Surface & Coatings Technology 237 (2013) 402–414

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Surface & Coatings Technology

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Growth kinetics and mechanical properties of boride layers formed at

the surface of the ASTM F-75 biomedical alloy
I. Campos-Silva a,⁎, D. Bravo-Bárcenas a, A. Meneses-Amador a, M. Ortiz-Dominguez b, H. Cimenoglu c,
U. Figueroa-López d, J. Andraca-Adame e
a
Instituto Politécnico Nacional, Grupo Ingeniería de Superficies, SEPI-ESIME, U.P. Adolfo López Mateos, Zacatenco, México, D.F. 07738, Mexico
b
Universidad Politécnica de Pachuca, Carretera Pachuca-Cd. Sahagún km. 20, Ex Hacienda de Santa Bárbara 43830, Mexico
c
Istanbul Technical University, Department of Metallurgy and Materials Engineering, Maslak 34469, Istanbul, Turkey
d
Tecnológico de Monterrey, Campus Estado de México Carretera al Lago de Guadalupe km. 4.5, Atizapán de Zaragoza 52926, Mexico
e
Instituto Politécnico Nacional, Centro de Nanociencias y Micro y Nanotecnologías, U.P. Adolfo López Mateos, Zacatenco, México, D.F. 07738, Mexico

a r t i c l e i n f o a b s t r a c t

Available online 27 June 2013 In this study, new data about the growth kinetics and indentation properties of cobalt boride layers formed
on the surface of the ASTM F-75 biomedical alloy were estimated. The boron diffusion at the surface of the
Keywords: biomedical alloy was conducted using a powder-pack boriding process at temperatures of 1223–1273 K with
Boriding different exposure times for each temperature. Two mathematical approaches were proposed to determine
Cobalt alloys the boron diffusion coefficients of the CoB and Co2B layers in the range of boriding temperatures, in which
Growth kinetics
the experimental results of the kinetics of the cobalt boride layers were compared with those estimated using
Diffusion model
Hardness
diffusion models.
Young's modulus Finally, the mechanical characterization of the cobalt boride layers was evaluated by indentation techniques
with applied loads of 0.98 N and 50 mN, respectively. According to the nanoindentation tests, a maximum
hardness value (30 GPa) and a maximum Young's modulus (380 GPa) were obtained near the surface region
(5 μm) of the borided cobalt alloy.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction Surface treatments are widely used to improve the performance of

Metals are the most favored materials for orthopedic surgery
metals because of their superior mechanical stability. The Co–Cr
alloys have been used extensively, in biomaterials for joint replacement
due to their superior fatigue strength, wear and corrosion resistance
[1,2]. The Co–Cr–Mo–C alloy, which complies with the ASTM F-75 stan-
dard, is primarily used in surgery implants. For example, the metal-on-
metal (MOM) bearings, which are composed of cobalt alloys, are
utilized in hip and knee prostheses. However, numerous reports have
indicated, that when these joints are subjected to the body fluids
under articulation, mechanical/chemical degradation of artificial
devices occurs, which causes clinically significant problems such as
metal debris formation and increased metal-ion release [3]. The metallic
ions of Co, Cr and Mo are released into the body by electrochemical
corrosion or chemical dissolution, wear, and mechanically accelerated
electrochemical processes such as corrosion fatigue and fretting corro-
sion, which significantly increase material loss [4]. The degree of wear
and corrosion of MOM surfaces are closely associated with the lubrica-
tion regime and wear mechanisms within joints [5].
⁎ Corresponding author. Tel.: +52 55 57296000x54768; fax: +52 55 57296000x54589.
E-mail address: icampos@ipn.mx (I. Campos-Silva).
biomedical alloy, enhance their mechanical properties or corrosion
resistance, and reduce the potential for implant failure. Boriding is a
thermochemical treatment that increases the wear and corrosion
resistance of ferrous and non-ferrous alloys by forming hard boride
layers at the surface of the material [6,7]. Some favorable superficial
wear-corrosion properties in borides include their crystalline structure
and the strength of their interatomic bonds. Boriding of the ASTM F-75
alloy may be beneficial for the medical applications, in the first instance,
if the boride layers are biocompatible (highly nontoxic and should not
cause any inflammatory or allergic reactions in the human body).
Unfortunately, there is no information in the literature about this topic.
In recent years, research on the boriding of cobalt alloys has
advanced, specifically regarding the wear and oxidation properties of
the cobalt boride layers [8–13]. In the work developed by Mu et al.
[12], cobalt boride layers were diffused on the surface of the CoCrMo
alloy, resulting in the increase of wear resistance attributed to the
high hardness of the Co2B layer (2002 HV0.1 near the surface region)
under dry-sliding conditions. In addition, cyclic oxidation tests were
performed at 1223 K with a total exposure time up to 50 h on the
surface of borided pure cobalt [13]. The boriding of the pure cobalt
was carried out at 8 h of exposure with different temperatures using
the powder-pack method. The results of the oxidation tests revealed
that the best performance was found on the surface of the pure cobalt

0257-8972/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
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 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414 403

that was exposed to boriding at 1223 K due to the presence of Co2B and where CBads represents the effective adsorbed boron concentration
Co2 B
Co2Si layers. during the boriding process [25], C up represents the maximum boron
Co B
According to the Co–B phase diagram [14], boriding causes the concentration in the Co2B layer, and C low2 represents the minimum
formation of the CoB (superficial layer) and the Co2B (inner layer) on concentration of boron in the Co2B layer (Fig. 1(B)) [14–16]. In
the surface of a cobalt alloy. The cobalt boride phases are composed of addition, t′ is the exposure time of the material during the boriding
15.5 wt.% B (CoB) and 8.4 wt.% B (Co2B), with a restricted narrow process (s), v is the depth of the layer (m), and v0 is a thin layer with a
boron composition [15,16]. In borides, boron atoms form distinctive thickness of ≈5 nm that formed during the nucleation stage [26]; thus
and normally complex lattices (chain, reticular or laminar); CoB exhibits v0 ≈ 0 when compared to the thickness of the boride layer (v). The
a rhombic crystal structure with a hardness of 18–20 GPa, and the Co2B linear boron concentration profile along the Co2B layer is described as
exhibits a tetragonal structure with a hardness of 15–16 GPa [17]. It has follows:
been established, that the mechanical and chemical properties (e.g. high
hardness, wear and corrosion resistance) of the boride layers are associ- Co B Co2 B
Co B C low2 −C up
ated with the specific features of the electronic structure of the com- C Co2 B ½xðt Þ ¼ C up2 þ x: ð4Þ
pounds forming these layers [18]. v
In addition, the mechanical and chemical behavior of the borided
samples are affected by the type of microstructure and thickness of The following assumptions are considered for the diffusion model
the boride layer, the boriding temperature, the exposure time, and the [27]:
boron potential that surrounds the surface sample [19,20]. Therefore,
(i) The growth kinetics is controlled by boron diffusion in the Co2B
estimating the kinetic parameters of developing boride layers during
layer.
the boriding process is crucial. Unfortunately, the literature about the
(ii) The growth of the boride layer is caused by boron diffusion
kinetics of cobalt boride layers is limited.
perpendicular to the specimen surface.
In a study by Knotek et al. [21], the evolution of CoB and Co2B
(iii) The boron concentrations remain constant in the boride layer
layers on the surface of a cast cobalt base alloy was estimated using
during the treatment.
the powder-pack boriding process. Different boron powder mixtures
(iv) The differences in specific volume per solvent atom for the
were employed to verify the growth of cobalt boride layers that formed
Co2B layer are fully represented in the diffusion direction.
at temperatures of 1073, 1173 and 1273 K with different exposure
(v) The influence of the alloying elements on the growth kinetics
times for each temperature. The formation of the total cobalt boride
of the layer is not considered.
layer (CoB + Co2B) on the surface of the borided cobalt alloy was rep-
(vi) The Co2B nucleates after a specific incubation time.
resented in plots of layer thickness against exposure time. The results
(vii) The boride layer is thin compared with the thickness of the
indicated that the growth of the total boride layer exhibited a parabolic
sample.
form for the set of experimental conditions.
(viii) The volume change during the phase transformation is not
In this study, the growth kinetics and indentation properties of the
considered.
CoB and Co2B layers formed on the surface of the ASTM F-75 alloy
(ix) A uniform temperature is assumed throughout the sample.
were evaluated. The boron diffusion coefficients in the boride layers
were estimated using two diffusion models based on the conditions The mass balance equation at the Co2B/substrate interface, which
of the boriding process in the Co–B system [22–24]. Moreover, the is schematically represented in Fig. 1(C), is defined as:
mechanical characterization of the cobalt boride layers was evaluated
with the Vickers and Berkovich indentation techniques. The indenta- Co B
!
C low2 −2C 0 þ C Co
up
2B
tions were performed along the depths of the layers using constant dxjx¼v ¼ J Co2 B ðx ¼ vÞdt v −J Co ðx ¼ v þ dvÞdt v ð5Þ
loads of 0.98 N and 50 mN, respectively; the behavior of the mechanical 2
properties such as hardness and Young's modulus were analyzed for the
set of experimental conditions of the borided cobalt alloy. where C0 is the boron concentration in the substrate. The fluxes J Co2 B
and JCo are given by Fick's First Law, J = −D{dC[x(t)] / dx(t)}, where
2. The diffusion models JCo = 0 because the boron solubility in cobalt is very low [14–16].
Thus, Eq. (5) is rewritten as:
2.1. The diffusion model for the growth of the Co2B layer
Co B
! Co B
In this approach, the growth of the Co2B layer occurs prior to the C low2 −2C 0 þ C Co
up
2B
dv C Co 2B
up −C low
2

¼ DCo2 B ; ð6Þ
growth of the CoB layer on the surface of the cobalt
alloy. In this 2 dt v v
case, the boron diffusion coefficient in the Co2B layer DCo2 B can be
determined independently. According to the Co–B phase diagram, a
linear boron concentration profile is assumed along the depth of the or
Co2B layer (v) (Fig. 1(A)). The initial and boundary conditions of the
Co B
diffusion problem are represented as: dv C Co 2B
up −C low
2

¼ 2DCo2 B   : ð7Þ
′
dt v Co2 B Co B
C low −2C 0 þ C up2 v
t ¼ 0; 0 ≤ x ≤ ∞; with C Co2 B ¼ C o ð1Þ

Co B
C Co2 B ðx ¼ v0 ≈ 0Þ ¼ C up2 (the superficial boron concentration is kept
A particular solution of Eq. (7) for a diffusion controlled growth is
constant), for  2  2 h i
total total total
given by v2 ¼ kCo2 B t v ¼ kCo2 B t ′ −t Co
0
2B
where kCo2 B is the
B
C ads N 8:57 wt:%B; ð2Þ growth constant, tv is the formation time of the Co2B layer, t′ is the
Co B exposure time, and t Co2B
ðT Þ is the Co2B incubation time as a function
C Co2 B ðx ¼ vÞ ¼ C low2 (the boron concentration at the interface is kept 0  
constant), for of the boriding temperature t Co 0
2B
N t CoB
0 [23,24,27–29]. A schematic
representation of the square of the layer thickness against linear time
B
C ads b 8:4 wt:%B; ð3Þ is depicted in Fig. 2.
404 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414

Co2 B
Fig. 1. (A) Schematic representation of the boron concentration profile in the CoB and Co2B layers, (B) schematic representation of the C up and C Co
low
2B
values obtained from the Co–B
phase diagram for a range of temperatures, and (C) schematic representation of the mass balance equation at the Co2B/substrate interface.

From Eq. (7) DCo2 B is defined as follows: 2.2. The diffusion model for the growth of the CoB layer

  Co2 B Co2 B  
total 2 C low −2C 0 þ C up
Assuming the boron concentration profile of the boride layers
DCo2 B ¼ kCo2 B   ; m2 s−1 : ð8Þ presented in Fig. 1(A), the boundary and initial conditions are defined
Co2 B Co2 B
4 C up −C low
as:

′
t ¼ 0; 0 ≤ x ≤ ∞; C i ðxÞ ¼ C o with i ¼ CoB; Co2 B ð9Þ

CCoB(x = u0 ≈ 0) = CCoB
up (the superficial boron concentration is kept
constant)

B
for C ads > 15:67 wt:%B; ð10Þ

CCoB(x = u) = CCoB
low (boron concentration at the interface is kept
constant),

B
for Cads < 15:5 wt:%B ð11Þ

Co B Co B B
C Co2 B ðx ¼ uÞ ¼ C int2 ; for C int2 wt:%B < C ads
< 15:67 wt:%B without the CoB ð12Þ

Co B
C Co2 B ðx ¼ vÞ ¼ C low2 (boron concentration at the interface is kept
constant),

B
Fig. 2. Schematic representation of the square of the layer thickness against linear time. for 8:4 wt:%B < C ads without the CoB; ð13Þ
 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414 405

C CoB
up represents the maximum boron concentration in the CoB layer, By solving Eq. (4), and applying the initial and boundary conditions
C CoB
low is the minimum concentration of boron in the CoB layer proposed in Eqs. (9)–(13), the boron concentration profiles in CoB and
Co B
(Fig. 3(A)) [14–16], and C int2 is the boron concentration at the Co2B are expressed as:
CoB/Co2B interface, which can be estimated from Eq. (4). In addition,
u is the depth of the layer (m), and u0 is a thin layer with a thickness CoB
C low −C up
CoB
CoB
of ≈5 nm that formed during the nucleation stage [26]; thus u0 ≈ 0 C CoB ½xðt Þ ¼ C up þ x ð15Þ
u
when compared to the thickness of the boride layer (u).
If the diffusivity of the material is constant for a particular temper-
ature, Fick's Second Law is reduced to an ordinary second-order
differential equation as follows:
Co B Co B
Co B C low2 −C int2
C Co2 B ½xðt Þ ¼ C int2 þ ðx−uÞ ð16Þ
l

2
d C i ðxÞ where l = v − u represents the thickness of the Co2B layer thickness
¼ 0; with i ¼ CoB; Co2 B: ð14Þ
dx2 in the presence of the CoB layer.

Fig. 3. (A) C CoB CoB

up and C low values obtained from the Co–B phase diagram for a range of temperatures and (B) schematic representation of the mass balance equation at the CoB/Co2B
and Co2B/substrate interfaces.
406 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414

Using similar assumptions for the growth of the Co2B layer A

(Section 2.1), the mass balance equation at the CoB/Co2B interface
(Fig. 3(B)) can be expressed by the following equation:
!
C CoB
Co2 B CoB
low −2C int þ C up
CoB
dxjx¼u ¼ J CoB ðx ¼ uÞdt u −J Co2 B ðx ¼ u þ duÞdt u :
2
ð17Þ
Co2 B 15 µm (avg.)
27 µm (avg.)
Furthermore, the continuity Eq. (17) can be rewritten as follows:
CoB Co B CoB
! CoB CoB Co B Co B
!
C low −2C int2 þ C up du C up −C low C 2 −C int2
¼ DCoB − −DCo2 B low :
2 dt u u l
ð18Þ
Co B Co B Co B Co B
C up2 −C low2 C CoB CoB
up −C low C low2 −C int2
The terms v , u , and l
represent the flux
slopes in the Co2B layer, thus:

Co B Co B CoB CoB
C up2 −C low2 C up −C low C Co2B Co B
−C int2
¼ ¼ low ð19Þ
v u l

and Eq. (18) can be expressed as follows: B

Co B
! Co B
!
C CoB CoB
low −2C int þ C up
2
du C CoB CoB
up −C low C Co 2B
up −C int
2

¼ DCoB − DCo2 B :
2 dt u u u CoB
ð20Þ
Co2 B 22 µm (avg.)
A
33 µm (avg.)

blocks of carbides C

laminar carbides CoB

Co2 B 29 µm (avg.)
B
40 µm (avg.)

α (fcc)
M23C6
Fig. 5. Microstructure of the cobalt boride layers formed at the surface of the borided
ASTM F-75 alloy at 1248 K with exposure times of: (A) 6 h, (B) 8 h and (C) 10 h.
α (fcc) + M23 C6

The solution to Eq. (20) can be obtained by considering the parabolic

growth equation of the CoB layer as:

Fig. 4. (A) Microstructure of the ASTM F-75 alloy as-received and (B) microstructure of
the ASTM F-75 alloy after solution treatment. u ¼ kCoB t 1=2
u ; ðmÞ ð21Þ
 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414 407

h i  
2 2 2 ′ CoB 2 solution treatment is presented in Fig. 4(B), in which the hardness of
u ¼ kCoB t u ¼ kCoB t −t 0 ðT Þ ; m ð22Þ
the substrate is approximately 362 HV0.1.

u is the CoB layer thickness, kCoB is the growth constant of the CoB layer, 3.2. The boriding process
tu is the time formation of the boride layer, t′ is the exposure time,
tCoB
0 (T) is the boride incubation time as a function of the temperature, The samples were embedded in a closed cylindrical case (AISI 304 L)
and [t′ − tCoB
0 ] is the effective growth time of the CoB layer. containing a B4C Durborid fresh powder mixture. The powder-pack
By substituting Eq. (22) with Eq. (20), the boron diffusion coeffi- boriding process was performed under Ar atmosphere at temperatures
cient in the CoB layer (DCoB) can be defined as: of 1223, 1248 and 1273 K with 6, 8 and 10 h of exposure respectively,
    for each temperature. The boriding temperatures were selected in
Co2 B Co B
  C CoB CoB
low −2C int þ C up
Co B
þ 4DCo2 B C up2 −C int2   accordance with the position of the solidus line in the Co–B phase dia-
2 2 −1
DCoB ¼ kCoB   ; m s : gram. Once the treatment was complete, the container was removed
4 C up −C low
CoB CoB
from the furnace and slowly cooled to room temperature.
ð23Þ The borided samples were cross-sectioned for metallographic
preparation, and the depths of the surface layers were observed in a
clear field by optical microscopy using a GX51 Olympus instrument.
Fig. 5 depicts the growth of the CoB and Co2B layers at the surface
3. Experimental procedure
of the borided cobalt alloy for a particular boriding temperature
(1248 K). Fifty measurements were collected in different sections of
3.1. Solution heat treatment
the ASTM F-75 borided samples to estimate the thicknesses of the CoB
and Co2B layers. All thickness measurements were collected from a
A Co–Cr–Mo–C alloy that complies with the ASTM F-75 standard
fixed reference on the surface of the borided cobalt alloy, as shown in
was employed. This alloy has a nominal chemical composition of 27–
Fig. 6. Finally, X-ray diffraction (XRD) was performed for the borided
30 wt.% Cr, 5–7 wt.% Mo, 0.25 wt.% Ni, 0.7 wt.% Si, and 0.25 wt.% C.
sample obtained at a temperature of 1273 K with 10 h of exposure by
Disk samples were cut from a cylindrical bar with a diameter of
applying glancing angle (0.5° and 1°) and regular 2θ–ω scan procedure
10 mm, and a thickness of 5 mm. The as-received material (Fig. 4(A))
[32,33]. An X'PERT PRO PANalytical instrument was used with CuKα
consisted of a cored-base Co-rich face-centered cubic matrix with
radiation at λ = 0.154 nm.
interdendritic and grain boundary carbides [30]. The carbides in the
material's matrix were partially dissolved through solution heat treat-
ment. The treatment was conducted in a resistance furnace under 3.3. Vickers indentation tests
argon atmosphere for 30 min at 1323 K followed by quenching in air
[31]. Prior to the boriding process, the specimens were polished, ultra- The ASTM F-75 borided alloy was indented on a commercial indenter
sonically cleaned in an alcohol solution and deionized water for (Wolpert 402, MVD equipment) according to the ASTM E384 and ASTM
15 min at room temperature, and dried and stored under clean-room C1327 procedures. The hardness-depth profiles were obtained across
conditions. The resulting microstructure of the cobalt alloy after the the boride layers with an applied load of 0.98 N, as shown in Fig. 7. For

Fig. 6. Schematic representations of the CoB and Co2B layer measurements.

408 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414

B
55
50
45
40
35

P (mN)
30
25
20
15
10 µm (CoB)
10
35 µm (Co2B)
5
0
0 50 100 150 200 250 300 350 400
h (nm)

Fig. 8. (A) Berkovich indentations performed across the cobalt boride layers with a
constant load of 50 mN. The boriding temperature was 1273 K for 8 h of exposure
(B) load-displacement plots obtained at 10 μm (CoB layer) and 35 μm (Co2B layer)
from the borided surface. The boriding temperature was 1273 K for 10 h of exposure.

evaluated considering the crack lengths developed from the indentation

corners; the crack lengths were measured using a GX51 Olympus instru-
ment and Image-Pro Plus software. The KC values on the cobalt boride
layers were estimated using the model proposed by Anstis et al. [34]:

 1=2  
E P
K C ¼ 0:016 3=2
:
H c

where 0.016 is a calibration factor, E is the Young's modulus of the cobalt

boride layer, H is the hardness, P is the indentation load, and c is the crack
length. The E values of the CoB and Co2B layers were obtained directly
from the results of the nanoindentation technique at 10 μm from the
surface (CoB layer), and in the “pure zone” of the Co2B layer for the set
of experimental conditions of the boriding process.

3.4. Berkovich nanoindentation technique

The cobalt borided samples were indented on a commercial

Fig. 7. Vickers indentation tests across the cobalt boride layers formed with the boriding
conditions of: (A) 1248 K and 6 h of exposure, (B) 1248 K and 8 h of exposure, and
(C) 1273 K with 8 h of exposure. The applied load was 0.98 N.
a particular distance from the surface of the borided cobalt alloy, three
indentations were performed for the set of experimental conditions. In
addition, the fracture toughness (KC) of the CoB and Co2B layers was
nanoindenter (TTX-NHT, CSM Instruments) with a Berkovich diamond
indenter. The nanoindentations were performed across the boride
layers (perpendicular to the diffusion front) with a constant applied
load of 50 mN (Pmax) (Fig. 8(A)) The load-displacement curves were
analyzed according to the Oliver–Pharr procedure [35] to assess the
evolution of the hardness (H) (in the nanometric depth regime, the
hardness values were obtained by considering the projected area of
the Berkovich mark and the contact indentation depth (hc), where
H = Pmax/24.5hc2) and the Young's modulus (E) for the set of experi-
mental conditions in the boriding process. For a particular distance
from the surface of the borided steels, three load-displacement curves
were automatically recorded. A schematic representation of the load-
displacement curves obtained at 10 μm from the surface (CoB) and
35 μm from the borided surface (Co2B) is shown in Fig. 8(B).
 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414 409

4. Results and discussions
The presence of the CoB and Co2B layers was verified by the XRD
patterns as shown in Fig. 9. The formation of the cobalt boride layers
is controlled by the diffusion of boron in the alloy surface, in which the
growth rate and phase composition of the boride layers are determined
by the activity of boron on the cobalt surface, the temperature of the
boriding process, and the composition of the substrate [17,20,23–29].
The microstructure of the cobalt boride layers is similar to the micro-
structure of the boride layers that formed on the surface of the high-
alloy and stainless steels [36–38]. According to the diffusion channel
theory proposed by Kunst and Schaaber [39], the formation of the
boride layers occurs in different stages: boron diffuses into the material
with a velocity that is slightly dependent on the lattice type (face or
body centered). When a suitable boron concentration is reached at
certain points on the surface of the cobalt alloy, Co2B crystals begin to
nucleate, and a surface layer composed of Co2B is formed, under which
a wide boron diffusion zone is located. The nucleation and growth of
the CoB layer on the outermost part of the ASTM F-75 alloy are a conse-
quence of high-boron potential at higher boriding temperatures, and the
influence of the chemical composition of the base alloy.
Similarly, alloying elements such as chromium and molybdenum in
the cobalt alloy, easily diffuse into the cobalt borides via substitutional
procedure, and tend to form compounds with the boron. The CrB and
Mo2B phases were detected on the surface of the borided cobalt alloy
as shown in Fig. 9. In addition, the flat-front morphology of the CoB/

Fig. 9. XRD patterns obtained at the surface of the borided ASTM F-75 cobalt alloy. (A) Regular 2θ–ω scan procedure, (B) glancing angle (0.5°), and (C) glancing angle (1°). The
boriding temperature was 1273 K for 10 h of treatment.
410 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414

A A -29.1
3000

1223 K lnD Co2 B = -21074T-1 -12.608

2500 R² = 0.9988

ln DCo2B(m2s-1)
2000 1248 K
v2 (µm2)

-29.4

1500
1273 K

1000
-29.7
500

0
0 5 10 15 20 25 30 35 40
-30
Time (x103) (s) 7.8 7.9 8 8.1 8.2
Inverse of temperature(x10-4) (K-1)
B 1600
1223 K
B -27.2
1400

1200 1248 K lnD CoB = -22795T-1 -9.5218

R² = 0.9702
1000
u2 (µm2)

1273 K
-27.6
800 ln DCoB(m2s-1)
600

400
-28
200

0
15 20 25 30 35 40
Time (x103) (s) -28.4
7.8 7.9 8 8.1 8.2
Fig. 10. The evolution of the boride layers as a function of exposure time: (A) (CoB + Co2B)
Inverse of temperature(x10-4) (K-1)
layer and (B) CoB layer.

Fig. 11. Boron diffusion coefficients as a function of boriding temperatures: (A) Co2B
layer and (B) CoB layer.

Co2B layer is most likely caused by the presence of chromium and mo-
lybdenum, which act as diffusion barriers in the boride layer/substrate
interface [37,40]. The presence of a diffusion zone underneath cobalt  2
total
represent the growth constants kCo2 B and k2CoB, whose incubation
boride layers was developed due to the precipitation of Cr-rich products
along grain boundaries. It has been established, as a general rule, that times are additional point on the graphs. The results, which are
considerable amounts of chromium can concentrate beneath boride summarized in Table 1, reflect a diffusion-controlled growth of
Co2 B
layers as a consequence of chromium–carbon chemical reactions (C is 0 ðT Þ N t 0
the cobalt boride layers, in which t CoB ðT Þ. By combining
insoluble in boride layers) more than to chromium redistribution phe- Eqs. (8) and (23) with the experimental results presented in Fig. 10,
nomena [41]. the boron diffusion coefficients in the Co2B and CoB layers ( DCo2 B
The evolution of the cobalt boride layers as a function of exposure and DCoB) were estimated for each exposure time at a constant
time is depicted in Fig. 10. The slopes of the straight lines in Fig. 10 boriding temperature. The mean values of DCo2 B and DCoB were
expressed as a function of the boriding temperatures (1223 to
1273 K) using the Arrhenius relationship (Fig. 11) as follows:
!
−6 175 kJ mol−1  2 −1 
DCo2 B ¼ 3:3  10 exp − m s ð24Þ
RT
Table 1
Growth constants and boride incubation times as a function of boriding temperature.
!
Temperature (K) Type of layer

total
2
  
−5 189 kJ mol−1  2 −1 
kCo2 B μm2 =s t 0Co2 B ðT Þ 103 ðsÞ DCoB ¼ 7  10 exp − m s : ð25Þ
RT
1223 Co2B 0.043 9.5
1248 0.058 9.4
1273 0.085 9.3 From Eqs. (24) and (25), the pre-exponential factors and the acti-
vation energy values are affected by the contact surface between the
Temperature (K) Type of layer (kCoB)2 (μm2/s) tCoB 3
0 (T)(×10 )(s)
boriding medium and the substrate, as well as the chemical composi-
1223 CoB 0.027 16.7 tion of the material [20,42]. An expression to validate the activation
1248 0.041 16.3 energy values of the Co2B and CoB layers obtained in this study has
1273 0.056 16.5
not yet been reported in the literature.
 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414 411

A Table 2
Estimated values of the cobalt boride layer thicknesses (v and u) obtained at 1323 K
with different exposure times.

Exposure Type Boride layer thickness (μm) Experimental boride

CoB time (s) of layer estimated by Eq. (26) layer thickness (μm)

21,600 Co2B 44.4 46 ± 2

28,800 56 55 ± 3
Co2 B 26 µm (avg.) 36,000 65.6 70 ± 3

Exposure Type Boride layer thickness (μm) Experimental boride

46 µm (avg.) time (s) of layer estimated by Eq. (27) layer thickness (μm)

21,600 CoB 23.2 26 ± 4

28,800 36.1 38 ± 3
36,000 45.5 48 ± 3

A
1320 55
B 5 10 15 20
25
40
45
60
50
30
35

Boriding temperature (K)

1300 55

CoB 40 45 50
5 10 15 20
25
1280 30 35

Co2 B 38 µm (avg.) 40
45

55 µm (avg.) 1260 5 10 15 20
25 35
30
40

1240
35
30
5 10 15 20 25

10 15 20 25 30 35
C Time (x103)(s)

B
1320
10
40
CoB 20
30
Boriding temperature (K)

1300

48 µm (avg.) 10
Co2 B 30
1280 20

70 µm (avg.)
30
1260 10
20

Fig. 12. Microstructure of the cobalt boride layers obtained at 1323 K with exposure
1240
times of: (A) 6 h, (B) 8 h and (C) 10 h.
20
10

In this case, the kinetics of cobalt boride layers proposed by the 18 20 22 24 26 28 30 32 34 36

diffusion models were verified by estimating the Co2B and CoB layer
Time (x103)(s)
thicknesses as a function of temperature and exposure time. A set of
boriding conditions in the ASTM F-75 alloy was examined at a tem- Fig. 13. Contour plots describing the evolution of boride layers obtained by powder-
perature of 1323 K with 6, 8 and 10 h of exposure (Fig. 12). From pack boriding of the ASTM F-75 alloy: (A) Co2B layer and (B) CoB layer.
412 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414

0 ′ 
CoB CoB
 
Co B Co B

CoB ′
11=2
Eqs. (8) and (23), the boride layer thicknesses are described as t DCoB C up −C low −DCo2 B C up2 −C low2 1−t 0 ðT Þ=t
u¼2 @ A ; ðmÞ:
follows: Co2 B
low −2C int þ C up
C CoB CoB

ð27Þ
 h i
total ′ Co B 1=2
v ¼ kCo2 B t −t 0 2
0   11=2 The results obtained from Eqs. (26) and (27) exhibit good agreement
DCo2 B t ′ C Co 1−t 0 2 ðT Þ=t ′
2B Co2 B Co B
up −C low with the experimental data over the range of exposure times as depicted
¼ 2@ Co B Co B
A ; ðmÞ ð26Þ
C low2 −2C 0 þ C up2 in Table 2. The CoB and Co2B layer thicknesses for the set of experimental
parameters of the borided ASTM F-75 alloy are represented in contour
plots as a function of the temperature and exposure time as shown in
Fig. 13. The variation in the CoB and Co2B layer thicknesses can be attrib-
A 20 uted to specific characteristics, such as wear, corrosion and oxidation
18 properties at the surface of the borided cobalt alloy [12,13].
6h
The hardness-depth profiles obtained at the surface of the ASTM
16
F-75 borided alloy with an applied load of 0.98 N are shown in Fig. 14.
14 8h A maximum hardness value (18 GPa approximately) was achieved on
HV (GPa)

12 the CoB layer (10 μm from the surface), independently of the boriding
10 h temperature and exposure time.
10
In the case of the Co2B layer, the hardness was 14 GPa for the
8 boriding temperatures of 1223 and 1248 K with an exposure time of
6 6 h (particularly for these boriding conditions, the indentations were
performed nearest the boride layer/substrate interface), whereas for
4
longer exposure times (8 and 10 h) the hardness tends to increase to
2 values of 16 to 17 GPa. The hardness results were compared with the
0 hardness values of the CoB and Co2B layers that formed on the surface
0 20 40 60 80 100 120 140 160 180 200 220 of the borided cast cobalt alloy [21], using Knoop microhardness testing.
Distance from the surface (µm) The Knoop hardness values (HK0.1) for the CoB and Co2B layers ranged
from 2200 HK0.1 to 1500–1600 HK0.1, respectively.
The fracture toughness of the cobalt boride layers was estimated
B 20 using the model proposed by Anstis et al. [34], and the measurements
18 of the crack lengths that were emanated from the corners of the
6h Vickers indentation marks. From the results summarized in Table 3,
16
low fracture resistance was obtained for both boride layers consider-
14 8h ing a radial–median cracking regime. The KC values of the Co2B layer
pffiffiffiffiffi
HV (GPa)

12 can be compared with those obtained for nickel borides (2.5 MPa m)
10 h
10 when an indentation load of 0.98 N is used [43].
Figs. 15 and 16 display the results of the hardness-depth and
8
Young's modulus-depth profiles across the cobalt boride layers with
6 a constant load of 50 mN. The mechanical parameters were obtained
4 by performing the indents in a direction perpendicular to the interface
(in cross-section), which eliminated the potential for contributions
2
from the substrate without restricting the maximum depth to 10% of
0 the total layer thickness [44,45]. According to the microstructure of
0 20 40 60 80 100 120 140 160 180 200 220
the cobalt boride layers, a maximum hardness (25 to 30 GPa) was
Distance from the surface (µm) obtained at 5 μm (CoB layer) from the free surface with modest changes
in the different boriding conditions; in the intermediate zone between
the CoB and Co2B layer, the hardness decreased to approximately
C 20 22 GPa; in the pure zone of the Co2B layer a Berkovich hardness value
18 of 18 GPa was obtained with few changes as a function of the process
6h duration and boriding temperature. Similar hardness results were
16
14 8h
HV (GPa)

Table 3
12
10 h The fracture toughness of the cobalt boride layers obtained with an applied load of
10 0.98 N.

8 Temperature (K) Time (h) Kc

pffiffiffiffiffi
MPa m
6
CoB layer Co B layer
4
1223 6 0.34 ± 0.05 1.74 ± 0.05
2
8 0.20 ± 0.02 2.05 ± 0.31
0 10 0.29 ± 0.09 2.32 ± 0.23
0 20 40 60 80 100 120 140 160 180 200 220 1248 6 0.29 ± 0.09 2.18 ± 0.93
Distance from the surface (µm) 8 0.27 ± 0.02 2.24 ± 0.34
10 0.18 ± 0.02 2.34 ± 0.16
1273 6 0.29 ± 0.15 2.46 ± 0.35
Fig. 14. Hardness-depth profiles obtained with Vickers indentations on the cobalt boride
8 0.21 ± 0.02 2.62 ± 0.30
layers formed at temperatures of: (A) 1223 K, (B) 1248 K and (C) 1273 K. The applied
10 0.22 ± 0.01 2.76 ± 0.09
load was 0.98 N.
 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414 413

A 35
A 380
6h 6h
30

Young´s Modulus (GPa)

350
8h
25 8h
Hardness (GPa)

10 h
320 10 h
20

15 290

10
260
5
230
0 0 5 10 15 20 25 30 35 40 45 50 55 60 65
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Distance from the surface (µm)
Distance from the surface (µm)

B B 380
30
6h

Young´s Modulus (GPa)

25 6h 350
8h
Hardness (GPa)

20 8h
10 h 320

15 10 h
290
10
260
5

230
0 0 10 20 30 40 50 60 70 80 90
0 15 30 45 60 75 90
Distance from the surface (µm) Distance from the surface (µm)

C C 410
35
6h 6h
30 380
Young´s Modulus (GPa)

8h
8h
25 10 h
Hardness (GPa)

350
10 h
20
320
15
290
10
260
5
230
0 0 10 20 30 40 50 60 70 80 90
0 10 20 30 40 50 60 70 80 90 100
Distance from the surface (µm) Distance from the surface (µm)

Fig. 16. Young's modulus-depth profiles obtained along the cobalt boride layers formed
Fig. 15. Hardness-depth profiles obtained in cross-section along the cobalt boride
at temperatures of: (A) 1223 K, (B) 1248 K and (C) 1273 K.
layers formed at temperatures of: (A) 1223 K, (B) 1248 K and (C) 1273 K. The applied
load was 50 mN.

obtained on the surface of the borided wrought cobalt-based alloy using
an ultralow-load indentation [46]; the values near the surface region
(6–12 μm) were ranged between 38 and 28 GPa.
Likewise, the increase of chromium content in the base alloy
promotes the formation of boron-rich reaction products, and consider-
ably modifies the structure and properties of the boride layers [47].
Thus, the formation of higher volume fraction of interstitial compounds
(CrB and Mo2B), which dissolve in the cobalt boride layers, probably
causes the increase of the superficial hardness values.
Similarly, the E values in the CoB layer ranged from 350 to 360 GPa
for temperatures of 1223 and 1248 K with little variation as a function
of the exposure times; at 1273 K a maximum Young's modulus of
approximately 380 GPa was obtained. The E values obtained by the
ultra-load indentation technique, and reported by Cooper [46] at differ-
ent distances (6–12 μm) from the surface of the borided wrought
cobalt-based alloy ranged from 376 to 423 GPa.
414 I. Campos-Silva et al. / Surface & Coatings Technology 237 (2013) 402–414
In the pure zone of the Co2B layer, the E values corresponded to
320 GPa, and gradually decrease to 240 GPa beneath the cobalt boride
layer for the set of experimental parameters in the boriding process.
5. Conclusions
New data about the growth kinetics of cobalt boride layers formed
at the surface of the ASTM F-75 alloy were estimated using two math-
ematical approaches. Both approaches considered the experimental
variables of the boriding process (temperature and exposure time),
and the boron concentration profile in the CoB and Co2B layers. The
validity of the diffusion models was examined by comparing the
thickness of the experimental boride layer obtained at a temperature
of 1323 K with 6–10 h of exposure with those estimated using the
models. Contour plots, which can be used for future applications of
the borided ASTM F-75 alloy, were proposed to estimate the thicknesses
of the CoB and Co2B layers in the temperature range of 1223 to 1323 K.
According to the Vickers tests performed on the cobalt boride
layers with an indentation load of 0.98 N, the hardness values were
ranged from 18 GPa (CoB layer) to 14–17 GPa (Co2B layer) as a function
of the experimental conditions of the boriding process. Moreover, the
cobalt boride layers exhibited low fracture resistance.
Finally, based on the Berkovich hardness results evaluated across the
cobalt boride layers with a constant indentation load of 50 mN, the
maximum hardness and Young's modulus values of the CoB layer
(30 GPa and 380 GPa, respectively) were obtained at 1273 K with little
variation as a function of the exposure time. The inner layer (Co2B)
exhibited an approximate hardness value of 18 GPa for different condi-
tions of the boriding process, and exhibited a maximum Young's modu-
lus value of 320 GPa at 1273 K.
Acknowledgments
This work was supported by research grant 150556 of the National
Council of Science and Technology, and research grant 20130534 of
the Instituto Politécnico Nacional in Mexico.
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