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Journal of Alloys and Compounds 484 (2009) 907–913

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Journal of Alloys and Compounds


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

Formation of porous Ni–Al intermetallics through pressureless reaction synthesis


H.X. Dong a , Y. Jiang a , Y.H. He a,∗ , M. Song a , J. Zou b,∗ , N.P. Xu c , B.Y. Huang a , C.T. Liu d , P.K. Liaw d
a
State Key Laboratory for Powder Metallurgy, Central South University, Changsha, Hunan 410083, PR China
b
Division of Materials and Centre for Microscopy and Microanalysis, The University of Queensland, Brisbane, QLD 4072, Australia
c
Membrane Science and Technology Research Center, Nanjing University of Technology, Nanjing 210009, PR China
d
Metals and Ceramic Division, Oak Ridge National Laboratory, Oak Ridge 37831, TN, USA

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

Article history: Pressureless reaction synthesis method was used to produce porous NiAl and Ni3 Al intermetallics using
Received 11 January 2009 elemental Ni and Al powder mixture in this investigation. The sintering behavior of Ni and Al mixed pow-
Received in revised form 12 May 2009 der compacts was investigated by applying XRD, SEM and EDS in the temperature range of 510–1000 ◦ C.
Accepted 15 May 2009
It has been found that the formation of porous Ni3 Al and NiAl was accompanied by the volume expansion
Available online 23 May 2009
due to the formation of intermediates and pores during the reaction synthesis procedure. The inten-
sive reaction and phase transformation procedures were similar in the Ni–14 wt% Al and Ni–30 wt% Al.
Keywords:
However, the maximum pore size, expansion ratio and porosity have been found to be varied with the
Ni–Al intermetallics
Powder metallurgy
sintering temperature and Al content in the compacts. The Al content in the green compacts could effec-
Porous tively influence the volume expansion and pores of the products: the volume expansion and maximum
Intermediates pore size of NiAl are much higher than that of Ni3 Al under the same sintering procedure.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction advantages of forming porosity during reaction synthesis can be


regarded as a method of producing cellular metals from sintering
Nickel aluminide intermetallics have been envisaged as good the powder mixture owing to different diffusion coefficients [9].
candidates for a number of industrial sectors, including aerospace, Although the reaction synthesis could produce porous material,
automotive, and power generation industries due to their low den- little attention has been paid to this area.
sity, high temperature stability and high strength to weight ratio Recently, porous intermetallics have attracted much attention
[1]. Owe to their excellent corrosion and oxidation resistance espe- for their unique properties with the prospect of various poten-
cially at the high temperature, nickel aluminides are also considered tial applications. Porous materials such as TiAl [10], FeAl [11], and
as materials that might replace current nickel-based superalloys in TiAlNb [12] have been fabricated by sintering elemental powder
rugged environments. compacts. Lotus-type porous Ni3 Al intermetallics have been pro-
Fabrications of nickel aluminide structural materials have been duced by unidirectional solidification of the melt in a pressurized
carried out through a variety of processing methods, including hydrogen gas [13]. All of research works indicate that the oxida-
investment casting, hot extrusion, rolling and forging [2]. In the tion resistance and adiabatic ability of the porous intermetallics
past two decades, a significant amount of work has been pub- are superior to that of conventional porous metals [10,14].
lished on the reaction synthesis of nickel aluminides including Although Morsi et al. [15] obtained cylindrical porous NiAl
combustive synthesis (CS), thermal explosive and self-propagating intermetallics with porosity of 60% through controlling the heat
high-temperature synthesis (SHS) [3–6]. The modeling of the reac- generation during reaction synthesis, there is rare report about
tion synthesis of Ni/Al powders mixtures was recently covered by preparing porous Ni–Al intermetallics from elemental powder
Farber et al. [7] and Li [8]. The advantages of the reaction synthe- without any additions through reaction synthesis, so that the pore
sis as a fabrication process include low processing temperature (in formation and phase transformation in the Ni–Al system has been
turn, low energy process), short processing time, the use of low cost not clarified. Moreover, in conventional reaction synthesis, a fast
equipment and the formation of pure products [3]. Nevertheless, heating rate is usually employed to avoid the formation of alu-
the reaction synthesis is also accompanied by some disadvantages minum rich intermediates before reaction synthesis temperature
including porosity and limited process control. However, the dis- [15]. In addition, most of the reaction synthesis experiments were
carried out in hydrogen or argon atmospheres, which contribute to
the porosity and lead to a complicated the reaction process and,
∗ Corresponding authors. Tel.: +86 731 8836144; fax: +86 731 8710855. in turn, a complicated pore evolvement during the procedure [7].
E-mail addresses: yuehui@mail.csu.edu.cn (Y.H. He), j.zou@uq.edu.au (J. Zou). In this study, we demonstrate our success of fabrication of porous

0925-8388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2009.05.079
908 H.X. Dong et al. / Journal of Alloys and Compounds 484 (2009) 907–913

Fig. 1. DSC curves of Ni + Al powder compacts at heating rate of 2 ◦ C/min. (a)


Ni–14 wt% Al and (b) Ni–30 wt% Al. Fig. 2. XRD patterns of the intermediates formed upon heating to the temperature
indicated during reactive synthesis of Ni–14 wt% Al powder compacts and dwelling
for 1 h. (a) Room temperature, (b) 550 ◦ C, (c) 640 ◦ C, (d) 670 ◦ C, (e) 750 ◦ C and (f)
Ni–Al alloys from elemental powder mixing compacts in vacuum 950 ◦ C.
furnace, which could maintain its green compacts shape and could
offset the uncontrollable compact shape made by self-propagating 4. Results
high-temperature synthesis (SHS) and thermal explosion. More-
over, based on the determined detailed structural characteristics, 4.1. Differential scanning calorimeter (DSC)
the mechanism of the formation of porous Ni–Al alloys is investi-
gated. DSC has been performed on the green compacts of Ni + Al pow-
der mixtures at a heating rate of 2 ◦ C/min in the temperature
2. Materials synthesis range 500–750 ◦ C. The DSC curves of the Ni–Al green compacts
in Fig. 1 indicates the occurrence of exothermic reactions for both
Commercially pure Ni (−400 mesh) and Al (−400 mesh) pow- cases. Since the starting temperatures for exotherms are not well
ders were mixed in the ratios of Ni–14 wt% Al and Ni–30 wt% Al, defined, the temperatures corresponding to maximum points in the
respectively, in order to gain final compositions of Ni3 Al and NiAl. curves are reported for the exothermic reactions. For Ni–14 wt%
The Ni and Al were gently ball-mixed for 10 h using a powder rota- Al compacts, only one exothermic peak was observed, while two
tor mixer. The ball-to-powder weight ratio was 3:1. Through the exothermic peaks were detected for Ni–30 wt% Al green compacts.
conventional die pressing, the mixed powders were formed into It can be noted that the exothermic peak around 637 ◦ C increases
disc with porosity less than 18% under a pressure of 200 MPa in a with increasing the Al content in the green compacts. In addition,
26 mm diameter cylindrical steel die to produce compacts of 2 mm the gradient of the curve increases before the appearance of the
thickness. The pressure was measured by a load cell and the number exothermic peaks, which indicates the exothermic reaction (solid
of compacts per sintering condition was three. The specimens were diffusion) between solid Ni and Al powders has happened.
then sintered in a vacuum furnace with a pressure of 1 × 10−3 Pa and
at temperatures of 520, 540, 590, 640, 670, 750, 950 and 1000 ◦ C, 4.2. X-ray diffraction analysis (XRD)
respectively, for durations ranging from several minutes to 1 h fol-
lowed by furnace cooling to room temperature. The heating rate was For the X-ray diffraction analysis, a Ni–14 wt% Al compact was
less than 5 ◦ C/min during the whole process in order to preserve the used as an example during the phase transformation since the for-
original shape and avoid the possible SHS procedure. During the sin- mation of intermediates are similar in the two systems when the
tering procedure, all the compacts were degassed at 120 ◦ C for 1 h.

3. Characterization

The differential scanning calorimeter (DSC:NETZSCH DSC 204)


was performed using 3–5 mg cold pressing samples placed into
alumina crucibles. The heating was conducted in argon at a con-
stant rate of 2 ◦ C/min up to 750 ◦ C. All the porous samples were
grinded into powders and analyzed by X-ray diffraction (XRD
Dmax 2500VB) using a Cu K␣ source. Each sintered pellet was
sectioned longitudinally, the cross-section specimens were then
polished using 1–3 ␮m diamond finish for cross-section microscop-
ical examination. Their morphologies were observed on the surface
and the cross-section of the disc by scanning electron microscopy
(SEM: JEOL, JSM-7000F) with an X-ray energy dispersive spec-
troscopy (EDS) system. The open porosity was measured by the
Archimedes method in water [16]. The maximum pore size was
measured by the bubble point method [17] on a BTP-3Ш porous Fig. 3. XRD patterns of the final products formed upon heating to 1000 ◦ C and held
material test instrument. for 1 h.
H.X. Dong et al. / Journal of Alloys and Compounds 484 (2009) 907–913 909

Fig. 4. SEM micrographs of the final products heated to 1000 ◦ C and held for 1 h: (a) Ni–14 wt% Al and (b) Ni–30 wt% Al.

Fig. 5. SEM micrograph (BSE mode) of the Ni + Al powder compacts heated to (a) 640 ◦ C, Ni–30 wt% Al, (b) 640 ◦ C, Ni–14 wt% Al, (c) 670 ◦ C, Ni–30 wt% Al, (d) 670 ◦ C, Ni–14 wt%
Al, (e) 750 ◦ C, Ni–30 wt% Al, (f) 750 ◦ C, Ni–14 wt% Al, (g) 1000 ◦ C, Ni–30 wt% Al and (h) 1000 ◦ C, Ni–14 wt% Al.
910 H.X. Dong et al. / Journal of Alloys and Compounds 484 (2009) 907–913

temperature is below 750 ◦ C. XRD diagrams for pressureless reac-


tion synthesis powder mixtures from room temperature to 950 ◦ C
are shown in Fig. 2. For comparison, the typical diffraction pattern
of green compact is shown in Fig. 2(a), indicating only Ni and Al are
present without other intermediates. At a temperature less than
520 ◦ C, no new phases were detected either. As the temperature
rises to 540 ◦ C, peaks related to the formation of Ni2 Al3 , NiAl and
Ni3 Al appear, while the Al peaks weaken. According to the DSC
analysis and the fact that the Al diffusion rate is larger than Ni,
aluminum rich intermetallics, namely Ni2 Al3 , has formed at the
interface between aluminum and nickel powders by the solid state
interdiffusion [18] below their eutectic temperature of 640 ◦ C, i.e.
the reaction synthesis temperature. For the compacts between 540
and 640 ◦ C, the five phases, Ni2 Al3 , NiAl, Ni3 Al, Al and Ni, co-exist,
however, Ni3 Al grow at the expense of Ni2 Al3 , Ni and Al. When
the temperature reaches 670 ◦ C, the Al and Ni2 Al3 peaks are com-
pletely replaced by those corresponding to NiAl and Ni3 Al, and the
Ni peaks weaken. As the temperature is raised to higher than 750 ◦ C,
the Ni peaks almost disappear and the Ni3 Al becomes the major
phase, only minor NiAl phase exists. After about 1 h at 950 ◦ C, the
reaction is complete and the samples only consist of Ni3 Al. Fig. 3
represents the X-ray diffraction pattern of the products for Ni–Al
alloys with different compositions sintered at 1000 ◦ C for 1 h. The
XRD results show the final products of NiAl and Ni3 Al in the samples
with 30 wt% Al and 14 wt% Al, respectively, confirming complete
reactions.

4.3. Microstructure development of Ni3 Al and NiAl

Fig. 4 illustrates the SEM images of porous Ni–Al with Al content


of 14 and 30 wt% sintered at 1000 ◦ C, respectively. As can be clearly
seen from these images, the general pore size of the NiAl alloys
is larger than that of Ni3 Al, which is consistent with the results
mentioned in Ti–Al system [16], indicating that the Al content has
a great influence on the pore structure of aluminide intermetallics. Fig. 6. Swelling behaviors of porous Ni–Al samples as a function of sintering tem-
Moreover, the total porosity of NiAl (∼50%) is also higher than that perature: (a) Ni–14 wt% Al and (b) Ni–30 wt% Al.
of Ni3 Al (∼30%) measured by the Archimedes method in water.
Fig. 5 shows the polished cross-sections back-scattered images
and Al. When the temperature rises from 640 to 670 ◦ C, Ni3 Al and
of the Ni–30 wt% Al and Ni–14 wt% Al compacts at different tem-
NiAl grow at the expense of intermediates, Al and Ni and becomes
peratures (between 640 and 1000 ◦ C). Different contrasts are seen
the main phase in the sample of Ni–14 wt% Al and Ni–30 wt% Al,
from these back-scattered images, indicating different phases. The
respectively. In addition, large connected pores are produced, espe-
EDS analysis was carried out to determine these phases and the
cially in the Ni–30 wt% Al sample (Fig. 5(c) and (d)). From 670 to
results were summarized in Table 1. The spherical Al powders
750 ◦ C, three-phase Ni/Ni3 Al/NiAl co-existed and Ni (white regions
deformed due to the cold pressing pressure of 200 MPa, result-
in the micrograph) almost disappear at 750 ◦ C (Fig. 5(e) and (f)).
ing in a continuous Al network surrounding the Ni powders in the
Moreover, some small fragments appear around the large parti-
Ni–30 wt% Al compacts, whereas the continuous Al network could
cles. When the samples were heated to 1000 ◦ C and subsequently
not form in the Ni–14 wt% Al due to the small amount of the Al
annealed for 1 h, no additional reaction was detected and the sam-
content. Intermediates such as Ni2 Al3 , NiAl and Ni3 Al are gener-
ples contained a uniform NiAl and Ni3 Al for the Ni–30 wt% Al and
ated during the pressureless reaction synthesis depending on the
the Ni–14 wt% Al samples, respectively (Fig. 5(g) and (h)). Large
temperature. Before 520 ◦ C, no other phases other than Ni and Al
amount of pores (black regions in the micrograph) existed in the
were detected by EDS, which are in accordance with the XRD analy-
range of 670–1000 ◦ C, although the pores tended to be smaller as
sis (the micrograph are not shown here). As temperature increases,
the temperature increases. In addition, most of the pores are inter-
intermediates form at the interface between Ni and Al. At 640 ◦ C,
connected in porous NiAl, while most of the large pores are isolated
a certain amount of intermediates are produced with less amount
in porous Ni3 Al.
of Al remaining and interstitial space (black regions in Fig. 5(a) and
(b)) forming due to the different solid diffusion coefficients of Ni
4.4. Swelling behaviors and maximum pores evolvement for
porous Ni–Al intermetallics
Table 1
EDS analysis of the phase in Fig. 5.
The swelling behavior is a common phenomenon during the
Phases Ni, at.% Al, at.% sintering procedure, so that it is necessary to clarify the relation-
A 46.83 60.17
ship between the swelling behavior and the sintering temperatures.
B 72.46 27.54 Fig. 6 shows the swelling behaviors of the Ni–Al sample with 14 wt%
C 91.04 8.96 Al and 30 wt% Al as a function of the sintering temperature, respec-
D 50.42 49.58 tively. It can be noted that the volume expansion increases almost
E 75.35 24.65
linearly with increasing the temperature before 670 ◦ C, and after
H.X. Dong et al. / Journal of Alloys and Compounds 484 (2009) 907–913 911

a furnace to the reaction temperature (usually above the eutectic


temperature of 640 ◦ C), then reaction happens and the heat raises
the temperature to an ‘adiabatic’ temperature that exceeds its melt-
ing point resulting in the production in molten form. The amount of
liquid phase during the reaction synthesis of nickel aluminides had
been calculated by thermodynamic and clarified by experiments
[4], indicating that both the amount of liquid phase and the prod-
uct density increase with the increasing of the Al content in the
green compacts. In our experiment, the discs were held at a tem-
perature lower than the eutectic temperature for a certain time to
form intermediates (i.e. Ni2 Al3 ), which have a high heat capacity
and can act as heat sink that leads to a reduction in the amount of
heat generated per volume [4]. Simultaneously, pores are formed
because of the different intrinsic diffusion coefficients between Ni
and Al [20,21], as shown in Fig. 5(a) and (b). It has been reported
that the intrinsic volume change in the formation of Ni2 Al3 from the
elemental Ni and Al is +11.93% [22]. The contact area between the
elemental Ni and Al powders in Ni–30 wt% Al is larger than that in
Ni–14 wt% Al. The intermediate amount of Ni2 Al3 in the Ni–30 wt%
Al alloy is more than that in the Ni–14 wt% Al alloy under the same
sintering condition, thus the former volume expansion of the for-
mer is larger than the latter. Moreover, the Al particles aggregates
together around the Ni particles in the Ni–30 wt% Al sample due
to its high Al content. When the liquid Al appears (as indicated in
Fig. 4(b)), the liquid phase quickly covers the surface of surround-
ing Ni powders and fills the small pores of the Ni powders in the
Ni–30 wt% Al alloy due to the capillary force [23]. This phenomenon
could hardly be found in the sample of Ni–14 wt% Al alloy due to
a small amount of liquid Al appearing in the compacts. Thus small
pores in green compacts still exist in the Ni–14 wt% Al sample. Large
pores are left at the sites previously occupied by Al powders and an
overall volume expansion of the sintered disc obtained due to the
pore formation and the liquid–solid exothermic reactions. Similarly,
Fig. 7. Maximum pore size of porous Ni–Al samples as a function of sintering tem-
a shortage of the liquid phase results in low density material after
perature: (a) Ni–14 wt% Al and (b) Ni–30 wt% Al. sintering, but an excess amount of the liquid phase appears to be
harmful in keeping the shape of the green compact during the reac-
tion synthesis [24]. Based on the above analysis, it can be easy to
that, a relatively decreasing value appears. The final volume expan- understand why the maximum pore size of NiAl is larger than that
sion of the Ni–30 wt% Al sample (∼33%) is much higher than that of of Ni3 Al when the powders with the same particle size were used. It
the Ni–14 wt% Al sample (∼6%). is worth noting that a further sintering promotes reaction through a
Fig. 7 displays the maximum pore size of both 14 wt% Al and slow solid state diffusion fashion, and that some fragments appears
30 wt% Al alloys as a function of the sintering temperature. The (see Fig. 5(e)) since the intrinsic volume changes in the formation of
maximum pore size has the same trend as the volume expansion NiAl and Ni3 Al are −12.6% and −5.2%, respectively [25]. Both sam-
behavior, reaching the maximum point at around 670 ◦ C and then ples begin to shrink above 670 ◦ C, leading to the reduction of the
decreasing. The comparison of Fig. 7(a) and (b) suggests that the maximum pore size. The comparison of the SEM images show that
final maximum pore of NiAl is much larger than that of Ni3 Al. the influence of the Ni branched structures on the final microscopy
Furthermore, the maximum pore size in the Ni–14 wt% Al alloys of the products of Ni3 Al is greater than that of NiAl, because part of
decreases sharply beyond 670 ◦ C, while the maximum pore size in small pores from green compacts still exists in the former sample.
the Ni–30 wt% Al alloys decreases slowly.
5.2. Effect of sintering temperature on the microstructure and
5. Discussion swelling behavior

5.1. Effect of the Al content on the microstructure and swelling The highly exothermic nature of the powder mixture of Ni + Al
behavior has been utilized for reactive sintering nickel aluminides. Accord-
ing to the Ni–Al diagram [26], the binary system exhibits five stable
In the Ni + Al powder mixture compacts, intermediates such as intermetallic compounds, namely NiAl3 , Ni2 Al3 , NiAl, Ni5 Al3 and
Ni2 Al3 , Ni3 Al and NiAl, form depending on the sintering tempera- Ni3 Al. Three of them have been detected in this study. The reac-
ture. The Al content in the compacts influences the final phase of the tion mechanism and microstructure transformation of the Ni–Al
products and the content of the intermediates, and has no influence powder compacts under pressureless reaction synthesis can be
on the intermediates formation (seen XRD and SEM analysis). determined as follows.
During the conventional reaction synthesis, the relative den- The gradient of the curve increases before the appearance of
sity of the products increases with increasing the Al content in the the exothermic peaks (see Fig. 1), indicating that the exothermic
green compacts [19], which is in contrast with our results. There- reaction (solid diffusion) between solid Ni and Al powders has
fore, it is important to clarify the mechanism of why the Al content happened. For the Ni + Al powder compact (Ni–30 wt% Al), two
can manipulate the porosity during the sintering procedure. Con- exothermic peaks are observed at 579 and 637 ◦ C, respectively.
ventional reaction synthesis usually heats the green compacts in A comparison of the temperature of the exothermic peaks and
912 H.X. Dong et al. / Journal of Alloys and Compounds 484 (2009) 907–913

Fig. 8. SEM morphology of Ni particles: (a) the whole morphology of Ni particle and (b) part magnification of Ni particles.

the XRD analyses results at these temperatures suggests that the is a sudden increase of the volume expansion and porosity when
exothermic at ∼579 ◦ C mostly corresponds to the formation of the sintering temperature reaches 670 ◦ C. There are two reasons for
Ni2 Al3 while the exothermic at ∼637 ◦ C may be due to the formation these: one is that the Al diffusion rate increases with the increasing
of NiAl in the Ni–30 wt% Al compacts. No further endothermic and temperature to promote the formation of Kirkendall pores, and the
exothermic peaks exist in the DSC curve, which means no further other is that small amount of remanent Al powders turn into liquid
extensive reaction when the sintering temperature is higher than phase when the temperature reaches its melting point to help to
637 ◦ C. The exothermic peaks at ∼637 ◦ C observed in both com- form large pores. The diffusion depth of Al can help us to determine
pacts suggest that the formation of the final phase was achieved in whether the liquid Al phase exists. The depth of diffusion can be
one-step. Zhu and Abbaschian [27] indicated the similar formation approximately estimated from the relation:
phenomenon when high heating rate was used. Here a contradic- 
tion appears: the final phase can be formed at 637 ◦ C in the DSC d= D×t (7)
analysis, while Ni2 Al3 , NiAl, Ni, Al, and Ni3 Al five phases co-exist
in the pressureless sintering at the same temperature. The reason where d represents the diffusion depth, D is interdiffusion coeffi-
may be that during the pressureless reaction synthesis, the sam- cient of Al/Ni couple (D = 8 × 10−18 m2 s−1 at 600 ◦ C [31]) and t is
ple dwells at 520, 550, 590 ◦ C for 1 h and then raises to 640 ◦ C, and the diffusion time. When the intermediate such as Ni2 Al3 appears,
a certain amount of intermediates (i.e. Ni2 Al3 ) have been formed, D increases to the value of 1 × 10−14 m2 s−1 at 600 ◦ C [32]. Because
which can act as heat buffer and reduce the contact area between the interdiffusion coefficient varies in different intermediates, here
the elemental powders. Therefore, the reaction during the pres- a mean value of 1 × 10−15 m2 s−1 was used. Therefore, the diffusion
sureless reaction synthesis is controllable and could not form the depth is about 6 ␮m after 1 h heat treatment around 600 ◦ C. Based
final product when the temperature reaches 640 ◦ C. Upon further on this analysis, some remanent Al powders always exist in the
heating, Ni3 Al and NiAl grow at the expense of Ni2 Al3 , Ni and Al compacts for 1–6 h annealing treatment under its melting point,
based on the SEM and XRD analysis. Both Al and Ni disappear at because the particle size is about 38 ␮m. When the temperature
temperature higher than 670 and 750 ◦ C, respectively. During the reaches 660 ◦ C, liquid phase appears and quickly covers the surface
whole reaction synthesis procedure, the intermediate such as NiAl3 of the surrounding particles leaving pores behind. In the tempera-
could not be found. The main point here is that the results from the ture range of 670–750 ◦ C, solid diffusion reaction still exists (see Eqs.
experiment do not agree with other literature [28] for the first phase (4) and (5)) and the volume decreases due to the intrinsic volume
formed at the interface. It has been suggested that the strong reac- change. Up to 1000 ◦ C, Ni–Al compacts become the final products
tion between nickel and aluminium atoms results in NiAl3 as the (see Table 1 (D) and (E)). Figs. 7 and 8 indicate that the volume
first phase to form at the Ni–Al interface, in agreement with the changes and maximum pore size of Ni3 Al reduces more than that
applications of the effective heat of formation rule. Based on lit- of NiAl due to many small pore structures in the Ni3 Al. The rela-
erature [29], the morphology and particle size could influence the tionship between shrinkage and temperature can be analyzed by
intermediates formation during the reaction synthesis mainly due the equation as follows:
to the branched structures of the electrodeposited nickel particles Q 
(see Fig. 8), which has vacancy-enriched zone and high diffusion K = A × exp (8)
RT
paths and, in turn, promotes the diffusion between the Ni and Al
[30]. Based on the above discussion, the formation sequence of the where K is the shrinkage rate, A is coefficient and Q represents
various phases during our experiment of Ni–Al powder mixture the sintering activation energy. Small pores increase the value of
compacts (i.e. Ni–14 wt% Al) is described as follows: Q and, in turn, lead to K increasing. Based on this analysis, porous
Ni3 Al shrinks more and the maximum pore decreases sharper than
Ni + Al → Ni2 Al3 (main reaction) (540–640 ◦ C) (1)
porous NiAl.

Ni + Ni2 Al3 → NiAl (540–640 C) (2)
6. Conclusions
Ni + NiAl → Ni3 Al (540–640 ◦ C) (3)

Ni + Al + Ni2 Al3 → Ni3 Al(Al-rich) (640–670 ◦ C) (4) According to the results presented here for the Al content and
sintering temperature on the porous microstructure of the reaction
NiAl + Ni3 Al + Ni → Ni3 Al (670–800 ◦ C) (5) synthesis starting from elemental Ni and Al powders, the following
Ni3 Al(Ni-rich) + Ni3 Al(Al-rich) → Ni3 Al (950–1000 C). ◦
(6) conclusions may be drawn:

The volume of the sample expands at the temperature range of 1. Porous NiAl and Ni3 Al could be successfully obtained through
540–640 ◦ C due to the formation of Kirkendall pores and interme- pressureless reaction synthesis from elemental powder mixture
diate such as Ni2 Al3 . As can be seen from Figs. 5(c), 6 and 7, there compacts.
H.X. Dong et al. / Journal of Alloys and Compounds 484 (2009) 907–913 913

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Acknowledgements
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