Characterization and tribological properties

of boride coatings of steels in a fluidized

bed reactor
K. David
Department of Mechanical Engineering, Technical University of Serres, Serres, Greece
K.G. Anthymidis
Applied Research Center of Serres, Serres, Greece
P. Agrianidis
Department of Mechanical Engineering, Technical University of Serres, Serres, Greece, and
G. Petropoulos
Department of Mechanical and Industrial Engineering, University of Thessaly, Volos, Greece

Abstract
Purpose The aim of the current research is to characterize boride coatings on steels and steel alloys produced in a CVD fluidized bed reactor.
Design/methodology/approach Heat treatments of alloys in fluidized bed reactors have been carried out for more than 25 years. Recently, this
technology has been used for surface engineering applications in the deposition of hard and/or corrosion-resistant layers. The present paper used
fluidized bed technology (FBT) to deposit boride coatings on to ferrous materials. The coatings were examined by means of optical microscopy, Vickers
microhardness measurements and X-ray diffraction in terms of coating thickness and morphology, phase formation and hardness determination. The
coatings tribological properties were evaluated under dry wear. Impact tests were also carried out to determine the fatigue resistance of the examined
coatings under dynamic impact loading.
Findings Boriding in a fluidized bed reactor is a simple, environmentally friendly and fast-coating process. The produced iron-boride coatings are
characterized by excellent quality and uniform tooth-shaped morphology. Fe2B was the predominant boride phase formed, exhibiting superior
tribological properties under dry wear conditions. Impact testing investigations revealed high-fatigue strength of boride coatings in combination with
limited deformable substrates.
Research limitations/implications The investigated coatings were deposited only on some structural and tool steel substrates.
Practical implications Boride coatings deposited using FBT are satisfactory abrasive wear- and fatigue-resistant coatings in comparison with those
produced using common boride coating methods.
Originality/value The outcome of the research is of great importance for the industry using abrasive wear coatings.

Keywords Tests and testing, Coatings technology, Steels

Paper type Technical paper

Introduction fluidization is described in great detail elsewhere (Gupta and

Fluidized bed technology (FBT) has been successfully used
for the formation of different types of coatings,
e.g. aluminizing, chromizing (Kingel et al., 1995; Perez et al.,
1999; Tsipas and Flitris, 2000), nitriding (Japka, 1983;
Reynoldson, 1993), carburizing and carbonitriding
(Reynoldson, 1993). On the other hand very limited
information exists on boride coatings obtained using FBT,
although this method is simple, efficient, environment friendly
and the boride coatings have been reported to have an
excellent combination of properties (Anil Kumar Sinha, 1997;
Arai et al., 1986; Tsipas et al., 1999). The theory of
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Industrial Lubrication and Tribology
60/1 (2008) 31 36
q Emerald Group Publishing Limited [ISSN 0036-8792]
[DOI 10.1108/00368790810839918]
Sathiyamoothy, 1999; Howard, 1989). Briefly, fluidization is
a process in which a bed of particles, e.g. Al2O3, behaves like a
liquid, when a carrier gas is fed through the bed. There are
several types of fluidized beds and their main advantages are
the high rates for mass and heat transfer. This leads to
uniformity of temperature throughout the volume of the
reactor and flash mix of all compounds in it, which results in
quality improvement of the coatings. Some other advantages
of this process are the capability of immediate adjustment of
the furnace atmosphere to specific requirements, the relatively
low-investment costs for equipment and the low-operation
costs. Some of the parameters that affect the quality of
fluidization in a fluidized bed reactor are the properties of the
solids and fluids used, the bed geometry, the gas flow rate, the
type of gas distributor and finally the reactor design.
This paper is concerned with the study of boride coatings
deposited on various types of steel, produced by the fluidized-
The authors would like to thank the Research Committee of Technical
University of Serres for the financial support of this research project.

31
 Characterization and tribological properties of boride coatings
K. David, K.G. Anthymidis, P. Agrianidis and G. Petropoulos
bed process. The boride coatings, which have been prepared
using FBT, were characterized by optical microscopy, X-ray
diffraction measurements and Vickers microhardness testing.
Finally, the coating fatigue strength ascertained by means of
impact testing, and the tribological properties of the
investigated coatings under dry wear conditions were evaluated.
Methodology
Coatings were deposited using a typical fluidized bed reactor
system, which is schematically shown in Figure 1. The system
consists of five main parts:
1 the fluidized bed reactor unit;
2 the gas preheating and reactants providing system;
3 the furnace for reactor heating;
4 the control panels and measuring instruments; and
5 the trapping of hazardous substances unit.
A detailed description of the experimental set up has been
given in a previous publication (Anthymidis et al., 2002). In
the present experiments boriding was carried out on
constructional (St37, Ck60, 42CrMo4), cold worked tool
(X210Cr12) and hot worked tool (X40CrMoV51) steels, at
temperatures of 9508C. Argon was used as fluidizing gas,
while the fluidizing media were composed of Al2O3, B4C and
halogen containing compounds.
The tribological properties of the coatings were evaluated
using a pin-on-disc testing machine under dry wear
conditions. The coating impact test was used as the most
convenient experimental method to study the fatigue strength
of the boride hard coatings under alternative impact loads.
The theory of impact testing is described in great detail
elsewhere (Knotek et al., 1992). Briefly, during the impact
testing a coated specimen is cyclically loaded by a hard ball
that repetitively impacts on the specimen surface (Figure 2).
The superficially developed Hertzian pressure induces a
complex stress field within the coating, as well as, in the
interfacial zone. Both stress states are responsible for distinct
failure modes, such as a cohesive or adhesive one.
Figure 1 The fluidized bed reactor system
Activator's
access
Cyclone
Fluidized bed
Plenum
Flowmeter
Argon
32
Industrial Lubrication and Tribology
Volume 60 Number 1 2008 31 36
Figure 2 Impact testing principle
The Impact Test
carbide ball
Fimp
coating
2
tcoat
substrate
The exposure of the layered compounds against impulsive
stresses generates the real conditions for the appearance of
coating fatigue phenomena, based upon structural
transformation, cracking generation and cracking growth,
which are responsible for the gradual micro-chipping and the
degradation of the coating.
In all impact craters resulted from the experiments three
different zones inside the impact cavity were identified
(Figure 3). A central zone in the middle of the impact cavity,
where the coating is strained with compressive stresses and a
gradual cohesive degradation takes place. The intermediate
zone inside the piled up rim formed around the impact cavity,
where tensile and shear stresses build up and both cohesive
and adhesive delamination arises. Finally, the peripheral zone
of the impact cavity, where macrocracks might propagate and
coating failure occurs. The coating failure mode and its extent
were assessed by SEM observations and EDX analysis.
The contact load leading to coating fatigue fracture was
recorded in diagrams (endurance strength curves) versus the
number of impacts (Figure 4). The impact load for which the
Temperature
Measurement
Field Point
Manometer
 Characterization and tribological properties of boride coatings Industrial Lubrication and Tribology
K. David, K.G. Anthymidis, P. Agrianidis and G. Petropoulos Volume 60 Number 1 2008 31 36

Figure 3 Impact crater with the developed coating failure

Imprint

Carbide
Impact ball
direction
Coating

te ~500m
Substra Central Zone
Middle Zone
Outer Zone

Figure 4 Typical coating endurance strength curve obtained by impact testing

Endurance strength curve

1000

800
Impact force (N)

600

400

200

0
0 5,00,000 10,00,000 15,00,000
Number of impacts

coating does not fail after 106 impacts is called limit of Figure 5 Typical tooth-shape morphology of boride coating deposited
continuous endurance of the coating. on 0.5%wt C steel (St37) in a fluidized bed reactor

Results and discussion 100m

In Figure 5, a typical morphology of boride coating deposited
on 0.5%wt C steel (St37) after 1 h and 30 min. of treatment is
shown. This coating had an average thickness of 80 mm,
Vickers microhardness values of 1,800-2,000 HV (Figure 6)
and it is characterized by very good adherence due to its
tooth-shape morphology.
With the aid of the X-rays patterns it was concluded that
the as-prepared coatings consist of a uniform compound,
which was found to belong to a Fe2B phase. Small traces
indicated of a-Fe phase are present in the thinner than in the
average coatings. It was also observed that in the case of the
coating with less than 1 h treatment crystallization proceeds
by formation of Fe2B crystallites with a preferred orientation.
Apparently, longer treatment induces secondary
recrystallization resulting in improvement of the coating
properties. In Figure 7, the typical morphologies of boride
coatings obtained on Ck60, 42CrMo4, X210Cr12 and
X40CrMoV51 after 3 h of treatment at 9508C are shown. Ck60, 35 mm for 42CrMo4, 30 mm for X210Cr12 and 25 mm
From the X-rays patterns it was found that mainly one phase for X40CrMoV51.
belonging to Fe2B (space group I4/mcm, a 5.110 A Via the tribological tests under dry wear conditions
c 4.249 A) was formed during the treatment. In the case (pressure 15 kp, SiC paper 220 grit, testing time 2 min,
of the cold worked tool steel X210Cr12 FeB phase is also velocity 30 rev/min.) the Fe2B layer showed an up to 50
present. The thickness of the boride layers was 35 mm for percent increased resistance to abrasive wear compared to the

33
 Characterization and tribological properties of boride coatings
K. David, K.G. Anthymidis, P. Agrianidis and G. Petropoulos
Figure 6 Measurement of the microhardness of the boride coating
deposited on 0.5%wt C steel (St37) in a fluidized bed reactor
100 m
170 Hv
254 Hv
1925 Hv
untreated steel. When the layer was removed (after
approximately 2 min of testing) the wear performance was
similar to that of the uncoated steel (Figure 8).
Impact tests were also carried out to determine the
fatigue resistance of the examined coatings under dynamic
impact loading. In Figure 9(a), spalling of the boride
coating is evident due to poor adhesion with the X210Cr12
substrate in the peripheral zone of the crater. Figure 9(b)
shows the development of perpendicular macrocracks
inside the coating layer due to high tensile stresses
Figure 7 Typical morphologies of boride coating obtained on various steels and steel alloys in a fluidized bed reactor: (a) X210Cr12; (b) 42CrMo4; (c)
Ck60; (d) X40CrMoV51
200 m
(a)
200 m
(c)
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Industrial Lubrication and Tribology
Volume 60 Number 1 2008 31 36
imposed by high deformation of the X40CrMoV51
substrate. The main failure of the most examined coating-
substrate compounds there occurred in the central zone of
the impact cavity with coating delamination. Figure 9(c)
shows coating delamination in the central zone of the
impact cavity (substrate 42CrMo4) and Figure 9(d)
extended coating fatigue failure both appearing in the
central zone, in the form of layer degradation and in the
peripheral zone of the impact cavity as adhesive wear
(substrate Ck60).
It is evident that when the tensile stresses at the peripheral
zone of the impact crater were too high, spalling of the coating
layer due to poor adhesion may occur.
For the examined hard boride coating in combination with
a relatively plastically deformable substrate (Figure 10(a)), the
high-tensile stresses in the immediate vicinity of the impact
caused the development of a large number of macrocracks in
the peripheral zone of the impact cavity. In general,
macrocracks arise inside the coating layer and
perpendicularly to its surface when the coating is not tough
or ductile enough to accommodate the stress induced by the
ball indenter and to follow the flexure and deformation of the
substrate.
On the contrary, in the case of slight plastically deformable
substrates resulting in small cavity volume, the coating
layer sustains the repetitive impacts without fatigue failure.
Only superficial abrasive wear could be observed though
(Figure 10(b)).
Figure 11 shows an overview of the endurance performance
of the boride coating deposited on St37 steel, produced by the
fluidized-bed process by means of the experimentally
100 m
(b)
100 m
(d)
 Characterization and tribological properties of boride coatings Industrial Lubrication and Tribology
K. David, K.G. Anthymidis, P. Agrianidis and G. Petropoulos Volume 60 Number 1 2008 31 36

Figure 8 Tribological properties of uncoated and borided steel (St37)

UNCOATED COATED

0.02

0.015

Weight lost (gr) 0.01

0.005

0
0 0.5 1 1.5 2
Treatment Time (min)
Notes: Test conditions: pressure 15 kPa, SiC paper 220 grit, testing time 6 min,
velocity 30 rev/min

Figure 9 Coating failure modes

(a) (b)

(c) (d)

Figure 10 (a) Development of perpendicular macrocracks inside the coating layer (substrate X40CrMoV51). (b) Coating abrasive wear without coating
fatigue failure (substrate 42CrMo4)

(a) (b)

35
 Characterization and tribological properties of boride coatings Industrial Lubrication and Tribology
K. David, K.G. Anthymidis, P. Agrianidis and G. Petropoulos Volume 60 Number 1 2008 31 36

Figure 11 Experimental determined fatigue curve of Fe2B coating reactor and their properties, Science and Technology of
deposited on steel (St37) Advanced Materials, Vol. 3 No. 4.
Arai, T., Endo, J. and Takeda, H. (1986), Chromizing and
600 boriding by use of a fluidized bed, paper presented at the
no failure
coating failure
5th International Conference on Heat Treatment of
500 Materials, 3, pp. 1335-41.
coating fatigue curve
Gupta, C.K. and Sathiyamoothy, D. (1999), Fluid
Impact force (N)

400 Bed Technology in Materials Processing, CRC Press,

300
200
100
0 formation of protective coatings, Steel Research, Vol. 66
1.0E+04 1.0E+05 1.0E+06
Number of impacts
determined fatigue curves. The Fe2B coating revealed
high-fatigue strength against cycle impact loading.
Conclusions
A simple, environment friendly, fast-boriding process was
carried out in a fluidized bed reactor. Samples of a typical
morphology of iron-boride coatings and of excellent quality
were produced. Fe2B was the predominant boride phase
formed and it showed improved tribological properties under
dry wear conditions. Impact testing investigations revealed the
high-fatigue strength of boride coatings in combination with
limited deformable substrates.
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Corresponding author
K. David can be contacted at: david@teiser.gr

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