Department of Mechanical Engineering

Chittagong University of Engineering and Technology

Oxides: Oxides are rust or scale that formed due to reaction with mainly oxygen. Oxides are
composed of grains that exhibit behavior similar to metals [14]

Oxides

Based on Based on
thickness protection

Protective Non protective

Thin oxides Thick oxides
Oxides
Oxides

The processes when metal surface is exposed to oxygen:

a) Adsorption of oxygen
b) Formation of oxide nuclei that grow laterally
c) Growth of a continuous oxide film

ME 6351 Oxidation and High Temperature Corrosion Page # 1

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Oxide Properties
Oxides can crystalize Exhibit grain growth
Act like semiconductors Show plasticity especially at high
temperature

Semiconducting oxides:
1. p (Positive carrier) – type Oxides: In the p - type, shift of stoichiometric proportions takes the
form of a certain number of missing metal ions in the oxide lattice called cation vacancies
represented by . At the same time, to maintain electrical neutrality, an equivalent number of
positive holes, ⊕ , form — that is, sites where electrons are missing. Examples - Cu2O, NiO, FeO,
CoO, and Cr2O3

Figure: Lattice defects in Cu2O [7]

ME 6351 Oxidation and High Temperature Corrosion Page # 2

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

2) n (Negative carrier) type Oxides: For n - type oxides, excess metal ions exist in interstitial positions
of the oxide lattice, and it is these, together with electrons, that migrate during oxidation to the outer
oxide surface. Examples - ZnO, CdO, TiO 2 , and Al 2O3

Figure: Lattice defects in ZnO [7]

ME 6351 Oxidation and High Temperature Corrosion Page # 3

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Thermodynamics of Oxidation

FREE ENERGY – TEMPERATURE DIAGRAM

Metals oxidation and reduction can be predicted using graph of the standard Gibbs free
energy of formation of oxides versus temperature as shown in the figure.

Obtainable Information
 the vertical axis of the graph - The standard Gibbs free energy of formation (ΔG°) for
any oxide directly (Example, the standard Gibbs free energy of formation at 1000° C of
NiO is approximately − 250 kJ for two moles of NiO)

 The straight lines through the points labeled O, H, and C - the equilibrium values of
𝒑𝑶𝟐 , CO/CO2 and H2 /H2O ratios in contact with metals and their oxides

ME 6351 Oxidation and High Temperature Corrosion Page # 4

Figure: Standard Gibbs free energy of formation of oxides as a function of temperature
[B. Mishra, in Metals Handbook , Desk Edition, 2nd edition, ASM International, Materials
Park, OH, 1998, p. 718].
Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Page # 5
 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Wagner’s Experiment: Wagner conducted an experiment by placing molten sulfur over two weighed
pellets of Ag2S and Ag for 1hr at 220 °C as shown in figure.

Outcome
 The top pellet gained weight chemically
equivalent to the loss in weight of metallic silver
 The bottom pellet neither gained nor lost weight

Figure: Formation of Ag2S from Ag and liquid S

[C. Wagner, Z. Phys. Chem.21B, 25 ( 1933 )]

Findings
 Ag+ ions and not S2− ions migrate through Ag2S

 Wagner also showed that by assuming independent migration of Ag + and electrons, the observed
reaction rate could be calculated from independent physical chemical data

ME 6351 Oxidation and High Temperature Corrosion Page # 6

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Oxidation or Iron and its alloys: Oxidation of iron at high temperature is complicated
by formation of as many as three distinct layers of iron oxide, and the proportions of these
layers change as the temperature or oxygen partial pressure changes.

Layers of Iron Oxides [7]

1) 2 layer Oxide (Fe3O4 plus Fe) below 570 °C or room temperature
2) 2 layers of Oxides (An inner FeO layer plus an outer Fe3O4) forms at 600 °C in atm
O2 for 100 min [M. Davies, M. Simnad and C. Birchenall, J. Metals 3, 889 (1951)]
3) 3- layer scale (90% FeO, 9% Fe3O4 and <1% Fe2O3) forms at 3900 °C for 100 min

ME 6351 Oxidation and High Temperature Corrosion Page # 7

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Alloying elements that improve oxidation resistance of iron

 Chromium
 Aluminum

Figure: Effect of alloyed chromium on oxidation of steels containing 0.5% C, 220 h

[E. Houdremont, Handbuch der Sonderstahlkunde , Vol. I, Chromst ähle, Springer, Berlin (1956), p. 815, Fig. 677]

ME 6351 Oxidation and High Temperature Corrosion Page # 8

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Hot Corrosion: Hot corrosion is the accelerated oxidation of a material at elevated

temperatures induced by a thin fi lm of fused salt deposit [Robert A. Rapp, Corrosion Sci.
44(2), 209 (2002)].
Properties of Hot Corrosion [7]
1. Occurs due to thin electrolyte film
2. Corrosion is commonly controlled by the diffusion of oxygen to the metal surface
3. The soluble oxidant is SO3 (S2O72−) in the fused salt
4. Hot corrosion may occur in the absence of metallic contaminants in the fuel
5. Oxide particles were observed to be dispersed in the adherent salt fi lm
6. Hot corrosion of marine turbine blades may occur even with use of very low - sulfur
fuels [P. Bergman, Corrosion 23, 72 (1967) ]
High-chromium alloys are more resistant to hot corrosion than low-chromium alloy

Sulfidation: The attack of sulfides on metals and alloys as inclusions or a network of

sulfides along grain boundaries

ME 6351 Oxidation and High Temperature Corrosion Page # 9

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Laws of Oxidation
Industrial oxidation at high temperature exhibit more complicated mechanisms
Laws based on simple oxidation that generally describe oxidation of pure metals
 Rectilinear Law

 Parabolic Law

 Logarithmic Law

ME 6351 Oxidation and High Temperature Corrosion Page # 10

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Rectilinear Law: When the reaction can proceed in a catastrophic manner due to the
corrosive oxidizing gas (e. g. Oxygen) can continue to penetrate easily and react with the
base metals

Conditions

 The oxide film or scale cracks are porous

 Replenishment of the oxygen that cannot keep pace with the oxide film thickening

The Law can be expressed as

dy/dt= k

⇒ y = kt + Constant

Where y = scale thickness and weight change, t= Time, k = constant dependent on

temperature and other conditions

ME 6351 Oxidation and High Temperature Corrosion Page # 11

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Parabolic Law: When the oxidation is controlled by diffusion through an oxide layer that
is continuously increasing in thickness

Conditions

 The oxide film or scale are continuous, adherent and prevents easy access to the
corrosive gas

 Diffusion through the oxide scale will be slow

 Diffusing component may be either oxygen moving inward or metal ions moving
outward

The Law can be expressed as

dy/dt= k/y

⇒ y2 = k′t + Constant

Where y = scale thickness and weight change, t= Time, k′= Rate constant dependent on
temperature and other conditions

ME 6351 Oxidation and High Temperature Corrosion Page # 12

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Logarithmic Law: This law applies at low temperatures and during initial stages of
oxidation followed by parabolic law

Conditions

 Mainly applicable to thin oxide film or scales

 Rarely applicable to high temperature oxidation

The Law can be expressed as

⇒ y = k′′t + Constant

Where y = scale thickness and weight change, t= Time, k′′ = Rate constant for corrosive
attack, c and b are empirical constants for particular conditions of Oxidation

ME 6351 Oxidation and High Temperature Corrosion Page # 13

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Figure 11.3. Equations expressing growth of fi lm thickness, y , as a function of time of oxida-

ME 6351 Oxidation and High Temperature Corrosion Page # 14

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Pilling–Bedworth(PB) Ratio
The Pilling – Bedworth ratio is a parameter that can be used to predict the extent to which
oxidation may occur.
The ratio of volume of the corrosion product to the volume of the metal from which the product
formed. Mathematically, expressed as

𝑴𝒅
𝑷𝑩 𝒓𝒂𝒕𝒊𝒐 =
𝒏𝒎𝑫
where M = The molecular weight of the corrosion product Scale /Oxide
D = The density of the corrosion product Scale /Oxide
m = The atomic weight of the metal
d = The density of the metal
n = the number of metal atoms in a molecular formula of scale
(Example- for Al2O3, n = 2)

ME 6351 Oxidation and High Temperature Corrosion Page # 15

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Cases that arises from PB ratio

𝑴𝒅 𝑴 𝒏𝒎
1) If < 1 or the scale is unstable - so crack will form (The oxide film/scale is
𝒏𝒎𝑫 𝑫 𝒅
in tension, the film may contain cracks, pores and be relatively nonprotective) Examples Na =
0.57, K = 0.45, Mg = 0.8

𝑴𝒅
2) When > 1, the scale is stable (the scale is in compression and protective of the
𝒏𝒎𝑫
underlying metal) Example – Be = 1.59, Ca = 1.16, Fe= 1.77, Al = 1.28

𝑴𝒅
3) If
𝒏𝒎𝑫
>> 1, the scale will crack or spall (The scale may buckle and detach from the surface
because of the development of higher stresses). Example - W= 3.4, Mo = 3.4, V = 3.18

 There are exceptions and limitations to the predictions of the PB ratio

 A PB ratio > 1 is not sufficient to predict corrosion resistance.

ME 6351 Oxidation and High Temperature Corrosion Page # 16

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Exercises:
1. Using the Gibbs free energy of formation versus temperature diagram at 600 ° C,
estimate

a) The minimum pressures of oxygen required to oxidize aluminum, chromium, and

silicon to Al2O3, Cr2O and SiO2

b) The maximum ratios of H2 /H2O required to produce the above oxides

c) The maximum ratios of CO/CO2 required to produce the above oxides

2. Calculate PB ratio and indicate whether the oxides are protective for aluminum
forming Al2O3 and for sodium forming Na2O.

3. Calculate the volume of the followings that results from the oxidation of 1 cm3 of iron.

a) FeO (d = 5.95 g/cm3)

b) Fe3O4 ( d = 5.18 g/cm3)

c) Fe2O3 ( d = 5.24 g/cm3)

ME 6351 Oxidation and High Temperature Corrosion Page # 17

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Exercises :
4. Copper oxidizes within the parabolic range at a higher rate the higher the

oxygen pressure.

( a) What is the quantitative relation [use Eq. (11.3) , Section 11.6 ]?

( b) Make the same calculation for nickel.

5. Estimate the free energy of formation of NiO at 780 ° C from the cell illustrated

in Fig. 11.7 (Section 11.7 ). Assume that NiO in borax is saturated. Compare

with reported values as follows:

Temperature (K) ΔG ° (kJ/mole)

1000 − 146.8

1100 − 137.7

ME 6351 Oxidation and High Temperature Corrosion Page # 18

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

High temperature Oxidation Resistance Alloys

Chromium–Iron Alloys Usage

a) Valves of IC engines (9 – 30% Cr alloys with Si, Ni and other alloying element)
b) Steam turbine blades (12% Cr – Fe alloy)
c) Furnace parts and burners (9 – 30% Cr alloys)
d) Oil - refinery Construction (4 – 9% Cr alloys )

Table: Approximate Upper Temperature Limits for Exposure of Cr – Fe Alloys to Air [7]

ME 6351 Oxidation and High Temperature Corrosion Page # 19

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

High temperature Oxidation Resistance Alloys

2. Alloy with reactive Elements

Reactive Elements - yttrium, hafnium, lanthanum, zirconium or cerium

Reactive Element Effect (REE): The addition of very small amount (1or less wt.%) of a reactive
element as alloy addition or coating to high temperature alloys containing chromium or aluminum is
called the reactive element effect (REE).

Advantages:
1. Reactive elements greatly improve the oxide spalling resistance of both chromia - forming and
alumina - forming alloys
2. Reactive element inhibits the diffusion of Cr and results in growth primarily by the inward
diffusion of oxygen

Disadvantages
1. Reactive elements have to be handled carefully

ME 6351 Oxidation and High Temperature Corrosion Page # 20