ARTICLE IN PRESS

Vacuum 73 (2004) 643–648

A mechanical aspect of borides formed on the

AISI 440C stainless-steel
Ibrahim Ozbeka, Saduman Sena, Mediha Ipeka, Cuma Bindala,
Sakin Zeytina, A. Hikmet Ucisikb,*
a
Department of Metallurgy and Materials Engineering, Engineering Faculty, Sakarya University,
54187 Esentepe Campus, Sakarya, Turkey
b
Bogazici University, Department of Prostheses, Materials and Artificial Organs, Institute of Biomedical Engineering,
Bebek-Istanbul 80815, Turkey

Abstract

In the present study, some properties of borides formed on AISI 440C stainless-steel have been investigated.
Boronizing was carried out in a solid medium consisting of EKabors powder at a temperature of 950
C for 2–8 h. The
presence of borides e.g. FeB, Fe2B, CrB, Cr2B, Mn2B and MnB were revealed by means of X-ray diffractometry,
scanning electron microscopy, and optical microscopy. The hardness of borides which was over 1500 VHN and boride
layer thickness were measured and it was observed that, the thicknesses of the boride layers were strongly dependent on
the process time, and chemical composition of the substrate materials. It was also found that the longer boronizing time
results in an increase in thickness layer; the thickness of boride layers ranged from 10 to 50 mm. Optical microscopy
examinations of the borides formed on the surface of AISI 440C stainless-steel substrate revealed a smooth and
compact morphology. To determine distribution of alloying elements from surface to the interior energy dispersive X-
ray spectroscopy was used.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Boronizing; Stainless-steel; Microstructure of borided zone; Indentation

1. Introduction choice for a wide range of tribological applications

Boronizing is a thermochemical diffusion sur-
face treatment in which boron atoms are diffused
into the surface of work piece to form hard borides
with the base material [1–4] and it is a prominent
*Corresponding author. Bogazici University, Department of
Prostheses, Materials and Artificial Organs, Institute of
Biomedical Engineering, Bebek-Istanbul 80815, Turkey. Fax:
+90-212-227-79-34.
E-mail address: hucisik@hotmail.com (A. Hikmet Ucisik).
where the control of friction and wear is of
primary concern [5]. Boronizing can be applied
to a wide range of steel alloys including carbon-
steel, low alloy-steel, tool-steel and stainless-steel.
In addition, materials such as nickel based alloys,
cobalt based alloys, molybdenum and titanium
can be boronized to obtain very high hardness and
wear resistant on their surfaces [6–11]. In parti-
cular, boronizing can increase the resistance of
low alloy steel to acids such as sulfuric, phosphoric
and hydrochloric acids. In addition, boronized

0042-207X/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2003.12.083
 ARTICLE IN PRESS
644 I. Ozbek et al. / Vacuum 73 (2004) 643–648
austenitic stainless-steel has excellent resistance to
hydrochloric acid [2,12–14]. In this study, we
investigated some properties of borides formed
on AISI 440C stainless-steel which is extensively
used for ball-bearings and races, seats, pump
parts, surgical tools, implant material and cutlery.
AISI 440C stainless-steels has also high carbon
and chromium content and therefore, it may be
hardened and tempered to increase wear resis-
tance.
At present study, we attempt to elucidate some
properties of boronized AISI 440C stainless-steel,
e.g. distribution of alloying elements, microstruc-
ture of borided zone etc. Specifically, we used a
Vickers indenter and an optical microscope to
determine hardness and microstructures of bor-
onized AISI 440C stainless-steel. To determine
distribution of alloying elements from the surface
to the interior energy dispersive X-ray spectro-
scopy (EDS) was used.
2. Experimental details
2.1. Substrate materials
The substrate material used in this study was
AISI 440C stainless-steel with chemical composi-
tion given in Table 1. The test pieces of AISI 440C
stainless-steel had a dimension of 15 mm 
15 mm  3 mm.
2.2. Boronizing
Boronizing was carried out in a solid medium
consisting of EKabor 2s powders (BorTec
GmbH). Test samples to be boronized were placed
in contact with EKabor 2s powders and then
placed in electrical resistance furnace. The test
samples were heated to a temperature of 950
C
under atmospheric pressure and hold for a
Table 1
The chemical composition of test material (wt.%)
C Si Mn P S Cr Mo
0.95–1.0 1.0 1.0 o0:04 o0:04 16–18 0.75max
predetermined amount of time (about 2–8 h). This
is followed by quenching in air.
2.3. Film characterization
The structure and type of borides formed on
AISI 440C stainless-steel is closely related to the
chemical composition of AISI 440C stainless-steel
substrate used in this study. The presence of
borides formed in coating layer was confirmed by
means of X-ray diffractometry (XRD), and optical
microscopy. A Phillips high resolution diffract-
ometer was employed for XRD analysis of the
borides formed on AISI 440C stainless-steel
surfaces. A CoKa radiation with a wavelength of
1.790 A( was used over a 2y range of 20
–90
.
Olympus BHM-313 optical microscope was also
utilized for examining microstructures. The dis-
tribution of alloying elements was confirmed via
EDS from surface to interior.
2.4. Hardness and thickness of coating layer
The microhardness of borides was measured by
using a Vickers microhardness tester and a load of
0.5 N. At least five indentations were made on each
coating film under each experimental condition to
check reproducibility of the hardness data. The
thicknesses of the coating layer were measured by
means of a digital thickness measuring instrument
attached to optical microscope.
3. Results
3.1. Microstructure
Optical cross-sectional examinations of the
borided AISI 440C stainless-steel revealed a
compact and smooth morphology to a depth of
about 50 mm. At higher magnifications, three
distinct regions were identified: (i) layer including
like Fe2B, FeB, CrB, MnB, Cr2B borides, (ii) the
region below boride layers, where boron makes
solid solution, which has hardness less than that of
borides and higher than that of original alloy, (iii)
steel matrix, which is not affected by boron. Fig. 1
shows an optical cross-sectional view of borided
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I. Ozbek et al. / Vacuum 73 (2004) 643–648 645

Fig. 1. The optical cross-sectional of borided AISI 440C stainless-steel for (a) 4 h, (b) 8 h.

AISI 440C stainless-steel. As shown in Fig. 1,

borides formed on the steel substrates had a
compact and smooth morphology. The higher
the alloying elements, the smoother the coating
layer. In coating layer, the FeB borides were
located near the surface and were about 10 mm
thick. The second phase, Fe2B, has a thickness of
50 mm. A boron diffusion zone was present
beneath the Fe2B phase (Fig. 1(b)). The distribu-
tion of alloying elements was confirmed via EDS
spectrum from the surface (Fig. 2) and line-scan
analysis from surface to interior (Fig. 3). As it can
be seen in Fig. 3 silicon concentarates at interface
due to insoluble in iron borides, chromium and Fig. 2. EDS spectrum of AISI 440C stainless-steel borided at
950
C for 4 h.
mangenese concentrate in coating layer by sub-
stituting for iron in the Fe2B and FeB, while no
remarkable change in molybdenum.

3.2. Hardness and boride layer

The hardness of borides formed on the surface

of borided AISI 440C stainless-steel is much
higher than that of substrate. It is possible to
claim that these are a consequence of presence of
FeB, Fe2B, CrB, Cr2B, MnB, and Mn2B which
verified by means of XRD (Fig. 4).
Vickers hardness values of boride layer and
matrix were up to 2500 and 600 HVN respectively.
The thickness of the coating layer was measured
by means of a digital thickness measuring instru-
ment attached to optical microscope in a range of Fig. 3. The distribution of alloying elements confirmed by EDS
10–50 mm. The variation of hardness of borided from surface to interior.
AISI 440C stainless-steel from surface into matrix
was shown in Fig. 5. As it will be seen in Fig. 5, the has three regions, which are (i) surface consisting
hardness of borides is considerably higher than of borides, (ii) transition region being rich with
that of steel matrix. Hardness distribution diagram boron, (iii) matrix.
 ARTICLE IN PRESS

646 I. Ozbek et al. / Vacuum 73 (2004) 643–648

100 1
1-FeB
2 2-Fe 2 B
80 3-CrB
4-Cr 2 B
5-M nB
Intensity 2 6-Fe 3 C
60 1 1
7-M nB 2

40
3 6
3 5
4 1 43 4 4
20 42 5 3 5 7
6 35 3 2 1
7 4 51

0
30 40 50 60 70 80 90
(a) 2θ,degree

100 1
1-FeB
2-Fe 2 B
80 3-CrB
5-MnB
6-Fe 3 C
2
Intensity

6
60 1 1

40 2

5
1 3 6 3
3 1 1
20 36 5
5 3 5 33 5 3 1
1
1

0
30 40 50 60 70 80 90
(b) 2θ,degree
Fig. 4. X-ray diffraction patterns of boronized samples for different times at 950
C for (a) 4 h and (b) 8 h.

Boride Diffusion 50
The thickness of boride layer, µm

Matrix
layer Zone
2500
40
2000
Hardness, HV

30
1500

1000 20

500
10
0
10 20 30 40 50 60 2 4 6 8
Distance from surface, µm Boronizing time, h

Fig. 5. The hardness variation of borided AISI 440C stainless- Fig. 6. Maxima, minima and average values of boride layer
steel as a function of distance. thickness for different periods of boronizing.

The depth of boride layer depends strongly on

process temperature, chemical composition of boronizing time. As it will be seen in Fig. 6, there is
substrate and boronizing time. The thickness nearly a parabolic relationship between depth of
of layer was plotted in Fig. 6 as a function of layer and diffusion time.
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I. Ozbek et al. / Vacuum 73 (2004) 643–648
4. Discussion
Optical microscopy examinations of borides
revealed a smooth and compact morphology
(Fig. 1) which is closely related to alloying elements
that base steel has and boronizing time. During
boronizing, the alloying elements in the steels
undergo considerable redistribution due to diffu-
sional phenomenon, the extent of which depends on
the solubility of each element in solid phases, as well
as on the temperature. As a result, the properties of
both the base material and the surface coating
are significantly modified. For example, chromium
and manganese preferentially enter the coatings
by substituting for iron in the Fe2B and FeB.
As a matter of fact that, alloying elements by
changing the diffusivity of boron atoms modify
coating-substrate interface. The higher the alloy,
the smoother and the compact coating layer. The
diffusivity of boron at 950
C is 1.82  108cm2 s1
for boride layer and 1.53  107cm2 s1 for diffu-
sion zone, respectively. As a corollary, the boron
containing diffusion zone is extended several fold
the depth of non-oxide ceramic boride layer into the
steel substrates [1]. Depending on boronizing time
and chemical compositions of steel substrates, the
depth of boride region ranged from 10 to 50 mm.
Previous thermochemical boronizing studies by
Pelleg [15] and Bindal et al. [13] showed that
boronizing of carbon steels usually leads to forma-
tion of two borides, FeB and Fe2B; FeB near the
surface and Fe2B in the vicinity of steel matrix. In
the present study, the presence of borides was
identified via XRD analysis.
EDS revealed that, nickel concentrates in the
base metal beneath the coating, chromium and
manganese preferentially enter the coatings by
substituting for iron in the Fe2B and FeB. Whereas
silicon which is insoluble in iron borides, concen-
trates strongly at the interface with the coatings
(Fig. 3). The boride coatings grown on the ternary
alloys generally constituted by an inner Fe2B
single-phase and an outer FeB-base polyphase
region containing FeBx ðx > 1Þ and an iron–boron
solid solution. With increasing contents of the
third alloying element in the alloys, both the depth
of FeB-base region and the FeB/FeBx ratio
increases [16].
647
Hardness measurements of borided AISI 440C
stainless-steel substrate were carried out from
surface to interior. Thus, the hardness of non-
oxide ceramic borides and base materials were
compared. It was observed that the hardness of
borides is much higher than that of base steel. We
believe that this is consequence of the presence of
hard FeB, Fe2B, CrB, Cr2B, MnB, and Mn2B in
the coating layer. Vickers hardness values of
borides formed on the surface of AISI 440C
substrate and base steel were 2500 and 600
VHN, respectively.
5. Conclusion
The following results may be drawn from the
present study.
(1) Borides formed on the surface of substrate
materials revealed a smooth and compact
morphology which is closely related to alloy-
ing elements that base steel has and boroniz-
ing time.
(2) Depending on boronizing time and chemical
compositions of steel substrates, the depth of
boride region ranged from 10 to 50 mm.
(3) In the present study, the presence of borides
(FeB, Fe2B, CrB MnB, etc.) was identified via
X-ray diffraction (XRD) analysis.
(4) Energy dispersive X-ray spectroscopy (EDS)
revealed that, chromium and manganese pre-
ferentially enter the coatings by substituting for
iron in the Fe2B and FeB. Whereas silicon
which is insoluble in iron borides, concentrates
strongly at the interface with the coatings.
(5) Vickers hardness values of borides formed on
the surface of AISI 440C substrate was over
2500 VHN.
Acknowledgements
Authors express their grateful thanks to Soner
Akkurt of Arcelik Company of Turkey for
performing the energy dispersive X-ray spectro-
scopy (EDS) analysis. Special appreciations are
extended to Technician Mizrap Canibeyaz of
 ARTICLE IN PRESS
648 I. Ozbek et al. / Vacuum 73 (2004) 643–648
Istanbul Technical University and Ersan Demir of
Sakarya University for assisting with experimental
studies.
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