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1 s2.0 S016943321632685X Main
1 s2.0 S016943321632685X Main
a r t i c l e i n f o a b s t r a c t
Article history: The present study is focused on the estimation of activation energy of boron in the plasma paste borided
Received 8 February 2016 Ti6Al4V alloy, which is extensively used in technological applications, using an analytical diffusion model.
Received in revised form Titanium boride layers were successfully produced by plasma paste boriding method on the Ti6Al4V alloy
18 September 2016
in the temperature range of 973–1073 K for a treatment time ranging from 3 to 7 h. The presence of both
Accepted 29 November 2016
TiB2 top-layer and TiB whiskers sub-layer was confirmed by the XRD analysis and SEM observations. The
Available online 11 December 2016
surface hardness of the borided alloy was evaluated using Micro-Knoop indenter. The formation rates
of the TiB2 and TiB layers were found to have a parabolic character at all applied process temperatures.
Keywords:
Titanium borides A diffusion model was suggested to estimate the boron diffusivities in TiB2 and TiB layers under certain
Plasma paste boriding assumptions, by considering the effect of boride incubation times. Basing on own experimental data on
Growth kinetics boriding kinetics, the activation energies of boron in TiB2 and TiB phases were estimated as 136.24 ± 0.5
Incubation time and 63.76 ± 0.5 kJ mol−1 , respectively. Finally, the obtained values of boron activation energies for Ti6Al4V
Activation energy alloy were compared with the data available in the literature.
© 2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apsusc.2016.11.227
0169-4332/© 2016 Elsevier B.V. All rights reserved.
230 M. Keddam, S. Taktak / Applied Surface Science 399 (2017) 229–236
Fig. 1. Schematic illustration of the practical procedure used to estimate the boride layers thicknesses.
2. Experimental procedures
[23]. The variable u the position of the (TiB2 /TiB) interface while v CTi (x(t = t) = v) = C0 (9)
represents the position of the (TiB/substrate) interface as a func-
The mass balance equations [30,31] are then described by Eqs.
tion of the treatment time. C0 represents the boron solubility in the
(10) and (11).
substrate.
TiB2 ), imposed by
The upper boron content in the TiB2 phase (Cup TiB
(Cup 2 − Clow2 )
TiB TiB − C TiB )
(Cup
du low
the boriding medium, gives rise to the two titanium borides TiB2 wTiB2 ( ) = DBTiB2 − DBTiB (10)
dt u (v − u)
and TiB. From a thermodynamic point of view; the both phases (TiB2
and TiB) exhibit a narrow composition range (of about 1 at.% B) as TiB − C TiB )
stated by the authors [24,25]. In fact, a linear concentration − profile dv du (Cup
wTiB ( ) + w ( ) = DBTiB low
(11)
through the TiB2 and TiB layers was assumed due to the narrow dt dt (v − u)
homogeneity ranges in both phases. In addition, a homogeneity
with
range for TiB around 49–50 at.% B was reported in the literature by
TiB2 TiB2 TiB2 TiB TiB
several authors [24,26–28]. Furthermore, the composition range for wTiB2 = 0.5 × (Cup − Clow ) + (Clow − Cup ) ; wTiB = 0.5 × (Cup −
the TiB2 phase was also found around 65.5–67 at.% B according to
the reference [29], 65.2–66.3 at.% B from Rudy and Windisch [24]
TiB
Clow TiB
) + (Clow − C0 ) ; w = 0.5 × Cup
TiB TiB
− Clow
and 65.5–67.6 at.% B from Thebault et al. [28].
The following assumptions are made in the diffusion model:
The TiB2 layer thickness u grows in a parabolic manner following
Eq. (12), where k1 represents the parabolic growth constant at the
– The kinetics is dominated by the diffusion-controlled mechanism
(TiB2 /TiB) interface.
– A linear concentration – profile is assumed through the TiB2 and
0.5
TiB layers u = k1 [t − t0nB2 (T )] (12)
– The growth of boride layers is a consequence of the boron diffu-
The distance, v, is the location of the (TiB/substrate) interface
sion perpendicular to the sample surface
and k2 its parabolic growth constant (Eq. (13)) and the difference
– The diffusion of boron in the Ti matrix is not considered
(l = v-u) denotes the layer thickness of TiB (Eq. (14)).
– The incubation times for titanium borides are taken into account
– TiB is a layer that is made up of the growing TiB whiskers embed- v = k2 [t − t0 (T )]0.5 (13)
ded in the Ti matrix. 0.5
– The boride layer is thin in comparison to the sample thickness l = v − u = k2 [t − t0 (T )] − k1 [t − t0TiB2 (T )]0.5 (14)
– Local equilibrium is attained at the moving interfaces with k2 k1 and t0 (T ) t0TiB2 (T )
– Planar morphology is assumed for the phase interfaces The boron diffusion coefficient in each titanium boride can be
– The volume change during the phase transformation is not con- obtained as follows:
sidered
– The diffusion coefficient of boron in each titanium boride is inde- (wTiB2 + w )k12 ˚(T ) + wTiB k1 k2
DBTiB2 = (15)
TiB TiB
pendent of concentration 2˚(T )(Cup 2 − Clow2 )
– The effect of Ti diffusion on layer growth is ignored.
– A uniform temperature is assumed throughout the sample. and
– The effect of alloying elements is not considered during the boron [(w k1 ˚(T ) + wTiB k2 ][k2 ˚(T ) − k1 ]
DBTiB = (16)
diffusion TiB − C TiB )
2˚(T )(Cup low
The initial conditions of the diffusion problem are set up as: with
1/2
CTiB2 x(t 0) = 0 = 0; CTiB x(t 0) = 0 = 0; CTi x(t 0) = 0 =0 (1)
t − t0 (T )
˚(T ) = (17)
The boundary conditions are given by the following equations: t − t0
TiB2
(T )
CTiB2 x(t = t0TiB2 (T )) = 0 TiB2
= Cup for Cads 30.10wt.%B (2)
Fig. 3 describes the temperature dependence of the ˚(T ) param-
eter. It is noticed that this parameter is linearly dependent on the
CTiB2 x(t = t0TiB2 (T )) = 0 TiB2
= Clow for Cads ≺ 30.10wt.%B and with TiB2 phase boriding temperature and can be approximated by Eq. (18) using a
linear fitting of experimental data with a correlation coefficient of
(3)
0.98:
4.1. Characterization
TiB2
CTiB2 (x(t = t) = u) = Clow (6)
Titanium borides were successfully formed on the Ti6Al4V alloy
TiB
CTiB (x(t = t) = u) = Cup (7) using Na2 B4 O7 paste in the H2 -Ar plasma environment. SEM micro-
graphs of the plasma paste borided Ti6Al4V alloy at temperatures
TiB
CTiB (x(t = t) = v) = Clow (8) of 973 and 1073 K for 7 h are presented in Fig. 4. The metallographic
232 M. Keddam, S. Taktak / Applied Surface Science 399 (2017) 229–236
Table 1
Surface microhardness values of plasma paste borided Ti6Al4V alloy.
3 5 7
Fig. 5. EDS line analysis from surface to interiorin the Ti6Al4V alloy plasma paste borided at 1073 K for 7 h.
Fig. 6. XRD patterns of Ti6Al4V samples plasma paste borided at 973and 1073 K for 5 h.
one-tenth of the layer thickness for the low layer thickness (<4 m) Table 2
Experimental values of parabolic growth constants at the (TiB2 /TiB) and
obtained at lower temperatures.
(TiB/substrate) interfaces with the corresponding boride incubation times.
Table 3
Estimated values of boron diffusivities in the TiB2 and TiB layers for an upper boron
content of 31.10 wt.% in TiB2 .
QBi
DBi = D0i exp(− ) (18)
RT
where: i = (TiB2 or TiB) and D0i is a pre-exponential constant, QBi
represents the boron activation energy of the i-phase, T denotes
Fig. 7. The optical micrograph of the Ti6Al4V alloy plasma paste borided at 1073 K
the absolute temperature in Kelvin and R = 8.314 J mol −1 K −1 is the
for 3 h showing non transformed ␣ +  microstructure at below the ␣ →  transfor-
mation temperature. ideal gas constant.
The value of boron activation energy in each boride layer was
determined by the slopes obtained in the plot of ln DBi as a func-
tion of the reciprocal temperature. Fig. 9 shows the temperature
dependence of boron diffusion coefficients in the TiB2 and TiB layers
according to the Arrhenius relationship. The value of boron activa-
tion energy in each boride layer can be readily obtained from the
slope of the corresponding curve. As a result, the boron diffusion
coefficients in the TiB2 and TiB layers are respectively given by Eqs.
(19) and (20):
(136.24 ± 0.5) kJmol−1
DBTiB2 = 3.918 × 10−8 exp − (19)
RT
and
(63.76 ± 0.5) kJmol−1
DBTiB = 1.334 × 10−11 exp − (20)
RT
Table 4
Activation energies of boron in the titanium borides for comparing the experimental results from this work with the data from the literature.
Substrate Boriding medium Temperature range Activation energy, Q Calculation method Refs.
(K) (KJ mole−1 )
5. Conclusions
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