4.

05 Diffusion Coatings
J. R. Nicholls, K. A. Long, and N. J. Simms
Cranfield University, Cranfield, Bedfordshire MK43 0AL, UK

ß 2010 Elsevier B.V. All rights reserved.

4.05.1 Introduction 2532

4.05.2 The Pack Cementation Process 2534
4.05.2.1 The Pack Aluminide Process 2534
4.05.2.2 Inward Growth Diffusion Coatings 2537
4.05.2.3 Outward Grown Diffusion Coatings 2538
4.05.3 Other Process Methods to Form Diffusion Coatings 2538
4.05.3.1 Slurry Cementation 2538
4.05.3.2 Fluidized Bed Techniques 2540
4.05.3.3 Metalliding 2541
4.05.3.4 Molten Salt Baths 2541
4.05.3.5 Gas and Vapor Phase Chemical Vapor Deposition Processes 2542
4.05.4 Modified Aluminide Coatings 2543
4.05.4.1 Platinum Aluminide Coatings and Bondcoats 2544
4.05.4.2 The Role of Impurities Introduced in Coating Manufacture 2546
4.05.4.3 Chromium- and Silicon-Modified Aluminides 2548
4.05.4.4 Reactive Element-Modified Aluminide Coatings 2549
4.05.5 Mitigating Substrate Alloy Interdiffusion Effects 2550
4.05.5.1 Smart Coating Concepts 2551
4.05.6 Summary and Conclusions 2552
References 2553

4.05.1 Introduction
Abbreviations
APS Air plasma spray
Diffusion coating processes have been applied for
CVD Chemical vapour deposition
more than half a century as a cost-effective method
DBTT Ductile to brittle transition temperature
of improving the environmental resistance of a base
EB-PVD Electron beam physical vapour
alloy by enriching the surface in Al, Cr, Si, B, Ti, Zn,
deposition
etc. The choice of surfacing material to be used
FBR-CVD Fluidized bed reactor-chemical vapour
depends on the base alloy and the final application of
deposition
the component once surface-treated. For example, bolt
HTLA High temperature, low activity – referring to
stock are widely available zinc-coated using the sher-
Al activity in the CVD process
adizing process to resist atmospheric and aqueous cor-
HVOF High velocity oxy-fuel
rosion, while for high temperature applications, similar
LTHA Low temperature, high activity – referring to
bolt materials could be chromized, that is, surface-
Al activity in the CVD process
enriched in chromium to produce a stainless steel
MCFC Molten carbonate fuel cell
surface layer. Probably the most exotic of these is the
PVD Physical vapour deposition
current practice to plate turbine blades with 5–10 mm
TCP Topological close packed
of platinum, diffuse and then vapor-aluminize to pro-
TMF Thermo-mechanical fatigue
duce a platinum aluminide, a high temperature oxida-
VPS Vacuum plasma spray
tion-resistant coating that may be also used as a

2532

bondcoat for thermal barrier coatings for first-stage
turbine blades in aero and industrial gas turbines.
Advanced applications include the surface engi-
neering of materials and components for aerogas
turbines, industrial gas turbines, medium speed diesels,
automotive petrol engines, steam turbines, various
power plant components, heat exchanges as well as
catalytic reactors in chemical and petrochemical pro-
cess plant. These illustrate the breadth of diffusion-
coating applications.
From a surface engineering perspective, the final
selection of the most suitable surface treatments/
coatings must consider the following:
(i) the operating temperature, both of the compo-
nent in service and the part/component during
coating manufacture and heat treatment;
(ii) the service environment, duty cycle, and load-
bearing capability of the treated components;
(iii) the desired design life and the influence of the
service temperature and duty cycle on long-term
metallurgical stability, with respect to oxidation,
corrosion and interdiffusion with the substrate;
(iv) ease of manufacture, reproducibility, and the
unit cost of the coating, compared to other
manufacturing routes that may involve more
costly corrosion-resistant alloys.
Obviously, loss of surface protection (passivation)
can result in very high rates of attack to the sub-
strate. In many cases, failure of a surface coating
could make substrate attack worse, and may, on
occasions, lead to catastrophic component failure.
Even when not catastrophic, it is bound to be costly
as a result of unplanned outage, downtime, and loss
of production. Hence, the principal reason for
applying a surface treatment of coating is to ensure
that the coating is capable of operating efficiently
throughout its design life. Diffusion coatings often
are proven to be a cost-effective solution in this
respect. Many diffusion-coating processes are so
well established that international standards exist
for their manufacture: for example, ASTM B 874-
96 (2008) ‘Standard specification for chromium dif-
fusion coating applied by pack cementation’1;
ASTM B 875-96 (2008) ‘Standard specification
for aluminum diffusion coating applied by pack
cementation’2; and British Standard BS 4921 ‘zinc
deposition using the ‘‘sherardising’’ process.’3
Pack-chromizing was in widespread use in the early
1950s4 to increase the oxidation/corrosion resistance
of low alloy steels. In the late 1960s, aluminizing was
first used for the protection of superalloy gas turbine
Diffusion Coatings 2533
aerofoils.5–7 Aluminide diffusion coatings are now rou-
tinely applied to nickel-base superalloy blades and
vanes used in the hot sections of gas turbines to
enhance their resistance to high temperature oxidation
and hot corrosion. Plain aluminides have provided
cheap and cost-effective solutions to protect superalloy
components within the high-pressure turbine of both
aero and industrial gas turbines. As such, they are
probably the most widely used coatings in service
within the gas-turbine industry. There was renewed
interest in siliconizing and silicon-modified aluminide
diffusion coatings for high temperature service in the
early 1970s8–11 when novel solutions to the low-
temperature hot corrosion problems associated with
contaminants in marine turbine plants burning impure
fuels were required. This interest continues with devel-
opment of multifuel-capable plants that may be fired
on gasified coal, biomass, or waste-derived fuels12 and
as coating methods to coat the internal cooling passages
of turbine blades.13,14
These aluminizing, chromizing, and siliconizing
processes result in enhanced corrosion resistance
through the formation of protective thermally grown
oxides of Al2O3, Cr2O3, and SiO2 as discussed else-
where in this book. It is also possible to produce diffu-
sion coatings containing a combination of aluminum
and chromium (chromaluminizing)15–26 or aluminum
and silicon8–13 plus modified aluminides containing
precious metals (Pt, Pd)6,27–34 or reactive elements (Y,
Hf and Zr).35–45 The performance of these modified
aluminide coatings will be discussed later in this
chapter.
Diffusion coatings can be applied to hot gas com-
ponents using a variety of techniques including pack
cementation, slurry cementation, and metallizing.
Comprehensive reviews of the methods of deposition
of diffusion coatings are given in Goward et al.,5
Goward and Boone,6 Grisaffe,7 Streiff and Boone,30
Meier and Pettit,31 Pichoir,46 Goward,47 Goward and
Cannon,48 Mevrel,49 Nicholls,50,51 and Pomeroy.52 All
diffusion coatings, whether depositing zinc vapor onto
steels (sheradizing) for aqueous/atmospheric corro-
sion protection, or forming high temperature oxida-
tion-resistant nickel or platinum aluminides, are
formed as a result of two distinctly similar process
steps, no matter what the manufacturing method used.
1. The solute elements must be brought into contact with
surface to be coated In the sheradizing process (zinc
deposition), the vapor pressure of zinc within the
pack (it is a pack cementation-based process) is
sufficiently high that no vapor-phase activator is
2534 Metallic and Inorganic Coatings
required; thus, zinc vapor generated in the pack
directly deposits onto the component surface,
ready for step 2, which is the ‘diffusion’ process.
However, for most metallic systems, this is not the
case; instead, an intermediate step is required,
which is the production of a vapor species with a
high solute metal content. This is most commonly
achieved through the use of a halide salt, or salt
mix, which may involve fluoride, chloride, or
iodide species. Bromide species are almost never
used for health reasons, although thermodynami-
cally there is no reason why they should not be
used. These halide additions are known as ‘halide
activators’ in the industry.
2. The solute diffuses into the component surface Step 2
is a key stage in the manufacture of a diffusion
coating. This diffusion step forms the surface alloy
or intermetallic compound. The process tempera-
ture influences the rate of diffusion, which species
may diffuse and the metallurgy of the surface
compound that may form and is, therefore, a criti-
cal parameter in the processing and manufacture
of diffusion coatings. This aspect will be explained
in more detail using the ‘pack-aluminizing’ pro-
cess as a case study (see Section 4.05.2.1). As well,
time at temperature defines the thickness of the
coating formed during this diffusion step.
Thus, the main differences between diffusion-coating
process routes reflect the method by which solute and
substrate are brought into contact. The time at tem-
perature controls the degree of interdiffusion, estab-
lishes the concentration gradients that will develop
from the surface to the interior of the coating and
defines the various layers that may form as dictated
by thermodynamic and kinetic considerations.
Table 1 summarizes the currently available
diffusion-coating process routes, together with a
selection of elements that may be enriched into the
substrate surface using these methods. Each of these
process routes will be briefly reviewed.
4.05.2 The Pack Cementation
Process
Pack cementation is still the traditional route used to
apply diffusion coatings, with standard procedures
established for chromium,1 aluminum,2 and zinc
deposition.3 For example, within the gas turbine
industry, pack cementation was introduced into aero-
engine service in 195748 and has been widely used to
coat turbine components since the mid-1960s.6,46–48
The coatings produced were based on the formation
of nickel or cobalt aluminides and this class of coating
is still extensively used, probably satisfying some
75–80% of the current world market, for protecting
turbine blades under aero, marine, and industrial
turbine service.
In this process, the components to be coated are
buried in a ‘pack,’ contained in a sealed retort. Figure 1
shows a schematic diagram of a typical retort used
to produce diffusion coatings, and Figure 2 shows a
photograph of the quarter-size commercial production
facility at Cranfield University.
The retort is heated to the desired processing tem-
perature under either an inert gas or hydrogen atmo-
sphere to prevent oxidation. The exact process cycle,
time, and temperature are dependent on the required
coating, coating thickness and the subsequent substrate
heat treatment. The pack contains a donor alloy that
releases solute material at a known rate and hence
determines the pack activity, a halide activator that
dissociates during the process cycle and acts to trans-
port the solute material from the pack to the compo-
nent to be coated and an inert oxide diluent to prevent
pack sintering.
Typical pack compositions used to produce a range
of metallic coatings are given in Table 2. Of these, the
three diffusion-coating processes that are most widely
used are: ‘sheradizing’ to zinc-alloy coat many small
steel parts in a wide range of manufacturing sectors
from the building industries, through domestic white
goods to many automotive parts to impart corrosion
resistance3; ‘chromizing’ which may be used to coat a
wide range of steel, stainless steel and nickel or cobalt-
based superalloys to impart improved corrosion resis-
tance for temperatures up to and sometimes in excess
of 800
C1; and ‘aluminizing’ which is widely used in
the aero and industrial gas turbine sector to develop
intermetallic surface layers that impart enhanced
corrosion resistance, thermal stability and, for some
applications, wear-resistant properties. The pack alu-
minizing process will be used as an example. The
formation of aluminide coatings by pack cementation
has been extensively studied, and details of the process
and characteristics of the coating are well documented
in the literature.3,5,6,15–18,20–31,35–42,46–52
4.05.2.1 The Pack Aluminide Process
During the aluminizing process, material from the
pack is transferred to the component surface through
the formation of intermediate volatile aluminum
Table 1 Diffusion coating process routes

Process route Process characteristics Diffusion coatings that may be produced on ferrous materials and superalloys

Al B C Cr Cu Mo N Nb Si Ta Ti V Zn

Pack cementation  Gas phase transport ▪ ▪ ▪ ▪ ▪ ▪ ▪ ▪ ▪ ▪ ▪ ▪

# source material as a powder
# halide activator
# 700–1200
C
 Solid state diffusion ▪ ▪
# source material as a fine
powder
# temperature below the alloy
melting point
# no activator
Slurry cementation  Spray or dip coat application ▪ ▪ ▪
# coating material, halide
activator and organic binder
prepared as a paint or slurry
# heat treated after coating
700–1200
C
Fluidized bed  Activated gas fluidization ▪ ▪ ▪ ▪ ▪
methods # the halide activator is
incorporated in the
fluidizing gas
# the coating material is in the
fluidizing bed
# 500–1100
C
Molten salt bath  Direct thermochemical ▪ ▪ ▪ ▪
processes processing
# 500–900
C
 Metallizing ▪ ▪ ▪
# an electrolytic process in

Diffusion Coatings
alkali fluoride solvents
# 500–1200
C
Gas or vapor phase  Over pack process ▪ ▪
processes # similar to pack process, but
components processed in
the gas above the pack
# 900–1200
C
 Vapor phase sources ▪ ▪ ▪ ▪
# Halide vapor phase sources
generated in a separate

2535
vapor generator
# 900–1200
C
2536 Metallic and Inorganic Coatings

monohalide gas, and as such the coating process is alloy results in the formation of the intermetallic coat-
probably more accurately described as a chemical ing, primarily NiAl, CoAl, FeAl, or TiAl depending on
vapor deposition (CVD) process. Interdiffusion bet- the alloy base, but containing, to a degree, most of the
ween the depositing aluminum and the substrate elements present in the base alloy, either in solution or
as dispersed phases.
Over-pack The CVD aluminizing process is best illustrated
specimen and described by the schematic in Figure 3, which
describes the various chemistries involved during alu-
minum deposition and the formation of a nickel alu-
minide coating from an aluminizing pack. The
Vapor processes involved in diffusion coating are complicated
even when only nickel and aluminum are considered,
as illustrated schematically in Figure 3. This behavior
Retort/boat Pack reflects the thermodynamic stability of the various
powder
phases in the nickel–aluminum binary system; the
Specimens range of compositions for which each nickel aluminide
phase is stable (which varies with process temperature);
Figure 1 Schematic of a pack cementation facility.
and the dominant diffusion processes in the newly
(near surface) formed alloy due to the interdiffusion
CVD hot wall chamber processes (which also depends on alloy composition).
Furnace raised position The deposition rate and morphology of the coat-
lowered position
ing depend on pack activity, process time and tem-
perature. Table 3 presents two pack compositions
used in research at Cranfield to produce nickel alu-
minide coatings described in this section and illu-
strated in Figures 4 and 5. Coatings are classified as
either ‘high activity,’ when inward diffusion of alumi-
num occurs or ‘low activity,’ when outward diffusion
of nickel occurs. Thus the first pack composition in
Table 3, with a higher aluminum content, is used at
lower temperatures, 700–950
C. This forms ‘low-
temperature high-activity (LTHA)’ nickel aluminide
Pack cementation retort coatings. (See Figure 4 for a sample micrograph of
this coating produced on the nickel-based superalloy
CMSX4.) For this case, a surface layer of Ni2Al3
forms and a further heat treatment is required to
Figure 2 Pack cementation facility at Cranfield University: convert this brittle surface layer to NiAl. This step
this is quarter size of an industrial production facility. is usually combined with the heat treatment required

Table 2 Typical compositions and deposition temperatures for halide activated pack cementation

Coating Pack composition Deposition temperature

(wt%) (
C)

Al 1.2–2.7% Al, 0.8–1.2% NaF, bal. Al2O3 900

B 80% B, 16% Na2B4O7, 4KBF4 900
Cr 48%Cr, 48% Al2O3, 4NH4Cl 850–1050
Cu 50% CuO, 50% NH4Cl –
Mo 75% Mo, 6% Mg, 18% TiO2, 1% NH4Cl –
Nb NbFe, Al2O3, NH4Cl 1000–1100
Ti 77% Ti, 20% TiO2, 3% NH4Cl –
V 40–50% FeV, 2% NH4Cl bal. Al2O3 900–1200
Zn 37.5% Zn, 43.5% ZnCl2, 19% KCl 300–350
 Diffusion Coatings 2537

Component Gas phase Pack

(HTLA) AlCl
outward diffusion of Ni
3AlCl + 2Ni → 2NiAl + AlCl3 NH4Cl → NH3 + HCl
6HCl +2Al → 3AlCl3 + 3H2
(LTHA) AlCl3 + 2Al → 3AlCl
inward diffusion of Al
3AlCl + 4NiAl → 2Ni2Al3 + AlCl3 AlCl3

Figure 3 Schematic illustration of the chemistry involved in the ‘pack aluminizing’ process.

Table 3 Example aluminide pack compositions

Pack Constituent Low-temperature high-activity (LTHA) pack High temperature low-activity

(HTLA) pack

Process temperature 700–950
C 950–1100
C

Aluminum flake: (to BS 388)40 1.7–2.7 wt% 1.2–1.5 wt%
Activator
NaF 0.8–1.2 wt% 0.8–1.2 wt%
KHF 0.05–0.15 wt% 0.05–0.15 wt%
NH4Cl 0.1–0.2 wt% 0.1–0.2 wt%
AlF3 Trace Trace
Alumina Balance Balance
Uncombined water <0.3 wt% <0.3 wt%

to recover substrate properties. This coating was 4.05.2.2 Inward Growth Diffusion Coatings
deposited using an aluminiding pack containing 2%
When the aluminizing process parameters are chosen
Al at 900
C, and was heat-treated for 2 h at 1120
C
such that the aluminum activity at the component
and then for 24 h at 845
C. Figure 5 illustrates,
surface is high, then reaction between the nickel-
similarly, a nickel aluminide coating produced using
based superalloy (g-Ni þ g0 -Ni3Al matrix) and
a high temperature low-activity (HTLA) process.
the depositing aluminum forms a surface layer of
The HTLA process results in the outward diffusion
d-Ni2Al3, over a subsurface layer of b-NiAl. This
of nickel from the superalloy to react with the
reaction is evident in the simple Ni–Al binary
depositing aluminum to form a monophase b-NiAl
phase diagram, for process temperatures between
intermetallic surface layer. The pack composition
854 and 1133
C (Figure 6), but may be further
(Table 3) used to deposit this coating has a lower
complicated by the addition of tertiary and quater-
aluminum content but is processed at high tempera-
nary elements which may modify the equilibrium
tures, 950–1100
C.
phase structures.
From this simple illustration, it is clear that the
In d-Ni2Al3, the diffusivity of nickel is near zero
properties and performance of an aluminide coating
when compared to aluminum, which diffuses rapidly
(or for that matter any diffusion coating) will depend
( Janseen and Rieck measured this diffusion rate as
upon the process methodology used, the substrate
1.8  108 cm2 s1 at 600
C)53; thus, the formation
temperature and the subsequent heat treatment. For
of a surface layer of d-Ni2Al3 ensures that the coat-
aluminide coating (also modified aluminizing coatings
ing growth results from the inward diffusion of
such as platinum aluminides, see Section 4.05.4.1),
aluminum. Phase equilibria require that beneath
the critical difference in the processes reflects
this layer b-NiAl is formed to accommodate the
whether the coating is formed by inward aluminum
aluminum flux. This b-NiAl phase can react further
diffusion, that is, inward grown diffusion coatings,
with the inward diffusing aluminum to form more
or outward nickel diffusion, that is, outward grown
d-Ni2Al3.
diffusion coatings.
2538 Metallic and Inorganic Coatings
50 mm
Figure 4 A nickel aluminide diffusion coating produced
using a low-temperature high-activity (LTHA) pack
cementation process.
Acc.V Spot Magn Det WD Exp 50 μm
20.0 kV 4.0 483x BSE 9.8 1 0.5 Torr
Figure 5 A nickel aluminide diffusion coating produced
using a high temperature low-activity (HTLA) pack
cementation process.
2NiAl þ Al ! Ni2 Al3
As a consequence of this inward growth process, slowly
diffusing alloying elements within the substrate can be
entrapped in the inwardly growing aluminide coating.
Thus, a high-activity aluminide coating contains pre-
cipitates that are rich in W, Mo, Ta, Re, and Cr within
the b-NiAl phase.
After aluminizing, the coated material is given a
high temperature heat treatment (usually linked to
the heat treatment necessary to recover the base
alloys’ mechanical properties). During this heat treat-
ment, nickel is able to diffuse outward from the
substrate, which results in the transformation of the
brittle d-Ni2Al3 phase into an aluminum-rich b-NiAl
(b-NiAl has a wide solubility range for nickel and
aluminum, from 46 to 74 at% Ni, 36 to 54 at% Al
measured at 1100
C).
4.05.2.3 Outward Grown Diffusion
Coatings
When the aluminizing process parameters are
selected such that the aluminum activity at the com-
ponent surface is low (low aluminum content in the
pack, high process temperatures), then aluminum is
deposited on the surface, but at a reduced rate, and
nickel simultaneously diffuses outward to the surface.
A b-NiAl surface layer now forms. For stoichiometric
and substoichiometric NiAl (Al contents less than
51 at%),55 the diffusivity of nickel in b-NiAl is
much higher than that of aluminum. Figure 7 pre-
sents the variation in nickel to aluminum diffusivity
at 1100
C as a function of the aluminum content of
the b-NiAl phase.55 Thus, this rapid nickel diffusion
to the surface, coupled with the low aluminum activ-
ity at the surface, effectively holds the surface alumi-
num content at 51 at%. Hence, HTLA coatings are
near-stochiometric at the surface and nickel-rich
within the subsurface b-NiAl phase that has formed.
This structure ensures outward nickel transport and
the outward growth of the coating microstructure.
Another important outcome of this outward diffusion
process is that slowly diffusing elements from the sub-
strate are unable to diffuse to form significant concen-
tration levels in the outwardly growing b-NiAl. The
outer zone of this coating therefore appears much
‘cleaner’ and is free from such precipitates as observed
in the inwardly grown, aluminum-rich coating formed
at lower temperatures and higher aluminum activities.
4.05.3 Other Process Methods to
Form Diffusion Coatings
4.05.3.1 Slurry Cementation
Slurry-based diffusion coatings are commercially
available, offering similar chemistries to those found
in conventional pack cementation aluminide coat-
ings. In slurry cementation, the coating materials
and halide activator are blended as a slurry or
particle-loaded paint system, using either an organic
binder or a water-based emulsion. The slurry/paint
system can be applied to the part to be coated
through dipping or spraying at or near room temper-
ature. The slurry spray is then cured onto the part
through a low-temperature thermal treatment, typi-
cally around 200
C. The cured pre-diffusion coating
 Diffusion Coatings 2539

Nickel (at%)
0 10 20 30 40 50 60 70 80 90 100
1800

1638 ⬚C
1600 L

1455 ⬚C
1400
AlNi

(Ni)
Temperature (⬚C)

1200
1133 ⬚C

1000

854 ⬚C
660.452
800
~700 ⬚C
639.9 ⬚C
600

Al3Ni2
Al3Ni

(Al) Al3Ni5 AlNi3

400
0 10 20 30 40 50 60 70 80 90 100
Al Nickel (wt%) Ni

Figure 6 The Ni–Al binary phase diagram. Reproduced from Singleton, M. F.; Murray, J. L.; Nash, P. In Binary Alloy
Phase Diagrams; Massalski, T. B., Ed.; ASM Materials Park: OH, 1990; Vol. 1, p 142.54

may contain only aluminum, aluminum þ chromium,

Cδ = 37.8 at %Al, Cβ =37.4 at % Al, showed pack pick up
43.0 39.0 aluminum þ silicon, or aluminum þ chromium þ
42.0 39.0
51.2
40.1
39.0
44.2
silicon, depending on the final service conditions
50.3 45.5 No pack pick up
51.5 45.5 envisaged. After this overlay of binder, activator and
51.5 47.2
53.0 39.0 reactive metals has been built up, the aluminum,
51.2 45.5
2.0 silicon and other additions are diffused into the sub-
6.0
1.5
5.0 strate by heating the precoated parts in a furnace at
4.0
3.0
temperatures between 650 and 1100
C depending on
1.0
the substrate to be coated and its final application.
ln DNi /DAl

DNi/DAl

2.0
0.5 The temperature is chosen such that the coating
0 1.0
material contained in the slurry reacts and interdif-
fuses with the substrate to form the final intermetallic
–0.5
0.5 coating. Reaction temperatures and the reaction che-
–1.0 mistries are similar to those for pack cementation for
0.3
–1.5
0.2
halide-activated slurry systems. For systems not
–2.0
involving halide activation, diffusion occurs through
0.1 direct contact between the molten aluminum or
–2.5
aluminum-silicon particles in the precured cement
–3.0
36 38 40 42 44 46 48 50 52 54
and the substrate to be coated.
Composition at marker plane (at, % Al) Sermatech was an early protagonist of this form of
Figure 7 Variation of DNi/DAl with composition in b-NiAl at
coating, with SermaLoy J (Figure 8) – one of the first
1100
C. Reproduced from Shanker, S.; Siegle, L. L. Met. widely adopted slurry aluminide coatings – providing
Trans. 1978, 9A, 1467. outstanding resistance to type II hot corrosion.56–58
2540 Metallic and Inorganic Coatings

Fluidized masteralloy
powder Furnace
(Al, Cr, Si...)

Sample

Ar, H 2, HCl

Figure 9 Schematic of a fluidized bed chemical vapor

deposition system.
20 ␮m 20 KV 00 074 R

Figure 8 Micrograph of SermaLoy J.

excellent mixing and dispersion within the bed, effi-
cient heat and mass exchange is ensured, giving
This slurry aluminide coating forms a silicon-enriched
uniform coatings on complex-shaped parts.63–65
outer layer containing Cr2Si phases in b-NiAl, and
This allows uniform aluminide coatings to be pro-
provides oxidation and corrosion protection up to
duced on ferritic steels in relatively short times at
1000
C.56–58 Later, as engine technologies advanced
temperatures below 700
C.66,67 For FBR-CVD, the
and directional solidified or single-crystal alloys were
fluidized bed (Figure 9) consists of a mixture of the
more widely adopted, less chromium was available
material to be deposited and an inert diluent, which
within the alloy to form CrSi2 (a critical phase within
forms the bulk of the fluidized bed and is most often
SermaLoy J)56; thus, joint research between Sermatech
alumina or silica. The halide activator is carried in
and Rolls Royce led to the development of SermaLoy
vapor form by the fluidizing gas and is introduced into
1515,59 a multilayered structure slurry aluminide coat-
the fluidizing gas usually from a separate vapor gener-
ing containing bands of CrSi2. This variant is capable of
ator or directly as HCl gas. This latter process is
providing hot corrosion protection to low-chromium-
widely used in laboratory-scale systems by fluidizing
containing single-crystal alloys.58,59 Other variants of
the bed in a once-through cycle with HCl in the
the slurry aluminide process are now available com-
fluidizing gas.66,68 In more commercial-size plants,
mercially, including IP1041 developed by Indestructi-
the fluidizing gas is recirculated and the level of HCl
ble Paints in the UK, and Ceral 10 by BWD Turbines
to H2 in the feed gas adjusted to control the generation
Ltd. The latter uses a water-based slurry process to
of the precursor vapor species. Also, when a vapor
deposit the prediffused overlay coating prior to heat
generator is used, it is possible to control the chemical
treatment and reaction to form the Si-containing alu-
activity of the active vapor supply to the fluidized bed
minide coating. Most recently, slurry aluminide coat-
reactor.
ing methods have been researched as a potential
Components to be coated can be hung in the
method for providing oxidation protection of Fe–Cr
fluidized bed or supported on custom-designed fix-
ferritic steels for steam power plants,60–62 where the
tures, depending on their size. The chemistries in
ability to form an iron aluminum oxidation-resistant
FBR-CVD has been extensively studied60–68 and is
coating at temperatures as low as 650
C, coupled with
similar to the LTHA aluminizing process of the pack
the capability to coat large steam turbine components
cementation method, when aluminum powder is part
at reasonable costs, makes the process commercially
of the fluidized bed medium. The primary differ-
competitive.
ences are that the halide vapors are flowing, rather
than diffusing, and that the carrier particle density is
4.05.3.2 Fluidized Bed Techniques
much lower in the fluidized bed than in the pack.
Fluidized bed reactor-chemical vapor deposition Specifically, the gas flow rate must be greater than
(FBR-CVD) offers a cross between pack cementation the minimum fluidization velocity; for a small labo-
and CVD processes. In addition, because of the ratory experimental system, this would require argon

gas flow rates between 0.35 and 1.1 l min1, with
the fluidizing gas containing 5–30 vol% H2 and
0.5–3 vol% HCl.66,68 Given a reactor tube diameter
of 3.5 cm in this laboratory scale system,66 this
equates to a linear fluidization velocity between 0.6
and 2.0 cm s1 when the fluidized bed has a height of
3 cm. Scaling to large fluidizing vessel sizes, there-
fore, requires high gas flows; for example, for a once-
through cycle, a 35-cm-diameter bed would require
gas flows in excess of 100 l min1. Thus, large quan-
tities of activator (HCl) and reactive gas (AlCl3 in the
case of aluminizing) would be lost to the scrubbing
system. For these reasons, commercial fluidized bed
systems use recirculating fluidizing gases, but this
requires that the pumps, pipework and flow control
equipment are designed for HCl service.
However, the benefits are that the use of a flui-
dized bed reactor for CVD deposition offers rapid
and uniform heating of parts to be coated and good
long-term stability (typically  0.5% variation in bed
temperature, even when the bed is 15 m in diameter).
These properties reflect the high heat and mass
transport rates reported for fluidized bed systems,63,64
improved process flexibility, lower capital and
operating costs, precise process control, better envi-
ronmental control, and the ability to automate the
coating process.67 Thus, in addition to aluminizing,
fluidized bed systems have been proposed for chro-
mizing, boronizing, nitriding, and carburizing.68–72
4.05.3.3 Metalliding
Metalliding uses molten alkali and alkaline-earth fluor-
ides as solvents for the electrolytic deposition of diffu-
sion coatings. This process is well documented for the
formation of alloy and intermetallic coatings following
high temperature electrolysis in these molten salts.73–78
The process is usually carried out at temperatures in the
range 500–1200
C in metallic vessels under inert gas,
principally argon. The metalliding process is a specific
method to deposit highly reactive metals that cannot be
normally plated from aqueous solutions. Thus, alumi-
num, various refractory metals, the actinides, and
many rare-earth metals can be deposited using the
metalliding process. This capability to deposit refrac-
tory metals means that the metalliding process pro-
vides a coating route for niche-market applications. It
has been used to manufacture protective refractory
metal carbide coatings to protect components in con-
tact with nuclear fuel73 and to manufacture protective
coatings for nickel cathodes (Ni3Nb) for use in molten
carbonate fuel cells (MCFCs).76
Diffusion Coatings 2541
The metalliding process was patented by N.C. Cook
in the 1960s,79,80 then at General Electric, to manu-
facture alloy and intermetallic coatings. Although
process temperatures between 500 and 1200
C are
quoted, it is now acknowledged that many of the
surface layers that are formed are thin unless pro-
cessed above 800
C.73 The process consists of a gal-
vanic cell where the anode is the reactive metal to be
deposited and the cathode is the component to be
coated.79–81 Three modes of coating manufacture
are now cited81:
1. Electrodeposition of a pure reactive metal onto
the cathode, followed by interdiffusion of the
metallic layers to form the alloy or intermetallic
coating.
2. Metalliding, using a galvanic cell, as originally
proposed by Cook.79,80 In this metalliding process,
interdiffusion occurs alongside the electrodeposi-
tion to form the alloy or intermetallic coating.
3. Thus, mode 1 can be used to deposit a surface
coating from a molten salt in the temperature
range 500–800
C, which is subsequently diffused
at higher temperatures or for longer times at the
deposition temperature, whereas mode 2, the orig-
inal patented metalliding process, requires higher
process temperatures, in excess of 800
C.
4. The third mode is similar to mode 1 but involves
deposition of the coating at the ‘under potential’
for the alloy formation, following some interdiffu-
sion process.81
In general, the purity of the fluoride solvents must be
very high if a good and reproducible diffusion coat-
ing is to be formed. Any impurity cations in the melt
will be codeposited.
Since metalliding reagents are electrochemically
more reactive than the components to be coated, each
coating material can only be deposited onto a spe-
cific group of metals to produce diffusion coatings.
The more active the metal, the larger the scope of
metallic substrates that can be coated. The most
useful metalliding reactions include boriding, alumi-
niding, siliciding, titaniding, chromiding, zirconiding,
and most recently the deposition of niobium and
tantalum intermetallic coatings ‘niobiding’ and ‘tan-
taliding’ for the niche metal carbonate fuel cell
markets.73,76
4.05.3.4 Molten Salt Baths
Molten salt baths have been widely used for the
direct thermochemical formation of diffusion coatings.
2542 Metallic and Inorganic Coatings
The formation of chromized coatings for corrosion
protection and chromized, carburized, carbo-nitrided,
nitrided, and borided diffusion coatings for wear pro-
tection are classic commercial examples of this form
of diffusion coating manufacture.
In this process, components are treated in a bath
containing a molten salt of the species to be depos-
ited, which is then diffused into the component sur-
face. For example, a mixture of chromous and
chromic chlorides is used to form a ‘chromized’ dif-
fusion coating.
Sodium and potassium cyanides are used in the
salt baths for carburizing, carbonitriding, and nitrid-
ing. At a given temperature, the percentage of sodium
or potassium cyanate generated in the bath deter-
mines whether a carburized or nitrided surface is
produced. For low cyanate and high cyanide concen-
trations, carburization of the component surface
occurs. At cyanate concentration around 10% and
for temperatures between 750 and 900
C, mixed
carbonitride surface coatings are produced. Increas-
ing the cyanate concentration to around 25% at
temperatures between 500 and 750
C results in the
formation of a nitride-rich surface layer (all salt bath
nitriding processes produce iron carbides as well as
iron nitrides).
Thermochemical liquid-phase boriding processes
are based on molten borax to which reducing agents
such as ferroboron or boron carbide are added.
4.05.3.5 Gas and Vapor Phase Chemical
Vapor Deposition Processes
Gas and vapor phase processes offer the most diverse
range of diffusion/chemical conversion coatings. The
largest volume production of coatings based on gas
and vapor phase CVD is used to combat wear. Pyro-
lysis of hydrocarbon gases, such as methane and pro-
pane, is used to carburize metal components. This
method is generally cheaper to operate and more
widely used for high-volume production than any
other method aimed at producing a carburized sur-
face treatment. The addition of ammonia to the
hydrocarbon gas results in the formation of carbon
nitride coatings; while pyrolysis of ammonia at tem-
peratures between 500 and 525
C produces a
nitrided surface.
Chromized, boronized, siliconized, and alumi-
nized diffusion coatings can also be produced by
vapor decompositions but not generally at the com-
mercial scale used for carburized and nitrided surface
treatments.
In the corrosion field, especially high temperature
oxidation and corrosion, chromizing and aluminizing
are the most widely applied CVD coatings. Although,
pack cementation (Section 4.05.2) is probably the
most versatile and easiest-to-install small-batch pro-
cess, the better process control of CVD – particularly
the ability to codeposit metals and add small reactive
element additions (see Section 4.05.4.4) – has seen
an increased use of CVD and vapor phase coating
routes to deposit high temperature corrosion-resis-
tant coatings. A further advantage of these purely gas
phase processes is the ability to coat internal cooling
passages of the gas turbine blades, by directly feeding
the vapor species into the existing cooling passages
cast into the turbine blades.13,14,43,44 Pressure ‘pulse
aluminizing’82 can also be used to aid vapor transport
into these narrow internal cooling passages.
(a) The out-of-pack or over-pack process operates in a
manner very similar to pack cementation, except
that the parts to be coated are suspended either
above the pack or downstream from the pack
(vapor generating) retort. The coating vapors
(AlCl and AlCl3, if aluminizing, depending on
temperature and aluminum activity) are trans-
ported to the parts to be coated by an inert carrier
gas. This approach results in a much cleaner coat-
ing, with no entrapped bed particles, but because
of the longer path lengths for vapor transport, out-
of-pack processes favor a low activity-type pro-
cess, with outward coating growth and reduced
coating deposition rates and thus longer proces-
sing times at any given temperature.
Figure 10, illustrates the modified retort used
at Cranfield University to provide vapor phase
coating deposition using an over-source deposi-
tion process. The process is entirely vapor phase
using a process very similar to the Snecma vapor
phase aluminizing process.83 No longer is a pow-
der pack required as a vapor source; instead, the
source material is a crushed Cr–Al intermetallic
alloy, which plays two roles: it lowers the alu-
minum activity creating a low-activity, outwardly
grown aluminide coating, but does not melt at the
desired processing temperatures. This means that
it is no longer necessary to blend pack composi-
tion, and activation of the process only requires
addition of the halide activator salt. Figure 11
illustrates a micrograph of the nickel aluminide
coating produced using this vapor phase route,
using NaF as the activator and a deposition tem-
perature of 1050
C.
 Diffusion Coatings 2543

Cranfield vapor
aluminizing equipment

Specimens

Cr–44Al granules &

AlF3/NH4F activator

Gas supply

Figure 10 Modified retort to permit vapor phase aluminizing using an ‘over-source’ process.

Top coat

β-PtNiAl high
temperature low activity
diffusion coating

Inter-diffusion
zone

Acc.V Spot Magn Det WD 20μm

20.0 kV 4.0 800X BSE 6.0

Figure 11 Micrograph of a nickel aluminide coating produced by the Cranfield vapor aluminizing process at a deposition
temperature of 1050
C.

(b) Gas phase chemical vapor deposition process
reaction gases are metered into the reaction
vessel from external sources, see Figure 12.
Thus, the aluminum halide source gas is generated
in an external vaporizer prior to being introduced
into the reaction chamber. This enables better
control over the reaction, since temperature, pres-
sure, chemical activity and the flow path of the
active gas can all be controlled independently.
Further, separate vapor sources can be used for
the external and internal aerofoil vapor circuits,
permitting the outer gas-washed surface and the
internal cooling passages to be coated with differ-
ent compositions/thicknesses. With recent interest
in adding active elements (see Section 4.05.4.4)
and modifying coating compositions through
codeposition, the ability to use a number of sepa-
rated, controllable vapor sources permits more
repeatable and reliable manufacture of the more
complex coating formulations. Recent patents by
Howmet have identified this approach as a method
to ensure cleaner ‘diffusion coatings.’84,85
4.05.4 Modified Aluminide Coatings
From the foregoing, it is clear that the properties of
an aluminum coating (or for that matter any diffusion
coating) depend on the process methodologies used
to deposit the coating, the substrate composition,
2544 Metallic and Inorganic Coatings

External

Carrier gas To
atmosphere
Internal Retort exhaust
AI

Hf

AI
Si
Scrubber

Mass
flow Pump
control

Source
gases
Figure 12 Schematic diagram of Howmet’s vapor aluminizing process using gas phase CVD. Reproduced from
Warnes, B. M.; Punola, D. C. Surf. Coat. Technol. 1997, 94–95, 1–6.

and the subsequent heat treatment. Thus, coatings 4. deposition of a metallic layer, using electroplating
produced by ‘pack cementation,’ ‘out-of-pack’ pro- or PVD (physical vapor deposition) techniques, prior
cesses or ‘chemical vapor deposition’ will all differ in to aluminizing, for example, a platinum-aluminide
performance as discussed later in Section 4.05.4.2. coating produced by depositing platinum onto the
Similarly, a ‘pack aluminide’ coating whether a simple superalloy prior to the aluminizing treatment.
aluminide or modified aluminide on IN100,83,86,87
Alloy additions may include chromium,15–26,92–97
IN738,84,88–91 IN792,34 CMSX4,31–34,52 AM1,83 Rene
silicon,8–13,56–58 platinum,6,27–34,50,93,100–113 and, most
80,31 or PWA 148031 would all be expected to behave
recently, various reactive element additions, includ-
differently. Typically, a ‘high activity’ pack aluminide
ing Hf, Zr, Ce, and Y.35–45 Probably the most signifi-
coating (e.g., PWA73) would be 50 mm thick (65 mm
cant advance in this area was the development of the
including the interdiffusion zone), with an aluminum
platinum-modified aluminum class of coating. The
content in excess of 30 wt% in the near-surface
first commercial coating in this class was designated
region of the diffusion coating.33,34 Such pack alumi-
LDC-2 and was produced by electrodepositing a thin
nide coatings offer satisfactory performance for many
layer of Pt, followed by a pack-aluminizing treatment
aviation, industrial and marine applications and pro-
at 1100
C.84 Since 1970, this process has been
vide satisfactory performance at relatively low cost. It
licensed to many manufacturers who produce their
is a mature technology first patented in 1961 and in
own variants of this basic coating design, see Figures
wide service for protecting turbine blades and vanes
14–16 for examples. Platinum aluminide coatings
since 1970 (as cited by Goward48 while reviewing the
have much improved high temperature performance
historical perspective of high temperature coatings).
over diffusion aluminides. Although typically 2–3
However, at temperatures above 1050
C, especially
times costlier than a conventional pack aluminide
under cyclic conditions, or under severe hot corro-
coating, they may last up to 3 times longer, depending
sion, these simple aluminide coatings offer limited
on the service environment and duty cycle. Much of
protection. Thus, from the 1970s onwards, develop-
this most recent work results from the recognition in
ments in diffusion coating technologies included
the 1990s that platinum-modified aluminide coatings
modification of the aluminide coatings.
develop stable alumina scales and hence perform as a
Modified aluminides have been fabricated using
useful bondcoat for EB-PVD thermal barrier coatings
one of the following techniques:
(see Section 4.05.4.1).
1. codeposition of elements from the same pack;
2. codeposition from two separate vapor sources (gen-
4.05.4.1 Platinum Aluminide Coatings and
erated using the over-pack process or by CVD);
Bondcoats
3. pretreatment of the superalloy before pack-
aluminizing (or vapor phase aluminizing), for Most commercial platinum aluminide coatings are
example, chromizing a part prior to aluminum; manufactured by first electroplating typically 5–7 mm

of platinum onto the component surface, and then
heat-treating the platinum-plated component to dif-
fuse the platinum into the nickel-based superalloy
surface, prior to aluminizing. The quantity of plati-
num varies from one manufacturer to another, with
between 2 and 10 mm in common usage. There is a
commercial drive to reduce the platinum thickness to
produce platinum-lean platinum aluminides with the
performance enhanced by adding various reactive
elements114 (see Section 4.05.4.4). Equally, platinum
need not be electroplated, and in a drive to develop
‘clean’ coating methods, alternative routes involving
the PVD (physical vapor deposition) of platinum
have been investigated, although electroplating
methods are still the most widely used in industry.
Both high-activity and low-activity aluminizing
may be used following platinum plating and its
partial diffusion into the component surface. Thus,
platinum aluminide coatings have been produced
commercially using pack cementation, out-of-pack
or over-pack processes and gas phase CVD (Warnes
and Punola84 provides a comparison of pack cemen-
tation and gas phases CVD for the production of
Surface
β-NiAl(Pt)
β-NiAl
Interdiffusion zone
Substrate
Surface
PtAl2
β-NiAl(Pt) + PtAl2
β-NiAl
Interdiffusion zone
Substrate
Figure 13 Schematic microstructures of platinum-modified diffusion coatings.
Diffusion Coatings 2545
platinum aluminum coatings, and will be discussed
in more detail in Section 4.05.4.2 on the role the
coating process has on introducing impurities into
the coating). Depending on the initial Pt thickness,
its diffusion heat treatment and the mode of alumi-
nizing, together with aluminizing parameters, a range
of microstructures can be produced. The four most
widely found structures are illustrated schematically
in Figure 13. Thus the platinum aluminide coating
can be single-phase (b-PtNiAl) platinum aluminide,
for example, MDC150, MDC150L, or CN91 (see
Figure 14 for example), or a two-phase platinum
aluminide, classified into one of three microstructures:
an outer zone consisting of a two-phase b-PtNiAl þ
PtAl2 over an inner b-phase NiPtAl layer (an RT22
type), an outer zone of PtAl2 over an NiPtAl b phase
and a structure that is a mix of both these morpholo-
gies, consisting on an outer PtAl2 layer, a middle zone
of PtAl2 þ b PtNiAl, and an inner layer of b-NiPtAl.
Figure 15 illustrates the single phase b-PtNiAl
microstructure manufactured using the coating facil-
ities at Cranfield to produce a microstructure similar
to CN91. The coating was produced by PVD
Surface
β-NiAl(Pt) + PtAl2
β-NiAl
Interdiffusion zone
Substrate
Surface
PtAl2
β-NiAl
Interdiffusion zone
Substrate
2546 Metallic and Inorganic Coatings
Acc.V Spot Magn Det WD Exp
20.0 kV 4.0 1000x BSE 10.0 1
Figure 14 Micrograph of MDC150L platinum aluminide coating, produced by a gas-phase CVD process.
Acc.V Spot Magn Det WD 50 μm
20.0 kV 5.0 500x BSE10.5 0.6 Torr
Figure 15 Single-phase platinum aluminide coating
(CN91 type).
deposition of platinum to a thickness of 7 mm, heat-
treated, then over-pack aluminized at 1080
C using a
HTLA process.
Figure 16 illustrates a two-phase PtAl2 þ
b-PtNiAl microstructure manufactured at Cranfield.
The platinum layer was again 7 mm by PVD and heat-
treated, but the aluminizing treatment was a high-
activity pack aluminizing process at 970
C.
During service at elevated temperatures (above
850
C), the microstructure of the coating contin-
uously evolves with time and temperature. The
effect of ageing up to 4000 h at 1000
C and
1050
C on the microstructure of RT22 is illustrated
in Figure 17, which demonstrates the effect of
platinum diffusion into the substrate: aluminum
20 μm
0.8 Torr Ref 95-BmA-1
Acc.V Spot Magn Det WD 50 μm
20.0 kV 5.0 500x BSE 10.1 0.6 Torr
Figure 16 Two-phase platinum aluminide coating
(RT22 type).
consumption by interdiffusion, oxidation, and the
formation of various TCP precipitate phases contain-
ing refractory metals that have diffused into the plat-
inum aluminide coating from the substrate.
4.05.4.2 The Role of Impurities Introduced
in Coating Manufacture
As discussed above, the way the coating is made as
well as its final microstructure and composition can
have a major influence on its performance and life-
time. With the aim of increasing oxidation life, How-
met84 undertook a research program on the role of
tramp impurities, introduced through the manufac-
turing process, on the cyclic oxidation lifetime of
platinum aluminide coatings.
 Diffusion Coatings 2547

Acc.V Spot Magn Det WD 50 μm Acc.V Spot Magn Det WD 50 μm

20.0 kV 5.2 500x BSE 10.0 1.0 Torr 20.0 kV 5.0 500x BSE 9.8 1.0 Torr

RT22 – 1000 ⬚C, 1000 h RT22 – 1050 ⬚C, 1000 h

Acc.V Spot Magn Det WD 50 μm Acc.V Spot Magn Det WD Exp 50 μm

20.0 kV 5.2 500x BSE 10.0 1.0 Torr 20.0 kV 5.0 500x BSE 10.8 1 0.6 Torr

RT22 – 1000 ⬚C, 2000 h RT22 – 1050 ⬚C, 2000 h

Acc.V Spot Magn Det WD 50 μm Acc.V Spot Magn Det WD Exp 50 μm

20.0 kV 5.0 500x BSE 10.0 0.6 Torr 20.0 kV 5.0 500x BSE 9.9 1 0.7 Torr

RT22 – 1000 ⬚C, 4000 h RT22 – 1050 ⬚C, 4000 h

Figure 17 Influence of long-term exposure on the microstructured degradation of the platinum aluminide coating
RT22 at 1000
C and 1050
C.

This research investigated three alternative routes
to manufacture a platinum aluminide coating depos-
ited onto an IN738 nickel-based superalloy substrate.
A common platinum plating method was used for all
three platinum aluminides with difference only in the
method of undertaking the aluminizing process. The
processes were:
(a) LDC2E: a high aluminum activity pack cementation
process, resulting in inward aluminum diffusion.
(b) MDC-150: a high aluminum activity, gas phase
CVD process. An inwardly grown aluminide
coating activated by AlCl3 generated external to
the CVD retort.
(c) MDC-150L: a low-activity aluminide coating
formed by outward nickel diffusion using the
gas phase, and external AlCl3 vapor source used
to manufacture the MDC-150 coating.
Four tramp impurity levels were studied: B, P, S, and
W. Three of these perceived harmful impurities come
from the IN738 substrate alloy, namely B, S, and W,
while the fourth (P) comes from the electroplating of
platinum. Table 4 illustrates the chemical analysis
results.84
The four elements were selected because they
could be introduced into the coating from three
potential sources:
(a) the superalloy substate: W, S, P, and B;
(b) the platinum plating process: P;
(c) the aluminizing process: S and B.
2548 Metallic and Inorganic Coatings
Table 4 Bulk chemical analysis of coated IN738 foils
Element As platinum plated LDC2E coated
B 120 140
P 450 440
S 6 7 8
W 23 900 23 000
All concentrations are in parts per million by weight (ppm).
Source: Warnes, B. M.; Punola, D. C. Surf. Coat. Technol. 1997, 94–95, 1–6.
Bulk chemical analysis of the coated foils reveals
some interesting results. First, the ‘low activity’
CVD aluminizing process is able to ‘clean up’ the
coating with respect to these tramp additions, reduc-
ing significantly the level of each tramp element
addition. Second, the high-activity aluminide pro-
cesses increase the level of B and S in the coating
over that of the ‘as-plated’ condition. For the pack
aluminide process (LDC 2E) this was thought to be
due to transfer of S and B from the source alloy
(analysis of the aluminum–chromium source gave
22 ppmw S and 310 ppmw B); however, the high-
activity vapor aluminizing process used 99.999 wt%
Al as a source in the AlCl3 vapor generator.
Further microprobe studies showed that in the
MDC150L coating, where the low activity aluminide
appeared to clean the process, concentrations of
impurities peaked in the interdiffusion zone and
dropped in the diffusion coating surface, with levels
at the surface significantly below that found in the
IN738 substrate. Such behavior is consistent with
the aluminizing process removing contaminants
from the surface as a result of a gas–solid surface
reaction.84 In the ‘as-coated’ condition, both ‘high
activity’ processes (LDC-2E and MDC-150) had a
two-phase (NiPtAl þ PtAl2) microstructure, while
the MDC-150L had a single-phase NiPtAl micro-
structure. After solution heat-treatment of the IN738,
all of the coatings were single phase, but varied in thick-
ness and surface aluminum and platinum contents:
LDC-2E 74 mm thick, 20.0 wt% Al, 30.6 wt% Pt;
MDC150 88 mm thick, 23.2 wt% Al, 22.6 wt% Pt;
MDC-150L 77.5 mm thick, 19.5 wt% Al, 19.0 wt%
Pt (the quoted thickness included the coating and
interdiffusion zone).
Cyclic oxidation tests at 1100
C (50 min at
temperature, 10 min cooling) on these three coating
variants (Figure 18) showed that the MDC150L
(low-activity aluminide, formed by outward nickel
diffusion) had a significantly longer life. The life-
time was defined as the time to ‘zero crossover’ (see
Figure 21 to illustrate this definition).
MDC 150 coated MDC 150L coated
150 50
390 140
5
5700 1300
A very important conclusion from this study is
that minor tramp element contaminants can influ-
ence the oxidation cyclic life, with higher contami-
nant levels lowering the life. Even more important is
the fact that the choice of processing route can influ-
ence the level of tramp contaminants in the coating
and that through a correct choice of processing it is
possible to ‘clean up’ the coating, thereby, giving
between 20% and 40% improvement in lifetime,
using rounded numbers.
4.05.4.3 Chromium- and Silicon-Modified
Aluminides
To combat hot corrosion, additions of chro-
mium56,57,92–97 and silicon98–100,103 were extensively
researched in the 1970s and 1980s. Research into the
influence of these additions still continues as addi-
tions to both standard aluminides and platinum-
modified aluminides, especially when considering
coating on the latest third- and fourth-generation
low-chromium-containing single-crystal alloys.
This early research plus service experience has
shown that chromium additions to aluminide coat-
ings offer little advantage over standard aluminide
coatings under high temperature oxidation condi-
tions. However, chromium additions are found to be
beneficial and offer improved performance in indus-
trial and marine turbine applications burning high-
sulfur fuels.15,19,20,46,49,94,97
Additions of silicon are also known to improve hot
corrosion resistance, but may also benefit the high
temperature oxidation performance of aluminide
coatings. Since the early work in the late 1970s
and early 1980s, a number of researchers have inves-
tigated the role of Si, both for high temperature
oxidation resistance and hot corrosion resistance, in
diffusion aluminide coatings.10,56–114 The possibility
of using silicon aluminides for protecting internal
cooling passages has also been investigated.14,115
The most commonly used silicon aluminide is the
commercial coating SermaLoy J, a CrSi2-dispersed

1.00
Average weight change (mg cm–2)
0.50
−0.00
−0.50
−1.00
−1.50
−2.00
0 1000 2000
Number of cycles
Figure 18 Cyclic oxidation lifetimes for various platinum
aluminide coatings on IN738 at 1100
C: The cycle is 50 min
at temperature, 10 min cool, cycled hourly, with failure
defined as the time to zero mass gain cross over (the cyclic
lives were calculated from data present in Warnes and
Punola).84
b-NiAl diffusion coating.11,56–58,100 The microstruc-
ture of this coating is illustrated in Figure 8.
SermaLoy J is manufactured using a slurry aluminiz-
ing process route. At about 10 wt% silicon in a diffu-
sion aluminide coating, the silicon aluminide coating
provides unsurpassed resistance to type I and II hot
corrosion. 11,58,100 It is, however, somewhat brittle and
this limits its use for internal cooling passage appli-
cations at this level of silicon content. Later, as
engine technologies advanced and single-crystal alloys
were widely adopted, with lower chromium contents,
there was less chromium available within the alloy to
form the CrSi2 precipitates – a critical component of
SermaLoy J56–58 – thus a research program between
Sermatech and Rolls Royce led to the development of
SermaLoy 1515. SermaLoy 1515 is a layer-structured
slurry aluminide diffusion coating containing bands
of CrSi2 precipitates as illustrated in Figure 19.
SermaLoy 1515 is, thus, specifically designed to pro-
vide hot corrosion resistance on low-chromium-
containing single-crystal alloys.56,58,59
For cooling passage applications,115,116 this silicon
content of the aluminide has to be reduced such
that is does not impact on the alloy mechanical per-
formance but must be sufficiently high to confer good
oxidation and hot corrosion protection. Reducing the
silicon level to between 1 and 2 wt% meets this cri-
teria. Testing coatings with silicon levels in this range
under Cyclic oxidation at 1100
C and 1 h hot dwell
Diffusion Coatings 2549
LDC - 2E
Acc.V Spot Magn Det WD Exp 50 μm
MDC - 150 20.0 kV 5.0 500x BSE 10.0 1 0.6 Torr
MDC - 150L
Figure 19 SermaLoy 1515 silicon aluminide coating on
3000 IN738 produced by a repeat slurry aluminizing process
route.
cycles gives a lifetime of 280–320 cycles.116 A result
superior to that of a standard aluminide (HTLA alu-
minide) was obtained, for which the cyclic lifetime
varied between 25 and 120 cycles, but was inferior to a
platinum aluminide. The worst of the platinum alu-
minides in Figure 18 gave a lifetime of 1174 cycles
under similar test conditions.
Under hot corrosion conditions, both type I and
type II, this coating with 1–2% silicon addition was
superior to a conventional aluminide, lasting approx-
imately twice as long to through coating penetration,
but was inferior to the performance of Sermaloy
J containing a higher silicon content.
4.05.4.4 Reactive Element-Modified
Aluminide Coatings
There has been continued interest in the ability to
incorporate active elements in b-NiAl to improve
cyclic oxidation resistance through enhanced scale
adherence. The benefits of oxygen-active elements
are well documented in the literature; for example,
yttrium levels below 0.5 wt% are widely added to
commercial overlay coatings to reduce oxidation
rates and improve scale adhesion. Even in the develop-
ment of the earliest MCrAlY coatings this was recog-
nized.48 The most recent MCrAlY overlays are far
more complex and may contain multiple active ele-
ments, including Y, Si, Hf, Zr, Ta, etc.11,28,99,117–120 and
even minor addition of precious metals.31,104–106,117
For systems based on b-NiAl, the systems are far
less advanced, with few reactive-element-modified
diffusion coatings commercially available.43,44 Most
of the research has been on model alloys36,121–125 and
2550 Metallic and Inorganic Coatings
40 ␮m
Figure 20 Yttrium-modified aluminide ‘over pack’ CVD
coating.
in particular on the roles of hafnium, zirconium, and
yttrium. Some research papers have considered the
incorporation of reactive elements as part of the
CVD process.35–44 Early published work by Bianco
and Rapp35–37 introduced reactive elements into the
CVD process such that codeposition of the reactive
element with the aluminide occurred. This approach
has also been adopted in the one published commer-
cial application in which Howmet used multiple
vapor sources to blend the vapor phase environment
from which the codeposited active-element-modified
aluminide is formed.84,114 In the work of Kim et al.,42 a
yttrium-modified aluminide was formed by first
pack-aluminizing the substrate alloy (in this case
IN738) and then depositing a thin layer of yttrium
by electron beam evaporation, prior to heat treatment
to interdiffuse the coating. It is only recently that
yttrium-modified aluminide has been able to be
produced using a simple pack cementation or the
‘over-pack’ CVD process.126 Figure 20 illustrates a
micrograph of a yttrium-modified aluminide using
the ‘over-pack’ CVD process developed at Cranfield.
Figure 21 compares the cyclic oxidation perfor-
mance (1100
C, 1 h hot dwell) of various aluminide
and modified aluminide coatings produced using
facilities at Cranfield University on an IN738 sub-
strate alloy. The improvement in performance of the
modified aluminides can be seen relative to that for
an uncoated IN738 alloy and IN738 aluminized using
a high-activity aluminide process. The uncoated
alloy failed (zero net mass gain crossover point) at
30  1 h cycles and the high-activity aluminide failed
at 620  1 h cycles, while the monophase (high tem-
perature, low activity) platinum aluminide and the
yttrium-modified aluminide did not fail (zero net
mass gain crossover) at the end of the test (900  1 h
cycles at 1100
C). Extrapolation of the oxide spalling
regime leads to an estimated life of 1000  1 h cycles
for both the platinum aluminide coating and the
yttrium aluminide coating, based on the zero net
mass gain crossover point. However, whereas the
platinum aluminide coating started to spall at
170  1 h hot cycles, the yttrium aluminide did not
start to spall until 800  1 h hot cycles at 1100
C.
4.05.5 Mitigating Substrate Alloy
Interdiffusion Effects
As is evident from the earlier sections reviewing
diffusion coating manufacture, all diffusion coatings
must involve an underlying material, usually the
substrate alloy, as part of the coating manufacturing
process. It is for this reason that similar diffusion
coating processes but on different substrate alloys
produce different coating systems, and hence the
lifetimes of such coatings, be it oxidation, cyclic
oxidation or high temperature corrosion, will be
influenced by alloying additions diffusing out from
the substrate into the coating. Some elements can be
beneficial, for example Cr, Si, Hf, Y, etc., while others
are clearly detrimental, such as W, Mo, V, possibly
Ru, either to the cyclic oxidation or hot corrosion
performance of the coating.
One of the benefits of the high temperature low-
activity aluminizing processes is the reduction of
refractory metals, such as W and Mo, that move
outward from the substrate into the coating owing
to the fact that the coating is formed as a result of
outward nickel transport, and the refractory metals
diffuse outward much more slowly than nickel. This
observation highlights one way of mitigating the det-
rimental effects of alloy additions and tramp elements
moving from the substrate into the coating during
manufacture: that is, to precoat the alloy with some
form of temporary or partial barrier (nickel plating
the substrate, for example, in its simplest form) prior
to aluminizing. A second is to deposit an MCrAlY
overlay coating as a partial diffusion barrier and then
aluminize the MCrAlY overlay coating.
Commercially, variants on this approach have
been used. General Electric has a patented process
for over-aluminizing an MCrAlY coating, previously
sprayed or EB-PVD-deposited onto the alloys sur-
face. GT29þ and GT33þ are examples of the ‘over-
aluminized’ version of GT29 (Co28Cr6Al0.5Y) and

4.0
3.0
Net mass gain (mg cm−2)
2.0
1.0
0.0
−1.0
−2.0
0 100
Figure 21 Cyclic oxidation performance of modified aluminide coatings, produced at Cranfield University: 1100
C, 1 h
hot dwell cycles (data from Long and Nicholls and Nicholls and Wing).116,126 (Note: " equals point of zero crossover for a
LTHA aluminide.)
GT33 (Ni22Cr9Al0.5Y). These coatings are used on
blades and vanes of GE industrial engines, models
7/9EA and 7/9FA/FAþ,127 making the performance
of the coating less dependent on the substrate
alloy chemistry from an oxidation and/or corrosion
perspective. These dual-layered over-aluminized
MCrAlY alloys provide surface layers with up to
25 wt% Al for good oxidation resistance, while
the MCrAlY base confers better hot corrosion resis-
tance because of the higher levels of Co and Cr.127
Additionally, the incorporation of Y from the MCrAlY
into the surface aluminide layer confers improved
scale adhesion to the alumina scale, improving the
cyclic oxidation resistance of this dual layer coating.
The surface aluminide layer is brittle, however, and
the higher ductile to brittle transition temperature
(DBTT) makes the surface layer prone to thermo-
mechanical fatigue (TMF) cracking during start/stop
cycling. The more ductile MCrAlY underlayer can
blunt these cracks, thereby, limiting their propagation
into the substrate. The presence of an outer aluminide
layer on a CoNiCrAlY basecoat (GT33þ compared to
GT33) can lower the TMF life by a factor of 2.5 at high
strain ranges, while at low strain ranges (0.45%e), the
TMF lives are comparable.127
Howmet now also offers these duplex MCrAlY þ
aluminide coatings.128 However, they claim that
by using low-activity aluminizing in addition to
Diffusion Coatings 2551
IN738 uncoated
LTHA Aluminide
Monophase Pt-Aluminide
Monophase Y-Aluminide
200 300 400 500 600 700 800 900 1000
Number of one hour cycles
the MCrAlY alloy, they can further improve the oxi-
dation performance when compared to a similar coat-
ing made by pack cementation.
4.05.5.1 Smart Coating Concepts
Smart overlay coatings129–131 are functionally gradient
coating systems designed to provide high temperature
oxidation and corrosion protection over a wide range of
operating conditions. The SMARTCOAT concept is
a natural extension of the ideas embodied in GT29þ
and GT33þ, the over-aluminized MCrAlYs, which
involves surface-treating a base overlay coating using
diffusion coating processes to obtain improved perfor-
mance and durability, but now extended to produce a
chemically graded structure that can provide both high
temperature oxidation protection as well as more opti-
mized protection to type I and II corrosion. Thus, the
SMARTCOAT design consists of an MCrAlY base
coating, which can be deposited by any spray deposi-
tion method (air plasma spray (APS), Vacuum plasma
spray (VPS), and high velocity oxy-fuel (HVOF)), by
occluded electroplating or by EB-PVD, which is
overcoated with successive layers to produce the
chemical gradient structure. A second layer,
enriched in chromium and/or silicon, is then depos-
ited prior to surface aluminizing, which then gener-
ates the required gradient chemical structure.
2552 Metallic and Inorganic Coatings
Acc.V Spot Magn Det WD 100 μm
20.0 kV 6.0 250x BSE 10.1 0.6 Torr
(a) SmC155
Figure 22 Micrographs of two SMARTCOAT structures: (a) SmC155, showing the three-layered structure characteristic
of SMARTCOAT, but produced using air plasma spraying; (b) SmC253E, produced by occluded electroplating of the
basecoat and chromium-rich interlayer.
Figures 22(a) and 22(b) illustrates two variants of
this SMARTCOAT design. SmC155 (Figure 22(a))
is produced by surface-treating an Amdry 995 base-
coat that has been deposited by air plasma spraying.
The chromium-rich interlayer is also deposited
by air plasma spraying before the bi-layer structure
is aluminized to give the final SMARTCOAT design.
The composition of the three-layered microstructure
critically affects performance. The outer alumi-
nide layer varies in composition between those of
Ni–15Cr–32Al and Ni–10Cr–21Al, with small addi-
tions of Y as a result of the aluminizing of an MCrAlY
base alloy, and is designed to produce a protective
alumina scale for oxidation- and cyclic-oxidation-
protection at temperatures above 900
C. However,
at lower temperatures, this alumina scale does not
reform fast enough to confer a protection under type
II hot corrosion conditions. SMARTCOAT is, there-
fore, designed with an intermediate chromium-rich
layer, which permits the rapid formation of chromia,
which are healing areas of type II corrosion damage.
Research into optimum corrosion-resistant alloy
compositions132,133 defined the useful composition
range of this interlayer, in the final chemical gradient
structure, between Ni–60Cr–20Al and Ni–35Cr–40Al,
adding tantalum may be beneficial. The basecoat may
be any MCrAlY alloy, Amdry 995 (Co–32Ni–21Cr–
8Al–0.5Y) for the SmC155 variant of SMARTCOAT.
Figure 22(b), a second variant of SMARTCOAT,
is produced using occluded electroplating134 to
deposit the basecoat and interlayer. Ghost images of
the original particles in the occluded electroplate can
still be seen. The base alloy is Amdry 963: a NiCrAlY
Acc.V Spot Magn Det WD Exp 50 μm
20.0 kV 5.0 500x BSE 10.0 1 0.6 Torr
(b) SmC253E
alloy; otherwise the coating procedure matches that
of the aluminized, plasma-sprayed MCrAlY, but with
the difference that the basecoat and interlayer were
deposited by electroplating.
Figure 23 illustrates the comparative perfor-
mance of three variants of SMARTCOAT, when
compared to two platinum aluminide coatings RT22
and CN91, and an over-aluminized CoNiCrAlY – a
similar process and structure to that of GT29þ, a
General Electric proprietary coating. For each coat-
ing system, the substrate was IN738. The hot corro-
sion tests were of 500 h duration and conducted at
700 and 800
C, using a salt recoat test procedure
with daily replenishment of an 80% Na2SO4/20%
K2SO4 salt mix at an equivalent salt deposition flux
of 0.015mg cm2 h1. The test was conducted in an
air þ300 vpm SO2/SO3 gaseous environment.
Under hot corrosion conditions, only the outer
aluminide region of the smart coatings was attacked.
The corrosion front effectively stopped at the
chromium-rich interlayer, whereas the platinum alu-
minide coating was consumed down to the interdif-
fusion zone at 700
C and completely penetrated at
800
C. For the over-aluminized CoNiCrAlY, the
worst attack was observed at 700
C, as a result of
severe type II pitting of the Co,Ni aluminide, and the
underlying CoNiCrAlY basecoat layer.
4.05.6 Summary and Conclusions
This chapter reviewed the methods and applications
of diffusion coatings. Diffusion coatings can offer a
 Diffusion Coatings 2553

160

140 Max. - 700 ⬚C

120 Mean - 700 ⬚C

Coating loss (um)

100

80

60

40

20

0
22

91

IY

15

3E

3S
15
rA
RT

15

25

23
C
C

C
m
oy
M
e

m
id

tS
id

al
d

tS

tS
in

in

rm
ize

oa
um

um

oa

oa
Se
in

tc
al

tc

tc
um
al

ar

ar

ar
um

Sm
um

al

Sm

Sm
r-
in

in

ve
at

at
Pl

O
Pl

Figure 23 Hot corrosion performance of SMARTCOAT SmC155 and SmC253E, relative to an over-aluminized CoNiCrAlY
and platinum aluminide coatings (RT22 and CN91) at 700
C.

low-cost solution for providing environmental pro- 4. Samuel, R. L.; Lockington, N. A. Met. Treat. Drop
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