Materials and Design 31 (2010) 3933–3936

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Materials and Design

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Short Communication

Effects of boronizing on mechanical and dry-sliding wear properties of CoCrMo alloy

Dong Mu a,b,1, Bao-luo Shen a,*, Xin Zhao c,2
a
College of Materials Science and Engineering, Sichuan University, Chengdu 610064, China
b
Department of Mechanical Engineering, Chengdu Electromechanical College, Chengdu 611730, China
c
Civil Aviation Flight University of China, Guanghan 618307, China

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

Article history: In this study, CoCrMo alloy was boronized at 950 °C for 2, 4, 6 and 8 h, respectively. The boronized sam-
Received 6 January 2010 ples were characterized by scanning electron microscopy, X-ray diffraction, microhardness tester and
Accepted 15 March 2010 ring-on-block wear tester. X-ray diffraction studies showed the boride layer formed at 950 °C for 2–8 h
Available online 18 March 2010
consisted of the phases Co2B and CrB. A large number of pores formed in diffusion zone were probably
attributed to the Kirkendall effect. Depending on boronizing time, the thickness of boride layer ranged
from 4 to 11 lm. The excellent wear resistance of the boronized CoCrMo alloy was attributed to the high
surface hardness of the Co2B and CrB under dry-sliding conditions when compared to the as-received
state.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction joint/cement/bone movement occurs. Thus there is renewed

The requirements for a biomaterial are excellent mechanical
properties like tensile strength, fatigue strength, high corrosion
and wear resistance and biocompatibility. One of the well-known
biomaterial is CoCrMo alloy. CoCrMo alloy is widely used in im-
plant devices due in part to its excellent mechanical and corro-
sion properties [1–3]. The molybdenum is added to produce
finer grains which results in higher strengths after casting or
forging. The chromium enhances corrosion resistance as well as
solid solution strengthening of the alloy [4]. In recent years, as
an alternative to metal-on-polyethylene (MoP) hip joint bearings
metal-on-metal (MoM) bearings are increasingly gaining more
acceptance. MoM bearings have excellent wear resistance for in-
stance the Muller type (CoCr–CoCr) has lower wear rates than
other material combinations such as High Density Molecular
Weight Poly Ethylene (CoCr/HDMWPE) [5,6]. It is generally ac-
cepted that wear particles from prosthetic implants induce
inflammatory reactions that provoke the release of inflammatory
mediators from macrophages. This inflammatory response in-
duces periprosthetic bone loss and subsequent loosening of the
prosthesis [7]. Wear debris form Co–Cr alloys are an important
factor in the failure of hip and knee prosthesis. Debris can be
generated from articulated surfaces and reverse surfaces if
* Corresponding author. Tel.: +86 13688456619; fax: +86 02885402231.
E-mail addresses: xhmd@163.com (D. Mu), shen_baoluo@163.com (B.-l. Shen),
xihuazx@163.com (X. Zhao).
1
Tel.: +86 15008226930; fax: +86 02884555464.
2
Tel.: +86 13658100176; fax: +86 08385183027.
interest in MoM bearings based on Co–Cr alloys as a solution
to this problem in view of their potential for greatly improved
wear performance.
Boronizing is a thermo-chemical treatment that diffuses boron
through the surface of metallic substrates. As boron is an element
of relatively small size it diffuses into a variety of metals; including
ferrous, non-ferrous and some super alloys [8,9]. The boronized
metal surface is of high hardness, good wear resistance, excellent
corrosion resistance and ideal oxidation resistance. Even though
there was not much study about boronizing of CoCrMo alloy, per-
formed studies showed that boronizing improved the mechanical
properties of CoCrMo alloy [10–12]. However, no investigation
has been reported on dry-sliding behavior of boronized CoCrMo al-
loy under a ring-on-block contact condition. Therefore, the purpose
of this paper is to investigate the wear properties and the mecha-
nisms of boronized CoCrMo alloy using a ring-on-block wear tester
under dry-sliding conditions.
2. Experimental
2.1. Test materials
The samples were prepared from CoCrMo alloy with the follow-
ing composition (wt.%): 30% Cr, 6% Mo, 0.3% C, 1% Si, 0.5% Mn
and balance Co. The samples were machined into a size of
6.8 mm  6.8 mm  6.8 mm. Before boronizing, all the samples
were ground with 600 grid emery paper to get the final surface
finish and then ultrasonically cleaned in acetone.

0261-3069/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2010.03.024
3934 D. Mu et al. / Materials and Design 31 (2010) 3933–3936
2.2. Boronizing
Boronizing was performed in a solid medium by using Commer-
cial LSB powders that had a nominal chemical composition of 88%
SiC, 8% B4C, and 4% KBF4. All samples to be boronized were packed
in the powders mix and sealed in a stainless steel container. Boron-
izing was performed in an electrical resistance furnace under
atmospheric pressure at 950 °C for 2, 4, 6 and 8 h, respectively, fol-
lowed by furnace cooling.
2.3. Characterization
The microstructure of the polished and etched cross-section of
the samples was observed by Scanning Electron Microscope
(SEM, HITCHIS-3400 N). The phase analyses were carried out using
a Philips X-ray diffractometer with Cu Ka radiation. The hardness
profile of the boride layer was assessed by the Vickers microhard-
ness tester (SHIMADZU/HMV-2) with the loads of 10 g.
The wear tests were carried out on a Type M200 ring-on-block
wear tester. A schematic view of the tester is shown in Fig. 1. The
block samples were unboronized and boronized CoCrMo alloys,
with size of 6.8 mm  6.8 mm  6.8 mm. The mated ring sample
was GGr15 steel (HRC52) with an inner diameter of 15 mm, an out-
er diameter of 50 mm and a width of 13 mm. All the wear tests
were performed at a normal load of 30 N and a constant speed of
200 rpm (equating to a linear sliding speed of 52.3 cm/s) under
atmosphere conditions (temperature: 2 ± 3 °C, relative humidity:
50 ± 10%). The sliding time was 900 s. The wear losses were mea-
sured by Type TG328A analytic balance with sensitivity of
0.1 mg. The wear rates of the unboronized and boronized samples
were calculated using the equation of K = W/S, where W is the wear
weight in mg, S is the total sliding distance in km. The worn surface
morphologies of the samples were examined under SEM to assist
the analysis of wear mechanisms.
3. Results and discussion
3.1. Microstructure
Fig. 2 shows SEM view of the CoCrMo alloy boronized at 950 °C
for 8 h. As can be seen the boride formed on CoCrMo alloy sub-
strate has a nearly uniform morphology. Boronized surface has
three regions, namely: (1) a layer having boride, (2) a diffusion
Fig. 1. Schematic illustration of the wear test device.
Fig. 2. SEM image of CoCrMo alloy boronized at 950 °C for 8 h, showing three
distinct regions: (1) a layer having borides, (2) a diffusion zone, being rich in boron,
and (3) a substrate, which is not affected by boron.
zone, being rich in boron, and (3) a substrate, which is not affected
by boron. There is another feature which is noticed throughout the
diffusion layer. This is the presence of a large number of pores,
which is probably due to the Kirkendall effect [13]. The Kirkendall
effect is based on unequal diffusion between the bottom boronized
layer and substrate, causing an excess of vacancies, which ulti-
mately become pores (Kirkendall pores). Fig. 3 reveals the X-ray
diffraction results of boronized CoCrMo alloy at 950 °C for 2, 4, 6
and 8 h. X-ray study shows the presence of Co2B and CrB phases
on the surface. The strongest peak from the Co2B boride was de-
tected, suggesting that a large amount of Co2B formed in the boride
layer. Co2B and CrB phases established at the surface of boride Co–
Cr–W–C alloy were also mentioned by other researchers [11].
3.2. Hardness and boride layer
Microhardness measurements were carried out from surface to
interior along a line to observe a variation of hardness of boride
layer, diffusion zone and substrate, respectively. An optical micro-
graph of boronized CoCrMo alloy at 950 °C for 8 h including Vickers
indentation marks is shown in Fig. 4a. Fig. 4b shows the changes in
hardness values from surface to interior of boronized CoCrMo alloy
at 950 °C for 2–8 h. The surface hardness values of boronized sam-
ples change between 1230 and 2002 HV0.01 with various time,
while the hardness of the substrate is 518 HV0.01. However, the
hardness of diffusion zone is around 115–355 HV0.01 and is lower
Fig. 3. X-ray diffraction patterns of CoCrMo alloy boronized at 950 °C for 2, 4, 6 and
8 h.
 D. Mu et al. / Materials and Design 31 (2010) 3933–3936
Fig. 4. (a) Micrograph of the boronized at CoCrMo alloy 950 °C for 8 h, showing the
hardness indentation variation with distance from surface to interior; (b) hardness
values of the boronized samples at 950 °C for 2, 4, 6 and 8 h.
than that of the substrate. It is possible to claim that this is a con-
sequence of presence of Kirkendall pores in diffusion zone. More-
over, the results of hardness measurements show that the
hardness values increase with increase in process time. X-ray dif-
fraction (XRD) results (see Fig. 3) reveal that the hard Co2B and
CrB formed on the substrates increase with increasing in boroniz-
ing time. As a result of this situation the hardness values increase
with increase in process time.
The relationship between boronizing time and thickness of the
boride layer is given in Fig. 5. The thickness of the boride layer
Fig. 5. The variation of the depth of boride layer for CoCrMo alloy as a function of
process time.
3935
ranges from 4 to 11 lm. During the thermo-chemical coating pro-
cesses, an increase in the process time and the temperature causes
to an increase in the coating layer thickness [14]. It is observed that
the thickness of the boride layer increases depending on the boron-
izing time.
3.3. Wear behavior
Table 1 presents the wear results of CoCrMo alloy unboron-
ized and boronized at 950 °C for 2, 4, 6 and 8 h. According to
the table, all the dry-sliding wear rates of the boronized samples
in time range of 2–8 h exhibit lower wear rate in comparison to
that of the unboronized one. Particularly, the sample boronized
at 950 °C/8 h, with the wear rate of 0.64 mg km 1, shows the
best wear resistance. In addition, we can come to a conclusion
from the data (Table 1) that the wear rates depend closely on
the boronizing duration. In other word, longer process duration
result in more excellent wear resistance. It is well know that
hardness of boride layer plays important role in improvement
of the wear resistance [15–17]. The relationship between the
surface hardness and wear rates of the boronized samples also
confirms that the wear resistance is improved with the hardness
increasing.
Fig. 6 shows the worn surface and wear debris of the unboron-
ized and boronized CoCrMo alloy dry-sliding against the GCr15 at
room temperature. Fig. 6b and d is the high magnification views
of the zones b and d marked in Fig. 6a and c. As shown in Fig. 6a,
the worn surface is essentially composed of scratch running along
the sliding direction. And a number of stuck worn debris particles
which are dragged through contact with the GGr15 ring observed
on the edge of the wear track of the unboronized sample. Under
the sliding wear condition, the worn surface of original CoCrMo
alloy is easy scratched and the wear behavior is featured as abra-
sive and adhesive wear, as shown in Fig. 6b. Boronized sample
show narrower wear track as compared with unboronized sample
(see Fig. 6c). Boronized metals are extremely resistant to abrasion
and adhesion on account of its great hardness. Furthermore, the
boride layer has low welding tendency [18]. The property is of
great consequence for adhesive wear and explains why boronized
samples show higher wear resistance. However, Fig. 6d shows
that small stuck worn debris particles distributed sporadically
on the rough metallic surface of the boronized sample. As seen
in Fig. 1, the boride layer on the surface of the boronized sample
does not have enough thickness. The Kirkendall pores occur in the
worn surface as a result of the boride layer removed from the sur-
face during the wear test. Since the boronized sample is per-
formed on the ring slider under the applied normal load of 30 N
in dry-sliding wear test, very high contact stress would occur
[19], thus leading to fracture in the diffusion zone owing to the
structural defects (e.g. Kirkendall pores). Small amounts of worn
particles produced via fracture are probably crushed down be-
tween slider and sample and then facilitated to adhesive and
abrasive wear on the boronized sample.
Table 1
Weight losses and wear rates of CoCrMo alloy unboronized and boronized at 950 °C.
Samples Boronizing time Weight losses Wear rates
(h) (mg) (mg km 1)
Unboronized 0 1.10 2.34
Boronized 2 1.03 2.19
4 0.95 2.02
6 0.72 1.53
8 0.30 0.64
3936 D. Mu et al. / Materials and Design 31 (2010) 3933–3936
Fig. 6. SEM micrographs of the worn surface morphologies under wear conditions (sliding speed 52.3 cm/s, normal load 30 N, against GGr15): (a) unboronized CoCrMo alloy,
(b) higher magnification in (a), (c) boronized CoCrMo alloy, (d) higher magnification in (c). The arrows indicate the wear sliding direction.
4. Conclusions
The following conclusions can be drawn from the experimental
study:
(1) The boride formed on the CoCrMo alloy has a nearly uniform
morphology. The microstructural studies show three distinct
regions: (1) a surface layer consisting of borides, (2) a diffu-
sion zone, being rich in boron, and (3) a substrate, which is
not affected by boron. A large number of pores formed in dif-
fusion zone are probably attributed to the Kirkendall effect.
(2) XRD studies confirm that Co2B and CrB phases are in the
CoCrMo alloy boronized at 950 °C for 2, 4, 6 and 8 h.
(3) Depending on boronizing time, the thickness of borides
formed on the surface of boronized CoCrMo alloy ranges
from 4 to 11 lm. It is found that increase in boronizing time
results in thick boride layer.
(4) The hardness of boride change between 1230 and
2002 HV0.01 with various process time, while the hardness
of the substrate is 518 HV0.01. However, the hardness of dif-
fusion zone is around 115–355 HV0.01 because of the pres-
ence of Kirkendall pores.
(5) Under dry-sliding conditions, the wear resistance of the bor-
onized CoCrMo alloy is higher than that of unboronized CoC-
rMo alloy due to the high surface hardness of the Co2B and CrB.
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