ISSN 1213–2489

August 2023, Vol. 23, No. 4 MANUFACTURING TECHNOLOGY e-ISSN 2787–9402

DOI: 10.21062/mft.2023.052 © 2023 Manufacturing Technology. All rights reserved. http://www.journalmt.com

High Temperature Protective Coatings for Aeroengine Applications

Jakub Jopek (0009-0003-5856-3578), Magdalena Mokrzycka (0000-0002-3153-0990), Marek Góral (0000-0002-

7058-510X)*, Barbara Koscielniak (0000-0002-1683-0354), Kamil Ochal (0000-0002-0708-2542), Marcin Drajewicz
(0000-0002-9600-6938)
Research and Development Laboratory for Aerospace Materials, Rzeszow University of Technology, Powstancow
Warszawy 12, 35-959 Rzeszow, Poland. Corresponding author * e-mail: [email protected]

Nickel superalloys are the main materials used in manufacturing of turbine blades and vanes in aerospace
industry. They works is extremely high temperature in a corrosive environment (oxidation, hot corrosion)
and undergo several different thermo-mechanical loads. Aluminide coatings are the main method of
protection of the surface of nickel superalloys against exhaust gasses environment in jet engine. In
presented article the microstructural characterization of aluminide coatings produced using two
industrial methods (pack cementation and out of pack) was conducted. The commercially available
powders manufactured by Oerlikon-Metco were used in aluminizing process using industrial Bernex
BPX Pro 325S CVD system. The Mar M247 was used as a base material. Amount of activator and pure
aluminum had a noticeable effect on the total thickness of obtained layers. Both samples with increased
activator and pure aluminum content formed 5 to 11.5 x thicker aluminide coatings in comparison to
other sample, which was aluminized using an Al-Co powder as aluminum source. Further investigations
are needed to specify precise phase composition of analyzed coatings.

Keywords: aluminide coatings, turbine blades, MAR M247, CVD

Introduction categories based on the aluminum activity of the pack

[6]. High activity low temperature process (HALT)
Contemporary aviation industry is mainly focused takes place at 700 – 900 °C. Coating is formed by a
on increasing gas turbine efficiency, which is predominant inward diffusion of aluminum atoms
inextricably linked with the process of raising into the nickel substrate. The resulting microstructure
temperature of hot gases in combustor chamber. One
consists of an external δ-Ni2Al3 phase and internal β -
of the factors that hasten this increase are materials
NiAl with dispersed MC and M23C6 carbides in both
and production technologies of high- pressure turbine
blades. They work under extremely high temperature layers. Because δ-Ni2Al3 is more brittle and oxidizable
in a corrosive environment and undergo several than β-NiAl, heat treatment is applied at 1050 – 1100
different loads. It creates the problem of proper °C. After that, microstructure has three visible layers.
material selection and a method of its protection Inner layers is composed by columnar grains of β -
against several degradation mechanisms that can occur NiAl phase with dispersed MC, M23C6 carbides and σ
in hot section of aircraft gas turbine. Only nickel- (Cr, Mo, Co) phase, while the outer layer comprises
based superalloys can withstand such a harsh equiaxed β -NiAl grains and substrate carbides. Middle
environment for a long time, and they are in use since layer is single-phase β -NiAl. Low activity high
1950s. One of them is polycrystalline Mar M-247 alloy, temperature process (LAHT) is conducted at 1050 –
which was developed in 1970s. It possesses excellent 1100 °C, when aluminum activity is low. Its kinetics is
oxidation resistance and high creep strength at controlled by outward diffusion of nickel atoms and it
elevated temperatures. After casting its microstructure has two zones. The inner zone is similar to that
is composed of: γ‘-Ni3(Al, Ti) strengthening phase (62 observed in HALT process and consists of β -NiAl,
vol. %), γ matrix, γ/ γ‘ eutectic and carbides [1]. MC, M23C6 carbides and σ phase. The outer zone
Although they offer outstanding mechanical
comprises β -NiAl phase with substrate alloying
properties in operating temperatures, they are very
elements dissolved [5,7,9-12]. In order to obtain
susceptible to oxidation which causes its unacceptable
optimal aluminide coatings on superalloy substrates,
degradation, drastically limiting components lifetime
many methods of aluminization were developed: pack
[2,3]. That is why aluminide protective coatings have
cementation, gas methods (vapor phase aluminizing-
been developed [4-8].
VPA and above the pack), chemical vapor deposition
Aluminide coatings can be divided into two main
(CVD) and slurry.

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Among many available methods, pack cementation features of CVD and pack cementation process. They
attracted the most attention of industry thanks to its are still relatively cheap and do not require
simplicity and low cost [9,13-16]. Thoroughly cleaned sophisticated apparatus, while providing good surface
and dried samples are immersed in powder mixture quality of coated samples. Moreover, they allow a
and placed in a sealed heat-resistant steel box. Powder proper coating of internal cooling channels of high-
mixture contains aluminum source (aluminum or its pressure turbine blades without insertion of powder
alloy), activator (fluoride salt such as NaF) and filler particles inside them. Coated parts are placed in the
(e.g. Al2O3 preventing mixture from sintering). Upon retort furnace, while being physically separated from
heating the pack to desired temperature, activator the pack or granules (in case of VPA method).
volatilizes and reacts with metal powder to form Aluminizing begins with the formation of aluminum
volatile aluminum compounds which diffuse towards subchlorides, which are being transported to the
the alloy surface. Subsequently, aluminum halides substrate by gaseous diffusion. Afterwards, reactions
react with the alloy and release aluminum atoms. resulting in the deposition of aluminum on the parts
Diffusion reactions take place after which aluminides surface take pace. In this moment, aluminum diffuses
are formed. As a result, aluminum activity on the into the substrate to form intermetallic phases, whilst
metallic substrate is lowered, allowing further reaction products diffuse back to the reactor. Solid-
continuation of the process [9,14,15]. Although this phase diffusion and vapor transport are the slowest
method has many advantages, it is unsuitable for the stages in the whole process, hence they control
coating of complex cooling channels. Difficulties arise kinetics of coating growth [12,17,19].
during feeding such channels and removing of mixture In our previous research the two aluminizing
after aluminization [5]. Furthermore, powder particles methods were analyzed – out of pack [20] as well as
might be built in the coating, lowering its functional CVD [21]. In paper [17] the initial comparative study
properties [12]. It forces additional machining to of aluminide coatings produced by slurry, pack
regain proper coating structure. That is why more cementation, out of pack and CVD methods in the
frequently engineers choose processes that do not aspects of their thickness, Al content and oxidation
involve any physical contact between powder mixture resistance was conducted.
and parts to be coated.
One of such methods is CVD where samples and Experimental
aluminum source are completely separated from each
other. Although being very complex, CVD has gained Mar M-247 superalloy (Tab. 1) was aluminized and
much attention because of the possibility to widely alumino-silicized in different conditions (Tab 2).
control process parameters, thus obtaining desired Supplied bar was cut into specimens, 20 mm in
structures of aluminized layers on different substrates. diameter and 4 mm in height, grinded and degreased
In an external generator, at a temperature of 300 °C, in isopropanol. All processes were conducted using
HCl gases pass through aluminum granules to form industrial CVD system Bernex 325S produced by Ion
aluminum chlorides. Then they are being heated to Bond (Switzerland). In the processes, retort low-
approx. 1000 °C and transported to the main reactor. pressure furnace with Ar-flow line installed in this
Upon their diffusion to the parts surface, AlClx vapor device was used. All processes were conducted under
pressure 100 mbar in argon atmosphere with a flow
react with nickel to form β -NiAl coating. Outer
0.6 LPM (Normal litres per minute). Pack aluminizing
generator enables to precisely control flow rate of
was done for processes signed as M1, M3, M4, M5.
gases, allowing to obtain eligible aluminum activity
Different powder mixtures and temperature were used
inside main reactor [12,17]. Chemistry of the coating
(Tab. 2). Samples were immersed in powder mixture
can be further changed by the incorporation of
and placed in specially designed refractory
additional elements (such as Hf, Y, Zr) at precise level
container.Alumino-silicizing out of pack was carried
[18]. Coatings produced by this method have
out by placing samples (M2) on holders above pack
exceptional quality and may be relatively easily
mixture. Pack contained 80% AMDRY 356 as an inert
modified for better corrosion resistance. However,
filler, 10% Al + 10% Si as the saturate sources and 2%
CVD has some serious drawbacks arising from its
NH4F as activator. The diffusion treatment was
complexity. This method is neither cheap, nor simple
conducted at 950 °C for 4 h (Tab. 2). The
and requires specialized equipment to conduct it
microstructural investigation of obtained aluminide
successfully. In order to meet specified quality
coating was conducted using Hitachi S-3400 Scanning
requirements of aluminum coatings at the lowest cost
Electron Microscope equipped with EDX detector
possible, another method is often chosen.
(Thermo). Coatings thickness was measured using
Gas methods (VPA and above the pack) merge the
ImageJ software.
Tab. 1 Chemical composition of Mar M-247 alloy
Element content (wt.%)
Alloy
Ni Co Cr Mo Al Ti Zr C Fe B W Ta Hf
Mar M-247 Bal. 10.0 8.6 0.8 5.6 1.0 0.06 0.16 0.2 0.020 10.0 3.0 1.5

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Tab. 2 Aluminizing conditions for M1 – M5 samples; process time: 4 h

Process Method T [°C] Powder mixture

M1 Pack cementation 950 90% AMDRY 356+ 10% CODEP + 2% NH4Cl

M2 Out of pack 950 80% AMDRY 356 + 10% Al + 10% Si + 2% NH4F

M3 Pack cementation 1040 100% AMDRY 353+ 2% NH4Cl

M4 Pack cementation 1040 50% AMDRY 353 + 50% AMDRY 356 + 5% NH4Cl

M5 Pack cementation 1040 80% AMDRY 356 + 20% Al + 2% NH4Cl

Composition of AMDRY 356: 100 wt. % Al2O3

Composition of AMDRY 353: 46.5 wt. % Co + 53.5 wt.% Al

Results and discussion conditions were used to aluminize In 713C alloy by

CVD method and a coating of 17 μm total thickness
M1 Coating
was obtained. It consisted of two visible layers: outer
First coating was obtained via pack cementation (8 µm) and inner (9 µm) [23]. Bozza et al. [24]
M1 process in 950°C/4h (Tab 2). It consists of two aluminized CM-247 LC alloy, a derivative of Mar
visible and uniform layers with total thickness of 17 M247, in a pack mixture (10 wt. % CoAl + 0.3 wt. %
µm (Fig. 2.) The outer layer is 10.1 (+/- 1.1 μm) thick, AlF3 + 89.7 wt. % Al2O3) in 950°C for 4 h. Hardness
while the interlayer (inner) 6.9 (+/- 0.4 μm). Interlayer measurements confirmed the presence of δ-Ni2Al3
accounts for nearly a half of the whole coating phase with large inclusions of titanium, tungsten and
thickness, which suggests that the process featured tantalum carbides. No interdiffusion layer was found.
mostly outward nickel diffusion. Sitek et al. [22] Formation mechanism of aluminized layer was
aluminized In100 alloy in the same conditions by proposed by an inward diffusion of aluminum atoms.
CVD method obtaining 11 μm thick coating: 5 μm In M1 sample, near the surface, aluminum content is
outer and 6 μm interlayer. β -NiAl phase was identified maximum (26.8 wt. %), whilst nickel is in amount of
and in the interlayer increased amount of chromium, 50 – 53 wt. % (Fig. 1).
titanium and carbon was observed. The same
60 60 Outer layer 60
Outer layer Inner layer Inner layer
50 50 Outer layer
50
Wt% of element
Wt% of element

Wt% of element
Substrate

Substrate
40 40 40 Inner layer
Substrate

30 30 30

20 20 20

10 10 10

0 0 0
0 5 10 15 20 0 5 10 15 20 25 30 0 5 10 15 20 25

Distance from surface [µm] Distance from surface [µm] Distance from surface [µm]
Ni Al Ni Al
Ni Al
Co Cr Co Cr
Co Cr

a) b) c)
60 60 Inner layer
Outer layer Outer layer
50 50
Wt% of element

Wt% of element
Subs trate

Substrate

40
Inner layer

40
30 30
20 20
10 10
0 0
0 20 40 60 80 100 120 0 30 60 90 120 150 180 210 240 270
Distance from surface [µm] Distance from surface [µm]
Ni Al
Ni Al
Co Cr
Co Cr

d) e)
Fig. 1 Cocnentration of Ni, Al, Co, Cr in the aluminide layers obtained on Mar M-247 alloy for different aluminide conditions:
(a) M1, (b) M2, (c) M3, (d) M4, (e) M5 (wt. %); The red lines separate the additive layer, the diffusion layer and the substrate

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Outer zone:
10.1 µm 14.6 µm
18.8 µm
Interlayer:
6.9 µm 12.7 µm

1.2 µm
Substrate

a) b) c)

86.8 µm

228.7 µm

13.0 µm

d) e)
Fig. 2 Cross-sectional back-scattered electron micrographs of as-prepared coatings on Mar M-247 alloy using different methods and
under different conditions: a) M1, b) M2, c) M3, d) M4, e) M5 with marked thickness measurement of outer layer (white line) and
inner layer(yellow line)
Tab. 3 Thickness of aluminide layers obtained on Mar M-247 alloy by different methods
Thickness of aluminide layers zone [μm]
Sample Outer Inner Sum
M1 10.1 6.9 17.0
M2 14.6 12.7 27.3
M3 18.8 1.2 20.0
M4 86.8 13.0 99.8
M5 228.7 2.1 230.8

Some bright phases are visible- these are probably Ti)) and carbides [26,27]. During aluminizing, nickel
Ni3Al or σ-Cr phases (Fig. 2a). According to the Ni- atoms diffuse to the sub-surface areas, while
Al equilibrium diagram [25], this might be β -NiAl aluminum diffuses in the opposite direction. Cr-, Ta-,
phase with alloying elements dissolved in it. Spherical Ti- and W- atoms diffusion rates are very low in such
dark areas are probably Al2O3 filler granules built in conditions, so they are practically immobile. Interlayer
the surface as a result of a physical contact between is formed as a result of a partial depletion of nickel
powder mixture and sample during coating (Fig. 2,3). atoms that diffuse towards surface, while Cr, Ta, W,
In the interlayer, aluminum content decreases (20 – 8 Ti form their own phases [13,22]. Chemical
wt. %) to reach its minimum at the distance of 20 μm: composition of areas in different shades of gray (Tab.
7.2 wt. % (Fig. 1), just beneath the interlayer. Nickel 4, spectrum 03 - 04) as well as elongated precipitates
content is minimum here: 38 – 44 wt. %. Intermetallic was analyzed (Tab. 4, spectrum 01 - 02). In its upper
phases that may be there are β -NiAl (dark grey) and part, this phases contained hafnium and more
Ni3Al (light grey) [25]. On the other hand, content of tantalum, whereas its elongated bottom part had more
some elements (W, Ta, Cr, Ti) reach its peak in there: tungsten and chromium. They might be identified as
18 wt.% W, 7.6 wt. % Ta, 10 .wt% Cr, 1.5 wt. % Ti. MC carbides consisting of two parts: the upper one
This indicates the presence of many precipitates, could be (Ta, W, Hf)C and the bottom one (W, Ta)C.
further confirmed by the SEM mapping analysis (Fig. Similar results were obtained in paper [28], where
3) and BSE images (Fig. 2a). They were formed during greater amounts of hafnium was observed in MC
aluminizing. Before the coating process, fully heat- carbides heads. There are also a few small hafnium-
treated Mar M-247 alloy has a microstructure mostly rich areas in the interlayer and beneath it (Fig. 3). They
may be HfC carbides, because this phases are very
composed of γ matrix, γ' strengthening phase (Ni3(Al,

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stable and hafnium is a carbide-forming element [29]. undissolved MC (M = W, Ta, Hf, Ti,) primary carbides
Numerous phases, visible at the coating/substrate (Fig. 2a) [22]. Aluminized layers on Mar M247 alloy
interface, are bigger than those above them. They have were also produced via a slurry method using Ceral 10
a shape close to columnar which reflects the direction suspension [17]. It consists of Al and Si powder with
of nickel and aluminum diffusion. Big, irregular phases an inorganic binder. After 4 h at 950°C, thickness of
were also present across the coating. As they contain coating reached 60 μm and the aluminum amount was
carbide-formers it is probable that those were 26 wt. %.

Powder
particles

Hf-rich
areas

Fig. 3 Elemental mapping of elements in M1 nickel-based superalloy

Tab. 4 Point analysis of enlarged area form Fig. 3
Element content (wt.%)
Area
Ni Al Co Cr Ti Ta W Hf Mo
01 31.60 10.06 6.47 7.55 2.33 17.82 12.36 8.94 0.81
02 35.77 10.74 9.08 11.13 1.41 9.76 18.55 - 1.47
03 45.19 13.10 8.20 9.30 1.99 8.08 11.22 - 0.80
04 38.98 11.91 8.09 14.56 1.79 7.73 13.87 - 1.01

M2 coating within the range of 1:9 – 9:1. If the silicon content

exceeds 50%, thickening of the coating will be
Aluminized layers modified with silicon are often
observed. In this case, Al/Si ratio equals 1:1 and
used to improve oxidation resistance of Ni-based
indeed resulting coating was thicker in comparison to
superalloys [5,7,30,31]. Coating on Mar M-247 alloy
M1 sample aluminized in the same conditions (Tab 3.).
was obtained by out of pack method (950°C/4h) using
Its structure suggests that it was formed by a
powder mixture that contained aluminum and silicon
predominant outward diffusion of nickel atoms. In the
(Tab. 2). It has a total thickness of 27.3 µm (Tab. 3): outer layer aluminum content is in the range of 30 –
the outer layer is 14.6 (+/-1.8 µm) thick and the 25 wt. % (Fig. 1), while nickel is in amount of 53 – 56
interlayer 12.7 (+/-1.1 µm) thick (Fig. 2b). According wt. %. The intermetallic aluminide phase present here
to ref. [13], to obtain aluminized coatings alloyed with may be β -NiAl [25]. Linear analysis shown that silicon
silicon, Al/Si ratio in the saturating mixture must be mass volume in this area is steady: ~3 wt. %. Similar

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results presented Wu et al. [32] as they identified 3.4 – and the upper part of substrate (Fig. 2b). Mapping of
4.0 wt. % Si in the outer and inner part of aluminized the coating and linear analysis showed that there is no
layer prepared by pack cementation process (10wt% nickel, aluminum and cobalt in these areas. On the
Al + 10 wt. % Si + 75 wt. % Al2O3 + 5 wt. % NaF) other hand, strong concentration of W, Ta, Hf, Ti and
on the IC20 superalloy substrate (1100°C/1.5h). Si was observed (Fig. 4). Silicon comes from the
Moreover, clear cobalt gradient concentration is powder mixture (Tab. 2)( and it was co-deposited
visible (Fig. 1b, 4 and). Concentration of chromium in during the process. According to [36] it might form
the outer layer is very low (less than 2wt%), due to its silicates with: W, Ta, Hf and Ti. The analysis revealed
limited solubility in β-NiAl phase (Fig. 1b) [33]. A that hafnium concentrated only in these precipitates
chain of micrometer globular areas in the lower part (Fig. 4). Chromium-rich phases are dispersed
of outer layer is visible (Fig. 2b). Some of them have throughout the outer and interlayer (Fig. 4). They are
increased concentration of oxygen and chromium smaller than carbides and irregular in shape. Their
(Fig. 4, marked with yellow arrow), while the others occurrence derives from a restrained solubility of
do not (Fig. 4, marked with red arrow). Those without chromium in β -NiAl phase (~10 at. % at 1050°C),
a clear concentration of any element might be which is significantly decreasing with decreasing
Kirkendall pores. Such defects form due to temperature [37] Nickel content is minimum here (38
unbalanced nickel flux towards surface which can lead wt. %), whereas the aluminum is steadily lowering to
to a deficiency of atoms at the outer/inner zone obtain the value of 7.2 wt. % at the distance of 30
interface and formation of large voids [34] μm(Fig. 1). Main intermetallic phases from the Ni-Al
Characteristic feature of interlayer is increased amount equilibrium diagram are probably: β -NiAl and Ni3Al
of some alloying elements that reach their maximum [25]. Tu et al. [38] prepared Al-Si coatings on the
in there: 20 wt. % W, 9 wt. % Ta, 10 wt. % Cr. Other substrate of IC211 superalloy by pack cementation
metals (Hf, Mo, Si, Ti) also reach their peaks in the method with a pack composition: 10 wt. % Al + 2 wt.
interlayer. Changes in element contents derive from % Si + 5 wt. % NaF + 83 wt. % Al2O3. After
the process of “pushing back” their atoms during the aluminizing for 1.5 h in 1000°C they obtained a
growth of β -NiAl grains [35]. In the interlayer and double-layer coating, ~150 μm thick, with a
substrate there are many bright spherical precipitates homogeneous concentration of ~1 at. % Si.
with a diameter of ca. 3 μm distributed in the interlayer

Silicon phases

Cr-rich phases

Fig. 4 Elemental mapping of elements in M2 nickel-based superalloy

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M3 coating specific mélange: dark-gray matrix with light-gray

feathery phases (Fig. 2c). SEM microanalysis revealed
Two layers are visible on the substrate of Mar M-
the presence of a few micrometer phases forming a
247 alloy aluminized by pack cementation process in
chain across the coating in the direction perpendicular
1040°C/4h (Fig. 2c): outer 18.8 (+/- 0.4 μm) thick and
to its surface (Fig. 2c). W, Ta, Ti and C were detected.
interlayer 1.2 (+/- 0.1 μm) (Tab. 3). No defects (pores, Observed phases are probably primary MC or M23C6
particle inclusions) are visible. Powder mixture used in carbides [22,39] The amount of Cr (5 – 8 wt. %), Co
this process (100% AMDRY 353) consists of (6 – 9.5 wt. %) and W (10 – 15 wt. %) is gradually
aluminum (53.5 wt. %) and cobalt (46.5 wt. %). increasing to reach their peaks at the coating/substrate
According to paper [13], presence of second alloying interface. Chromium, tantalum and tungsten are a bit
element in an aluminum source (e.g. Fe, Cr or Co) more concentrated in the narrow interlayer, while the
lowers its activity, decreasing thickness of the coating. content of aluminum is drastically lowering in there.
Therefore the M3 coating is much thinner (20 μm) in This was confirmed by mapping analysis (Fig. 5, white
comparison to M4 – M5 coatings (99.8 and 228.7 μm) arrow). Góral et al. [17] aluminized Mar M247 alloy
obtained in the same conditions (Tab. 3). Aluminum using different techniques and varying process
content is gradually decreasing in the range of 28 – 24 parameters. All of the most frequently utilized
wt. %, while nickel increasing (40 – 43 wt. %). High methods were investigated. After the VPA
temperature (1040°C) and lowered aluminum activity (1020°C/4h) with a powder mixture containing 44 wt.
were enough factors to inhibit the formation of δ- % Al, a 50 μm coating with 33 wt. % Al was obtained.
Ni2Al3 phase. Instead, highly-saturated with aluminum The pack cementation and out of pack methods based
and alloying elements (~30 wt. %) β -NiAl phase was on the same powder mixture: 30 wt. % Al + 1 wt. %
probably formed. On this basis, we might assume that AlF3 + bal. Al2O3. Processes were conducted in
the coating was produced via the inward diffusion of 1000°C for 4 h. First method allowed to produce a 70
aluminum. The coating itself is not featureless and is μm layer containing 29 wt. % Al, while the latter a 140
composed of two main components forming a μm coating with 33 wt. % Al.

Fig. 5 Elemental mapping of elements in M3 nickel-based superalloy

M4 Coating (Tab 2) resulted in a formation of two-zone uniform
M4 coating was obtained via pack cementation aluminized layer: outer (86.8 +/-1.9 μm) and inner
aluminizing in 1040°C/4h. The use of powder mixture (13.0 +/-1.3 μm). No defects were observed (Fig. 2d).
containing 50% AMDRY 353 and 50% AMDRY 356 Such a thick coating can be attributed to a very high

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amount of activator used (5% NH4Cl, for other diffusion during aluminizing (Fig. 1d). Also, clear
samples it was 2% NH4Cl) which strongly affects aluminum gradient is visible (Fig. 1d, 6). Maximum
resulting coating thickness [13]. Outer layer accounts concentration in this zone reach following elements:
for almost 90% of whole coating thickness, which Cr (9 wt. %), W (12.5 wt. %), Ti (1.3 wt. %). Two types
suggests that the coating was formed by a of carbides can be found in Mar M247 alloy [1, 39-41]
predominant nickel outward diffusion. The amount of First of them are primary MC (M = Ta, Ti, Hf, W)
nickel in this zone is within the range: 42 – 48 wt. %, carbides, coarse and elongated, with a diameter of 2 –
while aluminum: 28 – 20 wt. %. Moreover, there is 10 μm. These carbides were found to have a complex
approx. 29 wt. % of other alloying elements. Outer composition with different amounts of carbide-
layer is composed of two main phases with bright, formers [39] There are also secondary (0.2 – 0.8 μm in
small spherical precipitates rich in Cr, W and Ta (Fig. diameter) Cr-rich M23C6 carbides, which precipitate
7). On the other hand, gray matrix contains ca. 55 wt. along grain boundaries forming thin networks [1]. As
% Ni and 29 wt. % Al which implies the existence of the bright phases presented in (Fig. 6,7) are coarse and
β -NiAl phase (Tab 5, spectrum 08 in the bottom part elongated and contain fair amount of tantalum (Tab.
of outer zone). Interlayer comprises a dark-gray matrix 5, spectrum 05 and 06), it is probable that they are (Ta,
and numerous precipitates in different shapes of grey W, Ti, Hf)C carbides. Szczotok et al. [39] reported the
(Fig. 2d). EDS mapping analysis showed, that some of occurrence of similar carbides with almost the same
them are rich in chromium and others in: W, Ta, Hf chemical composition in casted MAR M-247 alloy
(Fig. 6,7) Elemental mapping and point analysis after thermal cycling. Jonšta et al. [42] also identified
showed that in the aluminized layer all hafnium (Ta, Hf, W, Ti)C carbides in as-casted condition. Their
concentrated in carbides (Tab. 5, Fig. 7) Interlayer is presence in the outer layer further confirms its
slightly depleted of nickel, due to its little outward formation mechanism.

Fig. 7

Fig. 6 Elemental mapping of elements in M4 nickel-based superalloy

05 08
Cr-rich phases

06 07

Fig. 7 Elemental mapping of elements in M4 nickel-based superalloy. Enlarged area form Fig. 6

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Tab. 5 Point analysis of enlarged area form Fig. 7. Weight % of elements in analyzed points
Element content (wt.%)
Spectrum
Label
Ni Al Co Cr Ti Ta W Hf Mo
05 14.56 3.13 2.34 2.43 7.67 46.19 13.39 9.33 0.95
06 15.65 2.47 2.92 3.16 8.09 42.68 18.42 5.36 1.24
07 57.87 8.03 8.72 6.37 1.10 6.04 11.59 - 0.29
08 54.50 29.44 8.11 4.23 0.4 - 3.33 - -

M5 coating diameter of ~1 μm (Tab. 6, spectrum 11 and 12)

Mar M247 alloy was also pack aluminized in dispersed in the matrix, which have a composition
1040°C/4h with a use of mixture containing 80% typical for β -NiAl phase (Tab. 6 spectrum 13). There
AMDRY 356 and 20% Al. Among all variation of are also numerous, nanometer-size bright precipitates-
powder mixture, M5 had the most pure aluminum as they were not analyzed in this paper. A slight gradient
a source (20 wt. %). Thus, resulting monolayer coating of aluminum concentration is visible from the
was the thickest among all obtained in the same maximum content of 36 wt. % just beneath the
conditions (Tab. 2): 228.7 +/-7.8 μm (outer layer) and surface. Nickel is within the range: 40 – 45 wt. % and
2.1 +/-0.4 μm (interlayer). According to ref. [13], no more than 28 wt. % of alloying elements can be
increased amount of aluminum powder results in found in the coating. A narrow interlayer can be
more available aluminum atoms that can saturate observed with increased W, Ta, Hf, Ti and Cr
substrate material. Aluminum activity is then higher concentration (Fig. 9, white arrows). Coarse and
and the coating becomes thicker. Due to high activity elongated phases are dispersed throughout the coating
of powder mixture, only a very narrow interlayer was and substrate (Fig. 8). Mapping analysis of enlarged
formed (Fig. 2e) and coating was created by an inward area (Fig. 9) as well as point analysis (Tab. 6, spectrum
diffusion of aluminum atoms. In its upper part, 09 - 10) revealed that they comprise carbon and
coating is composed of three main constituents (Fig. carbide-formers, so they could be identified as primary
10b). Spectrum 14 represents chemical composition (Ta, W, Hf, Ti)C carbides [39]. Substrate material
of big, irregular phases – they are rich in chromium, contains ~1.5 wt. % Hf (Tab. 1). In the aluminized
tungsten and aluminum (Tab. 6). Matrix is represented layers it concentrates entirely in MC carbides with
by spectrum 15 and its chemical composition suggests “Chinese script” structure [28,29,42], as no hafnium
was identified in other places (Tab. 6). Eslami et al.
the presence of β -NiAl phase. Spectrum 16 shows
[43] conducted gas phase aluminizing of GTD-111
chemical composition of small, dense phases that are
nickel-based superalloy using a mixture with different
rich in tantalum (11.74 wt. %) and tungsten (12.61 wt.
amounts of aluminum and activator (1040°C/4h).
%). In the bottom part of aluminized layer there are
With the use of 10 – 30 wt. % Al, 5 wt. % NH4Cl and
also three different phases (Fig. 10a). Chromium and
balance Al2O3, they obtained 22 – 30 μm coatings.
tungsten are concentrated in dense phases with a

Fig. 10b

Fig. 10a
Fig. 9

Fig. 8 Elemental mapping of elements in M5 nickel-based superalloy

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09 10

Fig. 9 Elemental mapping of elements in M5 nickel-based superalloy; Enlarged area of precipitates

13 16
11 14
15
12

a) b)
Fig. 10 Enlarged area of bottom outer zone (a) and upper outer zone (b) in M5 nickel-based superalloy
Tab. 6 Point analysis of inclusions presented in Fig. 9, 10
Spectrum Element content (wt. %)
Label Ni Al Co Cr Ti Ta W Hf Mo
09 15.45 4.32 2.79 2.63 7.36 43.19 15.08 8.01 1.17
10 15.73 4.26 2.87 2.79 7.48 42.87 14.78 8.21 1.02
11 33.90 31.55 6.20 7.95 0.52 4.63 14.68 - 0.57
12 27.20 31.05 5.13 10.70 0.50 4.77 20.24 - 0.41
13 44.75 33.03 7.61 3.83 0.38 5.23 5.17 - -
14 25.03 40.95 4.76 10.69 0.47 1.48 14.64 - 0.28
15 45.42 34.14 6.43 2.78 0.31 6.65 4.19 - 0.09
16 28.10 35.10 4.07 4.77 2.44 11.74 12.61 - 1.17

Summary composition and process temperature (Tab. 2).

Obtained samples were analyzed using SEM
The comparison of different aluminide coatings microscope with EDX detector. Thickness of
produced on Mar M-247 alloy was performed. aluminide coatings was measured using ImageJ
Samples were aluminized and alumino-silicized for 4 software. Thickness of produced layers varied
h by two distinct methods. Processes were carried out pronouncedly as an effect of different process
in special CVD system with various powder mixture conditions. Amount of activator and pure aluminum

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