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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 construction, and maintenance of concrete structures. The


3.6References main purpose of this report is to present the state of the art.
While several metals may corrode under certain conditions
Chapter 4Procedures for identifying corrosion when embedded in concrete, the corrosion of steel reinforce-
environments and active corrosion in concrete, ment is of the greatest concern, and, therefore, is the primary
p. 222R-21 subject of the report.
4.1Introduction
Chloride ions are considered to be the major cause of pre-
4.2Methods of evaluation
mature corrosion of steel reinforcement. Corrosion can oc-
4.3References
cur in some circumstances in the absences of chloride ions,
however. For example, carbonation of concrete results in re-
Chapter 5Remedial measures, p. 222R-23
5.1Introduction duction of its alkalinity, thereby permitting corrosion of em-
5.2General bedded steel. Carbonation, however, is usually a slow
5.3Applicability process in concrete which has a low water-cement ratio and
5.4The remedies and their limitations carbonation-induced corrosion is not as common as corro-
5.5Summary sion induced by chloride ions. Chloride ions are common in
5.6References nature and small amounts are usually unintentionally con-
tained in the mix ingredients of concrete.
Chapter 6References to documents of standard- Chloride ions also may be intentionally added, most often as
producing organizations, p. 222R-28 a constituent of accelerating admixtures. Dissolved chloride
ions also may penetrate unprotected hardened concrete in struc-
Appendix AStandard Test Method for Water- tures exposed to marine environments or to deicing salts.
Soluble Chloride Available for Corrosion of The rate of corrosion of steel reinforcement embedded in
Embedded Steel in Mortar and Concrete Using the concrete is strongly influenced by environmental factors. Both
Soxhlet Extractor, p. 222R-28
oxygen and moisture must be present if electrochemical cor-
CHAPTER 1INTRODUCTION rosion is to occur. Reinforced concrete with significant gradi-
1.1Background ents in chloride ion content is vulnerable to macrocell
Concrete normally provides reinforcing steel with excel- corrosion, especially if subjected to cycles of wetting and dry-
lent corrosion protection. The high alkaline environment in ing. Other factors that affect the rate and level of corrosion are
concrete results in the formation of a tightly adhering film heterogeneities in the concrete and the steel, pH of the con-
which passivates the steel and protects it from corrosion. In crete pore water, carbonation of the portland cement paste,
addition, concrete can be proportioned to have a low perme- cracks in the concrete, stray currents, and galvanic effects due
ability which minimizes the penetration of corrosion-inducing to contact between dissimilar metals. Design features also
substances. Low permeability also increases the electrical play an important role in the corrosion of embedded steel. Mix
resistivity of concrete which impedes the flow of electro- proportions, depth of cover over the steel, crack control mea-
chemical corrosion currents. Because of these inherent pro- sures, and implementation of measures designed specifically
tective attributes, corrosion of steel does not occur in the for corrosion protection are some of the factors that control the
majority of concrete elements or structures. Corrosion of onset and rate of corrosion.
steel, however, can occur if the concrete is not of adequate Deterioration of concrete due to corrosion results because
quality, the structure was not properly designed for the ser- the products of corrosion (rust) occupy a greater volume than
vice environment, or the environment was not as anticipated the steel and exert substantial stresses on the surrounding
or changes during the service life of the concrete. concrete. The outward manifestations of the rusting include
The corrosion of metals, especially steel, in concrete has staining, cracking, and spalling of the concrete. Concurrent-
received increasing attention in recent years because of its ly, the cross section of the steel is reduced. With time, structural
widespread occurrence in certain types of structures and the distress may occur either by loss of bond between the steel
high cost of repairs. The corrosion of steel reinforcement and concrete due to cracking and spalling or as a result of the
was first observed in marine structures and chemical manu- reduced steel cross-sectional area. This latter effect can be of
facturing plants.1.1,1.2,1.3 More recently, numerous reports of special concern in structures containing high strength pre-
its occurrence in bridge decks, parking structures, and other stressing steel in which a small amount of metal loss could
structures exposed to chlorides has made the problem partic- possibly induce tendon failure.
ularly prominent. The consequent extensive research on fac- The research on corrosion to date has not produced a steel
tors contributing to steel corrosion has increased our or other type of reinforcement that will not corrode when used
understanding of corrosion, especially concerning the role of in concrete and that is both economical and technically feasible.
chloride ions. It is anticipated that the application of the find- However, research has pointed to the need for quality con-
ings of this research will result in fewer instances of corrosion crete, careful design, good construction practices, and reason-
in new concrete structures and improved methods of repair- able limits on the amount of chloride in the concrete mix
ing corrosion-induced damage in existing structures. ingredients. Other measures that are being investigated in-
For these improvements to occur, the information must be clude the use of corrosion inhibitors, protective coatings on
disseminated to individuals responsible for the design, the steel, and cathodic protection. There has been some
CORROSION OF METALS 222R-3

success in each of these areas though problems resulting from one method of expressing electromotive forces. The Fe++ in
corrosion of embedded metals are far from eliminated. Eq. (2-1) is subsequently changed to oxides of iron by a
number of complex reactions. The volume of the reaction
1.2Scope products is several times the volume of the iron.
This report discusses the factors that cause and control At the cathode, reduction takes place. In an acid medium,
corrosion of steel in concrete, measures for protecting em- the reaction taking place at the cathode is the reduction of
bedded metals in new construction, techniques for detecting hydrogen ions to hydrogen. However, as will be shown later,
corrosion in structures in service, and remedial procedures. concrete is highly basic and usually has an adequate supply
Consideration of these factors, and application of the dis- of oxygen, so the cathodic reaction is
cussed measures, techniques, and procedures should assist in
reducing the occurrence of corrosion and result, in most in- 1/ H2O + 1/4 O2 + e- OH -
2
stances, in the satisfactory performance of reinforced and
prestressed concrete elements.
E = 0.401 Standard Redox Potential (2-2)
1.3References
1.1. Tremper, Bailey; Beaton, John L; and Stratfull, R. F. Causes and The corroding iron piece has an open circuit potential,
Repair of Deterioration to a California Bridge Due to Corrosion of Rein- also called a rest potential, related to the Standard Redox
forcing Steel in a Marine Environment II: Fundamental Factors Causing Potentials of the reactions in Eq. (2-1) and (2-2), to the com-
Corrosion, Bulletin No. 182, Highway Research Board, Washington, D.C.,
position of the aqueous medium, the temperature, and to the
1958, pp. 18-41.
1.2. Evans. U. R., The Corrosion and Oxidation of Metals: Scientific Prin- polarizations of these half-cells. The rate of corrosion is
ciples and Practical Applications, Edward Arnold, London, 1960, 303 pp. related to the polarizations as will be discussed later.
1.3. Biczk, Imre, Concrete Corrosion and Concrete Protection, 3rd 2.2.2 Availability of oxygen in concreteAlthough the
Edition, Acadmiai Kiad, Budapest, 1964.
availability of oxygen is one of the main controlling factors
for corrosion of steel, there appears to be little quantitative
CHAPTER 2MECHANISM OF CORROSION OF
STEEL IN CONCRETE information on its effect in concrete. Some information is
2.1Introduction shown, however, in Fig. 2.1, where the rate of oxygen diffusion
This chapter is divided into two sections. In the first, em- through water-saturated concrete of varying quality and
phasis is placed on the processes responsible for corrosion of thickness is illustrated.2.2 The rate of oxygen diffusion
steel reinforcement in concrete. The corrosion mechanism is through concrete is also significantly affected by the extent
generally accepted to be electrochemical in nature. Some of to which the concrete is saturated with water. A number of
the major causes of corrosion of steel in concrete are exam- investigations indicate that if the steel passivity is destroyed,
ined and related phenomena are discussed. conditions will be conducive to the corrosion of steel rein-
In the second part, a discussion is given on the concrete forcement in those parts of a concrete structure that are ex-
variables that influence corrosion, including concrete mix posed to periods of intermittent wetting and drying.
proportions, quality, and cover, and the effects of corrosion Investigations also indicate that, although chlorides are
inhibiting admixtures and carbonation. present, the rate of steel corrosion will be very slow if the
concrete is continuously water-saturated.2.3 In wet concrete,
2.2Principles of corrosion dissolved oxygen will primarily be diffusing in solution,
2.2.1 CorrosionAn electrochemical processAl- while in a partly dry concrete the diffusion of gaseous oxy-
though iron can corrode by chemical attack, the most com- gen is much faster. For oxygen to be consumed in a cathodic
mon form of corrosion in an aqueous medium is reaction, however, the oxygen has to be in a dissolved state.
electrochemical.2.1 The corrosion process is similar to the Since it is the concentration of dissolved oxygen that is im-
action which takes place in a flashlight battery. An anode, portant, all factors affecting the solubility of oxygen should
where electrochemical oxidation takes place, a cathode, also affect its availability. The effect of salt on the corrosion
where electrochemical reduction occurs, an electrical con- rate has been demonstrated by Griffin and Henry2.4 (see
ductor, and an aqueous medium must be present. Any metal Fig. 2.2). Corrosion increased as the sodium chloride con-
surface on which corrosion is taking place is a composite of centration increased until a maximum was reached. Beyond
anodes and cathodes electrically connected through the body this, the rate of corrosion decreased despite the increased
of the metal itself. Reactions at the anodes and cathodes are chloride ion concentration. This change in relationship be-
broadly referred to as half-cell reactions. tween corrosion and sodium chloride concentration is attrib-
At the anode, which is the negative pole, iron is oxidized uted to the reduced solubility and diffusivity of oxygen, and,
to ferrous ions. therefore, the availability of oxygen to sustain the corrosion
process. This represents corrosion in a salt solution; howev-
Fe Fe++ + 2e- er, the availability of oxygen in wet concrete may be different.
Problems due to corrosion of embedded steel have seldom
E = - 0.440 Standard Redox Potential (2-1) been observed in concrete structures that are continuously
submerged, even as in seawater.
The Standard Redox Potential is the potential generated 2.2.3 The importance of chloride ionsAs will be discussed
when the metal is connected to a hydrogen electrode and is 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

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
Fig. 2.2Effect of concentration of sodium chloride concrete have been published,2.9 but largely the literature ne-
on corrosion rate2.4 glects the interaction between concrete and chloride.
2.2.3.3 Electrochemical role of free chloride ions. There
environment for embedded steel. However, it is well are three modern theories to explain the effects of chloride
documented2.5-2.7 that the intrusion of chloride ions in rein- ions on steel corrosion:
forced concrete can cause steel corrosion if oxygen and (a) The Oxide Film TheorySome investigators believe
moisture are also available to sustain the reaction. No other that an oxide film on a metal surface is responsible for pas-
common contaminant is documented as extensively in the sivity and thus protection against corrosion. This theory pos-
literature as a cause of corrosion of metals in concrete. Chlo- tulates that chloride ions penetrate the oxide film on steel
ride ions may be introduced into concrete in a variety of through pores or defects in the film easier than do other ions
ways. Some are intentional inclusion as an accelerating ad- (e.g., SO4-). Alternatively, the chloride ions may colloidally
mixture; accidental inclusion as contaminants on aggregates; disperse the oxide film, thereby making it easier to penetrate.
or penetration by deicing salts, industrial brines, marine (b) The Adsorption TheoryChloride ions are adsorbed on
spray, fog, or mist. the metal surface in competition with dissolved O2 or hydrox-
2.2.3.1 Incorporation in concrete during mixing. One of yl ions. The chloride ion promotes the hydration of the metal
the best known accelerators of the hydration of portland ce- ions and thus facilitates the dissolution of the metal ions.
ment is calcium chloride. Generally, up to 2 percent solid (c) The Transitory Complex TheoryAccording to this
calcium chloride dihydrate based on the weight of cement is 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

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-
Fig. 2.5Iron electrode in concrete2.16 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-
Copper, chromium, nickel, and silver generally do not mally invisible film has been difficult to determine. It seems
corrode in concrete. However, they are somewhat suscep- clear, however, that it is made up of chemical combinations
tible to corrosion when the concrete is located in a marine of oxygen and is simply called an oxide film.
environment.2.14 When a potential is applied to an iron electrode, the rate of
2.2.7 Polarization of half-cellsThe equilibrium of a current flow depends on the state of passivity. Iron in con-
half-cell is characterized by its reversible potential which crete is generally passive, such that little current flows when
depends on the Standard Redox Potential, on the concen- a potential is progressively increased, eventually the current
trations (activities) of the species participating in the half-cell will flow. This is because, at this point, oxygen is evolved
reaction (e.g., OH-, Fe++, etc.), and on the temperature. and the electrode reaction involves the electrolysis of water
When a current flows through the half-cell, there is a shift (see Curve I, Fig. 2.5).
of its measured potential away from the reversible potential.
This shift is called polarization. For a given current, the po-
2H2O -> 4H+ + O2 + 4e- (2-4)
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 This phenomenon is called transpassivity. The use of a
high degree of polarization. corrosion testing procedure involving an impressed potential
has been reported.2.17 Grimes et al.2.18 found that when a
Some corrosion processes, although thermodynamically
high anodic voltage was applied to steel in concrete, the pH
more favored than others as indicated by the reversible po-
around the steel was changed to values ranging between al-
tentials of the half-cells, are actually slower in practice be-
most 0 and 4. He also found that a liquid pool formed quickly
cause of polarization effects.
around the reinforcing steel. Neither steel nor concrete is du-
There are three general kinds of polarization that apply
rable in a low pH (acidic) environment.
to the anode as well as to the cathode. These are concen-
2.2.9 Types of corrosion-controlling mechanismsAs
tration polarization, ohmic polarization, and activation
previously mentioned, it is necessary to have both a cathodic
polarization. These three kinds of polarization can be
and an anodic reaction for a corrosion process to occur.
present simultaneously.
However, different corrosion situations can be visualized by
(a) Concentration polarization occurs when the concen-
plotting, on the same graph, the log of the absolute current
tration of the electrolyte changes in the vicinity of the elec-
(I) versus potential (E) curves which would be obtained by
trode. An example of this would be depletion of oxygen
polarizing each half-cell with an auxiliary counter electrode
concentration at the cathode.
in absence of the other half-cell. For this discussion, we as-
(b) Ohmic polarization occurs because of the ohmic resis-
sume (a) no IR drop between anodic and cathodic areas and
tance of the electrolyte (e.g., moist concrete) and of any
(b) simple algebraic addition of the anodic and cathodic cur-
films on the electrode surface. This produces an ohmic po-
rents. Under these conditions, the rest potential or open cir-
tential drop in accordance with Ohms law (IR drop).
cuit potential of the corroding sample will be that at which
(c) Activation polarization occurs due to kinetic hindrance the two i versus E curves intercept. At this point no net, ex-
of the rate controlling step of the electrode reaction. ternal current flows, and the absolute value of current at the
Tafel2.1 has shown experimentally that for large currents intercept is equal to the corrosion current.
in the absence of concentration and ohmic polarization, the If the cathodic process is the slower process (the one with
measured polarization , which is the activation polarization, is the larger polarization), the corrosion rate is considered to be
directly proportional to the logarithm of the current density i cathodically controlled (Fig. 2.6). Conversely, if the anodic
= a + blog i process is slower, the corrosion rate is said to be anodically
controlled (Fig. 2.7).
where a and b are the so-called Tafel intercept and Tafel In concrete, one or two types of corrosion-rate-controlling
slope parameters, respectively. These parameters can be ob- mechanisms normally dominate. One is cathodic diffusion,
tained by plotting versus i on semilogarithmic paper. The where the rate of oxygen diffusion through the concrete
CORROSION OF METALS 222R-7

Fig. 2.6Cathodic control


Fig. 2.8Cathodic diffusion control

Fig. 2.7Anodic control Fig. 2.9Resistance control

determines the rate of corrosion. In Fig. 2.8, cathodic diffusion voltage than that of the anodic surface. The current then
control is shown for two different rates of oxygen diffusion. flows to the original anodic surface resulting in cathodic re-
The other type of controlling mechanism involves the de- actions occurring there. The difficulties in using this method,
velopment of a high resistance path. When steel corrodes in however, are to determine the correct potential to apply to
concrete, anodic and cathodic areas may be as much as several the system and to make sure that it is applied uniformly.
feet apart; therefore, the resistance of the concrete may be of 2.2.12 Effects of other salt ionsIt has been reported that
great importance. Fig. 2.9 illustrates two cases of resistance sulfate2.20 and carbonate2.21 salts can also cause reinforcing
control where the potential available for corrosion is the dif- steel to corrode. However, this has not been well document-
ference in the potential between anode and cathode minus
ed. Although the concrete may have cracked in certain cases
the relevant IR loss.
and the exposed steel may have appeared rusted, these salts
2.2.10 Stray current corrosionStray electric currents are
may not have been the primary cause. Their low solubility in
those that follow paths other than the intended circuit. They
a high calcium ion environment would reduce their availabil-
can greatly accelerate the corrosion of reinforcing steel. The
most common sources of these are electric railways, electro- ity. However, certain soluble salts, such as perchlorates, ac-
plating plants, and cathodic protection systems. Kondo et etates, and salts of halogens other than chlorine may be
al.2.9 reported corrosion of reinforcing steel embedded in corrosive to steel embedded in concrete. Hydrogen sulfide
concrete used in an electric railroad. has also been cited as a cause of corrosion.2.22
2.2.11 Cathodic protectionThe principle of cathodic 2.2.13 Stress corrosion crackingStress corrosion2.23 is
protection is to change the potential of a metal to reduce the defined as the process in which the damage caused by stress
current flow and thereby the rate of corrosion. This is accom- and corrosion acting together greatly exceeds that produced
plished by the application of a protective current at a higher when they act separately.
222R-8 ACI MANUAL OF CONCRETE PRACTICE

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
Fig. 2.10Rate of reaction of gypsum with tricalcium alu- weight of the cement. It may be that the protective qualities
minate in portland cement2.29 of the pozzolan are related to its source or generic type.
The use of blended cements might, under certain circum-
In stressed steel, a small imperfection caused by corrosion stances, be detrimental because of a reduction in alkalinity.
can lead to a serious loss in tensile strength as the corrosion However, blended cements can give a substantial reduction in
continues at the initial anode area. permeability and also an increase in electrical resistivity espe-
Another form of corrosion that is related to stress corrosion cially where a reduction in the water-cement ratio is made pos-
cracking is intergranular corrosion. In this case, a gas, usual- sible. Also, such blended cements may give concrete as much
ly hydrogen, is absorbed in the iron, causing a loss of ductil- as two to five times higher resistance to chloride penetration
ity and cracking. Hydrogen cracking in connection with than concrete made with portland cements.2.27 The effects
cathodic protection will be discussed in Chapter 5. Other ma- would be beneficial as far as corrosion is concerned and in
terials that may cause intergranular corrosion are hydrogen some circumstances the benefits associated with blended ce-
sulfide and high concentrations of ammonia and nitrate salts. ments more than offset the adverse effects.
The mechanism of how this type of corrosion proceeds is not Even for cements with the highest reserve basicity, the al-
fully understood; however, it is believed that it involves the kalinity may be reduced in a number of ways. Reduction of
reduction in the cohesive strength of the iron. Documented alkalinity by leaching of soluble alkaline salts with water is
examples of stress corrosion cracking of steel in concrete an obvious process. Partial neutralization by reaction with
have not been found in the literature. carbon dioxide (carbonation), as present either in air or dis-
solved in water, is another common process.
2.3Effects of the concrete environment on The silicates are the major components in portland cement
corrosion
2.3.1 Portland cementWhen portland cement hydrates, imparting strength to the matrix. No reactions have been de-
the silicates react with water to produce calcium silicate hy- tected between chloride ions and silicates. Calcium chloride
drate and calcium hydroxide. The following simplified accelerates the hydration of the silicates when at least 1 per-
equations give the main reactions of portland cement with water cent by weight is added.2.28 Calcium chloride seems to act as
an accelerator in the hydration of tricalcium silicate as well
2(3CaO SiO2) + 6H2O 3CaO 2SiO2 3H20 + as to promote the corrosion of steel.
3Ca(OH)2 (2-5) Also present in portland cement are C3A and an alumino-
ferrite phase reported as C4AF. The C3A reacts rapidly in the
2(2CaO SiO2) + 4H2O 3CaO 2SiO2 3H2O + cement system to cause flash set unless it is retarded. Calci-
Ca(OH)2 (2-6) um sulfate is used as the retarder. Calcium sulfate forms a
coating of ettringite (C3A 3CaSO4 32H2O) around the alu-
As previously mentioned, the high alkalinity of the chem- minate grains thereby retarding their reactivity (Fig. 2.10).
ical environment normally present in concrete protects the Calcium chloride also forms insoluble reaction products with
embedded steel because of the formation of a protective ox- the aluminates in cement (see Fig. 2.11). The most commonly
ide film on the steel. The integrity and protective quality of noted complex is C3A CaCl2 xH2O, Friedels salt (Table 2.1).
this film depends on the alkalinity (pH) of the environment. The rate of formation of this material is slower than that of
Differences in the types of cement are a result of variation ettringite (compare Fig. 2.10 with Fig. 2.11). The chloride-
in composition or fineness or both, and as such, not all types aluminate complex forms after ettringite and prevents further
of cement have the same ability to provide protection of 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

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.
Fig. 2.13Gradient of total chloride concentration depth
1251-1268.
depends on whether chemical reaction occurs with cement2.41 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.
sodium nitrite, and calcium nitrite. Organic inhibitors suggest- 2.5. Stratfull, R. F.; Jurkovich, W. J.; and Spellman, D. L., Corrosion
Testing of Bridge Decks, Transportation Research Record No. 539, Trans-
ed have included sodium benzoate, ethyl aniline, and mercap- portation Research Board, 1975, pp. 50-59.
tobenzothiazole. With some inhibitors, inhibition occurs only 2.6. Browne, Roger D., Mechanisms of Corrosion of Steel in Concrete
at addition rates sufficiently high to counteract the effects of in Relation to Design, Inspection, and Repair of Offshore and Coastal
chlorides. Sodium nitrite has been used with apparent effec- Structures, Performance of Concrete in Marine Environment, SP-65,
tiveness in Europe.2.38 Calcium nitrite2.39 is being studied in American Concrete Institute, Detroit, 1980, pp. 169-204.
2.7. Aziz, M. A., and Mansur, M. A., Deterioration of Marine Concrete
the United States since several side effects of the sodium salt Structures with Special Emphasis on Corrosion of Steel and Its Remedies,
would be avoided. Some of the side effects are low strength, Corrosion of Reinforcement in Concrete Construction, Ellis Horwood Lim-
erratic times of setting, efflorescence, and enhanced suscepti- ited, Chichester, 1983, pp. 91-99.
bility to the alkali-aggregate reaction.2.40 2.8. Gjrv, Odd E., Durability of Concrete Structures in the Ocean
Environment, Proceedings, FIP Symposium on Concrete Sea Structures
2.3.5 Concrete qualityConcrete will offer more pro-
(Tbilisi, Sept. 1972), Federation Internationale de la Precontrainte, Lon-
tection against corrosion of embedded steel if it is of a high don, 1973, pp. 141-145.
quality. A low water-cement ratio will slow the diffusion of 2.9. Foley, R. T., Complex Ions and Corrosion, Journal, Electrochemi-
chlorides, carbon dioxide, and oxygen and also the increase in cal Society, V. 122, No. 11, 1975, pp. 1493-1549.
strength of the concrete may extend the time before corrosion- 2.10. Pourbaix, M., Atlas of Electrochemical Equilibrium in Aqueous
Solutions, Pergamon Press Limited, London, 1976.
induced stresses cause cracking of the concrete. The pore vol-
2.11. Monfore, G. E., and Verbeck, G. J., Corrosion of Prestressed Wire in
ume and permeability can be reduced by lowering the water- Concrete, ACI JOURNAL, Proceedings V. 57, No. 5, Nov. 1960, pp. 491-516.
cement ratio. The type of cement or use of superplasticizing 2.12. Monfore, G. E., and Ost, Borje, Corrosion of Aluminum Conduit
and mineral admixtures may also be an important factor in in Concrete,Journal, PCA Research and Development Laboratories, V. 7,
controlling the permeability and the ingress of chlorides.2.31 No. 1, Jan. 1967, pp. 10-22.
2.13. Boyd, W. K., and Tripler, A. B., Corrosion of Reinforcing Steel
2.3.6 Thickness of concrete cover over steel-The amount Bars in Concrete, Materials Protection, V. 7, No. 10, 1968, pp. 40-47.
of concrete cover over the steel should be as large as possible, 2.14. Baker, E. A.; Money, K. L.; and Sanborn, C. B., Marine Corrosion
consistent with good structural design, the severity of the ser- Behavior of Bare and Metallic-Coated Steel Reinforcing Rods in Con-
vice environment, and cost. The effect of cover thickness is crete, Chloride Corrosion of Steel in Concrete, STP-629, ASTM, Phila-
more than a simple linear relationship. Considering the normal delphia, 1977, pp. 30-50.
2.15. Stern, M., and Geary, A. L., Electrochemical Polarization No. 1
diffusion of an electrolyte into a porous solid without chemi- Theoretical Analysis of the Shape of Polarization Curves, Journal, Elec-
cal reaction, a relationship such as shown in Fig. 2.13 would trochemical Society, V. 104, No. 1, 1957, pp. 56-63.
be anticipated. However, in the case of cement paste, the dif- 2.16. Rosenberg, A. M., and Gaidis, J. M., The Mechanism of Nitrite
fusion of chloride ions into the paste is accompanied by both Inhibition of Chloride Attack on Reinforcing Steel in Alkaline Aqueous
Environments, Materials Performance, V. 18, No. 11, 1979, pp. 45-48. e
physical adsorption and chemical binding. These effects re-
2.17. Corrosion of Reinforcement and Prestressing Tendons: A State of
duce the concentration of chloride ion at any particular site the Art Report, Materials and Structures/Research and Testing (RILEM,
and hence the tendency for inward diffusion is further re- Paris), V. 9, No. 51, May-June 1976, pp. 187-206.
duced. This is also illustrated in Fig. 2.13. 2.18. Grimes, W. D.; Hartt, W. H.; and Turner, D. H., Cracking of Con-
2.3.7 CarbonationCarbonation occurs when the con- crete in Sea Water Due to Embedded Metal Corrosion, Cor rosion, V. 35,
No. 7, 1979, pp. 309-316.
crete reacts with carbon dioxide from the air or water and re-
2.19. Kondo, Yasuo; Takeda, Akihiko; and Hideshima, Setsuji, Effect
duces the pH to about 8.5. At this low pH the steel is no of Admixtures on Electrolytic Corrosion of Steel Bars in Reinforced Con-
longer passive and corrosion may occur. For high-quality crete, ACI JOURNAL, Proceeding s V. 56, No. 4, Oct. 1959, pp. 299-312.
CORROSION OF METALS 222R-11

2.20. Eickemeyer, J., Stress Corrosion Cracking of a High-Strength CHAPTER 3PROTECTION AGAINST
Steel in Saturated Ca(OH)2 Solutions Caused by Cl and SO4 Additions, CORROSION IN NEW CONSTRUCTION
Corrosion Science, V. 18, No. 4, 1978, pp. 397-400. 3.1Introduction
2.21. Hamada, M., Neutralization (Carbonation) of Concrete and Measures which can be taken in reinforced concrete con-
Corrosion of Reinforcing Steel, Proceedings, 5th International Sym- struction to protect the steel against corrosion can be divided
posium on the Chemistry of Cement (Tokyo, 1968), Cement Associa-
tion of Japan, Tokyo, 1969, V. 3, pp. 343-360.
into three categories:
2.22. Treadaway, K. W. J., Corrosion of Prestressed Steel Wire in (a) Design and construction practices that maximize the
Concrete, British Corrosion Journal (London), V. 6, 1971, pp. 66-72. protection afforded by the portland cement concrete. l
2.23. Sluijter, W. L., and Kreijger, P. C., Potentio Dynamic Polar- (b) Treatments that penetrate or are applied on the surface
ization Curves and Steel Corrosion, Heron (Delft), V. 22, No. 1, 1977,
pp. 13-27. of the reinforced concrete member to exclude chloride ion
2.24. Weise, C. H., Determination of the Free Calcium Hydroxide from the concrete.
Contents of Hydrated Portland Cements and Calcium Silicates, Analyt- (c) Techniques that prevent corrosion of the reinforce-
ical Chemistry, V. 33, No. 7, June 1961, pp. 877-882. Also, Research ment directly.
Department Bulletin No. 127, Portland Cement Association.
2.25. Rosenqvist, I. T., Korrosjon av Armeringsstal i Betong, In the last case, two approaches are possible: to use
Teknisk Ukeblad (Oslo), 1961, pp. 793-795. corrosion-resistant reinforcing steel or to nullify the effects
2.26. Spellman, D. L., and Stratfull, R. F., Concrete Variables and of chloride ions on unprotected reinforcement.
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- 3.2Design and construction practices
ride Ions in Hardened Cement Pastes, Cement and Concrete Research, Through careful design and good construction practices,
V. 11, No. 3, May 1981, pp. 395-406. the protection provided by portland cement concrete to em-
2.28. Ramachandran, V. S., Calcium Chloride in Concrete, Applied bedded reinforcing steel can be optimized. It is not the so-
Science Publishers, London, 1976, 216 pp.
phistication of the structural design that determines the
2.29. Rosenberg, Arnold M., Study of the Mechanism through
Which Calcium Chloride Accelerates the Set of Portland Cement, ACI durability of a concrete member in a corrosive environment
JOURNAL, Proceeding s V. 61, No. 10, Oct. 1964, pp. 1261-1270. but the detailing practices.3.1 The provision of adequate
2.30. Mehta, P. K., Effect of Cement Composition on Corrosion of drainage and a method of removing drainage water from the
Reinforcing Steel in Concrete, Chloride Corrosion of Steel in Con- structure are particularly important.
crete, STP-629, ASTM, Philadelphia, 1977, pp. 12-19.
2.31. Gjrv, O. E., and Vennesland, ., Diffusion of Chloride Ions In reinforced concrete members exposed to chlorides and
from Seawater into Concrete, Cement and Concrete Research, V. 9, subjected to intermittent wetting, the degree of protection
No. 2, Mar. 1979, pp. 229-238. against corrosion is determined primarily by the depth of
2.32. Stratfull, R. F., Discussion of Long-Time Study of Cement cover to the reinforcing steel and the permeability of the con-
Performance. Chapter 12Concrete Exposed to Sea Water and Fresh
Water, by I. L. Tyler, ACI JOURNAL, Proceeding s V. 56, Part 2, Sept.
crete.3.2-3.6 Estimates of the increase in corrosion protection
1960, pp. 1455-1458. provided by an increase in cover have ranged between slight-
2.33. Helms, S. B., and Bowman, A. L., Corrosion of Steel in Light- ly more than a linear relationship3.3,3.7 to as much as the
weight Concrete Specimens, ACI JOURNAL, Proceedings V. 65, No. square of the cover.3.8 The time to spalling is a function of
12, Dec. 1968, pp. 1011-1016.
the ratio of cover to bar diameter,3.8 the reinforcement spac-
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 ing, and the concrete strength. Although conventional port-
Annual Offshore Technology Conference, Houston, May 1977, pp. land cement concrete is not impermeable, concrete with a
581-588. very low permeability can be made through the use of good
2.35. Tremper, Bailey; Beaton, John L.; and Stratfull, R. F., Causes quality materials, a minimum water-cement ratio consistent
and Repair of Deterioration to a California Bridge Due to Corrosion of
Reinforcing Steel in a Marine Environment II: Fundamental Factors with placing requirements, good consolidation and finishing
Causing Corrosion, Bulletin No. 182, Highway Research Board, Wash- practices, and proper curing.
ington, D.C., 1958, pp. 18-41. In concrete that is continuously submerged, the rate of cor-
2.36. Browne, R. D., Design Prediction of the Life for Reinforced rosion is controlled by the rate of oxygen diffusion that is not
Concrete in Marine and Other Chloride Environments, Durability of
Building Materials (Amsterdam), V. 1, 1982, pp. 113-125. significantly affected by the concrete quality or the thickness
2.37. Cavalier, P. G., and Vassie, P. R., Investigation and Repair of of cover.3.9 However, as noted in Chapter 2, corrosion of
Reinforcement Corrosion in a Bridge Deck, Proceedings, Institution of embedded steel is a rare occurrence in continuously sub-
Civil Engineers (London), Part 1, V. 70, 1981, pp. 461-480. merged concrete structures.
2.38. Woods, Hubert, Durability of Concrete Construction, ACI
Monograph No. 4, American Concrete Institute/Iowa State University Placing limits on the allowable amounts of chloride ion in
Press, Detroit, 1968, p. 102. concrete is an issue still under active debate. On the one side
2.39. Rosenberg, A. M.; Gaidis, J. M.; Kossivas, T. G.; and Previte, are the purists who would like to see essentially no chlorides
R. W., A Corrosion Inhibitor Formulated with Calcium Nitrite for Use in concrete. On the other are the practitioners, including
in Reinforced Concrete, Chloride Corrosion of Steel in Concrete, STP-
629, ASTM, Philadelphia, 1977, pp. 89-99.
those who must produce concrete under cold weather con-
2.40. Craig, R. J., and Wood, L. E., Effectiveness of Corrosion ditions, precast concrete manufacturers who wish to mini-
Inhibitors and Their Influence on the Physical Properties of Portland mize curing times, producers of chloride-bearing aggregates,
Cement Mortars, Highway Research Record No. 328, Highway and some admixture companies, who would prefer the least
Research Board, 1970, pp. 77-88.
restrictive limit possible. Since chlorides are present natural-
2.41. Verbeck, George J., Mechanisms of Corrosion of Steel in Con-
crete, Corrosion of Metals in Concrete, SP-49, American Concrete ly in most concrete-making materials, specifying a zero
Institute, Detroit, 1975, pp. 21-38. 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 steel in concrete exposed to chlorides in service. However, in
in concrete, the risk of corrosion increases as the chloride determining a limit on the chloride content of the mix ingre-
content increases. When the chloride content exceeds a cer- dients, several other factors need to be considered.
tain value (termed the chloride corrosion threshold), unac- As noted in the figures already given, the water-soluble
ceptable corrosion may occur provided that other necessary chloride content is not a constant proportion of the acid-
conditions, chiefly the presence of oxygen and moisture, ex- soluble chloride content. It varies with the amount of chlo-
ist to support the corrosion reactions, It is a difficult task to ride in the concrete,3.10 the mix ingredients, and the test meth-
establish a chloride content below which the risk of corrosion is od. All the materials used in concrete contain some chlorides,
negligible, which is appropriate for all mix ingredients and and, in the case of cement, the chloride content in the hardened
under all exposure conditions, and which can be measured concrete varies with cement composition. Although aggre-
by a standard test. gates do not usually contain significant amounts of chlo-
Three different analytical values have been used to desig- ride,3.15 there are exceptions. There are reports of aggregates
nate the chloride content of fresh concrete, hardened con- with an acid-soluble chloride content of more than 0.1 percent
crete, or any of the concrete mixture ingredients: (a) total, of which less than one-third is water-soluble when the aggre-
(b) acid-soluble, and (c) water-soluble. gate is pulverized.3.16 The chloride is not soluble when the ag-
The total chloride content of concrete is measured by the gregate is placed in water over an extended period and there is
total amount of chlorine. Special analytical methods are no difference in the corrosion performance of structures in
necessary to determine it, and acid-soluble chloride is often southern Ontario made from this aggregate when compared to
mistakenly called total chloride. The acid-soluble method other chloride-free aggregates in the region. However, this is
is the test method in common use and measures that chlo- not always the case. Some aggregates, particularly those from
ride that is soluble in nitric acid. Water-soluble chloride is arid areas or dredged from the sea, may contribute sufficient
chloride extractable in water under defined conditions. The chloride to the concrete to initiate corrosion. A limit of 0.06
result obtained is a function of the analytical test procedure, percent acid-soluble chloride ion in the combined fine and
particularly with respect to particle size, extraction time, coarse aggregate (by mass of the aggregate) has been suggest-
and temperature, and to the age and environmental expo- ed with a further proviso that the concrete should not contain
sure of the concrete. more than 0.4 percent chloride (by mass of the cement) de-
It is also important to distinguish clearly between chloride rived from the aggregate.3.17
content, sodium chloride content, calcium chloride content, There is thought to be a difference in the chloride corrosion
or any other chloride salt content. In this report, all referenc- threshold value depending on whether the chloride is present
es to chloride content pertain to the amount of chloride ion in the mix ingredients or penetrates the hardened concrete
(Cl-) present. Chloride contents are expressed in terms of the from external sources. When chloride is added to the mix,
mass of cement unless stated otherwise. some will chemically combine with the hydrating cement
Lewis3.10reported that, on the basis of polarization tests of paste. The amount of chloride forming chloroaluminates is a
steel in saturated calcium hydroxide solution and water ex- function of the C3A content of the cement.3.18 Chloride add-
tracts of hydrated cement samples, corrosion occurred when ed to the mix will also tend to be distributed relatively uni-
the chloride content was 0.33 percent acid-soluble chloride, formly and, therefore, has less tendency to cause the creation
or 0.16 percent water-soluble chloride based on a 2 hr ex- of concentration cells.
traction in water. However, it has been shown that the pore- Conversely, when chloride permeates from the surface of
water in many typical portland cement concretes made hardened concrete, uniform chloride contents will not exist
using relatively high-alkali cements is a strong solution of around the steel because of differences in the concentration
sodium and potassium hydroxides with a pH approaching of chlorides on the concrete surface resulting from poor
14. Since the passivity of embedded steel is determined by drainage, for example, local differences in permeability, and
the ratio of the hydroxyl concentration to the chloride con- variations in the depth of cover to the steel. All these factors
centration,3.11 the amounts of chloride that can be tolerated promote differences in the environment (oxygen, moisture,
in concrete are higher than those that will cause pitting cor- and chloride content) along a given piece of reinforcement.
rosion in a saturated solution of calcium hydroxide.3.12 Furthermore, most structures contain reinforcement at dif-
Work at the Federal Highway Administration ferent depths, and, because of the procedures used to fix the
laboratories3.5 showed that for hardened concrete subject to steel, the steel is electrically connected. Thus, when chloride
externally applied chlorides, the corrosion threshold was penetrates the concrete, some of the steel is in contact with
0.20 percent acid-soluble chlorides. The average content of chloride-contaminated concrete while other steel is in
water-soluble chloride in concrete was found to be 75 to 80 chloride-free concrete. This creates a macroscopic corrosion
percent of the content of acid-soluble chloride in the same cell that can possess a large driving voltage and a large cath-
concrete. This corrosion threshold value was subsequently ode to small anode ratio which accelerates the rate of corrosion.
confirmed by field studies of bridge decks including those in In seawater, it has been suggested that the permeability of
California3.13 and New York.3.14 These investigations show the concrete to chloride penetration is reduced by the precip-
that, under some conditions, a chloride content of as little as itation of magnesium hydroxide.3.19
0.15 percent water-soluble chloride (or 0.20 percent acid- In laboratory studies3.20 in which sodium chloride was added
soluble chloride) is sufficient to initiate corrosion of embedded to the mix ingredients, it was found that a substantial increase in
CORROSION OF METALS 222R-13

corrosion rate occurred between 0.4 and 0.8 percent chloride, Normally concrete materials are tested for chloride con-
although the moisture conditions of the test specimens were tent using either the acid-soluble test described in ASTM C
not clearly defined. Other researchers have suggested3.21 1152, Acid-Soluble Chloride in Mortar and Concrete, or
that the critical level of chloride in the mix ingredients to water-soluble test described in ASTM C 1218, Water-
initiate corrosion is 0.3 percent and that this has a similar Soluble Chloride in Mortar and Concrete. If the materials
effect to 0.4 percent chloride penetrating the hardened con- meet the requirements given in either of the relevant col-
crete from external sources. In studies in which calcium umns in the previous table they are acceptable. If they meet
chloride was added to portland cement concrete, it was neither of the relevant limits given in the table then they may
found3.22 that the chloride ion concentration in the pore so- be tested using the Soxhlet test method. Some aggregates,
lution remained high during the first day of hydration. It de- such as those discussed previously,3.16 contain a consider-
clined gradually, but it appeared that substantial able amount of chloride that is sufficiently bound that it does
concentrations of chloride ion remained in solution indefinitely. not initiate or contribute towards corrosion. The Soxhlet test
Chloride limits in national codes vary widely. ACI 318 al- appears to measure only those chlorides that contribute to the
lows a maximum water-soluble chloride ion content of 0.06 corrosion process, thus permitting the use of some aggre-
percent in prestressed concrete, 0.15 percent for reinforced gates that would not be allowed if only the ASTM C 1152 or
concrete exposed to chloride in service, 1.00 percent for re- ASTM C 1218 tests were used. If the materials fail the
inforced concrete that will be dry or protected from moisture Soxhlet test, then they are not suitable.
in service, and 0.30 percent for all other reinforced concrete For prestressed and reinforced concrete that will be exposed
construction. The British Code, CP 110, allows an acid-sol- to chlorides in service, it is advisable to maintain the lowest pos-
uble chloride ion content of 0.35 percent for 95 percent of the sible chloride levels in the mix to maximize the service life of
test results with no result greater than 0.50 percent. These the concrete before the critical chloride content is reached and a
values are largely based on an examination of several struc- high risk of corrosion develops. Consequently, chlorides should
tures in which it was found there was a low risk of corrosion not be intentionally added to the mix ingredients even if the
up to 0.4 percent chloride added to the mixture.3.23 However, chloride content in the materials is less than the stated limits. In
corrosion has occurred at values less than 0.4 percent,3.24 many exposure conditions, such as highway and parking struc-
particularly where the chloride content was not uniform. The tures, marine environments, and industrial plants where chlo-
Norwegian Code, NS 3474, allows an acid-soluble chloride rides are present, additional protection against corrosion of
content of 0.6 percent for reinforced concrete made with nor- embedded steel is necessary.
mal portland cement but only 0.002 percent chloride ion for Since moisture and oxygen are always necessary for elec-
prestressed concrete. Both these codes are under revision. trochemical corrosion, there are some exposure conditions
Other codes have different limits, though the rationale for where the chloride levels may exceed the recommended val-
these limits is not well established. ues and corrosion will not occur. Concrete which is continu-
Corrosion of prestressing steel is generally of greater ously submerged in seawater rarely exhibits corrosion-
concern than corrosion of conventional reinforcement be- induced distress because there is insufficient oxygen present.
cause of the possibility that corrosion may cause a local re- Similarly, where concrete is continuously dry, such as the in-
duction in cross section and failure of the steel. The high terior of a building, there is little risk of corrosion from chlo-
stresses in the steel also render it more vulnerable to stress- ride ions present in the hardened concrete. However, interior
corrosion cracking and, where the loading is cyclic, to cor- locations that are wetted occasionally, such as kitchens or
rosion fatigue. However, most examples of failure of pre- laundry rooms or buildings constructed with lightweight ag-
stressing steel that have been reported3.24-3.26 have resulted gregate that is subsequently sealed (e.g., with tiles) before
from macrocell corrosion reducing the load carrying area
the concrete dries out, are susceptible to corrosion damage.
of the steel. Nevertheless, because of the greater vulnera-
Whereas the designer has little control over the change in use
bility and the consequences of corrosion of prestressing
of a building or the service environment, the chloride content
steel, chloride limits in the mix ingredients are lower than
of the mix ingredients can be controlled. Estimates or judg-
for conventional concrete. Based on the present state of
ments of outdoor dry environments can be misleading.
knowledge, the following chloride limits in concrete used
Stratfull3.27 has reported the case of approximately 20 bridge
in new construction, expressed as a percentage by weight of
decks containing 2 percent calcium chloride built by the Cal-
portland cement, are recommended to minimize the risk of
ifornia Department of Transportation. The bridges were lo-
chloride-induced corrosion.
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-
Category Chloride limit for new construction struction, many were showing signs of corrosion-induced
Acid-soluble Water-soluble spalling and most were removed from service within 10
Test method ASTM C 1152 ASTM C 1218 Soxhlet* years. For these reasons, the committee believes a conserva-
Prestressed concrete 0.08 0.06 0.06 tive approach is necessary.
Reinforced concrete The maximum chloride limits suggested in this report dif-
0.10 0.08 0.08
in wet conditions
Reinforced concrete fer from those suggested by ACI Committee 2013.2 and
0.20 0.15 0.15
in dry conditions those contained in the ACI Building Code. When making a
*
The Soxhlet Method of Test is described in the appendix to this report. comparison between the figures, it should be noted that the
222R-14 ACI COMMITTEE REPORT

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.
Fig. 3.1Effect of water-cement ratio on salt penetration3.5 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
Fig. 3.2E ffect of inadequate consolidation on salt
0.40 water-cement ratio concrete was sufficient to protect
penetration3.5 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-
Fig. 3.3Effect of water-cement ratio and depth of cover struction practices must insure that the specified cover is
on relative time to corrosion3.5 achieved. Conversely, placing tolerances, the method of
construction, and the level of inspection should be consid-
ered in determining the specified cover.
figures in this report refer to acid-soluble chlorides while the
The role of cracks in the corrosion of reinforcing steel is
other documents make reference to water-soluble chlorides.
controversial. Two schools of thought exist.3.32,3.33 One
As noted previously, Committee 222 has taken a more con-
viewpoint is that cracks reduce the service life of structures
servative approach because of the serious consequences of cor- by permitting more rapid penetration of carbonation and a
rosion, the conflicting data on corrosion threshold values, means of access of chloride ions, moisture, and oxygen to the
and the difficulty of defining the service environment reinforcing steel. The cracks thus accelerate the onset of the
throughout the life of a structure. corrosion processes and, at the same time, provide space for
Various nonferrous metals and alloys will corrode in damp the deposition of the corrosion products. The other viewpoint
or wet concrete. Surface attack of aluminum occurs in the is that while cracks may accelerate the onset of corrosion, such
CORROSION OF METALS 222R-15

corrosion is localized. Since the chloride ions eventually (d) Maintain impermeability to chlorides and moisture un-
penetrate even uncracked concrete and initiate more wide- der service conditions, especially temperature extremes,
spread corrosion of the steel, the result is that after a few crack bridging, aging, and superimposed loads.
years service there is little difference between the amount of The number of types of products manufactured to satisfy
corrosion in cracked and uncracked concrete. these requirements makes generalization difficult. Any sys-
The differing viewpoints can be partly explained by the tem of classification is arbitrary, though one of the most use-
fact that the effect of cracks is a function of their origin, ful is the distinction between the preformed sheet systems
width, intensity, and orientation. Where the crack is perpen- and the liquid-applied materials.3.38 The preformed sheets
dicular to the reinforcement, the corroded length of inter- are manufactured under factory conditions but are often dif-
cepted bars is likely to be no more than three bar ficult to install, usually require adhesives, and are highly vul-
diameters.3.33 Cracks that follow the line of a reinforcement nerable to the quality of the workmanship at critical
locations in the installation. Although it is more difficult to
bar (as might be the case with a plastic shrinkage crack, for
control the quality of the liquid-applied systems, they are
example) are much more damaging because the corroded
easier to apply and tend to be less expensive.
length of bar is much greater and the resistance of the con-
Given the different types and quality of available water-
crete to spalling is reduced. Studies have shown that cracks
proofing products, the differing degrees of workmanship,
less than about 0.3 mm (0.012 in.) wide have little influence
and the wide variety of applications, it is not surprising that
on the corrosion of reinforcing steel.3.8 Other investigations laboratory3.39-3.41 and field3.14,3.42,3.43 evaluations of
have shown that there is no relationship between crack width membrane performance have also been variable and some-
and corrosion.3.34-3.36 Furthermore, there is no direct rela- times contradictory. Sheet systems generally perform better
tionship between surface crack width and the internal crack than liquid-applied systems in laboratory screening tests be-
width. Consequently, it has been suggested that the control cause quality of workmanship is not a factor. Although there
of surface crack widths in design codes is not the most ratio- has been little uniformity in both methods of test or accep-
nal approach.3.37 tance criteria, permeability (usually determined by electrical
For the purposes of design, it is useful to differentiate be- resistance measurements) has generally been adopted as the
tween controlled and uncontrolled cracks. Controlled cracks most important criterion. However, some membranes do of-
are those which can be reasonably predicted from a knowl- fer substantial resistance to chloride and moisture intrusion,
edge of section geometry and loading. For cracking perpen- even when pinholes or bubbles occur in the membrane.3.41
dicular to the main reinforcement, the necessary conditions Field performance has been found to depend not only on the
for crack control are that there be sufficient steel so that it re- type of waterproofing material used, but also on the quality of
mains in the elastic state under all loading conditions, and workmanship, weather conditions at the time of installation, de-
that at the time of cracking, the steel is bonded (i.e., cracking sign details, and the service environment. Experience has
must occur after the concrete has set). ranged from satisfactory3.43 to failures that have resulted in the
Examples of uncontrolled cracking are cracks resulting membrane having to be removed.3.44,3.45
from plastic shrinkage, settlement, or an overload condition. Blistering, which affects both preformed sheets and liquid-
Uncontrolled cracks are frequently wide and usually cause applied materials, is the single greatest problem encountered
concern, particularly if they are active. However, they can- in applying waterproofing membranes.3.46 It is caused by the
not be dealt with by conventional design procedures, and expansion of entrapped gases, solvents, and moisture in the
concrete after application of the membrane. The frequency
measures have to be taken to avoid their occurrence or, if
of blisters occurring is controlled by the porosity and mois-
they are unavoidable, to induce them at places where they
ture content of the concrete3.47 and the atmospheric conditions.
are unimportant or can be conveniently dealt with, by sealing
Water or water vapor is not a necessary requirement for blis-
for example.
ter formation, but is often a contributing factor. Blisters may
also result from an increase in concrete temperature or a de-
3.3Methods of excluding external sources of crease in atmospheric pressure during or shortly after appli-
chloride ion from concrete
cation of membranes. The rapid expansion of vapors during
3.3.1 Waterproof membranesWaterproof membranes
the application of hot-applied products sometimes causes
have been used extensively to minimize the ingress of chlo-
punctures (which are termed blowholes) in the membrane.
ride ions into concrete. Since external sources of chloride
Membranes can be placed without blisters if the atmo-
ions are waterborne, a barrier to water will also act as a bar-
spheric conditions are suitable during the curing period.
rier to any dissolved chloride ions.
Once cured, the adhesion of the membrane to the concrete is
The requirements for the ideal waterproofing system are usually sufficient to resist blister formation. To insure good
straightforward;3.38 it should: adhesion, the concrete surface must be carefully prepared
(a) Be easy to install, and be dry and free from curing membranes, laitance, and
(b) Have good bond to the substrate, contaminants such as oil drippings. Sealing the concrete pri-
(c) Be compatible with all the components of the system or to applying the membrane is possible, but rarely practi-
including the substrate, prime coat, adhesives, and overlay cal.3.48 Where the membrane is to be covered (for example,
(where used), 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 ommendations for safe storage and handling of the chemi-
placement of the membrane and the overlay. cals must be followed.
Venting layers have been used in Europe, but rarely in A bond coat of neat polymer is usually applied ahead of
North America, to prevent blister formation by allowing the the polymer concrete. Blistering, which is a common phe-
vapor pressures to disperse beneath the membrane. The dis- nomenon in membranes, has also caused problems in the ap-
advantages of using venting layers are that they require con- plication of polymer concrete overlays. A number of
trolled debonding of the membrane, leakage through the applications were reported in the 1960s.3.52,3.53 Many lasted
membrane is not confined to the immediate area of the punc- only a few years. More recently, experimental polymer over-
ture, and they increase cost. lays based on a polyester-styrene monomer have been
3.3.2 Polymer impregnationPolymer impregnation con- placed, using heavy-duty finishing equipment to compact
sists of filling some of the voids in hardened concrete with a and finish the concrete.3.54
monomer and polymerizing in situ. Laboratory studies have 3.3.4 Portland cement concrete overlaysPortland ce-
demonstrated that polymer impregnated concrete (PIC) is ment concrete overlays for new reinforced concrete are ap-
strong, durable, and almost impermeable. The properties of plied as part of a two-stage construction process. The overlay
PIC are largely determined by the polymer loading in the may be placed before the first-stage concrete has set or sev-
concrete. Maximum polymer loadings are achieved by dry- eral days later, in which case a bonding layer is used between
ing the concrete to remove nearly all the evaporable water, the two lifts of concrete. The advantage of the first alterna-
removing air by vacuum techniques, saturation with a monomer tive is that the overall time of construction is shortened and
under pressure, and polymerizing the monomer in the voids costs minimized. In the second alternative, cover to the
of the concrete while simultaneously preventing evaporation reinforcing steel can be assured, and small construction tol-
of the monomer. erances achieved because dead load deflections from the
In the initial laboratory studies on PIC, polymerization overlay are very small. No matter which sequence of con-
was accomplished by gamma radiation.3.49 However, this is struction is employed, materials can be incorporated in the
not practical for use in the field. Consequently, chemical ini- overlay to provide superior properties, such as resistance to
tiators, which decompose under the action of heat or a chem- salt penetration and wear and skid resistance, than possible us-
ing single stage construction.
ical promoter, have been used exclusively in field
applications. Multifunctional monomers are often used to in- Where the second stage concrete is placed after the first
stage has hardened, sand or water blasting is required to
crease the rate of polymerization.
remove laitance and to produce a clean, sound surface.
The physical properties of PIC are determined by the ex-
Resin curing compounds should not be used on the first-
tent to which the ideal processing conditions are compro-
stage construction because they are difficult to remove.
mised. Since prolonged heating and vacuum saturation are
Etching with acid was once a common means of surface
difficult to achieve, and increase processing costs substan-
preparation.3.55,3.56 but is now rarely used because of the
tially, most field applications have been aimed toward pro-
possibility of contaminating the concrete with chlorides
ducing only a surface polymer impregnation, usually to a
and the difficulty of disposing of the runoff.
depth of about 25 mm (1 in.). Such partially impregnated
Several different types of concrete have been used as con-
slabs have been found to have good resistance to chloride
crete overlays including conventional concrete,3.57 concrete
penetration in laboratory studies, but field applications have
containing steel fibers,3.57 and internally sealed con-
not always been satisfactory.3.5,3.50
crete.3.57,3.60 However, two types of concrete, low-slump
There have been a few full-scale applications of PIC to and latex-modified concrete, each designed to offer maxi-
protect reinforcing steel against corrosion and it must still be mum resistance to penetration by chloride ions, have been
considered largely an experimental process. Some of the dis- used most frequently.
advantages of PIC are that the monomers are expensive and 3.3.5 Low-slump concrete overlaysThe performance of
that the processing is lengthy and costly. The principal defi- low-slump concrete is dependent solely on the use of con-
ciency identified to date has been the tendency of the con- ventional materials and good quality workmanship. The
crete to crack during heat treatment. water-cement ratio is reduced to the minimum practical
3.3.3 Polymer concrete overlaysPolymer concrete over- (usually about 0.32) through the use of a high cement content
lays consisting of aggregate in a polymer binder have been (over 470 kg/m3 or 800 lb/yd3) and a water content sufficient
placed experimentally. to produce a slump less than 25 mm (1 in.). The concrete is
Most monomers have a low tolerance to moisture and low air-entrained and a water-reducing admixture or mild retard-
temperatures; hence the substrate must be dry and in excess er is normally used. The use of such a high cement factor and
of 4 C (40 F). Improper mixing of the two (or more) compo- low workability mixture dictates the method of mixing, plac-
nents of the polymer has been a common source of problems ing, and curing the concrete.
in the field. Aggregates must be dry so as not to inhibit the Following preparation of the first-stage concrete, a bond-
polymerization reaction. ing agent of either mortar or cement paste is brushed into the
Workers should wear protective clothing when working base concrete just before the application of the overlay. The
with epoxies and some other polymers because of the potential base concrete is not normally prewetted. The overlay con-
for skin sensitization and dermatitis.3.51 Manufacturers rec- crete is mixed on site, using either a stationary paddle mixer
CORROSION OF METALS 222R-17

or a mobile continuous mixer, because truck mixers are not 5. Air entrainment of the concrete is believed not required
suited to producing either the quantity or consistency of con- for resistance to freezing and thawing.
crete required. The concrete must be compacted and screed- 6. A combination of moist curing to hydrate the port-
ed to the required surface profile using equipment specially land cement and air drying to develop the film forming
designed to handle stiff mixtures. Such machines are much qualities of the latex are required. Typical curing times
heavier and less flexible than conventional finishing ma- are 24 hr wet curing, followed by 72 hr of dry curing. The
chines and have considerable vibratory capacity. The perme- film-formation property of the latex is temperature sensi-
ability of the concrete to chloride ions is controlled by its tive and film strengths develop slowly at temperatures be-
degree of consolidation, which is often checked with a nucle- low 13 C (55 F). Curing periods at lower temperatures
ar density meter as concrete placement proceeds. Wet burlap may need to be extended and application at temperatures
is placed on the concrete as soon as practicable without dam- less than 7 C (45 F) is not recommended.
aging the overlay (usually within 20 min of placing), and the Hot weather causes rapid drying of the latex-modified con-
wet curing is continued for at least 72 hr. Curing compounds crete, which makes finishing difficult and promotes shrinkage
are not used, since not only is externally available water re- cracking. Some contractors have placed overlays at night to
quired for more complete hydration of the cement, but the avoid these problems. The entrapment of excessive amounts
thin overlay is susceptible to shrinkage cracking and the wet of air during mixing has also been a problem in the field. Most
burlap provides a cooling effect by evaporation of the water. specifications limit the total air content to 6.5 percent. Higher
Low-slump concrete was originally proposed as a repair air contents reduce the flexural, compressive, and bond
material for concrete pavements3.55 and was developed for strengths of the overlay. Furthermore, the permeability to
patches and overlays on bridges3.61-3.63 in the early 1960s. chloride ions increases significantly at air contents greater
More recently, concrete overlays have been used as a pro- than about 9 percent. Where a texture is applied to the concrete
tection against reinforcing steel corrosion in new bridges. In as, for example, grooves to impart good skid resistance, the
general, the performance of low-slump overlays has been time of application of the texture is crucial. If applied too soon,
good.3.64-3.66 Local bond failures have been reported, but the edges of the grooves collapse because the concrete flows.
these have been ascribed to inadequate surface preparation3.64 If the texturing operation is delayed until after the latex film
or premature drying of the grout.3.66 The overlays are suscep- forms, the surface of the overlay tears and, since the film does
tible to cracking, especially on continuous structures, though not reform, cracking often results.
this is a characteristic of all rigid overlays. High material costs and the superior performance of latex-
3.3.6 Latex-modified concrete overlaysLatex-modified modified concrete in chloride penetration tests have led to
concrete is conventional portland cement concrete with the latex-modified concrete overlays being thinner than most
addition of a polymeric latex emulsion. The water of sus- low-slump concrete overlays. Typical thicknesses are 40 and
pension in the emulsion hydrates the cement and the poly- 50 mm (1.5 and 2 in.).
mer provides supplementary binding properties to produce a Although latex-modified overlays were first used in
concrete having a low water-cement ratio, good durability, 1957,3.67 the majority of installations were placed after
good bonding characteristics, and a high degree of resistance 1975. Performance has been generally satisfactory, though
to penetration by chloride ions, all of which are desirable extensive cracking and some debonding have been report-
properties in a concrete overlay. ed,3.68 especially in overlays 20 mm (0.75 in.) thick that were
The latex is a colloidal dispersion of synthetic rubber par- not applied at the time of the original deck construction. The
ticles in water. The particles are stabilized to prevent coagu- most serious deficiency reported has been the widespread oc-
lation, and antifoaming agents are added to prevent currence of shrinkage cracking in the overlays. Many of these
excessive air entrapment during mixing. Styrene-butadiene cracks have been found not to extend through the overlay and it
latexes have been used most widely. The rate of addition of is uncertain whether this will impair long-term performance.
the latex is approximately 15 percent latex solids by weight
of the cement. 3.4Methods of protecting reinforcing steel from
chloride ion
The construction procedures for latex-modified concrete The susceptibility to corrosion of mild steel reinforcement
are similar to those for low-slump concrete with minor mod- in common use is not thought to be significantly affected by
ifications. The principal differences are: its composition, grade, or the level of stress.3.69 Consequent-
1. The base concrete must be prewetted for at least 1 hr pri- ly, to prevent corrosion of the reinforcing steel in a corrosive
or to placing the overlay, because the water aids penetration environment, either the reinforcement must be made of a
of the base and delays film formation of the latex. noncorrosive material, or conventional reinforcing steel
2. A separate bonding agent is not always used, because must be coated to isolate the steel from contact with oxygen,
sometimes a portion of the concrete itself is brushed over the moisture, and chlorides.
surface of the base. 3.4.1 Noncorrosive steelsNatural weathering steels
3. The mixing equipment must have a means of storing commonly used for structural steelwork do not perform well
and dispensing the latex. in concrete containing moisture and chloride3.2 and are not
4. The latex-modified concrete has a high slump so that suitable for reinforcement. Stainless steel reinforcement has
conventional finishing equipment can be used. been used in special applications, especially as hardware for
222R-18 ACI COMMITTEE REPORT

attaching panels in precast concrete construction, but is coated reinforcing steel has increased substantially since it
much too expensive to replace mild-steel reinforcement in was first used in 1973.
most applications. Stainless-steel-clad bars have been evalu- The chief difficulty in using epoxy-coated bars has been
ated in the FHWA time-to-corrosion studies, and found to re- preventing damage to the coating in transportation and han-
duce the frequency of corrosion-induced cracking compared dling. Cracking of the coating has also been observed during
to black steel in the test slabs, but did not prevent it. Howev- fabrication where there has been inadequate cleaning of the
er, it was not determined whether the cracking was the result bar prior to coating or the thickness of the coating has been
of corrosion of the stainless steel or corrosion of the basis outside specified tolerances. Padded bundling bands, fre-
steel at flaws in the cladding. quent supports, and nonmetallic slings are required to pre-
3.4.2 CoatingsMetallic coatings for steel reinforcement vent damage during transportation. Coated tie wires and bar
fall into two categories, sacrificial and noble or nonsacrifi- supports are needed to prevent damage during placing. Ac-
cial. In general, metals with a more negative corrosion po- celerated time-to-corrosion studies have shown that nicks
tential (less noble) than steel, such as zinc and cadmium, and cuts in the coating do not cause rapid corrosion of the ex-
give sacrificial protection to the steel. If the coating is dam- posed steel and subsequent distress in the concrete.3.87 It
aged, a galvanic couple is formed in which the coating is the should be noted, however, that the damaged bars were not
anode. Noble coatings such as copper and nickel protect the electrically connected to uncoated steel in the early acceler-
steel only as long as the coating is unbroken, since any ex- ated tests. Subsequent tests3.88 showed that even in the case
posed steel is anodic to the coating. Even where steel is not of electrical coupling to large amounts of uncoated steel, the
exposed, macrocell corrosion of the coating may occur in performance of damaged and nonspecification bars was
concrete through a mechanism similar to the corrosion of un-
good, but not as good as when all the steel was coated.
coated steel.
Consequently, for long life in severe chloride environments,
Nickel,3.70,3.71 cadmium,3.72 and zinc3.70,3.73,3.74 have all consideration should be given to coating all the reinforcing
been shown to be capable of delaying, and in some cases pre-
steel. If only some of the steel is coated, precautions should
venting, the corrosion of reinforcing steel in concrete, but
be taken to assure that the coated bars are not electrically
only zinc-coated (galvanized) bars are commonly available.
coupled to large quantities of uncoated steel. A damaged
Results of the performance of galvanized bars have been
coating can be repaired using a two-component liquid epoxy,
conflicting, in some cases extending the time-to-cracking of
but it is more satisfactory to adopt practices that prevent
laboratory specimens,3.75 in others reducing it3.76 and some-
damage to the coating and limit touch-up only to bars where
times giving mixed results.3.77 It is known that the zinc will
the damage exceeds approximately 2 percent of the area of
corrode in concrete3.71,3.78 and that pitting can occur under
the bar.
conditions of nonuniform exposure in the presence of high
chloride concentrations.3.79 Studies have demonstrated that epoxy-coated, deformed
Field studies of galvanized bars in service for many years in reinforcing bars embedded in concrete can have bond
either a marine environment or exposed to deicing salts have strengths and creep behavior equivalent to those of uncoated
failed to show any deficiencies in the concrete.3.74 However, in bars.3.89,3.90 Another study3.91 reported that epoxy-coated
these studies, chloride ion concentrations at the level of the re- reinforcing has less slip resistance than normal mill scale re-
inforcing steel were low, such that the effectiveness could not inforcing, although, for the particular specimens tested, the
be established conclusively. Marine studies3.80 and accelerated epoxy-coated bars attained stress levels compatible with
field studies3.81 have shown that galvanizing will delay the on- ACI development requirements.
set of delaminations and spalls but will not prevent them. In
general, it appears that only a slight increase in life will be ob- 3.5Corrosion control methods
tained in severe chloride environments.3.82 When galvanized 3.5.1 Chemical inhibitorsA corrosion inhibitor is an ad-
bars are used, all bars and hardware in the structure should be mixture to the concrete used to prevent the corrosion of em-
coated with zinc to prevent galvanic coupling between coated bedded metal. The mechanism of inhibition is complex and
and uncoated steel.3.82 there is no general theory applicable to all situations.
Numerous nonmetallic coatings for steel reinforcement The effectiveness of numerous chemicals as corrosion in-
have been evaluated,3.83-3.86 but only fusion-bonded epoxy hibitors for steel in concrete3.69,3.92-3.94 has been studied.
powder coatings are produced commercially and widely The compound groups investigated have been primarily
used. The epoxy coating isolates the steel from contact with chromates, phosphates, hypophosphites, alkalies, nitrites,
oxygen, moisture, and chloride. and fluorides. Some of these chemicals have been suggested
The process of coating the reinforcing steel with the epoxy as being effective; others have produced conflicting results
consists of electrostatically applying finely divided epoxy in laboratory screening tests.
powder to thoroughly cleaned and heated bars. Many plants Many inhibitors that appear to be chemically effective pro-
operate a continuous production line and many have been duce adverse effects on the physical properties of the concrete,
constructed specifically for coating reinforcing steel. Integ- such as a significant reduction in compressive strength. More
rity of the coating is monitored by a holiday detector in- recently, calcium nitrite has been reported to be an effective
stalled directly on the production line. The use of epoxy- corrosion inhibitor3.95 and studies are continuing.3.88
CORROSION OF METALS 222R-19

Admixtures used to prevent corrosion of the steel by wa- 3.18. Roberts, M. H., Effect of Calcium Chloride on the Durability of
terproofing the concrete, notably silicones, have been found Pretensioned Wire in Prestressed Concrete. Magazine of Concrete
Resea rch (London), V. 14, No. 42, Nov. 1962, pp. 143-154.
to be ineffective.3.92 3.19. Haynes, Harvey H., Permeability of Concrete in Sea Water, Per-
3.5.2 Cathodic protectio nAlthough cathodic protection formance of Concrete in Marine Environment, SP-65, American Concrete
is a viable method of protecting reinforcing steel against cor- Institute, Detroit. 1980, pp. 21-38.
rosion in new construction, most installations to date have 3.20. Locke, C. E., and Siman, A., Electrochemistry of Reinforcing
Steel in Salt-Contaminated Concrete, Corrosion of Reinforcing Steel in
been to arrest corrosion in existing structures. Consequently, Concrete, STP-713, ASTM, Philadelphia, 1980, pp. 3-16.
the principles and performance of cathodic protection sys- 3.21. Browne, Roger D., Mechanisms of Corrosion of Steel in Concrete
tems are described in Chapter 5. in Relation to Design, Inspection, and Repair of Offshore and Coastal
It should be noted, however, that the reinforcement in Structures, Performance of Concrete in Marine Environment, SP-65,
American Concrete Institute, Detroit, 1980, pp. 169-204.
many offshore structures is connected to the cathodic protection 3.22. Diamond, S., and Lopez-Flores, F., Fate of Calcium Chloride Dis-
system used on the exposed steel. This results in protection solved in Concrete Mix Water, Journal, American Ceramic Society, V. 64,
of the reinforcement and current densities of 0.5 to 1.0 No. 11, Nov. 1981, pp. C 162-164.
mA/m2 (0.05 to 0.1 mA/ft2) have been reported.3.96 Thus ca- 3.23. The Role of Calcium Chloride in Concrete, Concrete Construction,
V. 21, No. 2, Feb. 1976, pp. 57-61.
thodic protection of the reinforcement, though unintentional, 3.24. Cornet, I., Corrosion of Prestressed Concrete Tanks, Materials
has been applied in several of the largest offshore structures. Protection, V. 3, No. 1, Jan. 1964, pp. 9-100.
3.25. Peterson, Carl A., Survey of Parking Structure Deterioration and
3.6References Distress, Conc rete International: Design & Construction, V. 2, No. 3,
3.1. Durability of Concrete Bridge Decks, NCHRP Synthesis No. 57, Mar. 1980. pp. 53-61.
Transportation Research Board Washington, D.C., 1979, 60 pp. 3.26. Monfore, G. E., and Verbeck, G. J., Corrosion of Prestressed Wire in
3.2. ACI Committee 201, Guide to Durable Concrete (ACI 201.2R77) Concrete, ACI JOURNAL, Proceedings V. 57, No. 5, Nov. 1960, pp. 491-516.
(Reaffirmed 1982), American Concrete Institute, Detroit, 1977, 37 pp. 3.27.A Manual for the Corrosion Control of Bridge Decks, Contract
3.3. Beaton, J. L., and Stratfull, R. F., Environmental Influence on Cor- No. DTFH-61-C-00016, Stratfull, R. F., ed., U.S. Department of Trans-
rosion of Reinforcing in Concrete Bridge Substructures, Highway portation, Washington, D.C.
Research Record No. 14, Highway Research Board, 1963, pp. 60-78. 3.28. Conduit in Concrete, Engineering Journal (Montreal), V. 38,
3.4. Ost, Borje, and Monfore, G. E., Penetration of Chloride into Con- No. 10, 1955, pp. 1357-1362.
crete, Journal, PCA Research and Development Laboratories, V. 8, No. 1, 3.29. Spalled Concrete Traced to Conduit, Engineering News-Record,
Jan. 1966, pp. 46-52. V. 172, No. 11, Mar. 12, 1964, pp. 28-29.
3.5. Clear, K. C., Time-to-Corrosion of Reinforcing Steel in Concrete 3.30. McGeary, Frank L., Performance of Aluminum in Concrete Con-
Slabs, V. 3: Performance after 830 Daily Salt Applications, Report taining Chlorides, ACI JOURNAL, Proceeding s V. 63, No. 2, Feb, 1966. pp.
No. FHWA-RD-76-70, Federal Highway Administration, Washington, 247-266.
D.C., 1976, 64 pp. 3.31. Erlin, B., and Woods, H., Corrosion of Embedded Materials Other
3.6. Stark, David, Studies of the Relationships between Crack Patterns, than Reinforcing Steel, Significance of Tests and Properties of Concrete
Cover over Reinforcing Steel and the Development of Surface Spalls in and Concrete-Making Materials, STP-169B, ASTM, Philadelphia, 1978, s
Bridge Decks, Special Report No. 116, Highway Research Board, Wash- pp. 300-319.
ington, D.C., 1971, pp. 13-21. Also, Resea rch and D evelopment Bulletin 3.32. Manning, D. G., Corrosion Resistant Design of Concrete Struc-
No. RD020E, Portland Cement Association. tures, Proceedings, Canadian Structural Concrete Conference, University
3.7. Cornet, I., Protection with Mortar Coatings, Materials Protection, of Toronto, 1981, pp. 199-223.
V. 6, No. 3, 1967, pp. 56-58. 3.33. Beeby, A. W., Corrosion of Reinforcing Steel in Concrete in Its
3.8. Atimay, E., and Ferguson, P. M., Early Chloride Corrosion of Rein- Relation to Cracking,The Structural Engineer (London), V. 56A, No. 3,
forced ConcreteA Test Report, Materials Performance, V. 13, No. 12, 1978, pp. 77-81.
1974, pp. 18-21. 3.34. Tremper, Bailey, The Corrosion of Reinforcing Steel in Cracked Con-
3.9. Gjrv, O. E.; Vennesland, .; and El-Busaidy, A. H. S., Diffusion of crete, ACI JOURNAL, Proceedings V. 43, No. 10, June 1947, pp. 1137-1144.
Dissolved Oxygen through Concrete, Paper No. 17, NACE Corrosion 76, 3.35. Martin, H., and Schiessel, P., The Influence of Cracks on the Cor-
National Association of Corrosion Engineers, Houston, Mar. 1976, 13 pp. rosion of Steel in Concrete, Preliminary Report, RILEM International
3.10. Lewis, D. A., Some Aspects of the Corrosion of Steel in Con- Symposium on the Durability of Concrete, Prague, 1969, V. 2.
crete, Proceedings, 1st International Congress on Metallic Corrosion, But- 3.36. Raphael, M., and Shalon, R., A Study of the Influence of Climate
terworths, London, 1962, pp. 547-552. on Corrosion of Reinforcement, Proceedings, RILEM Symposium on
3.11. Gouda, V. K., Corrosion and Corrosion Inhibition of Reinforcing Concrete and Reinforced Concrete in Hot Countries, Building Research
Steel I: Immersed in Alkaline Solutions, British Corrosion Journal (Lon- Station, Haifa, 1971, pp. 77-96.
don), V. 5, 1970, pp. 198-203. 3.37. Beeby, A. W., Concrete in the OceansCracking and Corrosion,
3.12. Arup. H., Recent Progress Concerning Electrochemistry and Cor- Technical Report No. 1, CIRIA/UEG, Construction Industry Research and
rosion of Steel in Concrete, ARBEM Symposium, Paris, Oct. 1982. Information Association/Department of Energy, London, 1978.
3.13. Stratfull, R. F.; Jurkovich, W. J.; and Spellman. D. L., Corrosion 3.38. Manning, David G., and Ryell, John, Durable Bridge Decks,
Testing of Bridge Decks,Transportation Research Record No. 539, Trans- Report No. RR203, Ontario Ministry of Transportation and Communications,
portation Research Board, 1975, pp. 50-59. Downsview, 1976, 67 pp.
3.14. Chamberlin, William P.; Irwin, Richard J.; and Amsler, Duane E., 3.39. Boulware, R. L., and Elliott, A. L., California Seals Salt-Damaged
Waterproofing Membranes for Bridge Deck Rehabilitation, Resea rch Bridge Decks, Civil Engineering-ASCE, V. 41, No. 10, Oct. 1971, pp. 42-44.
Report No. 52 (FHWA-NY-77-59-1), New York State Department of 3.40. Van Til, C. J.; Carr, B. J.; and Vallerga, B. A., Waterproof Mem-
Transportation/Federal Highway Administration, Washington, D.C., 1977, branes for Protection of Concrete Bridge Decks: Laboratory Phase,
43 pp. NCHRP Report No. 165, Transportation Research Board, Washington,
3.15. Hime, William D., and Erlin, Bernard, Chloride Free Concrete, D.C., 1976, 70 pp.
ACI JOURNAL, Proceedings V. 74, No. 10, Oct. 1977, p. N7. 3.41. Frascoia, R. I., Vermonts Experience with Bridge Deck Protec-
3.16. Rogers. C., and Woda, G., The Chloride Ion Content of Concrete tive Systems, Chloride Corrosion of Steel in Concrete, STP-629, ASTM,
Aggregate from Southern Ontario, Report No. EM-17, Ontario Ministry Philadelphia, 1977, pp. 69-81.
of Transportation and Communications, Downsview, 1977. 3.42. Spellman, D. L., and Stratfull, R. F., Bridge Deck Membranes
3.17. Impurities in Aggregates for Concrete, Advisory Not eNo. 18, Evaluation and Use in California, Report No. CA-DOT-TL-5116-9 73-38,
Cement and Concrete Association, London, 1970, 8 pp. California Department of Transportation, Sacramento, 1973.
222R-20 ACI COMMITTEE REPORT

3.43. Frascoia, R. I., Evaluation of Bridge Deck Membrane Systems 3.67. Cardone, S. M.; Brown, M. G.; and Hill, A. A., Latex-Modified
and Membrane Evaluation Procedures, Report No. 77-2, Vermont Depart- Mortar in the Restoration of Bridge Structures, Bulletin No. 260, High-
ment of Highways, Montpelier, 1977. way Research Board, Washington, D.C., 1960, pp. 1-13.
3.44. Corkill, J. T., A Field Study of the Performance of Bridge Deck 3.68. Bishara, A. G., Latex Modified Concrete Bridge Deck Overlays,
Waterproofing Systems in Ontario, Proceedings, 1975 Annual Conference, Field Performance Analysis, Report No. ODOT 2895, Ohio Department
Roads and Transportation Association of Canada, 1975, V. 2, pp. 79-100. of Transportation, Columbus, 1978.
3.45. Membrane Waterproofing for Bridge Decks, Final Report, Ore- 3.69. Verbeck, George J., Mechanisms of Corrosion of Steel in Con-
gon Department of Transportation, Salem, 1977. crete, Corrosion of Metals in Concrete, SP-49, American Concrete Insti-
3.46. MacDonald, M. D., Waterproofing Concrete Bridge Decks: Mate- tute, Detroit, 1975, pp. 21-38.
rials and Methods, TRRL Report No. LR636, Transport and Road 3.70. Tripler, Arch B.; White, Earl L.; Haynie, F. H.; and Boyd, W. K.,
Research Laboratory, Crowthorne, Berkshire, 1974, 32 pp. Methods of Reducing Corrosion of Reinforcing Steel, NCHRP Report
3.47. Legvold, T. L., Bridge Deck Waterproofing Membrane Study, No. 23, Highway Research Board, Washington, D.C., 1966, 22 pp.
Report No. R-262, Iowa State Highway Commission, Ames, 1974. 3.71. Baker, E. A.; Money, K. L.; and Sanborn, C. B., Marine Corro-
3.48. Meader, A. L., Jr.; Schmitz, C. G.; and Henry, J. E., Development sion Behavior of Bare and Metallic-Coated Reinforcing Rods in Con-
of a Cold Poured Bridge Deck Membrane System, Chloride Corrosion of crete, Chloride Corrosion of Steel in Concrete, STP-692, ASTM,
Steel in Concrete, STP-629, ASTM, Philadelphia, 1977, pp. 164-177. Philadelphia, 1977, pp. 30-50.
3.49. Steinberg, M., et al., Concrete-Polymer MaterialsFirst Topical 3.72. Bird, C. E., and Strauss, F. J., Metallic Coating for Reinforcing
Report, BNL 50134 (T-509) and USBR General Report No. 41, Brookhaven Steel, Materials Protection, V. 6, July 1967, pp. 48-52.
National Laboratory/U.S. Bureau of Reclamation, Denver, 1968. 3.73. Cornet, I.; Ishikawa, T.; and Bresler, B., The Mechanism of
3.50. Smoak, W. G., Development and Field Evaluation of a Technique Steel Corrosion in Concrete Structures, Materials Protection, V. 7, No.
for Polymer Impregnation of New Concrete Bridge Deck Surfaces, Report 3, Mar. 1968, pp. 44-47.
No. FHWA-RD-76-95, Federal Highway Administration, Washington, 3.74. Cook, A. R., and Radtke, S. F., Recent Research on Galvanized
D.C., 1976. Steel for Reinforcement of Concrete, Chloride Corrosion of Steel in
3.51. Tremper, Bailey, Repair of Damaged Concrete with Epoxy Res- Concrete, STP-629, ASTM, Philadelphia, 1977, pp. 51-60.
ins, ACI JOURNAL, Proceedings V. 57, No. 2, Aug. 1960, pp. 173-182. 3.75. Cornet, I., and Bresler, B., Corrosion of Steel and Galvanized
3.52. McConnell, W. R., Epoxy Surface Treatments for Portland Steel in Concrete, Materials Protection, V. 5, Apr. 1966, pp. 69-72.
Cement Concrete Pavements, Epoxies with Concrete, SP-21, American 3.76. Griffin, Donald F., Effectiveness of Zinc Coating on Reinforcing
Concrete Institute, Detroit, 1968, pp. 9-17. Steel in Concrete Exposed to a Marine Environment, Technical Note No.
N-1032, Naval Civil Engineering Laboratory, Port Hueneme, 1969, 42
3.53. Santucci, L. E., Polyester Overlays for Portland Cement Con-
pp.
crete Surfaces, Highway Research Record No. 14, Highway Research
3.77. Hill, George A.; Spellman, D. L.; and Stratfull, R. F., Labora-
Board, 1963, pp. 44-56.
tory Corrosion Tests of Galvanized Steel in Concrete, Transportation
3.54. Jenkins, J. C.; Beecroft, G. W.; and Quinn, W. J., Polymer Con-
Research Record No. 604, Transportation Research Board, 1976, pp. 25-30.
crete Overlays: Interim Users Manual, Report No. FHWA-TS-78-218,
3.78. Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous
Federal Highway Administration, Washington, D.C., 1977.
Solutions, translated from the French by J. A. Franklin, Pergamon Press,
3.55. Felt, Earl J., Resurfacing and Patching Concrete Pavements with
New York, 1966, pp. 409-410.
Bonded Concrete, Proceedings, Highway Research Board, V. 35, 1956,
3.79. Unz, M., Performance of Galvanized Reinforcement in Calcium
pp. 444-469.
Hydroxide Solution, ACI JOURNAL, Proceedings V. 75, No. 3, Mar.
3.56. Westall, William G., Bonded Resurfacing and Repairs of Con-
1978, pp. 91-99.
crete Pavements, Bulletin No. 260, Highway Research Board, Washing-
3.80. Sopler, B., Corrosion of Reinforcement in ConcretePart
ton, D.C., 1960, pp. 14-24.
Series D, Report No. FCB 73-4, Norwegian Institute of Technology,
3.57. McKeel, W. T., Jr., and Tyson, S. S., Two-Course Bonded Con- University of Trondheim, 1973.
struction and Overlays, ACI JOURNAL, Proceedings V. 72, No. 12, Dec. 3.81. Arnold, C. J., Galvanized Steel Reinforced Concrete Bridge
1975, pp. 708-713. Decks: Progress Report, Report No. FHWA-MI-78-R1033, Federal
3.58. Tyson, S. S., Two-Course Bonded Concrete Bridge Deck Con- Highway Administration, Washington, D.C., 1976.
structionInterim Report No. 2: Concrete Properties and Deck Condi- 3.82. Clear, K. C., Time-to-Corrosion of Reinforcing Steel in Con-
tion Prior to Opening to Traffic, Report No. VHTRC-R3, Virginia crete Slabs, V. 4: Galvanized Reinforcing Steel, Report No. FHWA-RD-
Highway and Transportation Research Council, Charlottesville, 1976. 82-028, Federal Highway Administration, Washington, D.C., 1981.
3.59. Jenkins, G. H., and Butler, J. M., Internally Sealed Concrete, 3.83. Castleberry, J. R., Corrosion Prevention for Concrete and Metal
Report No. FHWA-RD-75-20, Federal Highway Administration, Wash- Reinforcing in the Construction Industry, Materials Protection, V. 7, Mar.
ington, D.C., 1975, 106 pp. 1968, pp. 21-28.
3.60. Clear, K. C., and Forster, S. W., Internally Sealed Concrete: 3.84. Clifton, J. R.; Beeghley, H. F.; and Mathey, R. G., Nonmetallic
Material Characterization and Heat Treating Studies, Report No. FHWA- Coatings for Concrete Reinforcing Bars, Report No. FHWA-RD-74-18,
RD-77-16, Federal Highway Administration, Washington, D.C., 1977, 73 Federal Highway Administration, Washington, D.C., 1974, 87 pp.
pp. 3.85. Backstrom, T. E., Use of Coatings on Steel Embedded in Con-
3.61. Hilton, N., A Two-Inch Bonded Concrete Overlay for the Port crete, Corrosion of Metals in Concrete, SP-49, American Concrete Insti-
Mann Bridge, Engineering Journal (Montreal), May 1964, pp. 39-44. tute, Detroit, 1975, pp. 103-113.
3.62. OConnor, E. J., Iowa Method of Partial-Depth Portland Cement 3.86. Pike, R. G.; Hay, R. E.; Clifton, J. R.; Beeghly, H. F.; and
Resurfacing of Bridge Decks, Chloride Corrosion of Steel in Concrete, Mathey, R. G., Nonmetallic Protective Coatings for Concrete Reinforc-
STP-629, ASTM, Philadelphia, 1977, pp. 116-123. ing Steel, Transportation Research Record No. 500, Transportation
3.63. Bukovatz, J. E.; Crumpton, C. F.; and Worley, H. E., Bridge Research Board, 1974, pp. 36-44.
Deck Deterioration Study, Final Report, State Highway Commission of 3.87. Clear, K. C., FCP Annual Progress ReportYear Ending Sept.
Kansas, Topeka, 1973. 30, 1978, Project 4B, Federal Highway Administration, Washington,
3.64. Manning, D. G., and Owens, M. J., Ontarios Experience with D.C., 1978.
Concrete Overlays for Bridge Decks, RTAC Forum (Ottawa), V. 2, No. 3.88. Virmani, Y. P.; Clear, K. C.; and Pasko, T. J., Jr., Time-to-Corrosion
1, 1979, pp. 31-37. of Reinforcing Steel in Concrete Slabs, V. 5: Calcium Nitrite Admixture
3.65. Bergen, J. V., and Brown, B. C., An Evaluation of Concrete or Epoxy-Coated Reinforcing Bars as Corrosion Protection Systems,
Bridge Deck Resurfacing in Iowa, Special Report, Iowa State Highway Report No. FHWA-RD-83-012, Federal Highway Administration, Wash-
Commission, Ames, 1975. ington, D.C., 1983, 71 pp.
3.66. Tracy, R. G., Bridge Deck Deterioration and Restoration Inves- 3.89. Mathey, Robert G., and Clifton, James R., Bond of Coated Rein-
tigation No. 639, Interim Report, Minnesota Department of Transpor- forcing Bars in Concrete, Proceedings, ASCE, V. 102, ST1, Jan. 1976,
tation, St. Paul, Dec. 1976. pp. 215-229.
CORROSION OF METALS 222R-21

3.90. Clifton, James R.; Mathey, Robert G.; and Anderson, Erik D., 4.2Methods of evaluation
Creep of Coated Reinforcing Bars in Concrete, Proceedings, ASCE, Certain tools are used for identifying and quantifying cor-
V. 105, ST10, Oct. 1979, pp. 1935-1947. rosive environments, extent of active corrosion, and concrete
3.91. Johnston, D. W., and Zia, P., Bond Characteristics of Epoxy
deterioration.4.9 Following is a brief description of these
Coated Reinforcing Bars, Report No. FHWA-NC-82-002, Federal High-
way Administration, Washington, D.C., 1982. tools, together with their purpose and limitations.
3.92. Clear, K. C., and Hay, R. E., Time-to-Corrosion of Reinforcing 4.2.1 PachometerThis tool is used to locate reinforcing
Steel in Concrete Slabs, V. 1: Effect of Mix Design and Construction steel embedded in concrete, and to determine the amount of
Parameters, Report No. FHWA-RD-73-32, Federal Highway Adminis- cover over the steel. It is battery-operated and contains a transis-
tration, Washington, D.C., 1973, 103 pp.
torized oscillator that establishes an elecromagnetic field in a
3.93. Craig, R. J., and Wood, L. E., Effectiveness of Corrosion Inhibi-
tors and Their Influence on the Physical Properties of Portland Cement
search coil. In the presence of a steel reinforcing bar, the mag-
Mortars, Highway Research Record No. 328, Highway Research Board, netic field is distorted. By calibration, the distance from the bar
1970, pp. 77-88. may be read from the meter dial. Two styles of equipment are
3.94. Griffin, D. F., Corrosion Inhibitors for Reinforced Concrete, available. The first is a handheld device4.10 and the second is an
Corrosion of Metals in Concrete, SP-49, American Concrete Institute, automated device4.11 mounted on wheels. Automatic data re-
Detroit, 1975, pp. 95-102.
cording equipment is added to faciliate the speed with which a
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 survey can be conducted.
Reinforced Concrete, Chloride Corrosion of Steel in Concrete, STP-629, The knowledge of cover depth is essential if it is desired to
ASTM, Philadelphia, 1977, pp. 89-99. obtain samples of the concrete at the level of the reinforcing
3.96. Fidjestol, P.; Askheim, N. E.; and Roland, B., Location of steel for chloride ion analysis. It is also useful in determining
Potential Corrosion Areas in Concrete Marine Structures, Concrete in
the potential for corrosion and subsequent concrete deterio-
the Oceans, Phase II, Plc, Final Report.
ration since it has been well established that structures in
corrosive environments with inadequate concrete cover are
CHAPTER 4PROCEDURES FOR IDENTIFYING
CORROSIVE ENVIRONMENTS AND ACTIVE subject to early deterioration.
CORROSION IN CONCRETE 4.2.2 Delamination detectorsThere are many tools that
may be used to detect delaminations or subsurface fracture
4.1Introduction planes parallel to the concrete surface. These devices range
There are many approaches available for identifying cor- from simple chain drags or lightweight hammers to more so-
rosive environments and active corrosion of steel in con- phisticated devices such as the Delamtect.4.3,4.9 Almost any
crete. Generally, a visual inspection of the structure and the sounding device can be used to locate hollow areas or delam-
environment in which it serves is the first step in any exam- inations caused by corrosion of the reinforcing steel. The au-
ination. Visual inspections may range from a simple curso- tomated Delamtect is useful for surveying large numbers of
ry examination to those that are very detailed, wherein all bridge decks or other horizontal surfaces such as parking ga-
cracks and other visual evidences of physical deterioration rage floors if a record of the area of delamination is desired.
are plotted on scaled diagrams of the structure and specific However, the simpler chain drag is adequate for locating
information is gathered on environmental exposure. This delaminated areas during repair operations.
type of inspection may also include taking a limited num- 4.2.3 Electrical potential measuring equipmentThis
ber of cores to be examined visually for evidence of deteri- equipment, adapted for use with reinforced concrete by
oration due to corrosion. The detailed type of visual Stratfull,4,2 consists of a copper-copper sulfate half-cell
(CSE), a high-impedance voltmeter, and lead wires to con-
inspection is time-consuming and costly, and generally
nect the half-cell and the reinforcing steel to the voltmeter.4.9
only useful for research studies of structure performance. It
The equipment is used to determine if the reinforcing steel is
does not develop the type of information that is required for
in a passive or active state relative to active corrosion.4.2 De-
scheduling of maintenance.
tails of the test method are given in ASTM C 876.
There are several techniques and tools that can be used to The accuracy of the method is good when proper concrete
more specifically delineate areas of deteriorated concrete prewetting is used. The significance of the measurements
and areas of potential or active corrosion of steel.4.1-4.6 How- can be summarized as follows for structures exposed to air:
ever, an inspection program can become expensive if it is Potentials more negative than -0.35 V CSE: Very high
necessary to survey more than a nominal number of struc- probability of the presence of active corrosion.
tures. For purposes of planning a maintenance or rehabilitation Potentials more positive than -0.20 V CSE: Very high
program, techniques such as suggested by Stratfull, Jurkov- probability of no corrosion.
ich, and Spellman,4,5 or Manning,4.7,4.8 should be used to Potentials in the range of -0.20 V to -0.35 V CSE:
minimize expenses. These techniques have been derived Uncertainty as to whether or not corrosion is present.
from experience and include judicious use of visual exami- It is in the uncertain range that potential differences across
nations together with collection of specific information on a structure, and other detection methods, must often be relied
the extent of physical deterioration, active corrosion, chlo- on to deduce the probable condition. In Federal Highway
ride ion contamination, and depth of cover over reinforcing Administration studies, potential differences rarely exceed
steel. The references noted previously should be studied for 100 mV when corrosion was not active, or was active only at
more detailed information on these techniques. extremely low rates. In reinforced concrete undergoing
222R-22 ACI COMMITTEE REPORT

significant corrosion, the potential differences were com- concluded that either moisture or oxygen is not available,
monly over 200 mV.4.12,4.13 there would be no corrosion threshold. Such conditions may
It should also be noted that a potential value more negative prevail, for example, in concrete that is continuously sub-
than -0.35 V CSE on actively corroding field structures (with merged or in internal members in buildings where air condi-
many electrically interconnected anodes and cathodes) gen- tioning units maintain constantly low humidities. However,
erally provides information on only the presence or absence the difficulty of assessing the possibility of corrosion in the
of corrosion and not on corrosion rate. It is the potential dif- service environment is discussed more fully in Chapter 3.
ference between the anode and cathode that most closely re- 4.2.5 Rate of corrosion probesTwo basic types of
lates to corrosion rate rather than simply the magnitude of probes are available for embedment into concrete to provide
the anode potential. A common example in which highly an indication of rate of corrosion. One type involves the use
negative potentials are not indicative of high corrosion rates of two or three electrically isolated short sections of steel
is a totally water-saturated reinforced concrete structure. In wire or reinforcing steel and the use of linear polarization
such a structure, oxygen availability to the noncorroding techniques to estimate instantaneous corrosion rates.4.17 The
steel is severely restricted and cathodic polarization results. second, more widely used device is the electrical resistance
This drives both the anode and the cathode potentials to very rate-of-corrosion probe which provides cumulative rate of
negative values, and yet corrosion rate is most often quite corrosion data from periodic measurements of the electrical
low. By careful measurement of potentials on a closely resistance of a steel wire or hollow cylinder embedded in the
spaced grid pattern, high versus low corrosion rate situations concrete. Experiences to date with use of these probes have
can be identified by studying potential differences. Large po- been conflicting. However, based on recent Federal High-
tential differences generally indicate high corrosion rates. way Administration studies,4.12 this appears to be related
4.2.4 Chloride analysisMeasurements of chloride ion more to the rate of corrosion process of steel in concrete than
concentration at the level of reinforcing steel in concrete are to inaccuracies of the devices themselves. The Federal High-
made to determine if any environment exists that is conducive way Administration studies indicate that current flow within
to corrosion of the steel. Two wet chemical analysis tech- physically separated, macroscopic corrosion cells, such as
niques are used to isolate chloride from the concrete, one to the case of large quantities of steel in chloride-free moist
determine acid-soluble chloride and the other to determine concrete in close proximity and electrically coupled to steel
water-soluble chloride. As discussed in Chapter 3, the chloride in chloride-bearing concrete, are primarily responsible for
ion content measured by the water-soluble test is very sensi- the very high rates of corrosion on bridge decks. In contrast,
tive to the test procedures. Consequently, all values of chlo- microscopic self-corrosion of a small section of steel in
ride ion content in this report are referenced to the acid-soluble chloride-contaminated concrete most often results in only
test described in ASTM C 114 and also in AASHTO T 260. relatively low corrosion rates. Since the electrically isolated
The preferred method of sample procurement for chloride linear polarization devices only simulate this latter process,
measurement is to obtain concrete in powdered form without valid predictions of the overall effect of corrosion on the
the aid of liquid coolants that could leach out water-soluble structure are not possible. The electrical resistance probe, on
chloride. This can be done by using impact drilling equipment the other hand, can be electrically coupled with the reinforc-
and collecting the pulverized material. Alternatively, a 3-in. (80 ing steel in the structure and thus, potentially, can indicate
mm) diameter or larger core can be obtained by wet coring and macrocell activity. However, this is possible only if the
then extracting samples from the interior by dry sawing or other probe becomes the anode of a macrocell and current flow
pulverizing methods. Measurements for acid-soluble and within this macrocell is typical of that of a macrocell active
water-soluble chloride can be made on this type of sample using on the reinforcing steel. These are very important uncertain-
the standard test procedures. Additional guidance is given in ties and have generally limited the use of resistance probes
References 4.14 and 4.15. to research and field evaluation efforts in which special in-
In many existing concrete structures, the exact cement stallation procedures are required, and electrical potential
content is not known. Thus, chloride levels can be expressed and current measurements can be made to define the charac-
in terms of percent by weight of concrete, or, sometimes, teristics of the probe-reinforcing bar-macrocell. Continued
pounds of chloride per cubic yard of concrete. The latter re- study of these devices is needed, as well as lower cost options
quires an assumed or measured unit weight of the concrete. such as short sections of reinforcing steel installed in a spe-
A table in Reference 4.7 gives the conversion formulas for cific manner, and current flow measurements. To date, use of
the various methods of expressing chloride in concrete. For such procedures in the field to aid in studies on the effect of
greater precision, nonevaporable water contents (water rehabilitation procedures on corrosion rate have provided
chemically combined through cement hydration) can be excellent results.
measured on each powdered sample from a given concrete 4.2.6 Electrical resistance measuring equipmentThe
and used as correction factors for aggregate induced distortions primary use of these measurements is to determine the resis-
in measured chloride levels. tance of waterproof membranes that are made from dielectric
In any interpretation of chloride data, sound engineering materials. This equipment consists of a copper contact plate,
judgment must be used to assess the actual potential for cor- sponges, ohmmeter, and lead wire.4.1 One terminal of the
rosion. As stated earlier, free moisture and oxygen as well as ohmmeter is connected to the reinforcing steel, while the
chloride must be available to induce corrosion. If it can be other terminal is connected to the copper plate. The wetted
CORROSION OF METALS 222R-23

sponges are fastened to the bottom of the copper plate to fa- 4.12. Clear, K. C., FCP Annual Progress ReportYear Ending Sept.
cilitate contact. The electrical resistance can be measured at 30, 1981, Project 4K: Cost Effective Rigid Concrete Construction and
Rehabilitation in Adverse Environments, Federal Highway Administration,
any point by moving the copper contact plate to that point. Washington, D.C., 1979.
The resistance has been related to the number of holes in the 4.13. Clear, K. C., Time-to-Corrosion of Reinforcing Steel in Concrete
membrane and its permeability to water. This technique pro- Slabs, V. 4: Galvanized Reinforcing Steel, ReportNo. FHWA-RD-82-028,
vides a nondestructive method to evaluate the environment Federal Highway Administration, Washington, D.C., 1981.
4.14. Berman, H. A., Determination of Chloride in Hardened Cement
and potential for corrosion in concrete decks protected by a Paste, Mortar, and Concrete, Report No. FHWA-RD-72-12, Federal High-
membrane system. Advantages and cautions needed when way Administration, Washington, D.C., 1972, 22 pp.
using these measurements are discussed in Reference 4.7. 4.15. Clear, K. C., and Harrigan, E. T., Sampling and Testing for Chlo-
The technique has not proven satisfactory for evaluation of ride Ion in Concrete, Report No. FHWA-RD-77-85, Federal Highway
Administration, Washington, D.C., 1977, 25 pp.
epoxy resin coatings on reinforcing steel embedded in con- 4.16. Clear, K. C., and Hay, R. E., Time-to-Corrosion of Reinforcing
crete. Some work has been done on measurement of the re- Steel in Concrete Slabs, V. 1: Effect of Mix Design and Construction
sistance of these coatings using alternating current meters. Parameters, Repor t No. FHWA-RD-73-32, Federal Highway Administration,
However, the state of the art is not sufficiently advanced for Washington, D.C., 1973, 103 pp.
4.17. Lankard, D. R.; Slater, J. E.; Hedden, W. A.; and Niesz, D. E.,
general use as an evaluation technique. Neutralization of Chloride in Concrete, Report No. FHWA-RD-76-60,
Other techniques and tools to determine the condition of Federal Highway Administration, Washington, D.C., 1975, 143 pp.
the concrete and to detect the presence of a corrosive envi- 4.18. Holt, F. B., and Manning, D. G., Detecting Concrete Bridge
ronment or active corrosion have been studied to varying de- Deck Delaminations with Infrared Thermography, Public Works, Mar.
1979, pp. 66-69.
grees. Ultrasonic methods have been used successfully to
investigate the quality and condition of concrete.
CHAPTER 5REMEDIAL MEASURES
To a lesser extent, infrared and radar scans have been used 5.1 Introduction
to record the condition of concrete. Trial uses of these tech- This chapter discusses measures available to arrest, con-
niques on bridge decks have been encouraging,4.18 but more trol, or minimize corrosion activity on an existing reinforced
development work is needed, especially to determine their concrete structure after it is found unnecessary to completely
value in assessing the condition of asphalt-covered decks. replace the structure.
A study is underway to develop nondestructive procedures Some of the normally accepted and commonly implement-
for direct measurement of the rate of corrosion of reinforcing ed remedial measures for controlling corrosion on steel
steel in concrete.4.12 Three electrode-linear-polarization structures are not applicable to the reinforced concrete com-
measurements are encouraging. Because the measurements posite structure. For example, application of protective coat-
are made directly on the in situ reinforcing steel, many of the ings is an effective tool for controlling corrosion on an
problems discussed under the section on corrosion probes existing steel structure. Obviously, coating of the steel sur-
should not be present. faces to be embedded in concrete would have to be accom-
plished prior to or during the construction phase. Thus the
4.3References use of protective coatings for steel reinforcement is a design
4.1. Spellman, Donald L., and Stratfull, Richard F., An Electrical measure and has been discussed in Chapter 3.
Method for Evaluating Bridge Deck Coatings, Highway Research Record
Chemical inhibitors are commonly used to control corrosion
No. 357, Highway Research Board, 1971, pp. 64-71.
4.2. Stratfull, R. F., Half-Cell Potentials and the Corrosion of Steel in in a closed system. Inhibitors would need to be introduced as an
Concrete, Resea rch Report No. CA-HY-MR-51 16-7-72-42, California admixture during the concrete batching and mixing phase and
Department of Transportation, Sacramento, 1972. are not applicable to the existing reinforced concrete structure.
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.
5.2General
4.4. Clear, K. C., Evaluation of Portland Cement Concrete for Perma-
Remedial measures for controlling corrosion of steel em-
nent Bridge Deck Repair, Report No. FHWA-RD-74-5, Federal Highway bedded in portland cement concrete use sound corrosion en-
Administration, Washington, D.C., 1974, 48 pp. gineering principles directed toward:
4.5. Stratfull, R. F.; Jurkovich, W. J.; and Spellman, D. L., Corrosion 1. Insulating the concrete surfaces from the corrosive en-
Testing of Bridge Decks, Research Report No. CA-DOT-TL-5116-12-75-10, vironment.
California Department of Transportation, Sacramento, 1975.
4.6. Ross, Joseph E., Bridge Deck Deterioration Study, Resea rch 2. Modifying the environment to make it less corrosive.
Report No. 85, Louisiana Department of Highways, Baton Rouge, 1975. 3. Actively controlling the electron flow within the envi-
4.7. Durability of Concrete Bridge Decks, NCHRP Synthesis No. 57, ronment so that no metal is lost from the structure.
Transportation Research Board, Washington, D.C., 1979, 60 pp. 4. Applying a combination of the previous techniques.
4.8. Manning, David G., and Holt, Frank B., Detecting Delamination in
The reinforced concrete structure may be insulated from
Concrete Bridge Decks, Conc rete International: Design & Construction,
V. 2, No. 11, Nov. 1980, pp. 34-41. the corrosive environment through application of an imper-
4.9. Clear, K. C., Permanent Bridge Deck Repair, Public Roads, V. 39, meable, dielectric barrier between the structure and the cor-
No. 2, 1975, pp. 53-62. rosive environment. The barrier may be a coating or
4.10. Durability of Concrete Bridge DecksA Cooperative Study, membrane applied to the surface of the concrete, may be
Report No. 2 (EBO44E), Michigan State Highway Department/Bureau of
Public Roads/Portland Cement Association, Skokie, 1965, 107 pp.
formed as an integral part of the concrete matrix through
4.11. Rolling Pachometer, Operating Manual and Specification, Office of polymer impregnation, or may be an overlay of polymer
Development, Federal Highway Administration, Washington, D.C., 1975. concrete, low-slump concrete, latex-modified concrete, or
222R-24 ACI COMMITTEE REPORT

internally-sealed concrete. These have been discussed in detail progresses until structural integrity is threatened. These insu-
in Chapter 3 and will only be mentioned briefly in this chapter. lative measures, when used without initial decontamination,
The environment may be altered to reduce corrosion either should be considered as only a temporary remedy.5.7
by removing detrimental constituents (such as the chloride Also with insulative remedies an erroneous expectation
ion), or by removing or neutralizing stray current sources. is that a perfect seal is attainable in practice. All barriers
Cathodic protection can be used to control the direction of will contain discontinuities such as pinholes, breaks,
electron flow within the steel-environment electrochemical cracks, poor seams, or other defects that will allow intrusion of
circuit to stop corrosion of the reinforcing steel. contaminants in localized areas. Nevertheless, these insu-
lative methods can substantially reduce the rate of intrusion
5.3Applicability of harmful contaminants and retard the corrosion process-
All reinforced concrete structures are susceptible to es. In many cases, they can successfully extend the useful
corrosion. Although bridge decks5.1-5.3 are perhaps the most life of a structure.
notorious examples today, the literature contains many 2. Modification of the environment: Methods available for
references5.4-5.6 to other types of reinforced concrete struc- rendering the environment less corrosive include the remov-
tures where corrosion of the reinforcing steel is being or has al or elimination of harmful constituents from the electro-
been experienced. These include buildings, caissons, foun- lyte. These constituents could be in the form of chemicals
dations, parking garages, piers, piles, pipes, silos, tower foot- such as water and chlorides, gases such as oxygen or hydro-
ings, and water tanks. Some of these structures may be gen sulfide, or electrical currents.
totally or partially buried in soil. Others, such as offshore Water can often be eliminated by facilitating drainage
platforms, water tanks, and the internal surfaces of pipe, are away from rather than through a structure. Chlorides can be
exposed to aqueous solutions. Bridge decks, parking garag- eliminated by a process known as electrochemical chloride
es, and buildings are exposed to the atmosphere. removal. This process has been used to decontaminate
If the structure is buried or permanently underwater such that structures such as bridge decks5.8 in research studies. The re-
the concrete surfaces are not accessible for treatment, and it is moval is accomplished electrochemically, by using a suit-
impractical to expose them, treatment of the surfaces with sur- able electrolyte, an ion exchange resin, and a noble anode.
face coatings or membranes or by application of overlays is not The reinforcing steel is the cathode (negatively charged) in
applicable. Similarly, if the structure to be maintained is a bur- this electrochemical circuit. The negatively charged chloride
ied pipeline or an offshore platform exposed in a large body of ion (Cl-) is attracted to the positively charged anode where it
water, modifying the environment to make it less corrosive is trapped by the exchange resin. Although a field test at
would not be a practical solution. Thus, not all the remedies dis- Marysville, Ohio, on a bridge deck displayed promising re-
cussed here are applicable to all types of reinforced concrete sults, the method remains in its initial development stage. In
structures in the various environments. this test, up to 90 percent of the chlorides present in the con-
Cathodic protection is by far the most versatile method of crete above the top mat of reinforcement was removed. Dis-
corrosion control since it is applicable to any electrically contin- advantages are that the method is expensive and time-
uous structure within a suitable electrolyte. In as much as the consuming and requires the application of high direct current
steel embedded in concrete, and not the concrete, requires the voltage that generates heat (around 200 F [90 C]) which, in
protection from metallic corrosion, damp concrete serves as a turn, can induce cracking of the concrete. In addition, the
suitable electrolyte and even structures exposed to the atmo- permeability of the concrete was increased.
sphere, such as bridge decks, can be protected cathodically. Harmful gases such as oxygen and hydrogen sulfide can
be stripped by chemical processes from the electrolyte, thus
5.4The remedies and their limitations making it less corrosive. This method is applicable predom-
1. Insulative remedies: The insulative methods currently inantly for structures exposed in aqueous solution.
employed to isolate reinforced concrete structures from the Deep polymer impregnation5.9 of the critically contami-
corrosive environment include surface coatings and mem- nated concrete around the reinforcing steel is being evaluat-
branes, polymer impregnation and overlays of polymer con- ed. The method ties up the existing contaminants and
crete, low-slump concrete, or latex-modified concrete. These prevents intrusion of additional contaminants. Although the
methods are suitable only when the surfaces of the concrete theory is realistic, the practicality and economic feasibility
structure are exposed for treatment. Ideally, these barriers of deep polymerization are not established.
would prevent continued intrusion of harmful contaminants Corrosion of steel in concrete can be caused by environ-
and the availability of oxygen or moisture to sustain the cor- mental factors other than chemical constituents such as chlo-
rosion reactions. However, in existing structures active cor- rides, moisture, or oxygen. Stray electrical currents can
rosion is already underway and harmful species have result in corrosion by electrolysis, i.e., cathodic interfer-
contaminated the concrete. Insulative methods used after ac- ence.5.5,5.10 In corrosion by electrolysis, direct current strays
tive corrosion is experienced do not stop corrosion but may from an exterior source and is collected by the steel in a re-
mitigate the effects of the corrosion processes. However, if inforced concrete structure. Inasmuch as the collected cur-
insulative methods are used without initially decontaminat- rent must return to its source to complete the electrochemical
ing the concrete, sufficient amounts of the contaminants, ox- circuit, the current is discharged from the structure at some
ygen, and moisture may be entrapped such that corrosion locations. At the point of current discharge from the structure
CORROSION OF METALS 222R-25

Fig. 5.1Underground pipe crossing Layout Line A is


cathodically protected Fig. 5.3Mitigation with galvanic anodes (current returns
via low resistance anode)

Fig. 5.2Elevation showing current flow patterns Fig. 5.4Mitigation with resistance bond (current returns
via metallic path)

to the electrolyte, metal loss is experienced. The most com- (more negative) surfaces. When this is accomplished, there
mon sources of stray currents include cathodic protection sys- is no current flow between the formerly anodic and cathodic
tems, electrified railways, and electroplating plants. This type surfaces and corrosion is arrested. This represents a balanced
of corrosion is most commonly manifested in grounded struc- or equilibrium condition. In normal practice, sufficient cur-
tures, i.e., those in contact with the earth. A method of mitigat- rent is passed to the surfaces so that the formerly anodic ar-
ing this type of corrosion, implemented for many years in the eas will be receiving current from the electrolyte and their
buried pipe industry, is the installation of resistance bonds. In potential will be shifted to the more negative direction.
resistance bonding, the structure being affected is electrically There are two ways in which the protective electrochemi-
connected through a resistor to the source of the interference cal circuit can be established. One method uses an electrode
currents. In this manner, the current returns to its source via a made of a metal or alloy more negative than the structure to
metallic path such that no metal loss from the affected struc- be protected. For example, if the structure to be protected is
ture occurs. Another method uses galvanic anodes to drain the
constructed of steel, either magnesium, zinc, or aluminum
collected current. Collected current is passed on to the electro-
may be coupled with the structure. Inasmuch as a protective
lyte and back to its source from the surface of the anode which
galvanic cell is set up between the steel and the alloy select-
corrodes, rather than the structure.
ed, this method is known as the galvanic anode method of ca-
Examples of stray current intrusion and mitigation meth-
thodic protection. Also, since the galvanic anodes pass
ods are shown in Fig. 5.1 to 5.4.
current to the electrolyte, they corrode or sacrifice themselves
3. Active control of electron flowFrom the Pourbaix di-
to protect the structure. Hence, magnesium, zinc, and alumi-
agram for iron (Fig. 2.4), it can be seen that steel embedded
num are termed sacrificial anodes. Sacrificial anodes corrode
in concrete is normally passivated due to the highly alkaline
(high pH) concrete environment. The diagram shows anoth- at relatively high rates. Corrosion rates for magnesium, zinc,
er area wherein no steel corrosion occurs. This area at the and aluminum are of the order of 17, 26, and 12 lb per amp
lower portion of the diagram is labeled immunity. In this do- year, respectively.5.11,5.12
main, the potential of the steel is more negative than in any The high consumption rates, as well as low-driving volt-
naturally occurring condition, regardless of pH. age, are the primary disadvantages of the galvanic anode
The method of providing the highly negative steel potentials method of cathodic protection. The open circuit potential be-
required for immunity is referred to as cathodic protection. In tween steel and magnesium is on the order of 1 V, while zinc
cathodically protecting a structure, a favorable electrochem- and aluminum are somewhat less.5.11,5.12 Thus, with this
ical circuit is established by installing an external electrode method, it is imperative that a low-resistance circuit be es-
in the electrolyte and passing current (conventional) from tablished by installation of many anodes in a low-resistance
that electrode through the electrolyte to the structure to be media. The anodes installed should also be sized in accor-
protected. This current polarizes the potential of the cathodic dance with their respective consumption rates to provide the
surfaces (relatively positive) on the steel to that of the anodic necessary design life.
222R-26 ACI COMMITTEE REPORT

Fig. 5.5Galvanic cathodic protection (buried pipe)


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
Fig. 5.6Impressed current cathodic protection (buried pipe) 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
Table 5.1Comparison of electrochemical circuit is thus proven technology and the problems being currently
characteristics encountered deal with criteria of protection, design, and in-
Galvanic or sacrificial anode Impressed current spection of the installation.
1 No external power required External power required
In protecting buried structures or structures exposed in
Voltage variable over
2 Fixed, small driving voltage water or in soils, low-resistance electrochemical circuits can
wide range
3 Limited, small current output Current variable over normally be established. However, on other structures such
wide range
as bridge decks, a highly conductive overlay consisting of a
Interference of adjacent
4 structure not likely Interference can result coke breeze-asphalt mixture or closely spaced anodes to re-
5 Overprotection not likely Overprotection can result duce the circuit resistance and to promote uniform distribu-
6 Anodes rapidly consumed Anodes slowly consumed tion of current to all reinforcement is required.5.15,5.16 A
Sensitive to temperature and
7 moisture conditions 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
The other way in which the favorable electrochemical use the potential compared to a standard reference cell as the
sole criterion. The criterion for steel that is buried or sub-
circuit can be established is by introducing electrical cur-
merged is normally accepted as -0.85 V, or more negative
rent from an external source. Because an outside source of
than a copper/CSE (copper-copper sulfate reference elec-
current is used, this method is termed impressed current
trode). However, steel embedded in concrete exhibits more
cathodic protection. This method also requires the instal- noble potentials than exposed steel in the order of 0.2 to 0.3
lation of an external electrode in the electrolyte with the V more positive. Therefore, some investigators claim that
structure to be protected. However, since the current flow protection is provided at lower potentials, in the order of -0.5
is not dependent on the favorable potential difference be- V with CSE reference.5.17
tween the electrode and the structure to be protected, For steel embedded in concrete exposed to the atmo-
more noble materials can be selected for the anode. These sphere, research has indicated that the -0.85-V criterion may
materials include high-silicon cast iron, graphite, and not be attainable. Quite possibly the result may be sufficient
even more noble materials such as platinized-titanium or current to cause concern about lack of bond.5.18
platinized-niobium. These metals corrode or are con- The possibility of the loss of bond of the reinforcing steel
sumed very slowly, less than 1 lb per amp year.5.11,5.12 is related to high current densities, at least 25 mA/ft2.
CORROSION OF METALS 222R-27

However, it would be most unusual for a cathodic protection current to flow. Once the steel is made cathodic in that it re-
system, typically designed to operate at 2 mA/ft2 of steel sur- ceives current, the current causes oxygen to be reduced. This
face, to operate in excess of 25 mA/ft2 for sufficient time same amount of current may reduce oxygen faster than it is be-
(several years) to cause deterioration in bond strength unless ing replenished and result in polarization with an associated
the potential criterion was applied inappropriately. potential change. If the oxygen is replenished at the same rate
Corrosion of steel in concrete is controlled by oxygen ac- as it is reduced, no additional polarization will result. Thus, if
cess. Polarization of the steel is controlled by cathodic pro- the amount of current for cathodic protection will make all of
tection. As mentioned in Chapter 2, concrete is a very the steel cathodic and oxygen reduction is taking place, any
alkaline medium and cathodic reaction is the reduction of greater amount of cathodic protection current will simply be
oxygen to hydroxides. The same is true for the cathodic pro- wasted on reducing oxygen.
tection currents. If the current reduces the oxygen faster than In addition to disbondment, overprotection can result in hy-
it can be replenished, when cathodically protecting steel in drogen embrittlement.5.6,5.19 In Chapter 2 it was shown that in
concrete, the steel will polarize to a more negative value. If acid environments hydrogen ions are reduced at the cathode to
the oxygen supply is great, then to obtain greater degrees of atomic hydrogen which, in turn, combine to form gaseous hy-
polarization, the current supply must be increased. In some drogen. When overprotection results, hydrogen gas is formed
bridge decks, the current required to obtain the criterion of at a faster rate than can be diffused through the coating, in this
-0.85 V would be such that there would be fear for disbond- instance, concrete. When this occurs, gaseous pressure is de-
ment even though the half-cell potential was not even close veloped at the steel-coating interface which tends to either
to that value. Thus, cathodic protection of concrete embed- spall the coating (disbondment) or to diffuse as atomic hydro-
ded steel is not necessarily a standard procedure. gen into the metal. When hydrogen diffuses into the metal, it
For concrete that is buried or submerged, probably further strains the metal lattice, resulting in reduced ductility
moisture-saturated, the -0.85 V CSE criterion is easily ob- and toughness. These phenomena are referred to as hydrogen
tained at current densities as low as 25 A/ft2. For bridge embrittlement. Normally, hydrogen embrittlement affects
decks, where the concrete is comparatively dry and oxygen high-strength steels only, generally those having yield
is abundant, the criteria may be -0.85 V if obtainable with strengths of 90 ksi (620 MPa) or higher5.20,5.21 and is conse-
reasonable, current density (probably a maximum of 3 quently a potential problem in applying cathodic protection to
mA/ft2 of deck surface). If not, a shift of 400 mV for all prestressed concrete elements.
bridge deck half-cell potentials is a criterion developed from Because of the adverse effects possible from overprotection,
the statistical distribution of half-cell potentials that could polarized potentials (determined immediately after the cur-
change the least negative potential to equal or exceed the rent has been interrupted) are normally limited to -1.10 V
most negative half-cell potential, or to provide the current re- CSE to avoid the possibility of disbonding and hydrogen em-
quired to achieve the cathodic protection requirements as de- brittlement problems.5.22 In addition, protection above that
termined by the E-log I curve.5.18 In this latter case, the half- level would require more current and a costlier installation
cell potential of the bridge deck can vary wildly depending without achieving additional protection from corrosion.
on the moisture content and temperature of the concrete. It
also eliminates the need of a permanent half-cell which 5.5Summary
would be required in the case of half-cell potential control. Remedies for controlling corrosion on existing reinforced
The theory behind the constant current determined by the concrete structures use sound corrosion engineering principles
E-log I criteria is that the potential of steel is directly related to directed at insulation of the reinforced concrete from the cor-
oxygen reduction. The corrosion of the steel is directly related rosive environment, alteration of the environment, or control
to the corrosion current. Thus, with a constant current, vari- of electrical current flow within the environment. In dealing
ations in oxygen reduction will cause variations in the half-cell with the reinforced concrete composite, when corrosion is
potential of the steel. Conversely, if the cathodic protection cri- detected, the deleterious contaminants are already within the
teria is a constant half-cell potential, then the current output of concrete matrix. Insulative measures, although they mini-
the system will vary as the oxygen supply varies. mize the rate of corrosion or the intrusion of additional con-
When using the half-cell potential criterion as developed taminants, entrap the existing quantities of these corrosive
through the E-log I method, there is a risk that there will be contaminants. Their effectiveness can be improved by re-
times when the cathodic system will not completely control moval of contaminants prior to sealing such as by electro-
the corrosion of the steel. For example, if the concrete is near chemical chloride removal.
saturation, the steel can usually be polarized with relatively Many of the proposed remedies are in the early devel-
small current densities. Then if the rectifier is regulated by a opment stage. Such approaches as deep polymer impreg-
half-cell potential and the concrete dries so that oxygen be- nation and corrosion inhibitors have not been proven as
comes abundant, and the polarized potential drifts signifi- practicable methods of corrosion control on existing rein-
cantly less negative, it is likely that there will be insufficient forced concrete structures.
current capacity to raise the potential to the protective po- Of the remedies discussed, only cathodic protection has
tential value. proven to be capable of stopping corrosion on an existing
Corrosion is caused by the flow of electrons or current. The structure. The technology is proven and has been found to be
differences in half-cell potentials is the voltage that causes the 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 dilute (1+1) nitric acid until the solution is acidified. Add 3.0
gm sample representative of the core or cylinder. Experience 0.1 ml of hydrogen peroxide (30 percent solution) to the
has shown that the cooling water from core cutting will not solution. Proceed in accordance with the reference ASTM
dissolve a significant amount of chloride. C 114, starting with the procedure specified in Section
19.5.3 and continuing to the end of Section 19.5.8.
6 Sample Preparation 7.2.3 Make a blank determination by using the Soxhlet,
6.1Using the jaw crusher or hammer, reduce the sample
complete with thimble and glass wool, but containing no
so that it fits the sample holder using the minimum crush-
sample of cementitious material.
ing necessary. The sample shall not be crushed to a pow-
der since this would release chloride bound in some
8Calculation
aggregates which, as previously discussed, are known not
8.1Calculate percent of chloride to the nearest 0.001
to contribute to corrosion.
percent as the average chloride content of the triplicate samples,
each calculated as follows
7Procedure
7.1A single test shall consist of determination of chlo-
ride contents of three individual 30 gm samples. N 500
Chloride, percent = 3.5453 ( V 1 V b ) ----- --------- (1)
7.2Weigh each sample (30 g 5 g) to the nearest 0.01 g M V2
and place in the porous sample holder of a Soxhlet extractor.
Add a wad of glass wool. Place approximately 100 ml of de- where
ionized water in the lower flask. V1 = ml of 0.05 N AgNO3 solution used for titration of
7.2.1 Assemble the condenser complete with cooling wa- the sample (equivalence point)
ter supply pipes to the extractor and place on the heater. Turn Vb = ml of 0.05 N AgNO3 solution used for titration of
on both the heater and condenser cooling water and allow ex-
the blank (equivalence point)
traction to continue for 24 hr; adjust the heating rate to give
N = normality of 0.05 N AgNO3 solution, calculated to
a cycle about every 20 min.
0.001
7.2.2 At the conclusion of the extraction stage, transfer the
solution to a 500 ml volumetric flask. Rinse the Soxhlet flask M = mass of concrete or mortar sample, g
three times with distilled water, transferring the washings to V2 = volume of the 25 ml aliquot determined to 0.1 ml
the 500 ml volumetric flask; add distilled water to produce a (larger or smaller aliquots may be used depending on the
volume of 500 ml. With a pipette transfer a 25 ml aliquot to chloride concentrations present)
a 250 ml conical flask. Add 3 drops of methyl orange indica- 8.2Sufficient data are not available at this time to pro-
tor (prepared in accordance with ASTM C 114) and add vide precision and bias statements.