Abstract

In the present work, composite coatings made of Stellite 6 cobalt alloy and
boron carbide reinforcing particles were cladded on carbon steel samples
and their microstructural and hardness properties were investigated. In
order to obtain coatings containing reinforcing particles, boron carbide
powder was used to form pastes of different thicknesses and applied on the
substrate; then, GTAW method was employed to carry out surface welding
by Stellite 6 alloy fillers. EDS-coupled scanning electron microscopy and
optical microscopy were used to study micro-structural properties of welds
while XRD and Vickers microhardness tests were performed for phase
determination and hardness evaluation, respectively. It was revealed that
matrix in the coatings was enriched by cobalt and other existing phases
were Cr7C3 and Cr23C6 eutectic carbides (associated to Stellite 6 alloy) and
several secondary phases such as W 2B, WC, CrB2 and CoB2 which were
resulted from boron and carbon reactions with other elements. Besides,
increase in B4C content led to decrease in size of dendrites and increase in
concentration of interdendritic phases. Composite coatings were harder than
pure Stellite 6 alloy ones; B 4C addition also increased hardness so that with
20% of B4C the highest hardness value was achieved. Microstructural
changes and formation of secondary phases are considered as reasons of
hardness improvement in Stellite 6 coatings.
Introduction
Surface hardening is an engineered technology to improve surface
properties without variation of characteristics of the bulk material [recent
literature]. Being applicable for coating and surface modification; gastungsten arc welding method has been paid a great deal of attention in
recent decades. The produced coating in this process is less costly and
shows high density and good adhesion to substrate as well as few porosities
and oxides which is due to application of argon as shield gas [3- (myself?)
Author].
Cobalt based alloys are broadly used in cladding and surface modification
processes in order to improve wear and corrosion resistance properties.
Containing highly corrosion resistant elements such as chromium with the
ability to form various carbides like M 7C3 and M23C3 (M=?), Stellite 6 is best
known to be applied for such purposes. In addition, existence of tungsten
and molybdenum may lead to formation of MC and M 6C carbides as well as
Co3(Mo, W) intermetallic compounds through precipitation hardening and
consequently improve hardness and strength [6-4-Author]. Wear resistance
provided by solid solution strengthening processes and formation of metallic
carbides may not be sufficient in many application; thus, other carbide
particles such as WC, TiC, SiC and TaC as well as yttrium and aluminum
oxides are added to the Stellite alloy in order that wear resistance is further
enhanced. In such cases, B4C enjoying the following characteristics may be
an appropriate choice to be used as reinforcing component: (hardness: 27.4-

34.3 GPa, elastic module: 290-450 GPa, melting point: 2450 C and air
oxidation threshold: 600 C).
In a study [5, 6 and 7] on addition of reinforcing particles to Stellite based
coatings, it was reported that most of reinforcing particles were melted and
thus, hardness and wear resistance properties of coatings were improved. Li
et al. [8] and Abbas et al. [9] carried out many investigations on addition of
silicon carbide to a cobalt based alloy and Stellite which revealed its positive
effects on properties of coatings.
However, investigation of Stellite 6-boron carbide composites coated on
carbon steel substrates by gas-tungsten arc welding of the Stellite filler alloy
and application of B4C paste (pre-coated on the substrate) and evaluation of
microstructural and hardness properties of the coatings may come to
resolve many problems in this field.
Materials and methods
DIN 1.0113 carbon steel samples of 100*30*20 mm 3 and chemical
composition of were used as substrate materials in this study. Raw
materials included Stellite 6 filler alloy with chemical composition of and
boron carbide powder with mean particle size of 35 m and purity level of
99.5%. SEM micrograph of boron carbide powder is shown in Figure 1.
Samples were pre-ground and washed via acetone. In order to perform
cladding, a sample was initially welded with Stellite 6 filler alloy (Table 1)
and the obtained coating was weighed. Then, boron carbide paste of
different thicknesses was applied on the steel substrate with 20% sodium
silicate solution as adhesive agent by means of a palette knife; it was tried
to reach composites containing 5, 10, 15 and 20 wt% of boron carbide.
Samples were dried in air and later heated up to 100 C for complete
removal of humidity (for an hour). After all, surface fusion was carried out by
Stellite 6 filler alloy using GTAW method. The process is schematically
illustrated in Figure 2. Employed welding parameters are listed in Table 1.
Optical microscopy and scanning electron microscopy were used for
microstructural study of samples, existing phases were determined through
X-ray diffraction analysis and hardness profiles of samples were obtained via
Vickers hardness testing.
Results and discussion
Cross sectional micrographs of coating obtained by OM are shown in Figure
3. It is clear that addition of boron carbide reinforcing particles to Stellite 6
alloy led to gradual variations in microstructure of coatings which seem to
become more perceptible with increase in carbide percentage. As may be
observed in Figure 3, growth of cellular and columnar-dendritic structures
which is known as a characteristic feature of Stellite 6 coatings was
hindered by addition of boron carbide. In fact, the structure experienced a
cellular to equiaxed transition. This may be attributed either to solution of
reinforcing particles followed by alterations in chemical composition of

microstructural components and formation of new phases or simply to

physical presence of reinforcing particles in coatings [32, 33, 34, 7,10?]. It
may also be deduced from Figure 3 that by increase in boron carbide
content, no cracking or void was created. Meanwhile, a white area of planar
solidification was observed in micrographs which implies on creation of a
proper bonding between coating and substrate; observation of such area
was also reported in previous researches [32, 34, and 43]. Figures 4 and 5
show XRD patterns and cross sectional SEM micrographs of samples (for
SEM, samples were etched and distance from interface of coating and
substrate is 1700 m), respectively. XRD patterns revealed, of course,
presence of matrix phase of cobalt solid solution and several eutectic
carbides such as Cr23C6 and Cr7C3 (associated to Stellite 6 alloy) as well as
many new phases like Co 2B, CrB2, WC and W2B. The latter may be due to
decomposition of boron carbide and reaction of B and C with other elements
that exist in the coating. The more boron carbide added, the more intense
diffraction peaks became which shows increase in contents of these new
phases [reference]. Furthermore, Energy dispersive spectrometry results
obtained from matrix phase and interdendritic phases (highlighted in Figure
5] revealed alterations in chemical composition of microstructural
components in coatings with addition of boron carbide. According to
aforementioned results and other works, it may be concluded that boron
carbide decomposes in coatings and resulting carbon and boron atoms react
with other element that exist in the coating [40, mo?]. Finer grains of this
microstructure may be caused by chemical composition alterations and
formation of new phases. Such phenomena that are caused by addition of
reinforcing particles to Stellite 6 coatings were also observed in previous
works [32, 33, 34, 39, 43].
As may be observed in Figure 3, dendrites shortened in length (become
equiaxed) as addition of B 4C to Stellite 6 coating continued (Figure 3, b to e)
so that at 20 wt% of boron carbide, the microstructure near the interface
had become quite equiaxed. This may be explained by the following
expressions: 1- formation of fine grains near the surface due to undercooling
which hindered growth of dendrites. 2- Several phases with rather high
melting points such as CoB, CrB2, WC, W2B, CrB2 and Cr23C6 act as nucleating
agents in the melt pool and prevent growth of dendrites. Role of secondary
phases and interdendritic carbides in hindering growth of dendrites and
finely granulation of microstructure was also stated in other works [33, 32,
34, 43, mo].
Microhardness variations in cross section of samples (from substrate
towards coating) are illustrated in Figure 6. The most interesting
understanding is significant improvement of hardness caused by addition of
boron carbide reinforcing particles to Stellite 6 coatings. This may be
attributed to formation of secondary phases and their strengthening
influence on matrix of composite coatings. In addition, dendrites in matrix of
composite coatings are finer than those in pure Stellite 6 coatings which

may be attributed again to secondary phases and their preventive role [5-9,
10 and 11].
Gradual decline of hardness from coating surface towards interface with
substrate may be because of dilution phenomenon (presence of substrate
iron in coating), iron diffusion, however, is decreased by moving away from
the interface [ ]. SEM cross sectional micrograph of the coating with 20 wt%
boron carbide and linear chemical composition variations at the interface
(towards the coating) are shown in Figure 7.
The effect of dilution in coatings and reduction of iron diffusion depth from
interface towards the coating may be confirmed through Figure 7-b [12, 24].
As may be seen, iron diffusion led to decrease in cobalt and chromium
contents near the interface. Therefore, hardness of substrate may diminish
as eutectic chromium carbides are lessened.
Conclusion
1- Composite of Stellite 6 alloy and B 4C was successfully coated on carbon
steel substrates. The obtained coating enjoyed fine and equiaxed dendrites
and showed no imperfections.
2- All of boron carbide particles decomposed during the process and
changed chemical composition of Stellite 6 alloy. Cobalt and interdendritic
chromium carbide phases (associated to Stellite 6 alloy) as well as several
secondary phases caused by reaction of B and C with other element existing
in Stellite 6 alloy could be found in all coatings.
3- Some phases ( ) may act as nucleating agents due to their relatively high
melting points and hinder growth of dendrites.
4- Increase in B4C by 20 wt% led to shorter dendrites, more content of hard
interdendritic phases such as ( ) and consequently improvement of coatings
hardness properties.