Corrosion in Concrete

Contrary to common belief, concrete itself is a complex composite material. It

has low strength when loaded in tension and hence it is common practice to
reinforce concrete with steel, for improved tensile mechanical properties.
Concrete structures such as bridges, buildings, elevated highways, tunnels,
parking garages, offshore oil platforms, piers and dam walls all contain
reinforcing steel (rebar). The principal cause of degradation of steel reinforced
structures is corrosion damage to the rebar embedded in the concrete.

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Iron is unstable in nature, and because reinforcing steel used in precast

concrete is made largely of iron, it, too, becomes unstable when exposed to
corrosive agents such as salt, carbonation, and even air. Iron, as we commonly
recognize it, is not generally found in nature because of its instability. It takes
a great deal of energy to produce iron from its ore, and even then it is so
unstable that it must be coated to keep it from reverting back to its ore forms
(hematite, magnetite, and limonite).

The two most common causes of reinforcement corrosion are (i) localized
breakdown of the passive film on the steel by chloride ions and (ii) general
breakdown of passivity by neutralization of the concrete, predominantly by
reaction with atmospheric carbon dioxide. Sound concrete is an ideal
environment for steel but the increased use of deicing salts and the increased
concentration of carbon dioxide in modern environments principally due to
industrial pollution, has resulted in corrosion of the rebar becoming the
primary cause of failure of this material. The scale of this problem has reached
alarming proportions in various parts of the world.

Information Module

       Control

       Corrosion monitoring

       Magnitude of the problem

       Lime cements, plasters, mortars and concretes

       Nature
Corrosion Control in Concrete
Given the importance of the costs associated with the corrosion of
infrastructures, it is extremely important that all possible methods applicable
to controlling corrosion in existing concrete bridges be developed so that these
structures will not deteriorate prematurely. Equally important is developing
methods to avoid this costly corrosion problem in all new concrete bridges to
be constructed in the future. Accordingly, the control methods can be divided
into two major areas:

       Corrosion control in new concrete constructions

       Corrosion control for rehabilitation of existing concrete structures

The use of good construction design and procedures, adequate concrete cover
depth, corrosion-inhibiting admixture, and low-permeability concrete alone
will not abate the problem, because concrete has a tendency to crack
inordinately. Even corrosion-inhibiting admixture for concrete would likely not
be of use when the concrete cracked. This situation essentially leaves the
reinforcing steel itself as the last line of defense against corrosion. For this
very reason, the use of a barrier system on the reinforcing steel, such as epoxy
coating or other organic or even other possible metallic coatings, is even more
critical in abating this costly corrosion problem.

It is likely that there may never be any organic coating that can hold up to the
extreme combination of constant wetting and high temperature and high
humidity that reinforcing steel is often exposed to in the marine environments.
The many successful performance of embedded epoxy-coated steel bars in
different projects indicates that when used in exposure conditions that do not
keep the concrete constantly wet, the epoxy coating will provide a certain
degree of protection to the steel bars and, thereby, delay the initiation of
corrosion.

For existing chloride-contaminated concrete bridge decks, impressed-current

cathodic protection using titanium mesh anodes-provides the ultimate and
permanent solution to stopping reinforcing steel corrosion in the structures, as
long as associated rectifiers and electrical wiring are properly maintained.
Electrochemical chloride extraction provides an alternative rehabilitation
method for stopping steel corrosion in contaminated concrete, albeit less
permanently. This alternative has the advantage of having no rectifier or wiring
to maintain after the treatment.

Reinforced Concrete Structures

Corrosion monitoring systems consisting of linear polarization, concrete resistivity and
other probes have been installed in new structures to monitor durability and in existing
structures to evaluate rehabilitation strategies such as corrosion inhibitor application and
patch repairs. Corrosion monitoring, when used in association with “snapshot” surveys
can give a more complete picture of the changing condition of a structure in time as well
as in the three physical dimensions of the structure.

There are a number techniques that can be used to carry out such an assessment. All
these techniques can be used in isolation or combination to provide a “snapshot” of the
condition of a structure. However, if one is interested in the rate of deterioration of a
structure, it is useful to monitor the condition change with time. This is now being done
on new structures with long lifetime requirements and older structures when corrosion
damage has been found and repair is being deferred to cost, logistical or other reasons.

Half Cell Potentials:  It is not economic to install half cells all over a
      

structure to monitor its changing corrosion condition. However, either

during construction of after a condition survey, vulnerable and
representative locations can be determined and corrosion monitoring
installed. A half cell is a vital part of the corrosion monitoring system.
However, on very long life structures the use of normal embeddable half
cells may not be possible throughout the life of the structure without
replacement or installation of an alternative “pseudo reference”
electrode. This is because most half cells have a life of one or two
decades whereas some structures have lives in excess of a century.
Graphite, stainless steel, lead, mixed metal oxide or other pseudo
references can be used. However, these alternatives are less stable in
the short and the long term as the interface that produces the
electrochemical reaction against which the steel/concrete interface
potential is measured is exposed to changes in the environment itself
and will therefore be affected by changes in moisture, oxygen chloride
level and pH more directly than a “true” reference half cell. The half
cell potential measurement gives an indication of the corrosion risk of
the steel. The measurement is linked by empirical comparisons to the
probability of corrosion.

Linear Polarization Measurements: Linear polarization resistance (LPR)

      

is usually conducted in aqueous solutions on small, uniformly corroding

specimens. A number of LP devices are now available for steel in
concrete. The system consists of a half cell to measure the potential and
its change, an auxiliary electrode to pass the current and, in this case, a
guard ring around the auxiliary electrode to constrain the electric field
from the auxiliary electrode because of the size of the corroding rebar.
This ensured that a measurement is taken from a defined area of steel
and prevents gross errors in the area of measurement.

       New construction

        Existing structures

Macrocell Current Measurements:  In new construction a macrocell

      
current device can be set up using a configuration with a series of mild
steel working electrodes and a stainless steel cathode instead of a half
cell. This is fixed in the formwork on new construction with the first
working electrode resting on the form with minimal cover, and the last
at rebar depth. As each working electrode depassivates with incoming
chlorides (or carbonation), there is a step up in the current flow
between the depassivated working electrode as it becomes an anode,
and the stainless steel cathode.  

Concrete resistance and Resistivity Measurements: Two or four pin

      

probes can be embedded in the concrete at different depths to monitor

moisture movement and permanent changes that may be associated with
chloride ingress. These can be sets of pins or a series of “washers”
separated by insulating cylinders.

The Author has applied corrosion monitoring to different structures in the past two years.
These have included car parks, power station plant, wharves, and highway structures. In
one case inhibitors have been applied to reduce corrosion and the corrosion monitoring
system will be used to monitor the effectiveness of the treatment and to produce
recommendations for further inhibitor treatment or other repair.

Lime Cements, Plasters, Mortars and Concretes

There is a plethora of terms used to describe the various products derived from
calcined limestone. A definition of terms used in the context of this report are
outlined below. The definitions here are based on features identifiable in hand
specimen and are therefore intended for use by the field archaeologist.
Consequently these definitions may differ somewhat from those applied by
scientists employing microscopic and chemical techniques. (reference)

Limestone

Limestone is the natural rock type from which cements and concretes are
derived. A limestone is a sedimentary rock composed of carbonates, namely
the minerals calcite (calcium carbonate; CaCO3) and dolomite (calcium
magnesium carbonate; CaMg[CO3]2), derived either chemically or organically.
Being natural materials, limestones can have a wide range of depositional
environment and components and can contain varying amounts of non-
carbonate material. The type of limestone calcined to produce lime for the
manufacture of cements and concretes can profoundly affect the durability and
properties of the material produced.
Lime

"Calx", lime in Latin provides the etymological root for calcium, calcite and
calcination. Strictly speaking, lime is calcium oxide. This is acquired by burning
limestone, which in simplest terms, removes the carbon from the calcium
carbonate (calcite). Lime forms the base for all cements and concretes.
However the composition of the limestone being variable, the true composition
of the lime is also variable, and the term may be generally used to described
calcined limestone in general. Lime may also referred to as 'quicklime',
'unslaked lime' or 'lump lime'.

Slaked Lime

Lime will only harden into a cement when water is added to it. The process is
called ëslakingí, hence ëslaked limeí, also referred to as ëlime puttyí.

Cement

"Cement" is derived from caementa, which actually referred to the aggregates

mixed with the slaked lime rather than the bonding agent itself. Opus
caementicium refers to the masonry constructed from concrete coursework. In
the context of this work, the word cement is used exclusively in reference to
the hardened binding material of any aggregate. In simplest terms, this is the
slaked lime, which in the presence of air reverts to calcium carbonate. This
material may also contain finely powdered admixtures, such as ash or fired
ceramic. However, an alternative term for the hydrated lime binder is not put
forward. In geological parlance, the term cement is used strictly to define
material (often calcite, but occasionally silica) that adheres clasts in a rock,
and generally the word ëcementí is accepted in non-specialised use as a glue.
Consequently it is defined as the adhesive binder in this report.

Aggregate

An aggregate is material added to a cement. In this report, the term does not
include finely powdered additives to the cement such as ash. It is usually
composed of rock fragments, chosen for their strengthening properties and
occasionally for decorative reasons. Carefully chosen aggregates can make a
concrete or mortar resemble natural rock. Organic material, including grasses,
reeds and also bones can be used as aggregates, often in combination with rock
material. Aggregates can be sub classed into categories of fine aggregates -
that with dimensions less than 5 mm, and coarse aggregates - that with
dimensions greater than 5 mm.

Concrete and Mortar

Both concrete and mortar are materials composed of a cement plus an
aggregate. The two terms are very simply defined. A concrete is a material
where the majority of the aggregate has dimensions greater than 5 mm. A
mortar is a material having aggregate with dimensions less than 5 mm
(Prentice, 1990). "mortarí from the Latin mortarium, originally referring to the
trough in which the material was mixed, is often used wholesale to describe
the bonding material of concrete masonry. This is a fair use of the term as this
material binding brick-sized blocks, often laid in courses rather than
haphazardly poured, is composed of lime cement with fine aggregate. Concrete
should be used to describe material containing coarse aggregate generally used
to fill formwork.

Hydraulic Cements

Hydraulic cements are waterproof and will even set underwater. Consequently
most materials used in Roman and later periods for lining structures intended
to carry water and for construction in marine and riparian environments will be
hydraulic. Such materials are identified by the presence of finely pulverized
material added to the cement binder which will cause discoloration from white
to pale browns or pinks. Common additives, are volcanic ash or crushed
ceramic sherds. These materials are known as pozzolans.

Pozzolans

A pozzolan is defined as a siliceous and/or aluminous substance that will, in the

presence of water combine with lime to form cementitious compounds. Such
material include clays, that are rendered active by firing (fresh geological clays
would absorb too much water during the curing process, resulting in spallation
and ultimately cracking of the concrete), and other substances, including waste
products from blast furnaces and even rice husk ash (see Hill, et al., 1992 and
references therein). However, natural pozzolans are derived primarily from
volcanogenic products.

Plaster

The term "plaster" is one of the most universally used, describing a multitude
of products, usually those which will provide a smooth coat to a wall or other
surface. Plaster of Paris is powdered gypsum (CaSO4.2H2O, derived from rocks
distinctly different from limestones) which, with water added, will harden and
set. Lime plaster is simply a mixture of lime, water and sand, or just lime and
water in the case of whitewash. To avoid confusion, it is recommended that
these terms should be used in full to define compositional types.

Stucco
Stucco, like plaster, is a term of complex use.
However it is entrenched in all literature as
describing two distinct materials. Firstly it is used
to refer to a fine white mortar composed of lime,
crushed marble and glue-like binding additive
(egg-white for example) typically used for making
good surfaces for painting frescoes or generally for
smoothing walls. Alternatively it is used to
describe decorative work in plaster of Paris. In this
report, stucco will be used to define the former
case alone. Nature of the Problem
In order to understand the mechanisms behind corrosion of reinforcing steel in
concrete, one has to examine the chemical reactions involved. In concrete, the
presence of abundant amount of calcium hydroxide and relatively small
amounts of alkali elements, such as sodium and potassium, gives concrete a
very high alkalinity-with pH of 12 to 13. It is widely accepted that, at the early
age of the concrete, this high alkalinity results in the transformation of a
surface layer of the embedded steel to a tightly adhering film, that is
comprised of an inner dense spinel phase in epitaxial orientation to the steel
substrate and an outer layer of ferric hydroxide. As long as this film is not
disturbed, it will keep the steel passive and protected from corrosion.

When a concrete structure is often exposed to deicing salts, salt splashes, salt
spray, or seawater, chloride ions from these will slowly penetrate into the
concrete, mostly through the pores in the hydrated cement paste. The chloride
ions will eventually reach the steel and then accumulate to beyond a certain
concentration level, at which the protective film is destroyed and the steel
begins to corrode, when oxygen and moisture are present in the steel-concrete
interface.

In 1962, it was reported that the required minimum concentration of chloride

in the concrete immediately surrounding the steel to initiate corrosion, the
chloride corrosion threshold, is 0.15% soluble chloride, by weight of cement. In
typical bridge deck concrete with a cement factor of 7, this is equivalent to
0.025% soluble chloride, by weight of concrete, or 0.59 kg soluble chloride per
cubic meter of concrete. Subsequent research at FHWA laboratories estimated
the corrosion threshold to be 0.033% total chloride, by weight of concrete.
There are indications that the chloride corrosion threshold can vary between
concrete in different bridges, depending on the type of cement and mix design
used, which can vary the concentrations of tricalcium aluminate (C3A) and
hydroxide ion (OH-) in the concrete. In fact, it has been suggested that because
of the role that hydroxide ions play in protecting steel from corrosion, it is
more appropriate to express corrosion threshold in terms of the ratio of
chloride content to hydroxide content, [Cl-] / [OH-], which was recently
established to be between 2.5 to 6.

Once corrosion sets in on the reinforcing steel bars, it proceeds in

electrochemical cells formed on the surface of the metal and the electrolyte or
solution surrounding the metal. Each cell is consists of a pair of electrodes (the
anode and its counterpoint, the cathode) on the surface of the metal, a return
circuit, and an electrolyte. Basically, on a relatively anodic spot on the metal,
the metal undergoes oxidation (ionization), which is accompanied by
production of electrons, and subsequent dissolution. These electrons move
through a return circuit, which is a path in the metal itself to reach a relatively
cathodic spot on the metal, where these electrons are consumed through
reactions involving substances found in the electrolyte. In a reinforced
concrete, the anode and the cathode are located on the steel bars, which also
serve as the return circuits, with the surrounding concrete acting as the
electrolyte.

Corrosion can also occur even in the absence of chloride ions. For example,
when the concrete comes into contact with carbonic acid resulting from carbon
dioxide in the atmosphere, the ensuing carbonation of the calcium hydroxide in
the hydrated cement paste leads to reduction of the alkalinity, to pH as low as
8.5, thereby permitting corrosion of the embedded steel:

The rate of carbonation in concrete is directly dependent on the water/cement

ratio (w/c) of the concrete, i.e., the higher the ratio the greater is the depth
of carbonation in the concrete. In concrete of reasonable quality, that is
properly consolidated and has no cracking, the expected rate of carbonation is
very low. For example, in concrete with w/c of 0.45 and concrete cover 25
mm, it will require more than 100 years for carbonation to reach the concrete
immediately surrounding the steel. Carbonation of concrete or mortar is more
of an issue in Europe than in North America.