Pluhsophical Magazine, / - N jaylor & Francis

Vol. 85, Nos. 2-3, 11 January 21 Januury 2005. 331-344 V^

Surface mesostructure change of B2-type FeAl single

crystals by condensation of supersaturated
thermal vacancies

KYOSUKE YOSHIMltt*. 1 AK.AYUK1 KOBAYASHIt.

AKIRA YAMAUCHin. TOMOHIDE HARAGUCHMi
and SHUJI HANADAt
"Unstittite for Materials Research, Tohoku University,
Sendai. Miyagi 9S()-X577, Japan
JCenler for lnterdi.sei]ilinary Research, rohoku University.
Sendai, Miyagi 9SU-S578. Japan

Mesoporous surfaces arc tormed in B2-typc KeAl sinyle crystals h\ quenching

into Iced water, followed by stn-fiice treatments and an ageing heat treatment.
The pore shape changes depending on sm-face orientation, because the surfaces of
the mesoporcs are surrotindetl by ;i()()| planes in the same way as mesopores
observed inside rapidly solidifiet! FeAl ribbons. The pore size seems to increase
with increasing temperature of ihe ageing heat treatment. Two rcla.Kation peaks
were observed in DSC thermograms, and the acti\ation energy is estimated to
be appro.\imately l.84eV for the peak in a higher temperature range. TFM
observations suggest that the observed DSC peaks correspond lo vacancy
condensation and or absorption b\ (H)())-iype dislocations. The experimental
results also strongly suggesl thai ihe mesoporc formation near surfaces is
eatised by the condensation of quenched-in. supersaturated thermal vacancies.

I. Introduction

In our recent study on B2-type FeAl [I], it was found that, in rapidly solidified Fe-
45tTiol.% Al ribbons, a large number of tnesoporcs is fomicd, nol only inside the
ribbons but also near surfaces during ihe ageing heat treatment at 723 K.
Tratismission electron tnicroseopy (TEM) observations clarified that the ihree-
dimensional shape of the mesopores inside (he ribbons is euboidal and that their
six surlaees are faceled along the !IOO| planes. The tneasured coneentration of
supersaturated thertnal vacancies in the as-sptin ribbons was approximately 1.4%.
and their lattice parameter was almost completely restored by the ageing heal treat-
tnenl. Consequctitly. we concluded thai ihe niesopore formation is eattsed by the
condensation of supersaturated thermal vacancies. Several papers on ihe formation
of mesoporcs inside bulks by the condensation of cxce.ss thermal vacaneies have been
reported iov B2-lype intertnetallics such as NiAl [2 9] and CoGa [lOJ as well as FeAl

*Corresponding author. Email: yoshimiknf eir.tohokti.ae.jp

Phitosiiphkal Miigiizinc
tS.SN I47K f,4.15 [.riiit tSSN 147M 644.1 ontine i 2l)n5 Ta\lor & l-raricis Lid
htip: www.landl.co.uk journals
DOt: 10.10811 i47MM.ltM12.1.11.11574.1
332 A.'. Yoshitm cl al.

[I I], As regards FeAl. we have various reports on supersaturated vacancies and their
comple.\es other thati mesopores inside bulks [12-18]. However, Ihe formation
of ihe surface mesopores had tiol been addressed until our previous work [I].
Concerning surface morphology ehatige dtie to thertnul vacancy condensation,
thermal pil fortnation has been extensively studied, pattieulariy for Al. through
the I96()s to the early 1970s (eg, [20-26]) since it was lirst reported by Doherty
and Davis in 1959 [19]. The tnajor differences between the tnesopore fortnation in
the tapidly solidified Fe 45 mol. % Al ribbons atid the thennal pit fonnation in Al
arc (i) the size of the mesopoies in FeAl is stnaller in tnagnitude by at least two
orders than that ofthe thermal pits in Al, (ii) the tctnperature able to induce the
mesopore fottnation in FeAl is much lower than the tnelting point of FcAt (< 0.57',,,).
whereas the temperature at which the thermal pit formation occurs in Al lies in the
vicinity ofthe tnelting point of Al (>0.97"n,), and (iii) tnesopore formation can occur
Litider a vacuum in FeAl. but not in Al. These differetiees may cotne from the
difference in the concentration of supersaturated thertnal vacancies. Kasen et al.
[27] investigated the effect of the environmctit on the thertnal pit fortnation in AI.
and they found that large vacancy-condensation pits were formed by quenching
in air but the pit formation was completely inhibited in a vacuutn. As a result,
they concluded that surface oxidation is neeessary for the thetmal pit formation
in Al in order to etnit a large nutnber of vacancies. However, surfaee oxidation
hardly proceeds under the mesopore formation cotidition at 723 K in FeAl [28].
On the other hand. B2-type FeAl is well known as an intermetallic
compound with a high concentration of thertnal vacancies at high temperatures.
Ho and Dodd [29] experimentally tneasured the concentration of thertnal vaeaneies
in FeAl — approxitnately 0.9"/,, at 1173 K for stoichiometrie FeAl. Chang ct al. [30]
estimated the vaeatiey eotieen tra tion using therniodytiatnic calculations approxi-
mately 2.0% also at 1173K for stoichiometrie FeAl, In our previous works, the
concentrations of thermal vacancies quenched itito rapidly solidified ribbotis wete
approximately 0,3% for Fe 40mol."'oAl. 1.4% for F-""e-45mol.% Al and 2.5% for
Fe-50mol.%Al [2. 31. 32]. Actually, the concentration oi thermal vacancies has
obviotis eotiiposition depctidcnce in B2-type FeAl. i.e. it increases with increasing
Al concentration [29, 30, 33-36], Furthermore, the concetitrations of quenehcd-in.
supersaturated thermal vacancies experimentally determined for higher alutninium
concentrations [29, 35 37] are comparable to or higher than that oi the rapidly
solidified Fe 45tnol.%AI ribbons [I]. These experitnental restilts motivated us to
study quenched bulk FeAl, If the mesoporous surfaces can be produced in bulk
FeAl. its surface morphology would be controllable on a tiano- to mesosealc by
controlling the surfaee orientation, vacancy concentration, heat treatment and so
on. The purpose of this work is to investigate the condensation behaviour of super-
saturated thermal vaeaneies in FeAl single erystais through rapid quench and ageing
treatment.

2. Experimentui procedure

Polycrystallitie Fe-49mol,%AI was produeed by are-tnelting in an argon

altnosphere frotn 99.99 tnass % aluminiutn and 99.99 tnass "/a electrolytic iron.
The cast ingot was homogenized at 1373 K for 4S h. and sliced into disks of about
I mm thiekness. The sliced disks were annealed at 1273 K for 1 h, and then quenched
 Surface nicso'itriiciurc chaii.ae of B2-type te.M .•iiui^te cry.stals 333

in iee water. During this water-quenclnng process, the disks fractured along grain
boundaries, and consequently, rapidly quenched one-grain plates, i,e.. single crystal
plates, were obtained. The plate si/e was a lew millitnetres in diameter. One side
of the single crystal plates was grotmd. and thinned up to a thickness of about
0.5 mm. The ground surfaces were further tncchanically polished with a complex
of diamond shirry and altnnina paste, and subsequently electropolishcd in a solution
of CH3OH:HNOi = 2:l at about 5 V and 250 K. for 60s to retnove plastic strain near
the surfaces. Furthermore, the surfaces ofthe plates were cleaned using a South Bay
Technology PE-2000 plastna cleaner in an oxygen atmosphere with a forward power
of 20 W for lOtnin. and then in an argon attnosphere with 50 W for 15min. Then, the
plates were aged under a \acuuni (approximately 5 x 10" Pa). Finally, the surfaee
orientations oi the single crystal plates exatnined were detertnined by the Latie
method.
Surface morphology was examined using a Hitachi S-4300 scanning electron
microscope (SFM) and a Digital instruments Nanoscope III atomic force
microscope (AFM). Thertnal analysis was carried out for as-quenched single crystal
plates using a Netzsch DSC404 difTcrential scanning calorimeter (DSC). The
attnosphere of the isochronal tests was high-purity Ar gas. and the lie^ttitig cooling
rates were ranged between 5 and 50Ktnin '. Thin foils for ttanstnission election
microscopy (TEM) were prepared by electropolishing using a Struers Tenupol-3.
TFM observation was done using a JEOL JEX-2000 EX II at an acceleration voltage
of200kV.

3. Results

Mesoporous formation occurred near electropolished surfaces of rapidly quenched

single crystal plates after the ageing heat treatment in \acuutn; this formation was
never observed without electropolishing. The mesopore fortnation also occasionally
occurred in as-hotnogenized disks after eleetropolisbing and the ageing heat treat-
ment. However, the density of mesopores in the as-homogcnizcd disks was tnueh
lower than that in the rapidly quenched single crystal plates. Plasma cleaning suc-
cessfully removed contatninations adhered on the surfaces during the electropolish-
ing process. Figure 1 shows the surface morphology of single crystal plates aged at
723 K for 10 h. The surface orientation of each plate is shown in the standard ttiangle
of [001] [011] [11 I]. It is clear that the pore shape changes depending on the surface
orientation. It is interesting to note that the observed pore shapes corresponded well
with the shapes of tbe stirface orientations illtistrated in the unit cell. These results
indicate that the mesopores fortned near surfaces arc also surrounded by ; 100}
planes, as suggested in our previous work [1],
Figure 2 shows the efteet ofthe ageing tetnperature on the mesopore formation
near surfaces. The ageing time was fixed at 10 h for all oi the examined single
crystal plates. At and above 573 K, the occurrence of the pore fortnation is
confirmed, as shown in figures 2b-e. In contrast, no potes were observed at 523 K
(figure 2a), suggesting that the ageing temperature and or time was not high and/or
long enough, respectively, to diffuse and cotidense supersaturated thennal vacancies.
The pore size appears to iticrease with increasing ageitig temperature. Furthertnore,
at 873 and 973 K, the tnieropore formation beyond 500 ntn was often observed, as
shown in figures 2d and 2c. Figure 3 shows the SEM micrographs oi the surface
334 K. Yo.shimt ct ;i

001 011 001 oil

111

001 oil
Figure 1. SLirfiice-orientation dependence of the shape of siirf:ice mesopores formed by
aging heat treatment at 723 K fbr lOh. Each surface orientation is shown in the standard
triangle of [001] [Oil] [111].

morphology observed in other single crystal plates that were aged at S73K. It is
found that there are two types of pores near surfaces: one is large micropores and the
other is mesopores between the micropores. The shapes ofthe tnesopores are in good
correspondence with those predicted from the relatiotiship between the surfaee
orientations and the [100] planes, as shown in the attached schematic illustrations
of figure 3. On the other hand, some micropores obviously have new, additional
surfaces that arc difTerent from the 1100] planes. However, the indices ofthe addi-
tional surfaces have not yet been clarified.
The growth process of mesopores near surfaces was tracked with the ageing time
at a location of the surfaee of a single crystal plate. The plate was first aged at 723 K
 Surface mesoslructure change of B2-lype FeAl sint^le ervstals 335

Figure 2. Ageing temperature dependence ol' siirfiiee mesopore formation. The ageing time
is fixed at 10 h tor all the ageing heat treatments. ( a ) 5 2 3 K . ( b ) 573K.(c-) 723 K. (d) f<73k and
(e)973K.

for 600s in a vacuum of approximately 5 x 10 "'Pa. rollowcd by additional ageing

heat treattnents Ibr 1.2 ks and then I h tmder the same vacuum condition. The plate
was heated at a heating rate of 50 K tnin ' and air-cooled in the furnace by sliding
the heater otit fbr each ageing step, Figtire 4 shows the SHM micrographs taken at
the same position of the plate surfaee after each ageing step. As shown in figure 4a.
mesopores are already fortned near the surface dtiring the initial ageing step for
600s. Figures 4b and 4c show that with increasing ageing titne, some tnesopores,
e.g. those marked by arrows, coalesce and grow. Although the plate was further aged
at 873 K for I h after the ageing step at 723 K for 1 h, no further noticeable growth
or change ofthe mesopores was observed. The growth of surface tnesopores appears
complete during the ageing step at 723 K for I h.
Figure 5 shows the DSC ctirves of the heating steps obtained for as-quenched
single erystal plates during three-cycle isochronal tests at heating rates from 5 to
336 K. Yoshimi et al.

Oil

Figure 3. Mieropore formation during ageing heat treatment at 873 K for lOh. Each surface
orientation is shown in the siaiidard triangle of [001] [011] [111].

40Ktnin~', At the heating rate of 40Kmin ', a large exothermic peak appears in
the first step. The onset temperature ofthe peak lies between 673 and 723 K and the
peak temperature is about 900 K. However, no peak appears in the seeond and third
steps. This evidence indicates that the phenomena generating the cxotliertnic peak
is a one-way reaction and is not reversible. The peak height decreases and its position
shifts to a lower tetnperature as the heating rate decreases. For lower heating rates,
i.e. at and below 20 K min ', the peak faintly splits into two. The two peaks appear-
ing at the lower heating rates also shift to lower temperatures as the heating rate
decreases. The change in the peak position by the heating rate tneans that the
phenomena are cau.sed by relaxation processes. These exothermie relaxation peaks
should be related to the annihilation process of supersaturated thennal vaeaneies
accompanied with migration and clustering. The Kis.singer plots [38] for these peaks
arc shown in figure 6. In this figure, the data obtained in the lower temperatnre range
at the lower heating rates are otnitted, because they are not suffieiently reliable. The
peaks observed at higher heating rates and those in the higher temperature range at
lower heating rates have a linear relationship. The estimated activation energy is
approximately 1.84±0.03eV.
The substructures of single crystal plates were observed by TEM. Figure 7a
shows the TFM tnicrograph obtained in an as-quenehed single erystal plate. The
incident beam direction was neariy parallel to [101]. A certain number of dislocations
whose Burgers vectors are parallel to {100) already exist in the as-quenched single
crystal plate. Figure 7b shows the substructure of a single crystal plate heated up
to 723 K at a heating rate of 30 K min"' in a vacuutn and then air-eooled, without
any holding time in a furnace, by sliding the heater out. The temperature of 723 K
is close to the onset tetnperature of the exothertnie peak in the DSC curve obtained
at a heating rate of 30 K, tnin"', as shown in figure 5, The incident beatn direction
was nearly parallel to [101], There are matiy loops atid helices of the {IOO)-type
dislocations and the dislocation density is obviotisly increased by the heat trcattnent,
as shown in figure 7b. This result indicates the occurrence of vacancy condensation
 Surface mesostruetnre chiini;e of B2-lype FeAl single crystals 337

Figure 4. SEM mici\>giapli series taken at the same position aged at 72.3 K for (a) 600s,
(b) an additional l,2ks, and (c) an additional 1 li.

4CX) 450 500 550 600 650

Temperature, T / K
Figure 5. DSC eurves of heating steps obtained during three-cycle isochronal tests.
The heating/eooling rates, a. are shown in the figure.
338 K. Yoshimi et al.

-14

Y= \io + Mrx
MO 9.6264
Ml -21.293
-14.5 R 0.99959

-15.5 1.84 +0.03 eV

-16 -

1.08 1.1 1.12 1.14 1.16 1.18 1.2 1.22

Figure 6. Kissinger plot.s for e.\othermic peaks ttbserved in the DSC curves of figure 5.
Solid symbols correspoiid lo ihe peaks obtained at higher heating rates and open symbols
to those at lower heating rates,

und/or clitiibitig of the (lO(})-type dislocations by the absotption of supersaturated

thermal vacancies during the heat treatment. Figure 7c shows the substructure of a
single crystal plate heated up to 9I3K. at a heating rate of 30Ktiiin"' iti a vacuum
and then air-eooled in the satne way as that shown in figure 7b. The temperature of
913 K is just above the peak tetnperature of the exothermic peak in the DSC curve
obtained at a heating rate of 3()Kmin~'. The incident beatn direction was also
nearly parallel to [lOl]. In figute 7e, the density of {lt)O)-type dislocations is further
inereased by the heating treatment as compared with figure 7b. These disloeations
are well-arranged alotig (101) and (020} direetions. indicating that they are edge
disloeations. This dislocation arrangement is quite similar to the typical arrangement
of the (lOO)-type dislocatiotis formed by the vacancy condensation [II. 15].
Thetefore, it is strongly suggested that (he exothermic relaxation peaks observed
in figure 5 are related to the annihilation proeess of supersaturated thermal vacan-
cies. However, no internal mesopores were observed in any of the single crystal
plates that wete annealed through the above conditions.

4. Discussion

One of the mechanisms responsible for the pore growth near the surface should be
"coalesceiuv'\ The coalescence process still requites the supply of supersaturated
thennal vacancies toward surface pores, as shown in figure 4. Unfortunately, the
mechanistn(s) for the pore nueleation is unknown ut present. McCarty ct al. [39]
reported that, in NiAl. alotnic steps on surfaces behave as preferential sinks
and sourees of thermal vacaneies in the bulk. The surface pores may also
 Siirfme mesostructure ehanf^e of liJ-iype FcAt single crystals

Figure 7. T E M mierographs o\' typical substructures developed during heating at 30 K min"

and air-cooling in a fLirnaee. (a) as-qtieiiched. (b) heated up lo 723 K.. and (c) tip to 913 K.

nucleate preferentially at atomic steps on surfaces of FeAl. Riviere et at. [40]

previously studied the annealing kinetics of supersaturated thermal vacancies in
Fe-40mol.% Al. They reported that the critical size of clusters actitig as the nucle-
ation sites for disloeation loops corresponds to a clustering of four to six vacancies.
Comparable clustering of vacancies may also occur near stirfaces for the nucleation
ofthe surface pores. During the absorption process of supersaturated thermal vacan-
eies. if there are no lattiee defects such as dislocations and grain boundaries in
the area, stirfaces would be able to absorb ahnost all the supersaturated thermal
vacancies existing in a specific thickness just below the surface. Else, sotne of
the supersaturated thermal vacancies are absorbed, for example, by dislocations.
Thus, if the dislocations introduced by tnechanically polishing remain, the mesopore
fortnation would be suppressed, ln conttast. supersaturated thermal vacancies exist-
ing far from the surface would cluster locally or be absorbed by the other lattice
defects, as schematically illustrated in figure 8a. As a result, a defect-free zone would
be generated at a certain depth jttst below the surfaee. Considering this hypothesis,
we can construct a model for the distribution of surfaee pores formed by the con-
densation of supersattirated thermal vacancies. To simplify the model, we assume
that (i) the pore shape is euboidal. (ii) the size of all pores is identical to /;,. and (iii)
nucleation occurs homogeneously near the surface. Supersaturated thermal vacan-
cies are supplied from a thickness jusl beUnv the surface, (/. which is approximately
340 K. Yoshinii et al.

half t>f the defeet-free zone., as shown in figure 8a. Assuming that the total nutnber oi
pores formed in a surface area of /. x /, is z/^,. the average pore distance. (//,. is

(1)

By neglecting the lattice relaxation for the surface, pores., and vacaneies, the stim
of pore volumes is identical to the sutn of vacancy volumes. Hence, when the
concentration of supersaturated thennal vacancies is (\.. we obtain the following
re!ati<)nal expression,

L- d • Cy = n/,, (2)

Con,scqucntly. the average distance between surface pores fortned in the area
of L X L is simply expressed by cotnbining equations (I) and (2) as

(3)

Figure Sb shows the relationship between d^, and /^, as cited above. The values of
1 and 0.01% are applied for c\- in the tnodel. Although we are not aware of any
available published data on a defect-free zone below the surfaces of FeAl. here, d is
assutned to be 200 nm. because a pore-free zone of about 400 500 nin along grain
boundaries was observed near the surfaces of polyerystalline FeAl in our preliminary
work. The average pore distance is tnonotonously increased by increasing the pore
size irrespective ofthe vacancy concentration, as indicated in equation (3). In the
case of (•,.= 1%. //, > dj, when /,, < 2 n m . This means that, in the range of /^<2nm,
pores that are homogenously fortned near the surface overlap, as shown in figure 9a.
This overlapping bears resemblance to "co(dcscence\ The critical size of vacancy
clusters for nuciealion proposed by Riviere ct id. [40] is also estimated to be approxi-
mately 0.5 nm on the basis of this model. This value is much smaller than the
transition pore size of 2nm. suggesting that the coaleseence process proceeds to a
certain extent from the nucleation. On the other hand, the overlapping does not
occur in the present model when /^>4nm. as is scheinatiealiy shown in figure 9b.
This estimation suggests that, because ofthe exhaustion of supersaturated thermal
vacancies, the pore growth will stop at around I,, — 4 nm unless the coalescence due to
inhomogeneous nucleation occurs. Accordingly, the obtained results may suggest
that the pore nucleation is inhotnogeneous, whieh is induced at preferential nuclea-
tion sites. When <•,, — 0.01%, whieh may be regarded as the case for metals and
alloys, the transition pore size of/^ = d^, is 0.02 nm, which is very small and unrea-
listic. It is worth noting that this transition pore size is also much smaller than the
nucleus size of appro.ximately 0.5 ntn estimated from the proposal by Riviere et al.
[40]. and that dp at /,, = 0,5ntn is estimated to be 2.5 nm. These estimations indieate
that the coalescence is unlikely to occur at any stage ofthe condensation of super-
saturated thermal vacancies for r,. — O.OI'Vd. In other words, diftetent mechanisms,
such as surface oxidation, should be necessary for the thennal pit formation
observed in metals and alloys to etnit a large number of additional vacancies [27].
Although the valties estimated above have atnbiguities, the concepts obtained
through this model will be useful to discuss the surface pore formation mechanisms
hereafter.
 Surface incsostruitwc chan^n' af B2-l\pe Fc.-il sin^tv crystals .141

dp surface

•J— n

10'

E cy=200nm
c

0)
u
c
(0

o
0)
o
Q. 10'
a>
(0 2 nm
o 10"

10
10 10' 102

Pore Size, Ll nm
Figure K, (a) Schctnalic illustration ofn cross sei;tion near a surface for the pore dislribtitioii
model. Open circles indicate vacancies, (b) Relationship between average pore distance, d^.
and pore size, lp. for the vaeaney coneentralions of I and 0.01%,

The pore size appears lo increase by increasing llie lempcralure of the ageing
heal treatment, as shown in figure 1. In ihc above model, d may become large
in addilion to the activation of suiface diffusion wilh increasing temperalure.
Furthermore, the growth of micropores was observed al higher ageing lempetalures,
as shown in figure 3. However, it is very diificult lo explain the formation o\ such
large pores by the above model. The surface oxidation mechanism [4, 5, 27] should
be taken into account for the mieroporc formation. Our recent study on the surface
342 A.'. Ycshiini ct ;il.

r
'—-
f— 'r
J .
- — •

L.

'j -

(a) (b)
Figure 9^ Schcniiitu^ illtistrations of lhe modelled pore dislribulions near Ihe
(a) Ip > dp. (b) Ip « dp.

oxidation of FeAl single crystal under a high vacuum by auger electron speetroseopy
(AES) [28] revealed Ihat. in the higher temperature range, surface oxidation is gra-
dually enhanced with inereasing temperature. This result strongly supports the sur-
face oxidation mechanism responsible for lhe micropore formation.
From the DSC measurements, it was observed that ihere are two exothermic
reactions at lower heating rates, as shown in figure 5. Zaroual et al. [41] observed
a distinet exothermie peak between 674 and 873 K in the DSC ihermograms
in quenched FeAl bulks. From the results of magnetie susceptibility measurements,,
they eoneluded that the peak is attributed to the migration and relaxation
of supersaturated vacancies. They also reported an activation energy of l-2eV for
the relaxation process of Fe SOmoI.'Vn Al. This value is mueh lower than that of
I.84eV obtained in the present work, Sinee they derived the value al a time when the
fraction of the eliminated vaeaneles was 0.5, this dilTerent operation would lead to
different activation energies. Yang and Baker [42] also observed two exothemiie
peaks in lhe DSC measurements using Fe 40mol."/oA! single crystals. The peak
temperatures for these two peaks are eonsiderably lower than those observed in
the present work, whieh might be due to the difference in composition. The vaeaney
foimalion enthalpy of about I.OfieV for Fe-40mol%AI obtained by Yang and
Baker [42] is in good agreement with the values previously reported by Riviere
and Grilhe [13, 43], and Wi:irschum et al. [44]. These indicate that DSC measurement
is a convenient and competent method to investigate the thermodynamie behaviour
of supersaturated thermal vaeaneies. TEM observations (tigure 7) also strongly
suggested that the peaks lying in the temperature range correspond to vacancy
condensation and absorption by (lOO)-type dislocations. Thus, it is considered
that the exothermic relaxation peaks are related to the absorption proeesses of
supersaturated thermal vacancies accompanied with migration and clustering.
However, in lhe present work, the reactions ihat occur under lhe two peaks observed
at lower heating rates is still unelear. Further studies are required to clarify the
absorption processes of supersaturated ihernial vacancies in FeAl.
 Surface incsostrurna-c chaiii^c oJ B2-/ypc f'cAl siii^/c cry.\riils 343

5. Conclusions

In this paper, the condensation behaviour of supersaturated thermal vacancies in

FeAl single crystals is investigated. The mesoporous surfaces are formed through
some surface treatments and an ageing heat treatment after quenching in ice water.
The obtained results strongly suggest that the mesopore formation near surfaees
is caused by the condensation of supersaturated thermal vacancies. Though the
mechanism for the nucleation of the mesopores near the surface is unknown at
present, one of the mechanisms for the growth should he the eoalescenee of the
mesopores. Different mcchanism(s) such as surface oxidation should also be taken
into account for the growth process.

Acknowledgments

The authors thank M.H. Yoo of Oak Ridge National Laboratory. USA. for
his constructive diseussion and comments on this work. This work was supported
in part by the Grant-in-Aid for Science Research from the Ministry of
Education, Culture. Sports. Science and Technology of Japan, under the contract
No. 16360339.

References

[!] K.. Yoshimi. S, Hanada. T. Haraguchi, H. Kato. T. lioi and A. Inotie. Mater, Trans. 43
2897 (20(12).
[2] W. Yang. R.A. Dodd and P.R. Strutt. MetLtll. Trans. 3 2049 (1972),
[3] W..I. Yang and R.A. Dodd. Scripla met;!l!. 8 237 (1974),
[4] H.L. Fniscr. M,H, Lorclto. R.E. SiiKilIman and R J. Wasilewski. Phil. Mag. 28 639
(1973).
[5] H.L. Fraser. M.H. LorcUo, R.E. Smiillman and R.J. Wasilewski. Phil. Mag. 32 S73
(1975).
[6] J,E. Eibner. H.-J. Engell. H. Schtillz. !i. Jacobi and Ci. Schlatte. Phil. Mag. 31 739 (1975).
[7] J.E. Epperson, K,W. Gerslenbcrg. D. Berner. G, Kostorz and C. Ortiz, Phil, Mag, A38
529(1978).
[8] A. Parthasaratlii and H,L, Fniser. Phil. Mag, A 50 S9 (19X4).
[9] M, Zakaria and P,R. Mtjnroe. J, Mater. Sci, 37 71 (20(12),
[10] R, Schwab and V, Gcrokl. .Ada mctidl. 28 433 (I9S(I).
[11] M.A. Morris, O. George and D,G, Morris. Maler. Sci, Engng A 258 99 (1998).
[12] N. JtinLjua. i.C. Dcsoyer and P. Moinc. Phys. Stal. Sol, (a) 18 3S7 (1973).
[13] J,P, Riviere and J, Grilhe. Aeta melall. 20 1275 (1972).
[14] A, Fourdcux and P. Lcsbats, Phil, Mag, A 45 SI (1982),
[15] I. Baker and D.J. Gaydosh. Phys, Stal. Sol, (a) 96 185 (19X6),
[16] C L . Fu. Y,Y, Ye. M,H, Yoo and K M , Ho, Phys, Rev, B 48 6712 (1993).
[17] K, Yoshimi. S, Han;ida. T. Onutna and M,H, Yno. Phil, Mag. A 73 443 (1996),
[IS] D.G. Morris. J,C. Joye and M. Lebnciif. Phil, Mag. A 69 961" (1994),
[19] P,E. Dohcrly and R.S, Davis. Acta mcialL 7 IIS (1959).
[20] M.B. Kasai and D-H- Polonis. Ada melall. 10 821 (1962),
[21] J,R, Jasperse und P.L. Dohcrty. Phil, Mag. 9 635 (1964).
[22] B,K, Basil and C. Elbaum, Ada metali. 13 1117 (1965),
[23] B.K, Tariyal and B, Ritniaswami, .!, appl. Phys. 40 4822 (1969),
[24] B.K, Tariyal and B, Ramaswami, J. appl. Phys. 42 948 (1971).
[25] T.R. Anthony. Ada melall, 18 307 (1970),
344 Surface im'sostriicunr clnin^iL' of Bl-typc FcAl sini^lc cryslals

[26] T.R. Anthony. Ada mdall. 18471 (1970).

[27] M.B. Kascn. R. Taggarl and D.H. Polonis. Phil. Mag. L3 453 (1966).
[28] A. Yamauchi. K, Yoshimi. T, Haragtichi and S. Hanada. Mater, Trans, 45 365 (2004),
[29] K. Ho and R,A. Dodd, Scripta mdall. 12 1055 (1978),
[30] Y,A, Chang. L.M, Pike, C T . Liti. A.R. Bilbrey and D.S, Stone. Inlcrmelaliics I 107
(1993).
[31] T, Haragtichi. K, Yoshimi, H, Kalo. S, Hanada and A, lnotnj, iiHcrmdallics II 707
(2003),
[32] T. Haraguchi. K, Yoshimi. H. Kalo. S, Hanada and A. Inouc. Piiperpnwciiicciai Surface
Eiifiiiu'vriiii^ in .Maicrial.s .Siifiice ll (2003).
[3.1] D. Paris and P, Lesbals, .1, nuci, Maler, 69-70 62S (1978).
[34] H. Xiao and I, Baker. Acta mdall, mater. 43 391 (1995).
[35] M. Kogadii and T. Haragitdii. Mater, Sci. Engng A 230 124 (1997).
[36] L M . Pike. Y.A, Chang and C.T, Liu. Ada mater. 45 3709 (1997),
[37] D, Paris, P. Lesbals and J. Levy, Scripla metall. 9 1373 (1975).
[38] H,E. Kissinger. Anal, Chcm, 29' 1702 (1957).
[39] K.1-. McCarty. J,A, Mobcl and N,C. Bartclt, Nature 412 622 (2001).
[40] .I.P, Riviere, H, Zonon and Grilhe, .1,. Phys. Slal. Sol, (a) 16 545 (1973),
[41] S, Zaroual. O. Sassi. J, Aride, J, Bernardini and G, Moya, Mater, Sd. Engng A 279 282
(2000),
[42] Y, Yang and I. Baker. Maler, Res. Soc Symp, Proc, 552 KK8,22.l (1999).
[43] J.P. Riviere and J. Grilhe. Scripta melall. 9 967 (1975),
[44] R, Wiirschum. C. (irupp and H,-E. Schaefer. Phys, Rev, Lett, 75 97 (1995),