Aluminide Coatings on 304 Stainless Steel
Kevin L. Smith, Armen Kutyan, Shaghik A. Abolian, Tom F. Krenek,
Stephanie A. Salas, Vilupanur A. Ravi
California State Polytechnic University, Pomona
3801, W. Temple Avenue
Pomona, CA 91768
USA
ABSTRACT
Type 304 stainless steel coupons were aluminized at 650, 750 and 850°C for coating times in
the 1-25 hour range via halide activated pack cementation. Mass gains per unit area and
coating thicknesses were plotted as a function of time. Empirical rate equations and the
corresponding parabolic rate constants were obtained for the kinetics of aluminization for these
two metrics, i.e., mass change and thickness of coating. The Vickers micro-hardness values of
the coated regions ranged between 700-1114 HV. Coating surface phases were identified
using X-ray diffraction analysis as Al5FeNi, Al5Fe, Al86Fe14 and AlFe with one or more absent
depending upon coating temperatures and times. Scanning electron microscopy coupled with
energy dispersive spectroscopy was utilized to obtain diffusion profiles for aluminum,
chromium, nickel and iron.
Key words: coatings, pack cementation, aluminizing, stainless steel, high temperature
corrosion
INTRODUCTION
Austenitic stainless steels are becoming increasingly important in high temperature
applications largely due to a combination of desirable mechanical properties, ease of
fabrication, room temperature corrosion resistance during shutdown or maintenance periods
and overall cost effectiveness.1-4 The optimization of mechanical properties has to be balanced
against environmental stability.5 Depending on the industrial application, various forms of
corrosion can occur simultaneously which can include (but is not limited to) sulfidation,
carburization, hot corrosion and oxidation. One approach to retaining the mechanical
properties of the structural alloy while defending against corrosion is by the application of
protective coatings. Diffusion coatings are an effective method of achieving corrosion
resistance against the harsh conditions prevalent in high temperature environments. The
deleterious effects of oxidation can be mitigated through the application of an aluminide
diffusion coating.4 During high temperature exposures, the aluminum-rich surface oxidizes to a
highly protective aluminum oxide layer that inhibits corrosion by acting as a diffusion barrier.6
One of the more economical and effective methods for the application of aluminide coatings is
by halide activated pack cementation (HAPC).
HAPC is a coating process in which a halide vapor is generated inside a “pack” and ultimately
deposits a coating element on the surface of the substrate. 7-8 A typical “pack” in this process
includes a filler, master alloy, activator salt and a substrate. The filler is inert and is simply
used to achieve a uniform coating by allowing well distributed halide vapors consisting of the
master alloy and activator salt to reach the substrate. The activator salt constituent is used to
react with the master alloy to produce the halide vapor that will be deposited, and finally, the
master alloy is the constituent that contains the element that will be deposited on the substrate.
Aluminide coatings in this study were applied using pure aluminum as the masteralloy. In this
study, the HAPC process was used to aluminize the austenitic stainless steel alloy (304 SS).
The 300 series of austenitic stainless steels are a widely used class of materials and of these,
type 304 is a widely used grade, and was thus selected as a meaningful substrate for this
project.1
EXPERIMENTAL PROCEDURE
Stainless steel coupons, approximately 5 mm thick and 12.5 mm in diameter, were ground
down to a 600 grit finish. The mass and dimensions of each sample were measured. The
samples were then placed inside crucibles that contained “packs” of aluminum oxide,
aluminum and aluminum chloride powders. The experimental protocol was to use one sample
per crucible. The crucibles were sealed using a ceramic cement and heated in a furnace under
a flowing argon atmosphere to minimize oxidation. Austenitic stainless steel specimens were
aluminized at 650, 750 and 850°C for coating times in the 1-25 hour range. The mass and
dimensions for the coated samples were measured again and subjected to X-ray diffraction
(XRD) analysis and cross-sectional micro-hardness. Coating morphologies were examined
using optical and scanning electron microscopy (SEM) coupled with energy dispersive
spectroscopy (EDS).
RESULTS AND DISCUSSION
Coating Kinetics
As denoted by the Secondary Electron Images (SEI) in Figures 1 and 2, coating thickness
increased for higher coating temperatures (constant coating time) and longer coating times
(constant coating temperature). The images illustrate a cross-sectioned sample, where the
top, darker portion is the aluminide coating and the bottom lighter portion is the stainless steel
substrate.
(a)
(b)
(c)
Figure 1: Secondary Electron Images SEI of 304 SS aluminized for 1 h showing an
increase in coating thickness as temperature increases.
a) 650°C, b) 750°C and c) 850°C
(a)
(b)
(d)
(c)
(e)
Figure 2: Secondary Electron Images SEI of 304 SS aluminized at 650°C showing an
increase in coating thickness for longer coating times.
a) 1h, b) 4h, c) 9h, d) 16h and e) 25h
Figure 3 is a plot of the average coating thickness as a function of coating time. Each data
point is the average coating thickness based on 10 different measurements on 1 – 3 replicate
samples. The error bars represent  one standard deviation from the mean. The data points for
each coating temperature demonstrate that as the time was increased, the thickness increased
and followed a parabolic behavior of the form δ = kp (t1/2) + C in the 1 – 25 h time range, where
δ is coating thickness in μm, kp is the thickness rate constant in μm/hr1/2 and t is time in hours.9
Linear trend lines were fitted to each data set in the 1 to 25 hour range for 650, 750 and 850°C
shown below:
δ = 10.05*t1/2 + 12.68
@ 650˚C
(R2=0.96)
(1)
δ = 7.76*t1/2 + 36.56
@ 750˚C
(R2=0.90)
(2)
δ = 9.15*t1/2 + 50.84
@ 850˚C
(R2=0.95)
(3)
Coating thickness rate constants (kp) values were obtained at 650, 750 and 850°C from the
trend line slopes and were determined to be 10.05 μm/hr1/2, 7.76 μm/hr1/2 and 9.15 μm/hr1/2
respectively. The coefficients of determination (R2) are all reasonably high, with the 750C data
showing a noticeably lower value.
120.0
650°C
750°C
850°C
100.0
Thickness (µm)
80.0
60.0
40.0
20.0
0.0
0
1
2
3
Square Root of Time (√hr)
4
5
Figure 3: Thickness of the aluminide coating vs. square root time of the
aluminization process.
The average mass gain per unit surface area also increased as time increased in a similar
manner as thickness, however with a higher degree of uncertainty as shown in Figure 4. Each
data point represents an average of 2-5 replicates with the error bar representing  one
standard deviation from the mean. The samples in the 650°C temperature range exhibited
fewer errors as denoted by the smaller error bars. The samples in the 750°C temperature
range had larger mass gains than the 650°C range as anticipated, but showed larger scatter in
the data. The samples in the 850°C temperature range had larger mass gains than the 650°C
range but lower than the 750°C range. In addition, the 850°C trend line had a lower slope than
the corresponding ones at 650 and 750°C which was indicative of lower rates of mass gain at
this temperature. One possibility as to why the 850°C temperature coatings had lower mass
even though they formed thicker coatings may be attributable to a higher amount of porosity.
The other possibility is that the density of the phases formed may be lower. The data at 650°C
show a good fit to a parabolic rate equation (see equation 4 below) with a rate constant of 1.99
mg/ (cm2 h1/2), indicating a behavior of the form, (m/A) = km (t1/2) + C where m/A is the
mass gain per unit area, km is the rate constant, t is the time and C is a constant. The
coefficient of determination (R2) is reasonably high (0.94) for this fit.
20.00
650°C
750°C
850°C
Mass Gain (mg/cm2)
15.00
10.00
5.00
0.00
0
1
2
Time (√hr) 3
4
5
Figure 4: Mass gain vs. square root time for 304 SS aluminized at different
times and temperatures.
Mass gain = 1.99*t1/2 + 2.73
@ 650˚C
(R2=0.94)
(4)
It is important to note that the thickness equations corresponding to Figure 3 and the mass
gain per surface area equations corresponding to Figure 4 should only be utilized in the 1 to 25
hour range and are not valid in the 0 to 1 hour time range. At t = 0, the coating thickness
should be small and will be only due to the time interval during the temperature ramp-up.
Moreover the operating mechanisms may be different during this time.
X-Ray Diffraction
X-ray diffraction (XRD) was used to establish phase identities on the surface of the stainless
steel. From these studies, it was established that for long coating times (25h) at 650°C, the
surface of the coated alloys consisted mainly of the phases Al5Fe2 and Al5FeNi, while the
corresponding phases for the same coating time (25h) at 750°C were Al0.5Fe0.5 and Al86Fe14
and at 850°C the phase AlFeNi alone was detected. An example of the evolution of the
coating with time can be illustrated with the 750°C example. In this case, the surface
composition of the coatings evolved from AlFe and Al5Fe2 (1h) to Al0.5Fe0.5, AlFeNi, and
Al86Fe14 for longer coating times (9h and 25h). The corresponding coating evolution at higher
temperatures, 850°C, was from the phases Al86Fe14 and AlFeNi (1h) to AlFeNi at longer times
(25h). As shown in Figure 5, for coating times of 9 h, the surface of the coated alloy consisted
mainly of Al5FeNi and Al5Fe2 at 650°C, while the corresponding phases for the 750°C coatings
were Al86Fe14 and Al5FeNi as shown in Figure 6. At 850°C, however, Al86Fe14 and AlFe were
detected (see Figure 7). For longer times and higher temperatures the concentration of
aluminum increases. Also noted above, as times and temperatures increased, mass gain per
surface area increased denoting a higher ratio of the concentration of aluminum to iron with a
higher change in mass per surface area.
Figure 5: X-Ray Diffraction Pattern for 304 SS Aluminized at 650°C for 9h.
Figure 6: X-Ray Diffraction Pattern for 304 SS Aluminized at 750°C for 9h.
Figure 7: X-Ray Diffraction Pattern for 304 SS Aluminized at 850°C for 9h.
Micro-hardness
Figure 8 shows a micro-hardness profile as a function of distance into the 304 SS. The size of
the indents increased when transitioning from the coating to the substrate. Figure 9 shows the
Vickers micro-hardness values as a function of distance into the 304 SS. The 850°C profile
shows a small set of high hardness values close to the surface (HV 700 – 1114) with a
subsequent sudden drop at the coating/substrate (approximately HV 222 – 378). These values
were substantially less than those coated at 650 and 750°C.
Figure 8: Vickers micro-hardness profile for 304 SS aluminized at 750°C for 4h.
1200
650°C
750°C
850°C
Microhardness (HV)
1000
800
600
400
200
0
0
25
50
75
100
125
150
175
200
Depth (micrometers)
Figure 9: Plot of Vickers micro-hardness vs. depth for different coating temperatures.
Scanning Electron Microscopy (SEM)
SEM images of the coated cross-sections were obtained for representative samples subjected
to various coating temperatures (650, 750 and 850°C) and times (1 to 25 h). Coating
thicknesses ranged from 15 to 65μm for the 650°C temperature range, 30 to 70μm for the
750°C temperature range, and 35 to 100μm for the 850°C temperature range.
Using Energy Dispersive Spectroscopy (EDS) in conjunction with the SEM, the presence of
aluminum at the surface of 304 stainless steel was confirmed as shown in Figure 10. The
figure shows a backscattered electron image on the left and the corresponding elemental dot
map for aluminum on the right.
(a)
(b)
Figure 10: a) Secondary Electron image of the cross-section of 304 SS aluminized at
850°C for 1 h and b) Al X-ray map illustrating aluminum at the surface
The progress of the inward diffusion of aluminum was followed by plotting concentration (at. %)
versus distance into the alloy (micrometers). These concentration profiles were over-laid on
the corresponding electron image to give a visual representation of the effect of changing
chemical composition on the alloy microstructure. Figure 11 shows the variation of the
concentrations of Al, Cr, Fe and Ni as a function of the distance into the substrate. In general,
the aluminum concentration decreases with depth into the SS304 substrate. The aluminum
concentration profile shows noticeable step changes in concentration at approximately 10μm
and again at 25μm into the substrate. These sharp drops in aluminum concentration
demarcate phase boundaries.
Figure 11: Concentration vs. Depth for Al, Cr, Fe and Ni.
Figure 12 shows that the Al surface concentration remained fairly constant for the 650 and
750°C runs; however, the 850°C samples showed a decrease in surface concentration with
respect to time. This decrease is possibly due to activator and/or master alloy depletion in the
pack, subsequently leading to lower values for the mass gain at 850°C relative to 750°C as
shown earlier in Figure 4. Further experiments are underway to verify this hypothesis.
75.00
Al Concentration (Atomic %)
70.00
65.00
60.00
55.00
50.00
45.00
650°C
40.00
750°C
35.00
850°C
30.00
0
5
10
15
20
25
√time, (h)
Figure 12: Plot of Al surface concentration vs. aluminization time for 304 SS aluminized
at different times and temperatures.
The increase in the coating layer thickness and composition can be demonstrated by an
example (Figure 13), which shows the effect of increasing the process times on an aluminide
coating formed at 750°C. Initially the major phase is Al 5Fe2 and as time increases the major
phase becomes Al86Fe14 an intermetallic phase with an approximately 6 to 1 atomic ratio.
Figure 13: Schematic for Aluminized 304 SS at 750°C
CONCLUSIONS
Aluminum was successfully deposited onto type 304 stainless steel through the halide
activated pack cementation process. Rate equations and rate constants were obtained for
mass gain/unit area and coating thickness plots at 650, 750 and 850°C in the 1 – 25 h coating
period range. X-ray diffraction identified the surface phases as Al5FeNi, Al5Fe, Al86Fe14 and
AlFe depending upon the coating temperature and time. Coated steels had Vickers
microhardness values of 700-1114 HV.
ACKNOWLEDGEMENTS
The authors would like to acknowledge Edwards Life Sciences for their support in providing
access to scanning electron microscopy. In addition, they would also like to thank Mr. Ulus
Ekerman, Mr. Alejandro Cuevas, Mr. Samad Firdosy and Mr. Jordan Koch for help and
support. Financial support from Ms. Sylvia Hall, the LA Section of NACE International, Western
States Corrosion Seminar, Western Area Conference and the NACE International Foundation
is gratefully acknowledged.
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