CORROSION OF METALS 222R-1

ACI 222R-96

Corrosion of Metals in Concrete

Reported by ACI Committee 222

ACI COMMITTEE 222

Corrosion of Metals in Concrete
Brian B. Hope Keith A. Pashina
Chairman Secretary

John P. Broomfield Bret James Robert E. Price

Kenneth C. Clear Thomas D. Joseph D. V. Reddy
James R. Clifton David G. Manning William T. Scannell
Israel Cornet Walter J. McCoy David C. Stark
Marwan Daye Theodore L. Neff Wayne J. Swiat
Bernard Erlin Charles K. Nmai Thomas G. Weil
John K. Grant William F. Perenchio Richard E. Weyers
Kenneth C. Hover Randall W. Poston David A. Whiting

Associate Members
Stephen L. Amey Odd E. Gjorv Mohamad A. Nagi
Steven F. Dailey Clayford T. Grimm Morris Schupack
Stephen D. Disch Alan K. C. Ip Ephraim Senbetta
Hamad Farzam Andrew Kaminker Robert E. Shewmaker
Per Fidjestol Mohammad S. Khan Bruce A. Suprenant
Rodney R. Gerard Philip J. Leclaire William F. Van Siseren
Michael P. Gillen Joseph A. Lehmann Michael C. Wallrap

This committee report has been prepared to reflect the state CONTENTS
of the art of the corrosion of metals, and especially steel, in Chapter 1Introduction, p. 222R-1
1.1Background
concrete. Separate chapters are devoted to the mechanisms
1.2Scope
of the corrosion of metals in concrete, protective measures
1.3References
for new concrete construction, procedures for identifying
corrosive environments and active corrosion in concrete,
Chapter 2Mechanism of corrosion of steel in
and remedial measures. A selected list of references is concrete, p. 222R-3
included with each chapter. 2.1Introduction
2.2Principles of corrosion
Keyword; admixtures; aggregates; blended cements; bridge decks; calci- 2.3Effects of the concrete environment on corrosion
um chlorides; carbonation; cathodic protection; cement pastes; chemical 2.4References
analysis; chlorides; coatings; concrete durability; corrosion; corrosion re-
sistance; cracking (fracturing); deicers; deterioration; durability; marine at-
Chapter 3Protection against corrosion in new
mospheres; parking structures; plastics, polymers and resins; portland
construction, p. 222R-11
cements; prestressing steels; protective coatings; reinforced concrete; re- 3.1Introduction
inforcing steels; repairs; resurfacing; spalling; waterproof coatings.
3.2Design and construction practices
3.3Methods of excluding external sources of chloride
ion from concrete
ACI Committee Reports, Guides, Standard Practices, and 3.4Methods of protecting reinforcing steel from chlo-
Commentaries are intended for guidance in designing, plan- ride ion
ning, executing, or inspecting construction and in preparing
specifications. Reference to these documents shall not be ACI 222R-96 replaces ACI 222R-89 and became effective May 23, 1996.
made in the Project Documents. If items found in these doc- Copyright (c) 1997, American Concrete Institute. All rights reserved including
rights of reproduction and use in any form or by any means, including the making of
uments are desired to be part of the Project Documents, they copies by any photo process, or by any electronic or mechanical device, printed or
should be phrased in mandatory language and incorporated written or oral, or recording for sound or visual reproduction or for use in any knowl-
edge of retrieval system or device, unless permission in writing is obtained from the
in the Project Documents. copyright proprietors.

222R-1
222R-2 ACI MANUAL OF CONCRETE PRACTICE
3.5Corrosion control methods
3.6References
Chapter 4Procedures for identifying corrosion
environments and active corrosion in concrete,
p. 222R-21
4.1Introduction
4.2Methods of evaluation
4.3References
Chapter 5Remedial measures, p. 222R-23
5.1Introduction
5.2General
5.3Applicability
5.4The remedies and their limitations
5.5Summary
5.6References
Chapter 6References to documents of standard-
producing organizations, p. 222R-28
Appendix AStandard Test Method for Water-
Soluble Chloride Available for Corrosion of
Embedded Steel in Mortar and Concrete Using the
Soxhlet Extractor, p. 222R-28
CHAPTER 1INTRODUCTION
1.1Background
Concrete normally provides reinforcing steel with excel-
lent corrosion protection. The high alkaline environment in
concrete results in the formation of a tightly adhering film
which passivates the steel and protects it from corrosion. In
addition, concrete can be proportioned to have a low perme-
ability which minimizes the penetration of corrosion-inducing
substances. Low permeability also increases the electrical
resistivity of concrete which impedes the flow of electro-
chemical corrosion currents. Because of these inherent pro-
tective attributes, corrosion of steel does not occur in the
majority of concrete elements or structures. Corrosion of
steel, however, can occur if the concrete is not of adequate
quality, the structure was not properly designed for the ser-
vice environment, or the environment was not as anticipated
or changes during the service life of the concrete.
The corrosion of metals, especially steel, in concrete has
received increasing attention in recent years because of its
widespread occurrence in certain types of structures and the
high cost of repairs. The corrosion of steel reinforcement
was first observed in marine structures and chemical manu-
facturing plants.1.1,1.2,1.3 More recently, numerous reports of
its occurrence in bridge decks, parking structures, and other
structures exposed to chlorides has made the problem partic-
ularly prominent. The consequent extensive research on fac-
tors contributing to steel corrosion has increased our
understanding of corrosion, especially concerning the role of
chloride ions. It is anticipated that the application of the find-
ings of this research will result in fewer instances of corrosion
in new concrete structures and improved methods of repair-
ing corrosion-induced damage in existing structures.
For these improvements to occur, the information must be
disseminated to individuals responsible for the design,
construction, and maintenance of concrete structures. The
main purpose of this report is to present the state of the art.
While several metals may corrode under certain conditions
when embedded in concrete, the corrosion of steel reinforce-
ment is of the greatest concern, and, therefore, is the primary
subject of the report.
Chloride ions are considered to be the major cause of pre-
mature corrosion of steel reinforcement. Corrosion can oc-
cur in some circumstances in the absences of chloride ions,
however. For example, carbonation of concrete results in re-
duction of its alkalinity, thereby permitting corrosion of em-
bedded steel. Carbonation, however, is usually a slow
process in concrete which has a low water-cement ratio and
carbonation-induced corrosion is not as common as corro-
sion induced by chloride ions. Chloride ions are common in
nature and small amounts are usually unintentionally con-
tained in the mix ingredients of concrete.
Chloride ions also may be intentionally added, most often as
a constituent of accelerating admixtures. Dissolved chloride
ions also may penetrate unprotected hardened concrete in struc-
tures exposed to marine environments or to deicing salts.
The rate of corrosion of steel reinforcement embedded in
concrete is strongly influenced by environmental factors. Both
oxygen and moisture must be present if electrochemical cor-
rosion is to occur. Reinforced concrete with significant gradi-
ents in chloride ion content is vulnerable to macrocell
corrosion, especially if subjected to cycles of wetting and dry-
ing. Other factors that affect the rate and level of corrosion are
heterogeneities in the concrete and the steel, pH of the con-
crete pore water, carbonation of the portland cement paste,
cracks in the concrete, stray currents, and galvanic effects due
to contact between dissimilar metals. Design features also
play an important role in the corrosion of embedded steel. Mix
proportions, depth of cover over the steel, crack control mea-
sures, and implementation of measures designed specifically
for corrosion protection are some of the factors that control the
onset and rate of corrosion.
Deterioration of concrete due to corrosion results because
the products of corrosion (rust) occupy a greater volume than
the steel and exert substantial stresses on the surrounding
concrete. The outward manifestations of the rusting include
staining, cracking, and spalling of the concrete. Concurrent-
ly, the cross section of the steel is reduced. With time, structural
distress may occur either by loss of bond between the steel
and concrete due to cracking and spalling or as a result of the
reduced steel cross-sectional area. This latter effect can be of
special concern in structures containing high strength pre-
stressing steel in which a small amount of metal loss could
possibly induce tendon failure.
The research on corrosion to date has not produced a steel
or other type of reinforcement that will not corrode when used
in concrete and that is both economical and technically feasible.
However, research has pointed to the need for quality con-
crete, careful design, good construction practices, and reason-
able limits on the amount of chloride in the concrete mix
ingredients. Other measures that are being investigated in-
clude the use of corrosion inhibitors, protective coatings on
the steel, and cathodic protection. There has been some
 CORROSION OF METALS
success in each of these areas though problems resulting from
corrosion of embedded metals are far from eliminated.
1.2Scope
This report discusses the factors that cause and control
corrosion of steel in concrete, measures for protecting em-
bedded metals in new construction, techniques for detecting
corrosion in structures in service, and remedial procedures.
Consideration of these factors, and application of the dis-
cussed measures, techniques, and procedures should assist in
reducing the occurrence of corrosion and result, in most in-
stances, in the satisfactory performance of reinforced and
prestressed concrete elements.
1.3References
1.1. Tremper, Bailey; Beaton, John L; and Stratfull, R. F. Causes and
Repair of Deterioration to a California Bridge Due to Corrosion of Rein-
forcing Steel in a Marine Environment II: Fundamental Factors Causing
Corrosion, Bulletin No. 182, Highway Research Board, Washington, D.C.,
1958, pp. 18-41.
1.2. Evans. U. R., The Corrosion and Oxidation of Metals: Scientific Prin-
ciples and Practical Applications, Edward Arnold, London, 1960, 303 pp.
1.3. Biczk, Imre, Concrete Corrosion and Concrete Protection, 3rd
Edition, Acadmiai Kiad, Budapest, 1964.
CHAPTER 2MECHANISM OF CORROSION OF
STEEL IN CONCRETE
2.1Introduction
This chapter is divided into two sections. In the first, em-
phasis is placed on the processes responsible for corrosion of
steel reinforcement in concrete. The corrosion mechanism is
generally accepted to be electrochemical in nature. Some of
the major causes of corrosion of steel in concrete are exam-
ined and related phenomena are discussed.
In the second part, a discussion is given on the concrete
variables that influence corrosion, including concrete mix
proportions, quality, and cover, and the effects of corrosion
inhibiting admixtures and carbonation.
2.2Principles of corrosion
2.2.1 CorrosionAn electrochemical processAl-
though iron can corrode by chemical attack, the most com-
mon form of corrosion in an aqueous medium is
electrochemical.2.1 The corrosion process is similar to the
action which takes place in a flashlight battery. An anode,
where electrochemical oxidation takes place, a cathode,
where electrochemical reduction occurs, an electrical con-
ductor, and an aqueous medium must be present. Any metal
surface on which corrosion is taking place is a composite of
anodes and cathodes electrically connected through the body
of the metal itself. Reactions at the anodes and cathodes are
broadly referred to as half-cell reactions.
At the anode, which is the negative pole, iron is oxidized
to ferrous ions.
Fe Fe++ + 2e-
E = - 0.440 Standard Redox Potential (2-1)
The Standard Redox Potential is the potential generated
when the metal is connected to a hydrogen electrode and is
222R-3
one method of expressing electromotive forces. The Fe++ in
Eq. (2-1) is subsequently changed to oxides of iron by a
number of complex reactions. The volume of the reaction
products is several times the volume of the iron.
At the cathode, reduction takes place. In an acid medium,
the reaction taking place at the cathode is the reduction of
hydrogen ions to hydrogen. However, as will be shown later,
concrete is highly basic and usually has an adequate supply
of oxygen, so the cathodic reaction is
1/ H2O + 1/4 O2 + e- OH -
2
E = 0.401 Standard Redox Potential (2-2)
The corroding iron piece has an open circuit potential,
also called a rest potential, related to the Standard Redox
Potentials of the reactions in Eq. (2-1) and (2-2), to the com-
position of the aqueous medium, the temperature, and to the
polarizations of these half-cells. The rate of corrosion is
related to the polarizations as will be discussed later.
2.2.2 Availability of oxygen in concreteAlthough the
availability of oxygen is one of the main controlling factors
for corrosion of steel, there appears to be little quantitative
information on its effect in concrete. Some information is
shown, however, in Fig. 2.1, where the rate of oxygen diffusion
through water-saturated concrete of varying quality and
thickness is illustrated.2.2 The rate of oxygen diffusion
through concrete is also significantly affected by the extent
to which the concrete is saturated with water. A number of
investigations indicate that if the steel passivity is destroyed,
conditions will be conducive to the corrosion of steel rein-
forcement in those parts of a concrete structure that are ex-
posed to periods of intermittent wetting and drying.
Investigations also indicate that, although chlorides are
present, the rate of steel corrosion will be very slow if the
concrete is continuously water-saturated.2.3 In wet concrete,
dissolved oxygen will primarily be diffusing in solution,
while in a partly dry concrete the diffusion of gaseous oxy-
gen is much faster. For oxygen to be consumed in a cathodic
reaction, however, the oxygen has to be in a dissolved state.
Since it is the concentration of dissolved oxygen that is im-
portant, all factors affecting the solubility of oxygen should
also affect its availability. The effect of salt on the corrosion
rate has been demonstrated by Griffin and Henry2.4 (see
Fig. 2.2). Corrosion increased as the sodium chloride con-
centration increased until a maximum was reached. Beyond
this, the rate of corrosion decreased despite the increased
chloride ion concentration. This change in relationship be-
tween corrosion and sodium chloride concentration is attrib-
uted to the reduced solubility and diffusivity of oxygen, and,
therefore, the availability of oxygen to sustain the corrosion
process. This represents corrosion in a salt solution; howev-
er, the availability of oxygen in wet concrete may be different.
Problems due to corrosion of embedded steel have seldom
been observed in concrete structures that are continuously
submerged, even as in seawater.
2.2.3 The importance of chloride ionsAs will be discussed
later, concrete can form an efficient corrosion-preventive
222R-4 ACI MANUAL OF CONCRETE PRACTICE
Fig. 2.1Effect of water-cement ratio and thickness on diffusion of oxygen through mor-
tar and concrete2.2
Fig. 2.2Effect of concentration of sodium chloride
on corrosion rate2.4
environment for embedded steel. However, it is well
documented2.5-2.7 that the intrusion of chloride ions in rein-
forced concrete can cause steel corrosion if oxygen and
moisture are also available to sustain the reaction. No other
common contaminant is documented as extensively in the
literature as a cause of corrosion of metals in concrete. Chlo-
ride ions may be introduced into concrete in a variety of
ways. Some are intentional inclusion as an accelerating ad-
mixture; accidental inclusion as contaminants on aggregates;
or penetration by deicing salts, industrial brines, marine
spray, fog, or mist.
2.2.3.1 Incorporation in concrete during mixing. One of
the best known accelerators of the hydration of portland ce-
ment is calcium chloride. Generally, up to 2 percent solid
calcium chloride dihydrate based on the weight of cement is
added. Chlorides may be contained in other admixtures such
as some water-reducing admixtures where small amounts of
chloride are sometimes added to offset the set-retarding ef-
fect of the water reducer.
In some cases, where potable water is not available, seawa-
ter or water with a high chloride content is used as the mixing
water. In some areas of the world, aggregates exposed to sea-
water (or that were soaked in seawater at one time) can contain
a considerable quantity of chloride salts. Aggregates that are
porous can contain larger amounts of chloride.
2.2.3.2 Diffusion into mature concrete. Chlorides can
permeate through sound concrete, i.e., cracks are not neces-
sary for chlorides to enter the concrete.2.8 Approximate
determinations of the diffusion coefficients for chloride in
concrete have been published,2.9 but largely the literature ne-
glects the interaction between concrete and chloride.
2.2.3.3 Electrochemical role of free chloride ions. There
are three modern theories to explain the effects of chloride
ions on steel corrosion:
(a) The Oxide Film TheorySome investigators believe
that an oxide film on a metal surface is responsible for pas-
sivity and thus protection against corrosion. This theory pos-
tulates that chloride ions penetrate the oxide film on steel
through pores or defects in the film easier than do other ions
(e.g., SO4-). Alternatively, the chloride ions may colloidally
disperse the oxide film, thereby making it easier to penetrate.
(b) The Adsorption TheoryChloride ions are adsorbed on
the metal surface in competition with dissolved O2 or hydrox-
yl ions. The chloride ion promotes the hydration of the metal
ions and thus facilitates the dissolution of the metal ions.
(c) The Transitory Complex TheoryAccording to this
theory, chloride ions compete with hydroxyl ions for the
 CORROSION OF METALS 222R-5

ferrous ions produced by corrosion. A soluble complex of

iron chloride forms.2.9 This complex can diffuse away from
the anode destroying the protective layer of Fe(OH)2, per-
mitting corrosion to continue. Some distance from the elec-
trode, the complex breaks down, iron hydroxide precipitates
and the chloride ion is free to transport more ferrous ions
from the anode. Evidence for this process can be observed
when concrete with active corrosion is broken open. A light
green semisolid reaction product is often found near the steel
which, on exposure to air, turns black and subsequently rust
red in color.
Since corrosion is not stifled, more iron ions continue to
migrate into the concrete away from the corrosion site and to
react with oxygen to form higher oxides that result in a four-
fold volume increase. It is the expansion of iron oxides as
they are transformed to higher oxidation states that produce
internal stress, which eventually cracks the concrete. Formation
of iron chloride complexes may also lead to disruptive forces. Fig. 2.3Effect of pH on corrosion of iron in aerated
2.2.4 Corrosion rate and pHAs illustrated in Fig. 2.3, the soft water at room temperature2.1
corrosion rate of iron is reduced as the pH increases. Since
concrete has a pH higher than 12.5, it is usually an excellent
medium for protecting steel from corrosion. Only under con-
ditions where salts are present or the concrete cover has car-
bonated does the steel become vulnerable to corrosion.
2.2.5 Pourbaix diagramsPourbaix2.10 devised a com-
pact summary of thermodynamic data in the form of electri-
cal potential versus pH diagrams, which includes the
electrochemical and corrosion behavior of iron in an aqueous
medium. Fig. 2.4 indicates that iron is in a passive state at a
pH in the range of 8 to 13. This accounts for the protective
properties of concrete and the absence of steel corrosion in
concrete when no chloride ions, or only small amounts, are
present. A careful inspection of Fig. 2.4 indicates, however,
that corrosion may begin if the pH of the system is raised to
above about 13. In this case, a soluble ferrite, HFeO2-, forms.
Any mechanism where iron dissolves at an appreciable rate
in concrete can be considered serious corrosion. Thus, the
addition of materials that further increase the pH of concrete
may be detrimental; however, the occurrence of this phe-
nomenon in concrete has not been confirmed.
2.2.6 High-strength steels and other metalsThere is lit-
tle information in the literature suggesting that the newer Fig. 2.4Pourbaix diagram for iron2.10
high-strength steels are either more or less subject to corrosion
than the previous standard and lower strength steels. Al-
though information is lacking, it is expected that whatever Zn + OH- + H2O -> HZnO2- + H2 (2-3)
differences might exist would be secondary to the major fac-
tors influencing corrodibility of the steel. If galvanized steel is to be used in concrete, appropriate
Studies have been made on the corrosion of prestressed measures should be taken to prevent hydrogen evolution in
steel in concrete2.11 that demonstrate the hazards of adding the fresh concrete. A small amount of a chromate salt is gen-
chlorides to concrete containing prestressed steel. erally used.2.13
Aluminum corrodes in concrete and the rate of corrosion In submerged concrete structures having freely exposed
is higher if the aluminum is in contact with steel and chlo- steel components in metallic connection with the reinforcing
rides or if alkalies are present.2.12 Lead and tin (e.g., tin sol- steel, galvanic cells may develop with the freely exposed
der) can corrode similarly. steel forming the anode and the embedded steel the cathode.
At pH about 12.5, zinc reacts rapidly to form soluble This may cause an increased corrosion rate on the freely ex-
zincates and hydrogen gas is liberated posed steel.
222R-6 ACI MANUAL OF CONCRETE PRACTICE
Fig. 2.5Iron electrode in concrete2.16
Copper, chromium, nickel, and silver generally do not
corrode in concrete. However, they are somewhat suscep-
tible to corrosion when the concrete is located in a marine
environment.2.14
2.2.7 Polarization of half-cellsThe equilibrium of a
half-cell is characterized by its reversible potential which
depends on the Standard Redox Potential, on the concen-
trations (activities) of the species participating in the half-cell
reaction (e.g., OH-, Fe++, etc.), and on the temperature.
When a current flows through the half-cell, there is a shift
of its measured potential away from the reversible potential.
This shift is called polarization. For a given current, the po-
larization is large for half-cell reactions that are irreversible
or nearly so. For instance, the oxygen half-cell reaction
[Eq. (2-2)] is almost irreversible and can have a relatively
high degree of polarization.
Some corrosion processes, although thermodynamically
more favored than others as indicated by the reversible po-
tentials of the half-cells, are actually slower in practice be-
cause of polarization effects.
There are three general kinds of polarization that apply
to the anode as well as to the cathode. These are concen-
tration polarization, ohmic polarization, and activation
polarization. These three kinds of polarization can be
present simultaneously.
(a) Concentration polarization occurs when the concen-
tration of the electrolyte changes in the vicinity of the elec-
trode. An example of this would be depletion of oxygen
concentration at the cathode.
(b) Ohmic polarization occurs because of the ohmic resis-
tance of the electrolyte (e.g., moist concrete) and of any
films on the electrode surface. This produces an ohmic po-
tential drop in accordance with Ohms law (IR drop).
(c) Activation polarization occurs due to kinetic hindrance
of the rate controlling step of the electrode reaction.
Tafel2.1 has shown experimentally that for large currents
in the absence of concentration and ohmic polarization, the
measured polarization , which is the activation polarization, is
directly proportional to the logarithm of the current density i
= a + blog i
where a and b are the so-called Tafel intercept and Tafel
slope parameters, respectively. These parameters can be ob-
tained by plotting versus i on semilogarithmic paper. The
Tafel intercept parameter a is related to the exchange current
density io, which is the equilibrium current flowing back and
forth through the electrode electrolyte interface at equilibri-
um and a measure of the reversibility of the reaction.
The Tafel slope parameter b, on the other hand, gives an
insight according to modern electrode reaction theory2.15
into the mechanism of the electrode reaction.
2.2.8 Passivity and transpassivitySpecific to the anodic
half-cell in the corrosion process are the concepts of passiv-
ity and transpassivity. Passivity of a metal is generally char-
acterized by a thin and tightly adherent oxide film on the
metal surface, which tends to protect the metal against fur-
ther corrosion. The exact composition of the thin and nor-
mally invisible film has been difficult to determine. It seems
clear, however, that it is made up of chemical combinations
of oxygen and is simply called an oxide film.
When a potential is applied to an iron electrode, the rate of
current flow depends on the state of passivity. Iron in con-
crete is generally passive, such that little current flows when
a potential is progressively increased, eventually the current
will flow. This is because, at this point, oxygen is evolved
and the electrode reaction involves the electrolysis of water
(see Curve I, Fig. 2.5).
2H2O -> 4H+ + O2 + 4e- (2-4)
This phenomenon is called transpassivity. The use of a
corrosion testing procedure involving an impressed potential
has been reported.2.17 Grimes et al.2.18 found that when a
high anodic voltage was applied to steel in concrete, the pH
around the steel was changed to values ranging between al-
most 0 and 4. He also found that a liquid pool formed quickly
around the reinforcing steel. Neither steel nor concrete is du-
rable in a low pH (acidic) environment.
2.2.9 Types of corrosion-controlling mechanismsAs
previously mentioned, it is necessary to have both a cathodic
and an anodic reaction for a corrosion process to occur.
However, different corrosion situations can be visualized by
plotting, on the same graph, the log of the absolute current
(I) versus potential (E) curves which would be obtained by
polarizing each half-cell with an auxiliary counter electrode
in absence of the other half-cell. For this discussion, we as-
sume (a) no IR drop between anodic and cathodic areas and
(b) simple algebraic addition of the anodic and cathodic cur-
rents. Under these conditions, the rest potential or open cir-
cuit potential of the corroding sample will be that at which
the two i versus E curves intercept. At this point no net, ex-
ternal current flows, and the absolute value of current at the
intercept is equal to the corrosion current.
If the cathodic process is the slower process (the one with
the larger polarization), the corrosion rate is considered to be
cathodically controlled (Fig. 2.6). Conversely, if the anodic
process is slower, the corrosion rate is said to be anodically
controlled (Fig. 2.7).
In concrete, one or two types of corrosion-rate-controlling
mechanisms normally dominate. One is cathodic diffusion,
where the rate of oxygen diffusion through the concrete
 CORROSION OF METALS
Fig. 2.6Cathodic control
Fig. 2.7Anodic control
determines the rate of corrosion. In Fig. 2.8, cathodic diffusion
control is shown for two different rates of oxygen diffusion.
The other type of controlling mechanism involves the de-
velopment of a high resistance path. When steel corrodes in
concrete, anodic and cathodic areas may be as much as several
feet apart; therefore, the resistance of the concrete may be of
great importance. Fig. 2.9 illustrates two cases of resistance
control where the potential available for corrosion is the dif-
ference in the potential between anode and cathode minus
the relevant IR loss.
2.2.10 Stray current corrosionStray electric currents are
those that follow paths other than the intended circuit. They
can greatly accelerate the corrosion of reinforcing steel. The
most common sources of these are electric railways, electro-
plating plants, and cathodic protection systems. Kondo et
al.2.9 reported corrosion of reinforcing steel embedded in
concrete used in an electric railroad.
2.2.11 Cathodic protectionThe principle of cathodic
protection is to change the potential of a metal to reduce the
current flow and thereby the rate of corrosion. This is accom-
plished by the application of a protective current at a higher
222R-7
Fig. 2.8Cathodic diffusion control
Fig. 2.9Resistance control
voltage than that of the anodic surface. The current then
flows to the original anodic surface resulting in cathodic re-
actions occurring there. The difficulties in using this method,
however, are to determine the correct potential to apply to
the system and to make sure that it is applied uniformly.
2.2.12 Effects of other salt ionsIt has been reported that
sulfate2.20 and carbonate2.21 salts can also cause reinforcing
steel to corrode. However, this has not been well document-
ed. Although the concrete may have cracked in certain cases
and the exposed steel may have appeared rusted, these salts
may not have been the primary cause. Their low solubility in
a high calcium ion environment would reduce their availabil-
ity. However, certain soluble salts, such as perchlorates, ac-
etates, and salts of halogens other than chlorine may be
corrosive to steel embedded in concrete. Hydrogen sulfide
has also been cited as a cause of corrosion.2.22
2.2.13 Stress corrosion crackingStress corrosion2.23 is
defined as the process in which the damage caused by stress
and corrosion acting together greatly exceeds that produced
when they act separately.
222R-8 ACI MANUAL OF CONCRETE PRACTICE
Fig. 2.10Rate of reaction of gypsum with tricalcium alu-
minate in portland cement2.29
In stressed steel, a small imperfection caused by corrosion
can lead to a serious loss in tensile strength as the corrosion
continues at the initial anode area.
Another form of corrosion that is related to stress corrosion
cracking is intergranular corrosion. In this case, a gas, usual-
ly hydrogen, is absorbed in the iron, causing a loss of ductil-
ity and cracking. Hydrogen cracking in connection with
cathodic protection will be discussed in Chapter 5. Other ma-
terials that may cause intergranular corrosion are hydrogen
sulfide and high concentrations of ammonia and nitrate salts.
The mechanism of how this type of corrosion proceeds is not
fully understood; however, it is believed that it involves the
reduction in the cohesive strength of the iron. Documented
examples of stress corrosion cracking of steel in concrete
have not been found in the literature.
2.3Effects of the concrete environment on
corrosion
2.3.1 Portland cementWhen portland cement hydrates,
the silicates react with water to produce calcium silicate hy-
drate and calcium hydroxide. The following simplified
equations give the main reactions of portland cement with water
2(3CaO SiO2) + 6H2O 3CaO 2SiO2 3H20 + as to promote the corrosion of steel.
3Ca(OH)2 (2-5)
2(2CaO SiO2) + 4H2O 3CaO 2SiO2 3H2O + cement system to cause flash set unless it is retarded. Calci-
Ca(OH)2 (2-6)
As previously mentioned, the high alkalinity of the chem-
ical environment normally present in concrete protects the
embedded steel because of the formation of a protective ox-
ide film on the steel. The integrity and protective quality of
this film depends on the alkalinity (pH) of the environment.
Differences in the types of cement are a result of variation
in composition or fineness or both, and as such, not all types
of cement have the same ability to provide protection of
embedded steel. According to Pressler et al.2.24 a well-hy-
drated portland cement may contain from 15 to 30 percent
calcium hydroxide by weight of the original cement. This is
usually sufficient to maintain a solution at a pH about 13 in
the concrete independent of moisture content.
Rosenqvist2.25 has described an example of exceedingly
rapid steel corrosion in a tropical concrete wharf where a
pozzolan was added to the portland cement. Corrosion of the
reinforcement was observed shortly after construction was
completed. Measurements of pH in the extract from the con-
crete adjacent to the steel gave values from 5.7 to 8.5. When
the pozzolan was omitted, an increase in pH was obtained
and no damage was observed.
Other research2.26 showed that a pozzolan did not adverse-
ly affect the performance of steel in concrete that was partial-
ly immersed in a saturated salt solution. In this latter study,
the pozzolan studied was a calcined volcanic tuff that was
added to the concrete at dosages of 16 and 32 percent by
weight of the cement. It may be that the protective qualities
of the pozzolan are related to its source or generic type.
The use of blended cements might, under certain circum-
stances, be detrimental because of a reduction in alkalinity.
However, blended cements can give a substantial reduction in
permeability and also an increase in electrical resistivity espe-
cially where a reduction in the water-cement ratio is made pos-
sible. Also, such blended cements may give concrete as much
as two to five times higher resistance to chloride penetration
than concrete made with portland cements.2.27 The effects
would be beneficial as far as corrosion is concerned and in
some circumstances the benefits associated with blended ce-
ments more than offset the adverse effects.
Even for cements with the highest reserve basicity, the al-
kalinity may be reduced in a number of ways. Reduction of
alkalinity by leaching of soluble alkaline salts with water is
an obvious process. Partial neutralization by reaction with
carbon dioxide (carbonation), as present either in air or dis-
solved in water, is another common process.
The silicates are the major components in portland cement
imparting strength to the matrix. No reactions have been de-
tected between chloride ions and silicates. Calcium chloride
accelerates the hydration of the silicates when at least 1 per-
cent by weight is added.2.28 Calcium chloride seems to act as
an accelerator in the hydration of tricalcium silicate as well
Also present in portland cement are C3A and an alumino-
ferrite phase reported as C4AF. The C3A reacts rapidly in the
um sulfate is used as the retarder. Calcium sulfate forms a
coating of ettringite (C3A 3CaSO4 32H2O) around the alu-
minate grains thereby retarding their reactivity (Fig. 2.10).
Calcium chloride also forms insoluble reaction products with
the aluminates in cement (see Fig. 2.11). The most commonly
noted complex is C3A CaCl2 xH2O, Friedels salt (Table 2.1).
The rate of formation of this material is slower than that of
ettringite (compare Fig. 2.10 with Fig. 2.11). The chloride-
aluminate complex forms after ettringite and prevents further
reactions of sulfate with the remaining aluminates.2.29
 CORROSION OF METALS 222R-9

Table 2.1Comparison of producers analysis of

eight different portland cements with total amount of
calcium chloride that reacted with each cement2.29
1/ SO content* Amount of calcium
3 3 C3A + C4AF - 1/3SO3 chloride reacted
0.20 1.43 1.19
0.05 1.42 1.37
0.30 1.10 1.18
0.07 1.62 1.45
0.72 0.69 0.63
0.25 1.03 1.08
0.26 1.05 1.07
0.23 1.15 1.05
Average 1.18 1.13
*Data expressed in molar equivalents rather than usual percent for comparison pur-
poses. Wide differences in SO3 content obtained intentionally.

The chemical combining of C3A with chlorides is fre-

quently referred to as a beneficial effect in that it will reduce
the rate of chloride penetration into concrete. According to
Mehta,2.30 a chemical binding of penetrating chlorides can-
not be expected unless the C3A content is higher than about Fig. 2.11Rate of reaction of calcium chloride with
8 percent. However, recent experimental observations have portland cement2.29
shown that as much as 8.6 percent C3A does not effectively
reduce chloride penetration when concrete is immersed in
seawater2.31 and other studies have found more corrosion-
induced distress associated with high C3A contents.2.32
2.3.2 AggregateThe aggregate generally has little effect
on the corrosion of steel in concrete. There are exceptions.
The most serious problems arise when the aggregates con-
tain chloride salts. This can happen when sand is dredged
from the sea or taken from seaside or arid locations. Porous
aggregates can absorb considerable quantities of salt.
Care should be exercised when using admixtures contain-
ing chloride in combination with lightweight aggregates.
Helms and Bowman2.33 found that reinforcing steel in light-
weight concrete was particularly susceptible to corrosion
when exposed to moisture and changes in temperature.
Lightweight aggregate containing sulfides can be damaging
to high-strength steel under stress.
2.3.3 WaterThe effect of moisture content or degree of
water saturation on the rate of oxygen diffusion into concrete
has already been discussed. A high moisture content will
also substantially reduce the rate of diffusion of carbon diox-
ide and hence the rate of carbonation of the concrete.
An important effect of the moisture content of concrete is
its effect on the electrical resistivity of the concrete. Progres-
sive drying of initially water-saturated concrete results in
the electrical resistivity increasing from about 7 103
ohm cm to about 6000 103 ohm cm (Fig. 2.12).2.34 Field ob- Fig. 2.12Effect of water saturation on the resistivity
servations indicate that when the resistivity exceeds a lev- of concrete2.34
el of 50 to 70 103 ohm cm, steel corrosion would be
negligible.2.35 Other authors quote values of resistivity of
10 x 103 ohm cm2.36 and 12 103 ohm cm2.37 above admixtures, however, may retard time of setting of the cement
which corrosion induced damage is unlikely even in the or be detrimental at later ages. Many would be subject to
presence of chloride ions, oxygen, and moisture. leaching and hence less effective in concrete that has lost sol-
2.3.4 Corrosion inhibiting admixturesNumerous chemi- uble material by leaching. Among those compounds reported
cal admixtures, both organic and inorganic, have been sug- as inorganic inhibitors are potassium dichromate, stannous
gested as specific inhibitors of steel corrosion.2.13 Some of the chloride, zinc and lead chromates, calcium hypophosphite,
222R-10 ACI MANUAL OF CONCRETE PRACTICE
Fig. 2.13Gradient of total chloride concentration depth
depends on whether chemical reaction occurs with cement2.41
sodium nitrite, and calcium nitrite. Organic inhibitors suggest-
ed have included sodium benzoate, ethyl aniline, and mercap-
tobenzothiazole. With some inhibitors, inhibition occurs only
at addition rates sufficiently high to counteract the effects of
chlorides. Sodium nitrite has been used with apparent effec-
tiveness in Europe.2.38 Calcium nitrite2.39 is being studied in
the United States since several side effects of the sodium salt
would be avoided. Some of the side effects are low strength,
erratic times of setting, efflorescence, and enhanced suscepti-
bility to the alkali-aggregate reaction.2.40
2.3.5 Concrete qualityConcrete will offer more pro-
tection against corrosion of embedded steel if it is of a high
quality. A low water-cement ratio will slow the diffusion of
chlorides, carbon dioxide, and oxygen and also the increase in
strength of the concrete may extend the time before corrosion-
induced stresses cause cracking of the concrete. The pore vol-
ume and permeability can be reduced by lowering the water-
cement ratio. The type of cement or use of superplasticizing
and mineral admixtures may also be an important factor in
controlling the permeability and the ingress of chlorides.2.31
2.3.6 Thickness of concrete cover over steel-The amount
of concrete cover over the steel should be as large as possible,
consistent with good structural design, the severity of the ser-
vice environment, and cost. The effect of cover thickness is
more than a simple linear relationship. Considering the normal
diffusion of an electrolyte into a porous solid without chemi-
cal reaction, a relationship such as shown in Fig. 2.13 would
be anticipated. However, in the case of cement paste, the dif-
fusion of chloride ions into the paste is accompanied by both
physical adsorption and chemical binding. These effects re-
duce the concentration of chloride ion at any particular site
and hence the tendency for inward diffusion is further re-
duced. This is also illustrated in Fig. 2.13.
2.3.7 CarbonationCarbonation occurs when the con-
crete reacts with carbon dioxide from the air or water and re-
duces the pH to about 8.5. At this low pH the steel is no
longer passive and corrosion may occur. For high-quality
concrete, in situations where the rate of carbonation is ex-
tremely slow, carbonation is normally not a problem unless
cracking of the concrete has occurred or the concrete cover
is defective or very thin. Carbonation is not a problem in
very dry concrete or in water-saturated concrete. Maximum
carbonation rates are observed at about 50 percent water sat-
uration. A more complete discussion of carbonation and the
corrosion of steel in carbonated concrete is given in Refer-
ences 2.17 and 2.21.
2.4References
2.1. Uhlig, Herbert H.,Corrosion and Corrosion Control, 2nd Edition,
John Wiley & Sons, New York, 1971, 419 pp.
2.2. Gjrv, O. E.; Vennesland, ; and El-Busaidy, A. H. S., Diffusion of
Dissolved Oxygen through Concrete, Paper No. 17, NACE Corrosion 76,
National Association of Corrosion Engineers, Houston, Mar. 1976, 13 pp.
2.3. Shalon, R., and Raphael, M., Influence of Sea Water on Corrosion
of Reinforcement, ACI JOURNAL, Proceeding s V. 55, No. 8, Feb. 1959, pp.
1251-1268.
2.4. Griffin, Donald F., and Henry, Robert L., Effect of Salt in Concrete
on Compressive Strength, Water Vapor Transmission, and Corrosion of
Reinforcing Steel, Proceeding s, ASTM, V. 63, 1963, pp. 1046-1078.
2.5. Stratfull, R. F.; Jurkovich, W. J.; and Spellman, D. L., Corrosion
Testing of Bridge Decks, Transportation Research Record No. 539, Trans-
portation Research Board, 1975, pp. 50-59.
2.6. Browne, Roger D., Mechanisms of Corrosion of Steel in Concrete
in Relation to Design, Inspection, and Repair of Offshore and Coastal
Structures, Performance of Concrete in Marine Environment, SP-65,
American Concrete Institute, Detroit, 1980, pp. 169-204.
2.7. Aziz, M. A., and Mansur, M. A., Deterioration of Marine Concrete
Structures with Special Emphasis on Corrosion of Steel and Its Remedies,
Corrosion of Reinforcement in Concrete Construction, Ellis Horwood Lim-
ited, Chichester, 1983, pp. 91-99.
2.8. Gjrv, Odd E., Durability of Concrete Structures in the Ocean
Environment, Proceedings, FIP Symposium on Concrete Sea Structures
(Tbilisi, Sept. 1972), Federation Internationale de la Precontrainte, Lon-
don, 1973, pp. 141-145.
2.9. Foley, R. T., Complex Ions and Corrosion, Journal, Electrochemi-
cal Society, V. 122, No. 11, 1975, pp. 1493-1549.
2.10. Pourbaix, M., Atlas of Electrochemical Equilibrium in Aqueous
Solutions, Pergamon Press Limited, London, 1976.
2.11. Monfore, G. E., and Verbeck, G. J., Corrosion of Prestressed Wire in
Concrete, ACI JOURNAL, Proceedings V. 57, No. 5, Nov. 1960, pp. 491-516.
2.12. Monfore, G. E., and Ost, Borje, Corrosion of Aluminum Conduit
in Concrete,Journal, PCA Research and Development Laboratories, V. 7,
No. 1, Jan. 1967, pp. 10-22.
2.13. Boyd, W. K., and Tripler, A. B., Corrosion of Reinforcing Steel
Bars in Concrete, Materials Protection, V. 7, No. 10, 1968, pp. 40-47.
2.14. Baker, E. A.; Money, K. L.; and Sanborn, C. B., Marine Corrosion
Behavior of Bare and Metallic-Coated Steel Reinforcing Rods in Con-
crete, Chloride Corrosion of Steel in Concrete, STP-629, ASTM, Phila-
delphia, 1977, pp. 30-50.
2.15. Stern, M., and Geary, A. L., Electrochemical Polarization No. 1
Theoretical Analysis of the Shape of Polarization Curves, Journal, Elec-
trochemical Society, V. 104, No. 1, 1957, pp. 56-63.
2.16. Rosenberg, A. M., and Gaidis, J. M., The Mechanism of Nitrite
Inhibition of Chloride Attack on Reinforcing Steel in Alkaline Aqueous
Environments, Materials Performance, V. 18, No. 11, 1979, pp. 45-48. e
2.17. Corrosion of Reinforcement and Prestressing Tendons: A State of
the Art Report, Materials and Structures/Research and Testing (RILEM,
Paris), V. 9, No. 51, May-June 1976, pp. 187-206.
2.18. Grimes, W. D.; Hartt, W. H.; and Turner, D. H., Cracking of Con-
crete in Sea Water Due to Embedded Metal Corrosion, Cor rosion, V. 35,
No. 7, 1979, pp. 309-316.
2.19. Kondo, Yasuo; Takeda, Akihiko; and Hideshima, Setsuji, Effect
of Admixtures on Electrolytic Corrosion of Steel Bars in Reinforced Con-
crete, ACI JOURNAL, Proceeding s V. 56, No. 4, Oct. 1959, pp. 299-312.
 CORROSION OF METALS
2.20. Eickemeyer, J., Stress Corrosion Cracking of a High-Strength
Steel in Saturated Ca(OH)2 Solutions Caused by Cl and SO4 Additions,
Corrosion Science, V. 18, No. 4, 1978, pp. 397-400.
2.21. Hamada, M., Neutralization (Carbonation) of Concrete and
Corrosion of Reinforcing Steel, Proceedings, 5th International Sym-
posium on the Chemistry of Cement (Tokyo, 1968), Cement Associa-
tion of Japan, Tokyo, 1969, V. 3, pp. 343-360.
2.22. Treadaway, K. W. J., Corrosion of Prestressed Steel Wire in
Concrete, British Corrosion Journal (London), V. 6, 1971, pp. 66-72.
2.23. Sluijter, W. L., and Kreijger, P. C., Potentio Dynamic Polar-
ization Curves and Steel Corrosion, Heron (Delft), V. 22, No. 1, 1977,
pp. 13-27.
2.24. Weise, C. H., Determination of the Free Calcium Hydroxide
Contents of Hydrated Portland Cements and Calcium Silicates, Analyt-
ical Chemistry, V. 33, No. 7, June 1961, pp. 877-882. Also, Research
Department Bulletin No. 127, Portland Cement Association.
2.25. Rosenqvist, I. T., Korrosjon av Armeringsstal i Betong,
Teknisk Ukeblad (Oslo), 1961, pp. 793-795.
2.26. Spellman, D. L., and Stratfull, R. F., Concrete Variables and
Corrosion Testing, Highway Research Record No. 423, Highway
Research Board, 1973, pp. 27-45.
2.27. Page, C. L.; Short, N. R.; and El Tarras, A., Diffusion of Chlo-
ride Ions in Hardened Cement Pastes, Cement and Concrete Research,
V. 11, No. 3, May 1981, pp. 395-406.
2.28. Ramachandran, V. S., Calcium Chloride in Concrete, Applied
Science Publishers, London, 1976, 216 pp.
2.29. Rosenberg, Arnold M., Study of the Mechanism through
Which Calcium Chloride Accelerates the Set of Portland Cement, ACI
JOURNAL, Proceeding s V. 61, No. 10, Oct. 1964, pp. 1261-1270.
2.30. Mehta, P. K., Effect of Cement Composition on Corrosion of
Reinforcing Steel in Concrete, Chloride Corrosion of Steel in Con-
crete, STP-629, ASTM, Philadelphia, 1977, pp. 12-19.
2.31. Gjrv, O. E., and Vennesland, ., Diffusion of Chloride Ions
from Seawater into Concrete, Cement and Concrete Research, V. 9,
No. 2, Mar. 1979, pp. 229-238.
2.32. Stratfull, R. F., Discussion of Long-Time Study of Cement
Performance. Chapter 12Concrete Exposed to Sea Water and Fresh
Water, by I. L. Tyler, ACI JOURNAL, Proceeding s V. 56, Part 2, Sept.
1960, pp. 1455-1458.
2.33. Helms, S. B., and Bowman, A. L., Corrosion of Steel in Light-
weight Concrete Specimens, ACI JOURNAL, Proceedings V. 65, No.
12, Dec. 1968, pp. 1011-1016.
2.34. Gjrv, O. E.; Vennesland, .; and El-Busaidy, A. H. S., Elec-
trical Resistivity of Concrete in the Oceans,OTC Paper No. 2803, 9th
Annual Offshore Technology Conference, Houston, May 1977, pp.
581-588.
2.35. Tremper, Bailey; Beaton, John L.; and Stratfull, R. F., Causes
and Repair of Deterioration to a California Bridge Due to Corrosion of
Reinforcing Steel in a Marine Environment II: Fundamental Factors
Causing Corrosion, Bulletin No. 182, Highway Research Board, Wash-
ington, D.C., 1958, pp. 18-41.
2.36. Browne, R. D., Design Prediction of the Life for Reinforced
Concrete in Marine and Other Chloride Environments, Durability of
Building Materials (Amsterdam), V. 1, 1982, pp. 113-125.
2.37. Cavalier, P. G., and Vassie, P. R., Investigation and Repair of
Reinforcement Corrosion in a Bridge Deck, Proceedings, Institution of
Civil Engineers (London), Part 1, V. 70, 1981, pp. 461-480.
2.38. Woods, Hubert, Durability of Concrete Construction, ACI
Monograph No. 4, American Concrete Institute/Iowa State University
Press, Detroit, 1968, p. 102.
2.39. Rosenberg, A. M.; Gaidis, J. M.; Kossivas, T. G.; and Previte,
R. W., A Corrosion Inhibitor Formulated with Calcium Nitrite for Use
in Reinforced Concrete, Chloride Corrosion of Steel in Concrete, STP-
629, ASTM, Philadelphia, 1977, pp. 89-99.
2.40. Craig, R. J., and Wood, L. E., Effectiveness of Corrosion
Inhibitors and Their Influence on the Physical Properties of Portland
Cement Mortars, Highway Research Record No. 328, Highway
Research Board, 1970, pp. 77-88.
2.41. Verbeck, George J., Mechanisms of Corrosion of Steel in Con-
crete, Corrosion of Metals in Concrete, SP-49, American Concrete
Institute, Detroit, 1975, pp. 21-38.
222R-11
CHAPTER 3PROTECTION AGAINST
CORROSION IN NEW CONSTRUCTION
3.1Introduction
Measures which can be taken in reinforced concrete con-
struction to protect the steel against corrosion can be divided
into three categories:
(a) Design and construction practices that maximize the
protection afforded by the portland cement concrete. l
(b) Treatments that penetrate or are applied on the surface
of the reinforced concrete member to exclude chloride ion
from the concrete.
(c) Techniques that prevent corrosion of the reinforce-
ment directly.
In the last case, two approaches are possible: to use
corrosion-resistant reinforcing steel or to nullify the effects
of chloride ions on unprotected reinforcement.
3.2Design and construction practices
Through careful design and good construction practices,
the protection provided by portland cement concrete to em-
bedded reinforcing steel can be optimized. It is not the so-
phistication of the structural design that determines the
durability of a concrete member in a corrosive environment
but the detailing practices.3.1 The provision of adequate
drainage and a method of removing drainage water from the
structure are particularly important.
In reinforced concrete members exposed to chlorides and
subjected to intermittent wetting, the degree of protection
against corrosion is determined primarily by the depth of
cover to the reinforcing steel and the permeability of the con-
crete.3.2-3.6 Estimates of the increase in corrosion protection
provided by an increase in cover have ranged between slight-
ly more than a linear relationship3.3,3.7 to as much as the
square of the cover.3.8 The time to spalling is a function of
the ratio of cover to bar diameter,3.8 the reinforcement spac-
ing, and the concrete strength. Although conventional port-
land cement concrete is not impermeable, concrete with a
very low permeability can be made through the use of good
quality materials, a minimum water-cement ratio consistent
with placing requirements, good consolidation and finishing
practices, and proper curing.
In concrete that is continuously submerged, the rate of cor-
rosion is controlled by the rate of oxygen diffusion that is not
significantly affected by the concrete quality or the thickness
of cover.3.9 However, as noted in Chapter 2, corrosion of
embedded steel is a rare occurrence in continuously sub-
merged concrete structures.
Placing limits on the allowable amounts of chloride ion in
concrete is an issue still under active debate. On the one side
are the purists who would like to see essentially no chlorides
in concrete. On the other are the practitioners, including
those who must produce concrete under cold weather con-
ditions, precast concrete manufacturers who wish to mini-
mize curing times, producers of chloride-bearing aggregates,
and some admixture companies, who would prefer the least
restrictive limit possible. Since chlorides are present natural-
ly in most concrete-making materials, specifying a zero
chloride content for any of the mix ingredients is unrealistic.
222R-12 ACI COMMITTEE REPORT
However, it is also known that wherever chloride is present
in concrete, the risk of corrosion increases as the chloride
content increases. When the chloride content exceeds a cer-
tain value (termed the chloride corrosion threshold), unac-
ceptable corrosion may occur provided that other necessary
conditions, chiefly the presence of oxygen and moisture, ex-
ist to support the corrosion reactions, It is a difficult task to
establish a chloride content below which the risk of corrosion is
negligible, which is appropriate for all mix ingredients and
under all exposure conditions, and which can be measured
by a standard test.
Three different analytical values have been used to desig-
nate the chloride content of fresh concrete, hardened con-
crete, or any of the concrete mixture ingredients: (a) total,
(b) acid-soluble, and (c) water-soluble.
The total chloride content of concrete is measured by the
total amount of chlorine. Special analytical methods are
necessary to determine it, and acid-soluble chloride is often
mistakenly called total chloride. The acid-soluble method
is the test method in common use and measures that chlo-
ride that is soluble in nitric acid. Water-soluble chloride is
chloride extractable in water under defined conditions. The
result obtained is a function of the analytical test procedure,
particularly with respect to particle size, extraction time,
and temperature, and to the age and environmental expo-
sure of the concrete.
It is also important to distinguish clearly between chloride
content, sodium chloride content, calcium chloride content,
or any other chloride salt content. In this report, all referenc-
es to chloride content pertain to the amount of chloride ion
(Cl-) present. Chloride contents are expressed in terms of the
mass of cement unless stated otherwise.
Lewis3.10reported that, on the basis of polarization tests of
steel in saturated calcium hydroxide solution and water ex-
tracts of hydrated cement samples, corrosion occurred when
the chloride content was 0.33 percent acid-soluble chloride,
or 0.16 percent water-soluble chloride based on a 2 hr ex-
traction in water. However, it has been shown that the pore-
water in many typical portland cement concretes made
using relatively high-alkali cements is a strong solution of
sodium and potassium hydroxides with a pH approaching
14. Since the passivity of embedded steel is determined by
the ratio of the hydroxyl concentration to the chloride con-
centration,3.11 the amounts of chloride that can be tolerated
in concrete are higher than those that will cause pitting cor-
rosion in a saturated solution of calcium hydroxide.3.12
Work at the Federal Highway Administration
laboratories3.5 showed that for hardened concrete subject to
externally applied chlorides, the corrosion threshold was
0.20 percent acid-soluble chlorides. The average content of
water-soluble chloride in concrete was found to be 75 to 80
percent of the content of acid-soluble chloride in the same
concrete. This corrosion threshold value was subsequently
confirmed by field studies of bridge decks including those in
California3.13 and New York.3.14 These investigations show
that, under some conditions, a chloride content of as little as
0.15 percent water-soluble chloride (or 0.20 percent acid-
soluble chloride) is sufficient to initiate corrosion of embedded
steel in concrete exposed to chlorides in service. However, in
determining a limit on the chloride content of the mix ingre-
dients, several other factors need to be considered.
As noted in the figures already given, the water-soluble
chloride content is not a constant proportion of the acid-
soluble chloride content. It varies with the amount of chlo-
ride in the concrete,3.10 the mix ingredients, and the test meth-
od. All the materials used in concrete contain some chlorides,
and, in the case of cement, the chloride content in the hardened
concrete varies with cement composition. Although aggre-
gates do not usually contain significant amounts of chlo-
ride,3.15 there are exceptions. There are reports of aggregates
with an acid-soluble chloride content of more than 0.1 percent
of which less than one-third is water-soluble when the aggre-
gate is pulverized.3.16 The chloride is not soluble when the ag-
gregate is placed in water over an extended period and there is
no difference in the corrosion performance of structures in
southern Ontario made from this aggregate when compared to
other chloride-free aggregates in the region. However, this is
not always the case. Some aggregates, particularly those from
arid areas or dredged from the sea, may contribute sufficient
chloride to the concrete to initiate corrosion. A limit of 0.06
percent acid-soluble chloride ion in the combined fine and
coarse aggregate (by mass of the aggregate) has been suggest-
ed with a further proviso that the concrete should not contain
more than 0.4 percent chloride (by mass of the cement) de-
rived from the aggregate.3.17
There is thought to be a difference in the chloride corrosion
threshold value depending on whether the chloride is present
in the mix ingredients or penetrates the hardened concrete
from external sources. When chloride is added to the mix,
some will chemically combine with the hydrating cement
paste. The amount of chloride forming chloroaluminates is a
function of the C3A content of the cement.3.18 Chloride add-
ed to the mix will also tend to be distributed relatively uni-
formly and, therefore, has less tendency to cause the creation
of concentration cells.
Conversely, when chloride permeates from the surface of
hardened concrete, uniform chloride contents will not exist
around the steel because of differences in the concentration
of chlorides on the concrete surface resulting from poor
drainage, for example, local differences in permeability, and
variations in the depth of cover to the steel. All these factors
promote differences in the environment (oxygen, moisture,
and chloride content) along a given piece of reinforcement.
Furthermore, most structures contain reinforcement at dif-
ferent depths, and, because of the procedures used to fix the
steel, the steel is electrically connected. Thus, when chloride
penetrates the concrete, some of the steel is in contact with
chloride-contaminated concrete while other steel is in
chloride-free concrete. This creates a macroscopic corrosion
cell that can possess a large driving voltage and a large cath-
ode to small anode ratio which accelerates the rate of corrosion.
In seawater, it has been suggested that the permeability of
the concrete to chloride penetration is reduced by the precip-
itation of magnesium hydroxide.3.19
In laboratory studies3.20 in which sodium chloride was added
to the mix ingredients, it was found that a substantial increase in

corrosion rate occurred between 0.4 and 0.8 percent chloride,
although the moisture conditions of the test specimens were
not clearly defined. Other researchers have suggested3.21
that the critical level of chloride in the mix ingredients to
initiate corrosion is 0.3 percent and that this has a similar
effect to 0.4 percent chloride penetrating the hardened con-
crete from external sources. In studies in which calcium
chloride was added to portland cement concrete, it was
found3.22 that the chloride ion concentration in the pore so-
lution remained high during the first day of hydration. It de-
clined gradually, but it appeared that substantial
concentrations of chloride ion remained in solution indefinitely.
Chloride limits in national codes vary widely. ACI 318 al-
lows a maximum water-soluble chloride ion content of 0.06
percent in prestressed concrete, 0.15 percent for reinforced
concrete exposed to chloride in service, 1.00 percent for re-
inforced concrete that will be dry or protected from moisture
in service, and 0.30 percent for all other reinforced concrete
construction. The British Code, CP 110, allows an acid-sol-
uble chloride ion content of 0.35 percent for 95 percent of the
test results with no result greater than 0.50 percent. These
values are largely based on an examination of several struc-
tures in which it was found there was a low risk of corrosion
up to 0.4 percent chloride added to the mixture.3.23 However,
corrosion has occurred at values less than 0.4 percent,3.24
particularly where the chloride content was not uniform. The
Norwegian Code, NS 3474, allows an acid-soluble chloride
content of 0.6 percent for reinforced concrete made with nor-
mal portland cement but only 0.002 percent chloride ion for
prestressed concrete. Both these codes are under revision.
Other codes have different limits, though the rationale for
these limits is not well established.
Corrosion of prestressing steel is generally of greater
concern than corrosion of conventional reinforcement be-
cause of the possibility that corrosion may cause a local re-
duction in cross section and failure of the steel. The high
stresses in the steel also render it more vulnerable to stress-
corrosion cracking and, where the loading is cyclic, to cor-
rosion fatigue. However, most examples of failure of pre-
stressing steel that have been reported3.24-3.26 have resulted
from macrocell corrosion reducing the load carrying area
of the steel. Nevertheless, because of the greater vulnera-
bility and the consequences of corrosion of prestressing
steel, chloride limits in the mix ingredients are lower than
for conventional concrete. Based on the present state of
knowledge, the following chloride limits in concrete used
in new construction, expressed as a percentage by weight of
portland cement, are recommended to minimize the risk of
chloride-induced corrosion.
Category Chloride limit for new construction
Acid-soluble Water-soluble
Test method ASTM C 1152 ASTM C 1218 Soxhlet*
Prestressed concrete 0.08 0.06
Reinforced concrete
0.10 0.08
in wet conditions
Reinforced concrete
0.20 0.15
in dry conditions
*
The Soxhlet Method of Test is described in the appendix to this report.
CORROSION OF METALS 222R-13
Normally concrete materials are tested for chloride con-
tent using either the acid-soluble test described in ASTM C
1152, Acid-Soluble Chloride in Mortar and Concrete, or
water-soluble test described in ASTM C 1218, Water-
Soluble Chloride in Mortar and Concrete. If the materials
meet the requirements given in either of the relevant col-
umns in the previous table they are acceptable. If they meet
neither of the relevant limits given in the table then they may
be tested using the Soxhlet test method. Some aggregates,
such as those discussed previously,3.16 contain a consider-
able amount of chloride that is sufficiently bound that it does
not initiate or contribute towards corrosion. The Soxhlet test
appears to measure only those chlorides that contribute to the
corrosion process, thus permitting the use of some aggre-
gates that would not be allowed if only the ASTM C 1152 or
ASTM C 1218 tests were used. If the materials fail the
Soxhlet test, then they are not suitable.
For prestressed and reinforced concrete that will be exposed
to chlorides in service, it is advisable to maintain the lowest pos-
sible chloride levels in the mix to maximize the service life of
the concrete before the critical chloride content is reached and a
high risk of corrosion develops. Consequently, chlorides should
not be intentionally added to the mix ingredients even if the
chloride content in the materials is less than the stated limits. In
many exposure conditions, such as highway and parking struc-
tures, marine environments, and industrial plants where chlo-
rides are present, additional protection against corrosion of
embedded steel is necessary.
Since moisture and oxygen are always necessary for elec-
trochemical corrosion, there are some exposure conditions
where the chloride levels may exceed the recommended val-
ues and corrosion will not occur. Concrete which is continu-
ously submerged in seawater rarely exhibits corrosion-
induced distress because there is insufficient oxygen present.
Similarly, where concrete is continuously dry, such as the in-
terior of a building, there is little risk of corrosion from chlo-
ride ions present in the hardened concrete. However, interior
locations that are wetted occasionally, such as kitchens or
laundry rooms or buildings constructed with lightweight ag-
gregate that is subsequently sealed (e.g., with tiles) before
the concrete dries out, are susceptible to corrosion damage.
Whereas the designer has little control over the change in use
of a building or the service environment, the chloride content
of the mix ingredients can be controlled. Estimates or judg-
ments of outdoor dry environments can be misleading.
Stratfull3.27 has reported the case of approximately 20 bridge
decks containing 2 percent calcium chloride built by the Cal-
ifornia Department of Transportation. The bridges were lo-
cated in an arid area where the annual rainfall was about 5
in., most of which fell at one time. Within 5 years of con-
struction, many were showing signs of corrosion-induced
spalling and most were removed from service within 10
years. For these reasons, the committee believes a conserva-
0.06 tive approach is necessary.
The maximum chloride limits suggested in this report dif-
0.08
fer from those suggested by ACI Committee 2013.2 and
0.15
those contained in the ACI Building Code. When making a
comparison between the figures, it should be noted that the
222R-14 ACI COMMITTEE REPORT
Fig. 3.1Effect of water-cement ratio on salt penetration3.5
Fig. 3.2E ffect of inadequate consolidation on salt
penetration3.5
Fig. 3.3Effect of water-cement ratio and depth of cover
on relative time to corrosion3.5
figures in this report refer to acid-soluble chlorides while the
other documents make reference to water-soluble chlorides.
As noted previously, Committee 222 has taken a more con-
servative approach because of the serious consequences of cor-
rosion, the conflicting data on corrosion threshold values,
and the difficulty of defining the service environment
throughout the life of a structure.
Various nonferrous metals and alloys will corrode in damp
or wet concrete. Surface attack of aluminum occurs in the
presence of alkali-hydroxide solutions. Anodizing provides
no protection.
Much more serious corrosion can occur if the concrete
contains chloride ions, particularly if there is electrical (metal-
to-metal) contact between the aluminum and steel reinforce-
ment, because a galvanic cell is created. Serious cracking or
splitting of concrete over aluminum conduits has been re-
ported.3.28,3.29 Certain organic protective coatings have been
recommended3.30 when aluminum must be used and it is im-
practicable to avoid contamination by chlorides. Other met-
als such as zinc, nickel, and cadmium, which have been
evaluated for use as coatings for reinforcing steel, are dis-
cussed elsewhere in this chapter. Additional information is
contained in Reference 3.31.
Where concrete will be exposed to chloride, the concrete
should be made with the lowest water-cement ratio consistent
with achieving maximum consolidation and density. The ef-
fects of water-cement ratio and degree of consolidation on the
rate of ingress of chloride ions are shown in Fig. 3.1 and 3.2.
Concrete with a water-cement ratio of 0.40 was found to re-
sist penetration by deicing salts significantly better than con-
cretes with water-cement ratios of 0.50 and 0.60. A low
water-cement ratio is not, however, sufficient to insure low
permeability. As shown in Fig. 3.2, a concrete with a water-
cement ratio of 0.32 but with poor consolidation is less resis-
tant to chloride ion penetration than a concrete with a water-
cement ratio of 0.60. The combined effect of water-cement
ratio and depth of cover is shown in Fig. 3.3, which illus-
trates the number of daily applications of salt before the
chloride content reached the critical value (0.20 percent
acid-soluble) at the various depths. Thus, 40 mm (1.5 in.) of
0.40 water-cement ratio concrete was sufficient to protect
embedded reinforcing steel against corrosion for 800 appli-
cations of salt. Equivalent protection was afforded by 70 mm
(2.75 in.) of concrete with a water-cement ratio of 0.50 or 90
mm (3.5 in.) of 0.60 water-cement ratio concrete. On the ba-
sis of this work, ACI 201.2R recommends a minimum of 50
mm (2 in.) cover for bridge decks if the water-cement ratio
is 0.40 and 65 mm (2.5 in.) if the water-cement ratio is 0.45.
Even greater cover, or the provision of additional corrosion
protection treatments, may be required in some environ-
ments. These recommendations can also be applied to other
reinforced concrete components exposed to chloride ions
and intermittent wetting and drying.
Even where the recommended cover is specified, con-
struction practices must insure that the specified cover is
achieved. Conversely, placing tolerances, the method of
construction, and the level of inspection should be consid-
ered in determining the specified cover.
The role of cracks in the corrosion of reinforcing steel is
controversial. Two schools of thought exist.3.32,3.33 One
viewpoint is that cracks reduce the service life of structures
by permitting more rapid penetration of carbonation and a
means of access of chloride ions, moisture, and oxygen to the
reinforcing steel. The cracks thus accelerate the onset of the
corrosion processes and, at the same time, provide space for
the deposition of the corrosion products. The other viewpoint
is that while cracks may accelerate the onset of corrosion, such
 CORROSION OF METALS
corrosion is localized. Since the chloride ions eventually
penetrate even uncracked concrete and initiate more wide-
spread corrosion of the steel, the result is that after a few
years service there is little difference between the amount of
corrosion in cracked and uncracked concrete.
The differing viewpoints can be partly explained by the
fact that the effect of cracks is a function of their origin,
width, intensity, and orientation. Where the crack is perpen-
dicular to the reinforcement, the corroded length of inter-
cepted bars is likely to be no more than three bar
diameters.3.33 Cracks that follow the line of a reinforcement
bar (as might be the case with a plastic shrinkage crack, for
example) are much more damaging because the corroded
length of bar is much greater and the resistance of the con-
crete to spalling is reduced. Studies have shown that cracks
less than about 0.3 mm (0.012 in.) wide have little influence
on the corrosion of reinforcing steel.3.8 Other investigations
have shown that there is no relationship between crack width
and corrosion.3.34-3.36 Furthermore, there is no direct rela-
tionship between surface crack width and the internal crack
width. Consequently, it has been suggested that the control
of surface crack widths in design codes is not the most ratio-
nal approach.3.37
For the purposes of design, it is useful to differentiate be-
tween controlled and uncontrolled cracks. Controlled cracks
are those which can be reasonably predicted from a knowl-
edge of section geometry and loading. For cracking perpen-
dicular to the main reinforcement, the necessary conditions
for crack control are that there be sufficient steel so that it re-
mains in the elastic state under all loading conditions, and
that at the time of cracking, the steel is bonded (i.e., cracking
must occur after the concrete has set).
Examples of uncontrolled cracking are cracks resulting
from plastic shrinkage, settlement, or an overload condition.
Uncontrolled cracks are frequently wide and usually cause
concern, particularly if they are active. However, they can-
not be dealt with by conventional design procedures, and
measures have to be taken to avoid their occurrence or, if
they are unavoidable, to induce them at places where they
are unimportant or can be conveniently dealt with, by sealing
for example.
3.3Methods of excluding external sources of
chloride ion from concrete
3.3.1 Waterproof membranesWaterproof membranes
have been used extensively to minimize the ingress of chlo-
ride ions into concrete. Since external sources of chloride
ions are waterborne, a barrier to water will also act as a bar-
rier to any dissolved chloride ions.
The requirements for the ideal waterproofing system are
straightforward;3.38 it should:
(a) Be easy to install,
(b) Have good bond to the substrate,
(c) Be compatible with all the components of the system
including the substrate, prime coat, adhesives, and overlay
(where used),
222R-15
(d) Maintain impermeability to chlorides and moisture un-
der service conditions, especially temperature extremes,
crack bridging, aging, and superimposed loads.
The number of types of products manufactured to satisfy
these requirements makes generalization difficult. Any sys-
tem of classification is arbitrary, though one of the most use-
ful is the distinction between the preformed sheet systems
and the liquid-applied materials.3.38 The preformed sheets
are manufactured under factory conditions but are often dif-
ficult to install, usually require adhesives, and are highly vul-
nerable to the quality of the workmanship at critical
locations in the installation. Although it is more difficult to
control the quality of the liquid-applied systems, they are
easier to apply and tend to be less expensive.
Given the different types and quality of available water-
proofing products, the differing degrees of workmanship,
and the wide variety of applications, it is not surprising that
laboratory3.39-3.41 and field3.14,3.42,3.43 evaluations of
membrane performance have also been variable and some-
times contradictory. Sheet systems generally perform better
than liquid-applied systems in laboratory screening tests be-
cause quality of workmanship is not a factor. Although there
has been little uniformity in both methods of test or accep-
tance criteria, permeability (usually determined by electrical
resistance measurements) has generally been adopted as the
most important criterion. However, some membranes do of-
fer substantial resistance to chloride and moisture intrusion,
even when pinholes or bubbles occur in the membrane.3.41
Field performance has been found to depend not only on the
type of waterproofing material used, but also on the quality of
workmanship, weather conditions at the time of installation, de-
sign details, and the service environment. Experience has
ranged from satisfactory3.43 to failures that have resulted in the
membrane having to be removed.3.44,3.45
Blistering, which affects both preformed sheets and liquid-
applied materials, is the single greatest problem encountered
in applying waterproofing membranes.3.46 It is caused by the
expansion of entrapped gases, solvents, and moisture in the
concrete after application of the membrane. The frequency
of blisters occurring is controlled by the porosity and mois-
ture content of the concrete3.47 and the atmospheric conditions.
Water or water vapor is not a necessary requirement for blis-
ter formation, but is often a contributing factor. Blisters may
also result from an increase in concrete temperature or a de-
crease in atmospheric pressure during or shortly after appli-
cation of membranes. The rapid expansion of vapors during
the application of hot-applied products sometimes causes
punctures (which are termed blowholes) in the membrane.
Membranes can be placed without blisters if the atmo-
spheric conditions are suitable during the curing period.
Once cured, the adhesion of the membrane to the concrete is
usually sufficient to resist blister formation. To insure good
adhesion, the concrete surface must be carefully prepared
and be dry and free from curing membranes, laitance, and
contaminants such as oil drippings. Sealing the concrete pri-
or to applying the membrane is possible, but rarely practi-
cal.3.48 Where the membrane is to be covered (for example,
with insulation or a protective layer), the risk of blister for-
222R-16 ACI COMMITTEE REPORT
mation can be reduced by minimizing the delay between
placement of the membrane and the overlay.
Venting layers have been used in Europe, but rarely in
North America, to prevent blister formation by allowing the
vapor pressures to disperse beneath the membrane. The dis-
advantages of using venting layers are that they require con-
trolled debonding of the membrane, leakage through the
membrane is not confined to the immediate area of the punc-
ture, and they increase cost.
3.3.2 Polymer impregnationPolymer impregnation con-
sists of filling some of the voids in hardened concrete with a
monomer and polymerizing in situ. Laboratory studies have
demonstrated that polymer impregnated concrete (PIC) is
strong, durable, and almost impermeable. The properties of
PIC are largely determined by the polymer loading in the
concrete. Maximum polymer loadings are achieved by dry-
ing the concrete to remove nearly all the evaporable water,
removing air by vacuum techniques, saturation with a monomer
under pressure, and polymerizing the monomer in the voids
of the concrete while simultaneously preventing evaporation
of the monomer.
In the initial laboratory studies on PIC, polymerization
was accomplished by gamma radiation.3.49 However, this is
not practical for use in the field. Consequently, chemical ini-
tiators, which decompose under the action of heat or a chem-
ical promoter, have been used exclusively in field
applications. Multifunctional monomers are often used to in-
crease the rate of polymerization.
The physical properties of PIC are determined by the ex-
tent to which the ideal processing conditions are compro-
mised. Since prolonged heating and vacuum saturation are
difficult to achieve, and increase processing costs substan-
tially, most field applications have been aimed toward pro-
ducing only a surface polymer impregnation, usually to a
depth of about 25 mm (1 in.). Such partially impregnated
slabs have been found to have good resistance to chloride
penetration in laboratory studies, but field applications have
not always been satisfactory.3.5,3.50
There have been a few full-scale applications of PIC to
protect reinforcing steel against corrosion and it must still be
considered largely an experimental process. Some of the dis-
advantages of PIC are that the monomers are expensive and
that the processing is lengthy and costly. The principal defi-
ciency identified to date has been the tendency of the con-
crete to crack during heat treatment.
3.3.3 Polymer concrete overlaysPolymer concrete over-
lays consisting of aggregate in a polymer binder have been
placed experimentally.
Most monomers have a low tolerance to moisture and low
temperatures; hence the substrate must be dry and in excess
of 4 C (40 F). Improper mixing of the two (or more) compo-
nents of the polymer has been a common source of problems
in the field. Aggregates must be dry so as not to inhibit the
polymerization reaction.
Workers should wear protective clothing when working
with epoxies and some other polymers because of the potential
for skin sensitization and dermatitis.3.51 Manufacturers rec-
ommendations for safe storage and handling of the chemi-
cals must be followed.
A bond coat of neat polymer is usually applied ahead of
the polymer concrete. Blistering, which is a common phe-
nomenon in membranes, has also caused problems in the ap-
plication of polymer concrete overlays. A number of
applications were reported in the 1960s.3.52,3.53 Many lasted
only a few years. More recently, experimental polymer over-
lays based on a polyester-styrene monomer have been
placed, using heavy-duty finishing equipment to compact
and finish the concrete.3.54
3.3.4 Portland cement concrete overlaysPortland ce-
ment concrete overlays for new reinforced concrete are ap-
plied as part of a two-stage construction process. The overlay
may be placed before the first-stage concrete has set or sev-
eral days later, in which case a bonding layer is used between
the two lifts of concrete. The advantage of the first alterna-
tive is that the overall time of construction is shortened and
costs minimized. In the second alternative, cover to the
reinforcing steel can be assured, and small construction tol-
erances achieved because dead load deflections from the
overlay are very small. No matter which sequence of con-
struction is employed, materials can be incorporated in the
overlay to provide superior properties, such as resistance to
salt penetration and wear and skid resistance, than possible us-
ing single stage construction.
Where the second stage concrete is placed after the first
stage has hardened, sand or water blasting is required to
remove laitance and to produce a clean, sound surface.
Resin curing compounds should not be used on the first-
stage construction because they are difficult to remove.
Etching with acid was once a common means of surface
preparation.3.55,3.56 but is now rarely used because of the
possibility of contaminating the concrete with chlorides
and the difficulty of disposing of the runoff.
Several different types of concrete have been used as con-
crete overlays including conventional concrete,3.57 concrete
containing steel fibers,3.57 and internally sealed con-
crete.3.57,3.60 However, two types of concrete, low-slump
and latex-modified concrete, each designed to offer maxi-
mum resistance to penetration by chloride ions, have been
used most frequently.
3.3.5 Low-slump concrete overlaysThe performance of
low-slump concrete is dependent solely on the use of con-
ventional materials and good quality workmanship. The
water-cement ratio is reduced to the minimum practical
(usually about 0.32) through the use of a high cement content
(over 470 kg/m3 or 800 lb/yd3) and a water content sufficient
to produce a slump less than 25 mm (1 in.). The concrete is
air-entrained and a water-reducing admixture or mild retard-
er is normally used. The use of such a high cement factor and
low workability mixture dictates the method of mixing, plac-
ing, and curing the concrete.
Following preparation of the first-stage concrete, a bond-
ing agent of either mortar or cement paste is brushed into the
base concrete just before the application of the overlay. The
base concrete is not normally prewetted. The overlay con-
crete is mixed on site, using either a stationary paddle mixer
 CORROSION OF METALS
or a mobile continuous mixer, because truck mixers are not
suited to producing either the quantity or consistency of con-
crete required. The concrete must be compacted and screed-
ed to the required surface profile using equipment specially
designed to handle stiff mixtures. Such machines are much
heavier and less flexible than conventional finishing ma-
chines and have considerable vibratory capacity. The perme-
ability of the concrete to chloride ions is controlled by its
degree of consolidation, which is often checked with a nucle-
ar density meter as concrete placement proceeds. Wet burlap
is placed on the concrete as soon as practicable without dam-
aging the overlay (usually within 20 min of placing), and the
wet curing is continued for at least 72 hr. Curing compounds
are not used, since not only is externally available water re-
quired for more complete hydration of the cement, but the
thin overlay is susceptible to shrinkage cracking and the wet
burlap provides a cooling effect by evaporation of the water.
Low-slump concrete was originally proposed as a repair
material for concrete pavements3.55 and was developed for
patches and overlays on bridges3.61-3.63 in the early 1960s.
More recently, concrete overlays have been used as a pro-
tection against reinforcing steel corrosion in new bridges. In
general, the performance of low-slump overlays has been
good.3.64-3.66 Local bond failures have been reported, but
these have been ascribed to inadequate surface preparation3.64
or premature drying of the grout.3.66 The overlays are suscep-
tible to cracking, especially on continuous structures, though
this is a characteristic of all rigid overlays.
3.3.6 Latex-modified concrete overlaysLatex-modified
concrete is conventional portland cement concrete with the
addition of a polymeric latex emulsion. The water of sus-
pension in the emulsion hydrates the cement and the poly-
mer provides supplementary binding properties to produce a
concrete having a low water-cement ratio, good durability,
good bonding characteristics, and a high degree of resistance
to penetration by chloride ions, all of which are desirable
properties in a concrete overlay.
The latex is a colloidal dispersion of synthetic rubber par-
ticles in water. The particles are stabilized to prevent coagu-
lation, and antifoaming agents are added to prevent
excessive air entrapment during mixing. Styrene-butadiene
latexes have been used most widely. The rate of addition of
the latex is approximately 15 percent latex solids by weight
of the cement.
The construction procedures for latex-modified concrete
are similar to those for low-slump concrete with minor mod-
ifications. The principal differences are:
1. The base concrete must be prewetted for at least 1 hr pri-
or to placing the overlay, because the water aids penetration
of the base and delays film formation of the latex.
2. A separate bonding agent is not always used, because
sometimes a portion of the concrete itself is brushed over the
surface of the base.
3. The mixing equipment must have a means of storing
and dispensing the latex.
4. The latex-modified concrete has a high slump so that
conventional finishing equipment can be used.
222R-17
5. Air entrainment of the concrete is believed not required
for resistance to freezing and thawing.
6. A combination of moist curing to hydrate the port-
land cement and air drying to develop the film forming
qualities of the latex are required. Typical curing times
are 24 hr wet curing, followed by 72 hr of dry curing. The
film-formation property of the latex is temperature sensi-
tive and film strengths develop slowly at temperatures be-
low 13 C (55 F). Curing periods at lower temperatures
may need to be extended and application at temperatures
less than 7 C (45 F) is not recommended.
Hot weather causes rapid drying of the latex-modified con-
crete, which makes finishing difficult and promotes shrinkage
cracking. Some contractors have placed overlays at night to
avoid these problems. The entrapment of excessive amounts
of air during mixing has also been a problem in the field. Most
specifications limit the total air content to 6.5 percent. Higher
air contents reduce the flexural, compressive, and bond
strengths of the overlay. Furthermore, the permeability to
chloride ions increases significantly at air contents greater
than about 9 percent. Where a texture is applied to the concrete
as, for example, grooves to impart good skid resistance, the
time of application of the texture is crucial. If applied too soon,
the edges of the grooves collapse because the concrete flows.
If the texturing operation is delayed until after the latex film
forms, the surface of the overlay tears and, since the film does
not reform, cracking often results.
High material costs and the superior performance of latex-
modified concrete in chloride penetration tests have led to
latex-modified concrete overlays being thinner than most
low-slump concrete overlays. Typical thicknesses are 40 and
50 mm (1.5 and 2 in.).
Although latex-modified overlays were first used in
1957,3.67 the majority of installations were placed after
1975. Performance has been generally satisfactory, though
extensive cracking and some debonding have been report-
ed,3.68 especially in overlays 20 mm (0.75 in.) thick that were
not applied at the time of the original deck construction. The
most serious deficiency reported has been the widespread oc-
currence of shrinkage cracking in the overlays. Many of these
cracks have been found not to extend through the overlay and it
is uncertain whether this will impair long-term performance.
3.4Methods of protecting reinforcing steel from
chloride ion
The susceptibility to corrosion of mild steel reinforcement
in common use is not thought to be significantly affected by
its composition, grade, or the level of stress.3.69 Consequent-
ly, to prevent corrosion of the reinforcing steel in a corrosive
environment, either the reinforcement must be made of a
noncorrosive material, or conventional reinforcing steel
must be coated to isolate the steel from contact with oxygen,
moisture, and chlorides.
3.4.1 Noncorrosive steelsNatural weathering steels
commonly used for structural steelwork do not perform well
in concrete containing moisture and chloride3.2 and are not
suitable for reinforcement. Stainless steel reinforcement has
been used in special applications, especially as hardware for
222R-18 ACI COMMITTEE REPORT
attaching panels in precast concrete construction, but is
much too expensive to replace mild-steel reinforcement in
most applications. Stainless-steel-clad bars have been evalu-
ated in the FHWA time-to-corrosion studies, and found to re-
duce the frequency of corrosion-induced cracking compared
to black steel in the test slabs, but did not prevent it. Howev-
er, it was not determined whether the cracking was the result
of corrosion of the stainless steel or corrosion of the basis
steel at flaws in the cladding.
3.4.2 CoatingsMetallic coatings for steel reinforcement
fall into two categories, sacrificial and noble or nonsacrifi-
cial. In general, metals with a more negative corrosion po-
tential (less noble) than steel, such as zinc and cadmium,
give sacrificial protection to the steel. If the coating is dam-
aged, a galvanic couple is formed in which the coating is the
anode. Noble coatings such as copper and nickel protect the
steel only as long as the coating is unbroken, since any ex-
posed steel is anodic to the coating. Even where steel is not
exposed, macrocell corrosion of the coating may occur in
concrete through a mechanism similar to the corrosion of un-
coated steel.
Nickel,3.70,3.71 cadmium,3.72 and zinc3.70,3.73,3.74 have all
been shown to be capable of delaying, and in some cases pre-
venting, the corrosion of reinforcing steel in concrete, but
only zinc-coated (galvanized) bars are commonly available.
Results of the performance of galvanized bars have been
conflicting, in some cases extending the time-to-cracking of
laboratory specimens,3.75 in others reducing it3.76 and some-
times giving mixed results.3.77 It is known that the zinc will
corrode in concrete3.71,3.78 and that pitting can occur under
conditions of nonuniform exposure in the presence of high
chloride concentrations.3.79
Field studies of galvanized bars in service for many years in
either a marine environment or exposed to deicing salts have
failed to show any deficiencies in the concrete.3.74 However, in
these studies, chloride ion concentrations at the level of the re-
inforcing steel were low, such that the effectiveness could not
be established conclusively. Marine studies3.80 and accelerated
field studies3.81 have shown that galvanizing will delay the on-
set of delaminations and spalls but will not prevent them. In
general, it appears that only a slight increase in life will be ob-
tained in severe chloride environments.3.82 When galvanized
bars are used, all bars and hardware in the structure should be
coated with zinc to prevent galvanic coupling between coated
and uncoated steel.3.82
Numerous nonmetallic coatings for steel reinforcement
have been evaluated,3.83-3.86 but only fusion-bonded epoxy
powder coatings are produced commercially and widely
used. The epoxy coating isolates the steel from contact with
oxygen, moisture, and chloride.
The process of coating the reinforcing steel with the epoxy
consists of electrostatically applying finely divided epoxy
powder to thoroughly cleaned and heated bars. Many plants
operate a continuous production line and many have been
constructed specifically for coating reinforcing steel. Integ-
rity of the coating is monitored by a holiday detector in-
stalled directly on the production line. The use of epoxy-
coated reinforcing steel has increased substantially since it
was first used in 1973.
The chief difficulty in using epoxy-coated bars has been
preventing damage to the coating in transportation and han-
dling. Cracking of the coating has also been observed during
fabrication where there has been inadequate cleaning of the
bar prior to coating or the thickness of the coating has been
outside specified tolerances. Padded bundling bands, fre-
quent supports, and nonmetallic slings are required to pre-
vent damage during transportation. Coated tie wires and bar
supports are needed to prevent damage during placing. Ac-
celerated time-to-corrosion studies have shown that nicks
and cuts in the coating do not cause rapid corrosion of the ex-
posed steel and subsequent distress in the concrete.3.87 It
should be noted, however, that the damaged bars were not
electrically connected to uncoated steel in the early acceler-
ated tests. Subsequent tests3.88 showed that even in the case
of electrical coupling to large amounts of uncoated steel, the
performance of damaged and nonspecification bars was
good, but not as good as when all the steel was coated.
Consequently, for long life in severe chloride environments,
consideration should be given to coating all the reinforcing
steel. If only some of the steel is coated, precautions should
be taken to assure that the coated bars are not electrically
coupled to large quantities of uncoated steel. A damaged
coating can be repaired using a two-component liquid epoxy,
but it is more satisfactory to adopt practices that prevent
damage to the coating and limit touch-up only to bars where
the damage exceeds approximately 2 percent of the area of
the bar.
Studies have demonstrated that epoxy-coated, deformed
reinforcing bars embedded in concrete can have bond
strengths and creep behavior equivalent to those of uncoated
bars.3.89,3.90 Another study3.91 reported that epoxy-coated
reinforcing has less slip resistance than normal mill scale re-
inforcing, although, for the particular specimens tested, the
epoxy-coated bars attained stress levels compatible with
ACI development requirements.
3.5Corrosion control methods
3.5.1 Chemical inhibitorsA corrosion inhibitor is an ad-
mixture to the concrete used to prevent the corrosion of em-
bedded metal. The mechanism of inhibition is complex and
there is no general theory applicable to all situations.
The effectiveness of numerous chemicals as corrosion in-
hibitors for steel in concrete3.69,3.92-3.94 has been studied.
The compound groups investigated have been primarily
chromates, phosphates, hypophosphites, alkalies, nitrites,
and fluorides. Some of these chemicals have been suggested
as being effective; others have produced conflicting results
in laboratory screening tests.
Many inhibitors that appear to be chemically effective pro-
duce adverse effects on the physical properties of the concrete,
such as a significant reduction in compressive strength. More
recently, calcium nitrite has been reported to be an effective
corrosion inhibitor3.95 and studies are continuing.3.88
 CORROSION OF METALS
Admixtures used to prevent corrosion of the steel by wa-
terproofing the concrete, notably silicones, have been found
to be ineffective.3.92
3.5.2 Cathodic protectio nAlthough cathodic protection
is a viable method of protecting reinforcing steel against cor-
rosion in new construction, most installations to date have
been to arrest corrosion in existing structures. Consequently,
the principles and performance of cathodic protection sys-
tems are described in Chapter 5.
It should be noted, however, that the reinforcement in
many offshore structures is connected to the cathodic protection
system used on the exposed steel. This results in protection
of the reinforcement and current densities of 0.5 to 1.0
mA/m2 (0.05 to 0.1 mA/ft2) have been reported.3.96 Thus ca-
thodic protection of the reinforcement, though unintentional,
has been applied in several of the largest offshore structures.
3.6References
3.1. Durability of Concrete Bridge Decks, NCHRP Synthesis No. 57,
Transportation Research Board Washington, D.C., 1979, 60 pp.
3.2. ACI Committee 201, Guide to Durable Concrete (ACI 201.2R77)
(Reaffirmed 1982), American Concrete Institute, Detroit, 1977, 37 pp.
3.3. Beaton, J. L., and Stratfull, R. F., Environmental Influence on Cor-
rosion of Reinforcing in Concrete Bridge Substructures, Highway
Research Record No. 14, Highway Research Board, 1963, pp. 60-78.
3.4. Ost, Borje, and Monfore, G. E., Penetration of Chloride into Con-
crete, Journal, PCA Research and Development Laboratories, V. 8, No. 1,
Jan. 1966, pp. 46-52.
3.5. Clear, K. C., Time-to-Corrosion of Reinforcing Steel in Concrete
Slabs, V. 3: Performance after 830 Daily Salt Applications, Report
No. FHWA-RD-76-70, Federal Highway Administration, Washington,
D.C., 1976, 64 pp.
3.6. Stark, David, Studies of the Relationships between Crack Patterns,
Cover over Reinforcing Steel and the Development of Surface Spalls in
Bridge Decks, Special Report No. 116, Highway Research Board, Wash-
ington, D.C., 1971, pp. 13-21. Also, Resea rch and D evelopment Bulletin
No. RD020E, Portland Cement Association.
3.7. Cornet, I., Protection with Mortar Coatings, Materials Protection,
V. 6, No. 3, 1967, pp. 56-58.
3.8. Atimay, E., and Ferguson, P. M., Early Chloride Corrosion of Rein-
forced ConcreteA Test Report, Materials Performance, V. 13, No. 12,
1974, pp. 18-21.
3.9. Gjrv, O. E.; Vennesland, .; and El-Busaidy, A. H. S., Diffusion of
Dissolved Oxygen through Concrete, Paper No. 17, NACE Corrosion 76,
National Association of Corrosion Engineers, Houston, Mar. 1976, 13 pp.
3.10. Lewis, D. A., Some Aspects of the Corrosion of Steel in Con-
crete, Proceedings, 1st International Congress on Metallic Corrosion, But-
terworths, London, 1962, pp. 547-552.
3.11. Gouda, V. K., Corrosion and Corrosion Inhibition of Reinforcing
Steel I: Immersed in Alkaline Solutions, British Corrosion Journal (Lon-
don), V. 5, 1970, pp. 198-203.
3.12. Arup. H., Recent Progress Concerning Electrochemistry and Cor-
rosion of Steel in Concrete, ARBEM Symposium, Paris, Oct. 1982.
3.13. Stratfull, R. F.; Jurkovich, W. J.; and Spellman. D. L., Corrosion
Testing of Bridge Decks,Transportation Research Record No. 539, Trans-
portation Research Board, 1975, pp. 50-59.
3.14. Chamberlin, William P.; Irwin, Richard J.; and Amsler, Duane E.,
Waterproofing Membranes for Bridge Deck Rehabilitation, Resea rch
Report No. 52 (FHWA-NY-77-59-1), New York State Department of
Transportation/Federal Highway Administration, Washington, D.C., 1977,
43 pp.
3.15. Hime, William D., and Erlin, Bernard, Chloride Free Concrete,
ACI JOURNAL, Proceedings V. 74, No. 10, Oct. 1977, p. N7.
3.16. Rogers. C., and Woda, G., The Chloride Ion Content of Concrete
Aggregate from Southern Ontario, Report No. EM-17, Ontario Ministry
of Transportation and Communications, Downsview, 1977.
3.17. Impurities in Aggregates for Concrete, Advisory Not eNo. 18,
Cement and Concrete Association, London, 1970, 8 pp.
222R-19
3.18. Roberts, M. H., Effect of Calcium Chloride on the Durability of
Pretensioned Wire in Prestressed Concrete. Magazine of Concrete
Resea rch (London), V. 14, No. 42, Nov. 1962, pp. 143-154.
3.19. Haynes, Harvey H., Permeability of Concrete in Sea Water, Per-
formance of Concrete in Marine Environment, SP-65, American Concrete
Institute, Detroit. 1980, pp. 21-38.
3.20. Locke, C. E., and Siman, A., Electrochemistry of Reinforcing
Steel in Salt-Contaminated Concrete, Corrosion of Reinforcing Steel in
Concrete, STP-713, ASTM, Philadelphia, 1980, pp. 3-16.
3.21. Browne, Roger D., Mechanisms of Corrosion of Steel in Concrete
in Relation to Design, Inspection, and Repair of Offshore and Coastal
Structures, Performance of Concrete in Marine Environment, SP-65,
American Concrete Institute, Detroit, 1980, pp. 169-204.
3.22. Diamond, S., and Lopez-Flores, F., Fate of Calcium Chloride Dis-
solved in Concrete Mix Water, Journal, American Ceramic Society, V. 64,
No. 11, Nov. 1981, pp. C 162-164.
3.23. The Role of Calcium Chloride in Concrete, Concrete Construction,
V. 21, No. 2, Feb. 1976, pp. 57-61.
3.24. Cornet, I., Corrosion of Prestressed Concrete Tanks, Materials
Protection, V. 3, No. 1, Jan. 1964, pp. 9-100.
3.25. Peterson, Carl A., Survey of Parking Structure Deterioration and
Distress, Conc rete International: Design & Construction, V. 2, No. 3,
Mar. 1980. pp. 53-61.
3.26. Monfore, G. E., and Verbeck, G. J., Corrosion of Prestressed Wire in
Concrete, ACI JOURNAL, Proceedings V. 57, No. 5, Nov. 1960, pp. 491-516.
3.27.A Manual for the Corrosion Control of Bridge Decks, Contract
No. DTFH-61-C-00016, Stratfull, R. F., ed., U.S. Department of Trans-
portation, Washington, D.C.
3.28. Conduit in Concrete, Engineering Journal (Montreal), V. 38,
No. 10, 1955, pp. 1357-1362.
3.29. Spalled Concrete Traced to Conduit, Engineering News-Record,
V. 172, No. 11, Mar. 12, 1964, pp. 28-29.
3.30. McGeary, Frank L., Performance of Aluminum in Concrete Con-
taining Chlorides, ACI JOURNAL, Proceeding s V. 63, No. 2, Feb, 1966. pp.
247-266.
3.31. Erlin, B., and Woods, H., Corrosion of Embedded Materials Other
than Reinforcing Steel, Significance of Tests and Properties of Concrete
and Concrete-Making Materials, STP-169B, ASTM, Philadelphia, 1978, s
pp. 300-319.
3.32. Manning, D. G., Corrosion Resistant Design of Concrete Struc-
tures, Proceedings, Canadian Structural Concrete Conference, University
of Toronto, 1981, pp. 199-223.
3.33. Beeby, A. W., Corrosion of Reinforcing Steel in Concrete in Its
Relation to Cracking,The Structural Engineer (London), V. 56A, No. 3,
1978, pp. 77-81.
3.34. Tremper, Bailey, The Corrosion of Reinforcing Steel in Cracked Con-
crete, ACI JOURNAL, Proceedings V. 43, No. 10, June 1947, pp. 1137-1144.
3.35. Martin, H., and Schiessel, P., The Influence of Cracks on the Cor-
rosion of Steel in Concrete, Preliminary Report, RILEM International
Symposium on the Durability of Concrete, Prague, 1969, V. 2.
3.36. Raphael, M., and Shalon, R., A Study of the Influence of Climate
on Corrosion of Reinforcement, Proceedings, RILEM Symposium on
Concrete and Reinforced Concrete in Hot Countries, Building Research
Station, Haifa, 1971, pp. 77-96.
3.37. Beeby, A. W., Concrete in the OceansCracking and Corrosion,
Technical Report No. 1, CIRIA/UEG, Construction Industry Research and
Information Association/Department of Energy, London, 1978.
3.38. Manning, David G., and Ryell, John, Durable Bridge Decks,
Report No. RR203, Ontario Ministry of Transportation and Communications,
Downsview, 1976, 67 pp.
3.39. Boulware, R. L., and Elliott, A. L., California Seals Salt-Damaged
Bridge Decks, Civil Engineering-ASCE, V. 41, No. 10, Oct. 1971, pp. 42-44.
3.40. Van Til, C. J.; Carr, B. J.; and Vallerga, B. A., Waterproof Mem-
branes for Protection of Concrete Bridge Decks: Laboratory Phase,
NCHRP Report No. 165, Transportation Research Board, Washington,
D.C., 1976, 70 pp.
3.41. Frascoia, R. I., Vermonts Experience with Bridge Deck Protec-
tive Systems, Chloride Corrosion of Steel in Concrete, STP-629, ASTM,
Philadelphia, 1977, pp. 69-81.
3.42. Spellman, D. L., and Stratfull, R. F., Bridge Deck Membranes
Evaluation and Use in California, Report No. CA-DOT-TL-5116-9 73-38,
California Department of Transportation, Sacramento, 1973.
222R-20 ACI COMMITTEE REPORT
3.43. Frascoia, R. I., Evaluation of Bridge Deck Membrane Systems
and Membrane Evaluation Procedures, Report No. 77-2, Vermont Depart-
ment of Highways, Montpelier, 1977.
3.44. Corkill, J. T., A Field Study of the Performance of Bridge Deck
Waterproofing Systems in Ontario, Proceedings, 1975 Annual Conference,
Roads and Transportation Association of Canada, 1975, V. 2, pp. 79-100.
3.45. Membrane Waterproofing for Bridge Decks, Final Report, Ore-
gon Department of Transportation, Salem, 1977.
3.46. MacDonald, M. D., Waterproofing Concrete Bridge Decks: Mate-
rials and Methods, TRRL Report No. LR636, Transport and Road
Research Laboratory, Crowthorne, Berkshire, 1974, 32 pp.
3.47. Legvold, T. L., Bridge Deck Waterproofing Membrane Study,
Report No. R-262, Iowa State Highway Commission, Ames, 1974.
3.48. Meader, A. L., Jr.; Schmitz, C. G.; and Henry, J. E., Development
of a Cold Poured Bridge Deck Membrane System, Chloride Corrosion of
Steel in Concrete, STP-629, ASTM, Philadelphia, 1977, pp. 164-177.
3.49. Steinberg, M., et al., Concrete-Polymer MaterialsFirst Topical
Report, BNL 50134 (T-509) and USBR General Report No. 41, Brookhaven
National Laboratory/U.S. Bureau of Reclamation, Denver, 1968.
3.50. Smoak, W. G., Development and Field Evaluation of a Technique
for Polymer Impregnation of New Concrete Bridge Deck Surfaces, Report
No. FHWA-RD-76-95, Federal Highway Administration, Washington,
D.C., 1976.
3.51. Tremper, Bailey, Repair of Damaged Concrete with Epoxy Res-
ins, ACI JOURNAL, Proceedings V. 57, No. 2, Aug. 1960, pp. 173-182.
3.52. McConnell, W. R., Epoxy Surface Treatments for Portland
Cement Concrete Pavements, Epoxies with Concrete, SP-21, American
Concrete Institute, Detroit, 1968, pp. 9-17.
3.53. Santucci, L. E., Polyester Overlays for Portland Cement Con-
crete Surfaces, Highway Research Record No. 14, Highway Research
Board, 1963, pp. 44-56.
3.54. Jenkins, J. C.; Beecroft, G. W.; and Quinn, W. J., Polymer Con-
crete Overlays: Interim Users Manual, Report No. FHWA-TS-78-218,
Federal Highway Administration, Washington, D.C., 1977.
3.55. Felt, Earl J., Resurfacing and Patching Concrete Pavements with
Bonded Concrete, Proceedings, Highway Research Board, V. 35, 1956,
pp. 444-469.
3.56. Westall, William G., Bonded Resurfacing and Repairs of Con-
crete Pavements, Bulletin No. 260, Highway Research Board, Washing-
ton, D.C., 1960, pp. 14-24.
3.57. McKeel, W. T., Jr., and Tyson, S. S., Two-Course Bonded Con-
struction and Overlays, ACI JOURNAL, Proceedings V. 72, No. 12, Dec.
1975, pp. 708-713.
3.58. Tyson, S. S., Two-Course Bonded Concrete Bridge Deck Con-
structionInterim Report No. 2: Concrete Properties and Deck Condi-
tion Prior to Opening to Traffic, Report No. VHTRC-R3, Virginia
Highway and Transportation Research Council, Charlottesville, 1976.
3.59. Jenkins, G. H., and Butler, J. M., Internally Sealed Concrete,
Report No. FHWA-RD-75-20, Federal Highway Administration, Wash-
ington, D.C., 1975, 106 pp.
3.60. Clear, K. C., and Forster, S. W., Internally Sealed Concrete:
Material Characterization and Heat Treating Studies, Report No. FHWA-
RD-77-16, Federal Highway Administration, Washington, D.C., 1977, 73
pp.
3.61. Hilton, N., A Two-Inch Bonded Concrete Overlay for the Port
Mann Bridge, Engineering Journal (Montreal), May 1964, pp. 39-44.
3.62. OConnor, E. J., Iowa Method of Partial-Depth Portland Cement
Resurfacing of Bridge Decks, Chloride Corrosion of Steel in Concrete,
STP-629, ASTM, Philadelphia, 1977, pp. 116-123.
3.63. Bukovatz, J. E.; Crumpton, C. F.; and Worley, H. E., Bridge
Deck Deterioration Study, Final Report, State Highway Commission of
Kansas, Topeka, 1973.
3.64. Manning, D. G., and Owens, M. J., Ontarios Experience with
Concrete Overlays for Bridge Decks, RTAC Forum (Ottawa), V. 2, No.
1, 1979, pp. 31-37.
3.65. Bergen, J. V., and Brown, B. C., An Evaluation of Concrete
Bridge Deck Resurfacing in Iowa, Special Report, Iowa State Highway
Commission, Ames, 1975.
3.66. Tracy, R. G., Bridge Deck Deterioration and Restoration Inves-
tigation No. 639, Interim Report, Minnesota Department of Transpor-
tation, St. Paul, Dec. 1976.
3.67. Cardone, S. M.; Brown, M. G.; and Hill, A. A., Latex-Modified
Mortar in the Restoration of Bridge Structures, Bulletin No. 260, High-
way Research Board, Washington, D.C., 1960, pp. 1-13.
3.68. Bishara, A. G., Latex Modified Concrete Bridge Deck Overlays,
Field Performance Analysis, Report No. ODOT 2895, Ohio Department
of Transportation, Columbus, 1978.
3.69. Verbeck, George J., Mechanisms of Corrosion of Steel in Con-
crete, Corrosion of Metals in Concrete, SP-49, American Concrete Insti-
tute, Detroit, 1975, pp. 21-38.
3.70. Tripler, Arch B.; White, Earl L.; Haynie, F. H.; and Boyd, W. K.,
Methods of Reducing Corrosion of Reinforcing Steel, NCHRP Report
No. 23, Highway Research Board, Washington, D.C., 1966, 22 pp.
3.71. Baker, E. A.; Money, K. L.; and Sanborn, C. B., Marine Corro-
sion Behavior of Bare and Metallic-Coated Reinforcing Rods in Con-
crete, Chloride Corrosion of Steel in Concrete, STP-692, ASTM,
Philadelphia, 1977, pp. 30-50.
3.72. Bird, C. E., and Strauss, F. J., Metallic Coating for Reinforcing
Steel, Materials Protection, V. 6, July 1967, pp. 48-52.
3.73. Cornet, I.; Ishikawa, T.; and Bresler, B., The Mechanism of
Steel Corrosion in Concrete Structures, Materials Protection, V. 7, No.
3, Mar. 1968, pp. 44-47.
3.74. Cook, A. R., and Radtke, S. F., Recent Research on Galvanized
Steel for Reinforcement of Concrete, Chloride Corrosion of Steel in
Concrete, STP-629, ASTM, Philadelphia, 1977, pp. 51-60.
3.75. Cornet, I., and Bresler, B., Corrosion of Steel and Galvanized
Steel in Concrete, Materials Protection, V. 5, Apr. 1966, pp. 69-72.
3.76. Griffin, Donald F., Effectiveness of Zinc Coating on Reinforcing
Steel in Concrete Exposed to a Marine Environment, Technical Note No.
N-1032, Naval Civil Engineering Laboratory, Port Hueneme, 1969, 42
pp.
3.77. Hill, George A.; Spellman, D. L.; and Stratfull, R. F., Labora-
tory Corrosion Tests of Galvanized Steel in Concrete, Transportation
Research Record No. 604, Transportation Research Board, 1976, pp. 25-30.
3.78. Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous
Solutions, translated from the French by J. A. Franklin, Pergamon Press,
New York, 1966, pp. 409-410.
3.79. Unz, M., Performance of Galvanized Reinforcement in Calcium
Hydroxide Solution, ACI JOURNAL, Proceedings V. 75, No. 3, Mar.
1978, pp. 91-99.
3.80. Sopler, B., Corrosion of Reinforcement in ConcretePart
Series D, Report No. FCB 73-4, Norwegian Institute of Technology,
University of Trondheim, 1973.
3.81. Arnold, C. J., Galvanized Steel Reinforced Concrete Bridge
Decks: Progress Report, Report No. FHWA-MI-78-R1033, Federal
Highway Administration, Washington, D.C., 1976.
3.82. Clear, K. C., Time-to-Corrosion of Reinforcing Steel in Con-
crete Slabs, V. 4: Galvanized Reinforcing Steel, Report No. FHWA-RD-
82-028, Federal Highway Administration, Washington, D.C., 1981.
3.83. Castleberry, J. R., Corrosion Prevention for Concrete and Metal
Reinforcing in the Construction Industry, Materials Protection, V. 7, Mar.
1968, pp. 21-28.
3.84. Clifton, J. R.; Beeghley, H. F.; and Mathey, R. G., Nonmetallic
Coatings for Concrete Reinforcing Bars, Report No. FHWA-RD-74-18,
Federal Highway Administration, Washington, D.C., 1974, 87 pp.
3.85. Backstrom, T. E., Use of Coatings on Steel Embedded in Con-
crete, Corrosion of Metals in Concrete, SP-49, American Concrete Insti-
tute, Detroit, 1975, pp. 103-113.
3.86. Pike, R. G.; Hay, R. E.; Clifton, J. R.; Beeghly, H. F.; and
Mathey, R. G., Nonmetallic Protective Coatings for Concrete Reinforc-
ing Steel, Transportation Research Record No. 500, Transportation
Research Board, 1974, pp. 36-44.
3.87. Clear, K. C., FCP Annual Progress ReportYear Ending Sept.
30, 1978, Project 4B, Federal Highway Administration, Washington,
D.C., 1978.
3.88. Virmani, Y. P.; Clear, K. C.; and Pasko, T. J., Jr., Time-to-Corrosion
of Reinforcing Steel in Concrete Slabs, V. 5: Calcium Nitrite Admixture
or Epoxy-Coated Reinforcing Bars as Corrosion Protection Systems,
Report No. FHWA-RD-83-012, Federal Highway Administration, Wash-
ington, D.C., 1983, 71 pp.
3.89. Mathey, Robert G., and Clifton, James R., Bond of Coated Rein-
forcing Bars in Concrete, Proceedings, ASCE, V. 102, ST1, Jan. 1976,
pp. 215-229.
 CORROSION OF METALS
3.90. Clifton, James R.; Mathey, Robert G.; and Anderson, Erik D.,
Creep of Coated Reinforcing Bars in Concrete, Proceedings, ASCE,
V. 105, ST10, Oct. 1979, pp. 1935-1947.
3.91. Johnston, D. W., and Zia, P., Bond Characteristics of Epoxy
Coated Reinforcing Bars, Report No. FHWA-NC-82-002, Federal High-
way Administration, Washington, D.C., 1982.
3.92. Clear, K. C., and Hay, R. E., Time-to-Corrosion of Reinforcing
Steel in Concrete Slabs, V. 1: Effect of Mix Design and Construction
Parameters, Report No. FHWA-RD-73-32, Federal Highway Adminis-
tration, Washington, D.C., 1973, 103 pp.
3.93. Craig, R. J., and Wood, L. E., Effectiveness of Corrosion Inhibi-
tors and Their Influence on the Physical Properties of Portland Cement
Mortars, Highway Research Record No. 328, Highway Research Board,
1970, pp. 77-88.
3.94. Griffin, D. F., Corrosion Inhibitors for Reinforced Concrete,
Corrosion of Metals in Concrete, SP-49, American Concrete Institute,
Detroit, 1975, pp. 95-102.
3.95. Rosenberg, A. M.; Gaidis, J. M.; Kossivas, T. G.; and Previte, R.
W., A Corrosion Inhibitor Formulated with Calcium Nitrite for Use in
Reinforced Concrete, Chloride Corrosion of Steel in Concrete, STP-629,
ASTM, Philadelphia, 1977, pp. 89-99.
3.96. Fidjestol, P.; Askheim, N. E.; and Roland, B., Location of
Potential Corrosion Areas in Concrete Marine Structures, Concrete in
the Oceans, Phase II, Plc, Final Report.
CHAPTER 4PROCEDURES FOR IDENTIFYING
CORROSIVE ENVIRONMENTS AND ACTIVE
CORROSION IN CONCRETE
4.1Introduction
There are many approaches available for identifying cor-
rosive environments and active corrosion of steel in con-
crete. Generally, a visual inspection of the structure and the
environment in which it serves is the first step in any exam-
ination. Visual inspections may range from a simple curso-
ry examination to those that are very detailed, wherein all
cracks and other visual evidences of physical deterioration
are plotted on scaled diagrams of the structure and specific
information is gathered on environmental exposure. This
type of inspection may also include taking a limited num-
ber of cores to be examined visually for evidence of deteri-
oration due to corrosion. The detailed type of visual
inspection is time-consuming and costly, and generally
only useful for research studies of structure performance. It
does not develop the type of information that is required for
scheduling of maintenance.
There are several techniques and tools that can be used to
more specifically delineate areas of deteriorated concrete
and areas of potential or active corrosion of steel.4.1-4.6 How-
ever, an inspection program can become expensive if it is
necessary to survey more than a nominal number of struc-
tures. For purposes of planning a maintenance or rehabilitation
program, techniques such as suggested by Stratfull, Jurkov-
ich, and Spellman,4,5 or Manning,4.7,4.8 should be used to
minimize expenses. These techniques have been derived
from experience and include judicious use of visual exami-
nations together with collection of specific information on
the extent of physical deterioration, active corrosion, chlo-
ride ion contamination, and depth of cover over reinforcing
steel. The references noted previously should be studied for
more detailed information on these techniques.
222R-21
4.2Methods of evaluation
Certain tools are used for identifying and quantifying cor-
rosive environments, extent of active corrosion, and concrete
deterioration.4.9 Following is a brief description of these
tools, together with their purpose and limitations.
4.2.1 PachometerThis tool is used to locate reinforcing
steel embedded in concrete, and to determine the amount of
cover over the steel. It is battery-operated and contains a transis-
torized oscillator that establishes an elecromagnetic field in a
search coil. In the presence of a steel reinforcing bar, the mag-
netic field is distorted. By calibration, the distance from the bar
may be read from the meter dial. Two styles of equipment are
available. The first is a handheld device4.10 and the second is an
automated device4.11 mounted on wheels. Automatic data re-
cording equipment is added to faciliate the speed with which a
survey can be conducted.
The knowledge of cover depth is essential if it is desired to
obtain samples of the concrete at the level of the reinforcing
steel for chloride ion analysis. It is also useful in determining
the potential for corrosion and subsequent concrete deterio-
ration since it has been well established that structures in
corrosive environments with inadequate concrete cover are
subject to early deterioration.
4.2.2 Delamination detectorsThere are many tools that
may be used to detect delaminations or subsurface fracture
planes parallel to the concrete surface. These devices range
from simple chain drags or lightweight hammers to more so-
phisticated devices such as the Delamtect.4.3,4.9 Almost any
sounding device can be used to locate hollow areas or delam-
inations caused by corrosion of the reinforcing steel. The au-
tomated Delamtect is useful for surveying large numbers of
bridge decks or other horizontal surfaces such as parking ga-
rage floors if a record of the area of delamination is desired.
However, the simpler chain drag is adequate for locating
delaminated areas during repair operations.
4.2.3 Electrical potential measuring equipmentThis
equipment, adapted for use with reinforced concrete by
Stratfull,4,2 consists of a copper-copper sulfate half-cell
(CSE), a high-impedance voltmeter, and lead wires to con-
nect the half-cell and the reinforcing steel to the voltmeter.4.9
The equipment is used to determine if the reinforcing steel is
in a passive or active state relative to active corrosion.4.2 De-
tails of the test method are given in ASTM C 876.
The accuracy of the method is good when proper concrete
prewetting is used. The significance of the measurements
can be summarized as follows for structures exposed to air:
Potentials more negative than -0.35 V CSE: Very high
probability of the presence of active corrosion.
Potentials more positive than -0.20 V CSE: Very high
probability of no corrosion.
Potentials in the range of -0.20 V to -0.35 V CSE:
Uncertainty as to whether or not corrosion is present.
It is in the uncertain range that potential differences across
a structure, and other detection methods, must often be relied
on to deduce the probable condition. In Federal Highway
Administration studies, potential differences rarely exceed
100 mV when corrosion was not active, or was active only at
extremely low rates. In reinforced concrete undergoing
222R-22 ACI COMMITTEE REPORT
significant corrosion, the potential differences were com-
monly over 200 mV.4.12,4.13
It should also be noted that a potential value more negative
than -0.35 V CSE on actively corroding field structures (with
many electrically interconnected anodes and cathodes) gen-
erally provides information on only the presence or absence
of corrosion and not on corrosion rate. It is the potential dif-
ference between the anode and cathode that most closely re-
lates to corrosion rate rather than simply the magnitude of
the anode potential. A common example in which highly
negative potentials are not indicative of high corrosion rates
is a totally water-saturated reinforced concrete structure. In
such a structure, oxygen availability to the noncorroding
steel is severely restricted and cathodic polarization results.
This drives both the anode and the cathode potentials to very
negative values, and yet corrosion rate is most often quite
low. By careful measurement of potentials on a closely
spaced grid pattern, high versus low corrosion rate situations
can be identified by studying potential differences. Large po-
tential differences generally indicate high corrosion rates.
4.2.4 Chloride analysisMeasurements of chloride ion
concentration at the level of reinforcing steel in concrete are
made to determine if any environment exists that is conducive
to corrosion of the steel. Two wet chemical analysis tech-
niques are used to isolate chloride from the concrete, one to
determine acid-soluble chloride and the other to determine
water-soluble chloride. As discussed in Chapter 3, the chloride
ion content measured by the water-soluble test is very sensi-
tive to the test procedures. Consequently, all values of chlo-
ride ion content in this report are referenced to the acid-soluble
test described in ASTM C 114 and also in AASHTO T 260.
The preferred method of sample procurement for chloride
measurement is to obtain concrete in powdered form without
the aid of liquid coolants that could leach out water-soluble
chloride. This can be done by using impact drilling equipment
and collecting the pulverized material. Alternatively, a 3-in. (80
mm) diameter or larger core can be obtained by wet coring and
then extracting samples from the interior by dry sawing or other
pulverizing methods. Measurements for acid-soluble and
water-soluble chloride can be made on this type of sample using
the standard test procedures. Additional guidance is given in
References 4.14 and 4.15.
In many existing concrete structures, the exact cement
content is not known. Thus, chloride levels can be expressed
in terms of percent by weight of concrete, or, sometimes,
pounds of chloride per cubic yard of concrete. The latter re-
quires an assumed or measured unit weight of the concrete.
A table in Reference 4.7 gives the conversion formulas for
the various methods of expressing chloride in concrete. For
greater precision, nonevaporable water contents (water
chemically combined through cement hydration) can be
measured on each powdered sample from a given concrete
and used as correction factors for aggregate induced distortions
in measured chloride levels.
In any interpretation of chloride data, sound engineering
judgment must be used to assess the actual potential for cor-
rosion. As stated earlier, free moisture and oxygen as well as
chloride must be available to induce corrosion. If it can be
concluded that either moisture or oxygen is not available,
there would be no corrosion threshold. Such conditions may
prevail, for example, in concrete that is continuously sub-
merged or in internal members in buildings where air condi-
tioning units maintain constantly low humidities. However,
the difficulty of assessing the possibility of corrosion in the
service environment is discussed more fully in Chapter 3.
4.2.5 Rate of corrosion probesTwo basic types of
probes are available for embedment into concrete to provide
an indication of rate of corrosion. One type involves the use
of two or three electrically isolated short sections of steel
wire or reinforcing steel and the use of linear polarization
techniques to estimate instantaneous corrosion rates.4.17 The
second, more widely used device is the electrical resistance
rate-of-corrosion probe which provides cumulative rate of
corrosion data from periodic measurements of the electrical
resistance of a steel wire or hollow cylinder embedded in the
concrete. Experiences to date with use of these probes have
been conflicting. However, based on recent Federal High-
way Administration studies,4.12 this appears to be related
more to the rate of corrosion process of steel in concrete than
to inaccuracies of the devices themselves. The Federal High-
way Administration studies indicate that current flow within
physically separated, macroscopic corrosion cells, such as
the case of large quantities of steel in chloride-free moist
concrete in close proximity and electrically coupled to steel
in chloride-bearing concrete, are primarily responsible for
the very high rates of corrosion on bridge decks. In contrast,
microscopic self-corrosion of a small section of steel in
chloride-contaminated concrete most often results in only
relatively low corrosion rates. Since the electrically isolated
linear polarization devices only simulate this latter process,
valid predictions of the overall effect of corrosion on the
structure are not possible. The electrical resistance probe, on
the other hand, can be electrically coupled with the reinforc-
ing steel in the structure and thus, potentially, can indicate
macrocell activity. However, this is possible only if the
probe becomes the anode of a macrocell and current flow
within this macrocell is typical of that of a macrocell active
on the reinforcing steel. These are very important uncertain-
ties and have generally limited the use of resistance probes
to research and field evaluation efforts in which special in-
stallation procedures are required, and electrical potential
and current measurements can be made to define the charac-
teristics of the probe-reinforcing bar-macrocell. Continued
study of these devices is needed, as well as lower cost options
such as short sections of reinforcing steel installed in a spe-
cific manner, and current flow measurements. To date, use of
such procedures in the field to aid in studies on the effect of
rehabilitation procedures on corrosion rate have provided
excellent results.
4.2.6 Electrical resistance measuring equipmentThe
primary use of these measurements is to determine the resis-
tance of waterproof membranes that are made from dielectric
materials. This equipment consists of a copper contact plate,
sponges, ohmmeter, and lead wire.4.1 One terminal of the
ohmmeter is connected to the reinforcing steel, while the
other terminal is connected to the copper plate. The wetted
 CORROSION OF METALS
sponges are fastened to the bottom of the copper plate to fa-
cilitate contact. The electrical resistance can be measured at
any point by moving the copper contact plate to that point.
The resistance has been related to the number of holes in the
membrane and its permeability to water. This technique pro-
vides a nondestructive method to evaluate the environment
and potential for corrosion in concrete decks protected by a
membrane system. Advantages and cautions needed when
using these measurements are discussed in Reference 4.7.
The technique has not proven satisfactory for evaluation of
epoxy resin coatings on reinforcing steel embedded in con-
crete. Some work has been done on measurement of the re-
sistance of these coatings using alternating current meters.
However, the state of the art is not sufficiently advanced for
general use as an evaluation technique.
Other techniques and tools to determine the condition of
the concrete and to detect the presence of a corrosive envi-
ronment or active corrosion have been studied to varying de-
grees. Ultrasonic methods have been used successfully to
investigate the quality and condition of concrete.
To a lesser extent, infrared and radar scans have been used
to record the condition of concrete. Trial uses of these tech-
niques on bridge decks have been encouraging,4.18 but more
development work is needed, especially to determine their
value in assessing the condition of asphalt-covered decks.
A study is underway to develop nondestructive procedures
for direct measurement of the rate of corrosion of reinforcing
steel in concrete.4.12 Three electrode-linear-polarization
measurements are encouraging. Because the measurements
are made directly on the in situ reinforcing steel, many of the
problems discussed under the section on corrosion probes
should not be present.
4.3References
4.1. Spellman, Donald L., and Stratfull, Richard F., An Electrical
Method for Evaluating Bridge Deck Coatings, Highway Research Record
No. 357, Highway Research Board, 1971, pp. 64-71.
4.2. Stratfull, R. F., Half-Cell Potentials and the Corrosion of Steel in
Concrete, Resea rch Report No. CA-HY-MR-51 16-7-72-42, California
Department of Transportation, Sacramento, 1972.
4.3. Moore, William M.; Swift, Gilbert; and Milberger, Lionel J., An
Instrument for Detecting Delamination in Concrete Bridge Decks, High-
way Research Record No. 451, Highway Research Board, 1973, pp. 44-52.
4.4. Clear, K. C., Evaluation of Portland Cement Concrete for Perma-
nent Bridge Deck Repair, Report No. FHWA-RD-74-5, Federal Highway
Administration, Washington, D.C., 1974, 48 pp.
4.5. Stratfull, R. F.; Jurkovich, W. J.; and Spellman, D. L., Corrosion
Testing of Bridge Decks, Research Report No. CA-DOT-TL-5116-12-75-10,
California Department of Transportation, Sacramento, 1975.
4.6. Ross, Joseph E., Bridge Deck Deterioration Study, Resea rch
Report No. 85, Louisiana Department of Highways, Baton Rouge, 1975.
4.7. Durability of Concrete Bridge Decks, NCHRP Synthesis No. 57,
Transportation Research Board, Washington, D.C., 1979, 60 pp.
4.8. Manning, David G., and Holt, Frank B., Detecting Delamination in
Concrete Bridge Decks, Conc rete International: Design & Construction,
V. 2, No. 11, Nov. 1980, pp. 34-41.
4.9. Clear, K. C., Permanent Bridge Deck Repair, Public Roads, V. 39,
No. 2, 1975, pp. 53-62.
4.10. Durability of Concrete Bridge DecksA Cooperative Study,
Report No. 2 (EBO44E), Michigan State Highway Department/Bureau of
Public Roads/Portland Cement Association, Skokie, 1965, 107 pp.
4.11. Rolling Pachometer, Operating Manual and Specification, Office of
Development, Federal Highway Administration, Washington, D.C., 1975.
222R-23
4.12. Clear, K. C., FCP Annual Progress ReportYear Ending Sept.
30, 1981, Project 4K: Cost Effective Rigid Concrete Construction and
Rehabilitation in Adverse Environments, Federal Highway Administration,
Washington, D.C., 1979.
4.13. Clear, K. C., Time-to-Corrosion of Reinforcing Steel in Concrete
Slabs, V. 4: Galvanized Reinforcing Steel, ReportNo. FHWA-RD-82-028,
Federal Highway Administration, Washington, D.C., 1981.
4.14. Berman, H. A., Determination of Chloride in Hardened Cement
Paste, Mortar, and Concrete, Report No. FHWA-RD-72-12, Federal High-
way Administration, Washington, D.C., 1972, 22 pp.
4.15. Clear, K. C., and Harrigan, E. T., Sampling and Testing for Chlo-
ride Ion in Concrete, Report No. FHWA-RD-77-85, Federal Highway
Administration, Washington, D.C., 1977, 25 pp.
4.16. Clear, K. C., and Hay, R. E., Time-to-Corrosion of Reinforcing
Steel in Concrete Slabs, V. 1: Effect of Mix Design and Construction
Parameters, Repor t No. FHWA-RD-73-32, Federal Highway Administration,
Washington, D.C., 1973, 103 pp.
4.17. Lankard, D. R.; Slater, J. E.; Hedden, W. A.; and Niesz, D. E.,
Neutralization of Chloride in Concrete, Report No. FHWA-RD-76-60,
Federal Highway Administration, Washington, D.C., 1975, 143 pp.
4.18. Holt, F. B., and Manning, D. G., Detecting Concrete Bridge
Deck Delaminations with Infrared Thermography, Public Works, Mar.
1979, pp. 66-69.
CHAPTER 5REMEDIAL MEASURES
5.1 Introduction
This chapter discusses measures available to arrest, con-
trol, or minimize corrosion activity on an existing reinforced
concrete structure after it is found unnecessary to completely
replace the structure.
Some of the normally accepted and commonly implement-
ed remedial measures for controlling corrosion on steel
structures are not applicable to the reinforced concrete com-
posite structure. For example, application of protective coat-
ings is an effective tool for controlling corrosion on an
existing steel structure. Obviously, coating of the steel sur-
faces to be embedded in concrete would have to be accom-
plished prior to or during the construction phase. Thus the
use of protective coatings for steel reinforcement is a design
measure and has been discussed in Chapter 3.
Chemical inhibitors are commonly used to control corrosion
in a closed system. Inhibitors would need to be introduced as an
admixture during the concrete batching and mixing phase and
are not applicable to the existing reinforced concrete structure.
5.2General
Remedial measures for controlling corrosion of steel em-
bedded in portland cement concrete use sound corrosion en-
gineering principles directed toward:
1. Insulating the concrete surfaces from the corrosive en-
vironment.
2. Modifying the environment to make it less corrosive.
3. Actively controlling the electron flow within the envi-
ronment so that no metal is lost from the structure.
4. Applying a combination of the previous techniques.
The reinforced concrete structure may be insulated from
the corrosive environment through application of an imper-
meable, dielectric barrier between the structure and the cor-
rosive environment. The barrier may be a coating or
membrane applied to the surface of the concrete, may be
formed as an integral part of the concrete matrix through
polymer impregnation, or may be an overlay of polymer
concrete, low-slump concrete, latex-modified concrete, or
222R-24 ACI COMMITTEE REPORT
internally-sealed concrete. These have been discussed in detail
in Chapter 3 and will only be mentioned briefly in this chapter.
The environment may be altered to reduce corrosion either
by removing detrimental constituents (such as the chloride
ion), or by removing or neutralizing stray current sources.
Cathodic protection can be used to control the direction of
electron flow within the steel-environment electrochemical
circuit to stop corrosion of the reinforcing steel.
5.3Applicability
All reinforced concrete structures are susceptible to
corrosion. Although bridge decks5.1-5.3 are perhaps the most
notorious examples today, the literature contains many
references5.4-5.6 to other types of reinforced concrete struc-
tures where corrosion of the reinforcing steel is being or has
been experienced. These include buildings, caissons, foun-
dations, parking garages, piers, piles, pipes, silos, tower foot-
ings, and water tanks. Some of these structures may be
totally or partially buried in soil. Others, such as offshore
platforms, water tanks, and the internal surfaces of pipe, are
exposed to aqueous solutions. Bridge decks, parking garag-
es, and buildings are exposed to the atmosphere.
If the structure is buried or permanently underwater such that
the concrete surfaces are not accessible for treatment, and it is
impractical to expose them, treatment of the surfaces with sur-
face coatings or membranes or by application of overlays is not
applicable. Similarly, if the structure to be maintained is a bur-
ied pipeline or an offshore platform exposed in a large body of
water, modifying the environment to make it less corrosive
would not be a practical solution. Thus, not all the remedies dis-
cussed here are applicable to all types of reinforced concrete
structures in the various environments.
Cathodic protection is by far the most versatile method of
corrosion control since it is applicable to any electrically contin-
uous structure within a suitable electrolyte. In as much as the
steel embedded in concrete, and not the concrete, requires the
protection from metallic corrosion, damp concrete serves as a
suitable electrolyte and even structures exposed to the atmo-
sphere, such as bridge decks, can be protected cathodically.
5.4The remedies and their limitations
1. Insulative remedies: The insulative methods currently
employed to isolate reinforced concrete structures from the
corrosive environment include surface coatings and mem-
branes, polymer impregnation and overlays of polymer con-
crete, low-slump concrete, or latex-modified concrete. These
methods are suitable only when the surfaces of the concrete
structure are exposed for treatment. Ideally, these barriers
would prevent continued intrusion of harmful contaminants
and the availability of oxygen or moisture to sustain the cor-
rosion reactions. However, in existing structures active cor-
rosion is already underway and harmful species have
contaminated the concrete. Insulative methods used after ac-
tive corrosion is experienced do not stop corrosion but may
mitigate the effects of the corrosion processes. However, if
insulative methods are used without initially decontaminat-
ing the concrete, sufficient amounts of the contaminants, ox-
ygen, and moisture may be entrapped such that corrosion
progresses until structural integrity is threatened. These insu-
lative measures, when used without initial decontamination,
should be considered as only a temporary remedy.5.7
Also with insulative remedies an erroneous expectation
is that a perfect seal is attainable in practice. All barriers
will contain discontinuities such as pinholes, breaks,
cracks, poor seams, or other defects that will allow intrusion of
contaminants in localized areas. Nevertheless, these insu-
lative methods can substantially reduce the rate of intrusion
of harmful contaminants and retard the corrosion process-
es. In many cases, they can successfully extend the useful
life of a structure.
2. Modification of the environment: Methods available for
rendering the environment less corrosive include the remov-
al or elimination of harmful constituents from the electro-
lyte. These constituents could be in the form of chemicals
such as water and chlorides, gases such as oxygen or hydro-
gen sulfide, or electrical currents.
Water can often be eliminated by facilitating drainage
away from rather than through a structure. Chlorides can be
eliminated by a process known as electrochemical chloride
removal. This process has been used to decontaminate
structures such as bridge decks5.8 in research studies. The re-
moval is accomplished electrochemically, by using a suit-
able electrolyte, an ion exchange resin, and a noble anode.
The reinforcing steel is the cathode (negatively charged) in
this electrochemical circuit. The negatively charged chloride
ion (Cl-) is attracted to the positively charged anode where it
is trapped by the exchange resin. Although a field test at
Marysville, Ohio, on a bridge deck displayed promising re-
sults, the method remains in its initial development stage. In
this test, up to 90 percent of the chlorides present in the con-
crete above the top mat of reinforcement was removed. Dis-
advantages are that the method is expensive and time-
consuming and requires the application of high direct current
voltage that generates heat (around 200 F [90 C]) which, in
turn, can induce cracking of the concrete. In addition, the
permeability of the concrete was increased.
Harmful gases such as oxygen and hydrogen sulfide can
be stripped by chemical processes from the electrolyte, thus
making it less corrosive. This method is applicable predom-
inantly for structures exposed in aqueous solution.
Deep polymer impregnation5.9 of the critically contami-
nated concrete around the reinforcing steel is being evaluat-
ed. The method ties up the existing contaminants and
prevents intrusion of additional contaminants. Although the
theory is realistic, the practicality and economic feasibility
of deep polymerization are not established.
Corrosion of steel in concrete can be caused by environ-
mental factors other than chemical constituents such as chlo-
rides, moisture, or oxygen. Stray electrical currents can
result in corrosion by electrolysis, i.e., cathodic interfer-
ence.5.5,5.10 In corrosion by electrolysis, direct current strays
from an exterior source and is collected by the steel in a re-
inforced concrete structure. Inasmuch as the collected cur-
rent must return to its source to complete the electrochemical
circuit, the current is discharged from the structure at some
locations. At the point of current discharge from the structure
 CORROSION OF METALS
Fig. 5.1Underground pipe crossing Layout Line A is
cathodically protected
Fig. 5.2Elevation showing current flow patterns
to the electrolyte, metal loss is experienced. The most com-
mon sources of stray currents include cathodic protection sys-
tems, electrified railways, and electroplating plants. This type
of corrosion is most commonly manifested in grounded struc-
tures, i.e., those in contact with the earth. A method of mitigat-
ing this type of corrosion, implemented for many years in the
buried pipe industry, is the installation of resistance bonds. In
resistance bonding, the structure being affected is electrically
connected through a resistor to the source of the interference
currents. In this manner, the current returns to its source via a
metallic path such that no metal loss from the affected struc-
ture occurs. Another method uses galvanic anodes to drain the
collected current. Collected current is passed on to the electro-
lyte and back to its source from the surface of the anode which
corrodes, rather than the structure.
Examples of stray current intrusion and mitigation meth-
ods are shown in Fig. 5.1 to 5.4.
3. Active control of electron flowFrom the Pourbaix di-
agram for iron (Fig. 2.4), it can be seen that steel embedded
in concrete is normally passivated due to the highly alkaline
(high pH) concrete environment. The diagram shows anoth-
er area wherein no steel corrosion occurs. This area at the
lower portion of the diagram is labeled immunity. In this do-
main, the potential of the steel is more negative than in any
naturally occurring condition, regardless of pH.
The method of providing the highly negative steel potentials
required for immunity is referred to as cathodic protection. In
cathodically protecting a structure, a favorable electrochem-
ical circuit is established by installing an external electrode
in the electrolyte and passing current (conventional) from
that electrode through the electrolyte to the structure to be
protected. This current polarizes the potential of the cathodic
surfaces (relatively positive) on the steel to that of the anodic
222R-25
Fig. 5.3Mitigation with galvanic anodes (current returns
via low resistance anode)
Fig. 5.4Mitigation with resistance bond (current returns
via metallic path)
(more negative) surfaces. When this is accomplished, there
is no current flow between the formerly anodic and cathodic
surfaces and corrosion is arrested. This represents a balanced
or equilibrium condition. In normal practice, sufficient cur-
rent is passed to the surfaces so that the formerly anodic ar-
eas will be receiving current from the electrolyte and their
potential will be shifted to the more negative direction.
There are two ways in which the protective electrochemi-
cal circuit can be established. One method uses an electrode
made of a metal or alloy more negative than the structure to
be protected. For example, if the structure to be protected is
constructed of steel, either magnesium, zinc, or aluminum
may be coupled with the structure. Inasmuch as a protective
galvanic cell is set up between the steel and the alloy select-
ed, this method is known as the galvanic anode method of ca-
thodic protection. Also, since the galvanic anodes pass
current to the electrolyte, they corrode or sacrifice themselves
to protect the structure. Hence, magnesium, zinc, and alumi-
num are termed sacrificial anodes. Sacrificial anodes corrode
at relatively high rates. Corrosion rates for magnesium, zinc,
and aluminum are of the order of 17, 26, and 12 lb per amp
year, respectively.5.11,5.12
The high consumption rates, as well as low-driving volt-
age, are the primary disadvantages of the galvanic anode
method of cathodic protection. The open circuit potential be-
tween steel and magnesium is on the order of 1 V, while zinc
and aluminum are somewhat less.5.11,5.12 Thus, with this
method, it is imperative that a low-resistance circuit be es-
tablished by installation of many anodes in a low-resistance
media. The anodes installed should also be sized in accor-
dance with their respective consumption rates to provide the
necessary design life.
222R-26 ACI COMMITTEE REPORT
Fig. 5.5Galvanic cathodic protection (buried pipe)
Fig. 5.6Impressed current cathodic protection (buried pipe)
Table 5.1Comparison of electrochemical circuit
characteristics
Galvanic or sacrificial anode Impressed current
1 No external power required External power required
Voltage variable over
2 Fixed, small driving voltage
wide range
3 Limited, small current output Current variable over
wide range
Interference of adjacent
4 structure not likely Interference can result
5 Overprotection not likely Overprotection can result
6 Anodes rapidly consumed Anodes slowly consumed
Sensitive to temperature and
7 moisture conditions
The other way in which the favorable electrochemical
circuit can be established is by introducing electrical cur-
rent from an external source. Because an outside source of
current is used, this method is termed impressed current
cathodic protection. This method also requires the instal-
lation of an external electrode in the electrolyte with the
structure to be protected. However, since the current flow
is not dependent on the favorable potential difference be-
tween the electrode and the structure to be protected,
more noble materials can be selected for the anode. These
materials include high-silicon cast iron, graphite, and
even more noble materials such as platinized-titanium or
platinized-niobium. These metals corrode or are con-
sumed very slowly, less than 1 lb per amp year.5.11,5.12
Fig. 5.7Cathodic protection circuit using conductive mix
as secondary anode
These anodes are coupled to the structure via the external
source of electrical power. This source can be in the form of
batteries, thermoelectric generators, generators, or photovoltaic
cells. Most commonly, however, alternating current line
voltage is converted to direct current by a rectifier.
The two ways in which cathodic protection can be
achieved are shown in Fig. 5.5 and 5.6. A comparison of the
respective advantages and disadvantages of the system are
shown in Table 5.1.
Successful application of cathodic protection to buried
pipe were documented as early as 1946.5.13,5.14 The initial
application of cathodic protection to bridge decks was in
1974 and other applications have subsequently been made
with encouraging results.
The cathodic protection of reinforced concrete structures
is thus proven technology and the problems being currently
encountered deal with criteria of protection, design, and in-
spection of the installation.
In protecting buried structures or structures exposed in
water or in soils, low-resistance electrochemical circuits can
normally be established. However, on other structures such
as bridge decks, a highly conductive overlay consisting of a
coke breeze-asphalt mixture or closely spaced anodes to re-
duce the circuit resistance and to promote uniform distribu-
tion of current to all reinforcement is required.5.15,5.16 A
typical arrangement is shown in Fig. 5.7.
The criteria for protection of steel embedded in concrete
are not clearly defined. Most commonly, corrosion engineers
use the potential compared to a standard reference cell as the
sole criterion. The criterion for steel that is buried or sub-
merged is normally accepted as -0.85 V, or more negative
than a copper/CSE (copper-copper sulfate reference elec-
trode). However, steel embedded in concrete exhibits more
noble potentials than exposed steel in the order of 0.2 to 0.3
V more positive. Therefore, some investigators claim that
protection is provided at lower potentials, in the order of -0.5
V with CSE reference.5.17
For steel embedded in concrete exposed to the atmo-
sphere, research has indicated that the -0.85-V criterion may
not be attainable. Quite possibly the result may be sufficient
current to cause concern about lack of bond.5.18
The possibility of the loss of bond of the reinforcing steel
is related to high current densities, at least 25 mA/ft2.
 CORROSION OF METALS
However, it would be most unusual for a cathodic protection
system, typically designed to operate at 2 mA/ft2 of steel sur-
face, to operate in excess of 25 mA/ft2 for sufficient time
(several years) to cause deterioration in bond strength unless
the potential criterion was applied inappropriately.
Corrosion of steel in concrete is controlled by oxygen ac-
cess. Polarization of the steel is controlled by cathodic pro-
tection. As mentioned in Chapter 2, concrete is a very
alkaline medium and cathodic reaction is the reduction of
oxygen to hydroxides. The same is true for the cathodic pro-
tection currents. If the current reduces the oxygen faster than
it can be replenished, when cathodically protecting steel in
concrete, the steel will polarize to a more negative value. If
the oxygen supply is great, then to obtain greater degrees of
polarization, the current supply must be increased. In some
bridge decks, the current required to obtain the criterion of
-0.85 V would be such that there would be fear for disbond-
ment even though the half-cell potential was not even close
to that value. Thus, cathodic protection of concrete embed-
ded steel is not necessarily a standard procedure.
For concrete that is buried or submerged, probably
moisture-saturated, the -0.85 V CSE criterion is easily ob-
tained at current densities as low as 25 A/ft2. For bridge
decks, where the concrete is comparatively dry and oxygen
is abundant, the criteria may be -0.85 V if obtainable with
reasonable, current density (probably a maximum of 3
mA/ft2 of deck surface). If not, a shift of 400 mV for all
bridge deck half-cell potentials is a criterion developed from
the statistical distribution of half-cell potentials that could
change the least negative potential to equal or exceed the
most negative half-cell potential, or to provide the current re-
quired to achieve the cathodic protection requirements as de-
termined by the E-log I curve.5.18 In this latter case, the half-
cell potential of the bridge deck can vary wildly depending
on the moisture content and temperature of the concrete. It
also eliminates the need of a permanent half-cell which
would be required in the case of half-cell potential control.
The theory behind the constant current determined by the
E-log I criteria is that the potential of steel is directly related to
oxygen reduction. The corrosion of the steel is directly related
to the corrosion current. Thus, with a constant current, vari-
ations in oxygen reduction will cause variations in the half-cell
potential of the steel. Conversely, if the cathodic protection cri-
teria is a constant half-cell potential, then the current output of
the system will vary as the oxygen supply varies.
When using the half-cell potential criterion as developed
through the E-log I method, there is a risk that there will be
times when the cathodic system will not completely control
the corrosion of the steel. For example, if the concrete is near
saturation, the steel can usually be polarized with relatively
small current densities. Then if the rectifier is regulated by a
half-cell potential and the concrete dries so that oxygen be-
comes abundant, and the polarized potential drifts signifi-
cantly less negative, it is likely that there will be insufficient
current capacity to raise the potential to the protective po-
tential value.
Corrosion is caused by the flow of electrons or current. The
differences in half-cell potentials is the voltage that causes the
222R-27
current to flow. Once the steel is made cathodic in that it re-
ceives current, the current causes oxygen to be reduced. This
same amount of current may reduce oxygen faster than it is be-
ing replenished and result in polarization with an associated
potential change. If the oxygen is replenished at the same rate
as it is reduced, no additional polarization will result. Thus, if
the amount of current for cathodic protection will make all of
the steel cathodic and oxygen reduction is taking place, any
greater amount of cathodic protection current will simply be
wasted on reducing oxygen.
In addition to disbondment, overprotection can result in hy-
drogen embrittlement.5.6,5.19 In Chapter 2 it was shown that in
acid environments hydrogen ions are reduced at the cathode to
atomic hydrogen which, in turn, combine to form gaseous hy-
drogen. When overprotection results, hydrogen gas is formed
at a faster rate than can be diffused through the coating, in this
instance, concrete. When this occurs, gaseous pressure is de-
veloped at the steel-coating interface which tends to either
spall the coating (disbondment) or to diffuse as atomic hydro-
gen into the metal. When hydrogen diffuses into the metal, it
further strains the metal lattice, resulting in reduced ductility
and toughness. These phenomena are referred to as hydrogen
embrittlement. Normally, hydrogen embrittlement affects
high-strength steels only, generally those having yield
strengths of 90 ksi (620 MPa) or higher5.20,5.21 and is conse-
quently a potential problem in applying cathodic protection to
prestressed concrete elements.
Because of the adverse effects possible from overprotection,
polarized potentials (determined immediately after the cur-
rent has been interrupted) are normally limited to -1.10 V
CSE to avoid the possibility of disbonding and hydrogen em-
brittlement problems.5.22 In addition, protection above that
level would require more current and a costlier installation
without achieving additional protection from corrosion.
5.5Summary
Remedies for controlling corrosion on existing reinforced
concrete structures use sound corrosion engineering principles
directed at insulation of the reinforced concrete from the cor-
rosive environment, alteration of the environment, or control
of electrical current flow within the environment. In dealing
with the reinforced concrete composite, when corrosion is
detected, the deleterious contaminants are already within the
concrete matrix. Insulative measures, although they mini-
mize the rate of corrosion or the intrusion of additional con-
taminants, entrap the existing quantities of these corrosive
contaminants. Their effectiveness can be improved by re-
moval of contaminants prior to sealing such as by electro-
chemical chloride removal.
Many of the proposed remedies are in the early devel-
opment stage. Such approaches as deep polymer impreg-
nation and corrosion inhibitors have not been proven as
practicable methods of corrosion control on existing rein-
forced concrete structures.
Of the remedies discussed, only cathodic protection has
proven to be capable of stopping corrosion on an existing
structure. The technology is proven and has been found to be
cost-effective. The design procedures for such structures as
222R-28 ACI COMMITTEE REPORT

buried pipe and water tanks are well established, but the de- American Association of State Highway and Transportation
sign criteria for structures exposed to the atmosphere, such Officials
as bridge decks and parking structures, are still in the devel- T 260 Sampling and Testing for Total Chloride
opmental stages. Ion Content in Concrete and Concrete Raw
Materials
5.6References
5.1. Godfrey, Kneeland A., Bridge Decks, Civil EngineeringASCE, American Concrete Institute
V. 45, No. 8, Aug. 1975, pp. 60-65.
5.2. Manning, David G., and Ryell, John, Durable Bridge Decks,
201.2R Guide to Durable Concrete
Report No. RR203, Ontario Ministry of Transportation and Communications, 318 Building Code Requirements for
Downsview, 1976, 67 pp. Reinforced Concrete
5.3. Arnold, C. J., Bridge Decks in Michigan: A Summary of Research
and Performance, Conference on Federally Coordinated Program for
Research and Development, Pennsylvania State University, University ASTM
Park, Sept. 1976. C 114 Standard Method for Chemical Analysis of
5.4. Griffin, D. F., Corrosion of Reinforced Concrete in Marine Envi- Hydraulic Cement
ronments, Materials Protection, V. 4, No. 11, Nov. 1965, pp. 8-11. C 876 Standard Test Method for Half-Cell
5.5. Ellis, W. J., Corrosion of Cement Mortar Coated Pipelines, Amer-
ican Water Works Association Meeting, Honolulu, Oct. 1974.
Potentials of Reinforcing Steel in
5.6. Philips, E., Survey of Corrosion of Prestressing Steel in Concrete Concrete
Water-Retaining Structures, Technical Paper No. 9, Australian Water C 1152 Standard Test Method for Acid-Soluble
Resources Council, Canberra, 1975. Chloride in Mortar and Concrete
5.7. Frascioia, R. I., Waterproofing MembranesAre Their Problems
Insurmountable, FCP Project 4B Review, State College, Pennsylvania,
C 1218 Standard Test Method for Water-Soluble
Sept. 1976. Chloride in Mortar and Concrete
5.8. Slater, John E.; Lankard, David R; and Moreland, Peter J., Electro-
chemical Removal of Chlorides from Concrete Bridge Decks, Materials These publications may be obtained from the following
Protection, V. 15, No. 11, Nov. 1976, pp. 21-26.
5.9. Hay, R. E., The Bridge Deck ProblemAn Analysis of Potential
organizations:
Solutions, Public Roads, V. 39, No. 4, Mar. 1976, pp. 142-147.
5.10. Mudd, O. C., Control of Pipe-Line Corrosion, Corrosion, V. 1, American Association of State Highway and Transportation
No. 12, Dec. 1945, pp. 192-218, and V. 2, No. 3, Mar. 1946, pp. 25-58. Officials
5.11. Corrosion Prevention and Control Manual, Navdocks MO-306,
444 North Capitol St., NW
Department of the Navy, Bureau of Yards and Docks, Washington, D.C.,
June 1964. Suite 225
5.12. Peabody, A. W., Control of Pipeline Corrosion, National Associ- Washington, D.C. 20001
ation of Corrosion Engineers, Houston, 1967.
5.13. Henderson, D., Coated Pipe and Cathodic Protection, Consulting
American Concrete Institute
Engineer, Mar. 1962.
5.14. Deskins, R. L., Cathodic Protection of a Mortar Coated Steel P.O. Box 9094
Water Distribution System, Materials Protection, V. 5, No. 9, Sept. 1966, Farmington Hills, MI 48333-9094
pp. 35-37.
5.15. Stratfull, R. F., Experimental Cathodic Protection of a Bridge
ASTM
Deck, Transportation Research Record No. 500, Transportation Research
Board, 1974, pp. 1-15. 100 Barr Harbor Drive
5.16. Fromm, H. J., Cathodic Protection of Rebar in Concrete Bridge West Conshohocken, PA 19428-2959
Decks, Materials Performance, V. 16, No. 11, Nov. 1977, pp. 21-29.
5.17. Robinson, R. C., Cathodic Protection of Steel in Concrete, Cor- This report was submitted to letter ballot of the committee on an item-by-item basis.
rosion of Metals in Concrete, SP-49, American Concrete Institute, Detroit, The committee consists of 17 members. All items were approved by the necessary
1975, pp. 83-93. two-thirds vote.
5.18. Stratfull, Richard F., Criteria for the Cathodic Protection of
Bridge Decks, Corrosion of Reinforcement in Concrete Construction, Ellis
Horwood, Chichester, 1983, pp. 287-331.
5.19. Dykmass, M. J., Corrosion of Prestressing Steel in Concrete and Appendix AACI 222.1-96
How This Can Be Minimized or Prevented, National Association of Cor-
rosion Engineers Western Regional Conference, San Diego, Sept. 1976. Provisional Standard Test Method for Water-
5.20. Uhlig, Herbert H., Corrosion and Corrosion Control, John Wiley Soluble Chloride Available for Corrosion of
& Sons, New York, 1963.
Embedded Steel in Mortar and Concrete Using the
5.21. Fontana, M. G., and Greene, N. D., Corrosion Engineering, 2nd
Soxhlet Extractor
Edition, McGraw-Hill Book Co., New York, 1978, 448 pp.
5.22. Scott, G. N., The Corrosion Inhibitive Properties of Cement Mor-
tar Coatings, National Association of Corrosion Engineers Annual Con- Reported by ACI Committee 222
vention, Kansas City, Mar. 1962.

Some water-soluble chlorides, primarily in certain aggregates, do not induce

CHAPTER 6REFERENCES TO DOCUMENTS OF
corrosion of embedded reinforcing steel since these chlorides are bound within
STANDARD-PRODUCING ORGANIZATIONS
the aggregate. Currently, available test methods cannot distinguish between the
The documents of the various standards-producing organi- water-soluble chlorides that support corrosion and those that do not. This test
zations referred to in this document are listed below with method detects only water-soluble chlorides that contribute to the corrosion of
their serial designation. the reinforcing steel.
 CORROSION OF METALS 222R-29

Keywords: Water-soluble chlorides; corrosion; steel; mortar; concretes;

Soxhlet Extractor.

1Scope
1.1This test method provides procedures for the sam-
pling and analysis of hydraulic-cement mortar, concrete, or
aggregate for chloride that is water-soluble and available for
the corrosion reaction under the conditions of the test.
1.2This test method does not purport to address all of
the safety problems, if any, associated with its use. It is the
responsibility of the user of this test method to establish ap-
propriate safety and health practices and determine the ap-
plicability of regulatory limitations prior to use.

2Significance and Use

2.1Water-soluble chloride, when present in sufficient
amounts, may initiate or accelerate the corrosion of metals
such as steel embedded in or contacting a cement system
such as mortar, grout, or concrete. Other test methods exist
for the determination of water-soluble chloride in a cement
system.* However, some aggregates contain a considerable
amount of chloride that is bound in the aggregate and is not
available for the corrosion reaction. The test method de-
scribed in ASTM C 1218 measures a portion of the chloride
Fig. A1Soxhlet ext raction appa ratus
contained in these aggregates. However, the amount of chlo-
ride measured is very dependent on the degree of fineness to
which the aggregates are ground during sample preparation.
The problem with the ASTM C 1218 test method is therefore extractor consists of a heater, a lower flask to hold water, the
twofold: the test measures chlorides that are not generally sample compartment, and a condenser. The extractor con-
available for the corrosion reaction, and the test gives widely tains approximately 100 ml of distilled water in the lower
variable results. The test method described herein should be flask. Heat is applied to this flask; vapor from the boiling wa-
used when chloride-bearing aggregates influence the results ter passes to the condenser; and the condensate collects in the
obtained using ASTM C 1218. sample compartment. The sample is contained in a porous
2.2Sulfides are known to interfere with the determi- holder and the hot condensate collects around the sample.
nation of chloride content. Blast-furnace slag aggregates When the condensate reaches a critical height, the liquid is
and cement contain sulfide sulfur in concentrations high siphoned back into the lower flask and the process repeats.
enough to cause significant interference and produce er- The nonvolatile components extracted from the sample ac-
roneous test results. Treatment with hydrogen peroxide, cumulate in the lower flask, while each extraction involves
as discussed in ASTM C 114, shall be used to eliminate
fresh hot distillate. The heat input shall be sufficient to give
such interference.
an extraction cycle about every 20 min. For convenience,
suitable commercial equipment is available.**
3Apparatus
3.1Sampling Equipmen : tThe apparatus required for ob-
taining samples by coring or sawing is described in ASTM C 4Reagents
42. Sampling by drilling is not applicable for this test and 4.1The reagents required for the chloride determination
shall not be used. are given in the test method for chloride of ASTM C 114.
3.2Sample Processing Apparatus:
3.2.1 Samples too large to fit in the sample holder of the 5 Sampling
Soxhlet shall be reduced in size by means of a jaw crusher or 5.1Reduce the size of a minimum 300 gm sample as
by hammering. specified in Section 6, and divide this sample to a mini-
3.2.2 Extract chlorides from the sample using a Soxhlet ex- mum 30 gm representative sample for use in the chloride
tractor, a schematic of which is shown in Fig. A1. The Soxhlet determination. If the sample is taken from concrete or
mortar then the concrete or mortar shall be at least 7 days
*
ASTM Standard Test Method C 1218-92, Standard Test Method for Water-Soluble old before sampling.
Chloride in Mortar and Concrete.
For more information see The Determination of the Chloride Content of Con- Note 1Concrete cores taken in accordance with ASTM
crete by Brian B. Hope, John A. Page, and John S. Poland, Cement and Conc rete
Resea rch, V. 15, No. 5, Pergamon Press, New York, Sept. 1985, pp. 863-870. C 42 or concrete cylinders cast from the proposed mix may
ASTM Test Method C 114, Test Methods for Chemical Analysis of Hydraulic Cement.
ASTM C 42, Test Method for Obtaining and Testing Drilled Cores and Sawn **
Suitable Soxhlet extraction equipment is available from Fisher Scientific (catalog
Beams of Concrete. No. 09-551A) and other manufacturers.
222R-30 ACI COMMITTEE REPORT
be cut longitudinally or laterally to provide the required 300
gm sample representative of the core or cylinder. Experience
has shown that the cooling water from core cutting will not
dissolve a significant amount of chloride.
6 Sample Preparation
6.1Using the jaw crusher or hammer, reduce the sample
so that it fits the sample holder using the minimum crush-
ing necessary. The sample shall not be crushed to a pow-
der since this would release chloride bound in some
aggregates which, as previously discussed, are known not
to contribute to corrosion.
7Procedure
7.1A single test shall consist of determination of chlo-
ride contents of three individual 30 gm samples.
7.2Weigh each sample (30 g 5 g) to the nearest 0.01 g
and place in the porous sample holder of a Soxhlet extractor.
Add a wad of glass wool. Place approximately 100 ml of de-
ionized water in the lower flask.
7.2.1 Assemble the condenser complete with cooling wa-
ter supply pipes to the extractor and place on the heater. Turn
on both the heater and condenser cooling water and allow ex-
traction to continue for 24 hr; adjust the heating rate to give
a cycle about every 20 min.
7.2.2 At the conclusion of the extraction stage, transfer the
solution to a 500 ml volumetric flask. Rinse the Soxhlet flask
three times with distilled water, transferring the washings to
the 500 ml volumetric flask; add distilled water to produce a
volume of 500 ml. With a pipette transfer a 25 ml aliquot to
a 250 ml conical flask. Add 3 drops of methyl orange indica-
tor (prepared in accordance with ASTM C 114) and add
dilute (1+1) nitric acid until the solution is acidified. Add 3.0
0.1 ml of hydrogen peroxide (30 percent solution) to the
solution. Proceed in accordance with the reference ASTM
C 114, starting with the procedure specified in Section
19.5.3 and continuing to the end of Section 19.5.8.
7.2.3 Make a blank determination by using the Soxhlet,
complete with thimble and glass wool, but containing no
sample of cementitious material.
8Calculation
8.1Calculate percent of chloride to the nearest 0.001
percent as the average chloride content of the triplicate samples,
each calculated as follows
N 500
Chloride, percent = 3.5453 ( V 1 V b ) ----- --------- (1)
M V2
where
V1 = ml of 0.05 N AgNO3 solution used for titration of
the sample (equivalence point)
Vb = ml of 0.05 N AgNO3 solution used for titration of
the blank (equivalence point)
N = normality of 0.05 N AgNO3 solution, calculated to
0.001
M = mass of concrete or mortar sample, g
V2 = volume of the 25 ml aliquot determined to 0.1 ml
(larger or smaller aliquots may be used depending on the
chloride concentrations present)
8.2Sufficient data are not available at this time to pro-
vide precision and bias statements.