alloys studied. Banerjee et al. [48] produced Ti- Under very high cooling rates it was proposed that the boron, which has
2 wt%B composites during blown powder laser deposition and com- extremely low solubility in α and β Ti, becomes trapped in a super-
pared this with the same alloy produced by arc-melting and casting. In saturated titanium phase and can only precipitate during thermal re-
both cases the alloys contained TiB particles randomly distributed exposure as the next layer is deposited (simulating ageing). This leads
throughout the microstructure but the main difference being that the to the formation of extremely fine nanosized TiB evenly dispersed
additive manufactured components had considerably smaller TiB than throughout the component produced by AM [64]. Higher cooling rates
the cast samples (20–100 µm in cast vs 0.5–3 µm in AM). Attar et al. also produced finer columnar grains (and smaller dendrite arm spacing)
[61] also compared Ti-1.55%B alloys produced via casting and SLM and so eutectic TiB precipitation will be spread over a more uniform area, as
reported the same finding as Banerjee and co-workers, that is, the mi- opposed to a highly concentrated region between large grains. Mah-
crostructure in the AM produced alloy contained randomly distributed booba et al. [65] studied the effects of hypoeutectic boron during
TiB that was significantly smaller (typical length 0.1–0.5 µm in AM) electron beam deposition and reported very small borides (about 1 µm
than the cast alloys. Wang, Mei and Wu [62] and Genç et al. [63] in size) that were uniformly dispersed within columnar grains. The
produced Ti-6Al-4V-TiB metal matrix composites (containing up to phenomena observed here of large concentrated borides at columnar
3.1 wt% boron) through blown powder laser deposition and were able grain boundaries is a product of solidification conditions (low cooling
to achieve homogenous microstructures containing fine TiB and re- rate and growth mode, i.e. cellular vs dendritic) and is the subject of
ported no elongated TiB in build direction. In all of these studies the ongoing research. Reduced anisotropy and improved mechanical
alloy compositions were at near eutectic or hypereutectic compositions. properties may be achievable in higher cooling rate AM processes that
This will have important implications for the solidification sequence produce finer and more evenly dispersed TiB.
because in hypereutectic alloys the TiB will form before the β-Ti phase,
and therefore, their orientation in the microstructure is not dictated by 4. Conclusions
the solidifying β-Ti. This is in stark contrast to the present study where
trace boron (hypoeutectic) precipitates as TiB from the final pools of Trace additions of LaB6 and boron were introduced to Ti-6Al-4V
liquid, which under the prevailing solidification conditions, occurs during Wire Arc Additive Manufacturing and the response on the mi-
between solidified columnar β-Ti grains. crostructure and tensile properties were examined. The key findings

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M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

Fig. 7. Microstructures of fractured tensile specimens showing cracking of the borides which generally align with the build direction. In specimens containing LaB6, separation of the
La2O3 particles from the titanium matrix was also observed.

Fig. 8. Example of fracture surface in boron containing alloys tested in the longitudinal (horizontal) orientation. A) Ti-6Al-4V + B; B) high magnification of box in A, C) Ti-6Al-4V + LaB6
showing TiB and La2O3 particles at fracture surface. Arrows indicate cracked TiB.

were: and TiB. The La2O3 is evenly dispersed as small particles (< 3 µm)
and likely forms prior to solidification of β-Ti. The TiB forms during
• The alloying of lanthanum drastically changed the shape of the the final stages of eutectic solidification which under the prevailing
molten pool and subsequently the deposited bead shape. The bead thermal gradients occurs between columnar grains resulting in
aspect ratio (width: height) decreased from approximately 4 in highly orientated TiB needles aligned with the build direction. These
Ti6Al-4V and Ti-6Al-4V+B to around 1.7 when LaB6 was added, needles vary in size but TiB > 50 µm long were observed.
resulting in a poor surface finish. The presence of the rare earth is • The tensile strength increased with additions of trace boron and
proposed to reverse the direction of Marangoni flow resulting in a LaB6 by about 10%, but this came at the expense of ductility.
taller but narrower bead and may be exploitable in the design of • The presence of directional TiB in the components had a marked
components with unsupported overhangs. effect on anisotropy. The relative anisotropy increased dramatically
• LaB6 decomposes during additive layer deposition to form La2O3 with the addition of boron and LaB6 which was attributed to the

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M.J. Bermingham et al. Materials Science & Engineering A 719 (2018) 1–11

highly aligned TiB needles. The transverse (vertical) build orienta- 59 (2011) 5494–5510.
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Acknowledgements metallurgy (PM) titanium and titanium alloys, Titanium Powder Metallurgy:
Science, Technology and Applications, 2015, pp. 253–276.
The authors would like to acknowledge to support of the School of [26] C. Newell, S. Palas, C. Duty, L. Love, V. Kunc, R. Lind, C. Blue, Out of bounds
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Mechanical and Mining Engineering and the Queensland Centre for [27] A.V. Kartavykh, E.A. Asnis, N.V. Piskun, I.I. Statkevich, M.V. Gorshenkov,
Advanced Materials processing and Manufacturing. MJB acknowledges V.V. Tcherdyntsev, Lanthanum hexaboride as advanced structural refiner/getter in
the support of the Australian Research Council Discovery Program and TiAl-based refractory intermetallics, J. Alloy. Compd. 588 (2014) 122–126.
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is in receipt of Discover Early Career Researcher Award sintered microstructure and mechanical properties of titanium and titanium alloys,
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