Journal of Materials Processing Tech.

319 (2023) 118088

Contents lists available at ScienceDirect

Journal of Materials Processing Tech.

journal homepage: www.elsevier.com/locate/jmatprotec

Oxidation protection dynamics of NiAl droplet by inflight in-situ carbon

deoxidation during atmospheric plasma spraying for high performance
NiAl coatings
Li Zhang a, M. Mahrukh a, b, Di Wang a, Xian-Jin Liao a, Xiao-Tao Luo a, Chang-Jiu Li a, *
a
State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi’an Jiaotong University, Xi’an, Shannxi, PR China
b
Department of Mechanical Engineering, NED University of Engineering and Technology, Pakistan

A R T I C L E I N F O A B S T R A C T

Keywords: The oxidation of the metallic particles in plasma spraying leads to poor inter-lamellar bonding and thereby lower
Diamond corrosion and high temperature oxidation resistance. In this study, a novel approach is proposed to exclude the
NiAl coatings oxide of in-flight Ni-Al droplets by introducing diamond as a deoxidizer in Ni/Al powder during plasma spraying.
Atmospheric plasma spraying
NiAl coatings were deposited with Ni/Al/diamond composite powder prepared by mechanical alloying by at­
Oxidation
In-situ deoxidizing effect
mospheric plasma spraying at different spray distances to study the effect of the diamond addition on the
oxidation behavior of in-flight droplets. The results show that the oxygen content in APS NiAl coating (3.23 wt%)
was significantly reduced to 0.61 wt% by adding 2 wt% diamond to the Ni/Al powder. The measurement yields
particle temperatures of higher than 2200 ◦ C. Such high temperature contributes to the in-situ deoxidizing effect
of C-containing droplets, resulting in oxide-free NiAl droplets for the deposition of the coating with low oxide
content. This enhances both inter-lamellar cohesion and coating-substrate adhesion. Moreover, it was found that
the size effect of a molten droplet on its oxidation kinetics significantly influences deoxidizing efficiency. Smaller
particles require higher diamond content to ensure the in-flight deoxidizing to form oxide-free metal droplets.
The result was further confirmed theoretically by numerical simulation. The present work provides a new
approach to control the in-flight oxidation of metallic elements during plasma spraying, which has significant
implications for the preparation of high-performance protective metallic coatings.

1. Introduction and Baskaran et al. (2021) pointed out that both coatings can form a
protective Al2O3 layer on the surface when they are exposed to air at
Surface coatings with a high aluminum content such as nickel alu­ high temperatures.
minide coating are indispensable for oxidation protection of metal NiAl coatings are generally prepared by the thermal diffusion process
structures which are in service under high temperature environment. of Al into Ni-based alloys, such as pact cementation reported by Levin,
Gas turbines are one of those typical metal structures for power gener­ Caves (1974) and hot dipping in Al bath reported by Aghayar et al.
ation in which many components operate at high temperature. Thermal (2018). According to Davis (2001), diffusion aluminizing is a low-cost
barrier coatings (TBCs) are widely used in the hot-sections of gas-turbine process and has been applied to gas turbine blades since the early
engines to protect the superalloy components from oxidation during the 1950 s. However, it is performed at higher temperatures and is
thermal operating environments and improve the efficiency of the en­ time-consuming. Thus, besides aluminizing, many coating technologies
gines. TBCs usually consist of the ceramic top-coat and metal bond-coat have also been developed for the preparation of NiAl bond-coat, such as
on the superalloy substrate (Padture et al., 2002). As reported by Vassen electron beam physical vapor deposition (EB-PVD) mentioned by Gong
et al. (2022), the bond-coat is an oxidation resistant metallic coating et al. (2016) and thermal spraying reported by Ward et al. (2016), etc.
layer of high Al content and it directly determines the spallation failure Guo et al. (2023) and Li et al. (2021) found that the Ni-Al coating pre­
of the TBC. The typical bond-coat is either overlayer MCrAlY coating or pared by EB-PVD presents metallurgical bonding at the interface be­
thermal diffusion NiAl intermetallic-based coating. Culha et al. (2008) tween the coating and substrate. However, the preparation process of

* Corresponding author.
E-mail address: [email protected] (C.-J. Li).

https://doi.org/10.1016/j.jmatprotec.2023.118088
Received 4 April 2023; Received in revised form 25 May 2023; Accepted 14 July 2023
Available online 17 July 2023
0924-0136/© 2023 Elsevier B.V. All rights reserved.
L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

EB-PVD is usually complex, the coating is prepared in a vacuum and the Therefore, carbon can theoretically limit the oxidation of both Ni and Al
deposition efficiency is low. Therefore, this method is not recommended elements during plasma spraying. Taking into account that the Gibbs
for the preparation of coatings on the surface of large and complex free energy of CO formation decreases with the increase of the tem­
components. In contrast, thermal spraying has the advantages of being perature and the Gibbs free energy of all oxides increases with the in­
versatile, low cost and simple process, etc. Therefore, it has been widely crease of the temperature, using carbon as a deoxidizer could be more
utilized to deposit Ni-Al intermetallic coatings to protect critical com­ universal for generating oxide-free molten metal droplets in ambient
ponents from oxidation and corrosion. atmosphere.
Among various thermal spray techniques, atmospheric plasma Accordingly, a novel approach was proposed to achieve oxide-free
spraying (APS) is widely used to prepare metal coatings due to its cost- molten metal droplets using NiAl as typical material by using carbon
effectiveness and high deposition rate. Guo et al. (2023) indicated that as the deoxidizer added into Ni/Al powder during APS for the deposition
conventional APS coatings present a typical lamellar structure. The of high-performance NiAl coating. The Ni/Al composite powders were
coating/substrate interface bonding and inter-splat interface bonding prepared by ball milling with adding the diamond as the carbon source.
within the coating significantly affect the properties of the coatings. The NiAl coatings were deposited at the preliminarily optimized plasma
Therefore, improving the adhesion and cohesion of the coating is spray conditions. The deoxidation kinetics of carbon during in-flight of
essential to fulfilling the application requirements of thermal spray NiAl molten droplets were examined experimentally through the effect
coatings. According to Zhao et al. (2019), NiAl particles are always of spray distance on the oxygen content, carbon content, and micro­
severely oxidized due to the high temperature and oxygen-rich envi­ structure of the coatings along with measured particle temperature, and
ronment during APS. Alcala et al. (2001) and Neiser et al. (1998) particle size effect on the oxide inclusions in a splat. Moreover, the
considered that metal oxides can improve the wear resistance or deoxidation kinetics were also examined theoretically by numerical
compressive strength of the materials in some cases. However, in most simulation model and the results were compared with experimental
cases, their high brittleness and the difference in thermal expansion data.
coefficients with the surrounding metal will result in a weak coat­
ing/substrate interface bonding and interlayer bonding. Therefore, the 2. Experimental procedures
deposition of NiAl coating by APS is more challenging. The result of
Galedari et al. (2019) showed that the high oxide content caused by high 2.1. Preparation of powders
temperature spraying will reduce the ability to form a continuous pro­
tective Al2O3 layer against corrosion and oxidation in their service In this study, the Ni/Al and Ni/Al/diamond composite powders were
period, subsequently leading to the delamination and peeling of the prepared by the high-energy ball milling process. Commercial electro­
coating under service conditions, and deteriorating the lytic Ni powder (99.9 wt%, − 50 µm, Xingrongyuan Ltd, Beijing, China),
oxidation-resistance performance of NiAl bond coat. Due to these Al powder (99.9 wt%, − 50 µm, Quanxin Materials Ltd, Sichuan, China),
drawbacks, APS is generally not considered suitable for spray Ni-Al and diamond powder (99.9 wt%, 1–2 µm, Deke Ltd, Beijing, China) were
coatings. Orban et al. (2007) found that injecting high purity argon used as the raw materials. Ni and Al powders without diamond or with a
around the plasma jet could reduce the oxidation of Ni-Al coatings. Chen diamond content of 2 wt% were respectively pre-mixed by putting them
et al. (1993) proposed limiting the oxidation of coatings by vacuum into container and running the drum mixer for 2 h to ensure the raw
plasma spraying and found that the Ni-Al coatings formed by vacuum powders are fully mixed. The powder mixtures were then mixed with
plasma spraying were very dense and essentially free of oxides. These stainless balls of 6 mm at a ball-to-powder charge mass ratio of 10:1 and
methods prevent contact of the molten particles with the air by creating loaded into the ball milling canister. The canister was evacuated and
an inert environment around the plasma flame. However, vacuum filled with argon gas to avoid the oxidation of the powders. Finally, the
plasma spraying is costly, and shrouded plasma spraying is a complex mixtures were milled in a planetary ball mill (YXQM-20 L) at a rotation
process, which limits the application of NiAl coating in industries. speed of 180 rpm for 5 h. During the ball milling process of Ni/Al
Si, B, and C have a strong affinity for oxygen, and they can be used as composite powder, to avoid the limitation of powder fragmentation and
de-oxidants because these elements are preferred to react with oxygen cold welding caused by the powder adhere on the inner wall of the
compared with many alloying elements such as Fe-based and Ni-based milling container, the milling was interrupted for every 2 h to remove
alloys to form slag, as reported by Sun, Pehlke (1996) and Grigorescu the adhered powder particles. Before each ball milling, the canister was
et al. (1995). As a result, Zeng et al. (2009) reported that the Ni-based re-evacuated and re-filled with argon gas. To prevent an exothermic
self-fluxing alloy coating with low oxygen content can be formed by reaction between Ni and Al caused by excessive temperature rise within
plasma spraying due to the sacrificial oxidation of Si and B, and subse­ the milling canister, the milling process was suspended for 0.5 h to cool
quent evaporation of Si and B oxides. Recently, inspired by the above the canister after the powders were milled for 1 h. The Ni/Al and Ni/Al/
findings, our research group has also demonstrated that for NiCr, 2 wt%diamond composite powders were referred to as A powder and B
NiCrCu, and NiCu coatings, the oxide formation in an in-flight droplet powder, respectively.
during APS could be suppressed by the addition of B element along with
controlling of deoxidizing kinetics, and consequently, the porosity of the 2.2. Deposition of the coatings and splats
coating was reduced and the adhesion to the substrate was improved, as
reported by Dong et al. (2021), Ren et al. (2022) and Sun et al. (2021), In this study, the coatings were prepared by APS with Ar-H2 as
respectively. However, B addition is not applicable to Al-containing al­ plasma gases. The coatings were deposited on the GH4202 substrate
loys such as NiAl since the affinity of Al for oxygen is higher than that of with its surface blasted by alumina grits before spraying. The APS pa­
boron. Thus, no investigation on the de-oxidation effect of sacrificial rameters used are listed in Table 1. To ensure the effective heating of
elements on the Ni-Al coatings was reported yet according to our powder particles, an internal injector for powder feeding was adopted.
knowledge as an example of typical Al-containing coating materials. It is The coatings were deposited at different spray distances of 70 mm, 80
necessary to develop an effective approach that is more universal for mm, 110 mm, and 140 mm to examine the in-flight deoxidizing behavior
different materials. Although the result that deoxidizer fully protects the of diamond-containing NiAl particles and critical carbon content for
alloy elements from oxidation is explained in our previous papers (Dong high-temperature droplet oxidation protection. All those coatings were
et al., 2021), the detailed kinetics of deoxidation is still needed to clarify. referred to as NA2DX with the last number X indicating the spray dis­
According to the Gibbs free energy of oxides, the Gibbs energy of CO tance as shown in Table 1. For comparison, NiAl coating was also
formation through the reaction of carbon and oxygen becomes lower deposited using A powder without diamond addition, referred to as NA.
than that of Al2O3 when the particle temperature is higher than 2007 ◦ C. Furthermore, NiAl splats were deposited on polished GH4202 substrate

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

Table 1 flame jet and internal circulations are formed due to the surface shear
The detailed parameters for plasma sprayed coatings. stresses as shown schematically in Fig. 1. Us is the droplet surface ve­
Materials Spray parameters locity and U∞ is the plasma gas velocity. To capture the droplet dy­
namics in the domain, the VOF model is coupled with the Eulerian
Arc power Ar H2 Spray distance Coatings
(kW) (SLPM) (SLPM)) (mm) continuum model with the description of Hill’s vortex formation inside
A powder 46 45 6 80 NA the fully molten metal droplet. The internal circulations are considered
B powder 70 NA2D1 in the solver with the application of the set of governing equations
80 NA2D2 presented by Chen et al. (2011), Wang et al. (2017) and Shan and Hu
110 NA2D3
140 NA2D4
(2012). All governing equations for the two-dimensional model in the
cartesian tensor form are shown below. They are fully explained in
ANSYS Fluent Theory Guide (ANSYS, Inc, 2020) and are not repeated
at the spray distance of 80 mm, 110 mm, and 140 mm to reveal the here for brevity.
influence of diamond addition and spray particle size on the oxidation The continuity equation:
behavior of in-flight Ni-Al particles. The substrate was preheated to
∂ρ
200 ◦ C during splat deposition to obtain regular disk splats by removing + ∇ • (ρV) = 0 (1)
∂t
surface adsorbates. The other spraying parameters for the splats were
the same as for coating preparation in Table 1. The momentum equation:
∂ ( )]
2.3. Characterization of the powders and coatings (ρV) + ∇ • (ρVV) = − ∇p + ∇ • [μ ∇V + (∇V)T (2)
∂t

The morphologies and microstructure of the powders, splats, and The energy equation:
cross-sectional microstructure of the coatings were characterized by ∂
scanning electron microscope (SEM, MIRA 3 LMH, TESCAN). An (ρH) + V • ∇(ρH) = ∇ • (k∇T) + Sv (3)
∂t
attached EDS to SEM was used to analyze the elemental composition of
The species transport equation:
the coatings and splats. X-ray diffraction (XRD, D8 ADVANCE) was
utilized to identify the phase structure of the coatings. The oxygen ∂Yi
+ ∇ • (VYi ) = ∇ • (Di ∇Yi ) + Ri (4)
content of the coatings was measured directly using free-standing ∂t
coating by oxygen, nitrogen, and hydrogen analyzer (ELEMENTARC
The operating parameters along with the schematic representation of
ONH-p). The carbon contents of the powders and coatings were
the computational domain are shown in Fig. 2a and Table 2. The total
measured by carbon-sulfur analyzer (CS-520). The in-flight oxide con­
inlet radius of the control domain is H∞ = 2dp , with length L∞ = 10dp
tents of the coatings were estimated through image analyzing using SEM
(as shown in Fig. 2a). The domain geometry considered in the numerical
images of polished cross-sections of coatings, and then the oxide con­
simulations is 2D axisymmetric. The mesh consisted of 53 350 numbers
tents were converted to oxygen contents. The coating tensile adhesion
of nodes, and it is very fine inside the droplet and around the near re­
test was performed by the widely used ASTM C633–79 standard. The
gions of a droplet (Fig. 2b). The plasma gas axially gets into a domain
samples were mounted in a universal INSTRON1195 testing machine
with specified U∞ and T∞ , and the resulting gases move across the
with a self-aligning fixture and conducted at a speed of 0.5 mm/min
droplet surface and flow out axially through pressure outlet sections.
until the coating failed. The particle surface temperature during in-flight
The initial plasma-gas velocity (U∞ ), plasma-gas temperature (T∞ ), and
was measured by a commercial thermal spray particle property diag­
specified mass fraction of O2 (Cos = Co∞ ) are set up as per the varied
nostic system (DPV-2000, Tecnar Automation Ltd, Canada) against
spray distance (Table 2) for each set of numerical simulations. These
spray distance.
initial values with the droplet temperature-dependent material proper­
ties including specific heat capacity (Cp), specific enthalpy, specific
2.4. Numerical simulation computational modeling entropy, density (ρ), surface tension (σ), and viscosity (μ) are used in the
solver with the user-defined function (UDF) to numerically simulate the
Volume-of-Fluid (VOF) model from Ansys-Fluent software is used to droplet dynamics. The detailed results analysis is presented in Section 4.
estimate the oxygen absorption and deoxidizing kinetics of the in-flight
particles with different sizes during plasma spraying. Modeling of par­
ticle internal dynamics in the APS process involves the coupling of the
plasma flame jet dynamics with the droplet/particle dynamics.
In this work, the particles are considered to be fully molten droplets
at a spray distance of 50 mm. The molten droplets move into the APS

Fig. 1. The schematic representation of droplet in plasma streams, and droplet internal circulation velocity components in polar coordinate system.

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

Fig. 2. Schematic representation of the geometric domain (a), and zoomed section of grid generated inside and around the fully molten droplet with the boundary
conditions (b).

3.2. In-flight oxidation control for NA coating by preferential carbon

Table 2
oxidation
The Initial Conditions inside the control domain.
Spray Distances, Domain-inlet Velocity, Domain-inlet Temperature 3.2.1. NA coating microstructure features
mm (U∞ ), m/s (T∞ ), K
Fig. 4 shows the cross-sectional backscattered electron images of the
50 200 4154 NA coating. A typical lamellar structure can be observed, indicating that
60 180 3615 the melting of spray particles is sufficient. Combining the SEM picture
70 170 3230
80 160 2938
with the EDS analysis results (Table 3), the NA coating mainly consists of
90 150 2692 Ni3Al and NiAl phases which appear in the light gray and gray contrasts
100 140 2400 on the image, respectively. In addition, a large amount of oxides in a
110 120 2350 black contrast were observed in the NA coating. This is because the fluid
120 110 2300
dynamic effects cause a vortex within the in-flight Ni-Al droplets, and
130 105 2200
140 100 2100 the fresh surface of Ni-Al droplets is continually exposed to air, leading
to the continuous oxidation reaction of the molten Ni-Al droplets with
air and subsequently high oxide content in the NA coating. EDS results
3. Results show that the oxide in NA coating presents a high proportion of O
element with an O/Al atomic ratio of 59.77/37.97, which is close to
3.1. Microstructure of A and B powders Al2O3. The measurement yielded an oxygen content of 3.23 wt% for NA
coating. According to Javadi et al. (2011), the oxides will reduce the
The surface morphology and cross-sectional microstructure of A and coating adhesion by limiting particle interface bonding in the NiAl
B powders are shown in Fig. 3. These powders present a nearly spherical coating.
shape and the powder particles in a size range of 30–50 µm were
selected for the experiment. As seen from the cross-sectional micro­ 3.2.2. Thermodynamics of the deoxidization for Ni-Al molten particle by
structure, Ni and Al particles were well flattened and cold-welded to carbon
form A and B powders with a fine lamellar structure. Besides, the dia­ Fig. 5 shows the Gibbs free energy of the formation of Al2O3, NiO,
mond particles were uniformly distributed within the powders (Fig. 3b). and CO. The formation of CO yields a lower Gibbs free energy than that
The measured carbon content of B powder was 2.03 wt%, which is of both Al2O3 and NiO when the temperature becomes higher than
approximately the same as that of the initially added diamond. The 2007 ◦ C. This means that when carbon-containing Ni-Al particles with a
measured oxygen contents of A and B powders were 1.21 wt% and particle temperature higher than 2007 ◦ C are exposed to air, carbon will
0.83 wt%, respectively, which are maintained at a low level because the be oxidized preferentially. Most of the oxygen surrounding in-flight
ball milling process was carried out in an argon atmosphere. droplets can be consumed to form volatile CO during plasma spraying,
which will promisingly suppress the oxidation of Ni and Al in particles.
Fig. 6 shows the mean temperatures of Ni-Al particles against spray
distance generated using the plasma spray parameters shown in Table 1.
It was observed that B powder particles reached a mean temperature of

Fig. 3. The surface morphology and cross-sectional microstructure of the A (a) and B powders (b).

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

Fig. 4. Cross-sectional backscattered electron images of NA coating.

of Al is 2467 ◦ C. Besides, particle temperature tended to decrease with

Table 3
the increase in the spray distance. However, the particle temperature
Elements percentage in different regions of coatings in Fig. 4b.
was still higher than 2007 ◦ C even at a spray distance of 140 mm,
Regions color Ni/at% Al/at% O/at% indicating that most particle temperatures fulfilled the requirement for
Light gray 72.03 27.97 - in-situ deoxidation temperature of carbon. Therefore, it is theoretically
Gray 46.04 53.96 - possible to realize the in-situ in-flight deoxidizing during plasma
Black 2.26 37.97 59.77
spraying of carbon-containing NiAl particles.

3.2.3. Effect of carbon addition on the microstructure features of APS NA

coatings
Fig. 7 shows XRD patterns of the NA2D coatings. It revealed that the
coatings were composed of NiAl and Ni3Al intermetallic compounds. No
diffraction peaks of oxides were present in the coatings. However, it can
be observed from XRD patterns that the content of NiAl phase in the
coating decreases, and Ni3Al phase increases with the increase of the
spray distance. The NiAl phase content in the coatings was calculated
based on XRD data by the K-value method, it was found that the NiAl
phase content in the coating reduced from 87.9% to 70.6% when the
spray distance was increased from 70 mm to 140 mm. It can be attrib­
uted to the evaporation and oxidation of Al element leading to the de­
viation of the Ni/Al atomic ratio from the stoichiometry for NiAl in the
starting powder.
Fig. 8 shows the cross-sectional backscattered electron images of the
NA2D coatings deposited at different spray distances. It can be observed
that there are mainly three distinct regions with different contrasts
Fig. 5. Gibbs free energy for different reactions at different temperatures.
including light gray, gray and black in the coatings. Combining with the
EDS results in Table 4, the light gray and gray regions correspond to
Ni3Al and NiAl phases, respectively, while the black regions are oxide in
the coatings. Comparing the NA coating shown in Fig. 4 with those in
Fig. 8a and b, it can be seen that the oxides in the coatings were
significantly reduced and the coating presents a dense microstructure

Fig. 6. The mean surface temperatures of molten droplets at different

spray distances.

2338 ◦ C at the spray distance of 80 mm. Taking into account the fact
that intensive Al evaporation is endothermic during in-flight, some B
particles achieved nearly the highest temperature since the boiling point Fig. 7. XRD patterns of the NA2D coatings.

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

Fig. 8. Cross-sectional backscattered electron images of the NA2D coatings deposited at different spray distances: 70 mm (a); 80 mm (b); 110 mm (c) and
140 mm (d).

Table 4
Elements percentage in different regions of the coatings in Fig. 8.
Regions color Ni/at% Al/at% O/at%

Black 1 3.10 34.75 62.15

Gray 50.60 49.40 -
Light gray 74.50 25.50 -
Black 2 4.77 34.19 61.04

with few pores when 2 wt% diamond was added to A powder. It can be
attributed to the in-situ deoxidizing effect of high-temperature carbon-
containing droplets. The examination of the microstructure reveals that
small amounts of the crescent and nearly spherical oxides could be
observed in the NA2D1 and NA2D2 coatings. These tiny oxides are
attributed to the in-flight oxidation of smaller droplets due to deoxidizer
depletion on the droplet surface. When spray distance was increased to
110 mm and 140 mm, a thin oxide layer also appeared at the periphery
of some splats in addition to internal tiny oxides. Therefore, it can be Fig. 9. Oxygen content of the as-sprayed coatings and the oxygen content from
considered that the deoxidization of in-flight NiAl molten droplets took in-flight oxidation in the coatings.
place effectively by carbon at the spray distance up to 80 mm. Al
oxidation in in-flight droplets was well suppressed to form dense coat­ particles less than 50 µm are used, the in-flight oxidation dominates the
ings with much lower oxygen content. However, when spray distance oxygen content in the coating. It can be recognized that the in-flight
was further increased, the in-flight oxidation became gradually inten­ oxidation-induced oxygen content presents the same trend as the total
sive, leading to increasing oxide inclusions in the coatings. oxygen content in the coating with increasing spray distance. The dif­
ference in the total oxygen content from in-flight-oxygen-induced con­
3.2.4. Effect of carbon addition on the oxygen content of APS NiAl coatings tent represents the post-deposition oxidation-induced oxygen. The
Fig. 9 shows the oxygen contents in the NA2D coatings in comparison post-deposition oxidation depends mainly on the surface temperature
with those resulting from in-flight oxidation. At a spray distance of of the substrate or the deposited coating during spraying. Generally, the
80 mm, compared with the oxygen content of 3.23 wt% for the NA heat input from the plasma jet to the substrate and subsequently sub­
coating resulting from severe oxidation of the metal elements during in- strate surface temperature are reduced with increasing spray distance.
flight, the oxygen contents in NA2D2 coatings were significantly Therefore, the post-deposition oxidation-induced oxygen content tends
reduced to 0.61 wt%. However, the oxygen contents of the coatings to decrease with increasing spray distance and is less than 0.3 wt% in the
increased from 0.61 wt% to 1.91 wt% when the spray distance was present NiAl coatings. This result is consistent with that reported by
increased from 80 mm to 140 mm. According to Li et al. (2022), the Haskett and Settles (1994) for HVOF coatings. The fact that the oxygen
oxidation of metal elements during thermal spraying occurs in two content of the NA2D coating increases from 80 mm to 140 mm indicates
stages, in-flight oxidation and post-deposition oxidation. When small

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

that the in-flight oxidation still progressively occurred during the Adding diamond to A powder reduces the in-flight oxidation of molten
spraying of Ni-Al/2 wt%diamond particles. This fact can be attributed to droplets and subsequently the oxide content in the coatings and conse­
the reduced carbon content in NiAl droplets to a level lower than that is quently improving the inter-lamellar bonding. It was observed the
required for full protection of alloying elements in the droplet from microhardness of the NA2D coatings decreased with the increase in
oxidation. spraying distance. However, the NA2D1 coating exhibited the lowest
microhardness of 294 HV even though the oxidation of alloying ele­
3.2.5. Effect of spray distance on carbon content in the APS NA2D coatings ments during in-flight was suppressed. According to Xu et al. (2002),
The above result clearly showed that the in-flight deoxidization by The graphitization temperature of diamond is about 670 ◦ C, which is
carbon takes place effectively for C-containing NiAl droplets at the spray much lower than in-flight particle temperature during spraying. It im­
distance of up to 80 mm. However, this effect is decreased with droplets plies that the diamond is converted into graphite during spraying. The
flying to a further long distance. Fig. 10 shows the change in the carbon fact that the addition of graphite will reduce the mechanical properties
content in NA2D coatings with the spray distance. It can be seen that the of NiAl alloy has been demonstrated by Prakash and Pool (1981) and Hu
carbon content in Ni-Al droplets gradually decreased with increasing et al. (2014). Therefore, the microhardness of the NA2D1 coating is low
spray distance due to the consumption of carbon during spraying. As the due to the high carbon content. Fig. 11b shows the adhesive strength of
spray distance increased from 70 mm to 140 mm, the carbon content of the NA and NA2D coatings. NA coatings exhibit a minimum adhesive
Ni-Al droplets was reduced from 1.03 wt% to 0.16 wt%. Ren et al. strength of 30.7 MPa. The adhesive strength of NA2D2 coating has
(2022) have shown that there exists a critical deoxidizer content for significantly increased compared with NA coating, from 30.7 MPa to
effective deoxidization of the in-flight molten droplet when boron is 54.9 MPa. This is because the limited oxides within the coating improve
used as a deoxidizer. When the deoxidizer content in the droplet be­ the inter-lamellar interactions and lamellar-substrate interactions. The
comes less than the critical content, the other alloying elements will be adhesive strength of the coating decreased with increasing spray dis­
subjected to oxidation since full protection of alloying elements from tance, decreasing to 42.1 MPa and 38.3 MPa for NA2D3 and NA2D4
oxidation becomes a failure. According to Dong et al. (2021), Ren et al. coatings, respectively. This decrease in adhesive strength can be
(2022) and Sun et al. (2021), the critical boron content for full protec­ attributed to the high content of oxides.
tion of molten NiCr, NiCrCu, and NiCu droplets is about 0.5 wt%.
Therefore, the protective ability of carbon may be effective only in a 4. Discussion
limited spray distance range for Ni-Al molten droplets with 2 wt%dia­
mond in the starting powder, as the spray distance increases, the carbon 4.1. Particle size effect on in-flight in-situ deoxidation during APS of Ni-
is consumed rapidly and it is not enough to protect the in-flight molten Al/2 wt%diamond particles
droplets from oxidation. Taking into account the chemical and physical
properties of boron and carbon for the removal of active oxygen sur­ The present results demonstrated that adding 2%C can considerably
rounding in-flight particles, it can be inferred that the critical carbon suppress the in-flight oxidation of Al and Ni elements during APS and
content for effective deoxidation should be about 0.83 wt%. Therefore, deposit the dense coatings. However, there were still a small amount of
when the spray distance is larger than 80 mm, in-flight oxidation begins oxides present in the coatings. Li et al. (2022) showed that spray particle
to occur, and subsequently, the oxygen content of the coating increases size significantly affects the oxidation rate, resulting in a high oxygen
with increasing spray distance. content in the coatings deposited with smaller particles than with larger
particles. Therefore, to clarify the in-flight oxidation behavior of Ni-Al
particles and particle size effect, the structural and chemical features
3.3. Microhardness and adhesive strength of the coatings
of the NiAl splats of different sizes deposited at different spray distances
were examined. Fig. 12 shows the morphology of typical splats depos­
Fig. 11a shows the microhardness of NA and NA2D coatings. The
ited on GH4202 substrate at different spray distances. All splats present
microhardness of the NA coating is 280 HV, which is comparable to the
a disk-shape with similar morphology to those reported by Pandey et al.
hardness of plasma-sprayed NiAl coatings reported by Chen et al. (1993)
(2020). The splats in different diameters observed at a certain spray
and Starosta (2009). Compared with NA coating, the microhardness of
distance are due to spray particle size distribution in a range from 30 to
NAD2 coating increased from 280 HV to 458 HV. The low hardness of
50 µm. Some inclusions in a dark grey contrast were distributed on the
NA coating can be attributed to its high oxygen content, which leads to
splats surface. The EDS point analysis revealed that those inclusions are
the inclusion of oxide at the lamellar interfaces. These oxide inclusions
Al2O3 as shown by the compositions of those typical regions in Table 5
degrade the formation of metallurgical bonding at splat interface.
for the marked points 1 and 2 in Fig. 12e and i. The morphology of oxide
on the splat surface changes with spray distance and splat size and their
typical features will be explained as follows. At a distance of 80 mm,
only tiny small near-circular oxides were observed only on small splat
surfaces. For splats with a diameter larger than 60 µm, no oxide was
present on their surfaces. This fact indicates that the in-flight oxidation
of Ni and Al elements in the large Ni-Al droplets is effectively suppressed
by the introduction of carbon. The previous investigation revealed that
when spray particle size is reduced from 50 µm to 30 µm, the oxygen
content may be increased by a factor of 10. Correspondingly, the
deoxidizer consumption also changes significantly with spray particle
size. The measurement by confocal laser microscopy yielded the sizes of
molten droplets corresponding to deposited splats shown in Fig. 12
(Table 6). Owing to the evaporation of Al during spraying, the droplet
size became smaller by about 10 µm in diameter than starting nominal
particle size. Supposing that a mean carbon content of 0.62 wt% at a
spray distance of 80 mm corresponds to the spray particles of mean
particle size of 30 µm, the carbon content in smaller particles is lower
Fig. 10. Change of the carbon content in NA2D coatings with the than 0.62 wt%. Meanwhile, no oxide was observed on the splat b which
spray distance. was deposited by the droplet of a diameter of 36.5 µm. It can be

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

Fig. 11. Microhardness (a) and adhesive strength (b) of the NA and NA2D coatings.

Fig. 12. Splat morphology deposited at different spray distances: 80 mm (a, b, c), 110 mm (d, e, f), and 140 mm (g, h, i).

supposed that the carbon content in such a droplet was near the critical
Table 5
carbon content of 0.83 wt%. It could be reasonable by taking into ac­
Elements percentage in different regions of coatings in Fig. 12e and i.
count that the deviation of the tested carbon contents was about 0.07 wt
Regions Ni/at% Al/at% O/at% %. Thus, the Al oxidation occurred during in-flight to the droplets
Point 1 2.93 38.30 58.77 smaller than 36.5 µm. As a result, even at a spray distance of 80 mm, the
Point 2 4.43 35.55 60.02 oxide appeared on the splat a3 which was deposited by a droplet of
21.4 µm as shown in Fig. 12 c.
For the droplets with a diameter of about 40 µm, the in-flight

Table 6
The size of droplets depositing splats in Fig. 12.
Splat a b c d e f g h i

Droplet size (μm) 41.5 36.5 21.4 42.5 37.3 21.6 47.6 38.3 21.1

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

oxidation of carbon with droplet further flying leads to a reduction of the Fig. 14 shows the evolution of the remaining carbon content in the
carbon content to a level lower than the critical one. Subsequently, coatings and in-flight droplets, as well as the cumulative generated CO
besides the oxidation of carbon, the oxidation of Al became gradually content during the droplet flight. Fig. 14a indicates that the experi­
intensive. Consequently, the Al oxides are present on the surface of mental result of the carbon content in the coatings is consistent with the
splats deposited at the spray distance of 110 mm and further far. The simulation result, proving the credibility of the simulation result. For all
oxides on the surface of the large splat deposited at a spray distance of NiAl particles with the same initial carbon content, the carbon content
110 mm present a nearly circular shape with a size of 5–10 µm decreases with increasing spray distance (Fig. 14a). Correspondingly,
(Fig. 12d). When the spray distance was increased to 140 mm, a large the accumulated CO content generated by the reaction gradually in­
flake of oxides was observed at the periphery of the splat in addition to creases (Fig. 14b), indicating that the carbon is constantly consumed
small circular oxides (Fig. 12g). For the small droplet less than 30 µm in during plasma spraying to protect the Ni and Al elements from oxida­
diameter, say about 21 µm in Fig. 12f and i, more intensive oxidation of tion. However, it can be observed that the carbon content in the 30 µm
Al resulted in high content of Al oxide. This is because more carbon is and 40 µm droplets decreases faster and more CO is formed from the
consumed resulting in carbon content that may be already much lower reaction during the flight compared to the 50 µm droplets. This is
than the critical level at an early stage of inflight. Consequently, the attributed to the higher oxygen uptake of smaller droplets as explained
oxide scale coverage over splat increased with increasing spray distance earlier. Moreover, at a spray distance of 80 mm, the simulation results
as can be seen from splats of a similar size in Fig. 12c, f, and i. At the show that the carbon content in 30 µm droplet is already reduced to
spray distance of 140 mm, carbon in small droplets could have been 0.61 wt%, while the carbon content in 40 and 50 µm droplets becomes
depleted and therefore the oxide scale covered all splat surface. Such 0.68 wt% and 0.95 wt%, respectively. This result reveals that the critical
oxide scale appeared in the coating at the splat interfaces as observed in carbon content to maintain sacrificial deoxidation of carbon for NiAl
Fig. 8d. These results revealed that the spray particle size significantly droplet is consistent with the proposed value of 0.83 wt%. Therefore, at
influences the consumption of deoxidizer carbon and thus the protective a spray distance of 80 mm, the carbon content in a fraction of droplets is
effect of alloy elements from in-flight oxidation. less than the critical carbon content of 0.83 wt% for high-temperature
droplet oxidation protection. This means that some of the oxygen up­
takes in in-flight droplets react with metallic elements to form oxides. As
4.2. Numerical simulation of the effect of particle size on oxygen
the spray distance increased to 130 mm, the 30 µm droplet has almost
absorption and deoxidizing kinetics of carbon
no carbon source for oxidation protection, and only 0.09 wt% carbon
remains. Therefore, at a spray distance of 140 mm, the surface of small
To theoretically validate this effect, numerical simulations were
splat was almost completely covered by oxide scales (Fig. 12i). The
further used to estimate the oxygen absorption and deoxidizing kinetics
carbon content of > 0.82 wt% in the 50 µm droplets, which is the critical
of the in-flight particles with different sizes of B powder. Fig. 13 shows
carbon content to protect alloying elements from oxidation, is constantly
the cumulative oxygen uptake of different size droplets for reaction with
maintained until a spray distance of 90 mm. Nevertheless, as the spray
the spray distance. It is observed that the oxygen uptake increases with
distance increases to 140 mm, the carbon content in 50 µm droplets
increasing spray distance for all droplets, indicating constant oxidation
decreases to 0.15 wt%. As a result, oxide inclusions are present on the
of the droplets during flight. Furthermore, it can be seen that reducing
surface of splats deposited at spray distances of 110 mm and 140 mm
the droplet diameter intensifies oxygen uptake. At a spray distance of
(Fig. 12d and g).
50 mm, negligible oxygen uptake is observed for the 50 µm droplet. The
Based on the above results, smaller droplets consume carbon more
oxygen uptake of 30 and 40 µm droplets is much higher than that of
rapidly and form a surface layer with deoxidizer deficiency earlier.
50 µm droplets. When the spray distance is increased to 80 mm, the
Therefore, the Al oxide is formed on the molten droplet surfaces
50 µm droplet O2 content increases to 0.11 wt%, while the averaged
(Fig. 12c). One of the reasons could be attributed to particle temperature
oxygen uptake of the 30 and 40 µm droplets is still 5–6 times that of the
dependency on its size. Fig. 15a shows the surface temperatures of
50 µm droplet. The overall oxygen uptake by the smaller size particles
molten droplets with different particle sizes at different spray distances.
remains high and increases much faster compared to the larger size
It is observed that smaller particles have a higher surface temperature.
droplets. This can be attributed to the higher specific surface area (SSA)
Moreover, it is known that the reaction rate is directly dependent on the
and stronger vortex motion of smaller particles. Therefore, the smaller
particle temperature, and the higher the temperature the faster the re­
particle-size droplets will inevitably undergo more severe oxidation
action rate (Fig. 15b). The forward rate constant for the reaction kf,r is
during a flight than larger particle-size droplets due to more molecules
computed using the following Arrhenius expression:
of O2 available for reaction in the smaller droplet.
kf ,r = Ae(− E/RT)
(5)

Where A is the pre-exponential factor, E is the activation energy for the

reaction and R is the universal gas constant.
As seen in Fig. 15a, the 30 µm particle temperature remains higher at
all spray distances and thus the reaction rate is also higher for 30 µm
particles (Fig. 15b). The droplets ≤ 30 µm with higher surface temper­
ature consumed the carbon content lower than the critical one before
reaching the 80 mm. Thus, the Al oxidation started much earlier in
smaller size particles (as observed in Fig. 12c).

4.3. Model for the protection dynamics of NiAl droplet from oxidation by
in-flight carbon in-situ deoxidation

Based on the present experimental results (Fig. 12) and numerical

analysis, it was revealed that carbon can effectively protect metal ele­
ments in in-flight NiAl droplets from oxidation during APS. However,
Fig. 13. The oxygen uptake of different size droplets varied with the the droplet size significantly influences the carbon reaction rate with
spray distance. oxygen surrounding the droplet. The reaction rate of smaller droplet is

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

Fig. 14. (a) The numerical results are compared with experimental results of the droplets/coatings carbon content varied with the spray distance; (b) The numerical
results of cumulative generated CO content varied with the spray distance.

Fig. 15. The particles’ temperature extrapolated (SD=50-to-70 mm), actual experimental values from SD= 80-to-140 mm, and reaction rate calculated from
Equation-5, varied with the temperature of the particles.

much more rapid than that of larger droplet and thus the carbon is for achieving in-situ deoxidation throughout the droplet inflight process.
consumed faster to a level lower than the critical carbon content. A As the in-flight molten droplets are always maintained a highly over­
possible mechanism for in-situ sacrificial de-oxidation of carbon during heated state, high convection movements take place in the droplet. As a
APS is proposed in Fig. 16. When the powder particles are injected into result, a vortex flow occurs in in-flight molten particles, and rapid
high temperature flame, they will be heated up rapidly by the intensive mixing of fluid occurs, leading to a continuous supply of carbon to the
convection heat transfer effect. The exothermic reaction between Ni and surface layer from the inner core. Based on the phase equilibria in the
Al elements will be immediately ignited. This may significantly increase ternary system Ni-Al-C reported by Oden and Gokcen (1997), NiAl ex­
droplet temperature, which leads to the molten droplet fulfilling the hibits a solubility for carbon up to 2.03 wt% at a temperature of
thermodynamic requirement for in-situ in-flight deoxidizing. The rapid 2300 ◦ C. Therefore, it can be reasonably inferred that almost all of the
supply of carbon to the molten droplet surface is the kinetic requirement diamonds are dissolved in Ni-Al molten droplets because the mean

Fig. 16. Schematic for in-situ sacrificial de-oxidation of carbon during atmosphere plasma spraying influenced by change of carbon content resulting from de-
oxidation with traveling to show molten droplet size effect. (a) for large droplets of sufficient deoxidizing carbon maintaining oxide-free state (a1 and a2),
changing to local deoxidizer deficient permitting limited oxidation of alloying elements (a3 and a4); (b) for small droplet becoming deoxidizer-deficient rapidly at the
early stage (b2 forward) causing increasing of alloying elements to a severely oxidized state.

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

particle temperatures are higher than 2300 ◦ C before they impact the been designed to prevent the in-flight oxidation of Ni and Al in high
substrate. Therefore, during plasma spraying, the powder particles are temperature molten NiAl droplets during atmospheric plasma spraying
first rapidly heated up and the diamond is dissolved in Ni-Al molten of NiAl coating. The effect of particle size on the in-flight oxidation ki­
droplets to form the ultra-high temperature carbon-containing Ni-Al netics and deoxidization kinetics of carbon-containing NiAl droplets
droplets, as schematically depicted in Fig. 16a1 and b1. The molten were revealed through experimental studies and numerical simulations.
droplet surfaces are enriched with a large number of dissolved carbon. The results are summarized as follows:
At the early stage of the in-flight, the dissolved carbon on the molten
droplet surface is sufficient and will react preferentially with the sur­ (1) The layer-structured Ni/Al/diamond spray powder was prepared
rounding oxygen to form CO and evaporate rapidly thus protecting Ni by mechanical alloying to provide large Ni/Al interfaces for rapid
and Al elements from oxidation (Fig. 16a1, b1, and a2). At the same exothermic reaction during APS. The particles could be heated to
time, the strong convective motion within the droplet, caused by Hill’s a temperature higher than 2200 ◦ C to endow thermodynamic
vortex, transfers enough dissolved carbon to the surface of the in-flight possibility for the in-situ deoxidizing of carbon. Sacrificial
Ni-Al droplet to avoid oxidation of metal elements resulting from the oxidation of carbon was highly effective in suppressing the in-
depletion of the surface carbon. Therefore, oxide-free Ni-Al droplets can flight oxidation of metal droplets and consequently controlling
be achieved by introducing carbon as a deoxidizer element and main­ the oxide content in plasma-sprayed NiAl coating. The oxygen
tained during in-flight as far as carbon supply is more rapid than its content in NA2D2 coating was significantly reduced to 0.61%,
consumption, corresponding to a carbon content higher than the critical which is less than 1/5 of NA coating.
content of 0.83 wt%. (2) Complete deoxidization throughout in-flight requires the molten
For large droplets, the carbon deoxidant in the in-flight Ni-Al droplet droplets to maintain a critical carbon content (~0.83 wt%) and
is gradually consumed with in-flight resulting in insufficient deoxidizer sufficiently high temperature (＞2007 ◦ C) over the whole spray
content on the surface of molten particles with a larger size (Fig. 16a3). distance. When the droplet carbon content is decreased to less
Thereafter, besides the oxidation of carbon, the chemical reaction be­ than the critical carbon content, the oxidation of alloying ele­
tween Al on the surface of the molten metal droplet and oxygen occurs to ments starts.
form tiny Al oxide in splats as observed (Fig. 12e). With deoxidizing (3) The droplet size significantly influences the in-flight oxidation
becoming less efficient with the in-flighting of molten particles, the kinetics. Smaller droplets have a higher rate of oxygen uptake and
oxidation of Al in molten droplet becomes more and more intensive and a higher temperature that increases the reaction rate of CO for­
the oxides on the surface increase continuously with further in-flight due mation and carbon reduction. The on-set of Al oxidation during
to continuous reduction of carbon in the droplet (Fig. 16a4). NiAl droplet in-flight started earlier with smaller droplets
Due to their rapid oxidation, the smaller droplets consume carbon because the consumption of carbon by deoxidizing is more rapid
more rapidly, reach the critical carbon content and subsequently form a within the smaller particles. The quantitative analysis showed
surface layer with deoxidizer deficiency at an early stage. Therefore, the that the protective ability of carbon was effective for B powder in
Al oxide is formed on the molten droplet surfaces. Then, the oxides are a spray distance range of up to 80 mm.
entrained into the molten particle and mixed with the liquid Ni-Al by (4) Compared to other coatings, the NA2D coatings present a much
convective motion within the droplet due to the intensive convection denser microstructure, high microhardness, and high adhesion.
heat transfer effect (Fig. 16b2). With the droplet further flying, the The adhesive strength of the coating can be significantly
carbon is further depleted rapidly, and thereby the molten droplet sur­ increased from 30.7 MPa (NA) to 54.9 MPa (NA2D2). Therefore,
face is almost completely oxidized and an Al2O3 shell will be formed using the carbon-containing Ni/Al composite powder designed
(Fig. 16b4). As a result, at a spray distance of less than 80 mm, the for developing the in-situ in-flight deoxidizing effect is promising
coating is deposited by oxide-free large droplets and a small fraction of for depositing a high performance NiAl coating with limited
small droplets containing a few tiny oxides. At a long spray distance of oxides.
140 mm, since the carbon content of all molten particles is decreased to
less than the critical content, the coating is deposited by different-sized CRediT authorship contribution statement
molten droplets which correspond to different degree of oxidation. The
tiny oxides and long thin scales at intersplat boundaries are brought in Li Zhang: Validation, Formal analysis, Investigation, Writing −
by large and small droplets, respectively. original draft preparation, Data curation. M. Mahrukh: Software,
In summary, for the NA2D coatings deposited by Ni-Al-2 wt%.dia­ Methodology. Di Wang: Methodology, Investigation. Xian-Jin Liao:
mond composite powders, in-flight oxidation was greatly suppressed Writing − review & editing. Xiao-Tao Luo: Conceptualization, Writing
during the spraying process due to the addition of carbon deoxidizer. − review & editing. Chang-Jiu Li: Conceptualization, Funding acqui­
Consequently, the inter-lamellar interface and coating/substrate inter­ sition, Supervision, Writing − review & editing.
face bonding were improved. Compared to conventional NiAl coating,
the microhardness and adhesive strength of the NA2D coating were Declaration of Competing Interest
considerably improved. However, the carbon content in the small par­
ticles becomes lower than the critical value at a spray distance away The authors declare that they have no known competing financial
from 80 mm, resulting in the presence of oxides in the coatings. interests or personal relationships that could have appeared to influence
Therefore, to prepare oxide-free NiAl coatings throughout the whole the work reported in this paper.
spray distance, it is essential to ensure the smallest spray particles have
deoxidizer carbon content higher than the critical content. This can be Data availability
achieved by designing the spray powder particles with sufficient carbon
contents for different sizes of powders. Moreover, since necessary Data will be made available on request.
alloying elements can be added into powder feedstocks based on present
results, the effective deposition method to fabricate protective NiAl- Acknowledgments
based coatings with different alloying elements can also be developed.
This work was supported by the Key Program of the National Nature
5. Conclusions Science Foundation of China (No. U1837201, No. 52031010).

In this study, a novel carbon-containing Ni/Al composite powder has

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L. Zhang et al. Journal of Materials Processing Tech. 319 (2023) 118088

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