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Kinetics of boriding of AISI W1 steel

Article in Materials Science and Engineering A April 2003
DOI: 10.1016/S0921-5093(02)00607-X

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Materials Science and Engineering A347 (2003) 311
/314

www.elsevier.com/locate/msea

Kinetics of boriding of AISI W1 steel

K. Genel a, I. Ozbek b, C. Bindal c,*
a

Mechanical Engineering Department, Sakarya University, Esentepe 54187, Sakarya, Turkey

b
Vocational High School, Sakarya University, 54040 Izmit cad, Sakarya, Turkey
c
Metallurgical and Materials Engineering Department, Engineering Faculty, Sakarya University, Esentepe 54187, Sakarya, Turkey
Received 15 February 2002; received in revised form 6 August 2002

Abstract
A technologically interesting characteristic of boriding is the production of a hard, wear-resistant coating layer on the steel
substrate. In this study, case properties of borided AISI W1 steel has been investigated by conducting a series of experiments in
Ekabor-I powders at the process temperature of 1123
/1323 K at 50 K intervals for periods of 1
/8 h. The presence of borides FeB
and Fe2B formed on the surface of steel substrate was confirmed by optical microscopy and X-ray diffraction. Cross-sectional
observation in the optical microscope revealed smooth and compact morphology of the borided layer. The distribution of alloy
elements from the surface to the interior was confirmed by energy dispersive X-ray spectroscopy. The hardness of the boride layer
formed on the surface of the steel substrate was higher than 1500 HV. It was concluded that the optimum temperature for AISI W1
steel borided in Ekabor-I powders was approximately 1223 K for hardness in 10 mm depth, and the hardness change with boriding
temperature was related to the grain size of the treated steel. The kinetics of boriding show a parabolic relationship between layer
thickness and process time, and the activation energy for the process is 171.29/16.6 kJ mol 1. Moreover, an attempt was made to
investigate the possibility of predicting the iso-thickness of boride layer variation and to establish an empirical relationship between
process parameters of boriding and boride layer.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Boriding; Activation energy; Iso-thickness; Layer depth; Grain size; AISI W1 steel

1. Introduction
It is well known that boriding is of prime importance
to enhance wear resistance of ferrous and non-ferrous
alloys. The most relevant element of the procedure is the
production of very hard layers that can reach a hardness
of 20 GPa, allowing for a better resistance to friction
wear and abrasion than other thermo-chemical surface
treatments like carburizing and nitriding. Thermal
diffusion treatments of boron compounds used to
form iron borides typically require process temperatures
of 973
/1273 K in either gaseous, solid, or salt media.
Boron atoms, owing to their relatively small size and

* Corresponding author. Tel.: /90-264-346-0353x334; fax: /90264-346-0351

E-mail address: bindal@sakarya.edu.tr (C. Bindal).

high mobility, can diffuse easily into ferrous alloys,

forming FeB and Fe2B intermetallic, non-oxide, ceramic
borides. Boron atoms, in general, dissolve in iron
interstitially. Depending on process temperature, chemical composition of substrate materials, boron potential of the medium and boriding time, single-phase Fe2B
or two intermetallic phases (Fe2B, FeB) are obtained by
diffusing boron atoms into the surface of metallic
materials [1
/9]. It is known that boriding performed
at high temperature is a diffusion-controlled process. It
is very important to establish the process parameters
that affect the boriding kinetics in order to select process
parameters to attain the desired thickness of boride
layer and hardness. The primary objective of the present
study is to investigate characterization and kinetics of
borided AISI W1 steel. Moreover, an attempt was made
to establish an empirical relationship between process
parameters of boriding and boride layer.

0921-5093/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 5 0 9 3 ( 0 2 ) 0 0 6 0 7 - X

K. Genel et al. / Materials Science and Engineering A347 (2003) 311
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312

2. Experimental details
2.1. Substrate material and boriding
The chemical composition of a standard AISI W1,
water hardening plain carbon tool steel, used in the
study was given in Table 1. Test materials had a
rectangular shape with nominal dimensions of 10 /
10 /2.5 mm. Boriding was performed in a solid medium
consisting of Ekabor-I powders at a temperature of
1123
/1323 K at 50 K intervals for period of 1
/8 h.
2.2. The characterization of the boride layer
The type and morphology of borides formed on the
steel substrate were confirmed via optical microscopy.
The presence of phases formed in the coating layer was
checked by X-ray diffraction. CoKa radiation with a
was used over a 2u range of 20
/
wavelength of 1.7902 A
888. The hardness of the boride layer was measured
three times at the same distance from the surface by
means of a Vickers indenter with a load of 1 N. Prior
austenite grain size was measured following ASTM
standard E 112 on nital-etched cross-sections of borided
specimens. In order to evaluate the kinetics, the thickness of boride layer was identified by means of a digital
measurement instrument attached to optical microscopy. Thickness values are at least averages of at least
three measurements.

Fig. 1. An optical micrograph (cross-sectional view) of borided AISI

W1 steel at 1223 K for 6 h.

Fig. 2. X-ray diffraction pattern of a specimen borided at 1223 K for 6

h.

3. Results
3.1. Microstructure and characterization
Fig. 1 shows an optical microscope cross-sectional
view of borided AISI W1 steel at 1223 K for 6 h. A
smooth and compact morphology was revealed with a
depth up to 1789/8.8 mm. The X-ray diffraction patterns
of the borided steel at 1223 K for 6 h are given in Fig. 2.
EDS studies revealed no remarkable changes in chromium and carbon, but boron concentrated in the
coating layer (Fig. 3).
3.2. Hardness and kinetics studies
The distribution of hardness of borides formed on the
surface of AISI W1 steel ranged from 1690 to 1800 HV,
whereas the hardness of the unborided steel substrate is
Table 1
The chemical composition of AISI W1 steel used in the study (wt.%)
C

Cr

Mn

Si

Fe

0.85

0.18

0.36

0.24

Balance

Fig. 3. Energy dispersive X-ray spectroscopy line scan analyses of a

sample borided at 1223 K for 6 h.

260 HV. The variation of hardness has three distinct

regions which are (i) boride layer including FeB, Fe2B;
(ii) transition zone harder than the matrix, probably due
to boron solid solution hardening, (iii) matrix was not
affected by boron (Fig. 4). Fig. 5 represents the hardness

K. Genel et al. / Materials Science and Engineering A347 (2003) 311
/314

313

The graphical representation in Fig. 6 shows that the

boride layer thickness increases with boriding time for
each process temperature. Moreover, a contour diagram
derived from Fig. 6 facilitates the selection of process
parameters in industrial application (Fig. 7). In addition
to the graphical representation given in Fig. 7, an
empirical equation was constructed with a correlation
coefficient (R2) of 0.984 as follows:

Fig. 4. Micro-hardness profiles of specimens borided at 1223 K for 1,

2, 4, 6 and 8 h.




T  1467 2
d 567:8 exp 0:5
177
2 

t  8:5

4:5

(1)

where d is layer thickness (mm); T , boriding temperature

(K) and t is time (h).
The squared thickness of the boride layer as a
function of time is described by:
d 2 Kt

Fig. 5. The effect of boriding temperature on the hardness of the

specimen in 10 mm depth.

(2)

where K is the growth rate constant depending on the

boriding temperature. If the kinetics of layer progress
for the periods between 1 and 8 h is considered, it can
also be recognized that the layer thickness changes
linearly with time as seen in Fig. 8, (the inset shows
growth rate constant vs. temperature). The relationship
between rate constant, K and temperature can be
expressed by an Arrhenius equation as follows:

change with process temperature in 10 mm depth. The

hardness increases with temperature, up to approximately 1223 K, then decreases at higher process
temperatures. The decrease in hardness can be attributed to grain coarsening. The increase in grain size up to
1223 K is negligible, whereas grain sizes upto 175 mm are
attained at higher temperature. With longer process
time, e.g. 8 h, grain coarsening is clearly revealed.



Q
K  A exp 
RT

Fig. 6. Boride layer thickness vs. boriding time for various process
temperatures.

Fig. 7. Contour diagram of boride layer thickness of borided AISI W1

steel.

(3)

where A is a constant; Q , activation energy (J mol 1);

T , absolute temperature and R is the gas constant (J
mol 1 K 1). The plot of rate constant versus reciprocal
boriding temperature reveals a linear relationship and
an activation energy of 171.29/16.6 kJ mol 1 for the
process, as determined from the slope of Fig. 9.

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K. Genel et al. / Materials Science and Engineering A347 (2003) 311
/314

processing for 6 h at various temperatures, hardness

increases initially with temperature up to 1223 K, then it
tends to decrease for higher temperatures. This can be
attributed to grain coarsening.
The layer growth for periods between 1 and 8 h shows
that layer thickness changes parabolically with time. The
activation energy calculated for the process is about
171.29/16.6 kJ mol1. It is expected that the activation
energy varies with the boron potential of the medium
and the chemical composition of the substrate material.
The calculated value of the present study is in good
agreement with values reported in the literature [10,11].
Fig. 8. Square of the boride layer thickness vs. boriding time and
growth rate constant for various process temperatures.

5. Conclusion
The following conclusions can be derived.
i)

Fig. 9. Growth rate constant vs. temperature of borided AISI W1

steel.

4. Discussion
In general, boriding of carbon steels usually leads to
the formation of two borides, FeB and Fe2B, FeB near
the surface and Fe2B in the vicinity of the steel matrix
[2]. In the present study, borides were identified via Xray diffraction. Optical microscopy of borides formed
on the surface of AISI W1 steel substrate revealed a
smooth and compact morphology. Energy dispersive Xray analysis showed no remarkable changes in the
amounts of chromium and carbon during the process.
In general silicon, which is insoluble in iron borides,
concentrates at the interface with the coatings [5,12]. It
was observed that there is no appreciable change
distribution of silicon due to low content (Fig. 3). The
hardness of non-oxide ceramic borides formed on the
surface of AISI W1 steel ranged from 1690 to 1800 HV,
whereas the hardness of unborided steel substrate is 260
HV. It was observed that the case structure has three
distinct regions, which are (i) borides FeB, Fe2B; (ii)
transition zone; and (iii) matrix. It was seen that after

The surface hardness of the borided AISI W1 steel is

in the range of 1690
/1800 HV, while that of
unborided steel substrate is 260 HV.
ii) Hardness of the boride layer increases with increasing process temperature, up to 1223 K, with
decreasing rate. This process temperature can be
recommended for AISI W1 steel borided in Ekabor
I powders in industrial applications. It is also
considered the optimum process temperature if
process time does not exceed 6 h.
iii) An empirical equation was suggested for estimating
the layer thickness as a function of process time and
temperature.

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