ARTCULO 9

DEPENDENCE BETWEEN THE BORON SURFACE

CONCENTRATION AND THE GROWTH KINETICS OF
BORIDE LAYERS IN STEELS AISI 4140
M. Ortiz-Domnguez, N. Lpez-Perrusquia, D. Bravo-Brcenas,
O. Bravo-Brcenas, M. A. Dou-Ruz, I. Campos-Silva
INSTITUTO POLITCNICO NACIONAL,
GRUPO INGENIERA DE SUPERFICIES, SEPI-ESIME
INSTITUTO TECNOLGICO
de saltillo
SALTILLO, COAHUILA 21, 22 Y 23 DE OCTUBRE DEL 2009.

79
Dependence between the boron surface concentration and the growth kinetics of
boride layers in AISI 4140 steels

M. Ortiz-Domnguez, N. Lpez-Perrusquia, D. Bravo-Brcenas,
O. Bravo-Brcenas, M. A. Dou-Ruz, I. Campos-Silva

Instituto Politcnico Nacional, Grupo Ingeniera de Superficies, SEPI-ESIME,U. P. Adolfo Lpez
Mateos, Zacatenco, Mxico D.F., 07738, Mxico.



Abstract The present work estimated the growth kinetics of Fe
2
B layers formed at the surface of
AISI 4140 steels. The thermochemical treatment was applied in order to produce the Fe
2
B phase,
considering temperatures of 1123, 1173, 1223 and 1273 K with five exposure times (2, 4, 5, 6, and
8 h), using a 4 mm thick layer of boron carbide paste over the material surface. The growth of
boride layers was described by the mass balance equation between phases in thermodynamical
equilibrium, assuming that the growth of boride layers obeys the parabolic growth equation
( (( ( ) )) )
( (( ( ) )) )
/ /
( )
o
x t u k t t T = = = = = = = =
1 2 1 2
and the boron concentration at the interfaces remains constant. Also, the
boron diffusion coefficient at the Fe
2
B (
Fe B
D
2
) was established as a function of boriding
temperature. Likewise, the parabolic growth constant ( k ), the instantaneous velocity ( v ) of the
Fe
2
B/substrate interface and the weight-gain of borided steels were established as a function of
the parameters ( (( ( ) )) ) t and ( (( ( ) )) )
S
C , which are related to the boride incubation time ( t
0
) and boron
surface concentration (
S
C ), respectively.
Resumen La cintica de crecimiento de capas duras tipo Fe
2
B formadas en la superficie de un
acero AISI 4140 es estimada en el presente trabajo. El tratamiento termoqumico de borurizacin
en pasta fue aplicado a las temperaturas de 1123, 1173, 1223 y 1273 K con cinco tiempos de
exposicin (2, 4, 5, 6, y 8 h), empleando un espesor de 4 mm de pasta de carburo de boro sobre
la superficie del material. El crecimiento de las capas fue descrito por la ecuacin de balance de
masa en la interface de crecimiento, asumiendo que el crecimiento obedece la ecuacin
parablica ( (( ( ) )) )
( (( ( ) )) )
/ /
( )
1 2 1 2
o
x t u k t t T = = = = = = = = . Asmismo, el coeficiente de diffusion del boro en la fase
Fe
2
B (
Fe B
D
2
) fue expresado en funcin de la temperatura de borurizacin. Finalmente, la
constante de crecimiento ( k ), la velocidad instantnea de la interface Fe
2
B/substrato ( v ), y la
ganancia de masa de los aceros borurizados son establecidos en funcin de los parmetros ( (( ( ) )) ) t
y ( (( ( ) )) )
S
C , los cuales estn relacionados con el tiempo de incubacin del boruro ( t
0
) y la
concentracin de boro en la superficie (
S
C ), respectivamente.
Keywords: paste boriding process; boride layers; growth kinetics; diffusion coefficient; mass
balance equation.
Descriptores: borurizacin en pasta, capas boruradas, cintica de crecimiento, coeficiente de
difusin, ecuacin de balance de masa.

80
1. Introduction
Boriding is one important surface modification method of ferrous and non-ferrous alloys used to
enhance their surface hardness, wear and corrosion resistance [1-3]. The paste boriding is an
alternative method of work piece treatment. It is a simple method and more economical compared
to other boriding techniques as powder-pack, gaseous media and molten oxides. It minimizes
manual work and can be used with high work volumes and selective treatments [4]. The
morphology of the layers depends fundamentally on the chemical composition of the substrate.
Saw-toothed layers are obtained in low-alloy steels whereas in high-alloy steels these layers tend
to be flat [5]. If the activation energy of Fe
2
B boride phase is known, it would be possible to
automate and optimize the boriding process. The present work estimated the boron diffusion
coefficient in the Fe
2
B boride phase (
Fe B
D
2
) formed at the surface of AISI 4140 steels. Also, the
parabolic growth constants, the instantaneous velocity of the Fe
2
B/substrate and the weight-gain
( (( ( ) )) ) G t of borided samples were established as a function of ( (( ( ) )) ) t and ( (( ( ) )) )
S
C , parameters which
depend essentially on boride incubation time and boron surface concentration, respectively.

2. Mathematical Model
The model studied the case where the substrate is saturated with atomic boron. The boron
diffusion coefficient was obtained by the mass balance equation at the growth interphase,
considering that the layer growth is given by the equation ( (( ( ) )) ) ( (( ( ) )) )
( (( ( ) )) )
/ /
x t u k t t T = = = = = = = =
1 2 1 2
0
, where u is the
layer thickness (m), k is the parabolic growth constant (m/s
1/2
), t represents the treatment time (s)
and t
0
represents the incubation time (s). The assumptions for the diffusion model proposed in this
work were: (i) the boron concentration ( (( ( ) )) ) ( (( ( ) )) )
Fe B
C x t
2
at the Fe
2
B phase (mol/m
3
) (Fig. 1(a))
depended on the position ( (( ( ) )) ) ( (( ( ) )) )
x t , (ii) the boron concentration values at the surface and
Fe
2
B/substrate interface remain constants at the boride layer during the treatment, (iii) the
influence of the alloying elements on the growth kinetics of the layer was not taken into account,
(iv) the model considered the nucleation period (incubation time) of Fe
2
B phase and (v)
differences in specific volume per solvent atom for the Fe
2
B phase are accommodated fully in the
diffusion direction. The mass balance equation at the Fe
2
B/substrate interface was set as [6-7]:

( (( ( ) )) )
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
( (( ( ) )) )
Fe B
eFe B Fe B
x u
x u
dC x t dx t
C C D
dt dx t

= == =
= == =
| | | | | | | |
= = = =
| | | |
\ \ \ \
2
2 2
0
(1)

eFe B
C
2
is the boron concentration at the Fe
2
B/substrate interface
( (( ( ) )) )
. mol / m
eFe B
C = = = =
2
3 3
59 8 10 , C
0

is the initial boron concentration in the austenite phase
( (( ( ) )) )
3
mol/m C
0
0 and is the ratio of the
specific volume per solvent atom, /
m m
Fe B
V V = == =
2
0
2 (
m
V
0
is the molar volume of the substrate and

81
m
Fe B
V
2
is the molar volume of the Fe
2
B phase (m
3
/mol)).
Likewise, Eq. 1 is rewritten as follows:


( (( ( ) )) )
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
( (( ( ) )) )
Fe B
eFe B Fe B
x u
x u
dC x t dx t dt
C C D
dt dt dx t

= == =
= == =
| | | | | | | | | | | | | | | |
= = = =
| | | | | | | |
| | | |
\ \ \ \ \ \ \ \
2
2 2
0
(2)

After rearranging, it follows from Eq. 2:

( (( ( ) )) )
( (( ( ) )) ) ( (( ( ) )) )
eFe B
S
C
t
eFe B Fe B Fe B
x u
t C
k dt
C C D dC x t
t

= == =
= = = =

2
2 2 2
0
2
0
4
(3)

So, Eq. 3 is rewritten as:

( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
ln /
eFe B Fe B eFe B S
x u
k
C C t t T D C C
= == =
= = = =
2 2 2
2
0 0
4
(4)
where
S
C is the boron concentration at the surface
( (( ( ) )) )
3
. mol / m
S
C = = = =
3
100 5 10 [2].
Finally, Eq. 4 can be expressed in the form:
( (( ( ) )) )
ln
Fe B
t
D k
t T
| | | | | | | |
= == =
| | | |
| | | |
\ \ \ \
2
2
0
3
8
(5)

Fe B
D
2
is the boron diffusion coefficient (m
2
/s), while k is obtained by the slopes of the straight lines
in Fig. 1(b).

3. Experimental procedure
Samples of AISI 4140 commercial steel with dimensions of 8 x 8 x 5 mm was used for the
thermochemical treatment. The boriding process was carried out in a conventional furnace under a
pure argon atmosphere. The temperatures of 1123, 1173, 1223 and 1273 K with 2, 4, 5, 6 and 8 h
were selected. Four millimeters of boron carbide paste covered the samples. The metallographic
preparation employed a sequence of abrasion, down to 1000-grit silicon carbide abrasion paper,
followed by polishing with a diamond paste and ethylene glycol. The thicknesses of the boride
layers were measured by means of optical microscopy in clear field at 200X magnification. The
obtained images were analyzed using a MSQ PLUS software. In each sample, a minimum of 25
measurements were done at different points; the reported values were the average thickness of
the layers.

82

(a) (b)
Fig. 1 (a) Boron concentration profile at Fe
2
B phase, (b) Evolution of boride layer thicknesses as a
function of square root of time.

4. Results and discussions
The hard boride coating consisted of finger-like penetrations into the AISI 4140. In the iron borides,
boron diffuses more rapidly along the [001] crystallographic direction and perpendicular to the
surface [1,2,6]. Fig. 2 shows the cross sectional views of AISI 4140 borided samples at the
temperatures of 1173 and 1273 K with 6 h of treatment respectively. The growth kinetics of Fe
2
B
layers was evaluated by the measurement of the layer thickness for the different exposure times
and temperatures. Also, the boride incubation time is expressed as a function of boriding
temperature, and yields an additional point in the u vs. t plot as depicted in Fig. 1(b).


Fig. 2 Cross sectional views of AISI 4140 borided steels with 6 h of treatment and temperatures of:
(a) 1173 K, (b) 1273 K. Magnification 250X.

The
Fe B
D
2
was estimated by Eq. 5, and it is expressed as a function of the temperature by the
Arrhenius relationship, where the activation energy (Q) is obtained from the slope of the graph
(Fig. 3(a)). The Q value (172 kJ/mol) indicates the amount of energy for boron mobility in the

83
easiest path direction [001] along the Fe
2
B phase. The boron diffusion coefficient obtained in the
range of temperatures for the AISI 4140 borided steels is defined as:

( (( ( ) )) )
. exp . /mol / m / s
Fe B
D J RT

( ( ( ( = = = =
2
5 3 2
1 57 10 172 7 10 (6)

For the parabolic growth constant, Eq. (4) can be rewritten as follows:

( (( ( ) )) ) ( (( ( ) )) )
S Fe B
k t C D = == =
2
2

(7)

where ( (( ( ) )) )
S
C is a parameter proportional to the boron surface content (Fig. 3(b)), and ( (( ( ) )) ) t is a
parameter dependent of ( (( ( ) )) ) t T
0
for a set of experimental treatment times (Fig. (4a)). Likewise, k
2
is
valid in la range of
3 3
. mol/m . mol/m
S
C < < < < < < < <
3 3
59 8 10 100 5 10 ; values located in the limits of
concentration for the formation of the Fe
2
B phase at the material surface [1-2]. The plot k vs.
S
C depicted in Fig. 4(b), denote an optimum boron surface concentration (
3
mol/m
S
C = = = =
3
96 10 )
that produced good agreement with the experimental growth constants obtained in this work. The
data are summarized in Table 1. These results can serve as a tool for selection of the optimal
values of temperature and boron surface concentration with the purpose of increasing the growth
kinetics of iron boride and minimizing the amount of B
4
C paste used as a boron source.


(a) (b)
Fig. 3 (a) Dependence between the boron diffusion coefficient (
Fe B
D
2
) and boriding temperature,
(b) Behavior of parameter ( (( ( ) )) )
S
C as a function of boron surface content.





84


(a) (b)
Fig. 4 (a) Variation of the ( (( ( ) )) ) t parameter with treatment time, (b) Predicted growth constants
against boron surface content.

Table 1. Predicted growth constants obtained by Eq. 7, in the range of boriding temperatures (1123-1273 K).

Temperature [K] Experimental growth
constants
[m/s
1/2
]
Predicted growth
constants
[m/s
1/2
]
1123 0.416 0.413
1173 0.515 0.550
1223 0.663 0.672
1273 0.840 0.830

According to Fig. 1(a), it is possible to obtain, the instantaneous velocity of the Fe
2
B/substrate
interface as:

( (( ( ) )) )
( (( ( ) )) )
( (( ( ) )) ) ( (( ( ) )) )
( (( ( ) )) )
/ /
/
( )
o
S Fe B
x t u k t t T
dx
v t C D t
dt


= = = = = = = =
= = = = = = = =
2
1 2 1 2
1 2
1
1
2
(8)

The results from Fig. 5(a), with a boron surface content of
3
mol/m
3
96 10 , showed that the
interface velocity tends to an asymptotic behavior for long exposure times, perhaps, by the
reduction of boron active in the paste.
Also, the weight-gain at the surface of borided steel can be obtained from the simple relation:
( (( ( ) )) )
du
G t W t
dt
= == = (9)
( (( ( ) )) ) G t describes the evolution of the weight-gain per surface unit (mol/m
2
) associated at the
formation of the borided phase over the material surface from ( (( ( ) )) ) t t T > >> >
0
, and W is the amount of
solute accumulated in the layer to maintain a concentration-depth profile. Considering Eq. 7, the

85
weight-gain can be written in terms of the ( (( ( ) )) ) t and ( (( ( ) )) )
S
C as follow:
( (( ( ) )) ) ( (( ( ) )) ) ( (( ( ) )) )
( (( ( ) )) )
/
S Fe B
G t W t C D t = == =
2
1 2
1
2
(10)
The weight-gain was expressed as a function of boron surface concentration for constant
treatment time as shown in Fig. 5 (b).


(a) (b)
Fig. 5 (a) Instantaneous velocity of the Fe
2
B/substrate interface as a function of square root of
time, (b) Weight gain per unit area at different boron surface contents as well as different
temperatures with 8 h of treatment.
5. Conclusions
Through this work, the growth kinetics of boride layers formed at the AISI 4140 steels was
estimated by a simple model, that showed the influence of boride incubation time on the boron
diffusion coefficient at the Fe
2
B layers. Additionally, with the model adopted, it is feasible to
correlate the growth constant ( k ) with two parameters ( (( ( ) )) ) t and ( (( ( ) )) )
S
C , to obtain an optimum
boron surface value of mol/m
3 3
96 10 . Likewise, with the ( (( ( ) )) ) t and ( (( ( ) )) )
S
C parameters, the
instantaneous velocity of the Fe
2
B/substrate interface and the weight-gain at the surface of borided
AISI 4140 steels were estimated.

Acknowledgements
This work has been supported by the research grants 53859 of Consejo Nacional de Ciencia y
Tecnologa and PIFUTP08-84 of Instituto de Ciencia y Tecnologa del Distrito Federal at Mexico. I.
Campos thanks the project 20090010 chair supported by the Secretara de Investigacin y
Posgrado of the Instituto Politcnico Nacional.

.

86

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