Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎

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Progress in Aerospace Sciences

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

Advances in processing of NiAl intermetallic alloys and composites for

high temperature aerospace applications
Kamil Bochenek, Michal Basista n
Institute of Fundamental Technological Research, Polish Academy of Sciences, Pawinskiego 5B, 02-106 Warsaw, Poland

art ic l e i nf o a b s t r a c t

Article history: Over the last few decades intermetallic compounds such as NiAl have been considered as potential high
Received 17 July 2015 temperature structural materials for aerospace industry. A large number of investigations have been
Received in revised form reported describing complex fabrication routes, introducing various reinforcing/alloying elements along
15 September 2015
with theoretical analyses. These research works were mainly focused on the overcoming of main dis-
Accepted 16 September 2015
advantage of nickel aluminides that still restricts their application range, i.e. brittleness at room tem-
perature. In this paper we present an overview of research on NiAl processing and indicate methods that
Keywords: are promising in solving the low fracture toughness issue at room temperature. Other material properties
Nickel aluminide relevant for high temperature applications are also addressed. The analysis is primarily done from the
Intermetallics
perspective of NiAl application in aero engines in temperature regimes from room up to the operating
Turbine blades
temperature (over 1150 °C) of turbine blades.
Fracture toughness
Manufacturing techniques & 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Physical properties of NiAl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Methods of improvement of NiAl fracture toughness and ductility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Ductile phase toughening – the main field of current design methodology for NiAl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1.1. NiAl–Cr–Mo alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1.2. Overview of other modifications of NiAl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2. Other toughening mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2.1. Martensitic transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2.2. Heat treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Mechanical parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

1. Introduction
The NiAl intermetallic compounds have attracted industry's
attention as potential high temperature light-weight (5.9 g/cm3)
materials to replace nickel-base superalloys due to an exceptional
combination of high strength and low specific weight, thermal
stability, high thermal conductivity (76 W/mK) and good oxida-
tion/corrosion resistance up to 1400 °C [1,2], combined with its
ability to retain strength and stiffness at high temperature [3]. The
melting point of NiAl was determined by differential thermal
analysis (DTA) as 1676 °C [4], which is in perfect agreement with
the theoretical value (1676 °C) obtained from thermodynamic
calculations [5], cf. Fig. 1. Some papers provide the value of
1638 °C, which is assessed from the binary phase diagram of NiAl,
[6]. Intensive studies of the mechanical and physical properties of
NiAl have led to many suggestions for potential structural and

n
Corresponding author.
E-mail address: mbasista@ippt.pan.pl (M. Basista).

http://dx.doi.org/10.1016/j.paerosci.2015.09.003
0376-0421/& 2015 Elsevier Ltd. All rights reserved.

Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
2 K. Bochenek, M. Basista / Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎
Fig. 1. Binary Al–Ni phase diagram. Redrawn from [5].
non-structural applications of this material, such as jet engine
hardware, energy conversion (i.e. stationary gas turbines of power
plants), internal combustion engines and heat exchangers [7–9]. A
study of NiAl stability under heavy ion bombardment at very low
temperatures (
258 °C) where NiAl structure is not disordered
was also conducted [10]. However, it is well-known that the main
reason limiting this material's application in aerospace industry is
related to its low fracture toughness and low ductility at room
temperature [11,12].
A significant effort has been made during the last two decades
to improve the properties, processing and design methodology of
NiAl and its alloys. This includes attempts to alter the slip behavior
by powder preparation route, mechanical alloying, fine grain
toughening, ductile phase toughening, martensitic phase trans-
formation toughening and heat treatment. Unfortunately, up to
now applicability of this intermetallic material is still limited. La-
salmonie et al. [11] in 2000 stated that applying NiAl to a gas
turbine blade is too costly in addition to its poor mechanical
properties at room temperature. Darolia et al. [13–16] tested NiAl
alloys (research was performed on binary NiAl, single crystal alloys
AFN-12, AFN-20 and NiAl eutectic 33Cr–1Mo alloy) as turbine
engine blades, vanes and combustor shingles (Fig. 2). It was con-
cluded that NiAl panels would not survive real in-service condi-
tions for turbine blades at impact speeds near 300 m/s, where
catastrophic failures were observed. On the other hand at lower
impact speeds (e.g. 137 m/s), which are referred to vanes (Fig. 3),
NiAl alloy shows no damage in most conditions although in certain
cases larger particles can cause crack initiation. In the case of
combustor application, it was observed that even at impact
Fig. 2. Engine tested NiAl HPT nozzle vanes. Reproduced from [13] with the per-
mission of publisher.
Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
Fig. 3. NiAl HPT vane assembly (attached to inner and outer bands of an Ni-base
superalloy). Reproduced from [13] with the permission of publisher.
conditions higher than in a typical combustor both NiAl alloys
survived without any failures [17,18].
In 2004, Kanlayasiri et al. [19] invented a functional parallel-
flow NiAl microchannel array for high-temperature applications.
Frommeyer et al. [7] in 2008 developed and characterized NiAl-
base materials for structural applications in energy conversion
systems. Current trend is to focus also on implementation of nickel
aluminides as thermal barrier coatings for nickel based superalloys
[20,21]. Moreover, after downgrading of the scientific reports on
NiAl bulk material development in the beginning of the 21st
century, over the last few years one could observe that these
materials are regaining more and more attention stimulated by the
growing need for advanced material solutions in the aerospace
industry. This growing interest was reinforced by promising re-
sults furnished recently by mathematical modeling of the ductile
phase toughening of NiAl [22–24].
There are few other materials that may also replace nickel-base
superalloys i.e. niobium silicides, molybdenum borosilicides and
iridium-based superalloys [25–29]. However, similarly as for NiAl
based materials there are advantages and disadvantages of their
use. It is worth mentioning that another intermetallic compound,
TiAl, has successfully been applied as a material for low-pressure
turbine (LPT) blades since 2006 by General Electric [30], whereas
in 2000 [11] the use of TiAl was under the question mark. Today
this material is still being improved [31–33] and its applicability is
limited to middle range of the operating temperature (  750°C),
[34].
The purpose of the present paper is to provide a concise ac-
count of the current knowledge in the NiAl development as a
structural material that may be applied for turbine components in
aero engines or in other applications where, till now, the main
factor for rejecting this material was its poor fracture toughness at
room temperature. Other mechanical and physical properties such
us high temperature strength, fatigue or impact resistance should
meet the technical requirements of turbine components to com-
pete with nickel-based superalloys. The most important achieve-
ments in the application of NiAl in turbine engines until the year
2000 was presented by Darolia in [13], which includes one of the
few experimental results of NiAl alloys performance in real
working conditions. Our overview focuses mainly on the most
recent approaches to processing of NiAl intermetallic compounds,
including their composites and alloys, and the processing-struc-
ture-properties relationships. Some essential findings from a more
distant past are also recalled to show the reference state and the
progress in the considered field.
 K. Bochenek, M. Basista / Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎
2. Physical properties of NiAl
The poor ductility of NiAl is derived from B2-ordered structure,
which provides only three independent slip systems. According to
the von Mises criterion five independent slip systems are neces-
sary to achieve satisfying ductile deformation of a polycrystalline
material such as non-ordered metals Al, Fe, Ni or Co and their
alloys. Due to the fact that only three independent slip systems
exist in NiAl, the active deformation mechanisms may not provide
sufficient ductility and toughness as required for application in
aero engine components [7,24]. The brittle intergranular fracture
of polycrystalline NiAl is traced back to insufficient number of
independent slip systems [35]. Consequently, to increase the
ductility of polycrystalline NiAl it is necessary to activate addi-
tional slip systems [36,37].
The low density of NiAl combined with its high thermal con-
ductivity (up to 8 times higher than in Ni-base superalloys) gives
important payoffs in turbine blades application – the weight of the
rotating turbine blade is reduced and the temperature distribution
is much more uniform. These effects may lead to similar engine
durability as with Ni-base superalloys blades, even if the high
temperature strength of NiAl blade is lower [38].
The corrosion and oxidation resistance of NiAl is considered as
good or even excellent at high temperatures (up to 1400 °C) due to
the high content of alumina and formation of α-Al2O3 protective
layer. However, below 1000 °C these “excellent” properties are
exacerbated by the formation of transient oxide which may en-
hance the oxidation rate [2]. Furthermore, in some conditions, for
example in environments containing H2S, the formation of a
protective oxide layer might be hindered [39]. It has also been
proven that the oxidation resistance depends mainly on the
structure of NiAl. Kaplin et al. [40] have shown that conventional
grain sized and nanostructured NiAl samples obtained by cryo-
milling of NiAl feedstock powder and sintered via SPS differ sig-
nificantly in the oxidation rates. Conventional NiAl specimens have
oxidation rates across all tested temperatures of 10
11 g2/cm4/s,
while in nanostructured specimens a decrease in oxidation rates
along with an increase of temperature is observed, e.g. 10
13 g2/
cm4/s at 1050 °C (Fig. 4).
More detailed information about the crystal structure, ordering
behavior and examination of the slip systems along with other
physical properties of NiAl were reviewed by Dey et al. [1]. To
better understand the NiAl behavior Fu et al. [41] investigated
electronic, structural and dynamical properties of a single NiAl
Fig. 4. TGA data for conventional and nanostructured samples oxidized for 24 h in
air at 1050 °C. Reproduced from [40] with the permission of publisher.
Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
3
crystal using the DFT (Density Functional Theory) method and the
Debye model.
3. Methods of improvement of NiAl fracture toughness and
ductility
Numerous attempts have been undertaken to overcome the
NiAl low ductility including thermomechanical processing, micro-
alloying, macro-alloying [42–45] or PVD [46], which have resulted
in obtaining fine-grained materials with increased ductility at
room temperature. A well-known approach in NiAl manufacturing
is the mechanical alloying (MA), which is a solid-state powder
processing technique developed more than 50 years ago to syn-
thesize nickel-base oxide-dispersion strengthened (ODS) super-
alloys that combine the twin effects of precipitation hardening and
dispersion hardening. The mechanical alloying of nanocomposites
was reviewed by Suryanaryana et al. [47]. The first reported NiAl
synthesis by mechanical alloying was done in 1988 by Ivanov et al.
[48]. In 1990 Atzmon et al. [49] investigated reaction during me-
chanical alloying of NiAl, with the final conclusion that NiAl forms
in an explosive, exothermic reaction due to large heat of the in-
termetallic formation. Ur et al. [50] proposed a new processing
route for optimization of high temperature mechanical properties
of NiAl intermetallic with fine grain size through the oxide dis-
persion strengthening (ODS) and secondary recrystallization (SRx).
A review of composite materials prepared by the mechanical al-
loying was presented by Koch et al. [51].
Additionally, preparation of fine-grained material is also a
feasible approach to improve the room-temperature ductility of
materials, since a brittle material may be transformed into a
ductile one by grain refinement [44]. Obtaining nanocrystalline
NiAl intermetallic compounds has been accomplished by a num-
ber of powder metallurgy techniques, including vacuum hot
pressing [52], isostatic hot pressing [53] and spark plasma sin-
tering [54]. The grain growth and kinetics of nanocrystalline NiAl
obtained by mechanical alloying and hot pressing were examined
in [55]. Kubaskia et al. [56] estimated the changes in crystallite size
and the lattice strain of NiAl produced by mechanical alloying in a
planetary ball mill and an attritor mill. One of the best mechanical
properties of MA produced nanocrystalline NiAl sintered by va-
cuum-hot pressing were obtained by Liu et al. [57]. The sintering
temperature for the optimum material properties was set as
1300 °C for 60 min at 25 MPa. Rahaie et al. [58] also using NiAl
obtained by mechanical alloying and consolidated by hot-pressing
determined the sintering process parameters as 1180 °C under a
pressure of 48 MPa for 60 min. The results of both works are
presented in Table 1. Micropyretic synthesis (also known as self-
propagating high temperature synthesis – SHS) was also applied.
The main advantage of this method is almost a near net shape
processing, which is important from the economical point of view
[59].
The above mentioned papers show different techniques of NiAl
preparation: from in-situ created NiAl to the ones obtained from
commercial powders. Unfortunately, all of the described proce-
dures still did not open the way to use of nickel aluminide as a
turbine engine component.
3.1. Ductile phase toughening – the main field of current design
methodology for NiAl
An alternative approach to enhance ductility of NiAl is based on
alloying the intermetallic compound with other elements and to
control its microstructure through a careful preparation route.
Incorporation of a ductile phase in the brittle matrix is a technique
which had been investigated as a means to improve the toughness
4 K. Bochenek, M. Basista / Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎

and ductility. Positive effect on ductility by elemental addition into

Fracture toughness [MPa m ]

NiAl structure was proven by Lu et al. [24] by calculations per-
formed with the CASTEP code (Cambridge Sequential Total Energy
Package) [60]. Moreover, Ponomareva et al. [22] analyzed the ef-
fect of substitutional alloying on brittle vs. ductile behavior of B2–
NiAl–X (X¼Sc, Ti, V, Cr, W, Re, and Co) alloys, examining at the
atomic level the role of interatomic bonding in the ductility en-
hancement. In another article [23], the same authors carried out a

26.15
19.6

10.2

18.4
more detailed study of rhenium admixture influence on elastic
n/a
n/a

n/a
n/a
n/a
n/a

n/a

n/a
9.5
6

properties of B2 NiAl as a follow up of the previous promising

Vickers hardness [HV]

results. Frommeyer et al. [61], determined the site occupancies of

the transition metals – Cr, Fe, and Re dissolved in NiAl stoichio-
metric composition by the atom probe field ion microscopy (AP-
FIM). The results of that study have revealed that ternary alloying
elements have considerable influence on the mechanical and
624.85

physical properties of NiAl. These authors also fabricated NiAl

449
456
550
581
325

322

578
610

n/a
n/a
n/a
n/a
n/a
specimens with addition of refractory metals (Cr, Mo, Re, and W)
showing that NiAl reinforced with 1 at% of rhenium yields the best
Relative density [%]

mechanical properties [7,62,63]. This approach was also used in

[64] to demonstrate that introduction of appropriate rare earth
elements (REEs) can improve the mechanical properties of the
NiAl-base eutectic alloy at room temperature, Fig. 5.
99.73
99.4

95.3
96.3
96.1

n/a
n/a
n/a
n/a
n/a
n/a
n/a
98
92

3.1.1. NiAl–Cr–Mo alloys

Yield strength [MPa]

The NiAl–Cr–Mo system has drawn much attention of re-

1506 (compression)

1496 (compression)
1478 (compression)

1676 (compression)

280 (compression)
333 (compression)

490(compression)

searchers since 1970's when Walter and Cline [65–67] presented

NiAl–Cr–Mo eutectic alloy with Cr substituted by Mo. It resulted in
414 (tension)

a change of phase morphology from chromium rods in the NiAl

matrix to variable lamellar plates when the Mo level exceeded
0.6 at%. Also, the growth direction changed from 〈100〉 to 〈111〉
n/a

n/a

n/a
n/a
n/a

n/a

after molybdenum addition. This phase system enables an increase

Compressive strength (true stress) 560 MPa/true strain 8%

of both the fracture toughness and the creep strength at elevated

temperatures.
Compressive strength 1225 MPa/strain 0.2% offset RT

Once the microstructures had been characterized, Johnson et al.

[68] investigated NiAl–Cr–Mo alloys and their mechanical prop-
Compressive strength 2278 MPa/strain 28.9%

Compressive strength 2520 MPa/strain 19.2%

erties. A directional solidification was used through a containerless

Compressive strength 1900 MPa/strain 9.5%

Compressive strength 2282 MPa/strain 24%

Compressive stress 1974 MPa/strain 14.3%

mode by the electro-magnetically levitated zone process in an

ultrapure helium atmosphere for alloys manufacturing. The frac-
Tensile strength 459 MPa/strain 2%

ture toughness obtained for directionally solidified NiAl–28Cr–

Compressive strength 2117 MPa

6Mo alloys reached 22 MPa m as compared with 6 MPa m ,[58]

n/a (Elastic modulus 179 MPa)

corresponding to the polycrystalline NiAl. NiAl–Cr–Mo alloys are

Compressive ductility 14%
Maximum stress/strain

characterized also by a good combination of room- and elevated

Comparison of mechanical properties of selected NiAl-base alloys and composites.

temperature properties. However, the mechanical properties still

need to be improved to compete with the nickel based superalloys.
The other eutectic composition of Ni–33Al–33Cr–1Mo was in-
vestigated by Yang et al. [69] and later by Whittenberger et al. [70].
In both papers the fracture toughness of alloys obtained by di-
n/a

n/a
n/a

rectional solidification was of a similar level (17 and 16 MPa m ,

respectively). Whittenberger concluded that for higher withdrawal
Nanocrystalline NiAl (MA þHP 1300 °C/1 h/25 MPa) [57]
Nanocrystalline NiAl (MA þHP 1180 °C/1 h/45 MPa) [58]

speeds (above 127 mm/h) the fracture toughness decreased sig-

nificantly (from 16 to 7 MPa m ), which was attributed to the
microstructure transformation from lamellar-type into Cr(Mo) fi-
DS þ HIP þAging NiAl–28Cr–5.5Mo–0.5Hf [102]

bers/grains embedded in the NiAl matrix. In the case of Mo-rich

DS3 NiAl–28Cr–5.94Mo–0.05Hf–0.01Ho [78]

composite (Ni–33Al–31Cr–3Mo) the lamellar structure retained

DS NiAl–Cr(Mo)–(Hf,Dy)–4Fe, H-2 [103]

the faster growth rates. Moreover, it was observed that the inter-
SHS in-situ NiAl (grain 28 mm) [59]
HP NiAl þ10% SiC fibers (vol%) [84]

stitial element content (such as C, O, and N) did not appear to be

MA þHP NiAl þ6%Fe þ2%Mo [90]

the main factor for decreasing the toughness of Mo-modified NiAl

Ultrafine grain NiAl alloy [42]

MA þHP NiAl þ8%Mo2C [92]

composites.
After more than 40 years since the development of NiAl–Cr–Mo
NiAl–Cr–Mo–0.2Hf [72]
NiAl þ0.5 at% Au [91]

eutectic alloys, these materials still attract attention of scientists

NiAl–28Cr–6Mo [68]

NiAl–36Cr–6Mo [83]

due to the most promising properties obtained for NiAl alloys so

far. Cui et al. [71–73] and Guo et al. [74,75] proposed to add haf-
nium to NiAl–Cr–Mo alloys. Two types of alloys were selected:
Material

0.2 and 0.5 (at%) of Hf (Ni–32Al–28Cr–(6
x)Mo–xHf) (x¼ 0.2 and

Table 1

0.5 at%, respectively) manufactured by directional solidification. In

the first composition (0.2Hf) the dendritic structure was observed,

Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
 K. Bochenek, M. Basista / Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 5

Fig. 5. (a) Compressive ductility and (b) Yield strength at RT of all alloys. Reproduced from [64] with the permission of publisher.

Fig. 7. Combined compressive properties of NiAl–28Cr–6Mo–0.15Hf eutectic alloys

with various Ho content. Reproduced from [77] with the permission of publisher.

Fig. 6. True stress–true strain curves of the HT, MT1, MT2 and MT3 alloys at RT
with an initial strain rate of 1.0  10
3 s
1. Reproduced from [76] with the per-
mission of publisher.
while in 0.5Hf alloy the intercellular structure was formed. Addi-
tion of hafnium resulted in an enhancement of the high-tem-
perature strength and the brittle-to-ductile transition temperature
(BDTT) due to a different strengthening mechanism. The ductility
and creep resistance of NiAl–Cr–Mo alloys (Ni–33Al–28Cr–6Mo–
0.2Hf (at%) alloys with different temperature of strong magnetic
field treatments: HT – without SMF treatment, MT1–1 h at
1346 °C, MT2–1 h at 1446 °C and MT3–1 h at 1546 °C) have de-
creased as a result of the cellular structure disturbance caused by
hafnium. After heat treatment in a strong magnetic field a sig-
nificant improvement in creep properties at RT was observed [76],
(Fig. 6). This improvement was caused by a transformation of
hafnium from Heusler phase (Ni2AlHf) into Hf solid solution in
NiAl–Cr(Mo)–0.2Hf alloy.
A more sophisticated composition of NiAl alloy was proposed
by Guo et al. [77]. Following the previous research [64], the au-
thors proposed an addition of a small amount of Ho into NiAl–Cr–
Mo–Hf alloy. The alloys were produced by arc-melting under argon
atmosphere using a non-consumable tungsten electrode. Alloys
were remelted more than five times to obtain a homogeneous
chemical composition. The alloy buttons were homogenized at
1250 °C for 24 h in evacuated silica capsules followed by furnace
cooling to room temperature. The highest improvement of com-
pressive properties was observed when the Ho content was up to
0.1 at% (Fig. 7). The admixture of Ho resulted in a lamellar re-
finement in eutectic cells in NiAl–28NiAl–28Cr–6Mo–0.15Hf alloy.
Along with the increasing Ho content, the eutectic cells got refined
but the intercellular region became coarse. Liang et al. [78] pro-
posed fabrication of a similar NiAl alloy [NiAl–28Cr–5.94Mo–
0.05Hf–0.01Ho (at%)] by the liquid metal cooling technique used
by Johnson [68], with two growth rates (3 and 10 mm/min). The
aligned microstructure was finer and more disturbed at a growth
rate of 10 mm/min than that of 3 mm/min. The yield strength at
1100 °C was similar for the two alloys obtained with the growth
rate of 10 mm/min and 3 mm/min and higher than for an alloy
obtained by the Bridgman technique. This strengthening effect
was due to the better aligned microstructure, a more effective
solid solution strengthening, and the positive influence of Ho. The
fracture toughness of the alloy manufactured at the rate of 3 mm/
min was a little higher than that of 10 mm/min as a result of the
well aligned microstructure. Images of fracture surface after three-
point bending test are presented in Fig. 8.
Recently, a hypereutectic alloy Ni–31Al–32Cr–6Mo was pro-
posed in [79] and [80]. According to the underlying research idea,
in a hypereutectic alloy the volume fraction of toughening phase
increases, the melting point of the alloy may get higher and be
accompanied with an enhancement of mechanical properties.

Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
6 K. Bochenek, M. Basista / Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Fig. 8. SEM second electron images showing surfaces of (a) DS3 and (b) DS10 after the three-point bending tests. Reproduced from [78] with the permission of publisher.

Fig. 9. Fracture morphologies of directionally solidified NiAl–32Cr–6Mo hypereutectic alloy grown at (a) 6 μm s
1; (b)10 μm s
1. Reproduced from [80] with the permission
of publisher.

Moreover, to improve the fracture toughness the authors used the
results of the previous work, where in an off-eutectic alloy the
fully eutectic microstructure was obtained under higher tem-
perature gradient conditions [81,82]. These two features, i.e. the
hypereutectic composition and high temperature gradient may
significantly enhance the room-temperature fracture toughness.
The fracture toughness of Ni–31Al–32Cr–6Mo alloy reached
23.74 MPa m when solidified at 10 mm s
1 and had a planar
eutectic microstructure. In this alloy a quasi-cleavage fracture
mode was observed on the fracture surfaces (Fig. 9).
The highest fracture toughness reported so far (26.15 MPa m )
was obtained for NiAl–36Cr–6Mo hypereutectic alloy directionally
solidified by zone melted liquid metal cooling technique (ZMLMC)
at a withdrawal rate of 10 mm/s and temperature gradient of
600 K/cm [83]. Enhancement of the fracture toughness was a re-
sult of increasing the strengthening phase volume and obtaining a

Fig. 10. Fracture morphologies of directionally solidified NiAl–Cr(Mo) alloy grown at 6 μm/s: (a), (d), (e) NiAl–28Cr–6Mo eutectic alloy; (b) NiAl–32Cr–6Mo hypereutectic
alloy; (c) NiAl–36Cr–6Mo hypereutectic alloy, (LMC). Reproduced from [83] with the permission of publisher.

Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
 K. Bochenek, M. Basista / Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎ 7

well-aligned microstructure with a planar eutectic microstructure

in the hypereutectic alloy (Fig. 10).

3.1.2. Overview of other modifications of NiAl

Azarmi et al. [84] obtained NiAl composites reinforced with SiC
particulates by a hot-pressing technique. It was found out that
higher stiffness of SiC particulates as compared to NiAl matrix and
strong matrix/reinforcement interface properties may contribute
to an increase in creep properties of the reinforced composites.
However, the composite fabrication technique needs to be im-
proved due to the low relative density and poor strengthening
effect of the obtained composites.
It is well known that combination of a nanocrystalline inter-
metallic matrix and a dispersed strengthening phase may result in
an increase of strength at higher temperatures and material duc-
tility [85,86]. For example, Zhou et al. [87] produced a nanocrys-
talline NiAl–TiC powders, where two separate reactions of com-
pound formation occurred simultaneously. A thorough study on
the solid state reaction occurring during this mechanical alloying
process was performed by Krivorutcho et al. [88]. Efforts to in-
crease the mechanical properties of NiAl were also made by
Whittenberger et al. [89] where two different elevated tempera-
ture strengthening mechanisms were investigated. They con-
cluded that ODS (oxide dispersion strengthened) NiAl after cryo-
milling or roasting in nitrogen were not as strong as cryomilled
NiAl containing like amounts of AlN.
Mechanical alloying (MA) was used to fabricate NiAl compo-
sites with addition of refractory metals Fe, Ga and Mo, [90]. The
powders were finally consolidated by the hot pressing technique. Fig. 11. Fracture morphology of NiAl–Mo2C composite (8 wt% Mo). Reproduced
The highest mechanical properties were obtained for a combina- from [92] with the permission of publisher.
tion of transition elements (NiAl þ6%Feþ 2%Mo), and reached the
strain of 19.2%. Specimens were sintered at 1200 °C for 30 min, the
relative density of the sintered material was 96.3%. The values of 3.2.1. Martensitic transformation
strength, strain and yield stress are shown in Table 1. The effect of martensitic transformation of beta-NiAl was stu-
Sheng et al. [91] fabricated NiAl alloys with an addition of Au died in [94–96]. Martensitic transformation may occur in Ni-rich
up to 1 at%. The outcomes from their study were that (i) addition NiAl by rapid cooling (B2 to L10 structure). According to the results
of Au in the NiAl alloy refines the NiAl grains, (ii) a higher content obtained in [96], martensite phase deforms at lower stresses than
of Au results in the formation of α-AlAu2 phase, and (iii) Au ad- B2–NiAl. In [84] the authors investigated the influence of mar-
dition leads to a moderate solid solution strengthening at low tensitic transformation (thermal and stress induced) in NiAl on the
temperatures and strong solid solution strengthening at high fracture toughness. The martensitic transformation influenced the
temperatures. The selected properties of NiAl þ 0.5 at% Au are fracture toughness only in the case of an as-cast inhomogeneous
presented in Table 1. polycrystalline NiAl, where martensitic phase forms irreversibly at
In one of the newest papers Liu et al. [92] proposed an im- crack tips without re-transformation. Kainuma et al. [97] and
provement of high-temperature tribological and mechanical Thompson et al. [98] investigated the influence of ternary ele-
properties of NiAl by an addition of Mo2C. For consolidation the ments on the martensitic transformation of β-NiAl. The influence
hot-pressing technique was selected. Hardness and density in- of ternary elements on the martensitic transformation with regard
creased with the increasing Mo2C content, also mechanical para- to NiAl fracture toughness has not been reported yet. There were a
meters were higher than those of NiAl alloy (Table 1). Friction lot of papers describing the transformation in NiAl by molecular
coefficient at 700 °C reached 0.35 for 8 vol% content of Mo2C, dynamics simulations [99–101]. From the point of view of high-
whereas for NiAl it was equal to 0.48. A typical fracture mor- temperature applicability of NiAl the deviation from the stoichio-
phology of NiAl–Mo2C composite (8 wt% Mo addition) is explicitly metric relation, which is necessary for martensitic transformation
shown in Fig. 11, with a transgranular cleavage facet crack fracture in NiAl, will result in deterioration of physical and mechanical
mode along with a dimple fracture. properties at high temperatures (such as thermal stability). How-
A lot of interest was also put in doping of the NiAl structure by ever, this type of toughening may be interesting in other fields of
Hf with other elements. In 1994 Darolia [93] patented a NiAl single NiAl application.
crystal intermetallic alloy with an improved high temperature
strength, where the best results were obtained for the chemical 3.2.2. Heat treatment
composition of 0.05Ga, 0.5Hf and 5.0Ti (at%). There exist over a dozen of papers describing the effect of heat
treatment of NiAl alloys but only few refer to the influence on the
3.2. Other toughening mechanisms fracture toughness. A lot of work was done to improve the NiAl–
Cr–Mo alloys doped with Hf. As was mentioned in the preceding
Among the ductile phase toughening mechanisms of nickel section, the presence of Heusler (Ni2AlHf) phase, which is created
aluminides two other mechanism should be mentioned: in the NiAl–Cr–Mo–Hf alloy, reduces the mechanical properties.
(a) toughening by martensitic transformation, and (b) heat treat- With the increasing fraction of Heusler phase in the Hf-doped
ment, which may also be applied after the ductile phase alloy NiAl/Cr(Mo) the interface becomes weaker than the con-
toughening. stituent phase. Cracks can easily be initiated from interfaces where

Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
8 K. Bochenek, M. Basista / Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎

Ni2AlHf phase is distributed [72]. Early study of Cui et al. [102] has
shown that after HIPing and aged treatment (HIP at 1300 °C/
100 MPa for 2 h and then aged at 1050 °C for 40 h) the density of
the Heusler phase at the NiAl/Cr(Mo) phase boundary is sig-
nificantly lower, while the mechanical properties increased (cf.
Table 1). Recently, Wang et al. [103] presented the evolution of
fracture toughness during a heat treatment of NiAl–Cr(Mo)–(Hf,
Dy)–Fe alloy. After the heat treatment at 1250 °C for 48 h and
aging at 1050 °C for 24 h the fracture toughness of NiAl alloy
reached 18.4 MPa m , whereas as-cast material had 13.7 MPa m .
On the other hand, the disturbance in microstructure after ex-
posure to high temperatures, grain growth and change in me-
chanical parameters is objectionable from the application point of
view.

4. Mechanical parameters

From the analysis of available research papers it is clear that an Fig. 12. Stress rupture strength of NiAl alloys AFN-12 and AFN-20 compared to
superalloy Rene' 80 and Rene' N4. Reproduced from [13] with the permission of
improvement of mechanical parameters can be achieved by nu-
publisher.
merous factors, including the fabrication route, various composi-
tions and heat treatment. A selection of NiAl-base materials and
their mechanical parameters is presented in Table 1. As not all of
the analyzed papers included the fracture toughness measure-
ments or other mechanical properties, some data in this table are
missing (n/a).
As it was mentioned in Section 1, the high temperature
strength of a hypothetical NiAl-base turbine blade may be lower
than that made of Ni-base superalloys due to the lower weight and
high thermal conductivity, which result in a lower stress level
within the material, although this difference cannot be significant.
Darolia et al. [38] have presented five ways to increase the high
temperature strength: (1) elimination of grain boundaries, (2) so-
lid solution strengthening, (3) metallic phase strengthening,
(4) intermetallic phase strengthening, and (5) composite
strengthening. It was concluded that the addition of the group IVB
and VB elements across their solubility limits to NiAl creates
Heusler and/or Laves phases, which lead to the high temperature
strength improvement. Similar effect can be achieved by addition
of low solubility elements such as Cr, Mo and Re beyond their
Fig. 13. Specific stress rupture strength of NiAl alloys AFN-12 and AFN-20 com-
solubility limits, which precipitate in the form of particles/fibers
pared to superalloy Rene' 80, N4 and N6. Reproduced from [13] with the permis-
that finally increase the high temperature strength of NiAl. These sion of publisher.
five ways proposed to increase the high temperature strength
overlap with the methods used to increase the ductility. It can be of publishing of the overview paper [13] there has been little
stated that in most cases an increase of high temperature strength progress in the application of NiAl-base materials in turbine
is accompanied by increased fracture toughness and ductility. Still,
blades. The current research efforts in this field are predominantly
the main goal of research on NiAl is to find a balanced composition
directed to resolve the issues of low-ductility and low fracture
of NiAl-base material with alleviated low ductility and poor room
toughness, the other material properties relevant for high tem-
fracture toughness by an addition of a ductile phase and to
perature applications being not explored with a similar intensity.
maintain the desirable intermetallic properties, i.e. low density,
In the recently published reports [80,83,103] there is little in-
high thermal conductivity, thermal stability and oxidation
formation on the impact resistance, high temperature strength
resistance.
and creep life-time of the newly developed nickel aluminide ma-
The breakthrough result of NiAl-base turbine airfoils im-
plementation made 15 years ago by Darolia et al. [13] gave hope terials, such as NiAl–36Cr–6Mo alloy, [83]. Some data on high
that NiAl materials could compete with Ni-base superalloys in temperature tensile strength of modern NiAl alloys can be found in
terms of high temperature creep resistance and rupture strength. [64,73–75]. It is clear that once a processing technology has been
Fig. 12 presents the rupture strength for single crystal binary NiAl, developed for NiAl-base materials leading to the fracture tough-
AFN-12 and AFN-20 NiAl alloys compared with Rene' 80 and Rene' ness and ductility levels acceptable for turbine blades application
N4 superalloy plotted against the Larson Miller parameter, which requirements, extensive research programmes will follow with
combines both time and temperature on the same axis. When a regard to other material properties essential for the high tem-
density compensated rupture stress is implemented (Fig. 13), the perature applications.
AFN-20 NiAl alloy has equivalent properties as the third genera- When investigating the properties of NiAl-base materials, the
tion single crystal superalloy Rene' N6. Consequently, as was often specimen preparation must also be taken into account, especially
stated in the preceding Sections, the critical factor limiting the when comparing the fracture toughness data. It was shown in the
nickel aluminide application in aero engines remains in the first early study of Darolia et al. [104] on a NiAl single crystal with an Fe
place its inferior fracture toughness. Unfortunately, since the time addition that surface preparation can influence the room

Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
 K. Bochenek, M. Basista / Progress in Aerospace Sciences ∎ (∎∎∎∎) ∎∎∎–∎∎∎
Fig. 14. Summary of the effect of surface preparation techniques on RT plastic
elongation. Redrawn from [104] with the permission of publisher.
temperature tensile plastic elongations, e.g. from about 0.4% for
as-ground specimens to about 8% for electropolished specimens
where grinding marks were completely removed (Fig. 14).
5. Conclusions and outlook
Ductility improvement of NiAl intermetallic compounds is de-
rived from a growing need of industry to find new advanced
materials, which could increase engine performance and reduce
fuel consumption as well as service maintenance. Since the NiAl-
base materials may be considered as a possible replacement for
nickel-based superalloys mainly as structural materials in aero
engines, a number of requirements must be fulfilled. Bewlay et al.
[26,105] stated that to replace the nickel-based super-alloys (i) the
creep strength should be greater than 170 MPa at a creep rate of
2  10
8 s
1 at 1200 °C (for the assumed material density of 7 g/
cm3), and (ii) the minimum fracture toughness should be greater
than 20 MPa m .
While several significant challenges remain unresolved, an
excellent progress has been made in many aspects of the NiAl
development. Taking into account the results obtained so far the
prognosis for considering NiAl alloys and composites as high-
temperature structural materials is promising. After more than 40
years of research on NiAl an improvement in the fracture tough-
ness exceeding 400% has been achieved (from 6 MPa m , [58] to
26.15 MPa m , [83]). From these research results it follows that
chemical composition of high performance NiAl-base materials
should consist (besides nickel aluminide) of chromium, mo-
lybdenum in proper proportions and, perhaps, one or few ad-
mixtures of rare earth metals or other compounds in order to
challenge the nickel-based superalloys used in aero engines.
A comparison of the processing techniques of NiAl-base ma-
terials leads to the conclusion that the directional solidification
shows the best balance between mechanical properties, especially
when the process is combined with the zone melted liquid metal
cooling technique (ZMLMC) [81–83]. Also the arc-melting techni-
ques seem promising [64,77]. Powder metallurgy techniques may
be interesting [90–92], too but in view of the presented results this
method seems to be less effective than the directional solidifica-
tion. The NiAl alloys obtained by micro-alloying show very pro-
mising mechanical properties but the coarsening of grains during
high-temperature cycles must be taken into account as it may
result in a material degradation.
As was already mentioned, the brittle behavior of a
Please cite this article as: K. Bochenek, M. Basista, Advances in processing of NiAl intermetallic alloys and composites for high
temperature aerospace applications, Progress in Aerospace Sciences (2015), http://dx.doi.org/10.1016/j.paerosci.2015.09.003i
9
polycrystalline NiAl comes from insufficient number of in-
dependent slip systems [7,24]. The main factor for activating ad-
ditional slip systems in B2-ordered structure of NiAl to improve its
ductility is the introduction of an additional element into the in-
termetallic structure. The reported research results support this
statement and show that this approach can yield fruitful results as
regards the NiAl application in aero engines.
Even if NiAl alloys or NiAl-base composites could be applied in
turbine blades they will have to compete with the next generation
of nickel based superalloys. Currently the 6th generation TMS-238
Ni-superalloy shows applicability up to 1120 °C for 1000 h of creep
life at 137 MPa [106–107] and exhibits well-balanced mechanical
and environmental properties. On the other hand, the NiAl made
turbine blades, despite their inferior mechanical properties than
Ni-superalloys, may be more attractive if they manage to manifest
a higher temperature resistance, corrosion resistance or longer
creep life time, [108]. The use of NiAl should also be advocated in
other structural applications, not only be restricted to turbine
blades.
Finally, it can be concluded that NiAl is still considered as an
attractive structural material for high-temperature applications. A
considerable progress has been made until now in improving the
fracture toughness of NiAl-base alloys but a lot of design re-
quirements remain to be solved. It cannot be definitely stated that
in the near future more sophisticated NiAl-base materials will be
used as turbine engine components, but the results reviewed in
this paper are encouraging.
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