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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
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 - Cu 2O, NiO, FeO,
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
Thermodynamics of Oxidation
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 ,
CO/CO2 and H2 /H2O ratios in contact with metals and their oxides
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
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
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.
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
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
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
Replenishment of the oxygen that cannot keep pace with the oxide film thickening
dy/dt= k
y = kt + Constant
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
Diffusing component may be either oxygen moving inward or metal ions moving
outward
dy/dt= k/y
y2 = kt + Constant
Where y = scale thickness and weight change, t= Time, k= Rate constant dependent on
temperature and other conditions
Logarithmic Law: This law applies at low temperatures and during initial stages of
oxidation followed by parabolic law
Conditions
y = kt + 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
Cases that arises from PB ratio
1) If < 1 or the scale is unstable - so crack will form (The oxide film/scale is in tension, the
film may contain cracks, pores and be relatively nonprotective) Examples Na = 0.57, K =
0.45, Mg = 0.8
2) When > 1, the scale is stable (the scale is in compression and protective of the underlying
metal) Example – Be = 1.59, Ca = 1.16, Fe= 1.77, Al = 1.28
3) If >> 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
Exercises:
1. Using the Gibbs free energy of formation versus temperature diagram at 600 ° C,
estimate
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.
Exercises :
4. Copper oxidizes within the parabolic range at a higher rate the higher the
oxygen pressure.
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
1000 − 146.8
1100 − 137.7
Table: Approximate Upper Temperature Limits for Exposure of Cr – Fe Alloys to Air [7]
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:
3. Reactive elements greatly improve the oxide spalling resistance of both chromia - forming and
alumina - forming alloys
4. Reactive element inhibits the diffusion of Cr and results in growth primarily by the inward
diffusion of oxygen
Disadvantages
5. Reactive elements have to be handled carefully