Aluminide Coating:
It’s a type of diffusion coating and can be performed by two different processes;
1) Low Activity High Temperature (LAHT)
One-step process because only β‐NiAl coating is formed. Since the aluminum activity is quite very low it cannot
be the predominant diffusing species. Consequently, coatings are formed by the diffusion of Ni from the
substrate to the coating.
The outer area is usually β‐NiAl phase which is rich in Al, whereas the internal area is rich in Ni
2) High Activity Low Temperature (HALT)
In this process, first δ‐Ni2Al3 is formed which requires subsequent heating operations to convert it to δ‐NiAl.
Since the aluminum activity is high enough in gas phase and in coating surface to provide the inward diffusion of
Aluminum into the alloy substrate.
Limitations:
Aluminide Coating lose their flexibility at temperature less than 750 oC
Thermo-mechanical fatigue; cyclic strains due to temperature gradient lead to crack caused by thermal fatigue
Platinum-modified Aluminide Coating:
Why we use Pt-modified Coating?
Diffusion Aluminide Coating is limited to temperature greater than 1000 oC
o Due to internal diffusion and oxidation as well
o Wastage of Aluminum from the surface over time
Formation of Coating:
About 5-10 μm thick layer of Pt deposited by electroplating method
Annealing is performed to create diffusion bond b/w Pt and the substrate alloy
Finally Aluminizing leads to the formation of Pt-modified NiAl coating
Platinum-modified Aluminide Coatings exist in two forms:
i. A single phase Pt‐modified β‐NiAl;
It is obtained when pre-aluminizing heat treatment is performed such that significant diffusion of Pt into the
surface of the substrate
ii. A two phase PtAl2 ‐(Ni‐Pt‐Al);
Pre-aluminizing annealing is performed such that Pt diffusion is quite very small then the bi-phasic PtAl 2‐(Ni‐Pt‐
Al) forms.
Advantages of Pt-modified Coating:
Pt improves the stability of coatings
By providing surface phase which is rich in Aluminum which form the continuous alumina oxide shell
Improves the adhesion of the oxide film on the surface of the coating but it increases thickening and residual
stresses
Since Pt is a refractory metal, it improves the strength of the outer layer and also provide resistance to hot
corrosion of aluminide layer
One of the main reason to use Pt is to suppress the diffusion of refractory element (W, Mo) into the surface
layers of aluminide coating
Also suppress void formation b/w coating and alumina interface -> scale adhesion and oxidation and corrosion
resistance improves
These coatings are normally used at lower temperature and corrosive environments and also used as a bond coat in
TBCs.
Platinum Effect On The Oxidation Behavior Of Nickel-Aluminide Coatings
Introduction:
Oxidation Resistant Nickel aluminide coatings are designed to develop protective alumina scale during high temp
exposure.
Pt with 6-8% provides substantial improvement in oxidation resistant. Also improve adherence of Alumina Scales
Voids developed at alumina/NiAl interface where sulfur was segregated and contact surfaces as well lead spallation of
the scale while Pt prevents sulfur segregation and void formation at the alumina/NiPtAl interface resulting alumina scale
being adherent on the surface
Pt performs:
1) Adding Pt to β-NiAl significantly improves the adherence of alumina scale during high temp oxidation. That’s
why, Pt modified Aluminide coatings used for oxidation protection of nickel base superalloys in the hot sections
of gas turbines.
2) Pt also reduces interfacial void formation
In binary alloys, about 2 at% Sulphur could segregate at the oxide-alloy interface during oxidation results a huge
reduction in interfacial strength. That’s why, by reducing sulfur in alloy could improves the adhesion of scale on NiAl
coating. Or by using Pt also reduces sulfur segregation to NiAl surfaces under vacuum
Experiment:
Coating is performed on single crystal superalloy CMSX-4. Pt modified coating was performed by electroplating followed
by low activity CVD aluminizing while NiAl coating was deposited by using the same CVD process.
Both coating have the same microstructure consisting of an outer single-phase NiAl layer and an inner multi-phase
diffusion zone.
Concentrations of Al 44-45%at on the surface while 12-13%at in the alloy. Pt modified coating ; Pt concentrations on the
surface is about 5%at to the mid section of the coating is about 8%at and at the alloy-coating interface is 0%. The outer
layer of both coatings also contains small amounts of Co, Cr, Ti and Re, and the inner layer is slightly enriched with W
and Ta.
The surface roughness is about 1 μm
Oxidation Experiments were carried out at 1150 oC in air -> Isothermal and Cyclic Tests (10 min hot time per cycle) were
Performed. Heating and Cooling rates are 200 oC/min
Samples were examined using SEM and alumina/coating interface chemistry is obtain using Auger spectroscopy after
10h, 100h, 250h isothermal oxidation
Oxide Spallation near the scratch mark
Results:
1. Cyclic Oxidation Behavior of Both Coatings: NiPtAl continuous weight gain throughout the 2000
cycles while NiAl started to lose weight after 500-600 cycles.
By visually observation, spallation of oxide occurs after 200-300 cycles but fully adherent surface on the NiPtAl
even after 2000 cycles
2. Isothermal Oxidation Behavior of both Coatings: No spallation on the NiAl coating at 1150 oC for
10h but can easily scratched off. Also scratched induced areas revealed no voids. But after longer thermal
exposures, extensive scale spallation occurs along grain boundary ridges with or without interfacial voids.
NiPtAl surface after 250h isothermal oxidation shows the same ridges but with no scale spallation, plus the oxide
scale was difficult to scratch off indicating strong interface. Scratching only induced small areas of spalls, which
showed oxide imprints with no voids.
Roughening occurs in both the coatings during cyclic oxidation
but few observed in NiAl coating because continuous scale
spallation from ridges and peaks and in isothermal conditions
these spalled areas are free of voids
No spallation occurs on the NiPtAl coating after cyclic
oxidation even cracks are obtained in the alumina along
the ridges
Auger Analysis:
Sulfur segregation is found in Al2O3/NiAl interface,
results showed that amount of sulfur already
reached to the steady state after 10h. Voids that
were oxide-free shows significantly higher sulfur
content up to 15 at.% . No sulfur was found in
Al2O3/NiPtAl interface.
Discussion:
Pt additions significantly improve alumina scale
adhesion during both the isothermal and cyclic
oxidation.
It is suggested that improved scale
adhesion is due to reduced interfacial voids
But results showed that voids are not
necessary for spallation. Because spallation
during cyclic oxidation did not reveal any
voids and also during isothermal oxidation,
same degree of spallation occurs with or
without voids
Spallation of oxide on NiAl occurs along grain
boundary ridges where local tensile stresses normal
to the interface developed upon cooling due to the
oxide-metal thermal expansion mismatch. And also
scale was notably more adherent after 10h because
thermal expansion mismatch is quite very small. In addition these local stresses must be compressive so that the scale
will remain adherent.
In NiPtAl coating, the interface is significantly stronger resulting no spallation after prolonged cyclic oxidation. AES
showed that no sulfur segregation at the oxide-metal interface.
Conclusions:
Sulfur was found to segregate at the Al2O3/metal interface during oxidation of the NiAl diffusion coating. The amount of
sulfur after 10, 100 and 250 h isothermal exposure at 1150 °C was at a near constant level of 1.0 ± 0.3 at.%. No sulfur
segregation was detected on the NiPtAl coating deposited on the same superalloy. The presence or absence of
interfacial sulfur is believed to be the cause for the weak and strong oxide adhesion on NiAl and NiPtAl, respectively.
Numerous interfacial voids developed on the NiAl coating, but only after prolonged isothermal oxidation. Scale
spallation initiated by delamination along surface ridges, and the process appears to be unaffected by the presence of
interfacial voids.
