High-temperature sulfidation and oxidation resistance of

thermal diffusion coatings in Steels

Seminar Report

Supervised by:

Prof. Triratna Muneshwar

Submitted by:
Abhijeet Mohanta (22M1863)
M.Tech (MM2)

Department of Metallurgical Engineering and Material Science

INDIAN INSTITUTE OF TECHNOLOGY (BOMBAY)

Jan-April: 2023
 DECLARATION

I undersigned hereby declare that the seminar report “High-temperature sulfidation and oxidation

resistance of thermal diffusion coatings in Steels”, submitted for partial fulfillment of the

requirements for the award of the degree of Master of Technology of the Department of

Metallurgical Engineering and Materials Science, IIT Bombay is a bonafide work done by me.

This submission represents ideas written in my own words, and where ideas or words of others

have been included, I have adequately and accurately cited and referenced the original sources. I

also declare that I have adhered to ethics, honesty and integrity and have not misrepresented or

fabricated any data or idea or fact, or source in my submission. This report has not been previously

submitted for the award of any degree or similar title of any other institution/university.

Abhjeet Mohanta
Roll No.: 22M1863
 Table of Contents

Contents
1. Abstract ............................................................................................................................... 5
2. Key seminar learning outcomes: .......................................................................................... 6
3. Introduction ........................................................................................................................... 7
3.1. Oxidation ............................................................................................................................ 8
3.2. Sulfidation........................................................................................................................... 9
4. Literature Survey ................................................................................................................ 11
4.1. Thermodynamics of sulphidation and oxidation at high temperature: ...................... 11
4.2. Kinetics of sulphidation and oxidation at high temperature: ...................................... 15
4.2.1. Solid-State diffusion ..................................................................................................... 15
4.3. RATE EQUATIONS ....................................................................................................... 17
4.3.1. Linear kinetics .............................................................................................................. 18
4.3.2. Diffusion-controlled processes and parabolic kinetics .............................................. 18
4.4. Properties scales formed at high temperature .............................................................. 21
4.5. Factors affecting the stability oxide and sulfide scales ................................................. 22
4.6. Different types of aluminum coating processes ............................................................. 23
4.7. Mechanism of formation of thermal diffusion layer ..................................................... 25
4.8. Techniques for evaluation of performance of multi-layered thermal diffusion
coatings......................................................................................................................................... 28
5. Results and Discussions: ..................................................................................................... 29
5.1. Review previous research on Sulfidation-oxidation resistance of coated and uncoated
steel samples ................................................................................................................................ 29
5.2. The mechanisms of aluminide oxidation: ...................................................................... 30
5.3. The effects of coating composition, thickness, and structure on sulfidation-oxidation
resistance ...................................................................................................................................... 34
6. Conclusion ............................................................................................................................ 35
 List of Figures

Figure 1: Oxygen-sulfur-temperature diagram indicating some industrial operating conditions. .............. 12

Figure 2: Schematic stability diagram for the M-S-O system..................................................................... 14

Figure 3: An vacancy and interstitial defect in a single-component crystal lattice. .................................... 15

Figure 4: Reactions and transport processes involved in growth of an oxide scale. ................................... 17

Figure 5: Simplified diffusion model for mass transfer through growing metal oxide scale...................... 19

Figure 6: Schematic diagram of the formation model of the iron-aluminum alloy coating with a multilayer

phase structure. ........................................................................................................................................... 26

Figure 7: The Fe-Al phase diagram ............................................................................................................ 27

Figure 8: Schematic diagram of the apparatus used for corrosion studies. ................................................. 29

Figure 9: (a) Cross section micrograph of aluminide steel exposed at 850 °C for 8 h, (b) EDS results

showing the concentration variations of Al, Fe, Cr, and Si elements ......................................................... 31

Figure 10: Optical cross-sectional micrographs of specimens oxidized from 4 min to 56 h at 750, 850, and

950 °C, where a, b, c, d, e, f, and g is presented as variation of the microstructure as a function of test

duration at 850 °C; h and i for 750 °C, j for 950 °C. .................................................................................. 32

Figure 11: Schematic configuration for the growth stages of aluminide layer and internal void with oxides

during oxidation at high temperature. (a) as-coated steel. (b) inward Al diffusion and cracks formation. (c)

the growth of FeAl2+ Fe2Al5 and FeAl precipitation. (d) the growth of FeAl in FeAl2+ Fe2Al5 and

oxides formation. (e) loose metals formation in FeAl island. (f) internal voids formation. (g) the growth of

voids and FeAl in the inner aluminide layer. (h) the growth of FeAl phase through the entire aluminide

layer. ........................................................................................................................................................... 33
1. Abstract
The high temperature applications of structural steels under the highly corrosive atmosphere,

taking into consideration the components used in the fossil fired power plants. High temperature

sulfidation and oxidation protection by thermal diffusion coating is discussed in the report. The

mechanisms of the oxidation, sulfidation and formation of the diffusion layer is described in the

report. The performance of the thermal diffusion coating is also reported.

2. Key seminar learning outcomes:
 The mechanism of thermodynamics and kinetics of high temperature
oxidation and sulfidation at high temperatures.
 Properties and factors affecting the oxide and sulfide films at high
temperatures.
 The mechanism of formation and development of thermal diffusion layer.
 The performance of thermal diffusion coatings under high temperature
corrosive atmosphere.
3. Introduction
The global energy needs have been increasing constantly, although we are advancing towards renewable

and clean energy sources, still burning fossil fuel (coal, oil, and natural gas) contributes to around 80% of

our total energy needs. When it comes to electricity over 60% of worlds electricity is generated by fossil

fuel based power plants. In developing countries like India the percentage of energy produced by fossils

are still higher. Most of the Electricity production is achieved through coal based a thermal power plant

which is around 75% of the total power generation. Still it will take a long time to replace the fossil fuel

with the renewable sources and also the increasing prices of fossil fuels have made us think about increasing

the efficiency of the fossil fired power plants as well as reduce the CO2 emissions.

The increase in efficiency depicts increase in the operating temperature of that are required for the Super-

critical, Ultra Super-critical and Advanced Ultra Super-critical coal fired technologies. This requires the

use of high temperature resistant materials, including high-temperature alloys and advanced steels that can

withstand high temperature and pressure environments. In most power plants the major components like

the tubing for water-wall panels, boiler tubes, super-heaters and re-heaters and other components are made

up of different types of carbon steels, low-alloy steels even some components are made up of stainless steels

(mainly ferritic and martensitic stainless steels). These components are mostly exposed to steam at high

temperatures and pressures as well as corroding gasses containing Sulphur and H2S produced from the

combustion of the coal, biomass, oils and natural gases. As the operating temperatures exceed 400–600 °C,

these flowing gases severely exacerbate corrosion issues for tubing and other components in coal-fired

boilers, water-wall panels, super-heaters, and re-heaters. Primarily the materials are designed for high

temperature applications for their mechanical properties, but the corrosion due to high temperature

oxidation and sulfidation severely impacts the service life as well as the performance dependent on thermal

conductivity due to the oxide and sulfide scales that forms on the top of the materials. Along with corrosion

the service life of the components also depends upon the fatigue and creep factors at high temperatures.
However, there is now a growing understanding that at high temperatures corrosion like oxidation and

sulphidation may limit lifetime, either directly through metal wastage or indirectly through raising local

temperatures due to the lower thermal conductivity of the oxide and sulfide scale. Historically, materials

developed for use at high temperatures have been developed primarily for their mechanical properties.

Steels exposed to oxygen and sulfur-rich atmospheres while operating at high temperatures typically

experience rapid deterioration processes.

3.1. Oxidation
Steel oxidizes readily at higher temperatures. The partial pressure of oxygen required for oxidation under

higher temperature environment are significantly less than the partial pressure required at the room

temperatures. In steels a layer of non-protective scales is formed rapidly at the surface which leads to

spallation and accelerated attack. When steel is alloyed specially with Cr, Co, the elements with higher

oxygen affinities will oxidize more readily and form protective scales on the surface due the high-

temperature oxidation. However, it is limited to quick growth of the oxide scale, loss of mechanical

properties of the subsurface zones and embrittlement at relatively higher temperatures. Under high

pressures and in the presence of H2O during oxidation, higher Cr concentrations cause phase instabilities,

the production of brittle Cr-rich phases, and more significant volatilization of chromium oxide. Which leads

to breakaway oxidation leading to accelerated corrosion. Hence the issue of material lifetime and corrosion

protection depends upon the rate of oxidation, methods of slowing it down and the change in morphology

of these oxides. The oxidation rate of steel in presence of water vapor or steam tends to be a magnitude

higher than that of the dry oxygen. If there are small quantities of O2 present in the steam, then this small

quantity regulates pO2 rather than H2O dissociation. Nonetheless, it is probable that any such contaminants

would be swiftly removed by oxidizing metal reaction, restoring the water dissociation equilibrium in the

process. During the dissociation of water vapour and oxidation of the metal the hydrogen generation tends

to be an important factor. Thus the interaction of water vapour can take place in multiple ways.

M + H2O→ MxO + H2
H2O → H2 + ½ O2

M +O→ MxO

It may take part in surface interactions that change the scale-gas interface or potentially result in the

production of volatile hydrated species.

MO +H2O→ M(OH)2

The interaction of the dissolved water vapour within the scale, changes its microstructure, characteristics,

and transport behaviour. These interactions might lead to the hydrogen in the oxide dissolving and the

formation of lattice point defects. Ultimately, dissolution of hydrogen into metal formed due to. Reaction.

3.2. Sulfidation
Similarly, sulfidation is also a predominant phenomenon occurring in the fossil fuel- fired power plants. As

the H2S interacts with metal surface it forms a metal sulfide layer on the top of the component. Steel sulfide

scales are far less protective than oxide scales, and metal sulfidation rates are often substantially greater

than oxidation rates. The higher corrosion rates in H2S containing atmosphere are related to dissociation of

H2S into Hydrogen and Sulphur at far lower temperatures and then reaction of Sulphur with metal:

H2S → H2 + ½ S2

M + S→ MxS

M + H2S→ MxS + H2

The free energy for sulfide formation is quite low and are also not very stable and the dissociation of H 2S

also occurs preferentially at the surface of the sulfides formed at the surface. Interstitial hydrogen

infiltration into metals and scales produces lattice defects and hydrogen clusters, which in turn significantly

increases corrosion and embrittlement. Sulfidation may lead to the formation of low melting eutectics

containing a large concentration of mobile defects, due to which hydrogen and sulfur diffuses rapidly
through the porous scale leading to their interaction with base metal promoting further degradation of the

components.

Although the alloying of steel with semi-refractory and refractory metals from the IV-VI groups (Ti, Zr,

Hf, V, Nb, Ta, W, Mo) performs significantly better than that of than the conventional alloys under high

temperature oxidation and sulfidation conditions. These alloy steels increase the cost significantly. The

combined action of oxidation and sulfidation, may significantly change the corrosion rate of steels due to

the formation of sulphides and oxides with different adhesions to the steel surface and different coefficients

of thermal expansion. The surface engineering is a more feasible and economical route to provide corrosion

resistance at high temperature. In high temperature corrosion conditions, several coating materials and

methods may be taken into consideration to increase the integrity of the steel surface. There are various

methods by which the surface coating can be done like dipping, chemical electrolytic or electroless

deposition, cold and thermal spraying and cladding, physical vapor deposition (PVD) and chemical vapor

deposition (CVD), etc. The majority of these processes, are not ideal for the application as many of the

coating either perform poorly at high temperatures or are very thin with potential structural defects which

act as corrosion initiators. The porosities formed during various processes also inhabits corrosion by

accumulating the corrosion products in the pores giving rise to wedging effect which further increases the

corrosion rate. Some of these do not adhere properly at elevated temperatures and pressures leading to

detachment of the coating.

CVD based thermal diffusion processes may be considered a versatile route due to its flexibility of

application on the component surface with various configuration and dimensions also there is no

requirement of introduction reactive, often hazardous, gases into the process chamber. The boronizing and

aluminizing methods may be chosen as the most promising for protecting steels from high temperature

sulfidation when taking into account thermal diffusion technology, which is also known as thermo-chemical

processing or pack cementation. These procedures allow for the creation of protective coatings made of

either aluminides or iron borides. Due to the characteristics of diffusion processes, these coatings have
multi-layered structures with two or more protective layers forming concurrently within a single process

cycle. The intermetallic compounds like borides and aluminides having High crystalline lattice energies,

strong and short covalent bonds (such as Fe-B, Fe-Al, Cr-Al, etc.), corresponding to high chemical inertness

of the material as well as the diffusion-induced bonding between the protective layers and the steel

substrates. Also the formation of protective oxide scale at high temperatures, which is resistant to spalling

also makes it an attractive for high temperature corrosion applications. Further enhancement in corrosion

resistance can be achieved by application of the extra oxide layer of the Me-O bonds, such as SnO2, TiO2,

ZrO2, ThO2, Al2O3, Y2O3 with high crystalline lattice energy and a high degree of covalence on the top

of the diffusion layer.

The performance of these coatings is typically evaluated using high-temperature exposure tests, which

involve subjecting coated specimens to elevated temperatures and corrosive environments for extended

periods of time. The properties of the coatings and the underlying substrate are then analyzed to determine

the effectiveness of the coating in preventing degradation.

Several factors can influence the performance of these coatings, including the composition of the coating

material, the thickness of the coating layer, and the microstructure of the coating and substrate. Researchers

continue to study these factors to optimize the performance of thermal diffusion coatings and improve their

durability in high-temperature applications. Overall, the development of thermal diffusion coatings

represents a promising approach to improving the high-temperature sulfidation and oxidation resistance of

steels, and could help to extend the service life of high-temperature components in a variety of industrial

applications.

4. Literature Survey

4.1. Thermodynamics of sulphidation and oxidation at high temperature:

Typically, there are two types of sulfidizing-oxidizing atmospheres: those with SO2 carrying gas (such hot

corrosion in gas turbines) and those with low oxygen and high sulphur potentials. The latter category

includes a variety of industrial atmospheres, including coal gasification and low NOx burners in coal-fired
boilers. The oxygen-sulfur-temperature diagram may be used to show the two different types of sulfidizing-

oxidizing industrial operating conditions.

Figure 1: Oxygen-sulfur-temperature diagram indicating some industrial operating conditions.

The atmosphere with low-oxygen and high-sulfur potentials basically comprises of gases like H2O, H2, H2S

and CO. The oxidizing and sulphudizing potentials of the gases can be characterized by the equilibrium

partial pressures of oxygen (PO2) and sulfur (PS2) which are determines by the following reactions.

H 2O → H2 + ½ O2 …1

…1

H2S → H2 + ½ S2 …2

…2
Where, K1 and K2 are the equilibrium constant for the above reactions (1) and (2), ΔG01 and ΔG02 are the

standard Gibbs free energies of the above reactions (1) and (2) having units of J/mole, R and T are the gas

constant and the absolute temperature respectively.

Dividing the equations (1) and (2) we can get the expression

…3

The aggressiveness of a given environment can be accessed by the ratio PO2/PS2. Where lower ratio depicts

to a more aggressive environment and vice versa.

At the gas solid interface, the reactions can be given by

𝑥 1
𝑦
M + ½ O2 →𝑦MxOy …3

𝑥 1
𝑦
M + ½ S2 →𝑦MxSy …4

K3=(aMxOy)1/y/(aM)x/y(PO2)1/2=1/(PO2)1/2 …4

K4=(aMxSy)1/y/(aM)x/y(PS2)1/2=1/(PS2)1/2 …5

Where, K3 and K4 are equilibrium constants for the reactions (3) and (4), aM, aMxOy and aMxSy are the activates

of metal(M), metal oxide(MxOy) and metal sulphides(MxSy) respectively. The equations gives the

equilibrium partial pressure for M- MxOy and M- MxSy systems. This pressure is also known as the

dissociation pressure. When the partial pressure of Sulfur or oxygen are higher than the equilibrium pressure

the metal sulphides and oxides will form respectively. Depending on the environment we can decide what

partial pressure of oxygen and Sulfur is high enough for formation of oxides and sulfides by the respective

Ellingham diagrams. The stability of the oxides and sulfides can also be determined by Ellingham diagrams

the lower the free energy line the higher the stability.
The metal-oxide-sulfide stability diagram may be used to describe the thermodynamic interaction between

the metal and oxidants like oxygen and sulfur. This diagrams are also known also called predominance area

diagram.

Figure 2: Schematic stability diagram for the M-S-O system

The stability of the metal, its oxide and sulfide can be determined by the following reactions.

M + ½ O2 →MO …5

M + ½ S2 →MS …6

M + ½ O2=½ S2 + M …7

The dissociation pressure can be obtained from the above equations. The transition from oxidation to

sulfidation can be given by

(PO2/ PS2)1/2 < K5 …6

A stability diagram alone cannot anticipate the potential corrosion products. Other kinetic variables are

significant. High-temperature alloy corrosion behavior is significantly influenced by kinetic variables. They
influence the shape of the corrosion products in addition to the reaction rate. The corrosion products that

are produced may differ from depending upon the environment.

4.2. Kinetics of sulphidation and oxidation at high temperature:

Although we have discussed various thermodynamic factor above which are useful for the determination

of the mode of corrosion in an alloy, the long term application of the alloy can be predicted by kinetic factor

such as diffusivity of the different alloying and corroding elements. The sulfide and oxide on the surface

takes place by parabolic rate law usually. The rate at which sulfidation occur is much higher than that of

oxidation rate, as non-stoichiometry in sulfides is greater than that of oxides. Which signifies that sulfides

have sulfides have a higher defect concentration than oxides, which leads to a rapid growth rate of sulfide

scale.

4.2.1. Solid-State diffusion

Lattice diffusion, can occur by an interstitial or vacancy mechanism in a solid state crystal. The

probability of an atom jumping into an open lattice site is made possible by the presence of point defects

like vacancies and interstitials. The vacancy mechanism is more common for diffusion than interstitial

mechanism. In vacancy mechanism the diffusion is directly proportional to the no of vacancies present in

the lattice. In interstitial mechanism the diffusion occur by the movement of interstitial species to an

adjacent interstitial site this takes place for mostly interstitial impurities like C, N, H and O dissolved in

metal.

Figure 3: An vacancy and interstitial defect in a single-component crystal lattice.

In pure metals, self-diffusion happens through vacancies. It occurs when there is no gradient in

concentration (or chemical potential). Radioactive isotope tracers can be used to monitor this kind of

diffusion. The assumption is typically made that self-diffusion and tracer diffusion are equivalent. The jump

frequency Γ, and the diffusion coefficient DA, are related as follows:

DA=1/6αΓ …7

Where, α is jump distance.

An atom can make the jump if it has enough thermal energy to pass the activation energy barrier to

migration, Gm. The expression exp (-ΔGm/RT) gives the probability of successful jump. The jump

frequency also depends upon the availability of adjacent vacant site, the probability for which can be given

by zXV where z is the number of the nearest neighbor, Xv is the possibility that a site is vacant which is

same as the mole fraction of vacancies in the metal. Finally the jump frequency Γ can be written as

Γ= νzXVexp(-ΔGm/RT) …8

Where is vibration frequency of the atoms.

When the vacancies are in thermodynamic equilibrium

XV=XVeq= exp(-ΔGV/RT) …9

Now from the above three equations we can write

DA=1/6α2νz exp[-(ΔGm + ΔGV) /RT)] …10

Substituting, ΔG= ΔH-TΔS, and for most metals ν is ∼1013(S-1 ). In fcc metals z=12 and α = a/√2 the jump

distance. Equation can be rewritten as

DA= D0exp(-QSD/RT) …11

Where, D0=1/6α2νz exp[-(ΔSm + ΔSV) /RT)] and QSD= ΔHm + ΔHV. …12

Diffusion occurs by mass transfer due to presence concentration gradient or chemical potential. The

diffusion coefficient of the different chemical species in an alloy are different depending upon various

factors like activation energy, size of the element, diffusion mechanism, etc. Solid-state crystal defects with

more open structures include dislocations, grain boundaries, and interfaces. These defects produce high-

diffusivity routes which leads to a faster atomic migration than through in lattice.
 4.3. RATE EQUATIONS
When a metal comes in contact with the oxygen-containing gas, oxides develop if the partial pressure of

oxygen in the gas is greater than the metal oxides' dissociation pressure.. As an oxide layer grows to a

relatively uniform thickness, it may be described by a kinetic law, which is usually parabolic for protective

activity and linear for non-protective behaviour. This section will go through the two fundamental kinetic

laws. Because sulfidation and oxidation have comparable processes, the growth of oxide may be utilised to

describe the process and rate of increase.

The oxidation process may be broken down several steps:

 Supply of oxidant to the scale-gas interface by gas phase mass transfer.

 Oxygen incorporation into the oxide scale.

 Metal delivery from the alloy to the alloy-scale interface.

 Metal incorporation into the oxide scale.

 Metal and/or oxygen transport via the scale.

The figure below shows the reactions and transport processes involved in growth of an oxide scale.

Figure 4: Reactions and transport processes involved in growth of an oxide scale.

The gas phase mass transfer rate may be determined using fluid dynamics methods in step (1). The surface

chemistry may be utilised to study scale-gas interactions in step 2. Interfacial redox reactions are fast in

step (4) and normally do not contribute to rate control. Although each step has the potential to become a

rate-controlling process, steps (3) and (5), which are connected to solid-state mass transfer through diffusion

in the oxide and alloy, are typically used as rate-controlling processes.

4.3.1. Linear kinetics

Before the shift to parabolic growth rate, solid-state diffusion controlled kinetics, the oxidation or

sulfidation process is regulated by gas-phase transport and/or phase boundary reaction. Initially when the

metal surface is free from the scaling the rate of the oxidation or sulfidation does not depends upon the

distance depth x as diffusion occurs too fast. so we can write

𝑑𝑥
= kl …13
𝑑𝑡

After integration we get

x= klt …14

where, kl is the linear rate constant, x is the depth of the oxide layer and t is the time for oxidation. The

scale is so thin in the early stages of oxidation that diffusion across it is too quick to be rate limiting, and

the phase boundary reaction is considered as rate limiting step. The metal-oxide and oxide-gas interfaces

cannot be considered to be in equilibrium in this scenario. It is reasonable to assume that the reactions at

the metal-scale interface are rapid and that the process at the scale-gas interface is rate limiting.

4.3.2. Diffusion-controlled processes and parabolic kinetics

Equation illustrates what happens when the growth rate of a compact scale is governed by the diffusion of

a particular species through the scale: the parabolic rate law. At the oxide-metal and oxide-gas interfaces,

the concentrations of diffusing species are taken to remain constant. The oxide layer's diffusivity is also

thought to be constant and so unaffected by composition. The diffusion distance for O2- and M2+ increases

with scale thickness, x, increasing as a result,

 𝑑𝑥
= kp/x …15
𝑑𝑡

At time t=0 when scaling has not started,

X2 = kpt …16

where kp is the rate constant in the unit cm2s-1, and at t=0, x=0.

The determination of weight change can be done by

𝛥𝑊 2
( ) = 2kwt …17
𝐴

Kw has the unit g2cm-4s -1. If MxOy is the stoichiometry of oxide, the relationship between kp and kw is

Kp= (Vox/16y)2 kw …18

A simplified model of mass flow through the oxide scale is shown in the figure below. Where, C1 and C2

refers to concentrations at the boundaries and C is concentration of diffusing species.

Figure 5: Simplified diffusion model for mass transfer through growing metal oxide scale
Than the rate of diffusion in one direction can be defined by Fick’s first law.

…19
where J is flux, D is the diffusion coefficient and C is the concentration of a component. When

approximation is done by taking boundary value into the consideration then we get

…20

where C1 and C2 represent the concentrations of diffusing components at the interfaces between scale and

metal and gas, respectively.

The interfacial processes must be quick and can be considered to be locally at equilibrium if diffusion is

rate-controlling. Hence under steady state conditions we can write

Kp= ΩD(C1 - C2) …21

where is the volume of oxide formed per unit quantity of diffusing species.

Wagner was the one who originally developed the equation, demonstrating that the features of the oxide—

specifically, their diffusion coefficient and composition when they are in equilibrium with metal and

oxidant—determine the scaling rate. The rate constant in Wagner’s theory was given by

…22

Where DM is the diffusion coefficient of metal through the scale, μ’M and μ”M are chemical potentials of

metal at metal-scale and scale-gas interface.

The assumptions made by Wagner to describe the rate kinetics during the parabolic oxide layer growth

are:

 The oxide layer is a scale that is compact and fully adherent.

 The rate-controlling mechanism involves migration of ions or electrons over the scale.

 The scale-gas and metal-scale interfaces reach thermodynamic equilibrium.

 The ionic fluxes are independent of position within the scale since the oxide scale deviates from

stoichiometry very slightly.

 The scale is thick relative to the distances over which space charge effects (electrical double layer)

occur.

 The thermodynamic equilibrium is reached across the scale.

 oxygen solubility in the metal may be disregarded.

4.4. Properties scales formed at high temperature

When metals are exposed to high temperature sulfidation and oxidation environments, they can form

various types of scales or surface layers. The properties of these scales depend on the specific metal and

the environmental conditions, but some general properties include:

 Protective barrier: In many cases, the scale can act as a protective barrier, preventing further oxidation

or sulfidation of the underlying metal.

 Porosity: The scale can be porous, with gaps and voids that allow for the diffusion of gases and ions

between the metal surface and the environment.

 Adhesion: The adhesion of the scale to the underlying metal can vary depending on the specific metal

and environmental conditions. In some cases, the scale may adhere strongly, while in others it may

flake off or spall.

 Composition: The composition of the scale can vary widely depending on the specific metal and

environmental conditions. In some cases, the scale may consist primarily of metal oxides or sulfides,

while in others it may also contain other elements or compounds.

 Thickness: The thickness of the scale can vary depending on the duration and severity of exposure to

the oxidizing or sulfidizing environment.

 Crystallinity: The scale can be amorphous or crystalline, depending on the specific metal and

environmental conditions.

The properties of scales formed by high temperature sulfidation and oxidation of metals are complex and

dependent on a variety of factors.

 4.5. Factors affecting the stability oxide and sulfide scales
The stability of oxide and sulfide scales formed by parabolic rate at high temperature can be affected by

several factors, including:

 Composition of the substrate material: The composition of the underlying material can have a

significant impact on the stability of the oxide and sulfide scales. Certain elements can promote the

growth and stability of protective oxide scales, while others can lead to the formation of less stable or

even non-protective scales.

 Temperature and exposure time: The temperature and duration of exposure to the oxidizing or

sulfidizing environment can affect the structure and stability of the oxide or sulfide scales. Higher

temperatures and longer exposure times can lead to thicker and more stable scales, while lower

temperatures and shorter exposure times may result in thinner and less stable scales.

 Nature of the oxidizing or sulfidizing environment: The chemical composition and properties of the

oxidizing or sulfidizing environment can also impact the stability of the oxide or sulfide scales. For

example, the presence of water vapor, CO2, or other corrosive gases can lead to the breakdown of

protective scales and promote the formation of less stable or non-protective scales.

 Mechanical stresses: The presence of mechanical stresses, such as thermal cycling or mechanical

deformation, can also affect the stability of oxide or sulfide scales. These stresses can cause cracks or

other forms of damage in the scales, which can compromise their protective properties and lead to

further degradation.

 Surface morphology and microstructure: The surface morphology and microstructure of the oxide or

sulfide scales can also play a role in their stability. For example, a more uniform and dense

microstructure may lead to more stable scales, while the presence of voids or defects can make the

scales more susceptible to degradation.

 Impurities: The presence of impurities in the oxidizing or sulfidizing environment or in the substrate

material can affect the stability of the oxide or sulfide scales. These impurities can interfere with the
 formation of protective scales, promote the formation of less stable scales, or accelerate the degradation

of existing scales.

Overall, the stability of oxide and sulfide scales formed by parabolic rate at high temperature is a complex

and multifaceted issue that depends on a range of factors. Understanding these factors and their interactions

can help to optimize the formation and maintenance of protective scales in high-temperature applications.

4.6. Different types of aluminum coating processes

Aluminum coatings are widely used in high temperature applications of steels to improve their oxidation

resistance, corrosion resistance, and thermal stability. There are various methods by which aluminum can

be coated into the surface of the steel. Here are some of the most commonly used types of aluminum

coatings in high temperature applications of steels:

 Thermal spray aluminum (TSA) coatings: TSA coatings are applied by spraying molten aluminum

or aluminum powder onto the surface of the steel component using a thermal spray process, such

as flame spraying or arc spraying. TSA coatings provide excellent corrosion and oxidation

resistance and can withstand temperatures up to 800°C.

 Pack cementation aluminum coatings: Pack cementation is a diffusion-based process in which the

steel component is coated with a mixture of aluminum powder and other chemicals, such as halides,

in a sealed container at high temperatures. The aluminum diffuses into the surface of the steel to

form a protective aluminum-rich layer. Pack cementation coatings provide excellent oxidation

resistance at temperatures up to 1000°C.

 Chemical vapor deposition (CVD) aluminum coatings: CVD is a process in which an aluminum-

containing gas is introduced into a high-temperature vacuum chamber, where it reacts with the

surface of the steel to form a thin and uniform aluminum coating. CVD coatings provide excellent

thermal stability and corrosion resistance and can withstand temperatures up to 1000°C.
  Electrodeposited aluminum coatings: Electrodeposition is a process in which an aluminum-

containing solution is electrolytically deposited onto the surface of the steel. Electrodeposited

coatings provide good corrosion resistance at temperatures up to 300°C.

 Cladding with aluminum alloys: Cladding is a process in which a layer of aluminum alloy is bonded

to the surface of the steel using hot rolling or explosion welding. Aluminum alloy cladding provides

excellent corrosion resistance and thermal stability at temperatures up to 350°C.

Each of the coating have their own advantages and limitations. The selection of the most suitable type of

aluminum coating depends on the specific requirements of the application. Here are some of the properties

of aluminum coatings necessary for high temperature applications:

 Oxidation and sulfidation resistance: Aluminum coatings have excellent oxidation resistance at

high temperatures. When aluminum is heated, it forms a protective oxide layer that prevents further

oxidation of the underlying steel substrate. This helps to extend the service life of the coated steel.

Aluminum coatings also exhibit excellent sulfidation resistance. This oxide layer acts as a barrier,

preventing the underlying substrate from reacting with sulfur and sulfur-containing compounds.

 Corrosion resistance: Aluminum coatings are also highly resistant to corrosion. They can withstand

exposure to harsh chemicals and environmental conditions without deteriorating. This makes them

ideal for use in corrosive environments, such as chemical processing plants and marine

applications.

 Thermal stability: Aluminum coatings have high thermal stability and can withstand extreme

temperatures without degrading. This makes them ideal for use in high-temperature applications

such as furnaces, boilers, and heat exchangers.

 Thermal conductivity: Aluminum has a high thermal conductivity, which allows it to dissipate heat

quickly, reducing the risk of thermal damage to the substrate.

 Adhesion: Aluminum coatings have excellent adhesion to steel substrates. They form a strong bond

with the underlying steel, which helps to prevent the coating from peeling or flaking off over time.
  Ductility: Aluminum coatings have good ductility, which allows them to deform and stretch

without cracking or breaking. This is important in high-temperature applications where thermal

expansion and contraction can cause stress on the coating.

Overall, the combination of these properties makes aluminum coatings an excellent choice for high-

temperature applications of steels where oxidation resistance, corrosion resistance, and thermal stability are

critical.

4.7. Mechanism of formation of thermal diffusion layer

The process of heat diffusion resulted in the creation of the coatings. This process includes high-temperature

chemical reactions that take place within the chosen powder mixtures, such as the breakdown of the

halogen-containing activator and the high-temperature interaction of gaseous species with the active

ingredient (or "donor") that results in the production of active material vapours. As the active substance is

a vapour, it settles on the steel substrate and diffuses its atoms into the steel structure. Their dispersion is

aided by the vast distances in the fcc Fe structure and the tiny Al atomic sizes, which are less than those of

Fe. When aluminum is in contact with an iron surface, a layer of iron aluminide (FeAl) is instantly formed

due to the large negative free energy of formation.

The creation of additional aluminides is caused by the outward diffusion of Fe atoms (as well as Cr and Ni

in the case of stainless steel) from the substrate and their interaction with diffusing active atoms. Moreover,

the produced aluminides expand and solidify, creating a coating structure that is more intricate (i.e. two or

more layers). The initial FeAl film grows epitaxially on the substrate and then columnar growth occurs

without new nucleation, corresponding to zone III of Thornton's bulk diffusion controlled growth. The

outermost layer is formed by pure aluminum deposited on top and iron diffusing out through the initial

FeAl layer.
Figure 6: Schematic diagram of the formation model of the iron-aluminum alloy coating with
a multilayer phase structure.
The thickness of the top layer is determined by the flux of aluminum into and out of the layer, limited

by the rate of outward iron diffusion and aluminum diffusion through the FeAl layer. The composition

of the FeAl forming in the first layer is decided by the rates of aluminum transport onto the surface and

aluminum diffusion into the second layer. The absence of grinding marks on the lateral surface of the

coatings supports this mechanism. Overall, this process produces a FeAl layer with a microstructure

similar to that of the substrate, and the thickness of the coated specimen is nearly equal to the thickness

of the substrate before coating

The second layer in the coated specimen is formed due to the diffusion of aluminum from the top layer

into the iron substrate. This layer shows characteristics of a bulk solid state diffusion layer, and its

thickness increases with higher coating temperature and duration. The structure of this layer is either

B2 or bcc solid solution, depending on the aluminum content, as indicated by the phase diagram. The

substrate has an fcc structure at temperatures above the α-γ transition temperature. If the aluminum

content exceeds the solubility limit of fcc iron, the substrate would transform to a bcc structure with a
distinct boundary. The width of the second layer corresponds to the distance between the boundary of

the first layer and the boundary of the bcc region. The appearance of a third layer is due to an optical

contrast effect, where on cooling to room temperature, the substrate and the region with low aluminum

concentration transform from fcc to bcc structure, resulting in different contrast in optical micrograph.

This gives rise to the observation of the third layer. Overall, the second layer is formed by aluminum

diffusion into the substrate, and the third layer is a result of the structural transformation of the substrate

and low aluminum concentration region upon cooling.

Figure 7: The Fe-Al phase diagram

The in case austenitic stainless steels the chemistry is carefully balanced to give them austenite stability,

but when Al diffuses into the substrate during coating, the delicate balance is disturbed. The solubility

of Al in fcc austenite is very limited, while it is very high in ferrite. Substantial aluminizing is possible

only if ferrite is formed locally at the surface, but Ni, Mn, and C in the substrate oppose ferritization

due to their strong austenitizing tendency. However, heat-resisting stainless steels can be ferritized by
Al diffusion due to the formation of stable nickel aluminide intermetallic compounds. The higher Ni

substrates slow down the ferritization process induced by Al diffusion. The diffusion rate of Al in bcc

ferrite is much higher than in fcc austenite, so the diffusion-induced phase transformation to ferrite

helps Al diffusion.

4.8. Techniques for evaluation of performance of multi-layered thermal

diffusion coatings
The apparatus used for studying high temperature gas corrosion typically involves the use of

specialized test chambers and furnaces to maintain high temperature, gas flow rates and the corrosive

gas environment. The basic components for such apparatus are:

 Furnace for generating and maintaining required temperatures consisting of a heating element, a

control system and a temperature sensor.

 Test chamber typically made up of refractory materials. The sample is placed in this chamber

during the experiment. The sample holders are required to place the samples at the test chambers

are also made up of ceramics or graphite’s. Sometimes special wires are used to hang the sample

in the flowing gas environment.

 Gas delivery system is responsible for delivering the high temperature gas into the test chamber.

It includes components like gas cylinder, flow controller, gas analyzer and mass flow meter.

 We can install a TGA instruments within the test chamber so that weight change of a sample

exposed to the corrosive gas environment can be monitored regularly. By monitoring the weight

loss or weight gain over time, it is possible to determine the rate of corrosion.
 Figure 8: Schematic diagram of the apparatus used for corrosion studies.
The apparatus or test rig used for different high temperature gas corrosion may be different based on the

requirements of the experiments but the basic components required are same as mentioned above. The

apparatus are fairly complex and requires careful calibration and control to ensure accurate and repeatable

results.

5. Results and Discussions:

5.1. Review previous research on Sulfidation-oxidation resistance of coated

and uncoated steel samples
The effect of multi-layered protective coatings generated using thermal diffusion technology were

significantly better performing than those of uncoated steels in H2S/ H2O environment. When bare

stainless steel was exposed to H2S/H2O-Ar atmosphere it experienced a formation of sulfide and oxide

scale which was porous, readily spalling and not adherent to the substrate which was non protective in

the high temperature sulfidation environments. On the other hand, the aluminide-based coatings applied

to carbon steel and stainless steel showed almost no evidence of sulfide scale development. Further

analysis revealed that none of the thermal diffusion coatings had substantial case depth decrease or

alterations to their original structures, and that there was no pitting or blistering at the sulfidation site.

Almost negligible weight change was noticed in diffusion coated samples, which might be due to the

suldfidation resistance offered by the surface oxide of the aluminides.

 The higher chemical inertness of aluminides, which results from their high crystalline lattice energies

and strength Fe-Al/Cr-Al covalent bonds, multilayered structures, where each inert layer with

remarkable thickness protects the underneath inert layer and steel substrate, and diffusion-related

bonding between the protective layers and steel substrate are all factors that contribute to the improved

performance of the obtained coatings. The aluminide layer hardness measurements verified the integrity

of the high coatings. Due to the thin chemically inert Al2O3 coating that developed on the surface of

the aluminides as a result of high-temperature oxidation and which adheres perfectly to the substrate

surface, enhances the corrosion resistance significantly.

5.2. The mechanisms of aluminide oxidation:

The aluminide layers structure may be broken down into two layers: an outer layer made of aluminum and

an interior layer made of Fe-Al intermetallic compounds with dissolved Si and minimal Cr for a coated

steel. When exposed at 850 0C for 1 hours the outside, middle, and inner aluminide layers all exhibited

some porosity characteristics and developed quickly. With the exception of the porous area, where

aluminum diffused unevenly, the outer aluminide layer porous area saw some oxides develop. Coarsening

in internal defects too place when kept under oxidation condition for 24 hours, but Al, Fe, Si, and Cr were

evenly distributed throughout the aluminide layer. The aluminide layer had the same phases as the uncoated

specimen, which were Al, Si, FeAl3, Fe2Al5 and FeAl2. FeAl intermetallic predominated in the aluminide

layer period.

Five different phases were identified from the scale to the matrix: α-Al2O3+ FeAl, FeAl, FeAl2+η-

Fe2Al5, FeAl and steel substrate. The inclusion of Si in Al made the surface layer smooth and

enhanced the interfacial bond strength. It readily dissolved in the intermetallic compounds at the

surface and near surface with more solubility in FeAl than other compounds.
 Figure 9: (a) Cross section micrograph of aluminide steel exposed at 850 °C for 8 h, (b)
EDS results showing the concentration variations of Al, Fe, Cr, and Si elements
The cross-sectional micrograph of the specimens oxidized at different temperatures is shown below. The

Al present at the top layer disappears within no time due to inward diffusion of Al and outward growth of

aluminide layers. Small number of microcracks are also seen as the aluminides starts growing. The

generation of the cracks can be due to the mismatch in the thermal expansion of the brittle intermetallic

layers like Fe2Al5, FeAl2 and the steel substrate caused due to tensile stresses generated due thermal cycles.

The cracks developed rapidly when Fe2Al5 and FeAl2 were the main phases. As the Fe2Al5 and FeAl2

converted to FeAl the cracks were only seen in the top layer.

A very thin α-Al2O3 layer was developed even after substantial exposer to the oxidizing atmosphere.
 Figure 10: Optical cross-sectional micrographs of specimens oxidized from 4 min to 56 h
at 750, 850, and 950 °C, where a, b, c, d, e, f, and g is presented as variation of the
microstructure as a function of test duration at 850 °C; h and i for 750 °C, j for 950 °C.
As Al diffused inward and oxidation consumption, voids and cavities began to appear beneath the Al2O3

scale as the oxidation duration rose. In this stage, Al inward diffusion may be dominant, while Al

consumption by the oxide growth is likely of secondary importance in the cavity development. Whereas,

the outwards diffusion of Fe from steel substrate leads to FeAl(Cr,Si) precipitate formation in the

intermetallic layers. The formation of the precipitate loosens the material which can be attributed to the

inward diffusion of Al and outwards diffusion of FeAl which leads to growth and vacancies generation in

the FeAl island. The loosening of the FeAl precipitate can be due to the coalescence of vacancies as well

as volume change during the phase transformation. The mechanism by which internal voids formed was

compatible with the Kirkendall effect, in which vacancies were net fluxed to the interface where they

condensed into voids due to different Fe and Al diffusion rates. After a long time due to tensile stresses

caused due to the phase transformation the cracks open further and lets the oxygen penetrate into Voids

coalesce, and leads to the internal oxidation. Which further leads to spallation and accelerated corrosion
attack. The rate of oxidation increases with increase in temperature. The oxidation follows a parabolic

rate during the entire oxidation process at any temperature soon after the alumina layer is formed on the

surface as expected.

Figure 11: Schematic configuration for the growth stages of aluminide layer and internal
void with oxides during oxidation at high temperature. (a) as-coated steel. (b) inward Al
diffusion and cracks formation. (c) the growth of FeAl2+ Fe2Al5 and FeAl precipitation.
(d) the growth of FeAl in FeAl2+ Fe2Al5 and oxides formation. (e) loose metals formation
in FeAl island. (f) internal voids formation. (g) the growth of voids and FeAl in the inner
aluminide layer. (h) the growth of FeAl phase through the entire aluminide layer.

Initially the oxidation rate was controlled by the interfacial reaction of oxygen with the Al on the surface,

corresponding to a rapid increase in weight. As the alumina protective film was developed the diffusion of

oxygen through the Al2O3 layer becomes the rate controlling step. As the temperature is continuously

increased the thickness of the intermetallic layer also increases due to increase in inter-diffusion of the Fe

and Al which leads to a depletion in Al concentration in the near surface region for oxide layer formation.

Also the rapid increase in thickness of the brittle intermetallic layer leads to crack generation due to high
stress accumulation. This leads to the breaking of the protective oxide film and breakaway oxidation of the

steel substrate. This also limits the healing properties of the Al2O3 protective oxide layer.

Similar mechanism can also be expected during high temperature exposure to sulfidation atmosphere.

5.3. The effects of coating composition, thickness, and structure on

sulfidation-oxidation resistance
Aluminide coatings have been widely studied as a means of improving the sulfidation-oxidation resistance

of steels in high-temperature environments. The composition, thickness, and structure of aluminide coatings

all play important roles in determining their effectiveness in providing protection against sulfidation and

oxidation.

 Composition: The composition of the aluminide coating is critical in determining its resistance to

sulfidation and oxidation. Generally, the coating should have a high aluminum content (at least 90%)

to form a protective oxide layer on the surface of the steel. Other elements, such as silicon and

chromium, can be added to the coating to enhance its performance. The composition of the coating

influences its ability to form protective oxide film and repair. Al rich coating tends to form protective

alumina scales, however, excessive aluminum can lead to formation of brittle intermetallic phases

which can reduce the adherence and promote cracking.

 Thickness: The thickness of the aluminide coating is also important, as it affects the diffusion of sulfur

and oxygen through the coating. A thicker coating will generally provide better protection against

sulfidation and oxidation, but it may also increase the likelihood of cracking or delamination due to

thermal stresses. Optimal thickness varies depending on the specific application, but coatings in the

range of 20-50 microns are common.

 Structure: The structure of the aluminide coating can also impact its performance. The coating can be

either single-phase (Fe-AL) or multi-phase (Fe3Al, FeAl, Fe2Al5 and FeAl3 phases). The microstructure

of the coating can also vary, with different crystal structures and grain sizes affecting the coating
 properties. A finer-grained structure can improve the coating adherence and resistance to cracking.

Further the texture of the coating can affect its tendency to form continuous oxide film at the surface.

In order to achieve a better sulfidation-oxidation resistance the composition, thickness and structure oF the

coating should be optimal such that the damage to the substrate should be minimized.

6. Conclusion
Due to the versatility of the thermal diffusion coating it is applicable in various steels and alloys for high

temperature application. The ease with which the coating can be applied to the components with complex

shapes and sizes by various techniques makes it the one of the best coating process used in the high

temperature applications. The formation of the protective alumina coating as well as hard intermetallic

diffusion layer makes it a suitable candidate for the corrosion and wear resistance application at high

temperatures. The performance of the thermal diffusion coating with respect to the bare uncoated steel

under high temperature sulfidation and oxidation atmosphere is excellent. Where the bare stainless steel

forms non-protective oxide and sulfide scales leading to a spallation, a simple carbon steel coated with

aluminide coating tends to be inert under high temperature sulfidation and oxidation environment. But

slowly as the temperature increases the oxidation rates also increases. Also the growth on the brittle

intermetallic layer leads to generation of the cracks in the protective film. This leads to a breakaway

corrosion limiting the lifetime of the component. Breaking and detachment of the brittle intermetallic

layer can take place at high temperature exposing the substrate to accelerated attack and high temperature

corrosion.

The addition of the reactive elements like Zr, Mo, Y, Th etc can lead to a better adhesion property of the

intermetallic layer with the substrate which can enhance the lifetime and protect from breakaway

oxidation. A oxide layer coating of M-O bond like SnO2, TiO2, ZrO2, ThO2, Al2O3, Y2O3 with a high

crystalline lattice energy and a high degree of covalence can be carefully applied for protection on tgop of

the thermal diffusion coating.

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