CORROSION OF STEEL REINFORCEMENT

1) Lowering of pH is cause by carbonation. At lower pH, the oxide film is not continuous and corrosion
occurs

2) Even at high pH, chloride ions cause local breakdown of the passive film leading to corrosion –e.g.
chloride ions from deicing salts on road bridges, chloride ions from marine environment.

MICROSTRUCTURE

•The transport of the corrosion reactants (water, oxygen, and various ions), the e normally confined to
formation of the corrosion products, and the passage of the ionic current necessary to support
corrosion are normally confined to the cement paste phase.

•Consider the cement paste as a two-phase system consisting of a solid phase (the hydration products)
and the liquid phase (the pore solution). From the viewpoint of corrosion, the controlling parameters
are:
–The composition and quantity of pore solution

–The porosity and pore structure (interconnectivity)

–The quantity of Ca(OH)2 and the nature of C-S-H in the hardened paste.

PORE SOLUTION
• Composition of the pore solution is the main factor in determining whether embedded steel will be
passivatedor whether it will actively corrode.

•The pore solution of a hardened cement paste or concrete is essentially one of alkali hydroxides: after
about one day, the only ions present in concentration above a few mmoll-1 are K+, Na+, and OH-. The pH
is ≈ 12 –13.
PORE STRUCTURE
• the pore size distribution, and the interconnectivity of the pores (nature porosity) –is very important.
It determines the rate of penetration of chloride ions and carbon dioxide, and the availability of oxygen
and moisture at the steel surface.

•The maintenance of the passive film requires the availability of oxygen and moisture at the steel
surface; this is determined by the nature of the porosity (size distribution, and interconnectivity).

Ca(OH)2
•Ca(OH)2 has very limited solubility in aqueous solutions and the bulk of it remains as solid crystals
embedded in the cement paste.

•adds little to strength and other mechanical properties but provides a pH buffer for the pore solution
keeping it at a constantly high pH.

•the higher the content of Ca(OH)2 the longer it takes for a carbonation front to penetrate the cover
zone.
INITIATION OF ACTIVE CORROSION
Because of breakdown of passivity on the steel reinforcement .Major cause:
1) The presence of chloride ions; (included in the mix with new concrete raw materials or due to
penetration from the environment)
2) A decrease in the pH value of the pore solution - (carbonation)

CONSEQUENCE OF CORROSION
1) A reduction of the re-bar diameter.
2) Cracking, spalling and delamination of concrete cover; (due to the expansive nature of the iron
oxides).
3) A decrease of the steel / concrete bond.
4) Possible reduction in load carrying capacity of concrete structure or concrete structural member.
5) Depassivation is when the corrosion start to occur.

ELECTROCHEMICAL CORROSION CELL

1) It has four components:
The anode –which is the metal that is corroding, i.e. oxidation (the loss of electrons by a species or
substance in a reaction) occurs;
The cathode –which is a metal whose surface provides sites for the environment to react; i.e. reduction
(the gain of electrons by a species or substance in a reaction) occurs;
The electrolyte –the aqueous environment, in contact with both the anode and the cathode to provide a
path for ionic conduction;
The electrical connection between the anode and the cathode to allow electrons to flow between them.
2) In order for corrosion to occur the four basic elements (anode, cathode, electrolyte and electrical
connection) are required plus the supply of oxygen and water.
3) If any of these required elements is absent, corrosion will not be able to proceed.

MAJOR CAUSES OF ACTIVE CORROSION

1) Chloride ions present in concrete structure can cause the steel reinforcement to corrode if sufficient
oxygen and moisture are present to sustain the reaction.

2) expansion of the iron oxides as they are transformed to higher oxidation states

3) Chloride ions may be introduced into concrete in a variety of ways:

A) Intentional: The addition of calcium chloride accelerates the hydration of Portland cement. An
increased awareness of the deleterious effects of chlorides has led to this practice decreasing.There
are a large number of existing structures containing CaCl2 which will be susceptible to corrosion given
the appropriate environmental conditions. Some other types of admixtures, such as water-reducing
agents, may also contain small amount of chloride to offset minor set-retarding effects.
B) Unavoidable: In some countries, potable water and chloride free aggregates may not be available:
see water or water with high Cl content must be used as mixing water and porous aggregates that have
been exposed to sea water will contain significant amount of chloride. In these countries, the
incorporation of chlorides into concrete is unavoidable. Sea water attack (marine environment). Sea
water (e.g. Atlantic Ocean) contains about 11 g Na+, 20 g Cl-, 2.9 g of SO42-and 1.4 g of Mg2+ per litre.
The pH is usually ≈ 8.
•Below the tidal zone: The danger of corrosion decreases with depth due to lack of oxygen.
•In and above the tidal zone (splash zone): wetting and drying cycles occur; water is drawn in by
capillary action or enters as spray. Oxygen is readily available, permitting corrosion to occur.

C) De-icing salts
•In colder climates, the most common source of chloride, if not from sea water, is from de-icing salts.
•These are often applied to bridge decks and road slabs that are subject to freezing conditions.

TYPE CONCRETE OF CHLORIDE PENETRATION

1) Chlorides can penetrate any type of concrete .The type of penetration is dependent on moisture
content:
A) Almost dry concrete. -The most rapid form of penetration (capillary suction of salt water); up to a
few mm in several hours.
B) Wet or highly moist concrete. -Penetration occurs more slowly by diffusion of the Cl-ions through
the pore solution; concentration gradient is the driving force.
C) Typical diffusion rates are of the order of 10-12 m2/sec; -penetration of concrete cover zone can
therefore take many months.

CONCRETE BINDING
1) The degree of chloride binding within the microstructure is an important factor influencing the of the
critical concentration of Cl-reaches the steel.
2) Only those Cl-ions that are freely dissolved in the pore solution are available to attack the steel.
3) If chlorides are present in the initial mix or penetrate at low degree of hydration, some of the Cl-ions
can become chemically bound by reacting with the C3A to form Friedel’ssalt. The amount of C3A in the
cement influences the amount of Cl-remaining in the pore solution; the free chloride.
FACTORS INFLUENCE THE CHLORIDE BINDING
•C3A content;
•OH-:Cl-ratio;
•Cement content of concrete;
•W/B ratio;
•pH of pore solution;
•Presence of sulphateions;
•Specific surface area of C-S-H.
MECHANISM OF BREAKDOWN
1) The mechanism of breakdown of the passive film by Cl-attack is involve incorporation of Cl-ions into
it (replacing some of the O2-ions). This increases both its conductivity and its solubility resulting in the
layer losing its protective character.

2) A heterogeneous distribution of Cl-ions over the steel surface results in a heterogeneous

distribution of imperfections in the passive film. Therefore a local phenomenon and results in the
creation of macrogalvanic cells, as illustrated in the subsequent diagram.

ELECTROCHEMICAL CORROSION IN PRESENCE OF CHLORIDE

•The local active areas act as anodes where the Fe will readily dissolve at a relatively low potential,
and the remaining passive areas act as cathode where oxygen reduction takes place at a higher
potential.
•Other factors that control corrosion (e.g. Cl-concentration and O2 availability), the rate of dissolution
of Fe in the galvanic cells depend on:
–The cathode : anode area, and
–The electrical resistivity of the concrete. Because the electrochemical cell requires connection
between the anode and cathode by the pore solution, as well as the steel itself.
•The nature of the pore system is a major factor influencing corrosion. In electrical term, it is the
resistance of the ‘connection’ through the concrete that controls the flow of the current. The
electrical resistivity of concrete is greatly influenced by its moisture content, by the ionic composition
of the pore solution, and by the interconnectivity of the pores.
•The pattern of corrosion is affected by the distribution of the anodic and cathodic areas caused by the
localized nature of Cl-attack. In the concrete adjacent to the anode area, the concentration of Fe2+
ions increases, and the pH falls. The negatively charged free electrons e-pass through the steel to the
cathode where they combine with oxygen and water to form OH-ions.
These diffuse through the electrolyte (pore solution) and combine with the Fe2+ ions to form Fe(OH)2
which is converted by further oxidation to form Fe(OH)3.
•Anodic reactions:
–Fe Fe2+ + 2e-
–Fe2+ + 2OH-Fe(OH)2
–4Fe(OH)2+ 2H2O + O24Fe(OH)3

•Cathodic reaction:
–4e-+ O2+ 2H2O 4OH-
•Because of the local drop in pH at the anode, a soluble complex of iron oxide can form. This complex can
diffuse away from the anode, permitting corrosion to continue. Some distance from the electrode, where
both the pH and concentration of dissolved oxygen are higher, the complex breaks down,
Fe(OH)2precipitates, and the chloride is free to react further with Fe2+ ions at the anode.
The reactions involved are:
•Fe2+ + 2Cl-FeCl2
•FeCl2+ 2H2O Fe(OH)2+ HCl
•Therefore Cl-are not consumed and rust contains no Cl-, although FeCl2is formed at an intermediate
stage.
•This process can continue with Fe2+ ions migrating away from the steel and reacting further with
oxygen to form higher oxides or hydroxides. Consequently, instead of spreading laterally along the
reinforcing bar, the corrosion continues at the local anodic areas, causing the development of deep pits
and eventually severance of the bar.

THRESHOLD CONTENT OF CHLORIDE

•This is dependent on factors:
–Alkalinity and Cl-:OH-ratio;
–Proportioning of the concrete and type and specific surface area of the cement;
–W/B ratio;
–Sulphate content;
–Curing conditions, age, enviromental history of the concrete;
–Degree of carbonation;
–Temperature and relative humidity;
–Roughness and cleanliness of the rebar.