Surface and Coatings Technology 149 (2002) 21–26

Influence of the pack thickness of the boronizing mixture on the boriding

of steel

Vipin Jain, G. Sundararajan*

International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Balapur P.O., Hyderabad-500005, India

Received 2 January 2001; accepted in revised form 10 July 2001

Abstract

Boronizing, which involves diffusion of boron atoms into steel substrate to form iron borides, is a well-known diffusion coating
`
process and numerous studies have demonstrated the outstanding tribological properties of boronized steel vis-a-vis carburized or
nitrided steels. However, the high cost of the boronizing process has severely limited its applications. One way to bring down the
cost of the boronizing process is to reduce the thickness of the boronizing mixture to be packed around the component (called
pack thickness) to the minimum required level without compromising on the properties of the boride coating. The present study
attempts to estimate the optimum pack thickness required to form boride coating of adequate thickness and property in the case
of a low carbon steel boronized at 9408C for 2 h. Low carbon steel samples have been boronized with varying pack thickness in
the range 2–25 mm and the resulting boride coatings have been examined for thickness, microstructure, microhardness profile
and abrasion resistance. An analysis of the results obtained indicated that a pack thickness of 10 mm is sufficient to obtain boride
coatings of adequate thickness and optimum properties. 䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Boronizing; Pack boriding; Diffusion coatings; Pack thickness

1. Introduction in a container. The container is then heated up to the

Boronizing is a thermochemical treatment in which
boron atoms are diffused into the surface of a workpiece
and form borides with the base metal. The treatment
has been applied to a wide range of materials including
ferrous materials, non-ferrous materials and some super
alloys w1,2x. Boriding of ferrous materials is generally
performed between 840 and 10508C. The process can
be carried out in solid, liquid or gaseous medium. The
most frequently used method is pack boriding, a process
similar to pack carburizing. The pack usually contains
a source of boron, usually boron carbide (B4C) or
amorphous boron, an activator to deposit atomic boron
at the workpiece and a diluent. Pack boriding involves
placing the component in the powder mix and sealing it
* Corresponding author. Tel.: q91-40-4443167; fax: q91-40-
4443168.
E-mail address: gsundar@nettlinx.com (G. Sundararajan).
required temperature for the required time and cooled
in air. The diffusion of B into steel results in formation
of iron borides (FeB and Fe2B) and the thickness of the
boride layer is determined by the temperature and time
of the treatment.
Generally, the formation of a monophase (Fe2B) with
sawtooth morphology is more desirable than a double
phase layer with FeB and Fe2B w1–3x. The boron rich
FeB phase (containing approx. 16.23 wt.% B) is not
desirable because FeB is more brittle than the iron
subboride, Fe2B phase (containing approx. 8.83 wt.%
B). Furthermore, since FeB and Fe2B phases exhibit
substantially different coefficients of thermal expansion,
CTE (aFeBs23=10y6 y8C, aFe2Bs7.85=10y6 y8C),
crack formation is often observed at the FeByFe2B
interface of a double phase layer. These cracks often
lead to flaking and spalling when a mechanical load is
applied w4x. Through the control of boronizing process
parameters, i.e. boronizing powder composition, temper-

0257-8972/01/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 2 5 7 - 8 9 7 2 Ž 0 1 . 0 1 3 8 5 - 8
22 V. Jain, G. Sundararajan / Surface and Coatings Technology 149 (2002) 21–26
ature and time, Fe2B phase can be consistently achieved
during pack boriding w5–7x.
Boronized steel consistently outperforms nitrided and
carburized steels w1,8,9x essentially, because the iron
boride formed exhibits substantially higher hardness
(HVs1600–2000) as compared to carburized or nitrid-
ed steels (HVs650–900). In particular, boronized steel
exhibits excellent resistance to a variety of tribological
wear mechanisms w1,2,10,11x. In addition, the resistance
of boronized steel to attack by non-oxidizing dilute
acids, alkalis and molten metals in also outstanding
w1,2x.
The commercial boronizing mixture contains 5% B4C
as donor, 5% KBF4 as an activator and 90% SiC as
diluent. At our laboratory, a new boronizing mixture
(LABM) possessing low boron activity, which is being
patented has been developed w12x. The advantage of the
new composition lies in better control for formation of
a single phase Fe2B layer. Also, due to the low concen-
tration of the boron donor component in the said
mixture, it is comparatively cheaper than the commer-
cially available mixture, thus making the process less
costly.
Inspite of the low cost of LABM, boronizing as a
process is still more expensive as compared to carburiz-
ing and nitriding. Therefore, the application of boroniz-
ing has been essentially limited to very specialized
applications. In this context, there is a clear need to
bring down the cost of the boronizing process further.
One solution to the above problem is to limit the
thickness of the boronizing mixture pack to the lowest
possible level without affecting the properties of the
boride coating. The present study aims to find the
minimum acceptable pack thickness for the boronizing
of a low carbon steel with the LABM pack.
2. Experimental details
2.1. Boronizing treatment
Low carbon steel (0.2% C) samples of sizes
25=25=5 mm and 75=25=10 mm (for abrasion test)
were used as the substrate material. All the samples
were ground to get surface finish of 0.3"0.1-mm Ra
and then cleaned in ultrasonic cleaner. The samples were
then packed in the indigenously developed LABM
mixture. Thickness of the pack around the samples was
varied as 2, 5, 10, 15, 20 and 25 mm. The samples
along with the pack, were sealed in a steel container
and the container was heated at 9408C for 2 h followed
by cooling in air.
2.2. Characterization of borided samples
The surface roughness of the samples was measured
before and after boronizing using a Taylor–Hobson
Surface Roughness Tester (Model: Sutronic 3q). The
phases present in the boronized steel samples were
identified and the extent of their presence quantitatively
estimated utilizing a Philips X-ray Diffractometer.
Boronized samples, obtained with varying pack thick-
ness, were sectioned, mounted and then polished and
etched using standard metallographic techniques. These
surfaces were then examined using a JEOL Scanning
Electron Microscope (SEM) in back scattered mode.
The coating thickness was measured using an Image
Analysis System (Leica) attached to an Optical Micro-
scope. On the same sectioned surfaces, the microhard-
ness profiles as a function of the distance from the top
surface were also evaluated using a Vickers indentor at
50-g load.
The rubber wheel abrasion tests, conforming to ASTM
G-65, were conducted on boronized samples of size
75=25=10 mm. Silica sand of an average particle size
of 200 mm was used as the abrading material. The feed
rate of the sand was maintained at 220 gymin all
through the tests. The abrasion specimens were loaded
against the rubber wheel at a load of 10 kg and the tests
were generally conducted up to 6000 revolutions. How-
ever, the tests were interrupted at regular intervals (every
100 revolutions up to 1200 cumulative revolutions and
every 500 revolutions thereafter, up to 6000 cumulative
revolutions). Before and after each test interval, the
samples were cleaned in acetone, dried and weighed in
an electronic balance of 0.1-mg accuracy to estimate the
weight loss of the sample during the interval. This
weight loss data as a function of cumulative revolutions
was then utilized to estimate the steady state abrasive
wear loss (mgyrev.). The abrasive tests were conducted
not only on boronized samples obtained with varying
pack thickness but also on the uncoated plain carbon
steel.
3. Results
Fig. 1 shows the plot of effect of LABM pack
thickness on surface roughness of the boronized steel. It
can be observed that the initial roughness of the steel
sample prior to boronizing in the range 0.2–0.3-mm Ra,
is increased approximately by a factor of 2–3 on boron-
izing. However, the above increase in roughness is
clearly independent of the pack thickness employed.
The increase in roughness of the reasonably smooth
surface is due to chemical reaction at the surface
resulting into formation of iron borides (Fe2B in the
present case). The difference of the specific volumes
between the substrate and the boride layer results in a
positive dimensional change in the component, the
accommodation of which results in increased roughness
w2 x .
Fig. 2 illustrates the influence of pack thickness on
the phase content of the boride layer. The first point to
 V. Jain, G. Sundararajan / Surface and Coatings Technology 149 (2002) 21–26
Fig. 1. The effect of LABM pack thickness on the surface roughness
of borided steel in relation to the surface roughness prior to
boronizing.
be noted is that only Fe2B phase forms on boriding and
not FeB as expected. It is also seen that in the case of
steels boronized with a pack thickness of 10 mm and
above, only Fe2B phase is present. However, in the case
of samples boronized with pack thickness of 5 and 2
mm, along with Fe2B phase, a small amount of iron
oxide (Fe2O3) is also observed. The Fe2O3 phase content
is approximately 10% for a pack thickness of 5 mm,
increases to 20% when the pack thickness is reduced to
2 mm. On the basis of Fig. 2 it can be concluded that
when the pack thickness is lower than 10 mm, the
oxygen present in the container is able to penetrate the
pack, which reacts with Fe in the substrate to form
Fe2O3.
Fig. 3a,b,c,d,e,f show the SEM photographs (in back
scattered mode) of the sectioned surfaces of steels
boronized with varying LABM pack thickness viz. 2, 5,
10, 15, 20 and 25 mm, respectively. The microstructures
show a finger-like appearance characteristic of the boride
layer due to the preferred (002) crystallographic texture
w2x. It can be observed from the micrographs that coating
thickness is the least for steel boronized with 2 mm
thick pack and that the coating thickness increases with
increasing thickness of the pack up to 10-mm thickness
of the pack. The SEM micrographs also confirm the
presence of a single-phase Fe2B layer in all the cases
since the black layer indicating the presence of FeB (in
back-scattered mode) is absent. Little porosity, which is
a characteristic of the boride layer, is also observed in
all the micrographs in Fig. 3.
Since the coating has a finger-like appearance, the
definition of coating thickness is not obvious. Therefore,
the procedure suggested by Chatterjee-Fischer w2x and
depicted in Fig. 4 was followed. Fig. 5 shows variation
of the thickness of the boride coating with increasing
thickness of the LABM pack. It can be observed from
23
Fig. 5 that for 2-mm pack thickness, the average coating
thickness is approximately 40 mm, which increases to
68 mm for 5-mm pack thickness and finally, reaches a
constant value of 83 mm ("2 mm) at and above 10-
mm pack thickness.
The microhardness profiles carried out on the sec-
tioned surfaces of the boronized samples are presented
in Fig. 6. In all the samples, the value of microhardness
(i.e. Vickers hardness at 50 g load) attained a peak level
of approximately 1600, slightly below the top surface
and then decreased sharply with increasing depth from
the top surface (see Fig. 6). The microhardness vs.
distance from surface profiles were largely similar for
samples boronized with pack thickness of 10 mm and
above. For samples boronized with a pack thickness of
2 mm, the microhardness dropped very sharply from the
peak value and reached the base value at a depth of 40
mm from the surface consistent with the fact that the
boride coating thickness was only 40 mm in this sample
(see Fig. 5).
The variation of the weight loss experienced by the
boronized and uncoated steels during the course of the
abrasion test as a function of number of revolutions of
the rubber wheel is provided in Fig. 7. It is obvious that
the weight loss vs. number of revolution data for each
sample is linear, thereby indicating the attainment of
steady state with regard to abrasive wear. The slope of
the linear curve indicated by the numbers alongside
each curve thus, equals the steady state abrasive wear
rate (mgyrev.). It can be therefore concluded from Fig.
7 that the steady state abrasive wear rate of uncoated
steel (3.05 mgyrev.) is almost 500 times higher than
that of the steel boronized with a pack thickness of 10
mm (0.0065 mgyrev.), while the steady state wear rate
of steel boronized with a pack thickness of 2 mm
(0.0252 mgyrev.) is almost four times that of the steel
boronized with a pack thickness of 10 mm. The steady
Fig. 2. Quantitative phase analysis of boride coatings as a function of
LABM pack thickness.
24 V. Jain, G. Sundararajan / Surface and Coatings Technology 149 (2002) 21–26

Fig. 3. SEM micrographs of sectioned surfaces of boronized low carbon steel with varying LABM pack thickness: (a) 2; (b) 5; (c) 10; (d) 15;
(e) 20; and (f) 25 mm (mags500=).

state abrasive wear data are presented in Fig. 8 as a
function of pack thickness. It is once again obvious that
for steels boronized with a pack thickness of 10 mm or
higher, the abrasive wear rate does not depend on pack
thickness.
The most obvious reason should be that there is insuf-
ficient boron in the pack (especially at low pack thick-
ness) to form the boride layer of thickness dictated by
the boronizing treatment temperature and time. In order
to examine the above postulate, it is important to recall

4. Discussion

In the present study it has been observed that as long

as the pack thickness is P10 mm, the boride coating is
identical with respect to its thickness, phase analysis,
microstructure, microhardness profile and abrasive wear
resistance. Thus, it can be concluded that the pack
thickness should be at least 10 mm for boronizing of
plain carbon steel at the temperature and time conditions
utilized in the present study (i.e. 9408C, 2 h).
However, it is very important to understand the
reasons for the decrease in boride coating thickness Fig. 4. Schematic diagram illustrating the procedure for estimation of
when the pack thickness is reduced to below 10 mm. boride layer thickness (d).
 V. Jain, G. Sundararajan / Surface and Coatings Technology 149 (2002) 21–26
Fig. 5. The variation of boride coating thickness as a function of
LABM pack thickness.
the overall reaction that takes place during the pack
boronizing process w2x, i.e.:
BF3
B4Cq3SiCq3O2™4Bq2SiqSiO2q4CO. (1)
SiF4
It is to be noted that KBF4, added as an activator,
melts at the boronizing temperature and helps in sinter-
ing of the particles and thus, is not a source of free
boron. Based on the above fact and using Eq. (1), the
fraction by weight of active boron in B4C w f (B)B4Cx
can be obtained as:
fŽB.B4Cs4.aBywŽ4.aB.qaCx (2)
where aB and aC are the atomic weights of boron and
carbon, respectively. If the LABM mixture contains x%
B4C by weight, and if the weight of LABM packed
over a unit area equals WLABM (unitskgym2), the
weight of boron in LABM wW(B)LABMx is obtained as:
Fig. 6. Microhardness profiles measured on sectioned surfaces of
boronized steel with varying LABM pack thickness.
25
Fig. 7. The variation of abrasive weight loss as a function of the
number of revolutions of the rubber wheel for borided steel with var-
ying LABM pack thickness and uncoated steel. The numbers indicated
against each curve represent the slope of the straight-line portion of
the curve and represent the steady state abrasive wear rate (mgyrev.).
WŽB.LABMsWLABM.x.fŽB.B4C. (3)
It should be noted here that WLABM is a function of
the pack thickness. The weight of boron in the boride
layer consisting entirely Fe2B phase wW(B)Fe2Bx is
obtained as:
WŽB.Fe2Bsd.r.fŽB.Fe2B (4)
where d and r are the thickness of Fe2B layer (measured
experimentally) and density of Fe2B, respectively, and
f (B)Fe2B is given by the relation:
fŽB.Fe2BsaByŽ2.aFeqaB.. (5)
In the above equation, aB and aFe represent the atomic
weights of B and Fe, respectively.
A comparison of boron availability in the pack wEq.
(3)x with the boron in the boride layer wEq. (4)x is
Fig. 8. The variation of steady state abrasive wear rate of boronized
steel as a function of LABM pack thickness.
26 V. Jain, G. Sundararajan / Surface and Coatings Technology 149 (2002) 21–26
Fig. 9. A comparison of the boron available in the LABM pack (filled
circles) with boron present in the boride layer (unfilled circles) as a
function of LABM pack thickness.
presented in Fig. 9 as a function of pack thickness. The
values used for the various parameters in Eqs. (3) and
(4) are: aBs10.810; aCs12.011; aFes55.847; xs0.01;
and rs7430 kgym3. The values for WLABM are 0.02958,
0.07396, 0.1479, 0.2219, 0.2958 and 0.3698 kgym2 for
the pack thickness values 2, 5, 10, 15, 20 and 25 mm,
respectively. Fig. 9 clearly indicates that there is a
possibility of boron starvation at the lowest pack thick-
ness (i.e. 2 mm) given the fact that all of the boron in
the pack is unlikely to reach the steel substrate. Thus, it
can be concluded that the decrease in the thickness of
the boride layer at low pack thickness can be possibly
due to the non-availability of sufficient quantity of B
source in the pack. However, it should be noted that the
lower thickness of boride layer in the case of sample
boronized with low pack thickness was also associated
with the presence of significant quantity of oxides
(Fe2O3) in the boride layer. It is not clear whether the
oxides formed because of boron starvation (at low pack
thickness) or because the lower pack thickness allowed
the oxygen to reach the substrate and form oxides and
the oxide layer so formed slowed down the boronizing
process itself. Further studies are required to resolve this
important question.
Nevertheless, it should be clear that the presence of
Fe2O3 in the boride layer is largely responsible for the
higher abrasive wear rate in the case of samples boron-
ized with low pack thickness. This is so mainly because
the duration of the abrasive wear was insufficient to
remove the boride coatings even in samples having
lower boride thickness. In fact the experimentally meas-
ured wear depth was only of the order of 20 mm as
compared to the lowest boride coating thickness of 40
mm.
5. Conclusions
1. The present study indicates that a minimum pack
thickness of 10 mm is required to obtain boride
coatings of optimum thickness, microstructure and
properties in low carbon steel. However, it should be
emphasized that the above statement is valid only for
boronizing treatment carried out at 9408C for 2 h.
2. It appears likely that the non-availability of sufficient
quantity of boron source in the pack is responsible
for the decrease in boride layer thickness in the case
of samples boronized with low pack thickness.
3. Though it can be concluded that the presence of
significant amount of oxide in the boride layer is
responsible for the poor abrasion resistance in case
of samples borided with low pack thickness, the
`
exact reasons for the formation of the oxide vis-a-vis
boride formation is not clear and requires further
examination through additional experiments.
Acknowledgements
The authors thank Dr G.V.N. Rao (Head, Characteri-
zation Division, ARCI) for his contributions in XRD
analysis of the boronized samples.
References
w1x A.K. Sinha, ASM Handbook, 4, ASM International, Materials
Park, Ohio, USA, 1991, p. 437.
w2x R. Chatterjee-Fisher, in: T.S. Sundarshan (Ed.), Surface Modi-
fication Technologies, chap. 8, Marcel Dekker Inc, USA, 1989,
p. 567.
w3x D.N. Tsipas, J. Rus, H. Noguerra, Proceedings of Heat Treatment
‘88, The Metals Society, 1988, p. 203.
w4x A. Galibois, O. Boutenko, B. Voyzelle, Acta Metall. 28 (1980)
1753.
w5x J. Subrahamanyam, Mater. Lett. 1 (1982) 100.
w6x W. Fichtl, Mater. Eng. 2 (1981) 275.
w7x R. Chatterjee-Fisher, O. Schabber, Proceedings of Heat Treat-
ment, The Metals Society, 1976, p. 27.
w8x G. Sundararajan, B. Venkataraman, K. Lakshminarayana, G.B.K.
Harish, Studies on Boronizing of En 24 Steel, ARCI Technical
Report, Hyderabad, India, 1998.
w9x B. Venkataraman, G. Sundararajan, Surf. Coating Technol. 73
(1995) 177.
w10x K.H. Habig, R. Chatterjee Fisher, Tribol. Int. 14 (1981) 209.
w11x W.J.G. Fichtl, Heat Treat. Met. (1983) 79.
w12x K.G. Krishna, Vipin Jain, B. Verkataraman, K. Sampat, K.
Balasubramanian, G. Sundararajan, An Improved Boronizing
Composition, Indian Patent Application No. 289yMASy01,
April 3, 2001.