Journal of Nuclear Materials 495 (2017) 58e66

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Journal of Nuclear Materials

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Investigation of diffusional interaction between P91 grade ferritic steel

and Fe-15 wt.%B alloy and study of kinetics of boride formation at high
temperature
Arun Kumar Rai*, N. Vijayashanthi, H. Tripathy, R.N. Hajra, S. Raju, S. Murugesan, S. Saroja
Physical Metallurgy Division, Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research (IGCAR), Kalpakkam 603012, India

h i g h l i g h t s

Diffusion couple experiment between ferroboron and P91 steel has been carried out at 600, 700 and 800  C.

XRD and SEM characterizations have confirmed formation of boride phases at the interface of ferroboron and P91 steel.

Growth kinetics of borides has followed the parabolic law at each temperature.

Apparent activation energy of boride formation is determined.

The formation of borides is governed by bulk diffusion of boron element in matrix of P91 steel.

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

Article history: In the present study, the feasibility of employing the indigenously developed ferroboron alloy (Fe-
Received 14 February 2017 15 wt.%B) as an alternate neutron shield material in combination with 9Cr-based ferritic steel (P91) clad
Received in revised form in future Indian fast breeder reactors (FBR), has been investigated from a metallurgical perspective.
2 August 2017
Towards this goal, a series of diffusion couple experiments have been conducted at three different
Accepted 6 August 2017
Available online 8 August 2017
temperatures namely, 600, 700 and 800  C for time durations up to 5000 h. The thickness of interaction
layer has been monitored using standard metallographic procedures. The experiments revealed that
ferroboron/P91 combination exhibited a tendency to form complex intermetallic borides at the interface.
Keywords:
Ferroboron
The structural and microstructural characterization of the interface confirmed that the reaction layer
Ferritic steel consists predominantly of borides of Fe and Cr of type FeB, Fe2B, (Fe,Cr)2B and (Fe,Cr)B. The measured
Fast reactor variation of interaction layer thickness as a function of time and temperature have been modelled in
Shield material terms of diffusion mediated interaction. The growth kinetics of borided layer has followed the parabolic
Metallurgical compatibility law at each temperature, and the apparent activation energy for boride layer formation is found to be of
the order of 115 kJ mol1. This indicates that the kinetics of boriding could be governed by diffusion of B
into the P91 matrix. Based on the findings of present study, an extrapolative estimate of the clad attack
thickness at 550  C for 60 years of operating time has been made and it turns out to be 210 ± 15 mm,
which is less than the clad thickness of FBR shielding subassembly (4 mm) [1]. Thus, this study confirms
that at testing temperatures from 550 to 600  C, the ferroboron/P91 steel combination can be safely
employed for shielding subassembly applications in fast reactors.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction shielding in future Indian fast reactors to replace B4C, which is

A ferroboron alloy, with specific boron (10B) atom density of
about 0.7 g cm3, is being indigenously developed as an efficient
and cost effective candidate material for outer core neutron
* Corresponding author.
E-mail address: arunkumar@igcar.gov.in (A.K. Rai).
currently being used [1e4]. Neutron physics calculations have
shown that ferroboron with boron content up to 15 wt.% and with
an overall material density of about 4.2 g cm3 is a suitable shield
material [1,4]. However, it can only be used, if its metallurgical
compatibility at high temperatures with austenitic steel and 9Cr-
1Mo based ferritic steel clads are ensured similar to B4C [5e9]. The
metallurgical compatibility of ferroboron with 304 L austenitic

http://dx.doi.org/10.1016/j.jnucmat.2017.08.011
0022-3115/© 2017 Elsevier B.V. All rights reserved.
 A.K. Rai et al. / Journal of Nuclear Materials 495 (2017) 58e66
stainless steel was established in an earlier study [2,4]. The results
of these studies have provided a strong impetus to the choice of
ferroboron as a viable economic alternate shield material [2,4].
Compared to nuclear grade austenitic steels, ferritic steels are
cheaper, have high thermal conductivity, low thermal expansion
and improved void swell resistance, thus making them excellent
core candidate materials for high burn up fast reactor designs
[10e13]. With the increasing possibility of using ferritic steel for
cladding and wrapper in metal fuelled as well as in oxide fuelled
fast reactors in future, the choice of economically viable ferroboron
in combination with cheaper ferritic steel clad for shielding sub-
assemblies is very promising.
Hence, it is essential to have an understanding on the metal-
lurgical compatibility of ferroboron with ferritic steels at typical
operating conditions of fast reactors [14]. However, ferritic steels
have fundamental metallurgical differences compared to austenitic
steels with respect to high temperature thermal stability [12,13]. At
temperatures above Ac1, 9Cr-based ferritic/martensitic steels
transform to high temperature austenite phase, which exhibits
higher solubility for boron [13], which in turn would influence the
entire physical and mechanical metallurgy aspects of ferritic steels.
It would determine the high temperature limit of service for
employing ferroboron in combination with ferritic steels [14]. In
literature, there is very limited information on the high tempera-
ture metallurgical interaction between ferritic steels and ferro-
boron, although the interaction of pure boron with high Cr steel at
high temperature is well reported [15,16]. With respect to the fact, a
systematic study has been carried out to generate a knowledge base
on the metallurgical interaction between ferroboron and ferritic
steel at typical FBR service temperatures. Although the estimated
service lifetime of the shielding subassembly is about 60 years,
from a practical point of view, it is rather difficult to carry out such a
long time diffusion experiment at the anticipated maximum ser-
vice temperature of 550  C. Therefore, accelerated tests for shorter
time spans at higher temperatures, namely 600, 700 and 800  C,
have been carried for time durations of up to 5000 h. The diffusion
couples of P91 and ferroboron alloys annealed at different tem-
peratures for various time durations has been characterized using
standard light microscopy, scanning electron microscopy (SEM)
and X-ray diffraction (XRD) techniques. The applied experimental
methodologies are described in the following section.
2. Material and experimental details
2.1. Chemical composition and preliminary characterization
The chemical composition of ferroboron alloy and P91 grade
ferritic steel used in the current study are given in Table 1. The
ferroboron alloy used in the present study is prepared from iron
and commercial boron oxide lumps through a proprietary pyro-
metallurgical process. Ferroboron alloy has been received in the
form of granules with the particle size of 5e10 mm, which is me-
chanically crushed and ball milled into powders of size approxi-
mately in the range 10e15 mm. The chemical analysis of as received
Table 1
Chemical compositions of Ferroboron alloy and P91 steel used in this study.
Ferroboron alloy
Element B Si Al C S P O
Content (wt.%) 15.24 0.89 0.169 0.29 0.061 0.0046 0.03
P91 steel
Element Cr Mo V Nb C Mn Si B S P Ni Fe
Content (wt.%) 9.2 1.0 0.21 0.07 0.10 0.50 0.40 0.006 0.004 0.004 0.01 Bal.
59
ferroboron alloy, carried out using ICPAES (inductively coupled
plasma atomic emission spectroscopy) shows, that it contains small
amounts of Si, C, O and Al elements in addition to B. The purity of
ferroboron powder is further checked by carrying out powder X-ray
diffraction analysis and the results revealed that ferroboron alloy is
virtually free from the presence of any elemental boron and iron
particles and existed primarily as a mixture of Fe2B and FeB inter-
metallic phases [2]. Before studying the diffusional interaction
between P91 steel and ferroboron alloy, the as-received P91 steel
has been solutionized at 1050  C for 30 min, followed by air cooling
to room temperature. The tempering treatment has been done at
780  C for 15 min. The tempered P91 steel has been characterized
using standard metallography techniques. The microstructure has
been studied using Leica MeF4A aL-30 light microscope. Fig. 1
shows the typical microstructure of tempered 9Cr-ferritic steel,
containing copious amount of precipitated carbides of M23C6 types
(M ¼ Fe, Cr) dispersed in a-ferrite matrix and marked by red arrow.
2.2. Ferroboron/P91 steel compatibility experiments and its
characterization
In order to prepare diffusion couples between ferroboron and
P91 steel, diffusion jigs of P91 steel of cylindrical geometry with
internal diameter 11 mm and thickness 4 mm have been fabricated.
The experimental setup consists of a cylindrical cavity made of P91
steel into which the ferroboron alloy powder with particle size of
~10e15 mm is loaded. In order to achieve better contact between
powder and P91 steel plunger (diameter 10 mm), the plunger has
been pressed with the help of a screw by tightening it from the top
to down to the maximum limit. The main goal of the experiment
was to study the interaction between ferroboron powder and P91
plunger, therefore the surface of the plunger in contact with the
powder was polished to a mirror finish (surface roughness less than
0.5 mm). The entire diffusion jig assembly is hermetically sealed by
adjusting the screw from top and the diffusion jig assembly is
shown in Fig. 2a. A number of such ferroboron loaded diffusion jigs
have been made, which are then exposed to different temperatures
(600e800  C) in a muffle furnace for different time durations
ranging from 100 to 5000 h. At the end of the diffusion experiment,
the jigs are taken out of the furnace, allowed to cool in air to room
temperature, and subsequently sectioned vertically using high
precision cutting machine. A cross sectional view of a typical
annealed diffusion jig at 700  C for 500 h is shown in Fig. 2b, where
Fe
Bal.
Fig. 1. Microstructure of normalized and tempered P91ferritic steel showing the
presence of M23C6 type carbide marked by arrow.
60 A.K. Rai et al. / Journal of Nuclear Materials 495 (2017) 58e66

Fig. 2. (a). Diffusion jig assembly made of P91 steel, 2(b). Cross sectional view of annealed diffusion couple at a typical temperature of 700  C for 500 h showing the clear diffusion
bonding between P91 steel and ferroboron alloy.

it is seen that ferroboron powder is getting bonded with P91 steel due to the statistical nature of the diffusion phenomenon. An es-
plunger due to the diffusional interaction at high temperature. timate of this spread is obtained after several measurements (4e5)
The structural characterization of the interface of P91 steel/fer- of reaction layer depth at different locations. In the present study,
roboron couple was carried out using INEL® make XRD 3000 the emphasis is given to the maximum or upper bound estimate of
diffractometer operated at 40 kV and 30 mA with monochromatic the reaction layer thickness, as this pertains to the maximum attack
copper radiation (wavelength 1.54056 Å), with a 2q-scan step of probable under the given conditions. The spread in the measured
0.01. The pattern was collected with CPS 590 curved position reaction layer is typically found to be ±5%.
sensitive detector in two theta range from 10 to 100 in parallel
geometry mode. Further, the microstructural characterization of
3. Results
the interface between P91 steel and ferroboron has been carried
out using a high-resolution scanning electron microscope with field
3.1. Microstructural and structural characterization of reacted
emission gun (FEG-SEM) (Helios Nanolab 600i). The SEM has en-
interface using SEM and XRD
ergy dispersive spectroscopy (EDS) detector attachment and it is
employed for chemical analysis of the interface. Using EDS detector
In Fig. 3a, the microstructures at the interface of P91/ferroboron
elemental mapping has been carried out across a line and surface of
diffusion couple after 500 h of exposure at 700  C obtained by FEG
interest. The microstructure has been evaluated by Leica MeF4A aL-
SEM is shown. It is found that there is a strong diffusional inter-
30 light microscopy. Vickers microhardness profile has been
action between steel plunger and ferroboron at this temperature
measured across the interface of P91/ferroboron. The applied load
and the thickness of interaction zone is found to be of the order of
has been 50 g and dwell time 15 s. The thickness of interaction zone
60 mm for 500 h of exposure. The reacted zone is consist of different
at the interface of ferroboron and P91 steel has been measured
phases embedded in the steel matrix. These phases could be due to
using micrograph analysis software given in the SEM. The thickness
the formation of borides of Fe and Cr elements present in the steel
has been measured up to the distance where a clear boride phase
matrix as a result of diffusion of boron at high temperature from
was present. For each sample 4 to 5 measurements have been
ferroboron side. The formation of these borides is expected on
carried out and the average value is taken for each time and tem-
thermodynamic reasons, since the solubility of boron in both Fe
perature. However, there is a certain degree of spread or scatter
and Cr is restricted even at high temperatures [17]. In general, the
associated with the measured value of interaction zone thickness
diffusion layer consists of parallel tracks of fine intermetallic boride
 A.K. Rai et al. / Journal of Nuclear Materials 495 (2017) 58e66 61

Fig. 3. (a). SEM micrograph of interface of ferroboron and P91 steel plunger annealed at 700  C for 500 h showing the formation of different boride phases across the Zone I, II & III;
3 (b) Compositional line scan of Fe, Cr and Mo elements performed at the steps of 5 mm.

particles, embedded in the steel matrix. The composition of borides

is progressively modified as one moves away from the central line
of the reaction interface and this can be witnessed from Fig. 3b,
where the compositional line scan of Fe, Cr, B and Mo is shown. The
line scan has been performed at the steps of 5 mm and it is evident
that at the interface there is an enrichment of Cr and Fe elements at
select sites. However, no change in B and Mo elements composition
has been seen. It is further added that intensity of the boron
element shown in Fig. 3b is almost zero. This is due to the experi-
mental limitation in detecting boron by EDX technique.
The enrichment of these elements may be due to the formation
of borides of Fe (FeB, Fe2B) and Cr (CrB, Cr3B4, Cr2B3) elements or
complex borides such as (Fe,Cr)2B and (Fe,Cr)B as a result of boron
diffusion from ferroboron side to P91 steel. From the line scan, it is
clear that wherever Cr is more, Fe is less and this fact will be further
supported in later results. This could be due to the fact that Cr
might have replaced iron to form complex borides. In addition, the
Vickers hardness measured along the interface at different loca-
tions of diffusion couple after 500 h of exposure at 700  C is shown
in Fig. 4. The hardness values marked in Fig. 4 are the average of the
at least five indentations made along a line of specific regions. In
Fig. 4 only 2e3 representative indentations are shown for better Fig. 4. Hardness profile measurement across the interface of ferroboron and P91 steel
plunger annealed at 700  C for 500 h showing the formation of different boride phases.
clarity. It is evident that, the hardness of the borided region on P91
side is gradually increases from 250 to 1700 HV0.05. The hardness
value of 250 HV0.05 corresponds to a non-borided region of the P91 which is in accordance with the SEM thickness measurement. The
steel and 1700 HV0.05 correspond to the hardness taken at the hardness result also confirms the formation of boride phase along
interface of P91/ferroboron. In literature, the reported hardness for the interface. The structural integrity of the clad is kept perfectly in
FeB and Fe2B borides are found to be in the range of 1555e1800 tact at distances far off from the diffusion or interaction layer.
HV0.05 [18,19]. The intermediate zone has the hardness of the or- For the better understanding of actual nature and stoichiometry
der of 900 HV0.05. The hardness profile measurement across the of the borides, X-ray diffraction has been carried out on the surface
interface of P91/ferroboron couple annealed at 700  C for 500 h also of steel plunger facing the ferroboron powder and the corre-
confirms that the reacted zone thickness is of the order of 60 mm sponding result is shown in Fig. 5. The different XRD peaks
62 A.K. Rai et al. / Journal of Nuclear Materials 495 (2017) 58e66

(Fe0.6,Cr0.4)B having an orthorhombic crystal structure. On the

other hand, two more borides of type Fe2B and (Fe1.6,Cr0.4)B with
tetragonal structure have been observed. Finally, another boride of
Cr element of type Cr3B4 having orthorhombic crystal structure has
also been confirmed by XRD result. Similar results have been also
observed in our previous study on SS 304 L/ferroboron couple [2].
In literature, there are few studies reporting the effect of boriding of
ferritic steel, where boron diffusion at high temperature caused the
formation such borides that are observed in the present study
[15,16].
The XRD results clearly provide evidence of the formation of
above mentioned borides. In order to study the microchemistry of
these phases, the elemental mapping of Fe, Cr and Mo using energy
dispersive X-ray (EDX) spectroscopy of the interface of another
diffusion couple annealed at 700  C for 200 h has been carried out.
The corresponding result is given in Fig. 6. The thick borided tracks
seen along the interface and the grain boundary are rich in Cr and
correspondingly lean in Fe element. However, no change in the
Fig. 5. XRD result of P91 steel plunger surface exposed to ferroborn powder at 700  C composition of Mo element has been detected. In Fig. 3a, the three
for 500 h showing the formation of different complex borides of Fe and Cr elements.
distinct zones have been observed. Based on the available literature
[15,16] and the present study, it has been observed that two boride
observed in the present study has been indexed with available phases are formed as a separate layer at the interface. The zone I
ICDD data and listed in Table 2 along with their card number. The near the interface is consist of predominantly (Fe,Cr)2B type boride.
XRD result has confirmed the presence of six types of the borides of The presence of this boride in the zone I is confirmed on the basis of
Fe and Cr elements with different stoichiometry. However, no XRD hardness value 1700 HV0.05 which is normally reported for Fe2B
peaks for either free boron and iron or steel matrix have been type boride [15e18]. Zone II is consist of a mixture of (Fe,Cr)2B and
observed. The first three borides are of type FeB, (Fe0.88,Cr0.12)B and (Fe,Cr)B phases. However, zone III has only (Fe,Cr)B type of boride
phase along the grain boundary alone. It is reported [18] that during
the initial stage of boriding (up to 3 h of annealing) both FeB and
Fe2B type of borides are formed when boron concentration is suf-
Table 2 ficiently high and proceed to grow. But if the annealing is longer e.g.
X-ray diffraction details of Fe-B/P91 reaction diffusion couple.
500 h in the present study, the boron concentration in FeB phase
2q Phases (hkl) plane Crystal Structure/designation goes down and Fe2B phase grows at the expense of FeB phase
(Cu-Ka [17,18,22]. Both FeB and Fe2B phase dissolve the significant amount
degrees)
of Cr element but its distribution is rather irregular within each
27.38 (Fe0.88,Cr0.12)B (110) Orthorhombic (Pbnm) boride layers. This could be due to the nonequilibrium condition of
32.50 FeB (020) Orthorhombic (Pbnm) layer formation [15,16].
34.83 (Fe1.6,Cr0.4)B (200) Tetragonal (I4/mcm)
36.55 Cr3B4 (031) Orthorhombic (Immm)
The morphology of borided layer in the present study is found to
37.43 (Fe0.6,Cr0.4)B (011) Orthorhombic (Pnma) be flat unlike the saw tooth morphology reported by others [20].
39.08 FeB (120) Orthorhombic (Pbnm) The morphology of these borided layers actually depends on the
39.69 (Fe0.88,Cr0.12)B (120) Orthorhombic (Pbnm) chemical composition of substrate material [20]. It has been
41.15 FeB (111) Orthorhombic (Pbnm)
42.41 Fe2B (400) Tetragonal (I4/mcm)
43.93 (Fe0.6,Cr0.4)B (002) Orthorhombic (Pnma)
46.29 (Fe0.6,Cr0.4)B (102) Orthorhombic (Pnma)
48.02 (Fe0.88,Cr0.12)B (210) Orthorhombic (Pbnm)
51.83 Cr3B4 (141) Orthorhombic (Immm)
54.23 FeB (130) Orthorhombic (Pbnm)
56.54 FeB (220) Orthorhombic (Pbnm)
57.05 Fe2B (130) Tetragonal (I4/mcm)
62.40 (Fe0.6,Cr0.4)B (410) Orthorhombic (Pnma)
63.86 FeB (131) Orthorhombic (Pbnm)
68.85 Cr3B4 (240) Orthorhombic (Immm)
69.67 (Fe0.6,Cr0.4)B (302) Orthorhombic (Pnma)
72.92 FeB (022) Orthorhombic (Pbnm)
75.08 (Fe0.6,Cr0.4)B (410) Orthorhombic (Pnma)
76.59 (Fe0.6,Cr0.4)B (221) Orthorhombic (Pnma)
80.05 (Fe0.88,Cr0.12)B (311) Orthorhombic (Pbnm)
82.17 (Fe0.6,Cr0.4)B (221) Orthorhombic (Pnma)
84.02 (Fe0.6,Cr0.4)B (213) Orthorhombic (Pnma)
85.51 Fe2B (213) Tetragonal (I4/mcm)
87.22 (Fe0.6,Cr0.4)B (240) Orthorhombic (Pnma)
89.34 (Fe1.6,Cr0.4)B (402) Tetragonal (I4/mcm)
Details of ICDD reference cards
FeB Phase e Pdf card No e 00-032-0463
(Fe0.88,Cr0.12)B Phase e Pdf card No e 00-057-0489
(Fe0.6,Cr0.4)B Phase e Pdf card No e 04-004-0294
Fe2B - Phase e Pdf card No e 00-036-1332
(Fe1.6,Cr0.4)B Phase e Pdf card No e 00-057-0490
Fig. 6. EDS mapping of Fe, Cr and Mo elements across the interface of and P91 steel
Cr3B4 Phase e Pdf card No e 00-089-3535
plunger annealed at 700  C for 200 h showing the enrichment of Fe and Cr elements.
 A.K. Rai et al. / Journal of Nuclear Materials 495 (2017) 58e66
observed that in low alloy steel saw-tooth morphology are seen,
however in the case of high alloyed steel these layers are found to
be flat [20]. The saw-tooth morphology has been observed only
when the predominantly Fe2B type of borides are formed [15]. The
presence of Cr, Mo, Nb and V in P91 steel might be responsible for
inhibiting the growth of boriding layer by the substitutional pro-
cess [15,16,20]. For example, from Fig. 6 it is evident that Cr has
replaced Fe atoms to form complex borides rather than formation
of simple FeB and Fe2B borides. The Cr element might be getting
concentrated at the tip of boride column and reducing the active
boron flux on these zones, therefore minimizing the columnar
shape of the growth fronts [15,16].
3.2. Variation of interaction zone thickness as a function of
temperature and time
Analysis of the interface of different diffusion couples annealed
at 600, 700 and 800  C for time durations up to 5000 h has shown
that the interaction zone thickness steadily increases with increase
in temperature and time and gradually saturates for higher dura-
tions. In Fig. 7, the microstructures observed across the reaction
interface for various time durations at a typical test temperature of
700  C is shown. It can be seen that at 700  C the thickness of
borided zone increases with annealing time and the maximum
interaction thickness is measured to be of the order of 156 mm for
5000 h. In addition, coarsening of boride particles near the interface
can also be witnessed with the increase in the annealing time. In a
similar way for a fixed time duration of 1000 h the interaction zone
thickness is found to be drastically increasing with temperature
which can be clearly seen in Fig. 8.
Variation of the square of the interaction zone thickness (x2)
with temperature and time is presented in Fig. 9, where, x stands
for the reaction layer depth given in meters and time (t), in seconds.
As can be seen from Fig. 9, the good correlation between square of
interaction zone thickness (x2) and time (t) is observed in the range
of temperature, 600e800  C and for time up to 5000 h, where the
Fig. 7. Microstructural collage of the reaction layer formed at the interface between P91 steel and ferroboron powder for various time durations at 700  C.
63
following parabolic growth law is obeyed which is in agreement
with the literature [21e28].
x2 ¼ kt: (1)
where the rate constant k(T) is a function of temperature. The
parabolic behavior given in Eq. (1) is usually interpreted as sup-
portive of the operation of bulk diffusion as the probable rate
controlling step. Similar results have earlier been found in the case
of ferroboron/SS304L and B4C/SS304L combinations [2,6e9]. The
temperature dependence of k is usually represented by the
Arrhenius form.
kðTÞ¼ ko expðQ =RTÞ (2)
ko is the pre-exponential factor and Q is the apparent activation
energy for the overall reaction at the interface. With the help of Eq.
(1 and 2) all the three data obtained at three different temperatures
are fitted and value of k(T) is being derived. In Fig. 10, the variation
of ln{k(T)} with 1/T, is presented from which the apparent activa-
tion is evaluated. The activation energy Q estimated from the slope
of linear correlation is 115 kJ mol1. Considering the possible
intrinsic experimental uncertainty associated with the experi-
ments, especially with measurement of the interaction zone
thickness using microscopy techniques, another set of data, which
is within ±5% of the standard deviation has been used to cross
check the consistency of Q value obtained in this study. The value of
activation energy obtained in the present study is found to be in
reasonable agreement with reported activation energy in the range
of 116e149 kJ mol1 of boron diffusion in high Cr steels [15]. The
results obtained in the present study are compared with the
available literature data and discussed in the next section.
4. Discussion
The development of ferroboron alloy as alternate outer core
shielding material in place of B4C for fast reactors has been initiated
64 A.K. Rai et al. / Journal of Nuclear Materials 495 (2017) 58e66

Fig. 8. Microstructural collage of the reaction layer formed at the interface between P91 steel and ferroboron powder at various temperatures for 1000 h exposure. The arrow
marked in this figure show the formation of crack.

combination with SS 304 L steel can be safely used in fast reactors

for outer core shielding [1e4]. However, in future to achieve high
burn-up (200 GW d/t), metal-fuelled (U-Pu-Zr based) fast reactors
are planned, where 9Cr based ferritic steels (P91/T91 grade) will be
the structural material in place of austenitic steel, due to its low
void swelling, high thermal conductivity and low cost [10e13].
Therefore, it becomes necessary to study the compatibility of fer-
roboron with P91 grade ferritic steel. In this context, the high
temperature metallurgical compatibility study of ferroboron with
P91 grade ferritic steel has been carried out and compared with SS
304 L [2,3]. It has been observed that the nature of the interaction of
ferroboron with P91 steel is somewhat different from that of SS
304 L. However, the loss of clad thickness in P91 steel due to
diffusive interaction is more or less comparable to that found in SS
304 L. The process of metallurgical interaction of ferroboron with
P91 steel is explained in the following section.
Fig. 9. Variation of square of the interaction layer thickness with time at different
The experimental results obtained using XRD and FEG SEM in
temperatures.
this study clearly point to the possibility of strong solid-state
diffusional reaction taking place at the interface of both the ma-
terials. It is evident from Figs. 3, 5 and 6 that along the interface,
different borides namely, FeB, (Fe0.88,Cr0.12)B, (Fe0.6,Cr0.4)B, Fe2B
and (Fe1.6,Cr0.4)B are formed. Similar results have been observed in
the case SS 304 L/ferroboron interaction at temperature domain of
550e800  C [2,3]. The interaction layer thickness obtained as a
function time at 700  C for SS 304 L/FeB and P91/FeB couples is
compared in Table 3. It is evident that interaction zone thickness for
P91 steel is slightly higher than that of SS 304 L. It is reported that
the nature of chemical interaction between boron and steel ele-
ments resulting in the formation of various borides along the
interface is governed by the crystal structure and composition of
steel [15,16,21e28]. It is found that the reaction interface in general
is highly heterogeneous in its metallurgical character
[15,16,21e28]. The growth of these borides are often considered to

Table 3
Fig. 10. Variation of reaction rate constant k(T) with temperature in the range Comparison of interaction layer thickness found as function of time for SS304L/FeB
600e800  C. and P91/FeB couples at 700  C.

Time Interaction layer Thickness Interaction layer Thickness

(h) (mm) (mm)
at IGCAR [1]. Over the years, the feasibility has been established SS304L/FeB couple P91/FeB couple
based on neutronic attenuation capability, high temperature ther-
50 10 12
mal stability and its metallurgical compatibility with SS 304 L 100 14 18
[1e4]. 200 30 45
Application of ferroboron as an outer core shielding material is 500 48 65
studied also by other nuclear materials groups in the world [29]. 1000 75 90
2000 106 118
After several studies it has been established that ferroboron alloy in
5000 128 138
 A.K. Rai et al. / Journal of Nuclear Materials 495 (2017) 58e66
grow at the expense of diffusion of boron across the bulks
[15,18,21].
The higher interaction layer thickness in the case of P91 steel
could be due the fact that it has bcc structure in the temperature
domain of 600e800  C, in contrast to SS 304 L having fcc structure,
and it is well known that boron diffusion in bcc phase is faster than
in fcc phase of iron [30]. Additionally, it has also been reported that
boron may either adopt substitutional or interstitial diffusion or
mixed mode in both fcc and bcc matrix depending on temperature
[21,30]. In the temperature range of 600e800  C, in fcc matrix
boron diffuses predominantly via substitutional mechanism,
however in bcc matrix it diffuses through interstitial mode [21,30].
Since interstitial diffusion is faster than substitutional mode, it
could lead to faster boriding kinetics, or equivalently higher inter-
action layer thickness in P91 steel than in SS 304 L. In addition, in
P91 steel, the major alloying elements are Cr (9 wt.%) and Mo
(1 wt.%); however in 304 L the major alloying elements are Ni
(18 wt.%), Cr (8 wt.%), Mn (2.5 wt.%). The propensity to form borides
of these elements depends on their enthalpy of formation. It has
been reported that enthalpy of boride formation for Fe
(Fe2B ¼ 28 kJ mol1atom1, FeB ¼ -36 kJ mol1atom1) and Ni
(Ni2B 24 kJ mol1atom1, NiB ¼ 31 kJ mol1atom1) are lower
than Cr (Cr2B ¼ 35 kJ mol1atom1, CrB ¼ 45 kJ mol1atom1)
[31]. Therefore, Cr has a stronger propensity to form boride than Fe
and Ni. Due to this reason, Cr is enriched along the interface to form
complex boride with iron, as seen in Figs. 3 and 6. This process
happens in both P91 and 304 L steel but due to the presence of Ni in
304 L steel, Ni concentration is confined to the tip of boride col-
umns, thereby reducing the active boron flux on these zones, and
minimizing the further growth of borides. This confirms that the
presence of Ni suppress the boron activity more effectively than Cr
which in turn reduces the boron diffusion further in the iron ma-
trix. This may be the probable cause for higher interaction thickness
found in P91 steel as compared to SS 304 L.
At the studied temperature range, the interaction layer thick-
ness is found to vary with square root of time (√t), as given by Eq.
(1). This suggests that for fairly long exposure times, there is a
gradual reduction in interaction layer thickness, which is an ad-
vantageous factor, as compared to the linearly increasing growth
behavior. A similar behavior is seen in the case of SS 304 L/ferro-
boron diffusion couple; however, the apparent activation energy
for boron diffusion in P91 steel is found to be about ~115 kJ mol1,
which is significantly higher than 58 kJ mol1 obtained for SS 304 L
steel [2]. The value of activation energy is again influenced by the
mechanism of boron diffusion in fcc and bcc matrix of iron and the
presence of different alloying elements.
Several studies have reported that the boriding reaction also
plays a crucial role on the activation energy of boron diffusion in
different tool steel [22e28]. The activation energy of boron in fcc
matrix of pure iron is reported to be in the range of
88e142 kJ mol1; however in bcc matrix the activation energy is
turned out of the order of 95e115 kJ mol1 [21]. On the other hand,
in most of the tool steels with more than 0.3wt.% carbon, the
activation energy of boron diffusion is reported in the range of
168e230 kJ mol1 for different boriding processes [22e28]. Dunner
et al. [5] has reported a value of about 97.2 kJ mol1, for the B-atom
diffusion in g-austenite iron matrix. Azouani et al. [24] has pre-
sented a value of 199 kJ mol1 for the effective activation energy of
ferritic steels. Recently, Campos et al. has conducted a systematic
study of the kinetics of boriding of different steels [22]. They
mention varying activation energies ranging from 79 to
179 kJ mol1, depending on the fact whether the analysis is made
for individual FeB or Fe2B phase formation alone or for the com-
plete diffusion zone reaction [22]. In addition, Dybkov et al. [15,16]
has reported the over all activation energy of the order of
65
132 kJ mol1 for both FeB, and Fe2B formation in high Cr (13 wt.%)
ferritic steel. In the present study, the apparent activation energy is
estimated to be of the order of 115 kJ mol1 which is reasonably in
good aggrement with the findings of Dybkov [15]. The high degree
of variance is due to different process conditions, including tem-
perature and changes in the base composition of steel. Therefore,
the interfacial reaction that is taking place in the present case is one
of simple bulk boron transfer from boride phase into the ferritic
clad by diffusional processes.
Based on present findings, an Arrhenius type (Eqs. (1) and (2))
extrapolative estimate of the clad attack thickness at 550  C for a
time period of 60 years has been made. This value turned out to be
210 ± 15 mm, which is much less than the clad attack thickness
(4 mm) envisaged in FBR shielding subassembly applications [1].
Therefore, the current study shows that ferroboron alloy as
shielding materials in combination with P91 ferritic steel can be
safely used for the temperatures in the range of 550e600  C. For
higher temperatures, perceptible reactive diffusion of boron into
tempered a-ferrite matrix is assumed, resulting in the formation of
a thick layer of boride particles adjacent to the diffusion zone
(Fig. 8). This also leads to the formation of voids and microcracks
marked by red arrows at high temperatures (Fig. 8). The formation
of these microcracks and voids could be due various reasons [32].
The one of the reason is decohesion of the interface of boride
particle and P91 steel. The potential cause for such decohesion at
the interface is due to large difference in thermal expansivity of FeB,
Fe2B phases and P91 steel in the temperature domain of
700e800  C. When the annealing temperature increased more
than 600  C, the porosity in the boride layer increased greatly. The
formation of cracks and porosity in steel boriding has been reported
by many studies [32,33]. Thus, it is not advisable to apply ferro-
boron/ferritic steel combination at temperatures exceeding 600  C
for prolonged durations.
5. Summary
i. The high temperature metallurgical compatibility of ferro-
boron with P91-ferritic steel has been successfully estab-
lished by performing accelerated reaction couple tests in the
temperature range of 600e800  C.
ii. By carrying out a systematic interdiffusion study at different
temperatures (600e800  C) for annealing durations up to
5000 h, it has been clearly shown that ferroboron/P91
combination is thermodynamically unstable with a strong
propensity for formation of complex intermetallic borides
along the interface.
iii. SEM and XRD results have clearly pointed out that the
different borides namely FeB, F(Fe0.88,Cr0.12)B, (Fe0.6,Cr0.4)B,
Fe2B and (Fe1.6,Cr0.4)B are formed in majority along the
interface.
iv In this study, the valuable data on the borided layer thickness
as a function of time and temperature has been obtained.
Variation of thickness with time follows the parabolic law at
each temperature. This input serves to model the diffusion
mediated interaction between these materials using Arrhe-
nius analysis. The average activation energy for different
boride formation is estimated to be ~115 kJ mol1, which
clearly shows that formation of various borides is governed
by bulk diffusion of boron in P91 steel.
v. Based on the findings of present study, an extrapolative es-
timate of the clad attack thickness at 550  C for 60 years has
been calculated as 210 ± 15 mm, which is less than the clad
thickness of FBR shielding subassembly.
vi. From metallurgical perspective, it is found that ferroboron in
combination with P91 as clad can be employed safely as
66 A.K. Rai et al. / Journal of Nuclear Materials 495 (2017) 58e66
alternate shield/clad combination for T  600  C in fast
reactor applications.
vii In the future, it is planned to carry out similar studies in the
neutronic environment to simulate the actual reactor con-
ditions and study the effect of neutron irradiation on diffu-
sional interaction of ferroboron with P91 steel
Acknowledgments
The authors thank Dr. A. K. Bhaduri, Director, IGCAR, and Dr. G.
Amarendra, Director, Metallurgy and Materials Group for their
constant support and encouragement for this work. The encour-
agement and support received from all the task force members of
alternate shielding materials development is sincerely
acknowledged.
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