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Effects of Pack Aluminizing Temperatures α2-Ti3Al/γ-TiAl Intermetallics

towards Hot Corrosion Behavior at 850°C

Article · June 2013

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Effects of Pack Aluminizing

Temperatures α2-Ti3Al/γ-TiAl
Intermetallics towards Hot
Corrosion Behavior at 850°C
Fadhli Muhammada, Eddy Agus Basukib
Departement of Metallurgical Engineering, Institute
of Technology Bandung, Bandung
a
Email: fadhlim_08@students.itb.ac.id,
b
Email: basuki@mining.itb.ac.id

Abstrak

I
n this study, the hot corrosion of Ti-46Al-2Cr-2Mo intermetallics coated with pack aluminizing
methods at various temperatures is investigated. The hot corrosion resistance of the alloy has
also been evaluated in order to determine the best temperature process of pack aluminizing.
The hot corrosion testing is done in mixed of Na2SO4 + NaCl melts at 850°C. The experiment
results show that pack aluminizing at 900°C gives the best corrosion resistance followed by pack
aluminizing at 1000°C. However, pack aluminizing at 1100°C gives poor corrosion resistance due
to the formation of the crack on the coating layer. This crack makes pitting propagate and increase
corrosion rate. As a consequence, a severe corrosion occurs on the alloy coated at 1100°C. The pack
aluminizing process is best done at temperature between 900 - 1000°C for 10 hours.
Keywords—Coating; hot corrosion; intermetallics; pack aluminizing; titanium aluminide.

I. Introduction also Ni-Based superalloys in the lower pressure turbine

Intermetallics alloys of Ti-Al have attracted
considerable interest among industrial companies for
high temperature applications such as aeroengine and
automotive engine. Due to their lower density (a half
of nickel based superalloy density), high yield strength
at high temperature, good creep resistance, and good
oxidation/corrosion resistance. These intermetallics
alloys regarded as strong substitute candidate for
conventional titanium alloy in the compressor part and
part [1].
γ-TiAl alloys are currently being used for turbocharger
rotors in automotive engine [2] and have now been
introduced for turbine blades in General Electric’s
GENx engine [3]. The cast Ti-47Al-2Cr-2Nb, which
passed the FAR33 certification in 2007 for GENx
engines that will power the B787, is regarded as the
greatest breakthrough in the TiAl technology up to now
[1].

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One of the major problem from two phases

intermetallics alloys α 2-Ti3Al/γ-TiAl is their oxidation
resistance that relatively poor at temperature above
750°C. To improve oxidation resistance and hot
corrosion resistance of these alloys, these alloys are
protected by aluminum coating on their surface.
Generally, the formation of this coating layer is done
by enrichment of Al, Cr, and Si on the surface of the
material. Due to their abilities to form protective oxide
scale Al 2O3, Cr2O3, dan SiO2 [4]. Between these three
kind of oxide, Al 2O3 is the most stable oxide scale for
applications at temperature above 900°C. Cr2O3 and
SiO2 scale tend to form volatile phase at temperature
higher than 900°C [5].
Aluminide coating on Ti-Al system (TiAl 2 and TiAl3)
was done by pack aluminizing methods. This method
has been chosen because the process is easy, cheap,
and could applied on relatively complex shapes. In
this study, the effects of various temperatures of pack
aluminizing are evaluated towards hot corrosion
behavior on two phases intermetallics alloys α 2-Ti3Al /
γ-TiAl at 850°C.

II. Experimental Procedures

Substrate used in this experiments is intermetallics
alloys that contain 46%-at Al, 2%-at Cr, 2%-at Mo, and
the rest is Ti. Pack aluminizing was done at various
temperatures such as 900°C, 1000°C, 1100°C for Fig. 1. Flowchart of experimental
10 hours. The pack consists of 23%-wt Al powder as procedures.
coating source, 2%-wt NH4Cl as activator, and the rest
Al 2O3 as inert filler. Generally, the experiments was B. Pack Aluminizing
performed according to the flowchart on Fig.1.
Coating was done by pack aluminizing method with
A. Production of α2-Ti Al/γ-TiAl substrate various temperatures. The prepared pack was mixed of
aluminum powder, activator NH4Cl, and Al 2O3. The
The TiAl alloys were preapared by melting metals in
mixed composition of pack is served on Table 1.
an electric arc furnace (EAF-DC) under high purity
argon atmosphere. The buttons of the material were Table I
Pack Composition
then further homogenized by heating in a tube furnace
at 1100°C for 10 hours in argon atmosphere. The as Weight
Material Function
homogenized substrate was then cut to obtain several %
samples in a dimension of 8 mm x 7.5 mm x 2 mm using Aluminum Coating source 23
wire cutter. The samples were then polished by abrasive NH4Cl Aktivator 2
paper and cleaned by ultrasonic cleaner. This sample Al 2O3 Inert filler 75
will be used as substrate for pack aluminizing.

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The pack filler was dried first in an oven at 110°C for

24 hours to exclude the moisture. The pack materials,
retort, and samples were put into an argon box. Argon
gas was then flowed for ± 100 ml/minute and leave for
15 minutes to purge the air out from argon box. The
pack materials were mixed throughly for 15 minutes
and the samples were inserted into the retort made from
alumina, closed with the lid, and sealed with alumina
cement (showed in Fig. 2).
Retort that has been filled with pack materials and
samples were inserted into tube furnace. Argon was
flowed with the rate of 10 mL/minutes for 10 minutes
to purge the air. The furnace was heated at 175°C for 1
hour to remove the moisture. The temperature was then
increased at various operating temperature such as at
900°C, 1000°C, dan 1100°C, respectively, for 10 hours. Fig. 2. (a) Retort that has been filled and sealed, (b)
Schematic ilustration of the placement of the samples in
After 10 hours, the furnace was turned off and the argon retort, (c) Schematic ilustration of the placement of the
retort in tube furnace.
was kept flowed until the temperature reached room
temperature. The retort was then taken out of furnace,
washed by water and cleaned by ultrasonic cleaner. The
schematic ilustration of pack aluminizing process is
showed in Fig. 3.
C. Hot Corrosion Testing
Hot corrosion testing was performed to know the
resistivity of the sample that coated by pack aluminizing
process at various temperatures, and also to determine
which temperature of pack aluminizing process was
produced the best corrosion resistance. Hot corrosion
were carried out in 75%-wt Na 2SO4 + 25%-wt NaCl at
850°C for 1 hours, 5 hours, and 10 hours. The examined Fig. 3. Schematic ilustration of pack aluminizing process.
samples were completely immersed into the molten
salts in ceramic crucibles with lids at 850°C at muffle
furnace. D. Microstructure Characterization
The samples were removed from the furnace at regular The corroded samples were mounted by resin, grinded
interval, cooled in air, washed in boiling water to by abrasive paper, polished by diamond paste, and
remove the salts on the surface of the samples, and dried etched in a solution of 10 mL HF, 5 mL HNO3, and
in hot air. The corrosion kinetics was characterized by 85 mL water. The samples were then analyzed by
measured the oxide thickness that formed using optical optical microscope and scanning electron microscope
microscope. equipped by energy dispersive Spectroscopy (SEM/
EDS).
Na2SO4 salts was formed due to the present of sulphur
from fuel, air consisted of NaCl salts and moisture, and III. Results
also oxidative environment. The following reaction
Fig. 4 shows the microstructure of pack aluminizing
might happened in the combustion chamber at
samples, respectively, at 1100°C, 1000°C, and 900°C.
aeroengine :
Pack aluminizing at 1100°C was produced coating layer
2NaCl + ½ O2 + SO2 + H 2O → Na2SO4 + 2HCl. (1) with average thickness 35.45 µm and interdiffusion
Due to this reaction, the corrosion testing was done layer with average thickness 33.14 µm. Pack aluminizing
using the mixture of Na 2SO4 and NaCl salts. at 1000°C was produced coating layer with the average

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thickness 39.34 µm and the interdiffusion layer with IV. Discussions

the average thickness 12.40 µm. And pack aluminizing
at 900°C was produced coating layer with the average
thickness 80.08 µm and no interdiffusion layer was
produced.
Hot corrosion testing was done on the samples that
coated at 900°C, 1000°C, and 1100°C and the uncoated
samples to analyze the depth of corrosion so that the
corrosion rate can be calculated. The depth of corrosion
on each sample was measured using the software that
connected to optical microscope. Each sample was
measured ten times at different locations.
A. Mechanism of Coating Formation
The mechanism of coating formation on the substrate
can be described schematically in Fig. 6. In the first
stage aluminum atoms brought by Al-halides deposits
on the surface of the substrate. The deposited Al the
further will diffuse into the substrate (stage 2). The
aluminum content in the region close to the surface
will be increased and form TiAl 2 (stage 3). With the
time the amount of TiAl 2 phase increases (stage 4). The
coalescence of TiAl 2 phase would produce a continuous

Fig. 4. Cross sectional microstructures of pack aluminized sample at (a) 1100°C, (b) 1000°C, (c) 900°C.

Fig. 5. Cross sectional microstructures after hot corrosion for 10 hours for (a) The sample
coated at 1100°C, (b) The sample coated at1000°C, (c) The sample coated at 900°C.

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layer of TiAl 2 (stage 5).
Since the flux of Al atoms diffuse from TiAl 2 to the
substrate through the TiAl 2 – environment interface
cause the content of Al in the region close to the surface
of TiAl 2 increases (stage 6). When the Al content in
this region reaches the composition of TiAl3, The
intermetallic phase of TiAl3 is developed (stage 7). The
diffusion coefficient of TiAl3 ( TiAl3) is higher than the
diffusion coefficient of TiAl 2 ( TiAl 2). Consequently,
this causes the rate of interface movement of TiAl3
– TiAl 2 faster than interface movement of TiAl 2 –
substrate (stage 7). This leads to the thicker layer of
TiAl3 compared to TiAl 2 layers.
Fig. 6. Model of mechanism of coating
formation on α 2-Ti3Al/γ-TiAl.
B. Analysis of Corrosion Rate
Between all of the pack aluminizing process, pack
aluminizing at 900 shows the most effective coating
layer to protect substrate because it has the lowest
corrosion rate. From the graphic, we can conclude
that pack aluminizing at lower temperature give lower
corrosion rate. It was also confirmed from the thickness
data that the pack aluminizing at lower temperature
has given thicker coating layer. The coating layer of
TiAl3 was also comfirmed effective enough to protect
substrate againts hot corrosion.
There was a deviation at the graphic on Fig. 7. The
graphic showed that the alumina coated sample at
1100°C has higher corrosion rate than the uncoated
sample. This phenomena can possibly occur if the
process time of pack aluminizing was too long. If the
process time was too long, all of Al powder, which is
the coating source, would quickly deposit at the surface
of the substrate and running out while the activator
was still present, as a consequences, the Al that has
deposited at the surface of the substrate may rediffuse
outward to the pack due to the gradient of activity. This
process leads the cracks of the coating layer as showed
in Fig. 4(a). The cracks tend to form pits that could
increase the corrosion rate and trigger more corrosion
damage on the substrate than the uncoated sample with
flat surface structure.
Fig. 7. Corrosion kinetics of pack aluminizing smples at various
temperatures.
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Fig. 8 shows the initiation of pitting at the samples Fig. 9 shows the SEM analysis for the pack aluminide
exposured for 1 hour in the molten salts. The EDS samples at 1000°C that exposured in the molten salts
analysis shows the present of 72,49% Al 2O3, 25,77% for 10 hours with the magnification of 150x and 1500x.
TiO2 , and 1,74% Cr2O3. It can be seen that the oxide The oxide was thick and penetrate deep enough into the
mixture was formed pitting. The pitting formation was coating layer, the EDS analysis at the outer coating layer
caused by the present of NaCl that significantly increase (spot 1) shows the oxide that formed were dominated
the corrosion rate of TiAl alloy. by 72.21% Al 2O3 and 22.55% TiO2 scales, and also
small amount of Cr2O3 and MoO3. SO3 was also found
Generally, Al 2O3 and TiO2 formed on the alloy surface
at the outer layer. However, EDS analysis at the inside
at the beginning of corrosion. However, in the molten
coating layer (spot 2) shows the formed oxides were also
Na2SO4 + NaCl, it is possible that TiO2 and Al 2O3 react
dominated by 54.13% Al 2O3, 44.48% TiO2 , and 1.4%
with NaCl according to this following reaction [6,7,8] :
Cr2O3.
2NaCl + Al 2O3 + ½O2 → 2NaAlO2 + Cl 2 (2)
There was no sulfides present at all of the examined
NaCl + TiO2 + O2 → NaTiO4 + ½ Cl 2 (3) samples but it was found that small amount of sulphur
The Cl 2 produced is able to penetrate through oxide react with oxygen to form SO3, it is meant that a little
scales quickly along pores or cracks. Cl 2 may then react of sulfidation process was occured but the process was
with Ti and Al directly on the alloy surface to form not dominant. This phenomena may happen because
volatile chlorides. the hot corrosion testing was carried out at oxidizing
environments. At oxidizing environments, oxide scales
Ti + Cl 2 → TiCl 2 (4) form readily because of high oxygen activity. Thus,
Al + Cl 2 → AlCl3 (5) oxidation dominates the corrosion reaction. When the
environment is reducing (i.e., low oxygen potentials),
The volatile chlorides may diffuse outward through the
the corrosion reaction becomes a competition
cracks or pores to the outer surface of the alloy. At the
between oxidation and sulfidation. Thus, lowering
surface of the scales, where the oxygen potential is high,
oxygen activity tends to make the environment more
the volatile chlorides may reoxidize by this reaction :
sulfidizing, resulting in increased domination by
TiCl 2 + O2 → TiO2 + Cl 2 (6) sulfidation [9].
2AlCl3 + O2 → Al 2O3 + 3Cl2 (7)
Cl 2 is regenerated and ready to rediffuse into the alloy
surface. At the scale-alloy interface, the amount of
Al and Ti are consumed in the process, until, in the
meantime, pits will initiate on the alloy surface. Because
the oxygen potential is much lower at the botom of the
pits, the volatile chlorides form and are transported
outward. This process makes the pits propagate, so
the alloy surface is nonuniform. According to this
mechanism, the self-sustaining-corrosion process may
occur with only small quantities of chloride phases. The
chlorides just act as catalysts [7,8]. This mechanism is
also supported by SEM image at the examined samples
showed at Fig. 9(a). Many cracks presents as the result Fig. 8. SEM image of cross sectional microstructure after hot
corrosion for 1 hour at pack aluminized sample at 1000°C.
of pitting propagation.
The mechanism also explains the cause of pack
aluminizing at 1100°C suffer the severe corrosion
damage, as like explained before that the formation
of coating layer of TiAl3 has brittle properties and
has many cracks, these cracks could lead pitting to
propagate easily so that could increase corrosion rate.

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Fig. 9. SEM image of cross sectional microstructures after hot
corrosion for 10 hour at pack aluminized sample at 1000°C. (a)
150x magnification, (b) 1500x magnification.
V. Conclusions
In Na2SO4 + NaCl melts at 850°C, the severe corrosion
damage occurs on the uncoated samples and the
samples coated at 1100°C. This damage happened
because the pack aluminizing process was too long so
the Al that has deposited at the surface of the substrate
may rediffuse outward to the pack.
Pack aluminizing at 900°C showed the lowest corrosion
rate in the molten salts because of the formation of
dense TiAl3 layer that makes Cl2 difficult to diffuse
through the pore and crack. Therefore, this prevents
pitting to propagate.
The coating layer stability will decrease with the pack
aluminizing temperature increase at the same process
time. Therefore, the pack aluminizing process on two
phase intermetallic alloys 2 fasa Ti-46Al-2Cr-2Mo was
better done at 900 - 1000°C for 10 hours. The existence
of chloride, even in a little amount, can accelerate the
corrosion rate.
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Acknowledgment
The authors would like to thank Dr. Sunara
Purwadaria for allowing us to use the laboratory of
Electrometallurgy and Corrosion, and all technical staff
at Department of Metallurgical Engineering Institute of
Technology Bandung for their assistances.
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