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Influence of the thermal-spray procedure on the properties of a

CoNiCrAlY coating
V. Higuera
a,
*
, F.J. Belzunce
b
, J. Riba
b
a
Mechanical Engineering Department, University Campus, University of Oviedo, 33203 Gijo´n, Spain
b
Materials Science Department, University of Oviedo, 33203 Gijo´n, Spain
Received 4 May 2005; accepted in revised form 24 July 2005
Available online 7 October 2005
Abstract
A CoNiCrAlY coating was thermal-spray projected using different procedures (plasma, HVOF and HFPD) onto stainless steel
specimens. Thermal fatigue tests were conducted in an experimental combustion chamber under a similar atmosphere to power plant
service conditions.
The microstructure of the coatings depend on the projection method. The oxide content depends on both the maximum temperature
attained and the interaction time between powders and air that occurs during the spraying. Porosity is also related to the spraying
procedure by way of the particle size, average temperature and velocity attained by the particles when they impact with the cold
substrate.
The substrate-coating adherence of plasma and HVOF procedures are very high and are not significantly affected by thermal fatigue. On
the contrary, the adherence of HFPD spraying is significantly lower, as well as being reduced by thermal fatigue.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Thermal spraying; Spraying procedures; Coating microstructure; Coating adhesion
1. Introduction
Gas-fired turbine combined-cycle systems are expected
to account for a significant proportion of the projected new
electricity generation units to be constructed over the next
10 years. Such plants are available in a range of sizes of up
to more than 200 MW per turbine. Current combined-cycle
plants have professed cycle efficiencies in the order of 49%
and are capable of achieving environmental compliance for
SO
2
and NO
x
[1].
In order to achieve the aforementioned goals, the gas
turbine industry is making the utmost effort to allow
increased firing temperatures so as to improve engine
efficiency, as well as using a reduced cooling air / fuel ratio.
At the same time, increasing efficiency reduces fuel
consumption and therefore reduces emissions of nitrogen
oxides (NO
x
), carbon monoxide and hydrocarbons in order
to meet the expected lower limits for pollution in the future
[2].
The main requirements for land-based gas turbines are a
long life, maximum efficiency, reliability and minimum
cost. The durability of a gas turbine is limited by
components operating at high temperatures [3]. Oxidation
and high temperature corrosion of the materials used in their
high temperature regions are improved by the application of
protective coatings. MCrAlY coatings (M=Ni, Co or both)
are used worldwide for this purpose under the most
demanding conditions. They owe their protective effect to
the fact that they form a continuous, thermally stable oxide
layer (Al
2
O
3
) on the coating surface. These coatings are
normally applied using vacuum plasma-spray (VPS) pro-
cesses. This method produces dense coatings (low porosity)
with excellent adherence to the substrate and minimize
oxidation during the application.
0257-8972/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.07.070
* Corresponding author. Tel.: +34 985182356; fax: +34 985182022.
E-mail address: vhiguera@uniovi.es (V. Higuera).
Surface & Coatings Technology 200 (2006) 5550 – 5556
www.elsevier.com/locate/surfcoat
Other thermal-spray processes that are much more
economical and convenient, such as the high velocity
oxygen fuel (HVOF) and the detonation gun methods, have
been developed to produce quite dense coatings with a good
adherence to the substrate. More recently, the new high
frequency pulse detonation thermal-spray process (HFPD)
represents a cost-effective alternative for the production of
good quality coatings [4,5].
The aim of the present study was to analyse the influence
of thermal-spray procedures (plasma, HVOF and HFPD) on
the final characteristics of the coatings obtained using
commercially available CoNiCrAlY powders.
2. Thermal-spray processes
Thermal-spray processing is a very rapidly expanding
field of surface engineering. In all thermal-spraying
processes, the consumable coating material fed to the spray
gun is raised in temperature and projected at a high velocity
against the workpiece, on which the individual hot particles
form splats that interlock and gradually build up a coating of
the desired thickness. The main differences between the
available procedures are the energy source involved and the
type of gun used in the projection [6].
High velocity oxygen fuel (HVOF) is a high-energy
process. It employs specially designed spray guns that burn
oxygen and a fuel gas (hydrogen, propane or propylene). In
HVOF systems, the combustion process takes place within
the gun, and the gas flow rates are much higher than in
conventional flame spraying. The combination of these two
factors leads to supersonic flame speeds, up to approx-
imately 2000 m/s, with particle velocities that may reach
800 m/s. The maximum temperature attained in these
processes is around 2700–3200 K [6,7].
Plasma spraying is a high-energy process in which a
high-current arc is generated within the torch and a gas is
injected into the arc chamber, where it is heated and
converted into high-temperature plasma. In practice, pure
argon or nitrogen is used as the primary plasma gas, together
with additions of 2%–25% of a secondary gas (hydrogen or
helium). Powdered surfacing material is injected into this
plasma jet and is thus heated to a molten state and
accelerated onto the substrate. Plasma temperatures higher
than 10,000 K and particle velocities of up to 600 m/s have
been measured in some specific cases [8].
The high frequency pulse detonation (HFPD) spray
process is based on a carefully designed gun capable of
producing discontinuous behaviour (cycled explosions)
from a continuous supply of the detonable gases and
powders. The system permits the self-generation of discrete
batches of gases and powders for each cycle, opening up the
possibility of working within a wide range of explosion
frequencies (up to more than 100 Hz) and gas mixtures. In
the HFPD process, the flow of gaseous products from
cycled explosions in the gun is used to accelerate and heat
the sprayed particles. Typically, these particles attain very
high speeds (up to 800 m/s) and moderately high temper-
atures (lower than 4000 K) leading to quite dense, well-
bonded coatings of most commercially available powders
(metallic alloys, ceramics and cermets) [4]. One of the most
important consequences of the particular physical process
involved in HFPD cycled explosions is the low consump-
CoNiCrAlY powder ( 38-75 µm. ) CoNiCrAlY powder ( 10-45 µm. )
Fig. 1. Morphology of CoNiCrAlY powders.
Table 1
Grit blasting procedures
Grit blasting Plasma HVOF HFPD
Abrasive Angular steel Alumina Alumina
Air pressure (MPa) 0.7 0.5 0.7
Roughness, Ra (Am) 11.3T0.9 4.5T0.4 6.5T0.3
Table 2
Coating materials and thermal-spraying methods
Coatings: U V W
Powders CoNiCrAlY CoNiCrAlY CoNiCrAlY
Granulometry, Am 38–75 10–45 10–45
Thermal spraying: Plasma HVOF
a
HFPD
b
Coating thickness, Am 221T16 211T17 158T37
a
HVOF – High velocity oxygen fuel.
b
HFPD – High frequency pulse detonation.
V. Higuera et al. / Surface & Coatings Technology 200 (2006) 5550–5556 5551
tion of gases, especially when compared with alternative
continuous HVOF systems.
3. Experimental procedure
3.1. Materials
An AISI 310 (25% Cr, 19% Ni) austenitic stainless steel
in a fully annealed condition was used as substrate. All the
specimens used in the experiments were cylindrical, with a
diameter of 25.4 mm and a length of 25.4 mm, in
accordance with the ASTM C 633 standard [9], and were
obtained through calibrated profiles.
Two different gas atomized CoNiCrAlY commercial pre-
alloyed powders were thermally sprayed in accordance with
the different projection procedures. The powder composi-
tion was: 36.9–37.0%Co, 21.1–21.3%Cr, 8.5–8.9%Al,
0.48–0.52%Y (wt.%), balance Ni, and the size ranges were
respectively À75+38 Am (plasma) and À45+10 Am
(HVOF and HFPD). The differences in morphology of both
powders are better seen in Fig. 1.
3.2. Projection procedures
First, the stainless steel substrates were grit blasted
following the procedures described in Table 1, which also
presents the final specimen roughness after grit blasting.
The CoNiCrAlY coating was thermally sprayed onto the
stainless steel substrates by plasma (U), high velocity
oxygen fuel, HVOF (V) and high frequency pulse deto-
nation, HFPD (W) procedures. Table 2 shows the different
combinations of coatings and projection methods mentioned
above.
A Metco plasma-spray utility was used to project the
powders onto the substrates. The equipment used to carry
out the HVOF and HFPD projections were a Metco HDJ
and a PK200 Aerostar Coatings apparatus, respectively. The
most relevant projection parameters are listed in Table 3.
Samples were cleaned, grit blasted and coated with the
CoNiCrAlY within 2 h following cleaning. An automatic
device was used to minimize fluctuation of the spray
parameters in order to achieve coatings of homogeneous
thickness.
Table 3
Plasma, HVOF and HFPD spraying parameters
Spray method: Plasma HVOF HFPD
Frequency: 67 Hz
Arc power: 400 A ; 58 V
Carrier gas: Argon Nitrogen Nitrogen
Projection distance, mm 125 250 150
Plasma gases and pressure Primary: Argon at 0.7 MPa
Secondary: Hydrogen at 0.35 MPa
Fuel: Propylene Methane
Fuel flow: 87 l/min 85 l/min
Oxygen flow: 152 l/min 131 l/min
a b
c
Fig. 2. As-sprayed coatings: a) plasma, b) HVOF, c) HFPD.
V. Higuera et al. / Surface & Coatings Technology 200 (2006) 5550–5556 5552
3.3. Characterization tests
The thickness of the coatings as well as their micro-
structure, porosity and oxide content were determined by
means of optical microscopy techniques. Coating porosity
and volume fraction of oxides were evaluated on surface
and transversal sections, in accordance with the ASTM
E562 standard [10] by point counting on different fields.
Vickers microhardness tests using 200 gf load were also
performed within the same sections in order to assess the
coating hardness. The substrate plastic strain hardening
promoted by the high-speed projection was likewise
evaluated.
Thermal fatigue experimental tests were carried out in a
300 kWexperimental combustor specially designed to attain
temperatures as high as 1300 -C in environments that very
closely simulate the operating conditions of gas-fired gas
turbine combined-cycle systems. The combuster’s heating
system uses propane as a fuel and air, which is previously
heated with the flue gas stream generated in the combustion
reaction [5]. The combustion atmosphere composition was
approximately the same as that usually existing in actual
power plants of combined cycles with a free oxygen volume
percentage of 10%. The cyclic thermal fatigue tests were
carried out by means of repeating the following cycle ten
times: a heating period of 50 min to reach 1273 K
(DT
avg
=20 K/min), sustainment of this temperature for 4
h, followed by another 6 h for cooling to room temperature
(DT
avg
=3 K/min).
Adherence tests were also performed in accordance with
the ASTM C633 standard [10] in order to assess the quality
of the substrate-coating bonding and the influence of cyclic
thermal fatigue on the aforementioned adherence. Finally,
these samples were sectioned perpendicular to their surface,
ground, polished and analysed under optical and scanning
electron microscopes.
4. Results
4.1. Microstructure and microhardness
Fig. 2 shows the typical cross-sectional microstructures
corresponding to the three coatings obtained by means of
the different spray-coating procedures. Table 4 shows the
average microhardness of the coatings, along with their
porosity and volume fraction of oxides.
Table 4
Coating microhardness, porosity and volume fraction of oxides
Coatings: U (Plasma) V (HVOF) W (HFPD)
Microhardness (HV
300
)
Transverse section 155T18 418T31 304T23
Surface section 190T17 485T28 303T27
Porosity (% vol. avg.)
Transverse section 5.1T0.7 4.6T1.5 2.7T0.8
Surface section 3.6T0.9 5.1T1.4 4.3T1.0
Oxide content (% vol. avg.)
Transverse section 5.8T2.1 3.4T0.8 1.0T0.6
Surface section 1.8T0.2 0.6T0.3 1.3T0.3
0
100
200
300
400
500
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
Distance from interface (µm)
M
i
c
r
o
h
a
r
d
n
e
s
s


(

H
V

)
U (HV) V(HV) W (HV)
25
Substrate / coating interface
Fig. 3. As-sprayed substrate microhardness profiles. Distances are measured from the coating-substrate interface.
Fig. 4. Slip bands in the substrate region near the substrate-coating
interphase.
V. Higuera et al. / Surface & Coatings Technology 200 (2006) 5550–5556 5553
The coating hardness obtained using the different
thermal-spray procedures differ significantly. This hard-
ness is mainly related to the temperature and speed of
the particles when they impact onto the substrate: the
lower temperature and higher speed of the HVOF
projected particles explains this coating’s higher hard-
ness, the opposite occurring with the plasma projected
particles.
The dependence of porosity and oxide content on the
spray procedure can also be clearly seen. The oxide content
mainly depends on temperature and contact time with air
during spraying; the low temperature of the HFPD
procedure thus explains the lowest value obtained in this
case. The very high temperature of plasma spraying and its
lower particle velocity (longer interaction time) justify the
high oxide contents reported in the plasma procedure,
although their larger particles had a lower active surface.
On the other hand, the porosity obtained after plasma
spraying is the highest, mainly due to the larger size of the
projected particles and lower particle velocity at the impact
instant.
Fig. 3 shows the clear hardening of the substrate surface
due to grit blasting and also to the high-speed impact of
the projected particles during projection: hardness values
greater than 400 HV were measured on the substrate
region closer to the coating, while the average substrate
hardness was around 200 HV. The most distinctive
differences between the spraying methods is the lower
increase in hardness produced by HFPD and the thickness
of the hardened region, which is longer in the plasma
procedure (300 Am versus 100–200 Am), mainly due to
the larger particles used in this procedure. HFPD spraying
parameters do not seem to be optimised enough as the
kinetic energy of the particles when impacting on the
substrate may be too low.
Fig. 4 shows the slip bands produced by intense plastic
deformation, which takes place in the strain-hardened
region existing just below the coating. Maintaining the
coated materials at a high temperature modifies the
hardness of the aforementioned region, due to recrystalli-
0
50
100
150
200
250
300
350
400
450
500
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850
Distance from interface (µm)
S
u
b
s
t
r
a
t
e

m
i
c
r
o
h
a
r
d
n
e
s
s

(
H
V
)
U-CoNiCrAlY Plasma 160h to 1000°C ( HV )
W-CoNiCrAlY HFPD 160 h to 1000°C ( HV )
V-CoNiCrAlY HVOF 160h to 1000°C ( HV )
Substrate/coating interface
Fig. 5. Substrate microhardness profiles after 1273 K testing. Distances are measured from the coating-substrate interface.
Table 5
Coating adherence results
As sprayed (MPa) After thermal fatigue (MPa)
U (Plasma) >64
a
>54
a
V (HVOF) >64
a
>57
a
W (HFPD) 48 37
a
Failure of the adhesive used to perform the test according with the
ASTM C633 standard.

1 - Coating remains 2 – Substrate 3 - grit blasted substrate surface
Fig. 6. Adhesive failure of as-sprayed HFPD CoNiCrAlY coating.
V. Higuera et al. / Surface & Coatings Technology 200 (2006) 5550–5556 5554
zation processes taking place. This effect can be seen in
Fig. 5, which is the same representation already shown in
Fig. 3 but after 160 h of maintenance at 1273 K.
4.2. Coating adherence
Initial tensile adherence strengths of the coating-substrate
interface measured at room temperature after plasma-spray,
HVOF and HFPD projections are presented in Table 5,
along with the adherence strengths of the same materials
after thermal fatigue at 1273 K.
The as-sprayed average adherence values at room
temperature for the coatings applied by means of the
plasma-spray and HVOF methods is excellent, as the
adhesive used to apply the tensile load according with
the ASTM C633 standard was the weakest link in the
whole testing assembly. The as-sprayed adherence
obtained when using the HFPD projection decreases to
48 MPa: the failure of these last specimens was purely
adhesive along the substrate-coating interphase, as can be
seen in Fig. 6 (the grit blasted substrate surface is
clearly seen in the photograph). These values are not
related to the coating microstructure (in fact HFPD
coatings had the lowest porosity and oxide content
values), but with the substrate work hardening, see Fig.
3, as the substrate hardening obtained after HFPD
projection was the lowest of the three procedures. This
finding can only be justified by the lower temperature
and kinetic energy of the impacted particles when
employing this spraying method.
Moreover, under thermal fatigue conditions, the adher-
ence of the HFPD-sprayed coating decreases to quite low
values (37 MPa), while plasma-sprayed and HVOF coat-
ings maintain their adherence after thermal fatigue testing,
the failure of both these coatings yet again taking place in
the adhesive layer. Failure of the HFPD-sprayed coating
after thermal fatigue is adhesive–cohesive, along both the
coating-substrate interphase and also along the internal
oxides present between the flattened metallic particles that
constitute the coating, as can be seen in Figs. 7 and 8. Fig.
7 shows the change between an adhesive failure mode
(right side) to a cohesive one (left side) and Fig. 8 shows
the coating separated from the substrate along the
interphase in one of these tests.
5. Conclusions
Thermal-sprayed processes used to obtain protective
coatings, applied after prior grit blasting of the substrate
surface, produce an increased subsurface hardening of the
stainless steel substrate that is related with grit blasting
and with the kinetic energy of the impacted particles.
When these coatings are submitted to high temperature
conditions, recrystallization processes take place and the
hardness of this region decreases considerably.
The microstructure of the coating (porosity and oxide
volume fraction) depends on the projection method. The
lower temperature and higher speed of the HVOF
projected particles explains this coating’s higher hard-
ness, the opposite occurring with the plasma projected
particles. The oxide content mainly depends on temper-
ature and contact time with air during spraying; the low
temperature of the HFPD procedure thus explains the
lowest value obtained in this case. The very high
temperature of plasma spraying and its lower particle
velocity (longer interaction time) justify the high oxide
contents reported in the plasma procedure, although their
larger particles had a lower active surface. On the other
hand, the porosity obtained after plasma spraying is the
highest, mainly due to the larger size of the projected
particles and lower particle velocity at the impact
instant.
The substrate-coating adherence of plasma and HVOF
procedures are very high and are not significantly affected
by thermal fatigue, as failure took always place along the
adhesive layer. The adherence of HFPD spraying is
significantly lower, as well as being reduced by thermal
fatigue. Both these findings can be justified by the lower
impact energy of the projected particles as it is deduced
by the lower substrate hardness adjacent to the coating
layer.
Fig. 7. Adhesive–cohesive failure of HFPD CoNiCrAlY coating after
thermal fatigue.
1 - interface (grit-blasted substrate surface) 2 - coating
Fig. 8. Adhesive–cohesive failure of HFPD CoNiCrAlY coating after
thermal fatigue.
V. Higuera et al. / Surface & Coatings Technology 200 (2006) 5550–5556 5555
Acknowledgements
Financial support for this work was provided by the
‘‘Principado de Asturias’’ from de I+D+I (2001–04)
Regional Research Plan through the ‘‘Fundacio´ n para la
Investigacio´ n Cientı ´fica y la Tecnologı ´a’’ (FICYT), Astu-
rias, Spain, within the framework of an applied research
project with Hidroele´ctrica del Canta´brico S.A., Reference
Number PC-CIS01-10.
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V. Higuera et al. / Surface & Coatings Technology 200 (2006) 5550–5556 5556