Journal of Alloys and Compounds 829 (2020) 154529

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Characterization, corrosion resistance and hardness of rapidly

solidified NieNb alloys
Conrado R.M. Afonso a, **, Katherine Martinez-Orozco b, Vicente Amigo
c,

E. Spinelli a, *, Claudio S. Kiminami a
Carlos A. Della Rovere a, Jose
a
Department of Materials Engineering (DEMa), Federal University of Sa~o Carlos (UFSCar), 13565-905, Sa
~o Carlos, SP, Brazil
b
Graduation Program in Materials Science and Engineering (PPG-CEM), Universidade Federal de Sa ~o Carlos (UFSCar), Rod. Washington Luís, km 235,
13565-905, Sa ~o Carlos, SP, Brazil
c
Universitat Polit
ecnica de Val
nica y de Materiales, Camíno de Vera S/n, 46022, Val
encia (UPV), Departamento de Ingeniería Meca encia, Spain

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

Article history: In this research various Ni(-x)Nb (x ¼ 10, 15, 20, 30, 40, 45, 52 and 57 wt %) alloys samples were rapidly
Received 29 October 2019 solidified (RS) by using copper mold casting. High purity elements were used to produce the RS NieNb
Received in revised form samples. Even though NieNb alloys have been extensively investigated over the past decades regarding
31 January 2020
thermodynamics, phase diagram and heat treatment; as-solidified microstructures and properties
Accepted 25 February 2020
generated under non-equilibrium conditions remain undetermined for this alloy system. The NieNb
Available online 26 February 2020
system is characterized by two eutectic reactions (termed E1: 22.5 wt % Nb and E2: 52 wt % Nb) and
three Ni3Nb, Ni6Nb7 and Ni8Nb intermetallics, being the later barely reported in literature. The E1 group
Keywords:
Ni-Nb alloys
of alloys (i.e., x ¼ 10, 15, 20 wt%) showed the microstructures constituted by Ni-fcc cellular/dendritic
SEM matrix enveloped by Ni þ Ni3Nb eutectic. In contrast, the higher niobium (Nb) containing compositions
TEM (E2 group: x ¼ 40, 45, 52 and 57 wt%) exhibited plate-like morphologies associated with either Ni3Nb or
Microstructure Ni6Nb7 phases. Characterization of the microstructure (cell/dendrites) spacing associated with the E1
Hardness group of alloys allowed the cooling rates to be estimated. A mixture of irregular g00 -Ni3Nb and needle-like
Passive films d-Ni3Nb morphologies is present in the Nie20%Nb alloy solidified under a cooling rate of 1.7  103 K/s.
The passive range of the Nie30%Nb or higher Nb content alloys was demonstrated to be at least two-fold
higher when compared to that of the commercial 625 Ni-based superalloy. The concurrent evaluation of
key requirements for NieNb alloys such as Vickers microhardness and passivability were determined as
function of Nb content. They are both strongly affected by the Nb containing.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction In particular, Ni-based bulk metallic glass (BMG) show excellent

Ni-based superalloys are commonly used in advanced applica-
tions, such as aerospace industry, land-based turbine disks, nuclear
power plants, and petrochemical engineering [1]. A wide variety of
NieCreFe based superalloys have been developed so far. For
instance, Inconel 718 is used as a precipitation-strengthened alloy
with Mo, Nb, Ti, and Al as alloying additions [2]. On the other hand,
binary and multicomponent NieNb based alloys have been exten-
sively investigated under the conditions to form non-crystalline
structures. An example is the Ni62Nb38 (at%) glass former alloy [3].
* Corresponding author.
** Corresponding author.
E-mail address: spinelli@ufscar.br (J.E. Spinelli).
mechanical properties (e.g., high strength and suitable ductility),
high thermal stability and excellent corrosion resistance [4].
Additionally, ferromagnetic Fe, Co, and Ni-based multicomponent
amorphizable alloys, can reach the glassy state in micrometric
powders (size range of a few microns up to 500 mm) when sub-
mitted to rapid solidification processing routes such as gas atomi-
zation [5,6], in millimetric range pieces when cast by using copper
mold material [4], in hundreds of microns thick when coated by
laser cladding [6] and ribbons by melt-spinning [7]. All these pro-
cessing routes become viable to produce metallic glasses for cool-
ing rates from 103 to 106 K/s [6,7].
Ni based superalloys which do not achieve conditions to form
glassy solid tends to form a crystalline Ni-fcc matrix surrounded
with Ni þ Ni3Nb eutectic. The body-centered tetragonal (bct) g00 -
Ni3Nb intermetallic particles may compete with the equilibrium

https://doi.org/10.1016/j.jallcom.2020.154529
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2 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529
orthorhombic d-Ni3Nb particles as well as with the (Fe,Cr)2Nb Laves
phase. For instance, it has been observed that d - Ni3Nb grows at
expense of g00 - Ni3Nb in Inconel-625 and 718, after aging treatment
[8,9].
Even though NieNb alloys have been extensively investigated
over the past decades regarding thermodynamics, phase diagram
and heat treatment; as-solidified microstructures and properties
generated under non-equilibrium conditions remain undetermined
for this alloy system. There is also a lack of studies addressing the
microstructural aspects arising from the rapid solidification of the
binary NieNb alloys for an extended Nb composition range. Most of
the studied alloys with emphasis on microstructure and properties
consist of commercial Ni-based superalloys such as Inconel 625 and
718, among others with Nb contents up to 6.5 wt% [1]. On the other
hand, it can be found some literature devoted to BMG with high
contents of Nb around 30 to 40 at. % [3,4,10]. Leonhardt et al. [10]
levitated Ni84Nb16 (at.%) eutectic drops by means of electromag-
netic experiments. Such investigation demonstrated that lamellar
morphology in gas-cooled samples with small undercooling (i.e.,
slow cooling) preceding solidification may be replaced by a den-
dritic microstructure in quenched samples beyond a relatively
moderate undercooling of 30 K. In sum, the coupled eutectic
transitions into primary supersaturated a-Ni dendrite growth for
undercooling higher than 30 K.
Li and co-authors [11,12], in its turn, performed directional so-
lidification experiments using a Bridgman vertical vacuum furnace.
For conditions near to the thermodynamic equilibrium, that is,
pulling velocity of 1 mm/s (and temperature gradient of 160 K/cm),
complete coupled growth eutectic of the hypereutectic Ni-24.19 wt
% Nb alloy was observed. However, as the pulling velocity was
increased to 2 mm/s, primary Ni3Nb plate dendrites and coupled
growth eutectic microstructure appeared forming the
Fig. 1. NieNb equilibrium phase diagram. E1 and E2 refer to the two eutectic reactions which are associated with the tested NieNb alloys (dashed vertical lines) in the present
study.
microstructure.
NieNb superalloys have attracted attention due to their
outstanding high strength at temperatures close to their melting
points [11e14]. Most of these investigations are focused on the
eutectic composition of NieNi3Nb alloy, due to the high tendency to
form coupled growth microstructures. In contrast, off-eutectic
NieNi3Nb chemistries received less attention since lower growth
velocity is necessary to keep a planar interface growth, which is
considered a limitation to produce eutectic composites. However,
fast cooling conditions may propitiate interesting combination of a-
Ni and eutectic mixture proportions, which may facilitate adapt-
ability of functional properties to be attained for a certain alloy
composition. Furthermore, the effects of Nb variation in the
corrosion behavior of NieNb alloys remain undetermined, to the
best of the authors’ knowledge.
In the current study, NieNb samples were generated by arc
melting. The aim of this research is to characterize a broad range of
chemistries of rapidly solidified NieNb alloys so that microstruc-
tures, hardnesses and corrosion resistances could be compared to
each other. Such a study will form the basis for understanding the
contributions of Nb variations in the microstructures and functional
properties of rapidly solidified NieNb alloys. It is essential notice
that microstructure in the examined alloys can be designed and
realized flexibly by regulating the proportions of the different
phases within the eutectic mixture.
2. Experimental procedure
The NieNb system is characterized by two eutectic reactions
(termed E1: 22.5 wt % Nb and E2: 52 wt % Nb) and three Ni3Nb,
Ni6Nb7 and Ni8Nb intermetallics, being the later barely reported in
literature. Eight Ni-xNb alloy compositions (x ¼ 10, 15, 20, 30, 40,
 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529 3

45, 52 and 57 wt %) were produced by arc-melting under argon

atmosphere by using 99.9 wt% pure Ni and 99.95 wt% pure Nb. The
selection of these alloys was based on the analysis of the NieNb
equilibrium phase diagram as can be seen in Fig. 1. According to
the observed fields and their prevalent phases, the NieNb alloys of
interest were divided into two groups, named E1: x ¼ 10%, 15%, 20%
and 30% Nb and E2: x ¼ 40%, 45%, 52% and 57% Nb. E1 and E2 were
placed after eutectics 1 and 2, as illustrated in Fig. 1. Samples were
cross-sectionally cut, metallographicaly prepared and character-
ized by scanning electron microscopy (SEM) with a FEI Inspect S50
coupled to an X-ray energy dispersive spectroscopy (EDS) as well as
with a Phillips XL-30 FEG coupled to a BRUKER X-ray energy
dispersive spectroscopy (EDS). X-ray diffraction (XRD) was per-
formed using a Siemens D5005 diffractometer and Cu-Ka radiation
to confirm the formation of equilibrium and non-equilibrium
phases. A 2-theta range from 20 to 90 (BraggeBrentano reflec-
tion geometry with Cu-Ka radiation; l ¼ 1.5418 Å) was used. The
XRD patterns were compared with crystallographic JCPDS [15] and
ICPS [16] data, to index all the phases forming the microstructures.
The NieNb samples were also submitted to Vickers microhardness
(HV) measurements, using a Shimadzu HMV-G 20ST equipment
with a load of 300 g for 15 s. Localized corrosion tests were per-
formed by means of potentiodynamic polarization, according to
ASTM standard G61-86 [17].
Polarization measurements were carried out using a Gamry
Reference 3000 electrochemical system and a standard three-
electrode electrochemical cell with a platinum plate counter-
electrode and a KCl - saturated Ag/AgCl reference electrode (Ag/
AgCl). All the runs were taken at 25  C in a naturally aerated so-
lution of 0.6 M NaCl. To ensure good reproducibility, a minimum of
three curves were recorded for each sample and the average values
were considered. Before taking the polarization measurements, the
NieNb samples were polished mechanically up to 1 mm (mirror
finish), washed in distilled water, immersed in the test solution and
then subjected to open circuit conditions until a steady-state po-
tential was reached. This procedure was accomplished in 60 min
and the potential value obtained was considered the open-circuit
potential (EOC). Potentiodynamic polarization was carried out at
sweep rates of 1 mV/s, starting from a potential of 400 mV below
EOC, to a potential at which the current density reached 1 mA/cm2. Fig. 2. XRD patterns for the rapidly solidified (a) E1: Ni-10, 15, 20 and 30% Nb and (b)
E2: Ni-40, 45, 52 and 57% Nb alloys.
The exposed area of the sample to the solution was 0.2 cm2. The
corrosion current density (icorr) was determined by means of the
extrapolation of cathodic and anodic Tafel slopes back to the Ni3Nb and m - Ni6Nb7 intermetallic phases. As illustrated in Fig. 2(a),
corrosion potential (Ecorr) [18]. The pitting potential (Epit) was Ni-fcc pattern appears in the Nie10%Nb, Nie15%Nb and Nie20%Nb
considered as the potential in which a value of 10 mA/cm2 in current alloys. The d - Ni3Nb and g00 -Ni3Nb phases were both clearly identify
density was exceeded [19]. constituting only the Nie20%Nb alloy, being such occurrence firstly
The as-cast sample of the Nie20%Nb alloy was chosen to be reported in the literature. Besides Ni-fcc (g) and g00 -Ni3Nb, d - Ni3Nb
advanced characterized due to the coexistence of two morphol- intermetallic particles were identified for the Nie30%Nb alloy. On
ogies within the interdendritic regions. A 20 mm-thick thin sample the other hand, the peaks related to the g00 -Ni3Nb and m - Ni6Nb7
was extracted by means of a focused ion beam (FIB), Zeiss Auriga phases may be associated with the Nie40%Nb, Nie45%Nb, Nie52%
dual beam microscope. The analyses were carried out using a TEM Nb and Nie57%Nb alloys, as shown in Fig. 2(b).
Tecnai FEI G2 F20 microscope. It is equipped with a field emission Characteristic microstructures of the rapidly solidified NieNb
gun (FEG), coupled to energy dispersive spectroscopy (EDS) alloys are shown in Fig. 3 and Fig. 4. The darker regions in Fig. 3
microanalysis detector EDAX DX-4. Furthermore, the following are the pro-eutectic Ni-fcc phase, while the interdendritic pre-
image modes were considered: high resolution TEM (HRTEM), cipitates (lighter regions) were identified as the Ni3Nb interme-
scanning-transmission (STEM) in high angle annular dark field tallic. From this visual examination, the microstructures of the
(HAADF), with a Fischione Model 3000 detector of Z-contrast hypoeutectic Nie10%Nb, Nie15%Nb and Nie20%Nb alloys displayed
images. a pro-eutectic Ni phase and a (Ni þ Ni3Nb) eutectic structure.
Considering that dendritic arrangements were formed, primary
3. Results and discussion dendritic/cell spacing variation with cooling rate was analyzed for
the rapid solidified hypoeutectic Ni-10, 15 and 20% Nb alloys and
3.1. Microstructures and related cooling rates compared with the plots furnished by Ghosh and co-authors [20].
Cooling rates corresponding to the investigated samples have been
n
The XRD plots in Fig. 2 depict the phases detected for all NieNb estimated using the relationship: l1 ¼ AT_ established between
alloys, showing peaks related to g-Ni (fcc matrix), d - Ni3Nb, g00 -
4 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529
Fig. 3. SEM images in BSE mode of the rapidly solidified alloys considering both hypoeutectic and hypereutectic compositions related to the eutectic group E1: (a) Nie10%Nb, (b)
Nie15%Nb (wt.%), (c) Nie20%Nb and (d) Nie30%Nb.
the dendritic/cell spacing and the cooling rate (T). _ A and n are
demonstrated to be 800 and 0.57 respectively [20]. Table 1 gives a
summary of the estimated cooling rates corresponding to the each
of the examined chemistries. Higher Nb content induced lower
microstructural spacing in NieNb alloys if considered the solute
range from 10% to 20% of Nb. This is due to the change in cooling
rate as a result of increasing Nb.
It is well accepted in the literature that primary arm spacing or
cell spacing tends to decrease as cooling rate increases, either for
steady or unsteady growth conditions [21,22]. On the other hand,
some disagreement regarding the influence of the initial alloy
composition on primary spacing can be found in literature [23e25].
In the majority of cases l1 increases as initial alloy composition (for
hypoeutectic alloys) decreases. This was demonstrated with the
hypoeutectic NieNb alloys.
Another microstructural feature could be observed in Fig. 3. For
the Nie20%Nb alloy, the g"-Ni3Nb intermetallic exhibits irregular
morphologies as shown in the inset image in Fig. 3(c). Despite the
observation of needle-like and irregular morphologies, it appears
that dNi3Nb needles predominated. This suggests that further
advanced characterization is necessary to verify nature and crys-
talline structure associated with each of these morphologies. This
will be the target in ‘subsection 3.2’ of this research work.
Phases having similar morphologies with those found here were
already observed in previous researches with nickel based super-
alloys as Inconel 625 and 718, i.e., g00 -Ni3Nb and d-Ni3Nb phases.
According to the literature, superalloys characterized by high Nb/
(Ti þ Al) ratios and aging treatments between 600  C and 1000  C
for up to 200 h tend to promote the growth of the orthorhombic d-
Ni3Nb phase, which forms as coarse platelets or fine needles
[8,9,11]. As shown previously in the XRD patterns, d-Ni3Nb phase
was identified in the Nie20%Nb alloy. This is in perfect agreement
with the morphology stressed in the literature. It is important to
highlight that the needle-like d-Ni3Nb phase grew probably due to
rapid solidification conditions, without need of heat treatment. The
d-Ni3Nb phase is found to coexist with the irregular plate-shaped
g00 -Ni3Nb.
Even considering that the Ni solid solution and the Ni3Nb phase
define the character of the terminal equilibrium phases, the hy-
pereutectic Nie30%Nb alloy is described by a very distinct micro-
structure as can be seen in Fig. 3(d). This is explained by the first
formation of the Ni3Nb phase as the primary phase involved by the
eutectic mixture. The growth of faceted Ni3Nb dendrites can be
clearly seen in the inset image in Fig. 3(d). This structure has also
been observed by Li et al. [12]. This is explained by the kind of
eutectic system characterizing NieNb alloys, which is an nf/f
eutectic system (nf: non-faceted; f: faceted). Similar anomalous
broken appearance was reported by Song and Chuang [26], which
observed a faceted character growth of the primary Ag during so-
lidification of BieAg alloys.
Fig. 4 shows Ni3Nb and m-Ni6Nb7 as the terminal phases char-
acterizing the SEM microstructures, which are related to the
eutectic E2. The solidification behavior of these alloys is completely
distinct from that observed for the alloys having lower than 30% of
Nb.
The microstructures associated with the Ni-40% and 45%Nb al-
loys exhibited darker regions, which refer to the Ni3Nb and lighter
areas corresponding with the eutectic Ni3Nb þ m-Ni6Nb7. A dual-
 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529 5

Fig. 4. SEM images in BSE mode of the rapidly solidified alloys considering both hypoeutectic and hypereutectic compositions related to the eutectic group E2: (a) Nie40%Nb, (b)
Nie45%Nb (wt.%), (c) Nie52%Nb and (d) Nie57%Nb.

Table 1
Summary of the cooling rates corresponding to the arc-melted NieNb alloys.

Hypoeutectic alloy Primary/cell spacing, l1 (mm) Cooling rate (K.s1)

Nie10%Nb 17.5 820

Nie15%Nb 15.2 1050
Nie20%Nb 11.5 1700

phase microstructure can be seen in Fig. 4(c) for the arc-melted

Nie52%Nb alloy sample. It consists of lamellar and anomalous
eutectic morphologies as demonstrated by Leonhardt et al. [10],
with prevalent growth of lamellae in the present results. It is
important to point out that the Nie52%Nb alloy is considered an
important glass former. In the present investigation, sub-
micrometric size of the eutectic phases has been observed with
the m-Ni6Nb7 lamella having an average size of 0.4 mm. In the case of
the hypereutectic Nie57%Nb alloy, lighter areas correspond with
the primary m-Ni6Nb7 phase (see SEM inset image), in coexistence
with eutectic islands distributed across the microstructure, as can
be observed in Fig. 4(d).

3.2. Advanced characterization of the Nie20%Nb alloy
After assessment by SEM of all tested chemistries, advanced
characterization by TEM has been performed in the Nie20%Nb alloy
samples. This is explained by two reasons. First, these samples were
those solidified at higher cooling rates among the hypoeutectic
alloys pertaining to the E1 group. Second, and more importantly,
those samples showed the presence of either g00 -Ni3Nb or d-Ni3Nb
Fig. 5. SEM image of the Nie20%Nb alloy showing the presence of the needle-like d-
Ni3Nb phase surrounding the irregular g”-Ni3Nb phase embedded into the g-Ni (fcc)
matrix.
eutectic phases having significantly distinct morphologies between
each other.
A representative SEM image of the Nie20%Nb alloy is shown in
Fig. 5. The presence of a substantial number of Ni3Nb intermetallic
6 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529
Fig. 6. Combined TEM bright images in order to show the Nie20Nb alloy’s micro-
structure with an irregular g00 -Ni3Nb intermetallic surrounded by needle-shaped d-
Ni3Nb particles embedded within a Ni-fcc (g) matrix. The inset shows respective
selected area electron diffraction (SAD) of tetragonal g00 -Ni3Nb.
particles can be seen. The interdendritic zones are filled with two
morphologies characterizing the Ni þ Ni3Nb eutectic, which are
parallel needle-like (dashed circles) and irregular plate-like phases
composing the eutectic with the Ni-rich phase.
Fig. 6 shows a montage by using TEM bright field (BF) images in
order to confirm the irregular micrometric g00 -Ni3Nb interdendritic
precipitate surrounded by the needle-shaped d-Ni3Nb intermetallic
phase. The g00 -Ni3Nb occurs in a size range of a few microns up to
10 mm while the needle-like d-Ni3Nb phase occurs in ranges of a
few microns up to 5 mm long and from 50 to 150 nm width, as can
be seen in Fig. 6. The inset in the right upper corner in Fig. 6 shows
the respective selected area electron diffraction (SAD) regarding the
tetragonal g00 -Ni3Nb oriented in [1 1 1]g00 -Ni3Nb zone axis. Interphase
spacing measurements characterizing the eutectic constituent
(between the d-Ni3Nb needles) returned values of around 200 nm.
Fig. 7(a) depicts a high-magnified TEM image detailing the d-
Ni3Nb eutectic phase. The orthorhombic structure of the d-Ni3Nb
Fig. 7. TEM-BF micrograph of the Nie20%Nb alloy showing (a) a detailed view of the d-Ni3Nb and g-Ni phases, together with respective (b) nano beam diffraction (NBD) confirming
the orthorhombic structure of the d-Ni3Nb phase oriented in zone axis [0 1 1]d-Ni3Nb.
oriented in zone axis [0 1 1] is confirmed by using nano beam
diffraction (NBD), as can be seen in Fig. 7 (b). In the case of Nie20%
Nb alloy it was observed that the joint formation of the g00 -Ni3Nb
and d-Ni3Nb intermetallic particles together with g-Ni matrix can
lead to good mechanical properties. This is due to the resulting
average value of 306 HV associated with such alloy. This is much
higher than the values reported for the commercial Ni-based su-
peralloy Inconel 625 (179e250 HV). Silva et al. [27] demonstrated
the occurrence of needle-shape d-Ni3Nb phase after heat treatment
(aged microstructure at 950  C for 10 h), coexisting with Laves
(Cr2Nb) phase for welded Ni-based 625 alloy. In the present
investigation, the concurrent growth of g00 -Ni3Nb and d-Ni3Nb
intermetallic particles is probably due to the very high cooling rates
experienced during cooling stage of the as-solidified Nie20%Nb
alloy. The complex microstructure arrangement is attained without
further treatments.
Fig. 8(a) shows TEM-BF images detailing the eutectic phases as
found close to the border of the RS Nie20%Nb alloy sample. Fig. 8(b)
shows the SAD pattern of both d-Ni3Nb and g-Ni phases within the
eutectic constituent showing a respective orientation relationship
of [-1 -1 0]Ni-fcc//[-1 -1 0]d-Ni3Nb. Fig. 9 (a) shows, in its turn, a
detailed TEM-BF micrograph of the Nie20%Nb sample micro-
structure. It is possible to visualize the irregular g00 -Ni3Nb inter-
metallic surrounded by the g-Ni matrix. The SAD pattern in Fig. 9(b)
of the preceding image in Fig. 9(a) indicates the electron diffraction
pattern of only g-Ni (fcc matrix) oriented in [1 0 1]Ni-fcc zone axis.
Furthermore, a SAD containing both g00 -Ni3Nb and g-Ni phases
together shows the respective [1 0 1]Ni-fcc//[0 0 1]g00 -Ni3Nb orienta-
tion relationship between these phases.
Cortial et al. [28] submitted the Inconel 625 (3.5 wt% Nb) to heat
treatment at temperatures between 750  C and 950  C for about
8 h. It was demonstrated the occurrence of the needle-like phase
precipitation in the interdendritic spaces, but without the presence
of g00 -Ni3Nb. SEM images of the as-welded Inconel 625 alloy did not
show any evidence of the intermetallic d-Ni3Nb in the as-welded
condition. It means that the presence of Ni3Nb needles depends
on the heat treatment. Instead of that, interdendritic phases such as
Laves, MC and M6C were observed in the as welded samples. In
contrast to the present results, both needles and irregular shapes of
the Ni3Nb phase were obtained for as-cast condition according to
the present findings.
Heat treatment precipitation of the d-Ni3Nb phase may possibly
occur from Laves phase dissolution owing to Laves is a rich source
of Ni and Nb (42.6 wt% and 16.2 wt% respectively). Silva et al. [29]
 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529 7

Fig. 8. (a) TEM-BF combined images showing in detail the eutectic constituent (needle-like d-Ni3Nb þ g-Ni matrix) near the boundary of the Nie20%Nb sample; (b) SAD pattern of
both d-Ni3Nb and g-Ni phases showing the respective orientation relationship.

Fig. 9. (a) TEM-BF micrograph detailing the morphology of the irregular g00 -Ni3Nb intermetallic surrounded by the g-Ni matrix; (b) SAD patterns of previous image (Fig. 9(a)) with
focus on the electron diffraction pattern of only g-Ni oriented in the [1 0 1]Ni-fcc zone axis; and (c) SAD of both g00 -Ni3Nb and g-Ni phases showing the respective orientation
relationship.

demonstrated the formation of needle-shaped d phase after 8, 12
and 24 h of aging of a Ni-based superalloy (Inconel 718, according to
the given chemical composition) with 5.2 wt% Nb [29]. The needles
were distributed at the grain boundaries. Further, the formation d-
Ni3Nb particles having spherical morphology within the grains was
also observed. They reported that after 12 h of heat treatment the
spherical precipitates transformed into the needle-like morphology
and extended into the grains and so the former needles which
migrated from the grain boundaries. Finally after 24 h of aging, the
needles size became longer and resulted uniformly distributed into
the matrix. It was also observed an increment in the density of
needles. In a recent work carried out by Silva et al. [27] it was found
that after 10 h of aging treatment at 950  C in an Inconel 625
coating (3.53 wt% Nb), d-Ni3Nb intermetallic particles having
needle-shaped morphology formed in the interdendritic region.
The needles formed due to enrichment in Nb in the interden-
dritic region owing to Laves phase dissolution which improved
interdendritic level of microsegregation. According to the NieNb
equilibrium diagram (see Fig. 1), the chemical composition of the
Ni3Nb phase is between 33.1 and 36.0 wt% Nb, and a rich source of
Nb is necessary to promote its formation but it appears to be not
enough condition to form its orthorhombic d-Ni3Nb structure.
Even though d-Ni3Nb phase may appear in Inconel alloys after
several hours of aging treatment at expense of a Nb-rich phase
dissolution (e.g. Laves Cr2Nb phase), in the present research work
the Nie20%Nb alloy shows the d-Ni3Nb phase in the as-cast (rapid
solidification) state, which is not commonly found. This can be
explained due to the rapid solidification (metastable) conditions.
This state leads to a rejection of Nb from the matrix so that the
growth of the d-Ni3Nb phase could be possible. As can be seen,
8 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529

Table 2
Vickers microhardness measured for the rapidly solidified NieNb alloys correlated with the formed phases and resulting morphologies.

Alloy (wt.%) Identified Phases (SEM þ XRD) Phase’s Vickers Microhardness (HV0.3)
Morphology

pure Ni [ Ni-fcc e 70
Nie10Nb [ Ni-fcc (solid solution) Dendritic (g-Ni) 179 ± 8
Nie15Nb [ Ni-fcc þ Y g00 -Ni3Nb (Hypoeutectic E1) Dendritic (g-Ni)/Irregular g00 -Ni3Nb 193 ± 2
Nie20Nb [(g00 -Ni3Nb þ d-Ni3Nb) þ Y Ni-fcc Dendritic (g-Ni)/Irregular g00 /Needle d 306 ± 6
(Hypoeutectic E1)
Nie30Nb [d-Ni3Nb þ Y Ni-fcc (Hypereutectic E1) Dendritic d/Eutectic (g-Ni þ d-Ni3Nb) 413 ± 22
Nie40Nb [ g00 -Ni3Nb þ Y Ni6Nb7 (Hypoeutectic E2) g00 -Ni3Nb plates/Lamellar Eutectic (Ni3Nb þ Ni6Nb7) 572 ± 42
Nie45Nb [ Ni6Nb7 þ Y g00 -Ni3Nb (Hypoeutectic E2) g00 -Ni3Nb plates/Lamellar Eutectic (Ni3Nb þ Ni6Nb7) 682 ± 40
Nie52Nb [ Ni6Nb7 þ Y g00 -Ni3Nb (Eutectic E2) Lamellar Eutectic 863 ± 34
Nie57Nb [ Ni6Nb7 þ Y g00 -Ni3Nb (Hypereutectic E2) Ni6Nb7 plates/Lamellar Eutectic (Ni3Nb þ Ni6Nb7) 758 ± 44
Inconel 625 [29] Ni-fcc þ NbC þ Cr23C6 Dendritic 179 to 250

“Arrows” indicate the qualitative tendencies observed for the phase fractions in each alloy.

there is a coexistence of both, g00 -Ni3Nb and d-Ni3Nb, however, in throughout the microstructure, higher microhardness can be ex-
the as-cast state (see Figs. 5 and 6), in many cases, it can be pected, as it is the case for the Nie20%Nb alloy sample (average
observed that irregular morphologies are shaped by a set of plates. microhardness of 306 HV).
On the other hand, the d-Ni3Nb needle-like precipitates overlapped The Ni-10, 15%Nb alloys samples exhibit a predominance of Ni-
with the g00 -Ni3Nb particles. fcc matrix, the Nie20%Nb alloy exhibit g-Ni þ d-Ni3Nb eutectic
Sundararaman et al. [8] carried out a comprehensive study combined with intermetallic g00 -Ni3Nb (irregular phase) as
examining the precipitation of the d-Ni3Nb phase in Inconel 625 observed in Figs. 6 and 7, nonetheless the Nie30%Nb alloy sample
and 718 alloys, with special attention to its nucleation mode, presents a primary Ni3Nb matrix with interdendritic g-Ni þ d-
morphology, distribution and crystallography in samples submitted
to aging treatment in the range from 750  C to 950  C. They found
that g00 -Ni3Nb (D022) precedes d-Ni3Nb (D0a) precipitation in
temperatures below 900  C for the Inconel 718 and below 800  C
for the Inconel 625. These authors explained that, based on lattice
geometry, d structure can be generated by the introduction of
stacking faults in the g00 -Ni3Nb structure. As can be observed in the
present results, since the samples were produced by rapid solidi-
fication, it can be suggested that the d-Ni3Nb can nucleate on
stacking faults within pre-existing g00 -Ni3Nb precipitates. Other-
wise, at higher temperatures, d-Ni3Nb precipitates directly from the
austenitic matrix. Sundararaman et al. [8] also pointed out that all
Ni-based superalloys with g00 (D022) precipitation are susceptible
to d (D0a) formation, being a great quantity of Fe and Nb required to
form g00 -Ni3Nb.

3.3. Hardness and corrosion resistance of the NieNb alloys

Table 2 shows a synthesis containing the prevailing phases and

morphologies found for each tested composition. There is a sig-
nificant and progressive increment in Vickers microhardness as
function of Nb increase in the rapidly solidified NieNb alloys, as can
be seen in Table 2. At first, this increment in hardness is expected,
since Nb is one of the principal solid solution strengtheners in su-
peralloys [2]. Also, the hardness values can be attributed to the
presence of the intermetallics, that is, the increase in strength is
mainly connected with the type and nature of the formed inter-
metallic phases, as function of the Nb content.
Microhardness values associated with the Nie10%Nb and Ni-
15% Nb alloys are 179 ± 8 and 193 ± 2 HV respectively. Is impor-
tant to point out that these values remain inside the microhardness
range typically reported for the Ni based Inconel 625 superalloy
(between 179 and 250 HV), despite its lower Nb content
(3.15e4.15 wt%). The rapid solidification conditions produced finer
eutectic phases in the interdendritic regions of the Ni-15% Nb alloy
when compared with the alloy containing 10% Nb (Fig. 3(a) and (b)).
Moreover, smaller cell/dendritic spacings, as observed in the Ni-
15% Nb alloy, also contribute to a more extensive distribution of
the second phases (i.e., eutectic) and this explains its higher Fig. 10. (a) Potentiodynamic polarization curves and (b) passive range plots obtained
microhardness. Indeed, when hard particles are better distributed from the corrosion tests of the NieNb alloys in 0.6 M NaCl solution.
 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529
Ni3Nb eutectic. The related microhardness is 413 HV. Two principal
factors justifies such increase in hardness: the higher fraction of the
hard Ni3Nb phase throughout the microstructure and the size of the
Ni3Nb intermetallic, which is rather coarse, as observed in Fig. 3(d).
The Nie40%Nb and Nie45%Nb alloys are constituted by the primary
Ni3Nb coexisting with the eutectic Ni3Nb þ Ni6Nb7. The morphol-
ogies of the phases in both alloys are quite similar, however the
microhardness in the Nie45%Nb alloy is higher, due to the pro-
portion of the Ni6Nb7 intermetallic associated to it, as can be seen in
Fig. 4. This is explained basically on the knowledge of the hardness
of the phases. The Ni6Nb7 intermetallic phase has a higher hardness
(~758 HV) than that characterizing the Ni3Nb (~413 HV). Such
values were obtained from the current microstructures in which
the size of the phases permitted individual measurements on the
phases of interest. Further increment in Nb (i.e., 57%) did not result
effective to promote a higher microhardness, since stability was
recognized in the attained values for the Ni-52 and 57%Nb alloys.
This could be indicating that this property tends to remain stable in
this compositional range.
Fig. 10 (a) shows the representative potentiodynamic polariza-
tion curves of the NieNb alloys in 0.6 M NaCl solution. It is worth
noting that the alloys displayed a similar polarization behavior,
exhibiting potential-current curves typical of passive metals in a
chloride environment, which were characterized by: (i) a very low
corrosion current density (icorr) values (not exceeding 1 mA/cm2)
due to the effective oxygen diffusion barrier provided by the pas-
sive film on the alloys; (ii) an increase in current density at higher
electrode potentials due to the localized breakdown of the passive
film or transpassive dissolution (and/or oxygen evolution). How-
ever, the anodic behavior was different both in terms of Ecorr and
Epit parameters if compared the different alloy chemistries. This can
be attributed not only to the very distinct contents of Nb but also to
their resulting microstructures. It is essential to highlight that Nb is
not the only possibility to control corrosion in Ni-based alloys. Most
of the corrosion resistant nickel-based alloys contain molybdenum
Fig. 11. SEM images showing surface degradation after corrosion tests observed in the rapidly solidified alloys, where the pitting occurred preferentially in the Ni-fcc matrix: (a)
Nie10%Nb, (b) Nie15%Nb (wt.%), (c) Nie20%Nb and (d) Nie30%Nb alloys.
9
(Mo) which imparts resistance to environments such as the halide
acids (HCl, HBr and HF) and sulfuric acid, for example [30,31].
In addition, it is also evident, from this plot [Fig. 10 (a)], that the
polarization curves of Ni alloys with Nb content lower than 30%
exhibited a very limited passive range and a sharp rise in current
density due to the breakdown of passive film. This marked current
density increase during anodic scan for Nie10%Nb, Nie15%Nb, and
Nie20%Nb alloys is a characteristic behavior of pitting corrosion,
which occurrence was microscopically confirmed after the tests
(see Fig. 11(a-c)). On the other hand, Ni alloys with Nb contents
30% presented a well-defined and stable passive region until
potentials as high as 1600 mVAg/AgCl. The resulting corroded surface
of the Nie30%Nb alloy is shown in Fig. 11(d). In these alloys, the
current density increased slowly at high potentials, which cannot
be associated with the passive layer localized breakdown, since
there was no evidence of pitting occurrence in these samples after
the polarization tests. This increase in the current density can be
attributed to transpassive dissolution and/or oxidation of water to
form oxygen [32,33]. In addition, one can observe that the higher
the Nb content, the greater the stability of the passive film.
Table 3 describes the Ecorr and Epit parameters determined from
the potentiodynamic polarization curves. Although alloys with Nb
content 30% did not show pitting corrosion attack, the potential
values in which current density exceeded 10 mA/cm2 were taken as
“Epit values” simply for comparison purpose.
It can be noted that, as the Nb content increased, there was a
decrease in the Ecorr value of the alloys making them more active.
At the same time, there was an increase in the passive film stability
of the alloys, which was indicated by more noble values of Epit. This
behavior resulted in excellent localized corrosion resistance, which
can be measured by the extension of the passive range
(Dpassive ¼ Epit - Ecorr), as shown in Fig. 10 (b). For comparison
purpose of localized corrosion performance of NieNb alloys with
that of standard corrosion-resistant alloys, the typical passive range
of a type-304 austenitic stainless steel (SS 304) and an Inconel 625
10 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529

Table 3 A difference of about 175 mV (Ag/AgCl) can be observed if

Electrochemical parameters derived from polarization measurements of the NieNb compared both the Ni-10 and 52%Nb alloys (wt.%), for instance. This
alloys in 0.6 M NaCl solution.
means a difference of about 51% regarding the Ecorr value. In the
Alloy (wt.%) Ecorr (mVAg/AgCl) Epit (mVAg/AgCl)a case of these alloys, microstructural and chemistry differences are
Nie10%Nb 340 ± 71 58 ± 15b obvious. While the microstructure of the Nie10%Nb alloy is
Nie15%Nb 360 ± 46 55 ± 23b constituted by pro-eutectic Ni phase and a (Ni þ Ni3Nb) eutectic
Nie20%Nb 347 ± 61 431 ± 95b structure, the rapid solidified Nie52%Nb alloy is basically
Nie30%Nb 311 ± 40 1394 ± 90c
composed of lamellar Ni3Nb þ Ni6Nb7 eutectic structures. The Ecorr
Nie40%Nb 373 ± 17 1315 ± 32c
Nie45%Nb 440 ± 7 1424 ± 88c shift as a function of Nb content in Fig. 10 may be due to such
Nie52%Nb 515 ± 44 1516 ± 01c differences. Although Ecorr is roughly diminished as the Nb content
Nie57%Nb 448 ± 37 1566 ± 46c is increased, the same does not occur with the Epit, which oppo-
a
potential where the current density value exceeded 10 mA/cm2. sitely increases.
b
alloy presented pitting corrosion attack after the polarization test. One of the biggest challenges in engineering applications is to
c
alloy did not present pitting corrosion attack after the polarization test. improve a certain property without generating deleterious effects
in another. In this sense, the combined plots in Fig. 12 could allow
the design of an ‘‘ideal’’ range of Nb content. NieNb chemistries
Ni-based superalloy (625) in 0.6 M NaCl solution was also plotted
between 40 and 45 %Nb appear to allow a compromise between
[34e36]. It should be stressed that the passive range of Ni alloys
suitable HV and suitable Ecorr. It is important highlight that such
with up to 20% of Nb is smaller or similar to that of the SS 304
compositions further promote very stable passive film to be
(540 mV). However, for contents 30% of Nb, this range becomes at
formed, and, as a consequence, a remarkable corrosion protection is
least three-fold higher for NieNb alloys when compared to that of
attained. It is also patent that if some specific application is
the SS 304. Also, at least a two-fold increase in the passive range
considered, in which one characteristic should be more significant
was found for these high Nb content alloys in comparison with that
than the other one, this range of composition should be prevented.
of the commercial 625 Ni-based superalloy. These results can be
Contrasting the Nb contents investigated in this work with the
taken as evidence that Nb addition increases the electrochemical
Nb limit of the commercial superalloys of high Nb (~5.3 wt%) is of
stability of passive film, promoting an outstanding corrosion pro-
interest. Some of the NieNb alloys tested here contain 80e85% (in
tection in chloride media for the Ni alloys with Nb content 30%.
weight per cent) of Ni in their chemistries (i.e., Ni-15 and 20%Nb).
These findings are also in good agreement with previously
By way of comparison, nickel-chromium alloy 625 and nickel-iron
published studies [33,37e43]. These researches demonstrated that
alloy 718 contain Ni in lower quantities of 58% and 55% respectively.
the protectiveness of passive film of many metallic alloys is
This means that other alloying elements are necessary constituting
improved with Nb additions. The literature suggests that the
these commercial alloys. Even though much higher Ni content of
improvement on the corrosion behavior takes place because Nb
the tested Nie20%Nb alloy, suitable strength (306 HV), corrosion
modifies the passive film structure formed on the alloy, which in
resistance (Ecorr ¼ 347 mV) and passive range (Dpassive ¼ 778 mV)
turn improves physical barrier to corrosive substances diffusion,
could be achieved. It is worth noting that such properties are
such as chloride ions and oxygen [42]. Also, the reduction of anion
associated with fast cooling conditions without further heat
vacancies in the crystalline lattice, caused by Nb cations presence,
treatment.
make the passive layer more stoichiometric and reinforced, which
In addition, hardness of 572 HV, Ecorr of 373mV and Dpassive of
favour the corrosion resistance increase [38,41].
1688 mV characterized the Nie40%Nb alloy, suggesting it could
Experimental correlations between hardness, Ecorr and Nb
have potential application in the field of coatings. It follows then
content were plotted as depicted in Fig. 12. As can be observed, as
from our work that the arrangement of rapid cooling and Nb
hardness increases Ecorr tends to decrease, despite some scatter
alloying should yield improved and non-degraded mechanical and
fluctuations. In any case, it is evidenced that hardness and Ecorr are
corrosion properties. The determination of other application
inversely proportional. For Nb contents higher than 30%, Ecorr
properties of interest such as ductility and wear resistance is the
values are smaller and the alloys become more active.
subject of research in progress.

4. Conclusions

 Increasing of Nb content in the range from 10% to 20% of Nb

induced lower interdendritic spacing to happen. Furthermore, it
was demonstrated that larger cooling rates occurred thanks to
the increase on Nb alloying. Due to the nf/f nature growth of the
phases forming the E1 NiNb type of eutectic in the atomic level,
anomalous faceted d-Ni3Nb dendrites could be developed for
the Nie30%Nb alloy.
 The combined TEM, SEM and XRD results suggest that the
phases concurrently formed along the interdendritic zones of
the Ni-20% alloy are the g00 -Ni3Nb and the d-Ni3Nb. The mor-
phologies and sizes were assessed through TEM-BF images. The
irregular g00 -Ni3Nb phase occurs in a size range of a few microns
up to 10 mm whereas the needle-like d-Ni3Nb phase occurs in
ranges of a few microns up to 5 mm long and 50e150 nm width.
 The very distinct resulting microstructures permitted important
shifts in the anodic behaviors given by the polarization curves.
Fig. 12. Experimental correlations between average corrosion potential and average For Nb contents higher than 30% a stable passive region was
hardness with the Nb content for the rapidly solidified NieNb alloys. formed with no evidences of damage by pitting corrosion. For
 C.R.M. Afonso et al. / Journal of Alloys and Compounds 829 (2020) 154529
these high Nb content alloys, the passive range was demon-
strated to be at least two-fold higher when compared to that of
the commercial 625 Ni-based superalloy.
 Although increase of approximately 5 times in the Nb contain-
ing of the rapidly solidified NieNb alloys induces an increase of
about 5 times in the hardness, the high Nb content alloy is
associated with a decrease of about 50% in the corrosion po-
tential. As such, the control of hardness, passivability and Ecorr
properties of the rapidly solidified NieNb alloys can be metal-
lurgically accomplished. The main factor contributing to such
management of properties remains in the variety of micro-
structural scales and morphologies possibly happening in the
binary NieNb alloys.
Data availability
The raw/processed data required to reproduce these findings
cannot be shared at this time as the data also forms part of an
ongoing study.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
None.
CRediT authorship contribution statement
Conrado R.M. Afonso: Data curation, Formal analysis, Writing -
review & editing, Supervision. Katherine Martinez-Orozco: Data
curation, Formal analysis, Writing - original draft. Vicente Amigo
:
Writing - review & editing. Carlos A. Della Rovere: Writing - re-

E. Spinelli: Formal analysis, Writing - review &
view & editing. Jose
editing. Claudio S. Kiminami: Funding acquisition.
Acknowledgements
The authors are grateful to FAPESP (Sa ~o Paulo State Research
Foundation) Brazil, “Projeto Tema
tico” #2013/05987-8 for their
financial support. The authors would like to thank CBMM (Com-
panhia Brasileira de Metalurgia e Mineraça~o) for the donation of Ni-
Nb master alloy for tests. This study was financed in part by the
Coordenaç~ ao de Aperfeiçoamento de Pessoal de Nível Superior -
Brasil (CAPES) - Finance Code 001.
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