Surface & Coatings Technology 255 (2014) 62–68

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Surface & Coatings Technology

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Formation and oxidation resistance of Al/Ni coatings on low carbon steel

by flame spray
D. Chaliampalias, S. Andronis, N. Pliatsikas, E. Pavlidou, D. Tsipas, S. Skolianos, K. Chrissafis, G. Stergioudis,
P. Patsalas, G. Vourlias ⁎
Physics Department, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece

a r t i c l e i n f o a b s t r a c t

Available online 7 January 2014 In this work the effect of heat treatment on the structure and the durability of double layer Ni/Al coatings was
investigated. An initial Ni–Cr layer was primarily deposited by thermal spray, followed by a successive Al metallic
Keywords: layer in a second stage. The specimens were then heat treated in inert atmosphere. Nickel aluminide compounds
Thermal spray were formed as a result of the diffusion between the two layers upon annealing. Indeed, scanning electron
Protective coatings
microscopy, X-ray diffraction and X-ray photoelectron spectroscopy examinations of the coated samples
High temperature oxidation
revealed that the as sprayed coatings contain two distinct Al and Ni–Cr layers while the heat treated coatings
XRD
XPS
were gradually transformed to Al3Ni depending on the heat treatment parameters. The as sprayed and annealed
specimens were tested by subjecting them in an air environment at 700 °C and 800 °C, for the evaluation of their
durability and resistance. It was found that the annealed samples have superior high temperature resistance
compared with the as sprayed coatings and bare steel, which is attributed to the presence of Ni–Al compounds,
to the low coating porosity and to the formation of dense oxides on the coating surface.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction projected on the steel substrate in molten or semi-molten state, forming

Nickel is often used in the coating industry because of its enhanced
corrosion performance and its durability in harsh environments.
Moreover, nickel-based alloyed coatings are widely applied, because
of their proven good wear resistance and workability at high tempera-
tures, in association with low cost. Common applications of these
coatings are in mechanical components such as rollers, hot strip mills,
pumps, wearing plates and pistons [1,2]. Additions of chromium,
boron and silicon contribute to increase of the coating hardness and to
its self fluxing properties. This is realized by forming hard phases and
by forming compounds with lower melting point than the matrix
material [3,4]. Furthermore, aluminum coatings offer a combination of
attractive properties such as low density, good wear resistance, ease of
fabrication and resistance to oxidation at high temperature. The high
temperature resistance is based on the self-passivation by forming of a
continuous, protective Al2O3 layer [5,6], when exposed to oxidizing
atmospheres, because it provides a good diffusion barrier.
Such coatings can be developed by different methods in industrial
scale such as thermal spray, chemical and physical vapor deposition
(CVD and PVD, respectively) [7]. One of the easiest to apply and the
most productive method is combustion flame spraying process [8,9].
In this technique the powder is directly fed in the flame spray gun and
⁎ Corresponding author at: Department of Physics, Aristotle University of Thessaloniki,
GR 54124 Thessaloniki, Greece. Tel.: +30 2310 998066; fax: +30 2310 998171.
E-mail address: gvourlia@auth.gr (G. Vourlias).
thick resistant coatings. The advantages of this technique are its
high production rate, process rapidity, low environmental impact and
low cost.
Up to now, Al and Ni–Cr thermal sprayed coatings are examined
separately in several environments and were proved to improve signif-
icantly the resistance of the as coated substrates [10,11]. The combina-
tion of the protection of both types of coatings deposited together on
steel substrates is not extensively examined up to now [12]. The aim
of this work is to form oxidation resistant Al–Ni compounds [2,13,14]
by a two step combustion thermal spray process which is simple,
economic and less sophisticated, than the other referred deposition
methods. For this reason the structure and morphology of the deposited
samples were investigated before and after heat treatment, while selec-
tive specimens were tested by being exposed in high temperature air
environment in order to evaluate their resistance and their safe service
temperature that can operate.
2. Experimental
Hot-rolled sheets of steel (100 mm long × 30 mm wide × 3 mm
thick) containing 0.17% C, 1.6% Mn, 0.55% Si, 0.04% S (low carbon steel
St-37) are used as substrates and flame spray process is carried out
using a 5P-II Sulzer-Metco combustion powder gun. The multilayer
coating was the result of a two stage successive feeding of the flame
spray gun with two different feedstock materials. Firstly with a
NiCrBSiFe powder (Ni 7.5Cr 3.5Si 2.5Fe 1.7B 0.25C) and then with

0257-8972/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.surfcoat.2013.12.057
 D. Chaliampalias et al. / Surface & Coatings Technology 255 (2014) 62–68
an Al gas atomized powder (Al 99.0 +). Before the coating procedure
the substrates are abrasively cleaned with sandblast, in order to re-
move the remaining oxides which decrease the coating adhesion.
The distance between the flame spray gun and the substrate is
120 mm, while acetylene is used as the fuel gas. Afterwards, the as
sprayed surfaces were heat treated in an electric furnace at 500,
600 and 700 °C for 3 h in an inert atmosphere. The examination of
the high temperature oxidation resistance of the specimens was
accomplished through thermogravimetric measurements (TGA),
which were carried out with a TG-DTA SETARAM SETSYS 16/18.
The samples were placed in alumina crucibles for these measure-
ments and an empty alumina crucible was used as reference. During
the tests the samples were heated from ambient temperature up to
1000 °C in a 50 ml/min flow of air with a heating rate of 10 °C/min.
During the testing process continuous records of the sample temper-
ature, weight and heat flow were taken. The examination of the
specimens, before and after oxidation tests, was performed using a
JEOL 20kVolt JEOL 840A SEM equipped with an OXFORD ISIS 300
EDS analyzer and the appropriate software for point microanalysis,
linear microanalysis and chemical mapping of the area under exam-
ination. The structure identification is performed with X-ray diffrac-
tion analysis (XRD) using a Rigaku Ultima+ powder diffractometer
(40 KV, 30 mA, CuK α radiation) in Bragg–Brentano geometry. The
composition of the coatings and their chemical/oxidation state
have been identified by X-ray Photoelectron Spectroscopy (XPS) in
a KRATOS-Axis Ultra DLD system using the monochromated Al-Ka1
line as primary beam, a hemispherical sector analyzer (HSA) and a
128-channel detector. A pass energy of 20 eV resulting in a full
width at half maximum (FWHM) of 550 meV for the Ag-3d5/2 line,
has been used.
3. Results and discussion
3.1. Structure determination
The cross sectional micrograph corresponding to the as sprayed
multilayer Al/NiCrBSiFe coating is presented in Fig. 1. The coating is
characterized by typical morphological characteristics of flame sprayed
coatings. Multiple splat formations and remarkable superficial rough-
ness are distinguishable on the surface, which are attributed to the
presence of unmelted and partially melted metallic droplets together
with the liquefied donor material in the flame spray material flow.
Fig. 1. Cross sectional SEM micrograph of the NiCrBSiFe and Al coated sample with
flame spray.
63
Their existence is due to fast cooling of the melted material before
impinging on the steel substrate. These solid particles are incorporated
in the coating with very small changes of their shape, and consequently
the surface is impossible to be even or uniform. The roughness decrease
depends on the combination of several experimental parameters, such
as the powder feedstock rate, the viscosity of the liquid metal and
the momentum of the particles at impact [15]. The main features of
the structure are splat formations together with longitudinal grain
boundaries as a result of the high velocity impingement of the liquefied
coating material. The presence of numerous pores is also attributed to
the solidification of the metallic droplets. Finally, the coating thickness
was measured between 400 and 450 μm; the thickness varies due to
the high roughness of the coating. Separately the two distinct layers
of Ni–Cr (inner layer) and Al (external layer) were approximately
measured 220 μm.
The chemical content of the as-sprayed coating was confirmed with
EDS analyses performed at several parts of it. In the corresponding line-
scan graph (Fig. 2) the existence of the two different areas is clearly
illustrated. In this graph only the main elements are presented (Ni, Cr,
Al and Fe) as the rest of the elements have concentration close to the
detection limit. The chemical map images show a supervisory image
of the element distribution in the coating which is also in agreement
with the previously mentioned findings.
Moreover, several point EDS analyses were performed near the
two interfaces, between Ni–Cr coating and the substrate and between
the two coating layers. The results showed that no Fe amounts were re-
corded in the Ni–Cr coating as no compounds between the substrate
and coating materials were formed. Hence, only a mechanical bond is
established between the substrate and the sprayed coatings.
The identification of the corresponding XRD patterns revealed the
existence of pure Al as the penetration depth of the X-ray beam is
smaller than the thickness of the surface Al layer.
The coating structure of the samples annealed at 500 °C has similar
structure with the as sprayed ones. The only difference observed in
their structure, is the existence of small dispersed islands which are
formed rarely in the Al containing top layer. Point microanalysis on
these regions showed that they were mainly composed of Al together
with the main elements of the inner NiCrBSiFe layer such as Ni and Cr
(Fig. 3).
Based on the EDS elemental analysis the structure of the as formed
islands, it was found that their core is composed of the Ni–Cr
Fig. 2. EDS line scan along the deposition direction of the coating; insets: chemical maps
of Al, Ni and Cr spray.
64 D. Chaliampalias et al. / Surface & Coatings Technology 255 (2014) 62–68
Fig. 3. Cross sectional SEM micrograph of the sample after heat treatment at 500 °C for 3 h.
compounds. The peripheral area of the island was found to contain two
different Ni–Al compounds in which the Al content decreases and the Ni
content increases from the outer to the inner part of the island (Fig. 4).
Their formation is a result of interdiffusion of elements triggered by the
high temperature of the heat treatment, which resulted in the gradual
transformation of the Al layer in Al–Ni compound. The inset table of
Fig. 4 summarizes the concentration of every region.
The structure of the samples annealed at 600 °C was much different
than that of the samples annealed at 500 °C. In the later case, the islands'
density has substantially increased due to higher treatment tempera-
ture (Fig. 5). EDS elemental analysis revealed that they have aluminide
structure resembling that of the rare islands of the previous case.
Moreover, the aluminide's volume fraction is substantially increased;
as a result, their volume is sufficient to provide XRD peaks, as it is
shown in Fig. 6. Indeed, in Fig. 6 the XRD patterns of the as sprayed
Fig. 4. Magnification of the denoted area in Fig. 3 and the corresponding summary of the
EDS elemental analysis.
Fig. 5. Cross sectional SEM micrograph of the sample after heat treatment at 600 °C for 3 h.
samples and the heat treated at 600 °C and 700 °C samples are presented
together in order to show the structural differences among the various
cases. It is evident that in the as spayed coating there is no trace of
aluminide phase and only the diffraction pattern of Al (PDF#65-2869
[16]) is recorded; after heat treatment at 600 °C additional peaks
are emerging that they are attributed to the Al3Ni (PDF#65-2418,
#02-0416 [16], not shown in Fig. 6 for simplicity) and to Ni–Cr com-
pounds (denoted with *) located in the diffusion islands.
Further evidence for the formation of aluminides, after annealing
at 600 °C for 3 h, has been provided by XPS. Fig. 7 shows the high-
resolution spectra of the Ni-2p doublet (Fig. 7a), the Al-2p and the
Ni-3p peaks (Fig. 7b) for the as sprayed and annealed, at 600 °C for
3 h, specimens, acquired after surface cleaning by a 4 keV Ar+ ion
beam for 10 min. According to the ion beam current the removed
surface layer has been estimated to be 50 nm thick. Nevertheless,
this cleaning procedure is not absolutely effective due to the granu-
lar and porous morphology of the coatings; hence, the residues of O
giving rise to the Al–O bonding observed in Fig. 7b. From Fig. 7b, it
is also evident that after annealing Ni has diffused into the Al layer
reaching progressively the surface of the coating (Fig. 7b). In addition,
Fig. 6. XRD patterns of the as sprayed sample (lower curve) and after heat treatment at
600 °C (intermediate curve), and at 700 °C (upper curve) (Al:PDF#65-2869/Al3Ni:
PDF#65-2418, 02-0416, Ni–Cr(*):PDF#65-5559) [14].
 D. Chaliampalias et al. / Surface & Coatings Technology 255 (2014) 62–68
Fig. 7. XPS high-resolution spectra of the Ni-2p doublet for the as sprayed and annealed, at 600 °C for 3 h, specimens.
the Ni-2p doublet can provide crucial information on the chemical
state of Ni, by considering the energy separation of the main Ni-2p1/2
photoelectron line with the satellite peak that manifests in between
the Ni-2p1/2 and Ni-2p3/2 lines. According to Ohtsu et al. [17] this energy
separation is 6.6 eV for the pure metallic Ni and increases in aluminides
with increasing [Al]/[Ni] ratio. Therefore, the observation of this energy
separation at 8 eV for the annealed specimen is a straightforward proof
of the formation of aluminides after annealing.
In the last series of samples, which were annealed at 700 °C for 3 h,
the formation of the aluminide phase has progressed further as revealed
by XRD (Fig. 6, upper curve), resulting in homogeneous coatings of
low porosity (Fig. 8) due to enhanced bulk diffusion that occurs for
temperatures approaching the melting point Tm (in fact, for Al3Ni is
Tm = 854 °C, i.e. the annealing temperature of 700 °C corresponds to
the 82% of Tm). However, there are still some remaining areas, in contact
Fig. 8. Cross sectional SEM micrograph of the sample after heat treatment at 700 °C for 3 h,
showing residues of the NiCrBSiFe powder.
65
with the substrate, that are composed from the initial NiCrBSiFe sprayed
powder (Fig. 8).
Summarizing on the formation mechanism of Al3Ni compounds by
combustion thermal spray it was revealed that the application of a
heat treatment at 700 °C, which is close to the melting point of Al3Ni,
transforms the primer separate as sprayed Al and Ni layers into Ni–Al
compound by Ni diffusion in the Al layer. This is performed by the
creation of Ni rich islands in the Al matrix which gradually are enriched
by Al and finally form the Al3Ni phase. After 3 h heat treatment most of
the coating is transformed to Al3Ni and low Ni compound remains at the
lower regions of the coating. It is expected that for longer heat treat-
ment periods the whole deposition would be transformed in Al3Ni.
3.2. Oxidation resistance of the samples
High temperature oxidation was primarily studied by in-situ
thermogravimetric (TG) measurements. The marginal cases of an
as sprayed sample and of an annealed at 700 °C sample have been
Fig. 9. TG curves after non isothermal air oxidation from room temperature to 1000 °C.
66 D. Chaliampalias et al. / Surface & Coatings Technology 255 (2014) 62–68
examined, in order to investigate on the resistance of Al3Ni against
oxidizing environments. In Fig. 9 the mass gain per unit versus tem-
perature is presented for both cases. As it can be seen in this plot, for
both samples small mass reductions have been observed in the tem-
perature range 200–350 °C, which is attributed to the existence
of various contaminations entrapped in the pores of the samples
which evaporate under the effect of temperature. At higher temper-
atures the as sprayed sample begins to oxidize from 580 °C with high
rate while the annealed sample is oxidized at considerably lower
rate. The fact that both samples begin to oxidize at the same temper-
ature is mostly due to the existence of porous net in the structure of
the coatings which in the case of the annealed sample is more re-
stricted due to its denser morphology. The superior oxidation resis-
tance of the annealed samples is better revealed at 820 °C. The
oxidation rate of the annealed sample begins to increase slightly
while at much higher temperatures this rate begins to have a signif-
icant value. At the same temperature, the mass gain of the as sprayed
sample is very high, while the oxidation rate has substantially in-
creased value. Given this, it is concluded that the as sprayed coating
has deteriorated and leaves the underlying substrate unprotected.
The superiority of the Al3Ni coating is better distinguished compar-
ing the non-isothermal TG results with the similar ones performed
on bare steel [10]. It is reported that bare steel starts to oxidize
from 400 °C and at the temperature range at which Al3Ni still offers
significant protection, the bare substrate has significantly degraded.
The coated samples were also subjected to isothermal high temper-
ature oxidation test at 700 °C and 800 °C for 20 h in order to acquire a
complete estimation of their oxidation resistance. The structure of the
as sprayed samples, after oxidization at 700 °C process, has sustained
significant changes (Fig. 10a). EDS analysis, performed throughout the
Fig. 10. Cross sectional SEM micrograph of the as sprayed samples oxidized at 700 °C
(a) and 800 °C (b) for 20 h. Area 1 corresponds to Al2O3, area 2 corresponds to Al3Ni,
area 3 corresponds to NiCrBSiFe and area 4 corresponds to Fe2O3.
whole coating, revealed three different phases formed in the coating.
The external layer (Fig. 10a, dark area) consists exclusively of aluminum
oxide and it is lying over an aluminium nickel area. The formation of
Al2O3 on top of the coating has been explicitly confirmed by both XRD
and XPS measurements. Under the oxidised layer there is a significant
part of the NiCrBSiFe layer which remains non-oxidized. As a result,
the as sprayed coatings were proved to be prone to oxidize and it is like-
ly that they will gradually collapse at longer exposure periods leaving
the substrate unprotected.
The as sprayed samples subjected to isothermal oxidation at 800 °C
for 20 h were found to have collapsed under the effect of the harsh
environment (Fig. 10b) because the oxidant elements have reached
the substrate in this case. EDS analysis revealed that in addition to the
presence of aluminium oxide and aluminium nickel compounds, the
oxidized coating is also composed of a layer near the coating–substrate
interface consisting of iron oxide compounds. These are the oxidation
products of the reaction of oxygen with the ferrous substrate. Moreover
in this case no NiCrBSiFe layer is observed as the whole compound
was transformed to nickel aluminide under the effect of the high
temperature. The above results were also verified from XRD and XPS
measurements.
The oxidation results of the annealed samples are much more
different than the results of the as sprayed samples, which is mainly
attributed to the existence of Al3 Ni in the main structure of the
coating and to the formation of a passivating Al2O3 thin layer on its
surface. EDS analysis performed on sample oxidized at 700 °C for
20 h, revealed that the structure of the coating remains intact from
the attack of the oxidant agents (Fig. 11a). Moreover at the deeper
parts of the coating, scattered areas were found to contain their
primer NiCrBSiFe content, while at the top areas of the coating Al
oxides were also traced. Indeed, the chemical nature of the outer
layer of the coating has been investigated by high resolution XPS
spectra (Fig. 12). XPS has shown that even 50 nm below the surface,
the specimen is completely depleted of Ni and the remaining Al is
Fig. 11. Cross sectional SEM micrograph of the heat treated samples oxidized at 700 °C
(a) and 800 °C (b) for 20 h.
 D. Chaliampalias et al. / Surface & Coatings Technology 255 (2014) 62–68
Fig. 12. XPS high-resolution spectra of the Ni-2p and Al-2p doublet for the annealed specimens before and after oxidation at 700 °C for 20 h.
exclusively in oxidized state corresponding to Al2O3. This observation is
a clear evidence of selective oxidation [18] accompanied by segregation
of Al on the surface, due to the lower Gibbs free energy of formation
of Al2 O 3, ΔG Al2O3 = − 1582 kJ/mol [19] compared to that of NiO,
ΔGNiO = − 123.5 kJ/mol [20].
The same analysis performed on the same sample oxidized at 800 °C
revealed several differences with the previous case. EDS analysis traced
two different areas containing different Al and Ni contents. In particular,
the darker areas have the composition of Al3Ni2 and they are mainly
located in the intermediate area between the surface of the coating
and the underlying Al3Ni layer, which is closer to the interface
(Fig. 11b). The Ni enrichment of this intermediate layer is consistent
with the segregation of Al to the surface to form Al2O3, as revealed by
XPS. The EDS results were verified by XRD peak identification. In the
corresponding patterns of the annealed samples oxidized at 700 °C
and 800 °C, mixtures of Al3Ni + Al2O3 and Al3Ni + Al3Ni2 + Al2O3,
Fig. 13. XRD patterns of the annealed samples oxidized at 700 °C (lower curve) and
800 °C (upper curve) for 20 h. (Al 2 O 3 : 76-0144, Al 3 Ni:PDF#65-2418, #02-0416,
Al3Ni2:PDF#65-3454 [14]).
67
respectively, were identified [Al2O3: PDF#76-0144, Al3Ni:PDF#65-2418,
#02-0416, Al3 Ni2 :PDF#65-3454] (Fig. 13 lower and upper graph
respectively). In any case, the annealed samples show superior
oxidation resistance and are intact even after exposure to harsh
environments due to their denser structure, the formation of aluminides
and the existence of a passivating thin Al2O3 layer on the surface of the
coating, which is a diffusion barrier to oxidant agents.
4. Conclusions
In this examination the formation of Al3Ni was achieved by a two
stage thermal spray process and annealing at 700 °C. Annealing at
lower temperatures revealed the mechanism of its formation which
was by the creation of nickel diffusion islands which gradually were
enriched in Al at the appropriate concentration. From the high temper-
ature oxidation tests it was found that the as sprayed samples had less
oxidation resistance compared to the annealed ones. In particular, non
isothermal tests showed that the as sprayed samples have significant
higher oxidation rate than the annealed samples. Moreover the results
of isothermal oxidation at 800 °C for 20 h revealed that the as deposited
samples have limited resistance to the aggressive environment as sever-
al substrate oxidation products were tracked, while the annealed sam-
ples continue to reserve their integrity and only a thin Al2O3 layer was
formed as a result of Al oxidation, segregated from the Al3Ni phase
which offers additional protection to the coated material when exposed
in aggressive high temperature environments.
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