JTTEE5 23:10971104

DOI: 10.1007/s11666-014-0101-6
1059-9630/$19.00  ASM International

C.R.C. Lima, R. Libardi, F. Camargo, H.C. Fals, and V.A. Ferraresi

(Submitted November 1, 2013; in revised form March 14, 2014)
Thermal spray processes have been widely used to minimize losses caused by wear mechanisms. Sprayed
deposits using conventional wire and powder materials have been long solving tribological problems in
engineering equipment. More recently, the option for new different technologies and consumables like
nanostructured powder materials and nanocomposite cored wires have expanded the possibilities for
technical solutions. Cored wire technology allows the use of compositions that cannot be drawn into wire
form like carbides in metallic matrix and high-temperature materials, thus, intensifying the use of
spraying processes with low operating cost to demanding wear and corrosion applications. The objective
of this work was to study the mechanical characteristics and wear performance of coatings obtained by
Flame, Wire Arc, and HVOF spraying using selected nanostructured WC10Co4Cr, WC12Co, and
Fe-based 140 MXC powder and wire materials. Abrasive wear performance of the coatings was determinate following the ASTM G-65 standard. Based on the results, a higher abrasive wear resistance was
found for the HVOF-sprayed WC10Co4Cr nanostructured coating.

Keywords

abrasive wear, cored wire, flame spray, HVOF,

nanocoating, wire arc spray

1. Introduction
One of the leading causes for degradation and failure of
equipment parts is wear in its diverse forms as abrasion or
erosion. Frequently, in several industries, the erosive
environment presents corrosive agents making the search
for failure prevention still more challenging. As a less
costly alternative to parts fully made of wear and corrosion resistant materials, coatings have become a very
important part of equipment manufacture and repair.
Equipment parts can achieve improved performance if
properly coated. The recovery of pumps, valves, and other
parts of industrial machinery using engineered coatings
constitutes today one of the most important engineering
alternatives. Coatings are thick films that can be applied
by several techniques like physical vapor deposition,
electroplating, welding, and thermal spraying (Ref 1, 2).
Thermal spray processes are very suitable to obtain
C.R.C. Lima and R. Libardi, Methodist University of Piracicaba,
Santa Barbara dOeste, Sao Paulo, Brazil; F. Camargo,
OGRAMAC Surface Engineering, Santo Antonio de Posse, Sao
Paulo, Brazil; H.C. Fals, Oriente University, Santiago de Cuba,
Cuba; and V.A. Ferraresi, Federal University of Uberlandia,
Uberlandia, Minas Gerais, Brazil. Contact e-mail: crclima@unimep.br.

Journal of Thermal Spray Technology

co-atings of high performance for protection or repair of

components (Ref 3-5). All thermal spray processes use a gas
generator as kinetic component. In most cases, the gas is hot
and also serves as a heat generator. The balance between
heat and kinetic energy can vary in large proportions, which
results in coatings of different properties depending on the
technique used for thermal spraying (Ref 1, 6). The combination of a structurally adequate substrate material and a
proper coating has proven to be a highly flexible and economical manufacture strategy, mainly for the use in highly
aggressive environments (Ref 3). In this sense, knowing that
a wide range of materials and processes can be chosen for a
defined use and also the extreme difference in hardware and
processing costs from the several techniques available, it
becomes very relevant to compare different coating techniques. Despite the successful history of coating application,
there has still been a great scientific and industrial interest in
developing new coating procedures and materials as well as
studying the phenomena associated with the formation and
application of coatings (Ref 7, 8).
Nowadays, it is generally accepted that coating characteristics concerning hardness, wear, and corrosion
resistance as well as ductility are improved by using nanoscaled hard phases (Ref 9, 10). When facing heavy abrasive or erosive wear, precipitation or dispersion hardened
materials have proved to be appropriate for such application. Nanomaterials and composite materials may contain internal or external structures at the nanoscale that
were incorporated to confer some nano characteristics. As
the external dimensions of nanocomposites would be
typically larger than 100 nm, considering a definition

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Assessment of Abrasive Wear

of Nanostructured WC-Co and Fe-Based
Coatings Applied by HP-HVOF, Flame,
and Wire Arc Spray

Peer Reviewed

based just on external size would not consider most

nanocomposites to be nanomaterials. The internal structure with a size at the nanoscale would be an element to
refer such nanocomposites material as nanomaterial.
According to the European Commission (Ref 11),
Manufactured nanomaterials are that intentionally produced to have specific properties or specific composition, a
size range typically between 1 and 100 nm and material
which is either a nano-object (i.e. that is confined in one,
two, or three dimensions at the nanoscale) or is nanostructured (i.e. having an internal or surface structure at
the nanoscale).
There are two main routes for the production of
nanostructured consumables or coatings, respectively: i)
one for generating and application of nanoscale particles
itself, or ii) the manufacturing of materials which show a
nanostructured morphology or have the ability to generate
a nano structured layer when processed (Ref 12). A significant problem in the production of nanostructured
coatings from nanopowders, mainly used for plasma, CGS
(cold gas spraying), or HVOF spraying, is feeding the
nanopowders into the flame (Ref 12, 13). Nanopowders
may adhere to the walls of the feeding system, making it
extremely difficult to move them toward the spray torch
due to their high specific area and low mass. In order to
overcome this problem, it is imperative the rebuilding of
the nanoparticles into micrometer-sized granules. Several
works have demonstrated that the most favorable granule
size is in the range of 10-110 lm (Ref 14, 15). As an
alternative to this problem and also looking for less
expensive coating alternatives, cored wires and cords
based on nanoparticles have been developed. Flux cored
Fe-based wire materials have the ability to form nanoscale
phases embedded in a fine crystalline steel matrix. Coatings show high hardness values with good ductility in the
same time, which make them appropriate for use against
hitting impact loads. The second challenge is to retain
grain sizes at the nanometer scale in the coating (Ref 14).
The simplest and quickest way to obtain nanostructured
coating by thermal spraying technique is to utilize a nanotype of feedstock material (Ref 13).
Exceptional properties can be obtained if the nanocrystalline structure of the starting material is preserved
during spraying and reproduced in the coating (Ref 16).
Thermal spraying is a technique well suited for such a
deposition especially due to the very short processing time
of the sprayed powders at high temperature. However,
spraying conditions must be carefully adjusted to minimize
the coarsening or alteration of the nanograins and to
control the chemical reactions and phase stability of the
materials (Ref 16). In thermal spraying, feedstock materials in the form of powder or wire are fed into a heat
source of spray equipment, where they are fully or partially melted and accelerated in a gas stream toward a
substrate to be coated (Ref 1). The high-temperature
exposure and the following rapid quenching, typical of
thermal spraying, can either improve or deteriorate the
nanoscale microstructure of the coatings. Then, it is very
important to define the appropriate spray technique and
to control the process parameters leading to a better result

1098Volume 23(7) October 2014

in terms of coating properties, i.e., adhesion, stress level,

porosity, cracking, and so on.
In the Flame Spray Process, material in the form of cord,
wire, rod, or powder is fed into the gun. When using a cord, a
specially designed gun is used, having a nozzle which burns
Oxygen and Acetylene achieving temperatures up to
3000 C. The rod is fed through the center of the nozzle into
the flame where it is melted. Compressed air is concentrated
around the flame atomizing the molten material into fine
spherical particles and propelling these particles at high
velocity onto the prepared substrate (Ref 6). This process
can be reported as the simplest and cheapest one among all
thermal spray techniques.
HVOF or high velocity oxygen fuel process is a thermal
spray high input speed process. In this process, the fuel gas is
burned with oxygen under high pressure, generating a jet of
high velocity exhaust, allowing a very dense coating (Ref 5).
The flame temperature is relatively low when compared with
plasma spraying, but it is the same that in Flame Spray processes. As the velocity is much higher than in the case of
Flame Spray, the time during the powder is inside the flame is
very short reducing the oxide formation and making difficult
to spray ceramic materials. The main features of this process
are low formation of oxides, high density, and good adhesion
mainly because of the he high impact velocities of the particles reaching the substrate, which leads to high quality
coatings (Ref 1, 5). The nature and the stoichiometry of the
fuel, and the corresponding combustion gases play an
essential role in the final microstructure and properties of the
coatings. For the arc-sprayed material, the adjustment of
voltage and amperage as well as the pressure of the atomizing
gas are the main parameters to be controlled in the equipment. Arc spray or electric arc spray is a process that consists
of two consumable wire electrodes which are initially isolated
from each other, which move automatically to meet at one
point in a steam of atomizing gas. The process of electric arc
spraying has usually higher spray rates than other thermal
spray processes. The factors controlling application rate are
current from the power supply and wire feed rate. This is a
high-productivity process with high deposition rates, combined with low cost of consumables (Ref 1, 4).
This work aims to study the wear performance of coatings obtained by Flame, Wire Arc, and HVOF spraying
using selected nanostructured powder and wire materials.

2. Experimental Procedure
The substrate material was a SAE 1020 low carbon
steel due to its large industrial application and relative low
cost. All substrates were grit blasted with commercial
alumina just before spraying. The nanomaterials for
application in the coatings were chosen looking for a
combined abrasive and erosive wear performance,
including nanostructured metallic oxides and Fe alloys.
Commercial powder of WC10Co4Cr (Durmat 135, Durum, Willish, DE), Fe-based 140 MXC nanocomposite
tubular wire (Praxair, Concord, NH, USA), and WC12Co
flexicord (Hardkarb 12Co, Saint Gobain, Worcester, MA,

Journal of Thermal Spray Technology

Peer Reviewed
Fig. 1 Cross-sectional OM and SEM images of (a) typical nano manufactured wire or cord; (b) WC10Co4Cr powder particle with a
detailed image of the WC10Co4Cr nano scale crystal size and precipitations (Courtesy of Durum and Saint Gobain)

USA) were the feedstock materials (Fig. 1). WC10Co4Cr

is and agglomerated and sintered metal bound carbide
powder for coatings produced preferably by HVOF. With
a spherical particle shape, it exhibits fine carbides with an
average size of 0.4 lm. This powder is qualified especially
for near-net shape coatings with very low surface roughness and is suitable for a direct finishing process. Its Cr
content of 4% allows its use for corrosion resistance
applications. Fe-based 140 MXC is a nanocomposite cored
wire with amorphous matrix specially designed for Wire
Arc Spray. It presents a high percent of chromium which
makes it suitable also for moderate corrosion application.
WC12Co flexicord is a flexible extruded cored wire specially designed for Flame Spray as an alternative for
HVOF WC coatings. Distinct spraying techniques were
used for the application of the selected materials which,
beside technical results, would reflect in the economics
and coating procedure. The characteristics and chemical
composition of the feedstock materials are presented in
Table 1 which also shows the application process. The
techniques used for thermal spraying were Flame Spray
(Master Jet, Saint Gobain, Avignon, FR), Wire Arc Spray
(8830, Praxair-Tafa, Concord, NH, USA), and HPHVOF, High Pressure High Velocity Oxygen Fuel (JP5000, Praxair-Tafa, Concord, NH, USA).
Spray application parameters were adjusted for each
material according to supplier recommendation and are
presented in Table 2. The analysis of the coating morphology was conducted on cross section micrographs
acquired with a scanning electron microscope EVOMA 15
(Carl Zeiss, Jena, GE). Preliminary, the coated samples
were metallographically prepared.
Microhardness measurements were performed on a
Shimadzu computerized equipment with a capacity of
0.01-2 kg in Vickers scale. Ten measurements were performed for each sample. Roughness of the applied coatings was measured in the as-sprayed condition, and the
tabulated results are the average of five measurements
performed in each sample with Surftest 211 Mitutoyo
digital equipment. Five measurements were performed for
each sample. Abrasive wear tests were carried out
according to ASTM-G65-04 standard (dry sand/rubber
wheel test, procedure B) (Ref 17) for 2000 revolutions.

Journal of Thermal Spray Technology

The applied load was 130 N, quartz sand AFS 60/70

(Fig. 2) flow rate of 400 g/min, and 200 rpm rubber wheel
speed. Mass loss results obtained by direct weighing in
precision scale (0.001 g) were normalized for volume loss,
according to the following equation:
Volume loss (mm3

Masslossg  1000
Density g=cm3

Eq 1

The following density values were considered for each

material, according to the manufacturer specification:
6.7 g/cm3 for 140 MXC, 13.7 g/cm3 for WCa2Co, and
4.8 g/cm3 for WC10Co4Cr. Still according to the standard
and considering the wear of the rubber wheel during the
tests (1.9 mm in diameter), an adjustment was accomplished in the calculated value using Eq 1, showed in Eq 2:
Adjusted volume loss (mm3 Volume Loss 

228:6
226:7
Eq 2

3. Results and Discussion

3.1 Mechanical Properties
Table 3 shows the average results for microhardness,
thickness, and roughness of the obtained coatings. The
values for microhardness of WC-Co coatings are between
950 and 1060 HV approximately. These values for WC-Co
coatings sprayed by HVOF process are very similar to
those found in the literature, i.e., in the range of 900-1330
HV (Ref 18, 19).
It has been pointed out that nanostructured cermet
materials such as Cr3C2/NiCr and WC/Co coatings have
been shown to have higher hardness, strength, and corrosion resistance than the corresponding conventional coatings (Ref 13). From the analysis of the results in Table 1, it
can be observed that a coating with the higher hardness was
achieved by using the HP-HVOF process, case of
WC10Co4Cr, about 12% higher than the coating of 140
MXC applied by Arc Spray. Surprisingly, the second highest

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Table 1 Chemical composition of the used materials and process used for deposition
Chemical composition, wt.%
Material
140 MXC
WC12Co
WC10Co4Cr

Form

Process

Fe

Cr

Nb

Co

WC

Others

Wire
Cord
Powder

Arc Spray
Flame Spray
HP-HVOF

Bal.

25

15

12
10

Bal.
Bal.

16

Table 2 Thermal spray process parameters

Oxygen

Kerosene

Air

Pressure,
bar

Flow rate,
SLPM

Pressure,
bar

Flow rate,
SLPM

Pressure,
bar

Flow rate,
SLPM

Feed
rate, g/min

Standoff
distance, mm

WC10Co4Cr
(38 15 lm powder)

10

944

8.6

0.378

3.4

12

86

350

Arc spray

Air pressure, psi

Voltage, V

Amperage, A

Feed rate,
g/min

Standoff
distance, mm

50-60

30-35

140-180

70

180

Oxygen pressure, bar

Acetylene pressure, bar

Air pressure, bar

Feed rate,
g/min

Standoff
distance, mm

1.2

4.0

5.0

68

120

HVOF

140 MXC ( 1.6 mm wire)

Flame spray
WC12Co
( 4.75 mm cord)

Table 3 Mechanical characteristics of the obtained

coatings
Sample
WC10Co4Cr
140-MXC
WC12Co

Coating
thickness (lm)

Microhardness
(HV0,3)

RoughnessRa
(lm)

500 50
500 60
450 35

1064 35
948 30
1020 45

1.8 0.1
3.2 0.3
4.8 0.3

material, containing nanosized grains, ranging from 1040 to

1400 HV0,3, depending on the temperature and velocity of
processing, in a good agreement with the present results.
WC10Co6Cr coatings have presented the lowest surface
roughness, basically half of the other two coatings.

3.2 Microstructure of the Coatings

Fig. 2 SE Scanning Electron Microscopy of the quartz sand
AFS 60/70 used in the abrasive wear tests

hardness was presented by WC12Co applied by flame spray

which reached 1020 HV, only 4% lower than WC10Co4Cr.
Fe-based 140 MXC has 25 wt.% Cr and 15 wt.% W in its
composition which contributed to a high hardness.
WC10Co6Cr and WC12Co have over 80% content of WC,
leading to higher hardness. Marple and Lima (Ref 20) have
studied the influence of spraying parameters on the
mechanical properties and wear performance of WC-12Co
coatings obtained from conventional and nanosized powder
feedstock applied by different HVOF guns, including
JP-5000. With the use of this gun, the higher values for
micohardness were obtained for the multimodal feedstock

1100Volume 23(7) October 2014

Figure 3 shows the cross section of the sprayed coatings. A smooth coating was obtained for the three different materials and processes. The nanostructure of the
starting materials is preserved in the coatings, as can be
better observed in the merged higher magnification details
of Fig. 3(g)-(i). As expected, HVOF coatings of
WC10Co4Cr show a smoother interface, with homogeneous distribution of phases as well as lower intensity of
defects like pores or cracks. Compared to other thermal
spray techniques, one important advantage of HVOF
spraying is the ability to accelerate the melted powder
particles of the feedstock material at a relatively high
velocity, leading to a very dense microstructure (Ref 5). In
addition, the relatively low temperature regimes in HVOF

Journal of Thermal Spray Technology

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Fig. 3 SE Scanning Electron Microscopy cross-sectional images of the coatings (a), (d), and (g) WC10Co4Cr, (b), (e), and (h) WC12Co
and (c), (f), and (i) Fe-based 140 MXC; (g), (h), and (i) are enlarged feature details of the microstructure of the three coatings,
respectively

when compared with plasma spraying as well as the short

time the powder is inside the flame reduce oxide formation ensuring less decomposition of WC. Considering that
the spray techniques applied would lead the coating
materials to experience similar flame temperatures, the
flight time and mass transfer between the gas jet and the
in-flight particles prior coating formation would be the key
factors for decarburization, then contributing to a better
performance of the HVOF applied material mainly due to
the lower permanence time in the flame (Ref 21). The Febased 140 MXC coating surface presented lenticular
structures and splat formation, as expected for these
coatings. In comparison to the flame-sprayed coating
(Fig. 3b), it can be also visually observed a similar low
oxide content and low apparent porosity (dark gray and
dark regions of the figure, respectively). As defined by
Smith (Ref 22), the coating is based on an amorphous
matrix composed of chromium and niobium elements, and
nanostructured structures without preferred orientation
(Fig. 3c).

Journal of Thermal Spray Technology

Fig. 4 Results of the abrasive wear tests performed according to

ASTMG65 dry sand/ rubber wheel test, procedure B for 2000
revolutions. Applied load 130 N, quartz sand AFS 60/70 flow rate
of 400 g/min and 200 rpm rubber wheel speed

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3.3 Abrasive Wear Results

The results of abrasive wear tests are presented in
Fig. 4. The mean values of five tested specimens are presented for each coating. From the analysis of the results
showed in Fig. 4, it can be observed that the best performance was that of the WC10Co4Cr HVOF applied coating, followed by WC12Co and 140 MXC. The abrasive
wear performance for the nano WC10Co4Cr is by far the
best. But it should be also mentioned the performance of
the flame-sprayed WC12Co as well as the arc-sprayed Febased 140 MXC alloy which can be interesting alternatives
for specific applications.
Observing the microstructure of the as-sprayed coatings (Fig. 3), it is possible to infer an analogy between the

structure and behavior in abrasive wear. It can be also

visually observed a low oxide content and low apparent
porosity. A higher homogeneity in the distribution and
size of the carbides in the matrix of cobalt can be seen in
the WC10Co4Cr coating compared to WC12Co, which
may explain the difference in microhardness. Differences
in carbide sizes and distribution could also explain the
higher wear resistance, as evidenced by Yang et al. (Ref 23)
who show an increased rate of wear with increasing grain
size of carbides. In comparison to conventional WC12Co
coatings, the difference in the tungsten carbides size and
distribution is quite evident. The characteristics and
morphology of the starting feedstock material have a
strong influence on the coating microstructure and thus in
the wear results (Ref 24). The Fe-based 140 MXC coating

Fig. 5 Analysis of the worn surface of the coatings. (a), (b), (c) and (d), (e), (f) are respectively the as-sprayed and worn surface of the
coatings. (g), (h) and (i) are the enlarged details of the worn surfaces showing wear characteristics. Roughness profilometry from SEM is
also included (superior right side) for comparison before and after the wear tests

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Fig. 6 SE SEM images of the worn surface of WC10Co4Cr coating showing details of the wear mechanisms leading to micro cutting
after displacement and rubbing

surface presented lenticular structures and splat formation, as expected for these coatings. In the case of the 140
MXC coating, a structure with amorphous and nanostructured phases can justify its performance in wear tests.
Preliminarily, based on the coatings microstructures, it
would be expected that WC10Co4Cr coating (Fig. 3a)
presented a better response to abrasive wear. To further
analysis of the wear behavior of the coatings, an evaluation of the worn surface of the distinctive coatings was
performed and is presented in Fig. 5. The worn surfaces of
the coatings were examined by SEM on the top surface, in
the middle of the wear scars. In addition, surface profilometer adapted to SEM was used to compare the worn
surface roughness for each coating.
For the two WC10Co4Cr and WC12Co materials, large
numbers of dark regions can be seen in the wear area,
most identified as pits, more accentuated in the case of
WC12Co. For this coating, the wear track exhibited a
larger amount of material removal from the wear area.
Some fracturing of lamellae can be identified. In the case
of WC10Co4Cr coating, cobalt is softer phase and is likely
to undergo plastic deformation. It has been reported that
WCCo coatings from nanostructured powders have higher
extent of decarburization, but it is possible to reduce
nanocomposite degradation with liquid fuel systems like
JP5000 gun (Ref 25). Mechanism of wear was an initial
cobalt selective removal followed by carbide removal or
carbide fracture. Such general wear mechanism is also
observed by other authors (Ref 26). Micro cutting occurs
in the sequence of displacement and rubbing as can be
better observed in Figure 6. Since the hardness of the
applied coatings was very close to each other, the undermining of the carbide particles in the surface, and further
pull out was more accentuated for WC12Co, which can be
also justified by the expected lower cohesive strength of
the coating sprayed by flame spray as compared to the
HVOF-sprayed WC10Co4Cr, then leading to a higher
volume loss in the wear test. Additionally, the apparent
porosity of the WC12Co coating, which can be observed in
Fig. 3, causes accelerated removal of a less well-consolidated layer, as discussed by several authors (Ref 27, 28).

Journal of Thermal Spray Technology

Regarding the behavior of the iron-based coating 140

MXC containing Cr and W (Fig. 3c) in the abrasion tests, the
analysis of the microstructure previously showed a high degree of circular and elongated pores or pinholes as well as
some vertical and horizontal microcracks that would facilitate
detachment of particles with formation of craters and subsequent destruction of these craters and borders, then justifying the lower wear resistance when compared to the other
tested materials. Similar features can be seen in the lamellar
structure of WC12Co nanocoating (Fig. 5h) regarding pores
but with no apparent cracks. Observing the roughness profiles
included in Fig. 5, there is a severe modification for the Febased 140 MXC coating after wear test, much more intensive
than for WC10Co4Cr and WC12Co coatings.

4. Conclusion
Nanostructured tungsten carbides and iron-based
materials were deposited onto low carbon steel by three
distinctive thermal spraying processes, nominally HPHVOF, flame spray, and electric arc spray. The main results can be described as follows:
1. The obtained coatings have all shown homogeneous
lamellar microstructure with neither spallation nor
relevant level of defects. The roughness of the assprayed WC10Co4Cr coating applied by HVOF was
half of that of the other two coatings.
2. The abrasive wear resistance of the HVOF-sprayed
WC10Co4Cr nanostructured coating was found to be
up to five times higher than the other studied coatings.
The coating of nanostructured iron alloy applied by
wire arc spray and the flame-sprayed WC12Co have
performed quite similarly.
3. The mechanism of wear for HVOF-sprayed
WC10Co4Cr coating was an initial cobalt selective
removal followed by carbide removal or carbide
fracture. For flame-sprayed WC12Co coating, the
wear track exhibited a larger amount of material re-

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4.

moval from the wear area and fracturing of lamellae

could be identified.
The possibility of engineering nanostructured coatings
with superior wear resistance and extended life was
proved to be done by diverse thermal spray techniques. The general performance of nanostructured
materials applied by flame and arc spray processes in
the abrasive wear tests can be considered high. Then,
the choice for a specific thermal spray process and
material has to be application-oriented.

12.
13.

14.

15.

Acknowledgements
This study was conducted with support from CAPES,
the Brazilian government entity dedicated to training
human resources, Project 131/11. Carlos Lima also
acknowledges the financial support of CNPq - Brazil.

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