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Martensitic transformations in Ti-6Al-4V (ELI) alloy manufactured by 3D

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Article  in  Materials Characterization · September 2018

DOI: 10.1016/j.matchar.2018.09.042

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 Materials Characterization 146 (2018) 101–112

Contents lists available at ScienceDirect

Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Martensitic transformations in Ti-6Al-4V (ELI) alloy manufactured by 3D T

Printing
N. Kazantsevaa,b, , P. Krakhmalevc, M. Thuvanderd, I. Yadroitseve, N. Vinogradovaa, I. Ezhova
⁎

a
Institute of Metal Physics, 620990 Ekaterinburg, 18, S. Kovalevskaya Str., Russia
b
Ural Federal University, 620002 Ekaterinburg, 19, Mira Str., Russia
c
Karlstad University, SE-651 88 Karlstad, Sweden
d
Chalmers University of Technology, Department of Physics, Göteborg SE-412 96, Sweden
e
Central University of Technology, Free State, Department of Mechanical and Mechatronic Engineering, Private Bag X20539, Bloemfontein 9300, South Africa

ARTICLE INFO ABSTRACT

Keywords: In the present investigation, Ti-6Al-4V ELI samples were manufactured by the powder-bed fusion (PBF) process
Material or constituting phase(s) using the laser sintering (LS) technology. Microstructure, chemical and phase constitution, and mechanical
Titanium alloys properties were studied by means of the transmission electron microscopy, atom probe tomography, X-ray
Laser sintering diffraction, nanoindentation and mechanical testing. It was found that the structure of LS samples consisted of
Metastable phases
two different variants of metastable phases, namely the hexagonal α′ martensitic phase and small amounts of the
Mechanical properties
orthorhombic α″ martensitic phase. The martensitic α′-phase was formed because of the high cooling rates of the
LS method. The {1012} ⟨1011⟩ hexagonal martensite tensile twins were observed in the microstructure of the as-
build alloy. Small areas with inner twinning martensitic plates, which are typical for the metastable orthor-
hombic martensitic phase in titanium alloys, were identified by the transmission electron microscopy. Atom
probe tomography (APT) confirmed localization of β-stabilizing elements at interfaces, presumably at the twin or
lamella boundaries. The structure and origin of the martensitic phases in 3D printed Ti-6Al-4V alloys are dis-
cussed with respect to in-situ heat treatment during manufacturing.

1. Introduction starting temperature of the quenching and the concentration of the β-

stabilizing elements in the β-phase at solution treatments [8]. At
Ti-6Al-4V is a widely used alloy for aerospace and medical appli- quenching from temperatures above the β-transus, when alloying ele-
cations thanks to its excellent combination of strength, toughness, ments are homogeneously distributed in the β-phase, the α′ hexagonal
corrosion resistance and biocompatibility. In conventional Ti-6Al-4V martensite is usually formed. The saturated α′ martensite is found to be
alloy, a variety of microstructure and property combinations can be transformed from the β-phase when the concentration of vanadium in
achieved by a control of temperature and cooling rates at heat treat- the β phase is < 4.27 at.% (4.65 wt%). The HCP α′ martensitic phase
ment [1,2]. After furnace cooling from the β region, conventional Ti- (space group P63/mmc, a = 0.293 nm, c = 0.467 nm) forms in Ti-6Al-
6Al-4V is usually (α + β) alloy. In Ti-6Al-4V alloy, solubility of vana- 4V alloy under fast cooling [6]. A minimum cooling rate of 20 °C/s is
dium, which is the β-stabilizer, is about 2 wt% in the hexagonal close- necessary for the formation of the martensite phases. When the cooling
packed (HCP) α phase [3]. Thus, up to 10 vol% β-phase is stabilized in rate is higher than 525 °C/s, the entire microstructure can be featured
the microstructure after furnace cooling. as the α′ martensite [9]. In [9] a schematic diagram showing the de-
At higher cooling rates, formation of metastable phases has been pendence of the phase state on the rate of cooling for Ti-6Al-4V is
observed [4,5]. Two types of metastable martensitic transformations suggested. In this diagram a temperature of the start of the β → α′
were observed in Ti-6Al-4V alloys, namely β → α′ and β → α″. The α′ martensitic transition is as low as 575 °C, and the β-transus is about
and α″ metastable phases have crystallographic relationships with the 994 °C. The formation of α′ martensite promotes strengthening and
parent β phase: (110) β||(0001)α′ and 〈1−11〉 β||〈11−20〉 α′ [6] and, lowers the ductility of the alloy [8].
{001}α″||{110}β and 〈100〉α″||〈001〉β [7]. The type of the martensite, At quenching from the α + β two-phase region, the concentration of
α′ or α″, that is formed at quenching in Ti-6Al-4V alloy, depends on the alloying elements in the β-phase depends on temperature and varies

⁎
Corresponding author at: Institute of Metal Physics, Ural Branch of Russian Academy of Sciences, 18, S. Kovalevskaya Str., 620990 Ekaterinburg, Russia.
E-mail address: kazantseva@imp.uran.ru (N. Kazantseva).

https://doi.org/10.1016/j.matchar.2018.09.042
Received 12 July 2018; Received in revised form 8 September 2018; Accepted 26 September 2018
Available online 26 September 2018
1044-5803/ Published by Elsevier Inc.
N. Kazantseva et al. Materials Characterization 146 (2018) 101–112

by electron beam melting having lower cooling rates than that of the
laser sintering method, the martensitic microstructure depends on the
building thickness [16]. The laser powder-bed fusion process includes
rapid solidification of the molten alloy from high temperatures, which
often substantially exceed the melting point [17]. The microstructure of
LS Ti-6Al-4V is formed by martensitic transformation of β-phase at very
high cooling rates, about 106 K/s. The high cooling rates at laser sin-
tering of Ti-6Al-4V ELI (Extra Low Impurities) alloy do not allow sta-
bilizing of the β-phase enriched with vanadium. During solidification
under LS, the metastable α′ martensitic phase in the Ti-6Al-4V is usually
found inside of prior β grains [6,18,19]. Nevertheless, formation of the
metastable α″ orthorhombic martensite was also observed in Ti-6Al-4V
obtained by laser powder-bed fusion [20]. However, the authors of [20]
did not study this phase in detail. Thus, the conditions and causes of the
formation of the α″ martensitic phase in additive manufactured Ti-6Al-
4V alloys are still unclear. The study of the metastable phase transfor-
mations in titanium alloys manufactured by additive technologies is an
Fig. 1. X-ray diffraction pattern of the LS sample. actual scientific and industrial problem. It has a great scientific interest
because a formation of the metastable phases influences the mechanical
properties of the alloys.
The purpose of this work is the study of the features of the mar-
tensitic phase transformations in Ti-6Al-4V (ELI) alloy manufactured by
the powder-bed fusion process using the laser sintering technology, in
comparison with the conventional titanium alloys.

2. Experimental

Spherical argon-atomized Ti-6Al-4V (ELI) (45 μm) powder from TLS

Technik GmbH & Co Spezialpulver KG was used for this study. Samples
were produced by the EOSINT M280 (EOS GmbH), equipped with an
Ytterbium fiber laser, and operating at 1075 nm wavelength (IPG
Photonics Corp.); the laser beam had a Gaussian profile (TEM00 mode)
and 80 μm spot diameter. The process parameters for a Ti-6Al-4V alloy
are 170 W laser power and scanning speed of 1.2 m/s. A powder layer
Fig. 2. Microstructure of the studied LS sample, SEM. thickness of 30 μm and a back-and-forth scanning by strips with the
hatch distance of 100 μm was applied. The substrate and powder ma-
terial were similar in chemical composition. Argon was used as the
between the values mentioned above. Therefore, in dependence on the
protective atmosphere; the oxygen level in the chamber was
β-phase composition, α′ or α″ transformation products can be found.
0.07–0.12%.
Supersaturated α″ phase (5.45–8.0 wt% V) has an orthorhombic crystal
Structural study was done with the Tecnai G2 30 Twin transmission
structure [5,10]. In Ti-6Al-4V alloy, the α″-phase forms in the localized
electron microscope with scanning systems and energy dispersive
regions with the vanadium concentration in a range of 9 to 13 wt% [8].
spectrometer EDAX, GATAN-filter image and scanning electron micro-
This metastable phase is particularly interesting because of its
scope SEM Hitachi SU70. An X-ray diffractometer DRON-3 with CuKα
thermoelastic properties [7]. It is found the super elastic behavior in
radiation was used in this study. Mechanical properties were measured
β‑titanium alloys under the reversible stress-induced β → α″ martensitic
at room temperature with nanoindentor NanoTest; the load time was
transformation [11]. The martensitic α″-phase in β-Ti alloys is reported
10 s, the load F = 32 mN and the size of the indent trace about 2 μm
as a base-centered orthorhombic phase, which has a space group of
were used the measurement error was 2%. Tensile tests were performed
Cmcm and lattice parameters of a = 0.3152 nm, b = 0.4854 nm, and
with an Instron 1342 servo-hydraulic testing machine with clip-on ex-
c = 0.4642 nm [9]; the lattice parameters vary with alloy composition
tensometer of 12.5 mm and under constant strain rate of 1 × 10−4 s−1.
[12]. The orthorhombic α″ martensite is usually observed with an in-
Cylindrical vertical manufactured samples of standard dimension with
ternal twin structure, which is believed to accommodate the transfor-
the gauge length four times the diameter were used for mechanical
mation strains under transition from β to α″ [8,12]. The twinning
tests. The initial gauge length was 16 mm.
process in the orthorhombic martensitic α″ phase in β–titanium alloys
Preparation of needle-shaped specimens for APT analysis was per-
was analyzed in detail in [7,13,14]. Unlike the HCP α′ martensite, the
formed using the standard FIB/SEM lift-out procedure [21]. The sam-
appearance of the orthorhombic α″ martensite leads to softening and its
ples were analyzed in an Imago LEAP 3000× HR atom probe system.
decomposition leads to hardening of the titanium alloys [5,8,15]. Both
Field evaporation was initiated by laser pulsing with green light
α′ and α″ martensitic phases decompose at suitable aging to equili-
(λ = 532 nm) at a 200 kHz pulse rate, using 0.2 nJ pulse energy. The
brium α and β phases [8].
temperature of the specimens was held at 60 K and the pressure in the
Powder-bed fusion (PBF) is the additive technology for 3D printing
chamber was approximately 10−9 Pa. APT data was analyzed using the
of the metal alloys. In the PBF process, powder is deposited in a layer-
CAMECA IVAS 3.6.10 software. The reconstructions were made using
by-layer manner on a substrate. In this study, we used the laser sin-
the voltage method with a k-factor of 4.0, image compression factor of
tering (LS) method [15]. In Ti-6Al-4V alloy manufactured by additive
1.65, and an evaporation field of 25 V/nm. The heat map figures are
manufacturing, the final structure depends on the method and the
semi-quantitative, and display the variations in V and Al concentra-
process parameters. For instance, in the Ti-6Al-4V alloy manufactured
tions.

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Fig. 3. Twin region of a': (а) the bright-field image; (b) the dark-field image in (020)t twin reflex; (c) the dark-field image in (020)m matrix reflex; (d) SAED pattern to
(а) zone axis [011]m; (e) a schema to (d).

3. Results and Discussion 3.2. Structure Study

3.1. X-ray Results SEM results are presented in Fig. 2. In the microstructure of the
cross-section of the as-build sample the columnar grains with marten-
A part of the X-ray diffraction pattern, that should contain the most sitic needles inside of them.
intensive diffraction lines of β-phase is shown in Fig. 1 [22]. There are Similarly to X-ray results, TEM investigations did not reveal any
no β-phase lines in the diffraction pattern; the diffraction lines of HCP cubic β phase in the structure of the studied sample. The non-uniform
α′ phase are observed. Additionally, a weak diffraction line in the po- structure was observed in the as-build sample by TEM. Areas of the
sition of the most intensive (110) diffraction line of the metastable martensitic α′ phase with (1012)⟨1011⟩ twinning structure and without
orthorhombic martensitic α″ phase was detected. β precipitations were found (Fig. 3). The width of the twins was in the
range of 20–50 nm. Fig. 4 presents the transformation of the HRTEM
image of the twin region with Inverse Fast Fourier Transition (IFFT).

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Fig. 4. Twin region, HRTEM: (a) IFFT image; (b) FFT to (a), zone axis [011]m; (c) IFFT image with the mask used the matric reflexes, the location of the defect is
circled.

(1012) Twinning includes the atomic shuffling in prism-pyramidal slip the c-axis. The ⟨c + a⟩ slip on {1011} pyramidal planes, tensile twins,
planes (Fig. 5). IFFT image, which is obtained with the mask using the or compressive twins result in the deformation along c-axis.
matric reflexes, illustrates the partial twinning dislocations resulting in The (1012)HCP twinning system in titanium has the lowest critical
stacking faults in the crossing of the (1011) and (1010) atomic rows shear stress for twinning. The observed (1012)HCP twinning may be
(Fig. 4c). Ordering of these localized defects distorts the interlayer classified as the tensile one, and it results in 16.7% strain in the 〈1000〉
distance and promotes the twin formation. Twinning dislocations glide direction in hexagonal close packed structure [23]. Presence of the
along the twin interface form steps on the twinning plane and thus tensile twins in the structure means existence of a high level of the
increase or decrease the twin thickness (Fig. 5). preceding compressive stresses. This fact correlates well with the lit-
The non-twinned α′ region shows the defects in (0001) atomic rows erature results showed the high level of residual tensile stress in the
(Fig. 6). The defects in (1010) atomic rows were also found in these samples manufactured by selective laser method [24]. Additionally,
regions. It means that all ⟨a⟩ type of HCP α-Ti slip planes such as “easy another type of twins with different morphology was observed in the
slip” (1010) prism plane, (0001) basal plane, and (1011) pyramidal structure of the as-build Ti-6Al-4V sample, see Fig. 7. The acicular
plane may be observed in as-build LS Ti-6Al-4V samples. It is well martensite with the internal twins is found in the structure of the
known that ⟨a⟩ type of HCP α-Ti slip do not generate deformation along sample. Unlike the HCP twins observed in Fig. 3, these twins are

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Fig. 5. Twin region: (a) IFFT image with the mask used the matric and twin reflexes (a); increased magnification to (a); (c) a schema of twinning dislocation
producing a step in the twin boundary.

oriented across the needle-like plates. It has been reported that such a the specimen contains a planar feature passing through the whole
twin morphology is typical for the martensitic α″-phase [7,8]. The specimen thickness about half way down the APT specimen. These
width of the inner twins was from 10 to 20 nm. This type of twins was features could be associated with an internal interface or other planar
not found everywhere, but in some local areas of the sample. Positions defect in the microstructure. The distance between these observed
of the diffraction reflexes in the selected area electron diffraction planar defects was at least 100-150 nm, which is quite similar to the
(SAED) patterns taken from the twinning regions correspond to the thickness of α-twin, see Fig. 2, which allows to suggest that these de-
orthorhombic crystal lattice. The calculation of the positions of the fects are twin boundaries. Analysis of the change in a chemical com-
twinning reflexes shows the presence of the (110) orthorhombic twin- position across these defects was done using one-dimensional con-
ning plane, see Fig. 7(a–c). Two different twin classes were suggested centration profiles. The profiles represent the local concentration of V,
for orthorhombic twinning in [7]. The type of twinning was suggested Al and Ti across a cylindrical region of interests (ROIs) positioned
to be defined by the main strain, which was associated with the content through the interface, see Fig. 8b. Analysis of the elements distribution
of beta stabilizing elements in titanium alloy. According to [7], tensile in the specimen showed that the concentration of Al was apparently
strain leads to form {110} type twinning and compressive strain results constant, and no segregations of Al were observed at the investigated
in {111} type twinning. Reflexes of the HCP α′-phase were also found in interface, Fig. 9c. At the same time, an increased concentration of V and
the SAED pattern (Fig. 7d–e). The dark-field image taken with the HCP a decreased concentration of Ti was observed at the interface, Fig. 9d.
α′-phase reflex showed the area surrounding the plate with orthor- Another feature observed by APT was a linear defect like a dis-
hombic twins (Fig. 7d). location with segregation of V in the core. Fig. 10 also illustrates an-
Orthorhombic α″ martensite is usually observed in regions enriched other specimen with an interface, similar to the one presented in Fig. 6
with β-stabilizing elements [8,25]. In our case, we also found the in- but located near the top of the investigated tip. A heat map and iso-
creased vanadium content in such twinning regions of the studied concentration surfaces with 5 at.% V are presented in Fig. 10a, b and c.
sample (Fig. 8). Fig. 10d represents a box aligned with the dislocation and a corre-
sponding 2D projection of the V concentration. Concentration is re-
3.3. Atom Probe Tomography presented with a color map, where blue color corresponds to 2 at.% V
and red color to 5 at.% V respectively. Therefore, APT confirmed the
Results obtained with atom probe tomography (APT) of the speci- formation of regions enriched with V in the Ti-6Al-4V manufactured by
mens cut from the as-build LS Ti-6Al-4V ELI alloy showed the presence 3D printing using the power- bed fusion process with laser sintering.
of some characteristic regions in the microstructure. Fig. 9a, shows that

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N. Kazantseva et al. Materials Characterization 146 (2018) 101–112

Fig. 6. a'-phase region, HRTEM image: (a) IFFT; (b) FFT, zone axis [100]HCP; (c) IFFT, defect structure of (0001) atomic rows, the location of the defect is circled.

3.4. Mechanical Tests in the studied samples. This supports the observation that α′ martensite
is prevailing phase in the structure of the studied samples and correlate
Tensile stress-strain curves of the LS samples are presented in with the results of [30], where authors found very close values for the
Fig. 11. Results of the mechanical testing are presented in the Table 1. yield strength and the ultimate strength to failure and observed fully α′
The results of nanoindentation are well correlated with the results of martensitic structure. In the present investigation, nevertheless, ducti-
the mechanical testing and literature data (Table 1). Elastic modulus of lity was quite high and reached to 9.4%. This is higher than values of
nanoindentation E(id) = 114 MPa and microhardness of nanoindenta- 2–5% reported by others. We suppose that the parameters of the laser
tion 5.6 GPa were measured in the as-build sample. sintering taken in our study promoted the martensitic transformations.
Table 1 illustrates the comparative data of mechanical character- Namely, formation of metastable α″ martensitic phase could be a reason
istics of LS Ti6Al4V and Ti6Al4V (ELI) alloys with the different mi- for improved ductility of the LS as-build Ti6Al4V (ELI) sample manu-
crostructure, which were manufactured with different parameters of factured in the present investigation. The metastable α″ martensitic
laser sintering (laser scan strategy, laser density, and powder quality), phase was reported quite soft in comparison with α′ martensite [15].
presented in literature and obtained in the present investigation. It is Therefore, the formation of this phase in the microstructure during
seen that LS Ti6Al4V alloy demonstrates high strength and reduced manufacturing may lead to an increase in ductility. However, to get the
ductility. High value of the ultimate strength to failure was also found high level of ductility (up to 15%), the high percentage of orthorhombic

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N. Kazantseva et al. Materials Characterization 146 (2018) 101–112

Fig. 7. Region with orthorhombic twins: (a) the bright-field image; (b) the dark-field image in (0) matrix reflex, zone axis [122]ORT; (c) the dark-field image in (-111)
twin reflex, zona axis [12]ORT, (110) twin plane; (d) the dark-field image in a' reflex, zona axis [01-11]HCP; (e) SAED pattern to (a)–(d); (f) a schema to (e).

martensite should be created in the structure of the sample [15]. In our laser sintering process on the structure should be taken into account for
case, we found small regions of α″ martensitic phase. Because of that obtaining the materials with high mechanical properties. Temperatures
we have only small increasing in ductility, which is correlated with the of the heating of the inner regions (previously manufactured layers) of
decreasing of the value of yield strength (Table 1). In general, special the sample during manufacturing depend on scan strategy, laser density
increasing in the ductility of the LS samples with conserving of the high [1,16,26]. Because of that, the as built Ti-6Al-4V sample can have the
level of strength by creating of large amounts of orthorhombic mar- non-uniform structure. Schematic figure of the cyclic heating of the
tensite may be interesting future engineering task. different layers in the sample is presented in Fig. 12. As it has been
reported in [24], during laser sintering, the temperature of Ti-6Al-4V is
4. Discussion changed rapidly from 2900 K on the surface to 450 K. High cooling rates
promote the martensitic transition β → α′ that occurs under the
Features of the additive method and effect of the parameters of the quenching from high temperatures (above the β-transus) and requires a

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N. Kazantseva et al. Materials Characterization 146 (2018) 101–112

Fig. 8. Twin region, EDX spectra in STEM regime: (a) the dark-field image with line scan and spectrum; (b)–(c) the chemical composition of the studied region.

high super cooling [26]. Malinov et al. in [24] have also observed the α′ To understand the mechanisms behind the formation of the α″ or-
martensite and no retained β phase in conventional Ti-6Al-4V alloy thorhombic phase in LS Ti-6Al-4V ELI alloy, the thermal history of the
after fast cooling from temperatures above β-transus. Appearance of the materials should be taken into account. In the LS material, the thermal
martensitic α′-phase investigated in the present study in LS Ti-6Al-4V history has a complex character. Analysis of the schematic phase dia-
samples, is also in good agreement with results obtained in gram presented in Fig. 13 could explains processes which take place in
[9,14,19,24]. the Ti-6Al-4V material at power-bed fusion process with laser sintering.
Rapid cooling, however, does not fully explain the mechanisms of The nominal chemical composition of Ti-6Al-4V alloy is marked by a
the formation of the α″ orthorhombic phase. This phase is more vertical dashed line. When the material is cooled down from the melt
common for Ti-alloys with higher concentration of β-stabilizing ele- for the first time, a remarkable segregation of elements in the liquid is
ments [5,8]. Nevertheless, this phase has also been observed in con- not expected. Since cooling rates typical for PBF process are high, the
ventional Ti-6Al-4V after quenching from 750 to 850 °C followed by martensite is formed directly from the β-phase. Therefore only the α′
aging in a range of 600–700 °C [25]. The intensities of the α″ martensite with chemical composition close to the nominal is formed. Further on,
reflections observed by in-situ neutron diffraction increased with an due to the layer-by-layer manner of manufacturing, previously manu-
increase in the aging time at temperatures in a range of 600–700 °C. At factured layers of a sample are heated up and cooled down several
higher aging temperatures of 800, 900 and, 1000 °C, the α″ martensite times, in other words the material undergoes thermal cycling [1,16,26].
has not been detected [25]. Thus, this martensitic phase is an inter- The temperatures of those cycles depend on manufacturing parameters
mediate metastable phase and it does not require as large super cooling and may vary in a broad range.
as required for the formation of the α′-phase [5,26]. Formation of the In each thermal cycle, inner regions are subjected to heating and
α″ orthorhombic phase is associated with redistribution of V and Al cooling stages. At heating, temperatures in the inner regions can
between coexisting α and β-phase at aging at 600–700 °C. achieve values typical for the α + β temperature region. For example,

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Fig. 9. APT results of the LS sample: (a) heat map of the V concentration; (b) the cylinder shows the position of the concentration profiles shown in (c) Ti and (d) Al,
V.

the heating temperatures could be in an interval between T1 and T3 in presumably are the precipitations of the metastable martensitic phases.
Fig. 13. At these temperatures, the α′ is decomposed, so that α and β Presence of these phases was experimentally proven by TEM. Low
phases are formed. Cooling of the inner regions at PBF is rapid; there- amounts of the α″ (according to X-ray, the diffraction lines appear in
fore, the martensitic phase is formed again. In dependence on con- diffraction pattern at phase volume fraction in the sample of about 5%)
centration of β-stabilizers in the β phase, metastable phases like α′ or α″ suggest that formation of V-rich regions rather takes place at tem-
martensite can form at rapid cooling. In the inner regions heated to T1, peratures between T1 and T2, when diffusion is sufficiently high to form
concentration of β-stabilizer reached C1 and the hexagonal α′ marten- the V-rich regions.
sitic phase is formed at quenching. At intermediate temperatures, for If formation of the α′ hexagonal martensite is expected due to the
instance about T2, concentrations of β-stabilizers in the β-phase are high cooling rates, the mechanisms behind formation of the orthor-
around C2 and a mixture of α′- and α″-phases is formed. If the con- hombic phase could be explained with manufacturing conditions. Due
centration of β-stabilizers in β-phase reaches C3, β-phase is transformed to the layer-by-layer nature of manufacturing in PBF process, inner
to the α″ orthorhombic martensite at quenching. regions are subjected to an in-situ heating and cooling cycles. At the
Thermal cycling at PBF process differs from the conventional iso- heating, temperatures in the inner regions increases locally to α + β
thermal heat treatments. The main difference is a dwell time at the region for a short time repeatedly, which can lead to the activation of
temperature, which controls kinetics of all the diffusional processes. diffusional processes and result is formation of areas enriched with V, as
Malinov [25] reported several hours of an isothermal treatment to form it has been confirmed by APT in the present investigation. Herefore, one
the α″-phase, while in the additive manufacturing process time of a can conclude that the formation of metastable phases in 3D printed Ti-
thermal cycle is rather in a range of milliseconds. Therefore, equili- 6Al-4V strongly depends on parameters of laser sintering; the me-
brium concentrations of V, corresponding to points C2 or C3 in Fig. 13, tastable martensitic phases may be formed during manufacturing pro-
are difficult to be achieved. Instead of the β-phase with an equilibrium cess.
concentration of V, nano-scale metastable areas with an increased Change of the manufacturing parameters leads to change in the
concentration of V are formed. phase composition and structural morphology, which in turn, affect the
In the present investigation, presence of the regions enriched with V mechanical properties of the manufactured 3D Ti-6Al-4V materials.
was proven by APT method (Figs. 8–9). Those precipitations were re- This is positive factor of the 3D printing process, because it means that
vealed at thin planar interfaces or linear defects, and could be asso- appropriative laser sintering parameters may allow one to obtain the
ciated with twin or lamellar boundaries. These observed V-rich areas different structure and properties in the same material.

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Fig. 10. APT results showing the vanadium distribution in the LS sample: (a) heat map of V; (b) V atoms and iso-concentration surfaces; (c) same as (b), but rotated
90˚; (d) V enrichment at a dislocation.

5. Conclusion

The results obtained in this study can be summarized as follow:

1. Metastable martensitic phase transformations in Ti-6Al-4V (ELI)

alloy manufactured by 3D printing are studied. It is found that the
structure of laser-sintered samples has two different variants of
martensite such as the HCP martensite of α′-phase and orthor-
hombic martensite of α″-phase. Both of these phases are metastable.
2. High rate of cooling used in the power fusion process using laser-
sintering method promotes the martensitic α′-phase formation. The
(10–12) ⟨−1011⟩ HCP martensite tensile twins is observed in the
laser sintered samples.

Thermal cycling at intermediate temperatures leads to a non-uni-

form alloying element redistribution that prompts the β → α″ marten-
sitic transformation at cooling. Small local areas with inner twinning
Fig. 11. Stress-strain curve of LS samples. martensitic plates that are typical for the metastable orthorhombic
martensitic α″-phase in titanium alloys are also found by TEM.

Table 1
Tensile properties of LS sample.
Reference UTS, MPa YS, MPa Elastic modulus, GPa Elongation at break, % Density Micro-structure

Ti6Al4V [27] 1269 ±9 1195 ± 19 – 5 ± 0.5 – α′ martensitic laths

Ti6Al4V [20] 1407 1333 – 4.54 – α′ plates + very small amounts α″
Ti6Al4V [28] 1155 ± 20 – – 4.1 ± 2 99.79 ± 0.2 Fine acicular α′ martensite
Ti6Al4V [29] 1321 ± 6 1166 ± 6 112 2 ± 0.7 > 99.5 α′ plates
Ti6Al4V (ELI) [30] 1267 ± 5 1110 ± 9 109.2 ± 3.1 7.28 ± 1.12 Fully dense Acicular α′
Ti6Al4V (ELI) [31] 1206 ± 8 1137 ± 20 105 ± 5 7.6 ± 2 – Acicular α′
Ti6Al4V (ELI) present investigation 1265 ± 4.8 1098 ± 2 112 ± 2.1 9.4 ± 0.42 > 99.9 Acicular twinned α′ + twinned α″

110
N. Kazantseva et al. Materials Characterization 146 (2018) 101–112

Fig. 12. Schematic figure of the cyclic heating of the different layers in the LS sample during manufacturing.

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