THEORETICAL EXAMINATION

OF OXIDATION OF FERRITIC
STAINLESS STEEL

MTLE-4150  10/05/2020
Abstract

This is a theoretical experiment focused on determining whether the rate of physisorbion of

oxygen on the surface of ferritic stainless steels is consistent with the growth rate of oxide

layers on these steels. The impingement rate of oxygen was calculated and compared against

the growth rate of oxide layers. It was concluded that oxygen in air is in excess and therefore

does not affect the rate of growth reaction. Rather, the rate of growth is affected by oxide layer

thickness due to slower diffusion in thicker layers and an electrochemical mechanism of oxygen

diffusion.

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Contents
Abstract............................................................................................................................................1
Introduction.....................................................................................................................................3
Methods...........................................................................................................................................6
Experiment Overview...................................................................................................................6
Apparatus.....................................................................................................................................7
Procedures...................................................................................................................................7
Results and Discussion...................................................................................................................11
Conclusion......................................................................................................................................12
References.....................................................................................................................................13

Introduction

I conducted this theoretical experiment to determine the kinetic relation between physisorbed

oxygen on the surface of stainless steels and oxide growth on these stainless steels at high

temperature. I have also provided a theoretical mechanism by which gaseous oxygen is

stainless steels. This experiment draws its data from “Oxidation kinetics and mechanisms of

aluminum modified ultra-pure low chromium ferritic stainless steels” by Xu et al. Ferritic

stainless steels are a class of stainless steel that have between 10% and 30% chromium in

addition to other metals such as titanium and aluminum (Handbook of Materials failure).

Corrosion is the growth of oxides on metals which reduces structural integrity. This growth is

increased at higher temperatures due to kinetics and is as a result of oxygen atoms making

their way into metals. The movement of oxygen atoms through layers by bonding chemically

can be called diffusion. This study is related to exhaust systems which operate at high

temperatures and are expected to maintain structural integrity during use. Exhaust systems are

made using stainless steel, a corrosion-resistant metal, in order to prevent metal degradation

due to oxidation. A specific class of stainless steel, the ferritic stainless steels (FSSs), were

observed during the study. Oxide growth refers to what is typically known as “metal rust”. The

rusting of metal occurs as a result of a chemical reaction known as oxidation. Oxidation can be

defined as the addition of oxygen to a chemical species. It can also be defined as a loss of

electrons by a chemical species. The opposite of oxidation is reduction and reactions where

oxidation and reduction occur simultaneously are characterized as redox reactions. In order for

rusting of a metal to occur, oxygen must chemically bond to the metal atomic species. Air is

comprised of about 21% oxygen. Therefore when a metal is present in air at a high

temperature, oxidation reactions at the surface of the metal occur. The result of the oxidation

of a metal is a new compound (called a metal oxide) made of both the metal subject and

oxygen chemically bonded. This metal oxide forms a layer between the rest of the metal subject

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and the air, preventing further oxidation of the metal (Xu et al). As the metal oxide grows, the

distance that an oxygen molecule needs to travel through it in order to reach the metal

increases. This causes the rate of metal oxide growth to reduce as the metal oxide grows. It is

this phenomenon relating to a varying rate of reaction that enables a kinetic study of such

oxidation to occur. In tandem with the experimental results, a mechanism which took into

account the reduction in rate as the reaction progressed was proposed. In order to calculate

the amount of oxygen reaching the surface, a formula for the impingement rate (number of

particles which hit a surface per second and unit area), I, was used. Here is the impingement

rate as Equation 1

P atoms
I= ( 2 )
√2 πmk B T cm ⋅ s

28.84 g /mol
P=Pressure ( Pa ) ; m= 23
; k B=1.38 ×10−23 ; T =temperature ( Kelvin)
6.022 ×10 atoms/mol

Equation 1: Impingement rate

The rate of oxide growth is characterized as “parabolic oxidation”. This factors in the rate of

growth reducing as the oxide grows. This phenomenon can be shown as a curved graph as

shown below with its characteristic equation. In parabolic oxidation, there is a constant, k p,

known as the parabolic rate constant (Saunders et al)

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(Saunders et al)

Figure 1: Parabolic oxidation

dX k p
=
dt X

(Saunders et al)

Equation 2: Parabolic rate equation

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Methods

Experiment Overview

The experiment by Xu et al investigated at 800°C and 1000°C the oxidation behavior of ultra-

pure low chromium ferritic stainless steels over a time period of one hour. Xu et al produced

graphs of weight gain (mg/mm2 or μg/mm2) versus Oxidation time (hours) for each alloy tested.

Xu et al also provided a table consisting of data for each respective alloy: Temperature,

oxidation time and parabolic rate constant. I calculated the impingement rate of oxygen

molecules using Equation 1 with the assumption that pressure was equal to atmospheric

pressure because Xu et al did not measure pressure. In order to determine the kinetic

relationship with the rate of oxide growth, this impingement rate was compared to the oxide

growth rate. I assumed that every oxide was 50% oxygen and had a density of 5 g/cm 3. From my

calculations, the rate of oxygen impinging on the metal surface was in excess to the rate

necessary for oxide growth. Since oxide growth is fastest at the beginning of each experiment,

the weight shortly after the oxidation process began was used. From the Xu et al experiment,

this weight was estimated to be 0.02 mg. Dividing the k p by 0.02 mg results in a value much

smaller than the oxygen impingement rate. My next step was to form a mechanism of chemical

reactions to provide a theoretical method of oxygen reaching into the various oxide layers for

further growth. Xu et al provided electron microscope images of the samples which showed

complex mixing of different metal oxide layers adding to the thickness of the oxide layers. This

complex mixing was incorporated into the mechanism I proposed for gaseous oxygen reaching

the oxide layers. My mechanism took into consideration the fact that water (aqueous solvent) is

necessary for oxidation. I proposed sets of chemical equations by paying attention to the

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transfer of electrons in redox reactions. For the complex mixing of oxides, I considered the fact

that more reactive species can displace less reactive species in order to turn one oxide into

another.

Apparatus

This was a theoretical experiment. In order to perform it, an understanding of chemical kinetics,

basic chemistry and calculus was necessary. Lastly the experiment by Xu et al is necessary for

the data used

Procedures

Impingement rate of oxygen atoms compared to oxide growth rate

 From Equation 1 calculate the impingement rate of air. From the Xu et al experiment,

the two temperatures to be considered (T) are 800°C and 1000°C. Calculate an

impingement rate for each temperature

o The values listed under Equation 1 can be considered at standard for air

o Convert temperature in degrees Celsius to Kelvin by:

° K=° C+273.15

 Air is about 21% oxygen, therefore multiply each calculated impingement rate by factor

0.21

 Oxygen is a diatomic molecule (two atoms for every molecule) so multiply each

impingement rate by factor 2

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 atoms
 Equation 1 is in units ( ). Multiply each impingement rate by factor 3600 (s/hour)
cm 2 ⋅ s

atoms
in order to change units to ( )
cm 2 ⋅hr

atoms
 Multiply each impingement rate by factor 1 ×10−2 in order to change units to ( )
mm2 ⋅ hr

 One oxygen atom has a mass of 2.657 ×10−20mg/atom.

 Multiply the impingement rate at 1000°C by 2.657 ×10−20mg/atom to get units

mg
( )
mm2 ⋅ hr

o The oxide weight gain for T = 800°C was measured with micrograms instead of

milligrams. Doing calculations for 800°C obtained similar results so it is not

added to evaluation. However, by following the procedure with the mass of

oxygen in micrograms, the calculations may be obtained if desired.

 With the impingement rate of oxygen obtained, I calculated the rate of oxide growth to

see if there was sufficient oxygen for growth of oxide. Due to parabolic oxidation, the

rate is highest at the beginning. For the 1.51Al-0.12Ti alloy, the weight gain after

approximately 4 hours (out of a 100 hour experiment) was approximately 5.0 ×10−4

mg/mm2. The parabolic rate constant for this alloy at 1000°C was 1.1 ×10−7 mg2/(mm4hr)

o From Equation 2, the rate of increase in oxide mass is given by

d (weight gain) kp
=
dt ( weight gain)

o Do this calculation (parabolic rate constant/weight gain)

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 mg
o The units for this calculation should be ( )
mm2 ⋅ hr

 I observed that the impingement rate of oxygen was much larger than the oxide growth

rate at the beginning of the experiment.

o In addition, the oxides are assumed to be only 50% oxygen so the oxide growth

rate with respect to oxygen content is the growth rate divided by 2.

Mechanism for addition of oxygen into oxide layers

In order for oxidation of metals to occur. A solvent of some form is needed in order to allow

dissociation of chemicals into cations and anions (Ahmad). Since the experiment was not

carried out in any special conditions, I assumed an aqueous environment since there is an

amount of water in air. Water is a polar molecule. This means that on an atomic level the

density of the electron cloud around water molecules is shifted towards a specific atom. Since

water is made of hydrogen and oxygen, the larger electron density is situated around oxygen

because oxygen has a larger affinity for electrons than hydrogen. Due to these partial positive

and negative charges on each water molecule, water can attach to positive and negative ions

and break them apart (i.e. dissolve them). Therefore, I propose that hydrated metal hydroxides

are formed. After reverse hydrolysis (removal of water) (researchgate.com), these metal

hydroxides produce metal oxides. There are some decomposition and synthesis reactions as

well. The mechanisms consist of chains of ionic equations with the end products being oxides,

water and evolution of hydrogen. The overall ionic equations of the mechanism are detailed

below

Dissociation of water:

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2 H 2 O → H 2 +2 O H −¿¿

Formation of iron(III) oxide:

4 Fe+3 O 2+ H 2 +2 O H −¿→ 4 FeO (OH ) ¿

Method 1 :2 FeO ( OH ) → Fe2 O3 + H 2 O( Decomposition)

Formation of iron(II,III) oxide:

2+¿ (OH) +4 H ¿
8 2
3+¿ Fe ¿
−¿ → Fe ¿
3+¿+ Fe+ ¿+ 4 H +8 O H ¿
¿
2 Fe
2

Method 1 : Fe3 (OH )8 → Fe3 O 4 + 4 H 2 O( Decomposition )

Method 2 : FeO+ Fe 2 O 3 → Fe3 O 4 (Synthesis)

Formation of chromium(III) oxide:

2 Cr+3 H 2 +6 O H−¿→ 2Cr (OH ) +3 H 3 2 ¿

Method 1 :2Cr (OH )3 →Cr 2 O3 +3 H 2 O( Decomposition)

Formation of aluminum(III) oxide:

2 Al +3 H 2+ 6 O H −¿ →2 Al(OH ) +3 H 3 2 ¿

Method 1 :2 Al (OH )3 → Al2 O 3+ 3 H 2 O( Decomposition)

Method 2 :2 Al +Cr2 O 3 → Al2 O 3+ 2Cr ( Replacement )

Formation of titanium dioxide

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2 Ti+3 H 2 +6 OH −¿→ 2 H 2 TiO3 +4 H 2¿

Method 1 : H 2 Ti O 3 → TiO 2 + H 2 O( Decomposition )

Results and Discussion

From the experiment I concluded that the rate at which oxygen molecules are able to reach the

surface of each metal alloy is much higher than the rate of usage of oxygen (in forming metal

oxides) at any stage of the reaction, with the highest rate of usage of oxygen at the beginning.

As the oxide layers get thicker and more complex (i.e. different combinations of oxides), oxygen

atoms has a larger distance to diffuse across in order to react with the metal atoms to form

oxides. Also, the complexity of layers results in oxygen atoms having to go through a series of

reactions in order to reach the covered alloy surface. It is because of these reasons that Xu et al

observed parabolic oxidation, given the fact that the larger the oxide layers grow the stronger

the oxidation buffer. It can then be concluded that oxide layers can prevent further oxidation of

metals. However, Xu et al did not consider the effect of an excessively heavy oxide layer. In

such an event the oxide layer would fail under stress, in turn causing a burst of relatively rapid

oxidation (Handbook of Materials failure). This might result in downwards rusting of a metal

alloy (through its cross section - parallel) instead of the proposed surface rusting (on surface

perpendicular to cross section). Corrosion is an electrochemical process since it involves the

transfer of electrons through redox reactions in addition to “cathode-like” and “anode-like”

presences (for example hydrogen evolution at the “anodes” of these reactions) (Song). Further

evidence to corrosion being an electrochemical process lies in the facts that chromia (Cr2O3)

oxide scales are electrically conductive and corrosion behavior is influenced by electric current

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(Kodjamanova). In my proposed mechanism, there is a reaction in which aluminum displaces

chromium (in Cr2O3) leading to aluminum(III) oxide formation and the element chromium being

released back to react again. It is through these complex reactions that layers of multiple oxides

are formed.

Conclusion

I have developed a mechanism for the oxidation of FSSs through emphasis on the

electrochemical properties of oxidation and the occurrence of redox reactions. I have also

determined that the impingement rate of oxygen molecules on a FSS’s surface is in large excess

of the amount of oxygen necessary for FSS oxide growth.

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References

(1)

Xu, Y.; Fu, H.; Fan, L.; Lu, B.; Zhao, H.; Dong, H. Oxidation Kinetics and Mechanisms of Aluminum

Modified Ultra-Pure Low Chromium Ferritic Stainless Steels. Corros. Sci. 2019, 161 (108192),

108192.

(2)

Handbook of Materials Failure Analysis with Case Studies from the Aerospace and Automotive

Industries; Makhlouf, A. S. H., Aliofkhazraei, M., Eds.; Butterworth-Heinemann: Woburn, MA,

2016.

(3)

Saunders, S. R. J.; Nicholls, J. R. Oxidation, Hot Corrosion and Protection of Metallic Materials. In

Physical Metallurgy; Cahn, R. W., Haasen†, P., Eds.; Elsevier, 1996; pp 1291–1361.

(4)

Ahmad, Z. Principles of Corrosion Engineering and Corrosion Control; Butterworth-Heinemann:

Oxford, England, 2006.

(5)

https://www.researchgate.net/publication/293349477_Fe3O4_and_Fe_nanoparticles_by_che

mical_reduction_of_Feacac3_by_ascorbic_acid_Role_of_water (accessed Oct 7, 2020).

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(6)

Song, G.-L. Corrosion of Magnesium Alloys; Song, G.-L., Ed.; Woodhead Publishing: Cambridge,

England, 2011.

(7)

Kodjamanova, P.; Fu, Q.; Gautier, L. Electric Current Effects on the Corrosion Behaviour of High

Chromium Ferritic Steels. Oxid. Met. 2013, 79 (1–2), 53–64.

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