CORROSION

INTRODUCTION
Interactions of materials with corrosive environments → alter its composition and damage its
mechanical and physical properties.

In metals → material loss → by dissolution or by formation of nonmetallic film.

- ELECTROCHEMICAL CORROSION: metallic atoms in a solid material are removed by the

development of a current in an electrochemical cell = WET CORROSION

- OXIDATION: materials can react with the gaseous environment and deteriorate →
formation of oxide layers = DRY CORROSIONN

Ceramic materials = resistant to deterioration (only in extreme conditions) → CORROSION

In polymeric materials, the loss of properties → DEGRADATION

DRY CORROSION
Combination of metallic atoms with the ones of the aggressive environment

RUST: oxidation due to combination with oxygen

Drives the metal (over time) from a free state to a combined state with other elements (oxides,
carbonates, sulfates).

From elemental state → positive ions (cations) by loss of electrons.

GAVIMETRIC METHOD (mdd)

𝑚𝑔 𝑚𝑚
𝑉𝐶 = 𝑑𝑚2 ∗𝑑𝑎𝑦
dividing by the density = > 𝑉𝐶 = 𝑦𝑒𝑎𝑟

CORROSION RATE CORROSION RATE THICKNESS (thickness loss)

Reaction products remain attached to the material surface.

In some cases → protective films = isolate metals from corrosive agent.

Most common case:

ATTACK BY OXYGEN: an oxide layer is formed on the metal. In some cases, protects the
metal from further oxidation. Oxidation accelerates with temperature.

WET CORROSION
Metallic materials → corrosion process is normally electrochemical

Chemical reaction in which there is a transfer of electrons from one chemical species to another

Metal atoms lose electrons → cations → oxidation reaction

Metal is consumed and a by-product is generated

Occurs most often in aqueous mediums

In this process an electrical circuit is generated → ELECTROCHEMICAL CELL:

- ANODE: material that oxidizes, gives up electrons to

the circuit and corrodes.
- CATHODE: takes up the electrons and reduces. The by-
product (derivado) generates.
- ELECTRICAL CONTACT: the anode and cathode must
be electrically connected to allow the flow of
electrons.
- ELECTROLYTE: dissolved in the medium. It must be in
contact with the anode and cathode → metallic ions are transferred.

CORROSION OF ZINC IN ACID

Zinc immersed in acid solutions, containing hydrogen ions (H+).

ELECTRODE POTENTIALS

Not all metallic materials oxidize to form ions with the same degree of ease

GALVANIC COUPLE: 2 metals electrically connected in a liquid electrolyte. One becomes the
anode and corrodes and the other the cathode.

STANDARD HYDROGEN ELECTRODE: inert platinum electrode in a 1M solution of H+ ions at 25º

Platinum itself does not take part in the electrochemical reaction.

H atoms are oxidized or reduced → metals are ranked accorded to measure voltage → EMF
(electromotive force series)

CATHODE: V>0 ANODE: V<0

Metal with smaller Vº corrodes

𝑐𝑒𝑙𝑙 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 → ∆𝑉 = 𝑉º 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝑉º 𝑎𝑛𝑜𝑑𝑒

If ∆𝑽 > o → CORROSION

THE GALVANIC SERIES

The standard EMF series is generated under highly idealized conditions

havind limited utility

More practical ranking → galvanic series. Reactivity in seawater.

 - High degree of correspondence of the relative positions of the pure metals in emf and
galvanic series
- Most metals/alloys are more stable in ionic state than as metals (oxidation/corrosion is
likely): Occur in nature as compounds (minimum free energy in oxidized state)
- Exceptions: Noble gold and platinum

CORROSION RATES

Faraday’s equation describes the rate at which corrosion (anode) or plating (cathode) occurs in
an electrochemical cell

FORMS CORROSION

UNIFORM ATTACK → RUST

- Steel, iron, silver

- Most common form of corrosion
- Can be predicted and designed for easily

Prevention: paint, plate, sacrificial anode

GALVANIC CORROSION

Causes: Galvanic series:

- Dissimilar metals - Less noble metal → anode = corroded

- Exposed to an electrolyte - More inert metal →cathode =
- Electrically coupled (current path) protected

Corrosion rate depends on current density → HIGH CURRENT DENSITY for SAMLL ANODE

Prevention:

- Choose metals close in galvanic series

- Anode area is as large as possible
- Insulate dissimilar metals from each one
- CATHODIC PREDICTION:
o Supply electrons from an external source to protect the oxidizing metal, converting it
to a cathode: Reverse the oxidation into reduction direction
o Metal to be protected, electrically connected to another more reactive; Sacrificial
anode oxidizes giving up electrons to protect the metal from corrosion

CREVICE AND PITTING CORROSION

Localized corrosion attack

Causes:

- Concentration gradients in electrolyte in two different regions of

the same metal part
- Corrosion occurs in the locate area oxygen concentration
- Corrosion occurs in the shielded or restrictive environment

Mechanism:

- Initially anodic and cathodic processes all over the surface of the metal
- Oxygen in consumed in the crevice → net charge is positive
- Negative ions form solution flow into the crevice to balance the charge
- Metal ions produce acid (react with water) and form complexes with negative ions.
- Acid + negative ions encourage corrosion attack of the metal → autocatalytic process

Prevention:

- Weld-don’t rivet - ADD DRAINS → AVOID STAGNANT

- Use non absorbing gasket WATER
- Polish surfaces - Adjust composition (add Mo to SS)

INTERANGULAR CORROSION

Severe problem in welding of stainless steels

CAUSES:

- Occurs in specific alloys → precipitation of corrosive specimens along grain boundaries and
in particular environments
- Chromium carbide forming in SS, leaving adjacent areas depleted in Cr
Prevention:

- High temp heat treatment to re-dissolve carbides

- Lower carbon content in SS → minimize carbide
formation
- Alloy w¡ioth material that has stronger carbide
formation to Chromium (Ti or Nb)→ Cr remains in
solid solution

SELECTIVE LEACHING

Causes:

- Alloys in which one element is preferentially removed

o In brass, zinc is electrically active and is removed leaving porous copper (estructura
esponjosa sin ninguna propiedad mecánica)
- Occurs in other metals, such as Al, Fe, Co, Cr

Prevention:

- Use protective coating to protect surfaces

- Use alternative materials
CORROSION PREVENTION
DESIGN: SELECTION OF METALS AND ALLOYS

- General rule: to avoid any kind of heterogeneity forming an electrochemical cell: Use of
similar materials.
- Design to avoid crevices reachable by electrolyte.
- Uniform temperatures and electrolyte concentration.

CATHODIC OR SACRIFICIAL PROTECTION

- SACRIFICIAL ANODE: Cathodic protection of a buried steel pipeline: A sacrificial magnesium

anode assures that the galvanic cell makes the pipeline the cathode. Sacrificial anode -
Cathodic protection by which a more anodic material is connected electrically to the
material to be protected. The anode corrodes to protect the desired material.

- SACRIFICIAL VOLTAGE: An impressed voltage between a scrap iron auxiliary anode and the
pipeline assures that the pipeline is the cathode.