Basic corrosion (Oxidation & Aqueous)

Oxidation
Direct atmospheric attack
Generally metals and alloys form oxide compounds under expose to air at elevated temperature. Reactivity of metal with atmospheric oxygen (oxidation) is different.
Some active and other passive

 There are four mechanisms commonly identify with metal oxidation.

(a) Unprotective porous oxide film Non porous film that are protective against O2 (b) Cations diffuse (c) Anions diffuse (d) Both cations and anions diffuse

 Unprotective porous film

O2 can continuously pass and react at metal-oxide interface.
Oxide film

Metal

O2

Atmosphere

 Non porous film (Protective againt O2 permeation).

Cations diffuse through the film reacting with oxygen at the outer surface.

 Non porous film

Which O2- ions diffuse in order to react with the metal at the metal-oxide interface.
Oxide film

Metal

2O24e-

O2

Atmosphere

 Non porous film

Which both cations and O2- anions diffuse at roughly the same rate. Oxidation reaction occur within the oxide film rather than interface.
Oxide film

Metal

2O2(4 + n)eMn+

O2

Atmosphere

 Mechanism For (b) (d)

Metal-oxide interface
M Mn+ + ne2O2-

Air-oxide interface
O2 + 4e-

Growth Rate
Case (a) unprotective oxide
dy C1 dt
(1)

Where y is the thickness of the oxide film, t the time and C1 a constant. Integration of equation (1)

y c1t c2

(2)

 Where c2 is a constant representing film thickness at t=0. This time dependence is appropriately termed a linear growth rate law.

J O 2
CO2

c D x c D y J O 2 1 dy 1 or y dt y

x y

 For film growth that is limited by ionic diffusion, the growth rate diminishes as the film thickness grows. Growth rate;
dy 1 c3 dt y
(3)

Where C3 is constant different, from those in eq. 1 and 2. Integration gives

y c4t c5
2

(4)

 Where c4 and c5 are two additional constants. c4 = 2c3 , c5 is the square of the film thickness at t=0

Pilling-Bedworth
The tendency of a metal to form a protective oxide coating is indicated by an especially simple parameter known as the pillingBedworth ratio, R, given as
Md R amD
M is molecular weight of the oxide, D density of oxide m is a atomic weight of the metal, d density of metal

 For R<1, the oxide volume tend to be insufficient to cover the metal substrate. Oxide coating tend to be porous and unprotective. For R=1 or >1, the oxide tends to be protective.

Problem 1
A nickel based alloy has a 100 nm thick oxide coating at time (t) equals zero, upon being placed in an oxidizing furnace at 600C. After 1 hour, the coating has grown to 200 nm in thickness. What will be the thickness after 1 day, assuming a parabolic growth rate law.

Problem 2
Given that the density of Cu2O is 6.00Mg/m3 , calculate the Pilling-Bedworth ratio for copper.

Aqueous
Dissolution of a metal into an aqueous environment. The metal atoms dissolve as ions. A simple model of this aqueous corrosion is given in figure below. An electrochemical cell in which chemical change is accompanied by an electrical current.

 Concentration cell

Fe

Fe

Low Fe2+ concentration Anode (corrosion) Cathode (electroplating)

High Fe2+ concentration

Porous membrane

 The metal bar on the left side of the electrochemical cell is an anode. Anode will dissolves or corrodes and supplies electrons to the external circuit. The anodic reaction as below; Fe Fe2+ + 2e The reaction is driven by an attempt to equilibrate the ionic concentration.

 The porous membrane allows the transport of Fe2+ ions between the two halves of the cell while maintaining a distinct difference in concentration level. A metal bar on the right side of electrochemical cell is a cathode.

 Cathode accepts the electrons from the external circuit and neutralizes ion in a cathodic reaction; Fe2+ + 2eFe At cathode, metal builds up as opposed to dissolving. This process is known as electroplating.

An electrochemical cell consisting of iron and copper electrodes, each of which is immersed in a 1M solution of its ion. Iron corrodes while copper electrodeposits.

 Pure iron immersed in a solution containing Fe2+ ions of 1M concentration. The other side of the cell consists of a pure copper electrode in a 1M solution of Cu2+ ions. The cell halves are separated by a membrane, which limits the mixing of the two solutions.

 If the iron and copper electrodes are connected electrically, reduction will occur for copper at the expense of the oxidation of iron, as follows: Cu2+ Fe Cu Fe2+ Cu2+ ions will deposit (electrodeposit) as metallic copper on the copper electrode, Iron dissolves (corrodes) on the other side of the cell and goes into solution as Fe2+ ions.

 Thus, the two half-cell reactions are represented by the relations Fe Fe2+ + 2eCu2+ 2eCu When a current passes through the external circuit, electrons generated from the oxidation of iron flow to the copper cell in order that Cu2+ be reduced.

 The driving force for the overall cell is the relative tendency for each metal to ionize. The net flow of electrons from the iron bar to the copper bar is a result of the tendency of ionize. A voltage of 0.777 V is associated with the overall electrochemical process.