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Advances in processing of NiAl intermetallic alloys and composites for high

temperature aerospace applications

Article in Progress in Aerospace Sciences · September 2015

DOI: 10.1016/j.paerosci.2015.09.003

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 Progress in Aerospace Sciences
http://dx.doi.org/10.1016/j.paerosci.2015.09.003

Advances in processing of NiAl intermetallic alloys and composites for high

temperature aerospace applications

Kamil Bochenek and Michal Basista 1

Institute of Fundamental Technological Research
Polish Academy of Sciences
Pawinskiego 5 B, 02-106 Warsaw, Poland

Abstract

Over the last few decades intermetallic compounds such as NiAl have been considered as

potential high temperature structural materials for aerospace industry. A large number of

investigations have been reported describing complex fabrication routes, introducing

various reinforcing/alloying elements along with theoretical analyses. These research

works were mainly focused on the overcoming of main disadvantage of nickel aluminides

that still restricts their application range, i.e. brittleness at room temperature. In this paper

we present an overview of research on NiAl processing and indicate methods that are

promising in solving the low fracture toughness issue at room temperature. Other material

properties relevant for high temperature applications are also addressed. The analysis is

primarily done from the perspective of NiAl application in aero engines in temperature

regimes from room up to the operating temperature (over 1150OC) of turbine blades.

Keywords.

Nickel aluminide; Intermetallics; Turbine blades; Fracture toughness; Manufacturing

techniques

1
Corresponding author

1
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/m.K) and good oxidation/corrosion resistance up to

1400OC [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 1676OC [4], which is in perfect agreement with the theoretical value (1676OC)

obtained from thermodynamic calculations [5], cf. Fig. 1.

Fig. 1. Binary Al-Ni phase diagram. Redrawn from [5].

Some papers provide the value of 1638OC, 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 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], [8], [9]. A study of

2
NiAl stability under heavy ion bombardment at very low temperatures (-258 OC) 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 transformation toughening

and heat treatment. Unfortunately, up to now applicability of this intermetallic material is

still limited. Lasalmonie 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], [14], [15], [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).

Fig. 2. Engine tested NiAl HPT nozzle vanes. Reproduced from [13] with the permission
of publisher.

It was concluded that NiAl panels would not survive real in-service conditions for

turbine blades at impact speeds near 300 m/s, where catastrophic failures were observed.
3
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 conditions higher than in a typical combustor both NiAl alloys survived

without any failures [17], [18].

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.

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

4
results furnished recently by mathematical modelling of the ductile phase toughening of

NiAl [22], [23], [24].

There are few other materials that may also replace nickel-base superalloys i.e.

niobium silicides, molybdenum borosilicides and iridium-based superalloys [25], [26],

[27], [28], [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], [32], [33] and its

applicability is limited to middle range of the operating temperature (~750oC), [34].

The purpose of the present paper is to provide a concise account 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 compete with

nickel-based superalloys. The most important achievements 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-structure-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.

2. Physical properties of NiAl

5
 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 necessary 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 additional slip systems [36],

[37].

The low density of NiAl combined with its high thermal conductivity (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 1400OC) due to the high content of alumina and

formation of α-Al2O3 protective layer. However, below 1000OC these “excellent”

properties are exacerbated by the formation of transient oxide which may enhance 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 cryomilling of NiAl feedstock powder and sintered via SPS differ

significantly in the oxidation rates. Conventional NiAl specimens have oxidation rates

6
across all tested temperatures of 10-11g2/cm4/s, while in nanostructured specimens a

decrease in oxidation rates along with an increase of temperature is observed, e.g. 10-
13 2
g /cm4/s at 1050OC (Fig. 4).

Fig. 4. TGA data for conventional and nanostructured samples oxidized for 24h in air at
1050oC. Reproduced from [40] with the permission of publisher.

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 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], [43], [44],

[45] or PVD [46], which have resulted in obtaining fine-grained materials with increased

7
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 fifty years ago to synthesize nickel-base oxide-dispersion strengthened (ODS)

superalloys 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 Atzom et al. [49] investigated reaction during mechanical

alloying of NiAl, with the final conclusion that NiAl forms in an explosive, exothermic

reaction due to large heat of the intermetallic 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 dispersion strengthening (ODS) and

secondary recrystallization (SRx). A review of composite materials prepared by the

mechanical alloying 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 number of powder metallurgy

techniques, including vacuum hot pressing [52], isostatic hot pressing [53] and spark

plasma sintering [54]. The grain growth and kinetics of nanocrystalline NiAl obtained by

mechanical alloying and hot pressing were examined in [55]. Kubaski 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 vacuum-hot pressing were obtained by

Liu et al. [57]. The sintering temperature for the optimum material properties was set as

1300 OC for 60 min. at 25 MPa. Rahaei et al. [58] also using NiAl obtained by mechanical

8
alloying and consolidated by hot-pressing determined the sintering process parameters as

1180OC 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 procedures 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 and ductility.

Positive effect on ductility by elemental addition into NiAl structure was proven by Lu et

al. [24] by calculations performed with the CASTEP code (Cambridge Sequential Total

Energy Package) [60]. Moreover, Ponomareva et al. [22] analyzed the effect of

substitutional alloying on brittle vs. ductile behavior of B2-NiAl–X (X = Sc, Ti, V, Cr, W,

Re, Co) alloys, examining at the atomic level the role of interatomic bonding in the

ductility enhancement. In another article [23], the same authors carried out a more detailed

study of rhenium admixture influence on elastic properties of B2 NiAl as a follow up of the

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

transition metals – Cr, Fe, Re dissolved in NiAl stoichiometric composition by the atom

probe field ion microscopy (APFIM). The results of that study have revealed that ternary

9
alloying elements have considerable influence on the mechanical and physical properties

of NiAl. These authors also fabricated NiAl specimens with addition of refractory metals

(Cr, Mo, Re, W) showing that NiAl reinforced with 1% at. of rhenium yields the best

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.

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

a) NiAl-Cr-Mo alloys

The NiAl-Cr-Mo system has drawn much attention of researchers since 1970’s

when Walter and Cline [65], [66], [67] presented NiAl-Cr-Mo eutectic alloy with Cr

substituted by Mo. It resulted in 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> after molybdenum addition. This phase

system enables an increase of both the fracture toughness and the creep strength at elevated

temperatures.

10
 Once the microstructures had been characterized, Johnson et al. [68] investigated

NiAl-Cr-Mo alloys and their mechanical properties. A directional solidification was used

through a containerless mode by the electro-magnetically levitated zone process in an

ultrapure helium atmosphere for alloys manufacturing. The fracture toughness obtained for

directionally solidified NiAl-28Cr-6Mo alloys reached 22 MPa√𝑚 as compared with 6

MPa√𝑚, [58] corresponding to the polycrystalline NiAl. NiAl-Cr-Mo alloys are

characterized also by a good combination of room- and elevated 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 investigated by Yang et

al. [69] and later by Whittenberger et al. [70]. In both papers the fracture toughness of

alloys obtained by directional solidification was of a similar level (17 and 16 MPa√𝑚,

respectively). Whittenberger concluded that for higher withdrawal speeds (above 127

mm/h) the fracture toughness decreased significantly (from 16 to 7 MPa√𝑚), which was

attributed to the microstructure transformation from lamellar-type into Cr(Mo)

fibers/grains embedded in the NiAl matrix. In the case of Mo-rich composite (Ni-33Al-

31Cr-3Mo) the lamellar structure retained the faster growth rates. Moreover, it was

observed that the interstitial element content (such as C, O, N) did not appear to be the

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

After more than 40 years since the development of NiAl-Cr-Mo eutectic alloys,

these materials still attract attention of scientists due to the most promising properties

obtained for NiAl alloys so far. Cui et al. [71], [72], [73] and Guo et al. [74], [75] proposed

to add hafnium to NiAl-Cr-Mo alloys. Two types of alloys were selected: 0.2 and 0.5

(at.%) of Hf (Ni-32Al-28Cr-(6−x)Mo-xHf (x = 0.2 and 0.5 at.%, respectively)

manufactured by directional solidification. In the first composition (0.2Hf) the dendritic

11
structure was observed, while in 0.5Hf alloy the intercellular structure was formed.

Addition of hafnium resulted in an enhancement of the high-temperature 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 - 1h at 1346oC, MT2 – 1h at 1446oC and MT3 – 1h at

1546oC) have decreased as a result of the cellular structure disturbance caused by hafnium.

After heat treatment in a strong magnetic field a significant 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.

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 permission of publisher.

A more sophisticated composition of NiAl alloy was proposed by Guo et al. [77].

Following the previous research [64], the authors proposed an addition of a small amount

12
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 1250OC for 24 h in evacuated silica capsules followed by furnace cooling

to room temperature. The highest improvement of compressive properties was observed

when the Ho content was up to 0.1% at. (Fig. 7).

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.

The admixture of Ho resulted in a lamellar refinement in eutectic cells in NiAl-

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] proposed 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 1100OC was similar for the two alloys obtained
13
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.

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.

Recently, a hypereutectic alloy Ni-31Al-32Cr-6Mo was proposed 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. 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 temperature

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

14
when solidified at 10 µms-1 and had a planar eutectic microstructure. In this alloy a quasi-

cleavage fracture mode was observed on the fracture surfaces (Fig. 9).

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.

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 µm/s and temperature gradient of

600 K/cm [83]. Enhancement of the fracture toughness was a result of increasing the

strengthening phase volume and obtaining a well-aligned microstructure with a planar

eutectic microstructure in the hypereutectic alloy (Fig. 10).

b) 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

15
composite fabrication technique needs to be improved due to the low relative density and

poor strengthening effect of the obtained composites.

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.

It is well known that combination of a nanocrystalline intermetallic matrix and a

dispersed strengthening phase may result in an increase of strength at higher temperatures

and material ductility [85], [86]. For example, Zhou et al. [87] produced a nanocrystalline

NiAl-TiC powders, where two separate reactions of compound 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 increase

the mechanical properties of NiAl were also made by Whittenberger et al. [89] where two

different elevated temperature strengthening mechanisms were investigated. They

16
concluded that ODS (oxide dispersion strengthened) NiAl after cryomilling or roasting in

nitrogen were not as strong as cryomilled NiAl containing like amounts of AlN.

Mechanical alloying (MA) was used to fabricate NiAl composites with addition of

refractory metals Fe, Ga and Mo, [90]. The powders were finally consolidated by the hot

pressing technique. The highest mechanical properties were obtained for a combination of

transition elements (NiAl+6%Fe+2%Mo), and reached the strain of 19.2%. Specimens

were sintered at 1200 OC for 30 min, the relative density of the sintered material was

96.3%. The values of strength, strain and yield stress are shown in Table 1.

Sheng et al. [91] fabricated NiAl alloys with an addition of Au up to 1 atomic %.

The outcomes from their study were that (i) addition of Au in the NiAl alloy refines the

NiAl grains, (ii) a higher content of Au results in the formation of α-AlAu2 phase, and (iii)

Au addition leads to a moderate solid solution strengthening at low temperatures and

strong solid solution strengthening at high temperatures. The selected properties of

NiAl+0.5at. % Au are presented in Table 1.

In one of the newest papers Liu et al. [92] proposed an improvement of high-

temperature tribological and mechanical properties of NiAl by an addition of Mo2C. For

consolidation the hot-pressing technique was selected. Hardness and density increased with

the increasing Mo2C content, also mechanical parameters were higher than those of NiAl

alloy [Table. 1]. Friction coefficient at 700OC reached 0.35 for 8% vol. content of Mo2C,

whereas for NiAl it was equal to 0.48. A typical fracture morphology of NiAl-Mo2C

composite (8 wt% Mo addition) is explicitly shown in Fig. 11, with a transgranular

cleavage facet crack fracture mode along with a dimple fracture.

17
Fig. 11. Fracture morphology of NiAl-Mo2C composite (8 wt% Mo). Reproduced from
[92] with the permission of publisher.

A lot of interest was also put in doping of the NiAl structure by Hf with other

elements. In 1994 Darolia [93] patented a NiAl single crystal intermetallic alloy with an

improved high temperature strength, where the best results were obtained for the chemical

composition of 0.05Ga, 0.5Hf and 5.0Ti (at.%).

3.2. Other toughening mechanisms

Among the ductile phase toughening mechanisms of nickel aluminides two other

mechanism should be mentioned: (a) toughening by martensitic transformation, and (b)

heat treatment, which may also be applied after the ductile phase toughening.

a) martensitic transformation

The effect of martensitic transformation of beta-NiAl was studied in [94], [95],

[96]. Martensitic transformation may occur in Ni-rich NiAl by rapid cooling (B2 to L10

18
structure). According to the results obtained in [96], martensite phase deforms at lower

stresses than B2-NiAl. In [84] the authors investigated the influence of martensitic

transformation (thermal and stress induced) in NiAl on the fracture toughness. The

martensitic transformation influenced the fracture toughness only in the case of an as-cast

inhomogeneous polycrystalline NiAl, where martensitic phase forms irreversibly at crack

tips without re-transformation. Kainuma et al. [97] and Thompson et al. [98] investigated

the influence of ternary elements on the martensitic transformation of β-NiAl. The

influence of ternary elements on the martensitic transformation with regard to NiAl

fracture toughness has not been reported yet. There were a lot of papers describing the

transformation in NiAl by molecular dynamics simulations [99], [100], [101]. From the

point of view of high-temperature applicability of NiAl the deviation from the

stoichiometric relation, which is necessary for martensitic transformation in NiAl, will

result in deterioration of physical and mechanical properties at high temperatures (such as

thermal stability). However, this type of toughening may be interesting in other fields of

NiAl application.

b) heat treatment

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 fracture toughness. A lot of work was done

to improve the NiAl-Cr-Mo alloys doped with Hf. As was mentioned in the preceding

section, the presence of Heusler (Ni2AlHf) phase, which is created in the NiAl-Cr-Mo-Hf

alloy, reduces the mechanical properties. With the increasing fraction of Heusler phase in

the Hf-doped alloy NiAl/Cr(Mo) the interface becomes weaker than the constituent phase.

Cracks can easily be initiated from interfaces where Ni2AlHf phase is distributed [72].

Early study of Cui et. al [102] has shown that after HIPing and aged treatment (HIP at

19
1300°C/100 MPa for 2h and then aged at 1050°C for 40 h) the density of the Heusler phase

at the NiAl/Cr(Mo) phase boundary is significantly 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 48h and aging at 1050°C for 24h 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 exposure to high temperatures, grain growth and

change in mechanical parameters is objectionable from the application point of view.

4. Mechanical parameters

From the analysis of available research papers it is clear that an improvement of

mechanical parameters can be achieved by numerous factors, including the fabrication

route, various compositions 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 measurements 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)

solid 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

20
be achieved by addition of low solubility elements such as Cr, Mo and Re beyond their

solubility limits, which precipitate in the form of particles/fibers that finally increase the

high temperature strength of NiAl. These five ways proposed to increase the high

temperature strength overlap with the methods used to increase the ductility. It can be

stated that in most cases an increase of high temperature strength is accompanied by

increased fracture toughness and ductility. Still, the main goal of research on NiAl is to

find a balanced composition of NiAl-base material with alleviated low ductility and poor

room fracture toughness by an addition of a ductile phase and to maintain the desirable

intermetallic properties, i.e. low density, high thermal conductivity, thermal stability and

oxidation resistance.

The breakthrough result of NiAl-base turbine airfoils implementation made 15

years ago by Darolia et al. [13] gave hope that NiAl materials could compete with Ni-base

superalloys in terms of high temperature creep resistance and rupture strength. Fig. 12

presents the rupture strength for single crystal binary NiAI, AFN-12 and AFN-20 NiAl

alloys compared with Rene’ 80 and Rene’ N4 superalloy plotted against a Larson Miller

parameter, which combines both time and temperature on the same axis.

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
publisher.

21
 When a density compensated rupture stress is implemented (Fig. 13), the AFN-20

NiAl alloy has equivalent properties as the third generation single crystal superalloy Rene’

N6. Consequently, as was often stated in the preceding Sections, the critical factor limiting

the nickel aluminide application in aero engines remains in the first place its inferior

fracture toughness.

Fig. 13. Specific stress rupture strength of NiAl alloys AFN-12 and AFN-20 compared to
superalloy Rene’ 80, N4 and N6. Reproduced from [13] with the permission of publisher.

Unfortunately, since the time of publishing of the overview paper [13] there has

been little progress in the application of NiAl-base materials in turbine blades. The current

research efforts in this field are predominantly directed to resolve the issues of low-

ductility and low fracture toughness, the other material properties relevant for high

temperature applications being not explored with a similar intensity. In the recently

published reports [80, 83, 103] there is little information on the impact resistance, high

temperature strength and creep life-time of the newly developed nickel aluminide

22
materials, such as NiAl-36Cr-6Mo alloy, [83]. Some data on high temperature tensile

strength of modern NiAl alloys can be found in [64, 73, 74, 75]. It is clear that once a

processing technology has been developed for NiAl-base materials leading to the fracture

toughness and ductility levels acceptable for turbine blades application requirements,

extensive research programmes will follow with regard to other material properties

essential for the high temperature applications.

When investigating the properties of NiAl-base materials, the specimen preparation

must also be taken into account, especially when comparing the fracture toughness data. It

was shown in the early study of Darolia et al. [104] on a NiAl single crystal with an Fe

addition that surface preparation can influence the room 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).

Fig. 14. Summary of the effect of surface preparation techniques on RT plastic elongation.

Redrawn from [104] with the permission of publisher.

23
5. Conclusions and outlook

Ductility improvement of NiAl intermetallic compounds is derived 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 2x10-8s-1 at 1200oC (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 toughness 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, molybdenum in proper proportions and, perhaps, one or few

admixtures 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 materials 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], [82], [83]. Also the arc-melting techniques seem

promising [64], [77]. Powder metallurgy techniques may be interesting [90], [91], [92], too

24
but in view of the presented results this method seems to be less effective than the

directional solidification. The NiAl alloys obtained by micro-alloying show very promising

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 polycrystalline NiAl comes

from insufficient number of independent slip systems [7], [24]. The main factor for

activating additional slip systems in B2-ordered structure of NiAl to improve its ductility is

the introduction of an additional element into the intermetallic 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 1120oC 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

requirements 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.

25
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32
Figure Captions:

Fig. 3. Binary Al-Ni phase diagram. Redrawn from [5].

Fig. 4. Engine tested NiAl HPT nozzle vanes. Reproduced from [13] with the permission
of publisher.

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.

Fig. 4. TGA data for conventional and nanostructured samples oxidized for 24h in air at
1050oC. Reproduced from [40] with the permission of publisher.

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

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.

Fig. 11. Fracture morphology of NiAl-Mo2C composite (8 wt% Mo). Reproduced from
[92] with the permission of publisher.

33
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
publisher.

Fig. 13. Specific stress rupture strength of NiAl alloys AFN-12 and AFN-20 compared to
superalloy Rene’ 80, N4 and N6. Reproduced from [13] with the permission of publisher.

Fig. 14. Summary of the effect of surface preparation techniques on RT plastic elongation.
Redrawn from [104] with the permission of publisher.

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Tables:

Material Maximum stress / Yield Relative Vickers Fracture

strain strength density hardness toughness
[MPa] [%] [HV] [MPa√𝑚]

Ultrafine grain NiAl Compressive strength n/a 99.4 456 n/a

alloy [42] 1900 MPa / strain
9.5%
Nanocrystalline Compressive strength 1506 96.1 550 n/a
NiAl (MA+HP 2278 MPa / strain (compression)
1300oC/1h/25MPa) 28.9%
[57]
Nanocrystalline Compressive strength 1478 98 581 6
NiAl (MA+HP 2117 MPa (compression)
1180oC/1h/45MPa)
[58]
SHS in-situ NiAl Compressive ductility n/a 92 325 9.5
(grain 28µm) [59] 14%

HP NiAl + 10% SiC n/a (Elastic modulus 333 95.3 449 n/a
fibers (vol.%) [84] 179 MPa) (compression)
MA+HP Compressive strength 1496 96.3 610 n/a
NiAl+6%Fe+2%Mo 2520 MPa/ strain (compression)
[90] 19.2%
MA+HP Compressive strength 1676 99.73 624.85 n/a
NiAl+8%Mo2C [92] 2282 MPa / strain (compression)
24%
NiAl+0.5%at. Au Compressive strength 490 n/a 322 n/a
[91] (true stress) 560 MPa / (compression)
true strain 8%
NiAl-28Cr-6Mo [68] n/a n/a n/a n/a 19.6
NiAl-Cr-Mo-0.2Hf Compressive strength n/a n/a n/a n/a
[72] 1225 MPa / strain
0.2% offset RT
NiAl-36Cr-6Mo [83] n/a n/a n/a n/a 26.15
DS3 NiAl–28Cr– n/a 280 n/a n/a 10.2
5.94Mo–0.05Hf– (compression)
0.01Ho [78]
DS+HIP+Aging Tensile strength 459 414 n/a n/a n/a
NiAl-28Cr-5.5Mo- MPa / strain 2% (tension)
0.5Hf [102]
DS NiAl-Cr(Mo)- Compressive stress n/a n/a 578 18.4
(Hf,Dy)-4Fe, H-2 1974 MPa / strain
[103] 14.3%

Table 1. Comparison of mechanical properties of selected NiAl-base alloys and

composites.

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