Overview

Enhancement of high temperature

strength and room temperature ductility of
iron aluminides by alloying
Aruna Bahadur

The chemical ordering in intermetallics results in reduced atomic mobility and therefore increased resistance to
plastic deformation at elevated temperatures. This intrinsic source of high temperature strength leads to the inherent
brittleness of polycrystalline ordered intermetallics at room temperature. The requirements for optimum high
temperature strength and ductility at ambient temperature are often incompatible. Iron aluminides possess high
strength up to 873 K. There is an anomalous (positive) temperature dependence of yield and  ow strengths. Iron
aluminides have yet to achieve satisfactory elevated load bearing capability. Alloy additions have the potential for
improving elevated temperature strength and room temperature ductility; whichever is more critical for the
application. Elements such as Cr, Ti, Mn, Co, and Mo produce higher  ow stress due to solid solution strengthening.
Elements such as Zr, Ta, Nb, Re, and Hf go into solution partly, reprecipitate, effectively pin dislocations and
thereby cause strengthening. Mo, Zr, and Hf produce good tensile strength at elevated temperatures but ductility
decreases. Element B strengthens by grain boundary cohesion. The improvement in room temperature ductility can
be achieved through modiŽ cation of the crystal structure by changes in stoichiometry, macroalloying, microalloying,
and control of the environment. B, TiB2, and Cr are notable for enhancing ductility. The paper is an overview of the
present status of iron aluminides in this respect. MST/5682

The author is in the National Metallurgical Laboratory, Jamshedpur 831007, India (aruna@nmlindia.org).Manuscript received
29 October 2002; accepted 14 April 2003.
# 2003 IoM Communications Ltd. Published by Maney for the Institute of Materials, Minerals and Mining.

be maintained even up to about 0.7Tm in these materials,

Introduction which makes them attractive for high temperature applica-
tions. Iron aluminides are reportedly superior in strength to
Increasing demand for inexpensive materials with high 316 stainless steels and modiŽ ed 9Cr – 1Mo steels up to
strength and low density for elevated temperature applica- 873 K. The strengths of all three drop rapidly above this
tions in highly corrosive environments has stimulated temperature (Fig. 1).3 The peak in the yield and  ow
interest in the development of iron aluminides (Fe – Al). strengths for Fe 3 Al alloys (Fig. 2)4 depends upon the
Ordered intermetallics possess a stronger bonding between critical temperature Tc for the DO3 dB2 transition. The
dissimilar atoms and a strong tendency for chemical temperature– strength anomalous behaviour of Fe3 Al in
ordering, resulting in reduced atomic mobility and there- the DO3 region is associated with the degree of ordering.
fore, increased resistance to plastic deformation at elevated The strength peak is observed at some intermediate degree
temperatures. The principal effects of ordering on mechan- of DO3 below DO3 „B2 transformation temperature. A
ical properties arise from the changes in dislocation simplistic hypothesis to explain the anomaly is that the
conŽ guration due to the added constraints that ordering increase in YS on heating DO3 alloy occurs because of age
places on the nucleation and the motion of dislocations. hardening due to a precipitation as well as B2 formation.
This intrinsic source of high temperature strength leads to The rapid decrease in YS above Tc is considered to be due to
the inherent brittleness of polycrystalline ordered inter- overaging of this structure.5
metallics at room temperature. Both strength and ductility The Ž rst type of model to explain the yield strength
are important for structural applications, however, the anomaly (YSA) involves dislocation locking. For Fe 3 Al,
requirements for optimum strength at elevated tempera- only unit dislocations with associated anti phase boundary
tures during operation and optimum ductility at ambient (APB) trails are observed for Al less than 25% with DO3
temperature during fabrication and handling are often order. The spacing r between dislocation pairs comprising
incompatible and a compromise has to be arrived at. superlattice dislocations is inversely proportional to the
square of long range parameter L. Between 673 K and Tc ,
L decreases from 0.8 to 0.6 At low temperatures, L is high;
Mechanical properties of Fe – Al unit dislocations tend to associate in pairs. Their motion
does not create APBs and hence strength decreases. At
low values of L, r is large and energy of connecting
A large number of ordered intermetallics are shown to APBs is small, allowing constituent dislocations to glide
exhibit anomalous increase in yield strength at temperatures independently, leaving APB trails, creating wrong bonds,
around half the homologous melting point,1 but Fe – Al was and hardening the alloy. At T greater than Tc , L~0,
not believed to be one of them. Recent studies have shown strengthening is due to short range order and is less marked
that Fe – Al alloys do exhibit anomalous strengthening and compared to the strength in the presence of long range
a yield strength peak at around 0.45 of melting tempera- order. The strength is the maximum at intermediate values
ture.2 High quenched in thermal vacancy concentration at of L where superlattice dislocations # 111$ can dissociate
low temperatures as well as Ž ne grain microstructure raises into constituent # 001$ z# 110$ unit dislocations.7 ,8 The
the low temperature strength and obscured the yield dislocations multiplication is balanced by a strong exhaus-
strength peak earlier. Good mechanical properties can thus tion resulting from thermally activated locking.9 ,1 0 For a

DOI 10.1179/026708303225008266 Materials Science and Technology December 2003 Vol. 19 1627
1628 Bahadur Enhancement of high temperature strength and room temperature ductility of iron aluminides

3 Comparison of temperature dependence of yield stress

of large grained low temperature annealed FeAl alloys
near stoichiometry, strained at 1610 4 s 1 (Ref. 12)

strength peak can be pushed to higher temperatures. A

small addition of B (100 at. ppm) reportedly shifts the yield
strength peak 200°C and 175 MPa higher compared to the
B free alloy.1 0 The prominence in the yield strength peak
decreases as aluminium concentration increases (Fig. 3).1 2
No peak was observed in stoichiometric FeAl. 1 2 However,
this transition of type of dislocations alone cannot explain
the peak in yield strength since the temperature of the peak
stress appears to be approximately independent of compo-
1 a Yield strength and b ductility of various Fe3 Al type
alloys (courtesy C. G. McKamey, Oak Ridge National
sition, whereas the temperature of the slip transition
Laboratory3 ) depends strongly on composition. Also, a mechanism is
needed whereby # 111$ slip becomes increasingly difŽ cult
Fe – 40Al (all compositions in this paper are in at.-%), the with increasing temperature in order to produce a yield
change in deformation mode by # 111$ slip at low stress peak. The proposed decomposition of # 111$
temperature and # 100$ slip at higher temperatures appears dislocations locally into # 001$ and # 110$ segments,
to be responsible for the peak in YS.8 ,1 1 The dislocations are which then act as primary centres against # 111$ slip was
much less mobile at {100} planes. The reduction of YS at not observed in a boron doped Fe – 45Al, which exhibited
very high temperatures occurs because of enriched disloca- anomalous yield behaviour.1 3
tion mobility on {100} planes, which reduces and Ž nally The second model to explain YSA does not depend upon
eliminates the pinning centres formed at lower tempera- the change of slip vector. The concentration of thermal
tures. By adding elements which increase Tc , i.e. cause vacancies in intermetallic compounds with bcc derived
stability of DO3 structure relative to B2 structure, the yield ordered structures is generally high. It was suggested to be
on the basis of interaction between dislocations and thermal
vacancies.1 4 – 1 6 Since the vacancy concentration Cv varies as
exponential (21/T) and the hardening due to vacancies
varies as (Cv )1 /2 (Fig. 4),1 7 this model predicts an exponen-
tial increase in strength at intermediate temperatures
with increase in temperature. Accordingly, solid solution

2 Variation of 0.2% yield stress with temperature for 4 Relationship between microhardness and square root
Fe – 25Al alloy4 of vacancy concentration in FeAl17

Materials Science and Technology December 2003 Vol. 19

 Bahadur Enhancement of high temperature strength and room temperature ductility of iron aluminides 1629

3. Intrinsic weak grain boundaries leading to IG fracture

or because the disorder associated with the grain boundaries
leads to intrinsic poor cohesion.
4. Detrimental grain boundary segregation such as S is
responsible for extrinsic grain boundary brittleness.1 9
5. Environment effects: it has been established that Fe –
Al alloys are not inherently brittle, but extrinsic effects like
environment may be the reason for poor RT ductility.
Fe – Al exhibits a peak in susceptibility to hydrogen at
ambient temperatures, which diminishes to negligible levels
at temperatures more than 100 K above or below the
ambient.2 0 This may be due to the concentration of atomic
hydrogen at critical trap sites such as grain boundaries or
dislocations. Low temperatures limit diffusion rates and at
high temperatures, trap occupation decreases rapidly. Other
studies demonstrated that the embrittlement is due to the
chemical reaction of water vapours (not dry hydrogen) at
the metal surface (e.g. crack tip), resulting in atomic
hydrogen. It enhances dislocation mobility at crack tips,
reduces cohesive strength and causes crack propagation.2 1
5 Schematic diagram showing subdivision of yield stress15
The susceptibility to hydrogen embrittlement is enhanced
by atomic ordering, since transport of hydrogen by moving
hardening by thermal vacancies describes the anomalous dislocations can be effectively accompanied by planar slip in
yielding behaviour for FeAl quite well. It was suggested that ordered states.2 2 A threefold increase in percentage elonga-
at temperatures immediately below yield stress peak, region tion is reported in Fe3 Al in vacuum or oxygen atmo-
III in Fig. 5,1 5 thermal vacancies are essentially immobile sphere.2 3 Even Fe3 Al alloys heat treated to the DO3 state are
and impede dislocation motion. However, at temperatures found to be more susceptible to environmental embrittle-
above the peak, region IV in Fig. 5, and the vacancies are ment than those in the B2 state.2 4 This effect may be
sufŽ ciently mobile to migrate and assist climb, instead of correlated to the different superlattice dislocations exhibited
impeding dislocations so that deformation occurs by dis- by these structures or the differences that may exist in
location creep. This vacancy hardening model is supported surface chemistry, which may alter the rate of water
by many experimental observations and it predicts new dissociation.2 5 As the amount of Al increases, the suscept-
effects. Nevertheless, it has not been possible so far to ibility to hydrogen embrittlement increases. Alloys with Al
explain the orientation dependence of the yield peak in greater than or equal to 40% fail intergranularly and exhibit
single crystals. Also, the tension/compression asymmetry of low percentage elongation, irrespective of test environment.
the yield stress cannot be explained yet. RT embrittlement through the formation of hydrogen
Iron aluminides have yet to achieve satisfactory elevated leads to ductility being strain rate dependent because of
temperature load bearing capability for use in structural several time dependent steps in the embrittlement process.2 6
applications. Room temperature ductility of polycrystalline The ductility in air increases sharply with increase in strain
iron aluminides decreases rapidly with the onset of ordering. rates. At the highest strain rates of 6.66102 1 s2 1 , ductility
A sharply reduced ductility is reported at 477 K as the of Fe – 40Al tested in air, vacuum, and oxygen were found
Al content approaches 25%.1 8 Alloys made conventionally to be the same,2 7 thus eliminating the effect of environ-
by the ingot route containing 25 – 50%Al are usually mental embrittlement at this strain rate.
very brittle at room temperature (RT). The low ductility 6. Excess thermal vacancies: the mechanical properties
is however restricted to lower temperatures only. The of iron rich iron aluminides are strongly affected by the
challenge lies in developing materials with the strength of presence of thermal vacancies which may be retained in the
ceramics and the plasticity of metals. lattice following heat treatment. Most studies earlier were
conducted on materials that were not given a heat treatment
to remove excess thermal vacancies before testing. The
Why inadequate mechanical properties? comparison of data of different workers is therefore
difŽ cult. SigniŽ cant increase in hardness can be attained
The  ow behaviour consists of extensive cross slip of # 111$ in specimens by quenching or air cooling from temperatures
dislocations and there are more than Ž ve independent slip greater than 1000 K to achieve a supersaturation of thermal
systems present in Fe3 Al, yet it fails by brittle cleavage vacancies.2 8 – 3 0 Prolonged anneals at low temperatures
fracture. B2 alloy fails predominantly by intergranular :673 K to remove excess thermal vacancies lead to
fracture (IG) at ambient temperatures. Therefore, both softening3 1 and an increase in room temperature ductility.3 2
grain boundaries as well as crystalline planes are the The effect of hardening by thermal vacancies increases with
potential sites for brittle fracture in Fe – Al. The brittleness Al content. An increase in room temperature ductility is
in these alloys may be due to the following. obtained in FeAl by heat treatment to remove excess
1. Having Ž ve independent slip systems is a necessary, thermal vacancies3 2 and/or cavities.3 3 Random vacancy
but not sufŽ cient condition for good ductility. All slip distribution process is proposed as an elementary defect
systems should be operative simultaneously for dislocations mechanism in B2 FeAl.3 4
to pass through, otherwise dislocations move in a grain, pile
on the grain boundary building up pressure on both sides.
Grain boundaries decohesion takes place. Some grain bound-
aries are less stable than others due to wrong neighbour Improvement in mechanical properties
considerations. Fe3 Al gives straight slip lines on plastic
deformation, therefore, either, cross slip is impeded or only An improvement in high temperature strength and RT
one type of slip system prevails during deformation. ductility can be obtained through alloy design. The alloy
2. Large grain size: the tendency for both transgranular additions may adversely affect the oxidation resistance.
(TG) and cleavage fracture of highly alloyed ferritic alloys is However, the alloying approach is much cheaper and has
inversely proportional to the square root of the grain size. the potential for improving the strength and ductility

Materials Science and Technology December 2003 Vol. 19

1630 Bahadur Enhancement of high temperature strength and room temperature ductility of iron aluminides

whichever is more critical for the application under may be one of the reasons for improving ductility of DO3
consideration as follows: Fe3 Al alloy.4 3
Mn addition (6, 12%) raises Tc and improves RT
ductility.4 4 Si (3, 5%) raises Tc improving high temperature
SUBSTITUTIONAL ADDITIONS mechanical properties, however it reduces RT ductility
ModiŽ cation of the crystalline structure through macro- frequently.4 5
alloying (several per cent) and processing imparts better
mechanical properties. Fe 3 Al and FeAl have body centred Elements which show incomplete solubility
cubic (bcc) related structures, are inherently less desirable in Fe ± Al after long homogenising anneals at
than face centred cubic (fcc) related structures like L12 . The high temperature such as Zr, Hf, Nb, Ta, and Re
latter structure is stabilised through control of e/a (average They go into solution partly and form precipitate which
number of electrons per atom outside the inert gas shell). effectively pin grain boundaries and dislocations, causing
The ductility improves by changing to high symmetry strengthening. Flow stress is much greater than that of the
structures through macroalloying. binary. Zr and Hf produces good increase in YS and UTS at
RT and elevated temperatures (300 – 1100 K) due to grain
Elements that form single phase after homo- reŽ nement and precipitation hardening in Fe – 40Al.4 6
genisation such as Ni, Co, Ti, Mn, Cr, and Si However, ductility decreases at all temperatures for ternary
alloys. Additional increase in strength can be obtained on B
Solid solution strengthening takes place, increasing the
addition due to reŽ nement of the grain size. B addition
number of easy slip systems and improving the ductility. No
changes the fracture mode from IG to TG and the ductility
signiŽ cant increase in high temperature (1300 K) compres-
is restored to 5% up to 700 K. At higher temperatures,
sive  ow strength with respect to the binary B2 takes place.
strength and ductility decrease as diffusion assisted
The strengthening effect of the ternary addition of transi-
mechanisms including grain boundary sliding and cavita-
tion metals increased with the atomic number difference
tion become operative. Nb raises Tc and improves high
between iron and the metal. A linear relationship between
temperature tensile as well as creep strengths.4 7
the yield strength and atomic size misŽ t was established.3 5
Ti addition stabilises DO3 structure and leads to a
signiŽ cant expansion of the azDO3 phase Ž eld. Ti Elements which show no signi®cant solubility
substitutes for iron and increases Tc for B2 and DO3 in Fe ± Al such as Mo, W, and V
ordering and produces anisotropic APBs.3 6 This is bene- These lead to second phase strengthening, and  ow stress at
Ž cial as alloyed Fe – Al can be ordered at higher 1300 K increases by more than a factor of six in the case of
temperatures saving on precious processing times, as long Mo. Additional strength can be obtained by addition of B
ordering time for Fe 3 Al (823 K/100 h) restricts commercial which reŽ nes grain size and changes fracture mode from
applications. The mechanical properties of bcc material are inter to transgranular. The most effective elements for
sensitive to the presence of interstitial elements like C, N, increasing high temperature strength and room temperature
and O. Addition of 0.5%Ti to alloys with 0.03 – 0.05%C ductility of FeAl alloys are small additions of Mo, Zr, and B
forms a stable carbide. RT ductility of Fe – Al alloys in combination giving a synergistic effect.4 6 – 4 9 The Fe – Al
has recently been enhanced to 10% by composition modiŽ ca- based alloys containing Cr, Nb, Mo, Zr, C, and B possess
tion (1 – 2%Ti) and microstructure control.3 7 TiB2 disper- not only an optimised combination of mechanical proper-
sions in Fe3 Al reduces the grain size of atomised powders ties but good weldability has also been developed.5 0 Carbon
and increases ductility of recrystallised material.3 8 addition is effective in suppressing hot cracking and makes
Cr addition higher than 2% modiŽ es surface composition Fe – Al weldable.5 0 The simple core structure of the # 100$
by inducing a passive layer and reduces susceptibility to dislocations operative at high temperatures, suggests that
environmental embrittlement and improves ductility. Cr introducing strengthening phases such as carbides, nitrides
adversely affects sulphidation resistance of Fe3 Al alloys and borides for precipitation hardening is the only way to
above 2% and of Fe – 40Al alloys above 4%.3 9 Cr addition signiŽ cantly increase tensile and creep strengths at tem-
to Fe 3 Al lowers YS slightly but increases UTS due to work peratures above 873 K.5 1
hardening.4 0 ,4 1 It changes fracture mode from cleavage to Molybdenum stabilises the DO3 structure for a greater
mixed (IGzcleavage) failure, suggesting that Cr enhances range of Al2 0 ,5 2 by dramatically increasing the DO3 to B2
cleavage strength. Fine wavy slip lines indicate easier cross ordering temperature Tc up to 10%.5 3 Site substitution by
slip. It is expected that plastic deformation by slip will be solutes such as Mo, Ti, and Si leads to an increase in
enhanced if ordering energies (or critical temperatures) ordering energies of the DO3 superlattice. In addition to
become small and/or if the alloy is appreciably disordered. improvement in high temperature strength, Mo, W, and V
Relative to Fe – 28Al alloy, ordering energies and B2 critical additions also improve creep resistance and thermal
temperatures reportedly4 2 decrease with temperature in stability. However, ductility decreases at RT and all
Fe – 28Al – 5Cr alloy. Lowered ordering energies is respon- temperatures with Mo higher than 0.5%.5 4 Therefore, no
sible for improving RT ductility as observed in Cr bearing signiŽ cant commercialisation has yet taken place.
alloy. The increase in RT tensile ductility in Fe – 28Al – 4Cr
occurred irrespective of DO3 or B2 order tested in air or
vacuum as long as surface oxide coating persisted. The MICROALLOYING (ppm RANGE)
beneŽ cial effect of Cr is modiŽ cation of protective surface Electron donors such as B strengthen atomic bonding
oxide due to possible enhancement of atomic bonding and increase the cohesive strength of the grain boundaries
between Fe and Al atoms resulting in an increase in cohesive relative to the grains.5 4 B has a strong tendency to
strength across cleavage planes. Cr addition decreases segregate to the grain boundaries but not to free surfaces,
susceptibility of alloy to moisture embrittlement. The thus enhancing the grain boundary cohesion and suppres-
removal of oxide Ž lm by electropolishing showed no sing IG fracture.5 5 On addition of B to FeAl, inter-
ductility improvement. granular fracture is suppressed and the composition at
Addition of 1.5%Mn to Fe – 28Al decreased the degree of which ductility drops off is shifted to higher Al levels.
DO3 ordering, which is associated with decrease in grain size However, B does not signiŽ cantly improve ductility since
and antiphase domain size. Besides, Mn could promote slip environmental embrittlement occurs trans- granularly in
and cross slip of super dislocations in the alloy because FeAl5 6 unlike in Ni3 Al where it occurs intergranularly. The
of occurrence of mainly twofold super dislocations. This beneŽ cial effect of B in FeAl is limited to enhancement of

Materials Science and Technology December 2003 Vol. 19

 Bahadur Enhancement of high temperature strength and room temperature ductility of iron aluminides 1631

boundaries, in contrast to ordered fcc or LI2 compounds

like Ni3 Al, where B reduces k.6 4 Microadditions of reactive
elements bind harmful impurities such as S in innocuous
forms through precipitation.

Adjusting stoichiometry

It has been established earlier that up to 20%Al alloys

fracture in a ductile manner by void nucleation and
coalescence.1 8 Alloys containing 20 – 40%Al fail in a brittle
manner by TG mode, and higher Al alloys fracture in IG
mode. The exact composition of transition from TG to IG
fracture depends on grain size, point defect concentration,
grain boundary impurities, etc. Fe – 40Al with long duration
low temperature annealing to eliminate thermal vacancies
exhibits predominantly TG fracture.6 5 With increase in Al
concentration, intrinsic grain boundary weakness becomes
important in limiting the ductility of FeAl.
6 Strength increase per at.-% boron per unit strain, or ModiŽ cation of crystal structure can be achieved by
strength increase per fractional change in lattice para- adjusting the stoichiometry of alloys. The deviations from
meter, as a function of at.-%Al; left and right hand stoichiometry are accommodated either by the incorpora-
ordinates show absolute and value normalised with tion of vacancies in the lattice or by the location of antisite
respect to shear modulus, respectively57 atoms in one or either of the sublattices. Fe – Al alloys exist
over a range of compositions, but the degree of order
grain boundary cohesion. Low levels of B enhance RT decreases as the deviation from stoichiometry increases.
ductility as well as high temperature strength.5 B addition to Fe3 Al exists over the range 25 – 30%Al in the ordered DO3
FeAl shows strengthening at room temperature by increas- structure up to 813 K, in B2 ordered structure between 813
ing the lattice parameter, which induces lattice strain and 1033 K, and in the disordered state above that. FeAl
(Fig. 6).5 7 The strengthening effect of B was found to exists in the B2 ordered structure up to the melting point
depend on both the Al concentration and the presence of 1520 K. As the amount of Al increases above 25%, the DO3
vacancies, suggesting that B interacted with the vacancies in to B2 transition temperature decreases and the B2 ordering
the material.5 8 The synergistic effect of the formation of the temperature increases. Additional atoms may also be
boride precipitates on dislocation lines along with restric- incorporated in the structure without losing the ordered
tion of grain boundary sliding causes strengthening. B structure. The changes in stiochiometry affect not only YS
improves high temperature strength, especially in combina- but also dislocation substructure and fracture behaviour.
tion with Nb and Zr. B in FeAl presumably partitions The strength is sensitive to the microstructure and Al
between the grain boundaries and the lattice since B also content. In Fe – Al alloys (0 – 44%Al), the maximum in yield
provided some solute strengthening.2 9 For FeAl, ductility stress is observed near the DO3 critical temperature and the
increases with decrease in grain size. Part of the difference in maxima in isothermal yield stress is observed near the Fe 3 Al
ductility reported as a function of concentration is due to composition.4 The RT yield strength drops gradually and
the effect of grain size.5 9 The optimum B concentration RT ductility increase steadily with increase of Al above 25%
must vary with the grain size. If the B level is higher than Al.3 8 In tension tests in air, iron rich FeAl (å 45%Al)
that needed for grain boundary cohesion, then a dislocation exhibits ductility, whereas the stoichiometric compound is
structure containing stacking faults forms which results in brittle and fails before yielding. In vacuum, an approxi-
decrease of stacking fault energy making slip more difŽ cult mately linear relationship was observed between elongation
and increasing the matrix strength.6 0 A signiŽ cant increase and deviation from stiochiometic composition, as shown in
in strength is obtained at 300 – 640 K. However, when both Fig. 7.1 2 In contrast, even stoichiometric compounds can
the matrix as well as grain boundaries become strong, the show considerable ductility in compression. The stoichio-
advantage obtained through the grain boundary strength- metric composition actually contains both ordered and
ening alone is neutralised. For high levels of B, the rise in disordered phase, which may be responsible for the higher
YS causes fracture to occur by separation of cleavage planes strength. In another study,4 in the fully ordered condition at
before extensive plastic deformation. B retards recrystalli- RT, Fe – 25Al exhibited a higher YS and percentage
sation in FeAl and leads to slower grain growth, reŽ ning the elongation than Fe – 31Al alloy. At 25%Al and lower, RT
grain size. In the presence of nitrogen, B reacts to form plastic deformation consists of extensive movement and
boron nitride and renders B unavailable for any grain cross slip of ordinary dislocations and associated nearest
reŽ ning work. Ti addition takes care of nitrogen and leaves neighbour (NN) and next nearest neighbour (NNN) trails.
B free for grain reŽ ning work. When added even in The super stoichiometric alloy (31%Al) consists of limited
microadditions, B and Ti give rise to Ž ne precipitates, which movement of imperfect variants of super dislocations with
restrict grain growth. B has so far not succeeded in only NNN APB trails. It was suggested that in 25%Al alloy,
producing a spectacular improvement in ductility of Fe – the degree of order and the size of thermally produced APBs
Al as it has done for nickel aluminides. B microaddition have only a small in uence on RT tensile behaviour.4
leads to the best mechanical properties in stoichiometric In the author’s work,6 2 stoichiometric Fe 3 Al alloy shows
Ni3 Al. As the amount of Al increases, B segregation at grain the maximum UTS. and percentage elongation at RT. The
boundaries decreases. The critical amount of B is required hypo-stoichiometric Fe 3 Al alloys are found to be more
at grain boundaries. The optimum amount of B to Al ductile than hyper-stoichiometric alloys. These alloys were
concentration has not yet been struck.6 1 The sensitivity of not heat treated to produce DO3 order. At RT, it is easy
the fracture transition by slight changes of composition is to maintain B2 order. Whenever percentage elongation
well established. Also, B addition is known6 2 ,6 3 to increase increases, as in the case of stoichiometric alloys, environ-
the Hall – Petch slope k for Fe – 40Al. This means that B mental embrittlement does not take place. Therefore, UTS
increases the difŽ culty of slip transmission across grain also increases at RT.6 2 In B2 FeAl (34 – 50%Al), YS follows

Materials Science and Technology December 2003 Vol. 19

1632 Bahadur Enhancement of high temperature strength and room temperature ductility of iron aluminides

intergranular, intervenes before extensive plastic deforma-

tion can occur. To overcome the latter, B is added, which
segregates to grain boundaries and suppresses intergranular
fracture. When both embrittling mechanisms are overcome,
FeAl undergoes extensive plastic deformation prior to
fracture.
2. Heat treatment following forming. Retaining some
degree of B2 order by oil quenching above Tc at
973 – 1023 K results in stress relieved but unrecrystallised
microstructure. RT embrittlement is due to the entry of
hydrogen atoms along cleavage planes in loading. For
maximum strength and ductility at RT, a stress relieved but
unrecrystallised microstructure is desirable. This structure
minimises environmental effects. The mechanism could
involve texturing effects or enhancement of dislocation
mobilities due to quenched B2 order. Elongated grains
parallel to stress axis may disrupt the entry of hydrogen by
providing a minimum number of cleavage planes and a
7 Elongation versus aluminium concentration for low tem- minimum of grain boundaries.7 0 ,7 1
perature annealed FeAl; material tested in air had Ž ne 3. Addition of Cr. Cr presumably increases the resistance
grains while that tested in vacuum had large grain size12 to cleavage fracture by easing the cross slip (as shown by
wavy slip lines) and increases the cleavage strength. It
a Hall – Petch relationship and it is maximum at stoichio- changes the fracture mode to 50% TGz50% IG, improving
metric composition, but minimum around 45%Al.5 9 The the ductility. For a Fe – Al, approximately 15%Al is
ductility of well annealed FeAl drops off signiŽ cantly at Al required to suppress internal oxidation and overgrowth of
levels less than 37%, when tested in an ultrahigh vacuum Al2 O3 scale by iron oxides.7 2 Cr addition to Fe – Al
chamber.6 5 Therefore, FeAl becomes intrinsically brittle decreases the critical amount of Al required to form pure
when its composition approaches stoichiometric composi- Al2 O3 layer and decrease oxidation rate of alloys with less
tion. Fracture mode changes from TG to IG as ductility than 19.5%Al. Cr addition may accelerate the initial growth
decreases, conŽ rming earlier results based on tests in oxygen of Al2 O3 , which helps in quickly establishing an external
that grain boundaries in FeAl become intrinsically brittle as protective oxide Ž lm before exposure to aggressive or
Al content increases. In stoichiometric FeAl, there are NN deleterious environments.2 0 The beneŽ cial effect of Cr
Fe – Al bonds but no Al – Al bonds. At a grain boundary, addition on RT ductility of Fe – Al may relate to an
there will be some of these weak Al – Al bonds. Their oxidation effect during high temperature treatment and the
number will decrease as Al content decreases and hence scale that forms serves as a better barrier to hydrogen
grain boundary cohesion may improve with decrease in Al uptake at ambient conditions.
content, leading to an increase in RT ductility. Tensile tests on Fe – 28Al – 4Cr samples show signiŽ cant
Early data for FeAl suggested that both hardness and increase in percentage elongation when tested in air or
yield strength increase monotonically with Al content. vacuum, irrespective of the DO3 or B2 order as long as there
However, these data contained the effects of thermal was a surface oxide Ž lm. The removal of oxide showed no
vacancies, which also depend on composition.6 3 In FeAl improvement in percentage elongation. Moisture induced
(34 – 45%Al), it was found that the hardness and fracture hydrogen embrittlement can be completely eliminated by
strain of FeAl do not change signiŽ cantly over the alloying Fe – 28Al – 5Cr with 0.5%Zr and 0.05%C to
composition range if the material is given a long, low produce elongated microstructure7 3 ,7 4 or with 0.5%Zr and
temperature anneal to remove excess vacancies,6 4 but then 0.05%B.7 5 Elongated grain structures with a high aspect
rise rapidly towards the stoichiometric composition.6 6 The ratio substantially reduce embrittlement caused by moist
stoichiometric composition was found to be much stron- air. Hydrogen diffusivity experiments proved that hydrogen
ger.6 7 The mechanical properties of B2 ordered Fe – Al diffusion coefŽ cients are similar at the same temperature.
strongly depend upon the anneal temperature and/or Grain shapes and sizes do not affect hydrogen diffusion in
cooling rate. Varying either results in different concentra- Fe3 Al based alloy.7 1 Higher ductility of Fe 3 Al based alloy
tions of retained thermal vacancies, which are responsible with elongated grains in air may result from the increase of
for hardening and strengthening effects. The ductility in resistance of grain boundaries to crack propagation making
oxygen and air decreases with increasing annealing such structures intrinsically more ductile.7 5
temperatures. The excess vacancies affect the intrinsic
ductility of Fe – Al and not their susceptibility to environ-
GRAIN SIZE REFINEMENT
mental embrittlement.6 8 NiAl exhibits a critical grain size
below which polycrystalline aggregates are ductile in The tendency for brittle fracture depends on the critical
tension. This size is expected to decrease with deviations grain size below which ductility is high. The stress
from stoichiometry.6 9 The grain size becomes an important concentration is enhanced in coarse grains. The stress
factor and needs to be reŽ ned as we move away from required for crack to propagate increases with decrease in
stoichiometry. All these parameters affect the measured grain size and fracture will be delayed in compounds with
ductilities and lead to con icting data in the literature. The Ž ne grains below a critical size. Therefore, control of grain
subject of the nature and effects of lattice defects as a size throughout casting, hot working, and heat treatment
function of stoichiometry needs further exploration. is essential. Control of the hot rolling process to get a
reŽ ned microstructure, giving a partially recrystallised work
hardened microstructure produces Fe – 25Al with improved
CONTROL OF ENVIRONMENT properties such as ultimate tensile strength, proof stress,
It is possible to eliminate or alleviate the effect of and percentage elongation.7 6 The manufacturing of cold
environment as follows. workable sheets of Fe – 40Al alloys through an innovative
1. Solving the hydrogen embrittlement problem by combination of roll compaction and thermomechanical
testing in dry oxygen alone does not ensure good ductility processing is an example of progress in development
in the case of Fe – 40Al, since another brittle fracture mode, research.7 7 Such fully dense sheets have a Ž ne grain

Materials Science and Technology December 2003 Vol. 19

 Bahadur Enhancement of high temperature strength and room temperature ductility of iron aluminides 1633

microstructure and tensile elongation of 5% at room 2. x. li and i. baker: Scr. Metall. Mater., 1997, 361, 387.
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lipsitt: Metall. Trans. A, 1987, 18A, 283.
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PRECISE CONTROL OF DEFECT AND 18. m. j. marcinkowski, m. e. taylor and f. x. kayser: J. Mater.
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