Surface & Coatings Technology 200 (2006) 5395 – 5406

www.elsevier.com/locate/surfcoat

Mechanisms of oxidation and its role in microstructural evolution of

metallic thermal spray coatings—Case study for Ni–Al
S. Deshpande a,T, S. Sampath a, H. Zhang b
a
Center for Thermal Spray Research, Department of Materials Science and Engineering, State University of New York at Stony Brook,
Stony Brook, NY 11794, United States
b
Department of Mechanical Engineering, State University of New York at Stony Brook, Stony Brook, NY 11794, United States

Received 5 March 2005; accepted in revised form 4 July 2005

Available online 10 October 2005

Abstract

Thermal spray coatings are formed by successive impingement and interbonding among the splats (solidified individual molten particles).
Depending on the processing conditions employed during the spray process, deposits are produced with an assortment of microstructures and
properties. This study brings out how the basic microstructural differences are influenced by mechanisms involved during the spraying
processes. The Ni – 5 wt.% Al metallic system is chosen for a systematic study of cross comparison across different spraying techniques
because of the potential variety in coating microstructure and phases possible through application of the different spray processes as indicated
in the literature. Spray techniques such as Air Plasma spraying (APS), Wire Arc Spraying and, High velocity oxy-fuel spraying (HVOF), each
differ with respect to their feedstock injection and melting methods, spraying parameters and deposition efficiency as well as oxidation
involved during spraying. The goal of this study is to address the mechanisms of oxidation involved and present schematic models to explain
their role in the microstructural evolution of Ni – 5 wt.% Al coatings in case of different processes. In-flight oxidation and post-impact
oxidation occurring on top surface of splats are discussed in detail and the effects of these mechanisms on intersplat contact and coating
buildup are addressed.
D 2005 Elsevier B.V. All rights reserved.

Keywords: In-flight oxidation; Post-impact oxidation; Intersplat contact; Microstructure; Thermal spray coatings

1. Introduction of the deposit [2,3]. In some cases, however, metal oxides

An important aspect of thermally sprayed metal coatings
is the oxidation involved during processing. Oxidation of
thermally sprayed materials can significantly influence the
phase composition, microstructure, properties and therefore
performance of sprayed coatings. Oxides within the coating
change the deposit material properties as compared to bulk
material [1]. Metal oxides are brittle, their thermal expan-
sion coefficients are different than the surrounding metal
and they disrupt the chemical uniformity of surfaces
exposed to corrosive environments. Oxide layer at interfaces
being brittle can potentially reduce the strength and ductility
* Corresponding author. Izumi Garden Residences #1109, 1-5-3 Rop-
pongi, Minato-ku, Tokyo 106-0032, Japan. Tel.: +81 03 3589 4117.
E-mail address: swarnima_d@yahoo.com (S. Deshpande).
0257-8972/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.07.072
are also seen to improve certain properties like wear
resistance or strength under compressive loading [2,4].
Metal oxides residing along the splat boundaries can affect
intersplat cohesion whereas the oxide particles dispersed in
the splat or the supersaturated oxygen can also strengthen
the splat [2,5].
Controlling the extent of oxide formation during spray-
ing is important for microstructural control and for that it is
needed to understand how and where the oxidation occurs
during each spray process. Particle oxidation can be
classified as taking place in flight, at the splat surface and
between spray passes [6]. The contribution of the different
oxidation mechanisms to the oxidation content of the
coating depends not only upon the spray parameters but
also on the spray powder feedstock. Wan et al. have studied
the various effects involved during in-flight oxidation of
5396 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406
plasma sprayed Molybdenum [7]. Dobler et al. have studied
the oxidation of stainless steel during HVOF process and
have described it to occur in three regions out of which two
are during flight and one is after impact on substrate [8].
Particle oxidation occurs in flight as well as after impact
during splat cooling. This also varies with the processing
parameters involved. Sobolev and Guilemany have looked
at effect of oxidation on flattening behaviors of splats [9].
In-flight oxidation has been researched and modeled for the
thermal spray process by several groups [10 – 12].
This study is aimed at understanding the effect of
oxidation mechanisms in the formation of thermally sprayed
metallic coatings by studying the microstructures of Ni – 5
wt.% Al sprayed by different techniques such as Air Plasma
spraying (APS), Wire Arc Spraying and High velocity oxy-
fuel spraying (HVOF). Each process differs with respect to
its feedstock melting method, spraying gases and parameters
and hence oxidation involved during spraying. This paper
presents schematic models to describe the oxidation
phenomena that would result in the microstructures
observed experimentally in case of each process for the
same material.
2. Experimental methods
Ni – Al pre-alloyed powder and wire were chosen as a
model system for the comparative study across spraying
techniques. The characteristics of these materials are listed
in Table 1. Coatings were sprayed by different spraying
techniques as listed in Table 2. The spray parameters
involved in each process are specified in Tables 3– 5 [13].
The as-sprayed coatings were cut using a Buehler
ISOMET 2000 Precision Saw and a 15HC Diamond blade
and then mounted (infiltrated with Buehler EPO-THIN low
viscosity epoxy using vacuum impregnation). The polishing
was carried out on a Buehler ECOMET 3/AUTOMET 2
semiautomatic system using procedures outlined for thermal
sprayed metallic coatings in Technical notes published by
Buehler. These involve polishing on a 45 Am diamond grid
followed by cloth polishing with 9 and 3 Am diamond
suspensions and a final step of 0.05 Am alumina suspension.
The semi-automatic procedures helped to increase the
reproducibility of polishing cross-sections.
An FEG (LEO 1550) Scanning Electron Microscope
(SEM) was employed to obtain micrographs at different
magnifications. The procedure adopted for image acquis-
ition entailed a backscattered electron imaging mode for
higher contrast between pores, oxide areas and metal matrix.
Table 1
Characteristics of Ni – 5 wt.% Al raw powder and wire
Feedstock Manufacturer grade Description of feedstock
Ni – Al powder Sulzer Metco 4008 NS Spheroidal gas atomized
Ni – Al (wire) Sulzer Metco 8400 Alloy wire
Table 2
Thermal spray processes and equipments used for coatings
Thermal Spray process Spray equipment used
Twin Wire Arc Spraying Tafa Metco Smart Arc system
Atmospheric Plasma Plasma Technik F4 gun
Spraying (APS)
HVOF spraying Sulzer Metco Diamond Jet
(DJ-2700) torch
An accelerating voltage of 15– 25 kV, a working distance of
8 – 9 mm and an image size of 1024 * 1024 pixels was used
for getting quality images. Energy Dispersive X-ray
Spectroscopy (EDS) and X-ray mapping were employed
while imaging on SEM to obtain elemental composition at
different areas of the coating cross-section. Interfaces and
layers in the coating microstructure were seen in the low
magnification SEM images. High magnification SEM
images were taken to observe splat boundary coalescence.
TEM samples of coating cross-sections were prepared for
the Ni – 5 wt.% Al coatings sprayed by Wire Arc, APS and
HVOF processes. Dimpling and Tripod Polishing techni-
ques were employed for making thin samples and these
polished samples were ion milled to achieve electron
transparency. Transmission electron microscopy was carried
out by employing the Philips CM12 TEM, having the LaB6
filament. TEM bright field images as well as diffraction
patterns were obtained for the various areas in the samples.
Deposits were also evaluated for porosity content and
thermal conductivity. Image Analysis technique was
employed to measure porosity plus oxide content in the
coatings by converting the micrographs into binary images
and quantifying the percentage of dark areas in these
images. Surface connected porosity was measured by
mercury intrusion porosimetry (MIP) (Quantachrome Auto-
scan 33). Thermal conductivity measurements were carried
out on disk-shaped specimens, with 10 mm diameter, coated
with carbon using the laser flash technique (Holometrix
Laser Flash). Thermal conductivity is given by
k = q * Cp * diffusivity. Using 3 samples for each coating
and 5 runs per sample, an average value of thermal
conductivity was obtained.
3. Results and discussion
3.1. Porosity and oxidation
The main difference in metallic coating formation with
respect to ceramic coatings is the oxidation of metal
Composition Feedstock size
Ni – 5 wt.% Al 325 mesh, average 30 Am
Ni – 5 wt.% Al Gauge 14 (2 mm in diameter)
 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406 5397

Table 3
Twin Wire Arc spraying parameters for Ni – Al splats and deposits
Voltage Current Carrier Wire feed Torch Spray Substrate Particle Particle Particle
(V) (A) pressure rate traverse distance rotation temperature velocity size
(kPa) (in./min) speed (mm) speed (-C) (m/s) (Am)
(mm/s) (rpm)
28 250 350 100 42 200 stationary 2150 T 189 97 T 15 80a
a
From splats volume measurement with ZYGO surface profilometry [13].

particles that occurs at different stages of the coating
process. The oxide content in a coating depends on the
spraying technique and spraying parameters.
Fig. 1 displays cross-sectional SEM images of the
microstructures of Ni – 5 wt.% Al coatings sprayed by the
different spraying techniques.
Apparent from the images were dark areas, which
correspond to porosity and oxide formation. APS and Wire
Arc deposits were seen to be very porous with numerous
interlamellar pores. The HVOF process involves slightly
lower temperatures and higher particle velocities and as
such less oxidation or volatilization occurs. HVOF deposits
were seen to be very dense with very few interlamellar pores
compared to APS or Wire Arc.
In APS and Wire Arc deposits, Fhalf-penny_ shaped dark
areas, as marked in Fig. 3, were observed and these were
thought to be pores formed due to the expansion of trapped
air when the impacting particles were still molten [13].
However, SEM images of the same location in a coating
cross-section recorded by using the secondary electron
detector (giving topographic contrast due to higher depth of
field) and the backscattered electron detector (giving atomic
number contrast) could differentiate between porosity and
oxides as shown below in Fig. 2. Pores are associated with
some depth whereas oxides are in the same plane as the
remainder of the coating. This observation combined with
EDS results in Fig. 3 indicated that many of the big black
chunks and half-penny shaped areas were oxides.
Quantitative analysis and differentiation of these features
was possible by recourse to Mercury Intrusion Porosimetry
(MIP), Image Analysis and Energy Dispersive Spectrometry
(EDS).
An overall volume fraction of dark areas was obtained
using Image Analysis, as shown in Fig. 4 [14]. As shown in
the graph, both Wire Arc and APS produced coatings with
significant oxidation and porosity while HVOF displayed a
drastically lower value.
MIP then determined what percentage of these areas
corresponded to open porosity, also calculating the approx-
imate percentage due to oxide. The results for open porosity
and thermal conductivity of these coatings are tabulated
below in Table 6.
It was seen that thermal conductivity of the coatings is
higher in case of lower porosity content. However, it is
notable that the porosity in APS and Wire Arc coatings
being approximately same, there is a comparatively drastic
difference in thermal conductivity. This will be addressed
later in Section 3.6.
The mechanisms leading to development of these oxide
chunks and evolution of the overall microstructure is of
interest. The origin of these variations must depend on sub-
processes during spraying such as splat formation and
oxidation. There have been contradictory reports as to which
oxidation mechanism is dominant among the various
thermal spray processes (i.e. in-flight oxidation or post-
impact oxidation). For example, in case of powder fed
HVOF, the dominant mechanism of oxidation is splat
surface oxidation after impact but in case of wire fed
HVOF it is in-flight oxidation [15]. In order to understand
how these evolve and why differences exist in case of
different spray processes, it was considered necessary to
examine the microstructure in more detail at different length
scales.
3.2. In-flight oxidation
An oxidized particle likely to have resolidified without
forming the splat was observed in the deposit microstructure
of the Ni – 5 wt.% Al coating and is shown in Fig. 5. EDS
analysis was conducted at different spots on this particle. It
was seen that the oxide along the surface of the particle gave
Al – O peaks. Ni – O peaks were obtained from isolated areas
of oxides included in the particle. This particle suggests
oxidation to have occurred during its flight.
In-flight oxidation depends strongly upon the amount of
entrained air, particle temperature and nature and turbulence
of plasma flame. The quantity of air entrained in the HVOF
depends strongly upon the jet velocity and for plasma

Table 4
Plasma spraying parameters for Ni – Al splats and Deposits
Voltage Current Plasma Carrier Feed Torch Spray Substrate Particle Particle Particle
(V) (A) gas flow gas flow rate traverse distance rotation temperature velocity size
rate rate (g/min) speed (mm) speed (-C) (m/s) (Am)
(slpm)a (slpm) (mm/s) (rpm)
69 500 Ar: 50.5 H2: 8 Ar: 3 32 30 120 160 2340 7T 126 124 T 19 11 45
a
lpm: liter per minute.
5398 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406

Table 5
HVOF spraying parameters for Ni – Al splats and deposits
Pressure and flow rate Carrier gas Feed Torch Spray Substrate Particle Particle Particle
(O2, C3H6, Air) (kPa/slpm) and flow rate traverse distance rotation temperature velocity size
rate (N2) (g/min) speed (mm) speed (-C) (m/s) (Am)
(kPa/slpm) (mm/s) (rpm)
1050/164 700/83 735/500 1050/13.5 54 12 260 100 1980 T 167 614 T 111 11 45
SCFH: standard cubic foot per hour.

process, upon its velocity and viscosity [6]. In case of d.c.
plasma jets working with Ar – H2, the oxygen entrained in
the plasma core is almost instantaneously converted into
atomic oxygen of higher reactivity [6]. Thus the oxidation
conditions will be very different for HVOF and Air Plasma.
In case of Wire Arc and APS processes, the higher
particle temperature (Tables 3 and 4), entrainment of
surrounding air into the spray system and stronger gas
mixing give rise to significant oxidation. In the HVOF
process, however, the lower particle temperature (Table 5)
and decrease in volume fraction of liquid phase gives
reduced in-flight oxidation. The possibilities during in-flight
oxidation of particles are schematized in Fig. 6.
During in-flight oxidation a layer of oxide is formed
on the molten particle due to chemical reactions between
the surface of the liquid phase and oxygen or due to
diffusion of oxygen into the liquid. The turbulent mixing
of the liquid part of the powder particle during its flight
destroys the surface layer of oxides and causes the oxides
to be distributed more uniformly through the bulk volume
of the particle. But as the particle temperature starts to
drop, during the later part of the flight, these oxides start
to solidify and a thin oxide shell is formed around the
droplet.
It is proposed that in case of plasma spray, as the
particle velocity increases, this oxide also starts to
segregate toward the front end of the particle, as shown
in Fig. 6a, due to relative velocity effects between the
particle and the plasma velocities wherein, the liquid metal
is pushed back due to lower viscosity compared to the
oxide which gets pushed ahead. Apart from this, the high
radiation from segregated oxide areas causes cooling at the
front end of the particle. As such any liquid aluminum
oxide in the droplet also gets pushed from the hot region at
the back of the particle to the cooler front end as a result
of capillary flow.

10μm 10μm

a: Wire Arc coating - thicker splats b: APS coating - thinner splats

10μm

c: HVOF coating − very few visible splat boundaries

Fig. 1. Coating microstructures showing splats and splat boundaries.
 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406 5399

26
24 20.5
22

% (Porosity + Oxides)
20 16.5
18
16
14
12
10
8
6
4
3.1
2
0
(i) Wire-arc APS HVOF
(ii)
Fig. 4. Effect of spraying techniques on content of porosity and oxides.
Fig. 2. Dark phase in wire-arc deposit as seen by secondary electron
detector (i) and backscattered electron detector (ii). sufficiently melted particles. This is indicated by the average
particle temperature in Table 5.
Studies have been conducted where sprayed particles were Studies by Wan et al. [10] and Li and Li [11] have shown
collected using liquid nitrogen before they impacted onto that a decrease in particle radius leads to an increase in the
the substrate and formed splats, so as to examine them level of oxidation. Smaller particles have oxides distributed
microscopically and study the types and distribution of over the entire particle whereas with increase in particle
oxides formed. Volenik et al., Kotalik et al. and Li et al. size, it is found that the particle develops an oxide coating or
[16 –19] have presented evidence of the above mentioned shell. Thus, the oxidation of an in-flight particle proceeds
oxide shell formation for different plasma sprayed materials from particle surface towards the center. Oxide inclusions
such as nickel, alloy steels, iron and MCrAlY materials outlining the grain or splat boundaries have also been noted
respectively. by Wang et al. [12].
In case of HVOF spray, due to lower particle temper- The particle with more surface oxidation in Fig. 5 was
ature, the viscosity is higher and also the relative velocity observed in a Wire Arc sprayed deposit and it is very likely
between flame gas and particle is very low thus giving to form as suggested by Fig. 6a since Wire Arc droplets
internal oxides within particle and a thin oxide shell but no were large in size, 80 Am. In case of the Ni– Al coatings
segregation at the front end of the particle, shown in Fig. 6b. studied, HVOF coatings indicated that oxidation involved
This is plausible in the particular coatings examined because was different from that occurring in APS or Wire Arc
the HVOF spray parameters used in this study give rise to processes and showed less in-flight oxidation with mostly
internal oxides as in Fig. 6b.

3.3. Formation of first splat—effect of in-flight oxidation

In-flight particle temperature and local environment

are very different for different spray processes. Conse-
quently, in-flight oxidation of a molten metal droplet can
yield various entrained oxide morphologies within a
10 μm
deposit that further differ based on the spray process.
Here below the possible origins of each of the morphol-
ogies are discussed.
‘half-penny’ shaped The coating microstructure in Fig. 7a shows splats on top
of each other separated by alternating oxide layers. This
dark area
type of microstructure was seen in case of Wire Arc and
APS coatings. Due to higher particle temperature, entrain-

Table 6
Porosity and thermal conductivity of coatings
Spraying Porosity Thermal
process measured by conductivity
MIP (%) (W/m K)
APS 6.0 10.7
Wire Arc 5.7 17.0
Fig. 3. EDS analysis on dark areas in Wire Arc coating show Al and O
HVOF 2.0 22.2
peaks.
5400 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406

3 μm

a: Wire arc coating with oxide

1 μm layers and resolidified particle
b: Wire arc coating – oxides within 7000X
resolidified particle -30000X

Ni Ni Ni Ni
O

O
Al
Al Al

c: EDS patterns from different spots

Fig. 5. Oxidized particle within Wire Arc coating.

Void
Molten particle Internal Oxide, Molten particle
NiO
NiAl
Oxide, Al2O3
Void Oxide shell,
Al2O3
a: Particle with oxide shell on surface b: Particle with internal oxides
Fig. 6. Schematics for oxidation of particles in-flight.

20 μm 20 μm
APS coating [SEM image – 2000X] HVOF coating [SEM image – 2000X]

Al K

2 μm
OK

Ni L
2 μm 5 μm

a: Splats with splashed oxide beneath b: Splat with internal oxides

Fig. 7. Oxide distribution around splats in coating—effect of in-flight oxidation.
 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406 5401

Oxide from
oxidation during flight Oxide trapped inside splat

Substrate Substrate

Solidification begins Complete spreading of molten splat before

Splashed oxide solidification begins
a: Oxide shell splashing beneath splat b: Splat with internal oxides
Fig. 8. Schematic for formation of first splat—effect of in-flight oxidation.

ment of the surrounding air into the spray system and
stronger gas mixing in the vicinity of the in-flight particle,
these processes result in significant in-flight oxidation of the
molten metal particles.
A closer look at the micrograph in Fig. 7a reveals half-
penny shaped chunks of oxide that gave Al – O peaks
when EDS was carried out. They are assumed to originate
from the oxide shells formed on the droplet surface as
suggested in Fig. 6a. It is proposed that when the oxidized
molten particle with oxide segregation, as in case of APS,
reaches the substrate it starts to spread and the oxide layer
splashes underneath the metal splat since rapid solid-
ification also occurs upon impact [20]. This spreading and
splashing of the molten droplet is shown schematically in
Fig. 8a.
The coating microstructure in Fig. 7b does not show as
much fragmented oxide. Internal oxides trapped inside
splats are more apparent. This kind of splat structure was
observed in HVOF sprayed coatings where in-flight
oxidation is reduced. The higher particle velocities and
lower particle temperatures in flight lead to a decrease in the
volume fraction of melted phase thereby resulting in lower
amount of oxidation of coatings [6].
It is hypothesized that when a molten particle, such as
shown in Fig. 6b with well distributed internal oxides but no
significant oxide shell, as in case of the HVOF process,

Ni L

CK

Ni L

Al K
1 μm
CK
a: Oxide layer grown on top surface of 10 μm
splat (APS coating)
b: Al depleted region below oxidized area
Solidified Oxide growing
Solidified Splat of splat surface (HVOF coating)
oxide on top of splat Splat area
depleted of Al

Substrate

c: Oxide growing on top d: Al depletion region below growing

of splat oxide
Fig. 9. Post-impact oxidation on splat surface.
5402 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406
impacts the substrate, there is no oxide splashing below the
splat. The presence of dissolved oxygen in the solidifying
splat improves the splat substrate wetting, which in turn
influences flattening [21]. No localized solidification occurs
and the particles spread out very thinly with reduced
splashing as shown in Fig. 8b. The tiny oxides embedded
in solidified splats, Fig. 7b, are the oxide inclusions within
molten droplets.
3.4. Oxidation on splat surface after impact
The impinging gas jet can cause oxidation of splat
surface before the arrival of the new molten droplet. The
length of time for which post-impact oxidation occurs is
determined by the time lag between two successive splats
and this in turn depends on the powder feed rate, torch
traverse speed and deposition efficiency of the process [22].
Splats with a higher flattening ratio would have an increased
surface to volume ratio and would be more suitable for
oxidation. Higher initial splat temperature would accelerate
the kinetics of oxidation [23].
The microstructure in Fig. 9a was observed in case of an
APS coating. In case of APS, post-impact oxidation is quite
pronounced. Thin oxide layers formed on the top surfaces of
splats are seen in the microstructure, Fig. 9a and the
schematic depicting this process is shown in Fig. 9c.
2 μm
(a) SEM image
γ Al2O3 γ Al2O3
(111) (311)
γ Al2O3
(200)
Ni (020) Ni (220)
Ni (200)
100 nm
(c) TEM image of APS coating cross-
section shows alternate layers of Ni
grains and alumina bands
Fig. 10. Oxide layers separating consecutive splat layers in APS coating.
The HVOF microstructure as in Fig. 9b also showed thin
oxide bands but more interspersed within the coating. In
addition it also revealed light gray areas beneath these oxide
bands. In case of HVOF process, because of thin splats, the
increased surface to volume ratio is suitable for oxidation
but exposure time is reduced because of larger particle
velocities. This leads to a reduced number of instances of
oxide bands in a given thickness of coating. However,
presence of internal oxides in the splat liquid phase reduces
its thermal diffusivity and slows down solidification [24].
As such oxidation on the surface of the splat also results in
depletion of Al from the splat beneath and this appears as
the light gray area right below the oxide layer. This is shown
in the corresponding Fig. 9d.
The initial in-flight oxidation process as well as the
solidification rates involved in each thermal spray process
dictates this phenomenon. If the solidification time scale is
large as in case of HVOF process [24], then due to
nucleation delay, oxidation occurs while the top portion of
the splat is still liquid [25]. Thus macrosegregation will
cause the depletion of Al in layer below oxide bands. On the
other hand in APS/Wire Arc coatings the in-flight oxidation
is much more extensive because of longer dwell time in
flight and larger extent of melting as compared to HVOF
process. Hence these coatings are already devoid of Al to a
larger degree than HVOF coatings. This could be the reason
1 μm
(b) TEM image
 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406 5403

deposited splat, the kinetics of spreading, splashing and

100 nm
Fig. 11. Adjacent splats separated by oxide layer in Wire Arc coating.
why there is no elemental or phase contrast observed below
the oxide bands in APS or Wire Arc coatings.
3.5. Formation of consecutive splats—effect of post-impact
oxidation
Post-impact oxidation takes place, as seen above in
Section 3.4, at the upper surface of the solidifying splat,
which is exposed to the surrounding oxygen rich
atmosphere. When the new droplet impinges onto a pre-
flattening are quite different compared to the substrate.
The thermal resistance of the oxidized layer plays an
important role but the primary factor is wetting [26]. This
determines the nature of contact between the two
consecutive splats and dictates the solidification rate and
microstructure.
In case of APS coating microstructure, as seen using
SEM in Fig. 10a, in-flight oxidation of particles and splat
formation followed by post-impact oxidation gets man-
ifested into the microstructure in the form of layered oxide
bands separating consecutive splats. TEM images of the
APS coating showed splat layers with large grains, few of
which were columnar. However, almost every layer with
large grains was adjacent to thin layers which appeared
similar to white bands, as seen in Fig. 10b. These most
likely correspond to the layers that appeared black in the
SEM images and represent oxide layers separating splat
lamellae. Investigation of detail splat structure using TEM
revealed alternate layers of fcc Ni splats and alumina,
Fig. 10c.
The white banded layers due to oxidation were seen in
the Wire Arc coating as well, Fig. 11, but in fewer areas
along the coating thickness compared to the APS coating.
This is consistent with the thicker splats and lower number
of interfaces here than in the APS coating attributed to the
larger droplet size in case of Wire Arc as compared to the
powder size used in APS.

No peaks

1 μm

Al K

a: Void area
between new splat OK

and oxide on previous

2 μm
splat giving no EDS
peaks (APS coating) Ni L b: Inter- splat
contact in APS coatings

1 μm

Fig. 12. (a) Void area between new splat and oxide on previous splat giving no EDS peaks (APS coating). (b) Intersplat contact in APS coatings.
5404 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406

Coalescence between It is proposed that the higher wetting angle in case of

Void area between new two metal splats
metal splat and oxide
with no oxide in between.
of previous layer
Substrate
Interlamellar
Fig. 13. Formation of consecutive splat on oxidized and non-oxidized
regions of pre-deposited splat (APS process).
Void areas were observed just above such oxide bands in
APS or Wire Arc coatings, and these showed no peaks when
EDS analysis was carried out, Fig. 12a.
Fig. 12b displays that both Wire Arc and APS deposits
also showed occurrences of partially coalesced splat –splat
boundaries while in some areas successive splats were seen
to be separated by a lamellar pore.
When new molten droplets arrive and impact on the pre-
deposited splat, they either impact on an oxidized region or
on a metal splat area that is not oxidized. The spreading and
flattening of these droplets and their bonding to the previous
layer are dependent on the wetting angle [26].
molten metal impacting on the oxidized part leads to a void
between the new splat and oxidized portion of previous
splat. The molten droplet arriving onto the non-oxidized
area of the splat however is in complete contact with the
previous splat showing splat coalescence, most likely a
consequence of the under layer remelting upon the arrival of
a droplet or diffusive interaction between splats. There are
certain areas of poor contact where the interlamellar pores
are formed. These differences are schematized in Fig. 13.
The HVOF coating microstructure, on the other hand,
shows a much larger incidence of splat boundary coales-
cence with less discernible splat boundaries as seen in Fig.
14a. Thin strips of oxide are observed in fewer places as
opposed to large oxide ‘‘chunks’’ as seen in APS. Some tiny
oxides and/or pores are visible within the splats here too.
The HVOF coating splat structure when analyzed using
TEM also showed more instances of adjacent splats in
contact with each other and having coalesced boundaries as
in Fig. 14b.
In fewer places, like shown in Fig. 15a, these metal (Ni)
splats are separated by oxide (Al2O3) stringers that are very
thin.
In case of HVOF spray process, since the exposure time
of the previous splat is reduced, it then reduces oxidation

1 μm

a: HVOF coating with less

discernible splat boundaries and
fewer oxide layers (SEM image)

200 nm

b: TEM image of HVOF cross-section showing consecutive splats with coalesced boundaries
Fig. 14. (a) HVOF coating with less discernible splat boundaries and fewer oxide layers (SEM image). (b) TEM image of HVOF cross-section showing
consecutive splats with coalesced boundaries.
 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406 5405

γ Ni γ Ni
γ Ni (022) (111) γ Ni
(-400) (200)

γ Ni
(-111)
γ Ni γ Ni
NiO (-311) (-200)
(-2-20)

200 nm

a: Thin oxide layer between splats with columnar grains of Ni

2 μm

c: HVOF Splats spreading

completely on previous splats

b: Pores and Internal

junctions at splat boundaries

Fig. 15. (a) Thin oxide layer between splats with columnar grains of Ni. (b) Pores and internal junctions at splat boundaries. (c) HVOF splats spreading
completely on previous splats.

content. Very thin lines of oxide develop when formed at Thus the proposed schematics explain the development
intersplat boundaries in the coating. of the various microstructural differences discernible at
TEM study also showed that in some areas interlamellar different length scales, in the coatings sprayed by different
pores separated these splats and at some places there were processes.
connection points between splat layers (internal junctions),
Fig. 15b. 3.6. Effect on thermal conductivity
The new oncoming droplets during this process also have
reduced particle temperatures, lower viscosity and no oxide After this careful examination it is possible to explain
segregation as seen in Section 3.2. As such it is proposed the thermal conductivity discrepancy between APS and
that they spread without much splashing on the pre-
deposited splat and with improved contact with the previous
layer as shown by red arrows in Fig. 15c. Coalescence between two Contact area between new
Most areas illustrate splat – splat coalescence where metal splats metal splat and oxide of
there is metal – metal contact and even the droplet with no oxide in between previous layer
impacting onto the oxidized area of the splat shows better
contact because of high velocity impact, as schematized in
Fig. 16. In case of HVOF coatings, the amount of
oxidation is much lower and, as such, a greater number
of oncoming droplets are hypothesized to arrive onto non-
oxidized areas of pre-deposited splats thereby resulting in Interlamellar
more occurrences of splat coalescence as observed in the Fig. 16. Formation of consecutive splat on oxidized and non-oxidized
coating microstructure. regions of pre-deposited splat (HVOF processes).
5406 S. Deshpande et al. / Surface & Coatings Technology 200 (2006) 5395 – 5406
Wire Arc coatings noted in Section 3.1. APS coatings
have an oxide layer after almost every splat and the
number of interfaces in a given thickness of APS coating
is more than for a Wire Arc coating that has thicker
splats. This is bound to further reduce their thermal
conductivity with respect to Wire Arc because if this
oxide layer is Alumina then its thermal conductivity is
about 20 – 30 W/m K whereas the splat layers have grains
which are primarily fcc Nickel and the thermal con-
ductivity of Ni is about 91 W/m K. By the same token,
HVOF has very less oxidation at intersplat boundaries
and hence very high thermal conductivity. Also we have
seen how the presence of an oxide layer on top of a splat
causes a void area and lack of intersplat contact between
successive splats. Through thickness thermal conductivity
is controlled by the effective bonding area and void
morphology and thus this poor intersplat contact also
causes a reduction in thermal conductivity for APS
coatings.
4. Conclusions
This paper discusses the different oxidation mecha-
nisms involved in the formation of metallic coatings and
how they play a role in the microstructure evolution.
Oxidation occurring during spraying as well as after
impact affects the nature of splats and intersplat contact
and generates the microstructural divergence in these
coatings.
Schematic models were proposed for describing the
various probable mechanisms occurring in case of the
above studied Ni – 5 wt.%Al coatings sprayed by different
spraying techniques. These were in agreement with and
explained the microstructural details observed through
careful examination at all length scales.
In-flight oxidation can lead to an oxide shell on the
periphery of the particle, which splashes upon impact and
results in a coating microstructure with distributed chunks
of oxide as well as splats separated by oxide bands. Or
sometimes internal oxides in the particles are more
prominent and these in turn give rise to less fragmented
and more flattened disk shaped splats. Further post-impact
oxidation in each case once again gives rise to micro-
structural differences. Al depleted regions are observed
below the oxide bands only in some cases wherein the
solidification is slower and oxidation of top surface of
splat occurs in liquid state. The presence or absence of an
oxide layer on top surfaces of pre-deposited splats
determines the wetting angle between them and the newly
arriving molten droplets. This defines the extent of wetting
and hence the nature of the intersplat interface or the
splat – splat coalescence. This intersplat contact ultimately
affects the coating properties and performance.
Acknowledgements
We would like to thank Glenn Bancke and Jonathan
Gutleber (CTSR) for preparation of the specimens and
spraying diagnostics. The authors would also like to thank
Raphael Benary (Sulzer Metco) for preparation of speci-
mens. The MRSEC program of the National Science
Foundation under award number DMR 0080021 supported
this research.
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