Chloride Limits Concrete PDF

PCA R&D Serial No.
2438
Chloride Limits in Reinforced Concrete
by David A. Whiting, Peter C. Taylor, and Mohamad A. Nagi
© Portland Cement Association 2002

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PCA Research and Development SN 2438
KEYWORDS
alkalies, calcium chloride, chlorides, codes, corrosion, fly ash, portland cement, reinforced
concrete, reinforcing steel, water-cement ratio
ABSTRACT
Reinforcing steel in concrete is normally passive and will not corrode. However, when chloride
ions are initially present in a concrete mixture, steel may corrode if the concentration of chloride
exceeds a certain threshold level. Limits on permissible amounts of chloride initially present in
concrete have been set by ACI and other code bodies. Questions have been raised as to the
applicability of these limits. In this study, current chloride limits were reviewed, a literature
review of chloride thresholds was completed, and an experimental laboratory test program was
carried out. Concretes were prepared over a range of cement tricalcum aluminate contents,
concrete water-to-cement ratios, and chloride ion concentrations. The effects of fly ash and
cement alkali content were also included. The use of a Soxhlet extraction procedure to determine
amount of leachable chloride in chloride-bearing limestone aggregates was also investigated.
Results indicate that for static conditions such as those seen in building interiors, where concrete
may be occasionally wetted, the amount of chloride needed to initiate corrosion is between 0.3%
and 0.4% water-soluble chloride by mass of cement. It is recommended that the ACI limit for
concrete not exposed to external sources of chloride but in a moist environment be maintained at
0.3% water-soluble chloride ion. It is also recommended that the deliberate addition of chloride-
based set accelerators be discontinued in reinforced concrete construction, even when concrete is
expected to stay dry. Aggregates that yield high amounts of chloride when tested by current
water-soluble procedures may be subjected to the Soxhlet extraction procedure to determine the
amount of leachable chloride. If no chloride is leached using this procedure then results of this
study indicate that the aggregate would be safe to use in concrete.
REFERENCE
Whiting, David A., Taylor, Peter C., and Nagi, Mohamad A., Chloride Limits in Reinforced
Concrete, R&D Serial No. 2438, Portland Cement Association, Skokie, Illinois, USA, 2002, 76
pages.
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TABLE OF CONTENTS
Page
Keywords i
Abstract i
Reference i
Table of Contents ii
Chapter 1 Introduction and Scope 1
Introduction 1
Significance and Objectives 2
Scope 3
Task 1. Literature Review 3
Task 2. Laboratory Investigation 3
Chapter 2 Origins of Chloride Limits 5
Chloride Corrosion Thresholds 5
Development of ACI Chloride Limits 6
Chapter 3 Laboratory Test Program 9
Scope and Organization 9
Materials 9
Concrete Mixtures 10
Series 1 Mixtures 10
Mixing Procedures 11
Test Specimens and Procedures 11
Potentiostatic Testing 11
Long Term Exposure 12
Compressive Strength 13
Chloride Analyses 13
Chapter 4 Results and Discussion 15
Series 1- Plain Concrete Mixtures 15
Potentionstatic Test Results 16
Statistical Analyses 17
Half Cell Potentials 19
Visual Observations 20
Series 2 – Effects of Cement Alkali Content and Fly Ash 21
Cement with Added Alkali 21
Fly Ash Series 22
Series 3 – Aggregate Effects 22
Potentiostatic Test Results 23
Visual Observations 24
Compressive Strength 25
ii
Chapter 5 Conclusions and Recommendations 26

Conclusions 26
Recommendations 27
Acknowledgement 28
References 28
Tables 31
Figures 45
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CHLORIDE LIMITS IN REINFORCED

CONCRETE
By David A. Whiting, Peter C. Taylor, and Mohamad A. Nagi
CHAPTER 1 INTRODUCTION AND SCOPE
INTRODUCTION
The overall excellent performance exhibited over many decades by reinforced concrete
structures depends on the stability of reinforcing steel within the concrete environment. Under
the alkaline conditions normally existing in portland cement concrete, a passive film is formed
on the surface of reinforcing steel (Mayne, Mentor, and Pryor, 1950). This film, however, may
be disrupted (Ford and Mason, 1996) by materials such as chloride ion
(Cl – ). When this occurs, the underlying steel is no longer protected and corrosion may be
initiated. The corrosion products (iron hydroxides and oxides) occupy a greater volume than that
of the parent steel. This excess volume may be up to 10 times that of the steel consumed
(Broomfield, 1997). Thus, stresses are exerted on the surrounding concrete. When these stresses
exceed the tensile capacity of the concrete, cracking, spalling, and delamination of the surface of
the concrete occur. There must also be sufficient moisture present to support the electrochemical
corrosion reactions and sufficient oxygen to form the oxide corrosion products. In
atmospherically exposed structures the oxygen availability is almost always sufficient to form
the necessary oxides. Tuutti (1982) has shown that corrosion is initiated in chloride-
contaminated concrete when internal relative humidities exceed 60 percent. Other factors
including temperature, the presence of galvanic couples or stray electrical currents, carbonation
of the concrete cover, or the presence of other corrosive substances also may play a role.
However, in concrete designed in accordance with the provisions of ACI 318 (American
Concrete Institute, 1999), in the vast majority of cases corrosion will occur only when the
concentration of chlorides at the level of the reinforcing steel exceeds a certain “threshold”
amount, and the aforementioned moisture and oxygen requirements are satisfied.
This threshold may be exceeded through three mechanisms; (1) during exposure to
severe, chloride-contaminated environments, (2) by inclusion of chlorides in the initial
concrete mixture (for instance through use of calcium chloride dihydrate (CaCl2•2H2O) as
a set accelerator), or (3) through a combinations of the first two
mechanisms. It is the authors’ opinion that chloride-induced corrosion cannot be controlled
simply by specification of a limit on chloride in the initial concrete mixture if that concrete
is to be subsequently exposed to external chlorides. The ability to predict exactly how
much chloride will then be present at the reinforcing steel at any given point in time has
not yet been perfected. Therefore, the focus of the current project was on concrete to which
chloride has been initially added, but which will not be exposed to further sources of
chloride during its service life.
The search for a universal “threshold” chloride content for initiation of corrosion in
reinforced concrete has spanned many decades, and a value that will fit all situations has
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proven to be elusive. In a review of the available literature, Taylor, et al. (1999) found
experimentally determined values of the “threshold” needed to initiate corrosion in
reinforced concrete varied over an order of magnitude from 0.1% to 1.0% when expressed
as acid-soluble (total) chloride based on mass of cement in the concrete. These studies
represent a wide range of materials, exposure conditions, specimen types, and test
procedures used to obtain the final result. Based on such studies, other experiences, and
consensus procedures, limits on permissible levels of chloride ion which may be present in
fresh concrete have been set by ACI and other authorities. Because of the aforementioned
range of reported threshold values, it is easy to understand why various national code
bodies have adopted different values (ACI 222, 1996; Whiting, 1997) for their chloride
limits, and have attempted to define the conditions under which some values may be more
appropriate than others. The fact that conditions of exposure may change over time creates
additional complexity with regard to selection of limits on tolerable chloride contents.
Current issues relating to chloride limits are summarized in Chapter 2 of this report.
There are various reasons why chlorides may be initially present in a concrete
mixture. As noted above, CaCl2•2H2O or other admixtures containing this material may be
used as set accelerators or to improve early strength gain of concrete. Free chlorides may
be present in certain aggregate sources, such as sea-dredged aggregates. Certain limestone
sources (Lamar, 1957) may contain bound chlorides, which are released after powdering
using acid or hot water dissolution of the sample following standard ASTM procedures for
determination of acid- or water-soluble chlorides (ASTM, 1998). Some of these aggregate
sources may contribute to corrosion, while others may not.
SIGNIFICANCE AND OBJECTIVES

There is a need to set conservative, yet reasonable, limits on the amount of chloride which may
be permitted in the initial concrete mixture prior to exposure to service conditions. These limits
must reflect knowledge of the amounts of chloride needed to initiate corrosion under the
conditions to be expected for the exposures anticipated. Since, for the reasons noted in the
introduction, exposure to external chloride environments has been excluded from this
investigation, this study deals solely with limits on the permissible amount of chloride in
concretes which will not be subsequently exposed to chlorides. This is significant for interior
elements of buildings, which for the most part are dry, but may be exposed to moisture during
such procedures as floor cleaning, or through inadvertent leaks in the building envelope. It is also
significant for exterior elements of buildings or other structures in inland areas that are exposed
to the environment but not to chlorides.
The objectives of the project described in this report were twofold:
1. Recommend appropriate limits on chloride content of concrete to prevent
corrosion of reinforcement due to the presence of concrete-making materials
containing chloride.
2. Verify the applicability of a Soxhlet chloride extraction method (ACI, 1997) for
establishing potential leachability of chloride from aggregate.
2
SCOPE
The research described in this report was carried out within the following project scope divided
into the Tasks described below:
Task 1. Literature Review

1. A literature review of current chloride limits set by ACI and other code bodies
and agencies was carried out. Foreign sources were also included, as limits
overseas may differ significantly from those in North America. A report
describing results of this survey was published by PCA (Whiting, 1997).
2. A review of research into the threshold amount of chloride needed to initiate
corrosion was carried out. Results of the search helped to establish the variables
and experimental design of the second Task of the project. A literature review
report was published by PCA (Taylor, et al., 1999).
Task 2. Laboratory Investigation

A primary series of corrosion experiments on concrete mixtures was designed with water-to-
cement ratio (w/c), tricalcium aluminate (C3A) content of cement, and percentage of chloride ion
as the three independent variables. The w/c was set at 0.40, 0.50, and 0.60. Cements of low
(~3%), moderate (~7%), and high (~12%) C3A contents were used. Chloride was added as a
solution of calcium chloride dihydrate at chloride ion equivalents (Cl–) of 0%, 0.1%, 0.2%,
0.4%, 0.7%, 1.0% and 2.0% by weight of cement. All concretes were moist cured for 7 days.
Specimens consisted of 75 x 150-mm cylinders containing a centrally located reinforcing bar.
Potentiostatic corrosion tests were carried out at 7 days. Powder samples were taken from
additional non-reinforced specimens and were analyzed at 28 days for acid-soluble and water-
soluble chlorides following standard ASTM techniques. Chloride analyses using non-standard
extraction techniques, including the ACI Soxhlet method, were carried out on unpowdered
samples taken from the same specimens. Companion reinforced specimens were subjected to
wet-dry cycling for 1 year, then split and examined for presence and extent of corrosion.
• A secondary series of short and long-term experiments was carried out on concretes
where alkali content was increased to a level of approximately 1% water-soluble
alkali. Only the moderate level of C3A and w/c of 0.50 were included in this series.
Standard ASTM chloride analyses were carried out on companions to this series.
Long-term exposure time for this series was 6 months.
• A third series of short and long-term corrosion tests were carried out on concretes
where Class C and F fly ashes were used to replace 25 percent of the cement. Again,
only the moderate level of C3A and w/c of 0.50 were included in this series, and
long-term exposure was 6 months.
• A series of experiments on aggregates that release chlorides when powder samples
are tested in accordance with standard ASTM techniques was also included in this
Task. A suite of limestone aggregate samples was obtained from the Illinois
Department of Transportation. Standard chloride analyses were carried out on a total
of 4 of these limestones, plus an additional chloride-free siliceous aggregate which
had been “doped” with a fixed amount of free chloride ion. Reinforced concrete
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specimens were prepared at the moderate level of C3A and w/c of 0.50.
Potentiostatic tests, as well as 6 months exposure to a “wicking” condition designed
to facilitate transfer of chloride from the aggregates, were carried out. The full set of
chloride analyses was run on the aggregates themselves as well as on companion
concrete specimens.
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CHAPTER 2 ORIGINS OF CHLORIDE LIMITS
CHLORIDE CORROSION THRESHOLDS

Ideally, any limit on chloride to be added to a concrete mixture should be based on a rational
chloride “threshold,” representing the minimum amount of chloride ion needed to initiate
corrosion of reinforcing steel. The steel is assumed to be in uncracked, uncarbonated concrete,
which, in the absence of chlorides, would provide a protective environment for the embedded
metal. The difference between “thresholds” and “limits” must be clearly understood. The
threshold for corrosion, as defined above, is set by natural conditions. As noted earlier in this
report, there may not be one universal chloride threshold for initiation of corrosion, but a series
of threshold levels relating to specific concrete properties and exposure conditions. The term
"limits" refers to the amount of chloride which is permitted in fresh concrete by code authorities.
This is not necessarily equal to the "threshold" for corrosion, even when limits are apparently set
to take into account such factors as cement composition and environmental exposure. In addition
to the physical factors inherent in the threshold, limits may include such items as implied safety
factors (i.e. if the threshold chloride content is believed to be 0.4%, then set a lower value for the
limit as a measure of safety), economic considerations, and consensus bargaining. All quoted
threshold values and chloride limits in this report will be expressed by mass of cement unless
otherwise noted.
A large number of studies have been carried out with the objective of defining a
threshold chloride content for reinforcing steel in concrete. Not surprisingly, a wide range
of recommended thresholds have been derived from these studies. As noted by Taylor,
et.al. (1997), values from 0.1% to 1.0% chloride ion by mass of cement have been
reported. It is important to realize that this range represents a wide variety of concretes,
experimental techniques, and exposure conditions. Additionally, many of these studies
were carried out before analytical techniques for determination of chloride ion in hardened
concrete had been standardized. Included also are studies carried out in solutions or cement
pastes, and possibly not representative of actual concrete. Bodies that set limits, such as
ACI or Comité Européen de Normalisation, have tended to focus on the lower end of this
range when utilizing threshold values as guidelines. The thresholds determined by FHWA
studies in the 1970s (Clear, 1976) apparently have been the basis for some of the ACI 318
chloride limits, and so merit some more detailed discussion.
A threshold chloride content of 0.20% acid-soluble (total) chloride is generally
believed to have been established based on work carried out at FHWA (Clear, 1976) in the
early 1970s. In fact, Clear based his suggested threshold on an earlier series of experiments
(Lewis, 1961). Lewis found that a concentration of 0.32% total chloride ion, based on
portland cement content, produced corrosion. However, his experiments were carried out in
a “synthetic pore water” solution, not actual concrete. For the particular materials used by
Lewis, only 50% of the total chloride was water-soluble. Therefore, approximately 0.16%
water-soluble chloride was needed to initiate corrosion. Applying this value to his own
(higher) ratio of water-soluble to total chlorides (80% in his case), Clear obtained a
chloride corrosion threshold of 0.20% when expressed as acid-soluble (total) chloride.
Thus, the often-quoted value of 0.20% for chloride threshold based on total chloride
5
content was conceived.

Data obtained from some well-documented field studies (Matta, 1992, Stratfull, et
al., 1975, Vassie, 1976) include this value in a range of thresholds from 0.15% to 0.30%.
However, it should be noted that field exposure results in ingress of chloride in a non-
uniform distribution, as well as wide variability in temperature and moisture, creating
differential concentration cells which may accelerate the onset of corrosion. Additionally,
most of Lewis’ work (on which the 0.20% threshold was based) and all field studies refer
to the effects of sodium chloride, rather than calcium chloride, which is the form of
chloride primarily added to fresh concrete as a set accelerator. Indeed, when Lewis (1961)
used calcium chloride in an additional series of experiments using actual concrete
specimens, threshold values of 0.50% total chloride were reported. Anderson and Black
(1985) supplied anecdotal evidence supporting the successful use of 2% calcium chloride
dihydrate (~1% chloride ion) by mass of cement in precast reinforced concrete members.
Results of the current study do not support use of such high chloride levels in reinforced
concrete. However, the apparent sensitivity of the threshold to the particular form of
chloride salt used and subsequent exposure of the concrete made it desirable to obtain
information on thresholds expected under interior exposure conditions where exposure to
more severe environmental factors and additional sources of chlorides are not an issue.
DEVELOPMENT OF ACI CHLORIDE LIMITS

As one of the principal purposes for this report is to supply information which could be used in
development of revised chloride limits for particular applications, it is instructive to review the
current limits set by ACI and other codes. Before doing this, a brief review of how the limits
came to be established is appropriate. A more detailed treatment of this subject can be found in a
previous PCA publication (Whiting, 1997).
Prior to about 1960 there had been some studies on the effects of chloride on reinforcing
steel, but results were conflicting and reached no clear consensus as to limitations on the use of
calcium chloride as an accelerating admixture in concrete. In 1963, ACI 212 recommended that
calcium chloride not be added to concrete where stray currents are present, nor to prestressed
concrete. In 1971, the ACI Building Code contained the statement, "Admixtures for prestressed
concrete or concrete which will have aluminum embedments shall not contain deleterious
amounts of chloride ion." This edition of the code did not define what a "deleterious" amount
was. The commentary suggested a limit of 500 ppm, but this was not mandatory.
In 1977, ACI Committee 201 published its first set of limits on chloride content in
concrete. It is customary for individual technical committees to recommend items under the
jurisdiction of their committee to the ACI 318 Building Code Committee for consideration. The
limits from this document (ACI 201.2R-77) are shown in Table 2-1. The first limit shown in
Table 2-1 (0.06%water-soluble chloride) is for prestressed concrete, and this limit has generally
been accepted up to the present day. The next two values referred to reinforced concrete in a
moist environment exposed to chlorides, and reinforced concrete in a moist environment not
exposed to chlorides, with limits of 0.10% and 0.15%, respectively. According to Anderson and
Black (1985) the first of these limits was most likely based on studies carried out by Clear at the
FHWA (1973) reflecting a conversion factor of 0.75 from acid-soluble to water-soluble chloride.
Cook and McCoy (1977) questioned the application of limits based on Clear's work (which
refers to existing concrete exposed to deicing salts penetrating from the external environment) to
6
the case where one is setting limits on chloride in fresh concrete, as the two circumstances
appear to be quite different. The second limit of 0.10% for concrete which may eventually be
exposed to external chloride appears to be simply a matter of applying some type of arbitrary
factor to the 0.15% limit, recognizing that if chlorides will eventually penetrate into the concrete,
one will be better off if there is initially less chloride in the concrete.
The final limit proposed by ACI 201-77 is for "Above ground building construction where
the concrete will stay dry." For this case, no limit was set, it being reasoned that the concrete
would eventually dry below the moisture content needed to support corrosion, and then the
amount of chloride in the concrete would not influence the corrosion process. It was noted by
ACI 201, however, that rarely does concrete contain over 1% chloride by weight of cement
(approximately equivalent to 2% calcium chloride flake), as this is the normal upper dosage
range for use of calcium chloride set accelerators.
After discussions spanning a number of years, ACI 318 eventually adopted a modification
of the limits suggested by ACI 201-77. The current ACI 318 limits, adopted in 1983, are shown
in Table 2-2. The limit on prestressed concrete (0.06%) remained the same and the limit on
reinforced concrete exposed to chlorides in service (0.15%) was slightly increased. The "no
limit" of ACI 201-77 in dry conditions was replaced by a limit of 1%. This allows the use of 2%
flake calcium chloride as an accelerator, but no more than this. The limit on "other reinforced
concrete" (0.30%), which, by process of elimination, is the same as concrete not exposed to
chloride but which will be wet in service, was double the ACI 201-77 value.
The situation with regard to chloride limits stayed fairly static until the early 1990s, when
concern was raised that chloride contained in some limestone aggregates might contribute to
corrosive conditions. "Thornton limestone," a high quality aggregate used in many structures in
the Chicago area, has been found to contain up to 0.06% chloride ions when tested by ASTM C
1218 water-soluble procedures. This would be equivalent in a typical concrete mix to 0.18%
water-soluble chloride by mass of cement. According to the ACI 318 limits, this would not be
acceptable for use in prestressed concrete, or in reinforced concrete exposed to chlorides, even
though there have not been any problems attributable to these aggregates during their many
years of use.
Similar situations have been reported for other Midwest U.S. sources and aggregates in the
Canadian Shield and on the east coast. This was referred to ACI Committee 222 on Corrosion of
Metals in Concrete. Prior to this, the committee had examined a Soxhlet extraction method
(Hope et al. 1985) to leach water-extractable chloride out of concrete specimens. It did not,
apparently, extract the chloride present in the limestone aggregates, and as Hope indicated, it
could be used to accept these materials. Limits based on use of this method (ACI 222.1-96), plus
the traditional acid and water-soluble techniques, were combined into a set of limits suggested
by ACI Committee 222 (Table 2-3). These allow one to progress from most severe to least
severe test conditions when attempting to have concrete approved. The acid-soluble test can first
be run; this is the simplest and cheapest test for chloride in concrete.
The limit on prestressed concrete in ACI Committee 222 is effectively the same as
ACI 318, as ASTM C1152 is acid-soluble chloride and ACI 318 is water-soluble. The limit for
reinforced concrete in wet conditions is 0.10% acid-soluble, versus 0.30% water-soluble for ACI
318, a considerable difference. There is no separate category for concrete exposed to chloride in
service, as there is in ACI 318. It is easily seen that the ACI 222 limit of 0.10% is stringent
enough, so no separate limit on concrete exposed to chloride is needed. The limit on reinforced
concrete in dry conditions is 0.20%, less than the ACI 318 limit for concrete in wet conditions.
7
Limits on chloride content of reinforced concrete have also been set by overseas agencies.
Detailed tables of limits as of 1997 can be found in a previous report (Whiting, 1997). In
summary, agencies in the U.K. and Europe have generally standardized on a limit of 0.4% acid-
soluble chloride by mass of cement, irrespective of exposure condition. Furthermore, no
deliberate addition of chlorides to concrete (such as by use of calcium chloride as a set
accelerator) is permitted. Most other industrialized countries (with the exception of the U.S. and
Canada) have also adopted this restriction.
8
CHAPTER 3 LABORATORY TEST PROGRAM
SCOPE AND ORGANIZATION

The laboratory test program was designed to develop information on the amount of chloride ion
needed to initiate corrosion when chloride is added as an admixture to a concrete mixture and the
concrete is exposed to a relatively static indoor environment which may only occasionally be
wetted by fresh water. Exposure to severe environments where chlorides may penetrate from the
outside under large temperature gradients was not included in this test program. Included as
independent variables were the chloride level, tricalcium aluminate (C3A) content of the cement,
and the water-to-cement ratio (w/c) of the concrete mixture.
The test program was organized into three separate series. In Series 1, concretes were
prepared from three portland cements of differing C3A contents at three w/c and seven levels of
chloride ion (0%, 0.1%, 0.2%, 0.4%, 0.7%, 1.0% and 2.0 % by mass of cement). The mix matrix
is shown in Table 3-1. The design is a partial factorial, as in most current concrete specifications
for reinforced structural concrete w/c as high as 0.60 are rarely encountered. However, in order
to extend the range of the w/c variable this value was included for the intermediate C3A content
cement to develop more information on effects of w/c on corrosion. In Series 2, the effects of
alkali content and the partial replacement of portland cement with fly ash were investigated. This
was done with the intermediate C3A cement only and chloride levels of 0%, 0.2%, 0.4%, 0.7%,
and 1.% . In Series 3, the effects of chloride content of aggregates were investigated. Aggregates
included were (1) the same siliceous gravel used for Series 1 and 2, but in this case “doped” with
2 levels of free chloride, and (2) a series of limestones obtained from the Illinois Department of
Transportation having a range of chloride contents. No additional free chloride was added to the
Series 3 mixtures. Tests carried out for all series are listed below:
• Short-term corrosion behavior using a potentiostatic technique.
• Long-term corrosion behavior by exposure of test specimens to a wet-dry cycle.
• Analyses for chloride ion, including acid-soluble, water-soluble, and water-extractable
techniques.
• Compressive strength at 28 days (Series 1 and 3 only).
Details on specimens and procedures are given in a subsequent section of this chapter.
MATERIALS
The three portland cements used in this study were selected to cover a range of C3A contents.
Chemical compositions are given in Table 3-2. Cements were received in bags, then ribbon-
blended to obtain a homogeneous composition and stored in sealed steel drums until used.
Cements were identified as to their C3A content as “Low (L),” “Moderate (M),” or “High (H).”
The coarse aggregate used for the majority of the study was Eau Claire, Wisconsin river
gravel. This is a rounded, primarily siliceous stone, which has a low baseline chloride content.
Fine aggregate in all mixtures was sand from the same source. Physical properties of these
aggregates and gradations are given in Table 3-3. Two sizes of coarse aggregate were used. The
9.5 mm and 4.75 mm topsize aggregates were blended in a ratio of 70:30 to achieve the desired
9
gradation. Topsize was restricted to 9.5 mm to obtain representative specimens, as cover over
the reinforcing steel in the test specimens was approximately 32 mm. For Series 3, additional
limestone aggregates were introduced. These were selected to cover the range of chloride
contents encountered in Illinois limestones and were provided by the Illinois Department of
Transportation. Chloride contents can be found in Table A-6. In addition, in Series 3 the
originally chloride-free Eau Claire coarse aggregates were soaked in 25% and 50% (by mass)
solutions of calcium chloride dihydrate to obtain a wide range of free chloride content in the
aggregate. The effects of free chloride in aggregate could then be compared with the effects of
the primarily bound chloride in the as-received Illinois limestones.
In Series 2, the effects of alkali and fly ash were investigated separately. Free alkali (as a
40% solution of sodium hydroxide) was added to mixtures prepared with cement M. This
cement had an initial water-soluble alkali (as Na2O equivalent) content of 0.12%. Sufficient
sodium hydroxide was added to bring this to 1.12%. Thus, the difference between the original
and alkali-enriched cements amounted to 1.0 percent water-soluble alkali.
Chemical compositions of fly ashes used in Series 2 are given in Table 3-4. A class F and
class C ash were included in the study. Only cement M concretes were included in this series,
and only at a w/cm of 0.50.
Chloride ion was added to the concrete mixtures as reagent grade calcium chloride
dihydrate (CaCl2 • 2H2O). Anhydrous CaCl+ was assayed at 75.9% of the total weight of
dihydrate. The reagent was dissolved in a portion of the concrete mix water prior to mixing.
With the exception of the sodium hydroxide used in Series 2, no other chemical admixtures were
used in the study.
CONCRETE MIXTURES
Series 1 Mixtures
As noted earlier, concretes were prepared at three w/c for this series. These were fixed at w/c of
0.40, 0.50, and 0.60, spanning the range of general contemporary concretes, but not including
High Performance Concretes (HPC), which would normally have w/c less than 0.40. Cement
contents were adjusted to achieve the desired placeability, a slump greater than 100 mm being a
target for consolidation into the relatively small test specimens. Cement contents were higher for
Cement H, as this particular cement exhibited less workablity than L or M. All concretes were
non-air-entrained so as to eliminate the possible effect of variable air contents. No chemical
admixtures other than calcium chloride were used, again to eliminate possible uncontrolled
influences. Mixture proportions for series 1 are shown in Tables 3-5, 3-6, 3-7. For the w/c of
0.60, mixtures were prepared using Cement M only. As such high w/c are rarely specified in
modern reinforced concrete construction, this w/c was only included for one of the cements in
order to increase the range of this variable. For each cement and w/c, seven mixtures were
prepared at chloride contents of 0.0%, 0.1%, 0.2%, 0.4%, 0.7%, 1.0% and 2.0% chloride ion by
mass of cement. Thus, there were a total of 49 mixtures prepared under Series 1 of the study.
10
Series 2 Mixtures
Mixture proportions for Series 2 mixtures incorporating additional alkali are given in Table 3-8.
These were prepared at w/c of 0.50 using cement M only. Chloride was added at 0.0%, 0.2%,
0.4%, 0.7%, and 1.0% by mass of cement.
Mixture proportions for the fly ash concretes are given in Table 3-9. Identical proportions
were used for each fly ash. Water content was held to a water-to-cementitious materials ratio
(w/cm) of 0.50. Calcium chloride was added at 0.0%, 0.2%, 0.4%, 0.7%, and 1.0% by mass of
portland cement, as chloride limits in current specifications are based on the mass of cement and
not on the mass of the blended cementitious materials.
Series 3 Mixtures
Mixture proportions for Series 3 mixtures using limestone aggregates are given in Table 3-10.
Cements M and L were used. Because of the increased angularity of the limestones, workability
of trial mixtures was found to be poor. As the purpose of this series was to examine whether
chloride would leach out of the limestone and initiate corrosion of the embedded steel, w/c was
increased to 0.60 to obtain the desired workability and to facilitate leach-out of chloride into the
more open pore system which occurs at higher w/c. The w/c of the mixtures utilizing the
chloride-doped siliceous gravel was maintained at 0.50, and mix design was identical to the
Series 1 mixtures using the same cements.
Mixing Procedures
All mixing was carried out in a 0.02 m3 counter-rotating pan mixer. Coarse aggregate was added
to the mixer in the dry state. Fine aggregate was pre-conditioned so as to obtain a moisture
content slightly above SSD. The aggregates were blended in the mixer, then a portion of the
batch water added and the aggregates allowed to soak for 10 minutes so as to expose the coarse
aggregate to an excess of water and satisfy its absorption prior to mixing. The cement was then
added along with the remainder of the mix water, into which the required amount of calcium
chloride dihydrate had been dissolved. For Series 2 mixtures, sodium hydroxide solution was
added after the calcium chloride solution had been mixed in the concrete. Mixing was continued
until the initial 3 minute mix period had elapsed. The batch was then allowed to rest for 3
minutes, followed by a final 2 minutes of mixing.
TEST SPECIMENS AND PROCEDURES
Potentiostatic Testing
An adaptation of a technique proposed by Berke, et al. (1994) for corrosivity testing of concrete
admixtures was used as a rapid test for determining the chloride content needed to initiate
corrosion (i.e. the “threshold chloride content”) for each of the concrete mixtures. The
experimental setup is shown in Figure 3-1. The test specimen consists of a 10-mm diameter x
11
200-mm long deformed reinforcing bar (grade 60) embedded along the longitudinal axis of a
75-mm diameter x 150-mm long concrete cylinder. The bar is degreased with acetone prior to
assembly of the specimen. All reinforcing steel used in the study was obtained from a single
heat, meeting ASTM A 615M-96A. A 75-mm long section of the bar was used as the test area.
The remainder of the bar was masked with electrical-grade heat-shrink tubing. A 25-mm long
plug of solid acrylic was fixed to the bottom of the bar to serve as a spacer between the bottom of
the test cylinder and the beginning of the exposed test area on the bar. The bars were centrally
located within a set of plastic cylinder molds by a clamping arrangement, and concrete carefully
consolidated by rodding the concrete and tapping the sides of the molds. Specimens were
allowed to initially cure under wet burlap for 18 to 24 hours, then demolded and placed in a
moist room for 7 days. Testing was carried out at the end of this 7-day period.
The potentiostatic test setup is also shown in Figure 3-1. The 10-mm reinforcing bar is
used as the working electrode. The reinforced concrete test specimen is placed in a 4-L plastic
container filled with limewater to within 25 mm of the top of the concrete cylinder. Anodic
current is applied to the rebar through a stainless steel mesh counter electrode. The potential of
the steel is monitored using a saturated calomel (Hg/HgCl) reference electrode. A laboratory
potentiostat is used to maintain the potential of the reinforcing bar at +100-mV relative to the
calomel electrode for a period of 24 hours. The potentiostat is multiplexed to allow simultaneous
testing of six specimens, each in a separate container. Triplicate specimens were tested for each
batch of concrete prepared. The current, in milliamps, is monitored over the course of the 24
hours of test. At the end of the test the current is integrated over time to obtain the amount of
electrical charge passed during the test. By dividing this quantity by the test time (in seconds), an
“average” current may be calculated. This average current is then divided by the exposed area of
steel (25.5 cm2) to obtain average current density over the 24-hour period. It is this quantity
which is presented in this report as the test result for the potentiostatic testing.
Long Term Exposure

For each set of three specimens subjected to 100-mV potentiostatic testing, a companion set of
three additional specimens identical to those used for the potentiostatic tests was cast. These
three specimens were also moist cured for 7 days, then transferred to a laboratory maintained at
23 ± 1.7°C and 50 ± 4 % R.H. The specimens were exposed to this laboratory air for 3 weeks,
then placed in a 4-L container of limewater for 1 week. The level of limewater was maintained
25 mm below the top of each specimen. This 3-week dry – 1-week wet cycle was continued for a
period of 12 months for specimens in Series 1, and 6 months in Series 2 and Series 3. For Series
1 specimens, at the conclusion of each wet cycle the potential of the embedded exposed area of
reinforcing steel was measured relative to a solid-state Copper/Copper Sulfate Electrode (CSE).
As the information developed from these potential measurements added little to an understanding
of the corrosion behavior, CSE measurements were not taken for the subsequent series. The mass
of each specimen was also measured at the end of each wet cycle. At the completion of long-
term exposure each specimen was split longitudinally and the reinforcing steel was removed
from the concrete. Visual examinations of the surfaces of the reinforcing steel were carried out at
a magnification of approximately 4X using a hand-held lens.
12
Compressive Strength
Compressive strength of companion 75 x 150-mm cylindrical specimens was measured at an age
of 28 days in accordance with ASTM C 39 “Standard Test Method for Compressive Strength of
Cylindrical Concrete Specimens.” All specimens were moist cured until the age of test.
Triplicate specimens were tested for each batch of concrete prepared. As the effects of calcium
chloride on compressive strength have been well known for many years (Shideler, 1952),
compressive strength data were obtained for informational purposes only.
Chloride Analyses
Standard powder analyses. A companion 75 x 150-mm plain concrete cylinder from each
batch was removed from moist storage at the age of 28 days. A series of 25-mm diameter x 75-
mm long plugs was removed from each cylinder. To obtain analytical samples, the plugs were
reduced to smaller particles which were then milled to pass an 850-µm sieve. Analyses for acid-
soluble (total) chloride were then carried out using the powdered samples in accordance with
ASTM C 1152-97, “Standard Test Method for Acid-Soluble Chloride in Mortar and Concrete.”
Analyses for water-soluble chloride were carried out in accordance with ASTM C 1218-97,
“Standard Test Method for Water-Soluble Chloride in Mortar and Concrete.”
Soxhlet extractions. The procedure described in ACI 222.1-96, “Provisional Standard Test
Method for Water-Soluble Chloride Available for Corrosion of Embedded Steel in Mortar and
Concrete Using the Soxhlet Extractor,” was followed. This procedure has also been tentatively
adopted by ASTM as ASTM PS 118-99, “Provisional Standard Test Method for Water-
Extractable Chloride in Aggregate (Soxhlet method).” It should be noted that the ASTM version
at the current time is meant to apply to aggregates only, while the ACI method allows the testing
of concrete specimens as well. Otherwise, the two procedures are very similar. For concrete, the
ACI method was applied to 10-mm thick discs cut from the plugs taken for the chloride analyses.
Two discs were used for each extraction. The mass of each disc was approximately 15 g. For
aggregate, a 30-g as-received sample was used. A schematic view of the Soxhlet extractor is
shown in Figure 3-2. The apparatus consists of three sections. The first is a boiling flask, which
contains reagent water at the start of the test. The second is the extractor, which contains the
sample inside a porous extraction thimble. The third is the condenser mounted on top of the
extractor. When the water in the flask reaches the boiling point it is vaporized and condenses to
liquid in the condenser. Drops of water then percolate down to the sample. When the level of
water in the sample reaches close to the height of the siphon tube, a reflux occurs, which allows
the water to return to the boiling flask. A cycle occurs approximately every 20 minutes. Samples
are run for a 24-hour period. At the conclusion of the extraction the flask is washed three times
with reagent water and the entire extract is then analyzed for chloride ion. This is the chloride
that was leached from the unpowdered sample during the 24-hour period. The primary utilization
of the Soxhlet procedure in this study was for the aggregates and concretes in Series 3, where the
question of leachable free chlorides in chloride-bearing limestones was addressed. There was
only limited application of this technique to Series 1 concretes, where chloride added to the fresh
concrete mixture is known to exist as free ions in the concrete porewater.
13
Modified C 1218 extractions. As the Soxhlet procedure requires relatively expensive

equipment, which must be dedicated to a single sample for the entire 24-hour extraction period,
an alternate procedure was investigated. This is essentially the same procedure as described in C
1218, except that the unpowdered 10-mm x 25-mm discs are used as the sample rather than the
powdered concrete as specified in C 1218. In the modified procedure two discs are placed in a
250-mL beaker, and 50-mL of reagent water is added. The water is brought to a boil for 5
minutes. The heat is then removed and the beaker is allowed to stand for 24 hours. At the end of
this time period the liquid is filtered and the filtrate analyzed for chloride ion as described in C
1218. As for the Soxhlet extraction procedure, major application of the C 1218 modified
technique was in Series 3.
14
CHAPTER 4 RESULTS AND DISCUSSION
SERIES 1 – PLAIN CONCRETE MIXTURES
Chloride Analyses
The full set of chloride analyses for all specimens in the test program is contained in Appendix
A. In Table A-1a, acid-soluble and water-soluble chloride contents for concretes prepared with
cement M are shown. The acid-soluble results are, with the exception of the 0.0% chloride
mixtures, somewhat less than the amount of chloride added to the mix. This may represent a
slightly less than ideal recovery, but most likely is the result of cumulative sampling errors. That
is, a 75- x 150-mm concrete sample may differ somewhat from the batch as a whole, a 25-mm
plug may differ somewhat from the cylinder, and the final powder that is solubilized may differ
somewhat from the plug. Since the chloride is being expressed by mass of cement, these possible
errors apply to cement content of each sub-sample as well. The presence of chloride in the
“0.0%” mixtures can be attributed to cumulative normal background levels in the various
materials used to batch the concrete.
Water-soluble chloride contents (ASTM C 1218) are also shown in Table A-1a. When
expressed as a percent of acid-soluble (total) values, water-soluble chloride averages for each set
range from 62 to 69%. Studies carried out by FHWA (Clear and Harrigan, 1977) show ratios of
water-soluble to acid-soluble chloride over a range of 28 to 96 percent for a large number of
samples taken from field concrete structures. These averages exclude the data for 0.0% chloride
mixtures, as the analytical results were close to detection limits for these samples. Within each
set there is a general trend of increasing ratio of water-soluble to acid-soluble chloride as the
amount of chloride added to the mix increases. This is not surprising, as the amount of chloride
which complexes with aluminates may be less soluble than that remaining free in the pore
solution. Once the aluminates are satisfied, then additional added chloride is more easily
solubilized in the C 1218 procedure.
Table A-1b shows results of “modified” C 1218 and Soxhlet extractions for the same
concrete samples. These are compared with the standard C 1218 water extractions from the
powder samples. For the modified C 1218 test, results for the mixture where no chloride was
added were close to detection limit. For the samples with added chloride, average amount of
chloride extracted with the modified C 1218 method runs from 14 to 36% of standard. For the
Soxhlet method, however, considerable chloride was present in samples to which no chloride
had been added. This indicated a possible contamination of some of the samples, although it
should be noted that the series 3 Soxhlet extractions did not exhibit high levels of chloride for
the limestone concretes. The Soxhlet results, expressed as a percentage of standard C 1218
results, are highest at low chloride levels, but are considerably less than extracted using the
standard powder test at the higher levels of chloride. Because of these inconsistencies in the non-
standard procedures, no further work using the C 1218 modified or Soxhlet extraction was done
in series 1.
Acid-soluble and water-soluble chloride results for concretes prepared from cement L
(having the lowest C3A content) are shown in Table A-2. Again, recovery using acid dissolution
is less than 100% on average. Water-soluble chlorides, expressed as a percent of acid-soluble,
15
are within the same range as for the moderate C3A cement. As the amount of chloride added
increases, the ratio of water-soluble to acid-soluble chloride recovered also increases. In terms of
absolute amount of chloride recovered by the water-soluble procedure, for the two lowest levels
of chloride added (0.1 and 0.2 percent) there is more water-soluble chloride recovered in the
concretes prepared from cement L as opposed to cement M. Again, this most likely reflects the
complexing of chlorides by the higher amount of C3A in cement M as opposed to cement L.
Once this has been satisfied, at the higher levels of chloride added there is no consistent
difference between the two cements.
Chloride results for cement H concretes are shown in Table A-3. Trends for acid- and
water-soluble chlorides are similar to those for cement M. Cement H, however, exhibits the
lowest average water-soluble to acid-soluble chloride ratios. As this cement is highest in C3A it
is likely that more of the chloride is bound and less able to be solubilized.
Potentiostatic Test Results

Cement M (moderate C3A). The results of potentiostatic testing are best discussed in context of
the amount of chloride added to each concrete mixture. In Figure 4-1 results for cement M
concretes prepared at three different w/c ratios are shown. For each w/c ratio concrete the
resultant average current density, in mA/cm2, is plotted against the amount of acid-soluble
chloride ion added to each mixture. On a linear scale virtually all the data points overlap on the
bottom of the vertical axis until the 0.7 percent level of chloride ion has been exceeded. A larger
difference is seen (on this scale) for the highest level of chloride ion (2.0%). A more useful
representation of these data can been seen in Figure 4-2 where a log scale for the vertical axis has
been used. In this manner those points at lower values of current density can be more closely
examined. Berke, et al. (1994) have suggested a criterion of 1.0 mA/cm2 as representative of the
transition from passive to actively corroding behavior. Additionally, the point at which a
significant jump in average current occurs can also be viewed as a transition zone. In Figure 4-2
the 1.0 mA/cm2 criterion is exceeded only after more than 0.5 % chloride ion has been added to
the mixture. This also appears to be the point at which a significant jump in average current
density occurs.
Figure 4-3 and 4-4 show the same average current density data plotted against the amount
of acid-soluble chloride ion that was analyzed for each sample. As noted earlier, the amount of
chloride ion recovered was less than that added to the mix. Most specifications that utilize total
or acid-soluble chloride values refer to the amount extracted from the concrete by an analytical
procedure. Therefore, the values in Figures 4-3 and 4-4 more closely relate to chloride limits.
Again, as in the previous figures, a jump in current above the 1.0 mA/cm2 criterion occurs in the
vicinity of 0.5 percent chloride ion. Values at 0.4 percent appear to still be passive, while those
at 0.7 percent are more active.
In ACI 318 chloride limit values of water-soluble chloride are specified. Results of C 1218
testing are shown in Figures 4-5 and 4-6. In Figure 4-5 on a linear scale of current density the
highest amounts of average current are seen at the highest amount of added chloride, equivalent
to 1.2 to 1.4 percent water-soluble chloride for these concretes. Figure 4-6 shows the lower
values of average current expanded by use of a log scale. Here, a jump in average current
appears to occur between about 0.3 and 0.4 percent water-soluble chloride. If, at least
preliminarily, we interpret this to signify the presence of a “corrosion threshold” in this range,
16
then this would correspond approximately to the current ACI 318 limit of 0.30 percent water-
soluble chloride for reinforced concrete construction that may be wet but not exposed to external
chlorides. Little difference is seen between the concretes in terms of w/c.
Cements L (low C3A) and H (high C3A ). Concretes were prepared from cements L and H at
w/c of 0.40 and 0.50. Average current density as a function of added chloride is shown in Figures
4-7 and 4-8. Only those values for 1.0 percent added chloride and lower are included so as to
allow a clear representation using a log scale for the current density axis. All current densities at
2.0 percent added chloride were high, though it should be noted that those for cement H were
considerably lower than those for cements L or M at equivalent w/c. Trends in Figure 4-7 for
cement L concretes are different from those seen earlier for cement M. Here, after the 0.1 percent
chloride level is exceeded, the trend is nearly linear on the log scale. No transition zone or
“jump” point can be distinguished. The value at which the 1.0 A/cm2 criterion is exceeded is
somewhat over 0.4 percent added chloride, compared with somewhat above 0.5 percent for
cement M. Figure 4-8 shows the data for cement H concretes. Here the slope of the log-linear
trend is much lower, with all data points up to the 1.0 percent chloride addition level below the
1.0 mA/cm2 criterion. Again, as for cement M concretes, there is no consistent difference
between w/c for any of the data shown in Figure 4-7 or 4-8. Trends versus acid-soluble analyzed
chloride (Figures 4-9 and 4-10) were very similar to those for total added chloride. In Figure 4-
10 only those concretes having the highest level of chloride exceeded the 1.0 mA/cm2 criterion,
as total analyzed chloride is less than added due to the less than 100% recovery noted earlier. No
distinction between the two levels of w/c was evident.
Results for water-soluble chlorides for cements L and H are shown in Figures 4-11 and
4-12. For cement L the criterion of 1.0 mA/cm2 is exceeded somewhere above 0.30 percent
water-soluble chloride, again close to the current ACI 318 limit for these conditions of exposure.
For cement H the criterion is not exceeded until the level of water-soluble chloride is over 0.5
percent.
Statistical Analyses
For series 1 of this research program there was one dependent variable (average current density)
and three independent variables (w/c, C3A content, and chloride level). Analysis of variance
(ANOVA) statistical techniques are most commonly employed in data analysis when there are a
number of factors which may influence a process but one does not know which are truly
significant. While it is technically possible to carry out a full-factorial analysis of the data, a
different approach was selected for the following reasons:
1. Specimens were prepared at a w/c of 0.60 only for one of the three cements. A full
(3-way) ANOVA would be accurate only if there were no significant interactions
between the independent variables. The significance of interactions could not be
determined simply by cursory examination of the data.
2. It was quite clear from examination of the 100-mV test data that chloride content was
highly significant. Obviously, if it were not, there would have been no reason to carry
out the research. Therefore, inclusion of the chloride data as a factor may overwhelm
some of the more subtle variations in the other factors of interest.
3. Effects of C3A content and w/c could best be examined by partialization of the test
matrix, examining subsets of the full complement of test results and gaining more
17
insight into the significance of these two factors and their interaction at various
separate levels of chloride content.
The first ANOVA was carried out on the data subset shown in Figure 4-13. Here, w/c of
0.40 and 0.50 were examined for all three cements. For each cell there are seven levels of
chloride (i.e. 0.0, 0.1, 0.2, 0.4, 0.7, 1.0, and 2.0). A two-way ANOVA with w/c and cement (L,
M, or H) as factors was carried out at each level of chloride. Results of the analysis are shown in
Table 4-1. Shown are the F and P statistics. The F statistic is the ratio of the mean square
variance between levels of the factor to the mean square of the error variance (the underlying
variability of the population). The larger the value of F the greater the probability that the
observed data are a result of changes in levels of the factor rather than random testing variability.
The P value is the probability of being wrong in the hypothesis that there is a real difference
between the levels of the factor. The smaller the P value the higher the probability that the factor
has a significant influence on the independent variable. Typically, a P criterion of 0.05 (i.e. 95%
confidence level) is chosen. From Table 4-1 we can see that w/c is significant at this 95%
confidence level at only 2 levels of chloride (0.2 and 0.7), and C3A is significant at four (0.2,
0.7, 1.0, and 2.0) out of the total of seven levels. The interaction between w/c and C3A is
significant at only one level (0.7). As there is no apparent physical reason why the interaction
should be significant at only this level, we assume that this is coincidental and that there is no
real interaction between these variables. The fact that C3A is significant at four levels, and that
three of these are the highest levels investigated, may indicate that at most of the levels all
cements are able to complex enough chloride to inhibit corrosion, but that at the higher levels of
chloride one begins to see a separation between cements.
The interpretation of the results with respect to w/c is more problematical. Significant
differences were found at only two levels, and one of these (0.7% chloride) is where the
anomalous interaction effect occurred. That is, the effect of w/c depends on the level of C3A for
0.7% chloride. A pairwise multiple comparisons test was performed to determine the
significance of the w/c effect at each level of C3A. There was a significant difference between
the levels of w/c only for cement M. On the whole, then, the effect of w/c on the average current
in the 100-mV test appears to be much less than the effect of C3A.
In the previous two-way ANOVA the effect of the third level of w/c (0.60) had not been
included. To examine this level the matrix was again partitioned, as shown in Figure 4-14. Here
the data for cement M alone were chosen so as to include all levels of w/c. Results of the one-
way ANOVA are shown in Table 4-2. Here w/c is seen to be a significant effect at chloride
levels of 0.2, 0.7 and 2.0 percent. Further analysis indicated that the only clear effect was at the
2.0% level. At 0.2% Tukey’s test was significant only for comparison of w/c = 0.60 versus 0.40,
and at 0.7% the statistical power of the test was less than desirable. The power of a test is the
probability that the test will detect a significant difference among the groups if there really is a
difference. Typically, a power of 0.80 is selected. At 2.0% chloride all w/c comparisons were
significant.
As results of the two-way ANOVA with w/c of 0.40 and 0.50 indicated that there was a
low probability of significant interactions between the variables, and as the one-way ANOVA
indicated that w/c may be significant at the higher levels of chloride content, the two-way
ANOVA was run with the 0.60 data included and no interactions were assumed for the analysis.
Results are shown in Table 4-3. Here, w/c is significant at the 0.2% and 2.0% chloride levels,
and C3A at 0.2, 1.0 and 2.0%. At 0.2%, however, comparison testing indicated significant
differences between the means for 0.60 versus 0.40 only, and no significant differences were
18
detected between the various pairs of cements (though overall the cement effect was significant).
At 2.0%, while w/c was found to be significant, there were no significant pairwise comparisons,
and the power of the test was less than 0.80. For C3A at 1.0 and 2.0% all pairwise comparisons
were significant and powers were over 0.8.
To compete the analysis of the series 1 data, knowing that interactions were most likely
not significant, and the C3A effect was strongest at the higher levels of chloride, the full data set
was subjected to a 3-way ANOVA. Results are shown in Table 4-4. Chloride content, of course,
is highly significant. C3A is also highly significant. The w/c is not significant. The interaction of
C3A and chloride content is significant, as seen from the two-way ANOVA. No other
interactions are significant.
While the significance of the effects of chloride content and C3A require little additional
explanation, caution must be taken regarding the w/c effect, as it is open to some
misinterpretation. Previous studies (Ruettgers; et al. 1935, Whiting, 1988) have shown that w/c
has an important effect on permeability of concrete. Therefore, when concrete is exposed to
external sources of chloride, w/c is highly significant, as the time-to-corrosion will be inversely
proportional to the w/c of the concrete. However, in this study chloride was present in the
concrete at the time of mixing, and the specimens were not exposed to additional sources of
chloride. Therefore, the effect of w/c is much less than in externally exposed structures.
Half Cell Potentials

Potentials of embedded reinforcing bars were measured on each series 1 specimen using a
portable CSE at the end of every wet cycle. While potentials tended to fluctuate, most specimens
showed a steady trend towards more electropositive potentials with time. This may be indicative
of a passivation with time. The most electronegative potentials were found to occur early in the
test period. As the mass of the specimens was fairly constant over time, the trend towards more
positive potentials with time may reflect increasing hydration of the cement, which would tend to
increase resistivity of the concrete (Whittington, et al., 1981), and reduce localized corrosive
conditions. Additionally, chloride may also become complexed into cement hydration products,
lowering the amount of free chloride available to support corrosion. For these reasons, only those
potentials obtained at the end of the first wetting period (35 days after casting) will be discussed.
Potentials measured on specimens prepared from cement M are shown in Figure 4-15,
plotted against the total added chloride ion content. Results are very similar to the 100-mV data
(see Figure 4-1). A jump in potential is seen only after a value of approximately 0.5 percent
chloride ion has been exceeded. There is little consistent influence of w/c. Results in terms of
water-soluble chloride ion are shown in Figure 4-16. Here, an increase in potential towards more
electronegative values begins to occur at a point slightly under 0.5 percent chloride. Again, this
is similar to the 100-mV results (Figure 4-6).
Potentials measured on specimens prepared from cement L (low C3A) are shown in
Figure 4-17, plotted against the total added chloride ion content. As with the 100-mV data for
this cement, a transition appears to occur around 0.4 percent chloride, somewhat lower than for
cement M. In 100-mV potentiostatic testing of companion cylinders the value at which the 1.0
mA/cm2 criterion was exceeded was somewhat over 0.4 percent added chloride (Figure 4-7).
When potential is plotted against water-soluble chloride (Figure 4-18) a transition occurs at a
level somewhat less than 0.3 percent.
Potentials measured on specimens cast from cement H (high C3A) are given in
19
Figure 4-19, plotted against added chloride. No jump in potential is seen until a value of 1.0
percent chloride has been exceeded. For water-soluble chloride (Figure 4-20), the transition
occurs somewhere above 0.8 percent water-soluble chloride. While such high chloride additions
would not be advisable under most service conditions, the results do again illustrate the ability of
cement high in tricalcium aluminate to reduce the amount of chloride available to catalyze the
corrosion process.
Visual Observations
Observations of reinforcing steel carried out when rebars were removed from concrete test
specimens after 1 year of exposure are given in Table 4-5. The observations are condensed from
condition records of each bar. As such, they represent a qualitative “average” of the condition of
each set of bars after test. There was no visible corrosion on any of the “control” specimens, that
is, specimens cast from those concretes where no calcium chloride had been added to the batch.
Figure 4-21 shows the surface of such a “clean” bar (cement M, w/c=0.50) after removal from
the concrete. Overall, there was essentially no corrosion for specimens where 0.1 percent
chloride had been added to the concrete. As noted in Table 4-5, for cement L a couple of flecks
of rust were noted at this low level of chloride, however, considering that the specimens had
been exposed for over a year, this small amount of rust can be considered relatively insignificant.
At a chloride level of 0.2 percent most of the sets still continued to exhibit no
manifestations of corrosion. These included the specimens cast from cements M and H at w/c of
0.4 and 0.5. At w/c of 0.60 specimens cast using cement M (the only cement tested at this w/c), a
few specks of rust were noted. However, most current specifications for reinforced concrete
construction would likely not permit such a high w/c. Cement L on the other hand, exhibited
somewhat larger spots of corrosion on many of the deformations at w/c=0.50, as shown in
Figure 4-22. Spots of corrosion were also present on specimens cast using cement L at w/c=0.40,
but these were considerably smaller and much less prevalent.
At the next increment of chloride (0.40% added), generally, a few specks of rust were
noted on specimens cast using cement M and H for the two lower w/c. Again, at the highest w/c
(0.60), four to five larger areas of corrosion were noted. The similarity of appearance for most all
specimens from the moderate and high C3A cements at this level of chloride indicate that at this
level, or slightly above, a “threshold” for the activation of corrosion may be said to occur. It was
noted in the previous discussion of 100-mV potentiostatic test results that a jump in average
current generally occurred in this range of chloride concentration. Interestingly, this corresponds
with the current European CEN limit (0.40%) on total chloride that may be present in fresh
concrete. While the extent of corrosion at this level is very limited, and it is not clear whether
under the uniform conditions present in building interiors that it would progress to a damaging
extent, it might be prudent to consider this as a conservative limit on added chloride for such
cements.
At a chloride level of 0.70 percent, corrosion is significant on all specimens, though the
severity is considerably less in those produced using the high C3A cement (cement H). Figures
4-23 through 4-25 compare observations on rebars taken from concrete with w/c=0.50 for the
three cements. The progressive spread of corrosion areas as the C3A content of the cement is
increased is evident from these photographs.
At the highest chloride levels (1.0 and 2.0%) there is widespread corrosion on all
specimens, though again on cement H severity is lower. Pitting is evident on a number of
20
specimens, as illustrated in Figure 4-26. This shows pits developed on a rebar cast into concrete
using cement M at w/c=0.50 at the 2.0% chloride level. Obviously, at these high levels of
chloride, corrosion has the potential to be very severe and, in all probability, would result in
eventual damage to the reinforced concrete structure. The 1.0% level of added chloride
corresponds approximately to 2% calcium chloride dihydate addition, a value historically used
for acceleration of set and early strength gain of concrete. With the widespread availability of
non-chloride accelerators and other means of achieving higher early strengths, deliberate
addition of such high levels of chloride to reinforced concrete can, in the authors’ opinion, no
longer be supported.
SERIES 2 – EFFECTS OF CEMENT ALKALI CONTENT AND FLY ASH
Cement with Added Alkali

Chloride contents. Acid-soluble and water-soluble chloride contents for aggregates and
concretes made with cement M, to which alkali had been added to yield a sodium oxide
equivalent of 1.12%, are given in Table A-4. By comparison with Table A-1(a) differences can
be seen. With regards to total analyzed chloride, somewhat greater amounts of chloride are
extracted from the alkali-rich cement than from the original material. The ratio of analyzed to
added chloride, therefore, is greater for the alkali-enhanced material. For the water-soluble
extractions, the amount of water-soluble chloride is also, in most cases, higher for the alkali-
enhanced mixture.
Potentiostatic test results. Results of 100-mV potentiostatic testing are given in Figure 4-27.
The only clear “jump” in current occurs at total (analyzed) chloride values in excess of 0.6% and
water-soluble values in excess of 0.5%. Measured average current at these chloride levels is
considerably less than for companion specimens made with cement M with no added alkali (see
Figure 4-4). It is possible that the increased pH reduced corrosion activity at the time of testing at
7 days, however, visual observations, as noted below, do not support this hypothesis in terms of
longer-term behavior.
Visual observations. Observations of reinforcing steel carried out when rebars were removed
from concrete test specimens after 6 months of exposure are given in Table 4-6. The
observations are condensed from condition records of each bar. As such, they represent a
qualitative “average” of the condition of each set of bars after test. Corrosion appears first at a
lower value of chloride than for cement M with no added alkali and progressively becomes more
severe as the chloride content is increased. For example, at an added chloride content of 0.4%
there was only spotty minor corrosion for cement M with no added alkali, yet with the added
alkali the corrosion areas were more numerous. At the next highest level, 0.7%, considerable
corrosion was observed for both.
21
Fly Ash Series

Chloride contents. Acid-soluble and water-soluble chloride contents for concretes made with
cement M, to which Class F and C fly ashes had been used to replace 25 percent of the cement
are given in Table A-5. Results are expressed as percent of concrete sample mass, and as a
percent of the cement (not including the fly ash) in the concrete. On the average, nearly 100
percent of the added chloride is recovered during acid dissolution of these fly ash concrete
samples. Water soluble chlorides are approximately 75 percent of the acid-soluble values.
Potentiostatic test results. Results of 100-mV potentiostatic testing are given in Figure 4-28.
Here previous results for concrete with no fly ash are compared to the two fly ash concretes over
the range of added chloride contents. Up to 0.2% added chloride the fly ash concretes maintain
passive behavior, while average current continually increases for the plain concrete. At 0.4%,
however, there is a jump in current level for the class F fly ash concrete, but no corresponding
jump for the class C ash. At 1.0% added chloride the class C ash concrete still appears passive,
while average currents for the class F ash and non-fly ash concrete are above 1.0 mA/cm2. Figure
4-29 shows the same average current data plotted against total analyzed chloride. Similar effects
are seen, with the control and class F ash concretes exhibiting more active behavior at chloride
contents above 0.5 %.
Visual observations. Observations of reinforcing steel carried out when rebars were removed
from concrete test specimens after 6 months of exposure are given in Table 4-6. The appearance
of corrosion does not occur until a value of 0.4% added chloride has been reached. This is
similar to observations on the specimens removed from concrete cast with cement M but not
containing fly ash. At higher levels of chloride observations for specimens removed from class F
fly ash concretes are similar to those for non-fly ash concrete. For the class C ash concrete,
however, the amount of rust at 0.7% chloride is less severe than that observed on the other
concretes at this level.
SERIES 3 – AGGREGATE EFFECTS
Chloride Analyses
Acid-soluble and water-soluble chloride contents for aggregates and concretes made with these
aggregates are given in Table A-6(a). As noted earlier, chloride-free Eau Claire gravel
aggregates were soaked in 25 and 50 percent solutions of calcium chloride dihydrate to obtain
high levels of soluble chlorides in the pore system of these aggregates. Results shown in Table
A-6(a) show that high levels were indeed achieved. Water-soluble chloride contents of the
treated aggregates were 0.18% and 0.44% for the samples soaked in 25 percent CaCl2 • 2H2O
and 50 percent CaCl2 • 2H2O, respectively. For the Illinois limestones samples, a range of total
chloride values were obtained, from essentially baseline values for the Alton stone to 0.11% for
the Cleveland source. By examining the difference between the water-soluble and acid-soluble
chloride values for the chloride-soaked gravel as compared with the limestones, the nature of the
relative strength of chloride binding in the respective sample may be deduced. In the chloride-
soaked gravel the water-soluble values are only from 6 to 9 percent lower than the acid-soluble
22
data. For the Cleveland and Romeoville stone however, the water-soluble values are more than
50 percent lower. As all aggregates were reduced to the same fineness prior to extraction of
chloride, it may be inferred that the chlorides are bound much more strongly into the limestone
aggregates and the boiling water regimen is only able to extract about half of the total.
Concretes were prepared from all aggregates using cements M and L. Specimens were
moist cured for 28 days, then samples were obtained for chloride analyses. Results are expressed
by mass of cement in Table A-6(a). It can be seen that significant amounts of chloride are
present in all concrete samples except for those prepared from the low-chloride Alton stone. The
levels of chloride contributed to the concrete from the two chloride-contaminated gravel samples
exceed current ACI limits, and would be expected to contribute to corrosive conditions. Indeed,
as described in subsequent sections, reinforced concrete specimens prepared using these treated
aggregates exhibited corrosive behavior in the potentiostatic testing and rebar was found to be in
a corrosive condition when removed from the concrete. Water-soluble chloride for the Cleveland
stone concrete did not exceed current limits of ACI 318 for reinforced concrete not exposed to
external chlorides (0.30%), but would exceed the more stringent ACI 222 limit on water-soluble
chloride for concrete in wet conditions (0.08%), if the optional Soxhlet procedure were not
employed. It should be noted, however, that if the CEN total chloride limit of 0.40% were
applied, the Cleveland stone concrete would exceed this limit.
Results of modified C 1218 and Soxhlet extraction chloride analyses are given in Table
A-6(b). Test procedures were previously described. For the chloride-soaked gravel samples it is
apparent that significantly more chloride is removed from these aggregates using the modified C
1218 procedure than by the Soxhlet extraction. Indeed, the amount of chloride removed from the
unpowdered samples in the modified C 1218 procedure is at most 10 percent less than that
extracted from the powder sample using the standard C 1218 procedure. This result is
reasonable, as one would expect almost all of this chloride to be mobile and easily removed,
whether the sample be as-received or powdered. The Soxhlet procedure, however, removes only
a small percentage of the water-soluble chloride. Therefore, the efficiency of this extraction
technique for concrete is questionable. When the results for the limestone aggregates are
examined, it can be seen that both techniques indicate little, if any, extractable chloride to be
present. Essentially no chloride is removed either by the modified C 1218 or Soxhlet procedures.
Results for concretes prepared from these aggregates are also shown in Table A-6(b). For
the modified C 1218 procedure much less chloride is removed from the small chunks of
unpowdered concrete than from the standard C 1218 powder sample. This is understandable, as
most of the aggregate surface in the modified procedure is covered by a paste layer and not
directly exposed to the boiling water. Chloride must diffuse through the paste in order to reach
the outside of the sample. Again, as for the aggregate itself, much less chloride is extracted by
the Soxhlet procedure then by the modified C 1218. For the limestone concretes both procedures
again show essentially baseline values of chloride.
Potentiostatic Test Results

Potentiostatic tests using the 100-mV procedure were carried out on reinforced concrete
specimens moist cured for 7 days. Average current densities versus total (analyzed) chloride
contents of the 6 mixtures (Eau Claire aggregates being prepared at two chloride concentrations)
are shown in Figures 4-30 and 4-31 for concretes prepared using cements M and L, respectively.
23
Two data points are shown for the chloride-doped siliceous aggregate, as two concentrations of
soaking solution were used. All data points representing concretes produced using the limestone
aggregates show relatively low corrosion currents for both cements. It is of interest that the
limestone concrete having the highest amount of acid-soluble chloride exhibits the lowest
average current. This indicates that most, if not all, of this chloride is trapped within the
crystalline structure of the rock and unavailable to support corrosion. Where chloride is freely
available (in the chloride-doped gravel) corrosion current is marginally higher for the specimen
containing gravel soaked in 25% calcium chloride solution using cement M. The corresponding
specimens made using cement L show much higher current levels. It is likely that this is due to
the decreased chloride-binding capacity of the low C3A cement. Those produced from the gravel
soaked in 50% calcium chloride solution show very high current levels. The same average
current data plotted against water-soluble (ASTM C 1218) chloride contents are shown in
Figures 4-32 and 4-33 for the same set of specimens. The points are generally translated toward
lower values on the chloride axis, as less chloride is leachable from the powder when hot water is
used for extractions as opposed to acid. For the chloride-doped gravel average current jumps
dramatically upwards near 0.5% water-soluble chloride. A similar transition point was seen for
series 1 mixtures where free chloride was added to the concrete mixture (see Figures 4-6 and 4-
8). This indicates that corrosion activity will be similar independent of whether the chloride is
deliberately introduced as an admixture in the mix water or is introduced as an aggregate
contaminant, provided that it may be freely solubilized in the concrete.
Plots were not created for C 1218 modified or Soxhlet extracted chloride data on
limestones, as chloride contents of limestone concretes obtained using these techniques were all
near baseline levels. Relationships between C 1218 modified, Soxhlet chlorides and average
current densities are shown in Figure 4-34. Chloride content is shown on a log scale as there is
an order of magnitude difference between the amount of chloride ion extracted using the
modified C 1218 and the Soxhlet techniques. For both techniques the average current density
increases with the amount of chloride extracted by each method. It can also be seen that if the
1.0 mA/cm2 criterion is used, then “threshold “chloride contents using the modified C 1218
technique would be approximately 0.1%, and for the Soxhlet somewhat less than 0.02 percent. In
series 1, where various amounts of chloride were added to cement M concretes at w/c=0.50, a
threshold somewhat above the 0.4% chloride addition level was observed. This corresponds to
0.08 percent chloride extracted by the modified C 1218 method from the same concrete, which
agrees well with the 0.1% value seen here in series 3. However, in the series 1 concrete the 0.4%
chloride ion addition level corresponded to approximately 0.14% chloride when the Soxhlet
procedure was used, as opposed to the value of 0.02 percent seen in series 3. Again, such a large
discrepancy may represent the difficulty in extraction of chloride from the aggregate by the
Soxhlet procedure when the aggregate is contained within the concrete.
Visual Observations
Observations of reinforcing steel carried out when rebars were removed from concrete test
specimens after 6 months of exposure are given in Table 4-7. The observations are condensed
from condition records of each bar. As such, they represent a qualitative “average” of the
condition of each set of bars after test. There was no visible corrosion on any of the specimens
prepared with any of the four limestone aggregates. This is not surprising, considering the
24
indications from the chloride analyses that most, if not all, of the chloride contained in these
aggregates was not leachable to any significant extent. Furthermore, potentiostatic testing had
also indicated a lack of corrosion activity in these specimens.
Specimens cast using the siliceous gravel soaked in calcium chloride solution were
another matter. Corrosion was observed for both solution concentrations, the most severe being
observed for those aggregates soaked in 50% calcium chloride. For the specimens soaked in
25% calcium chloride, corroded areas were noted on a few deformations for rebar extracted from
specimens prepared with cement M (Figure 4-35). Pits (Figure 4-36) were apparent on rebars
embedded in the cement L concretes. For those specimens prepared with cement M and the
gravel soaked in 50% calcium chloride, severe corrosion of reinforcing bars was noted (Figure 4-
37). Specimens extracted from concretes prepared from the same aggregate but using cement L
were more severely corroded (Figure 4-38). The results indicate that naturally occurring
limestones in the Midwestern US, while they may contain significant amounts of chloride, do
not represent a corrosion risk, as this chloride is apparently not solubilized into the porewater of
concrete to an extent that would contribute to corrosion of reinforcing steel. In order for this to
occur the chloride must be freely soluble in the pores of the aggregate. Such aggregates do exist,
however, such as in marine-dredged sources. Such aggregates should be evaluated for their
corrosive potential prior to source acceptance.
COMPRESSIVE STRENGTHS
Compressive strengths for series 1 concretes prepared with cement M are presented in Table 4-8.
Each datum represents the mean of three cylinders. Corresponding results for series 1 concretes
prepared with cements L and H are given in Table 4-9. Finally, compressive strength results for
series 2 concretes are given in Table 4-10. As there is no direct relationship between compressive
strength and the onset of corrosion, these data are presented for informational purposes only and
will not be discussed within the context of this report.
25
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS
CONCLUSIONS
The laboratory test program described in this report was designed to develop information on the
amount of chloride ion needed to initiate corrosion when chloride is added as an admixture to a
concrete mixture or when chloride contaminated aggregate is used. The concrete is exposed to a
relatively static indoor environment that may only occasionally be wetted by fresh water. Based
on results obtained from this series of laboratory experiments the following conclusions may be
drawn:
1. Based on results of short-term potentiostatic testing and long term examination of
reinforcing steel extracted from test specimens, a threshold value for the initiation of
corrosion under relatively uniform conditions seems to be somewhat over 0.4%
added chloride by mass of cement, except when low C3A cement is used as noted
below. When expressed on a water-soluble chloride basis, indications of the onset of
corrosion from potentiostatic testing occur somewhere between 0.3 and 0.4% water-
soluble chloride ion.
2. The Bogue-calculated tricalcium aluminate (C3A) content of the cement has a
statistically significant effect on average current measured under potentiostatic test
conditions. At any given chloride level, average current tends to be less for rebars
embedded in concrete with higher levels of C3A indicating reduced risk of corrosion.
The effect of w/c ratio on measured average current was determined not to be
significant.
3. From results of visual examinations, it was apparent that C3A content also played a
significant role in long term performance. Specimens cast from the cement having the
lowest C3A content exhibited some rusting at a chloride level of 0.2%, as opposed to
the aforementioned threshold of 0.4% for the other two cements.
4. Visual examinations of specimens stored for one year indicated some effects of w/c
ratio on the progress of corrosion. Corrosion was more widespread on rebars cast into
concretes having the highest w/c in this study (0.60).
5. At added chloride levels of 0.4 and 0.7%, corrosion was more widespread on rebars
embedded in high alkali cement than in cement containing moderate levels of alkali.
6. Potentiostatic test results indicated that average currents for control and class F fly
ash concretes were similar. However, average current at any level of chloride was
less for the class C fly ash concretes.
7. Corrosion was initiated at around 0.4% added chloride for both fly ash and control
concretes. However, the amount of rust present was less for the class C fly ash
concrete.
8. The study also included evaluation of aggregate effects. Limestones obtained from
Midwestern formations were found to contain considerable quantities of acid soluble
chloride when reduced to fine powders and tested according to standard techniques.
Very little chloride was obtained by water leaching of as-received aggregates using
Soxhlet extraction.
9. While appropriate for determination of potentially corrosive amounts of chlorides in
aggregate samples, the Soxhlet technique appears to yield erratic results when applied
26
to hardened concrete.
10. Potentiostatic testing of specimens cast from a variety of chloride-bearing aggregates
exhibited no trends toward active corrosion. The exception were aggregates which
had been pre-soaked in solutions of calcium chloride prior to test. In these cases the
chloride was free to diffuse out of the aggregate into the concrete pore system where
it was available for initiation of corrosion.
11. Examination of rebars cast into specimens containing chloride-bearing limestones
after 6 months of exposure to a wicking environment exhibited no evidence of active
corrosion. In comparison, examination of rebars extracted from specimens where free
chloride had been deliberately added to the concrete exhibited significant amounts of
corrosion.
RECOMMENDATIONS
Based on results of the laboratory test program described in this report the following
recommendations can be made. It is hoped that these recommendations may be taken into
consideration by the appropriate ACI and ASTM committees.
Currently ACI 318-99 specifies limits on water-soluble chloride in concrete to meet four
separate conditions of service (see Table 2-2 in this report). Two of these—prestressed concrete,
and concrete that will eventually be exposed to external sources of chloride, were beyond the
scope of this study. The remaining two categories deal with concrete that will remain dry in
service, and “other” construction. By elimination, the latter refers to reinforced concrete that is
not prestressed, not subject to external chlorides, and not expected to remain dry. The current
ACI 318-99 limit is 0.30% water-soluble chloride ion for this category. Based on testing carried
out in this investigation, for the conditions employed, 0.40% added chloride appears to be an
apparent threshold for initiation of corrosion. Therefore, the current ACI 318-99 limit appears
rational and prudent, and should be retained. However, since it can never be guaranteed that a
reinforced concrete element will always remain dry, consideration should be given to adding
commentary to caution code users about selecting appropriate limits from the table. In selecting
these limits, consideration must be given to the potential for change in usage of a given structure
in the future.
ACI Committee 222 has recommended reduction of the limit on water-soluble chloride
for concrete in wet conditions (essentially the “other” category in 318-99) to 0.08%. Based on
data developed in this investigation, this appears overly conservative, it being highly unlikely
that corrosion will be initiated at such a low level of chloride ion, under these service conditions.
In the authors’ opinion such a limit is unduly restrictive and should not be adopted.
The Soxhlet extraction procedure appears to be valid for extraction of free chloride ion
from aggregate sources. It can therefore be used as a screening procedure for such aggregates.
However, it yields erratic results when applied to what seem to be unrepresentative small chunk
sample of concrete. Therefore, revision of the ASTM standard for Soxhlet extraction to allow
application to hardened concrete is not recommended at this time.
27
ACKNOWLEDGEMENT
The research reported in this paper (PCA R&D Serial No. 2438) was conducted by Construction
Technology Laboratories, Inc., with the sponsorship of the Portland Cement Association (PCA
Project Index No. 97-03). The contents of this paper reflect the views of the authors, who are
responsible for the facts and accuracy of the data presented. The contents do not necessarily
reflect the views of the Portland Cement Association.
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and Commentary (ACI 318R-99), American Concrete Institute, Farmington Hills,
Michigan, 1999.
American Concrete Institute, Corrosion of Metals in Concrete (ACI 222R-96), American

Concrete Institute, Farmington Hills, Michigan, 1997.
American Concrete Institute, Provisional Standard Test Method for Water-Soluble Chloride
Available for Corrosion of Embedded Steel in Mortar and Concrete Using the Soxhlet
Extractor (ACI 222.1-96), American Concrete Institute, Farmington Hills, Michigan, 1997.
Anderson, A.R., and Black, R.W., "Questioning the Limit," Concrete International, Vol. 7, No.
9, September 1985, pp. 28-34.
ASTM C 1152/C 1152M-97, “Standard Test Method for Acid-Soluble Chloride in Mortar and
Concrete”, Volume 04.02, Annual Book of ASTM Standards, American Society for
Testing and Materials, West Conshohocken, PA, 1998.
ASTM C 1218/C 1218M-97, “Standard Test Method for Water-Soluble Chloride in Mortar and
Concrete”, Volume 04.02, Annual Book of ASTM Standards, American Society for
Testing and Materials, West Conshohocken, PA, 1998.
Berke, N.S., Hicks, M.C., Hoopes, R.J., and Tourney, P.J., “Use of Laboratory Techniques to
Evaluate Long-Term Durability of Steel Reinforced Concrete Exposed to Chloride
Ingress,” Proceedings – Third International Conference on Durability of Concrete, Nice,
France, pp. 299-329, ACI SP-145, V.M. Malhotra, ed., American Concrete Institute,
Farmington Hills, MI, 1994.
Broomfield, J.P., Corrosion of Steel in Concrete, pg. 26, E & FN Spon, London, UK, 1997.
Clear, K.C., and Harrigan, E.T., "Sampling and Testing for Chloride Ion in Concrete," Report
No. FHWA-RD-77-85, Federal Highway Administration, Washington, DC, August 1977,
25 pp.
Clear, K.C., and Hay, R.E., "Time-to-Corrosion of Reinforcing Steel in Concrete Slabs, V.1:
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Federal Highway Administration, Washington, DC, April 1973, 103 pp.
Clear, K. C., “Time-to-Corrosion of Reinforcing Steel in Concrete Slabs,” Federal Highway

Administration, PB 258 446, Vol. 3, April , 1976.
Cook, H.K., and McCoy, W.J., "Influence of Chloride in Reinforced Concrete," Chloride
Corrosion of Steel in Concrete, STP-629, ASTM, Philadelphia, 1977, pp. 20-29.
Ford, S.J. and Mason, T.O., “Combined Bulk and Interfacial Studies of the Cement/Steel System
by Impedance Spectroscopy,” Techniques to Assess the Corrosion Activity of Steel
Reinforced Concrete Structures, ASTM STP 1276, N.S. Berke, E. Escalante, C.K. Nmai
and D. Whiting, eds., pp. 146 – 157, American Society for Testing and Materials, West
Conshohocken, PA, 1996.
Hope, B.B., Page, J.A., and Poland, J.S., "The Determination of the Chloride Content of
Concrete," Cement and Concrete Research, Vol. 15, 1985, pp. 863-70.
Lamar, J.E., and Shrode, R.S., “Water Soluble Salts in Limestones and Dolomites”, Economic
Geology, Vol.48, No. 2, pp 97-112, 1953.
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30
TABLES
Table 2-1. Chloride Limits Published by ACI Committee 201 in 1977
Limits for water-soluble chloride ion in concrete prior to service

exposure, expressed as a percent by weight of cement
Type of member Limit

Prestressed concrete 0.06
Conventionally reinforced concrete in a moist 0.10
environment and exposed to chloride
Conventionally reinforced concrete in a moist 0.15
environment but not exposed to chloride†
Above ground building construction where the No limit for
concrete will stay dry corrosion‡
†
Includes locations where the concrete will be occasionally wetted and areas with
potential moisture condensation such as kitchens, parking garages, waterfront structures.
‡
If calcium chloride is used as an admixture, a limit of 2 percent is generally
recommended for reasons other than corrosion.
Table 2-2. Current Chloride Limits in ACI 318-99
Type of member Maximum water-soluble

chloride ion (Cl–) in
concrete, percent by
weight of cement
Prestressed concrete 0.06
Reinforced concrete exposed to chloride in 0.15
service
Reinforced concrete that will be dry or protected 1.00
from moisture in service
Other reinforced concrete construction 0.30
31
Table 2-3. Current Limits Published* by ACI Committee 222 in 1997
Category Chloride limit for new construction

Acid-soluble Water-soluble
Test method ASTM C 1152 ASTM C 1218 Soxhlet
Prestressed concrete 0.08 0.06 0.06

Reinforced concrete 0.10 0.08 0.08
in wet
conditions
Reinforced concrete 0.20 0.15 0.15
in dry
conditions
* ACI 222R-96 (March 1997).
Normally concrete materials will be tested for chloride content using either the acid-
soluble test described in ASTM C 1152 or water-soluble test described in ASTM C 1218.
If the materials meet the requirements given in either of the relevant columns in the
above table, they are acceptable. If they meet neither of the relevant limits given in the
table, then they may be tested using the Soxhlet test method. Some aggregates contain
a considerable amount of chloride, which is sufficiently bound that it does not initiate or
contribute towards corrosion. The Soxhlet test appears to measure only those chlorides
which contribute to the corrosion process thus permitting the use of some aggregates
which would not be allowed if only the ASTM C 1152 or ASTM C 1218 tests were used. If
the materials fail the Soxhlet test, then they are not suitable.
32
Table 3-1. Concrete Mixture Matrix for Series 1 of Test Program.
C3A Content
w/c = 0.40 w/c = 0.50 w/c = 0.60
(approx.)
3 X X
7 X X X
12 X X
Note: all mixtures prepared at chloride levels of 0, 0.1, 0.2, 0.4, 0.7, 1.0 and 2.0 percent by
mass of cement.
Table 3-2. Chemical Composition of Cements used in Study.
Component Weight, percent

Cement L Cement M Cement H
(Low C3A) (Moderate C3A) (High C3A)
Silicon dioxide (SiO2) 21.82 20.43 20.74
Aluminum oxide, (Al2O3) 3.88 4.67 5.35
Ferric oxide (Fe2O3) 4.25 3.26 1.59
Calcium oxide (CaO) 63.40 64.66 64.07
Magnesium oxide (MgO) 2.31 1.24 3.25
Sulfur trioxide (SO3) 2.24 2.85 2.57
Loss on ignition 0.83 1.37 1.23
Insoluble residue 0.30 0.41 0.38
Alkalies (Na2O equivalent) – total 0.41 0.28 0.12
Alkalies (Na2O equivalent) – water-soluble – 0.12 –
Tricalcium silicate (C3S) 54 64 58

Dicalcium silicate (C2S) 22 10 16
Tricalcium aluminate (C3A) 3 7 12
Tetracalcium aluminoferrite (C4AF) 13 10 5
33
Table 3-3. Gradations and Characteristics of Eau Claire Aggregates.
Fine aggregate
Grading, cumulative % retained on sieve size indicated
4.75 mm 2.36 mm 1.18 mm 600 µm 300 µm 150 µm
1 17 36 58 85 98
Fineness Bulk specific Absorption,
modulus gravity, SSD % by mass
2.94 2.63 0.85
Coarse aggregates
Grading, % retained Bulk specific Absorption,
on sieve size indicated gravity, SSD % by mass
9.5 mm 4.75 mm 2.36 mm
Coarse aggregate no. 1 0 100 100 2.67 1.55
Coarse aggregate no. 2 0 38 100 2.71 1.42
Table 3-4. Chemical Composition of Fly Ashes Used in Study.
Component Weight, percent

F Ash C Ash
Silicon dioxide (SiO2) 50.82 34.26
Aluminum oxide, (Al2O3) 19.38 18.74
Ferric oxide (Fe2O3) 17.80 6.15
Total (SiO2 + Al2O3 + Fe2O3) 88.00 59.15
Calcium oxide (CaO) 4.72 26.31
Magnesium oxide (MgO) 0.98 5.97
Sulfur trioxide (SO3) 1.73 2.50
Loss on ignition 0.35 0.30
Alkalies (Na2O equivalent) 2.20 2.26
Moisture content 0.10 0.11
34
Table 3-5. Concrete Mixture Proportions for Series 1 Concretes Prepared Using
Cement M.
Constituent Mixture proportions, kg/m3

w/c = 0.40 w/c = 0.50 w/c = 0.60
Cement 495 350 295
Fine aggregate 835 912 924
Coarse aggregate no. 1 593 648 657
Coarse aggregate no. 2 258 282 286
Water 198 175 177
Table 3-6. Concrete Mixture Proportions for Series 1 Concretes Prepared using
Cement L.

w/c = 0.40 w/c = 0.50 w/c = 0.60
Cement 495 350 —
Fine aggregate 835 912 —
Coarse aggregate no. 1 593 648 —
Water 198 175 —
Cement H.
w/c = 0.40 w/c = 0.50 w/c = 0.60

Cement 545 400 —
Fine aggregate 791 880 —
Water 218 200 —
35
Cement M and Additional Water-Soluble Alkali.
w/c = 0.40 w/c = 0.50 w/c = 0.60
Cement — 350 —
Fine aggregate — 912 —
Coarse aggregate no. 1 — 648 —
Sodium hydroxide — 4 —
Water — 175 —
Cement M and Fly Ashes.

w/c = 0.40 w/c = 0.50 w/c = 0.60
Cement — 264 —
Fly ash — 88 —
Fine aggregate — 900 —
Water — 176 —
Limestone Aggregates.

w/c = 0.40 w/c = 0.50 w/c = 0.60
Cement (M or L) — — 350
Fine aggregate — — 896
Coarse aggregate — — 909
Water — — 210
36
Table 4-1. Results of Two-Way ANOVA on Series 1 Data for w/c = 0.40 and 0.50 (See
Page 23.)
w/c C3A w/c x C3A

Chloride level
F P F P F P
%
0.0 2.71 0.13 1.27 0.33 0.11 0.90
0.1 1.81 0.20 0.68 0.94 0.04 0.96
0.2 5.54 0.04* 3.75 0.05* 0.24 0.79
0.4 1.04 0.33 2.29 0.14 0.64 0.55
0.7 6.48 0.03* 4.62 0.03* 9.73 0.003*
1.0 0.17 0.69 13.55 0.001* 1.59 0.25
2.0 4.24 0.06 5.66 0.02* 3.38 0.07
* Significant at 95% confidence level.
Table 4-2. Results of One-way ANOVA on Series 1 Data for Cement M Only (See
Page 24.)
Chloride level
F P
%
0.0 1.62 0.28
0.1 1.23 0.36
0.2 8.91 0.02*
0.4 1.72 0.26
0.7 5.37 0.04*
1.0 0.09 0.92
2.0 25.80 0.001*
37
Table 4-3. Results of 2-Way ANOVA on Series 1 Data for w/c = 0.40, 0.50 and 0.60
Assuming no Interactions (See Page 25.)
w/c C3A
Chloride level,
%
F P F P
0.0 2.86 0.09 1.51 0.25
0.1 3.12 0.07 0.088 0.92
0.2 8.48 0.003* 3.99 0.04*
0.4 0.93 0.41 2.73 0.09
0.7 3.07 0.07 2.26 0.14
1.0 0.07 0.94 7.83 0.005*
2.0 4.43 0.03* 4.82 0.02*
Table 4-4. Results of 3-way ANOVA on Series 1 Data Assuming no Interactions

(See Page 25.)
Source F P
Chloride 21.13 0.001*
C3A 9.33 0.001*

w/c 0.61 0.44
C3A x chloride 7.22 0.001*
C3A x w/c 0.54 0.58

w/c x chloride 0.31 0.90
w/c x C3A x chloride 1.15 0.34
38
Table 4-5a. Visual Observations of Rebar Removed from Series 1 Specimens,

wc= 0.5.
Chloride, Observations
% Cement M Cement L Cement H
0.0 no visible corrosion no visible corrosion no visible corrosion
2 flecks [<1 mm2] of rust on
0.1 no visible corrosion no visible corrosion
entire bar
larger spots [4 mm2] on
many deformations
numerous areas of
few specks of rust on small rust flecks on 2
0.4 corrosion on deformations,
deformations deformations
light rust along ribs
more frequent larger widespread corrosion on
small rust areas on 4
0.7 areas of corrosion along most deformations, spotty
deformations
deformations corrosion on ribs
some deformations widespread corrosion on
small rust areas on 4
1.0 corroded along entire and between deformations,
deformations
length spotty corrosion on ribs
large areas of corrosion widespread corrosion and widespread corrosion, a few
2.0
and some pitting pitting pits
Table 4-5b. Visual Observations of Rebar Removed from Series 1 Specimens,

wc= 0.4.
2 flecks [<1 mm2] of rust on
entire bar
a few deformations show
small areas of corrosion
few specks of rust on small flecks of corrosion on
0.4 numerous corrosion areas
deformations a few deformations
significant corrosion on 3
deformations and rust large areas of corrosion on small flecks of corrosion on
0.7
spots between deformations a few deformations
deformations
many deformations with large areas of corrosion on more numerous flecks of
1.0
significant corrosion deformations corrosion
widespread corrosion large areas of corrosion on larger areas of corrosion on
2.0
and pitting deformations and pits a few deformations but no
pitting
39
Table 4-5c. Visual Observations of Rebar Removed from Series 1 Specimens,

wc= 0.6.
0.0 no visible corrosion n/a n/a
0.1 no visible corrosion n/a n/a
few specks of rust on

0.2 n/a n/a
deformations
0.4 4 - 5 larger areas of rust n/a n/a
0.7 similar to 0.4 % n/a n/a
larger areas of corrosion

1.0 n/a n/a
and some pitting
more widespread
2.0 n/a n/a
corrosion and pitting
Table 4-6. Visual Observations of Rebar Removed from Specimens Containing

Added Alkali and Fly Ash.
%
Added Alkali Class F Fly Ash Class C Fly Ash
0.2 few flecks of rust no visible corrosion no visible corrosion
a number of corrosion small rust flecks on some

0.4 scattered flecks of rust
areas deformations
numerous corrosion widespread corrosion over small rust areas on 3

0.7
areas and pits rebars deformations
1.0 widespread corrosion large areas of corrosion significant corrosion
40
Table 4-7. Visual Observations of Rebar Removed from Series 3 Specimens.
Observations
w/c Aggregate
Cement M Cement L
0.60 Thornton limestone no visible corrosion no visible corrosion
0.60 Cleveland limestone no visible corrosion no visible corrosion
0.60 Alton limestone no visible corrosion no visible corrosion
0.60 Romeoville limestone no visible corrosion no visible corrosion
Siliceous gravel – soaked Corroded areas on a few Corroded areas on

0.50
in 25% calcium chloride deformations numerous deformations
Siliceous gravel – soaked

0.50 Severe corrosion Severe corrosion with pitting
in 50% calcium chloride
41
Table 4-8. Moist Cured 28-Day Compressive Strengths of Series 1 Concretes

Prepared With Cement M.
Cement w/c Chloride Content, % Compressive Strength, MPa

M 0.4 0.0 61.4
0.1 64.4
0.2 56.3
0.4 66.7
0.7 66.3
1.0 63.4
2.0 66.8
M 0.5 0.0 47.0
0.1 46.5
0.2 46.4
0.4 47.5
0.7 46.5
1.0 47.8
2.0 49.6
M 0.6 0.0 35.7
0.1 35.3
0.2 37.5
0.4 34.3
0.7 36.1
1.0 32.7
2.0 34.8
42
Table 4-9. Moist Cured 28-Day Compressive Strengths of Series 1 Concretes

Prepared With Cements L and H.

L 0.4 0.0 51.3
0.1 53.6
0.2 53.9
0.4 49.4
0.7 48.3
1.0 62.9
2.0 46.3
L 0.5 0.0 42.3
0.1 47.8
0.2 47.1
0.4 41.5
0.7 45.8
1.0 40.7
2.0 40.0
H 0.4 0.0 53.3
0.1 52.6
0.2 53.5
0.4 50.3
0.7 49.4
1.0 54.7
2.0 56.1
H 0.5 0.0 44.7
0.1 43.9
0.2 47.4
0.4 44.3
0.7 42.3
1.0 40.8
2.0 45.0
43
Table 4-10. Moist Cured 28-Day Compressive Strengths of Series 2 Concretes.
M - high 0.5 0.0 44.0

alkali 0.2 44.7
0.4 45.0
0.7 49.1
1.0 49.9
M – class 0.5 0.0 34.2

F fly ash 0.2 32.9
0.4 29.3
0.7 32.3
1.0 32.8
M – class 0.5 0.0 40.7

C fly ash 0.2 38.4
0.4 40.3
0.7 37.7
1.0 36.5
44
FIGURES
Figure 3-1. Specimen and experimental setup for potentiostatic testing
45
Figure 3-2. Soxhlet extraction apparatus
46
200
180
w/c=0.4
Average current density, mA/cm2
160 w/c=0.5
140 w/c=0.6
120
100
80
60
40
20
0
0.0 0.5 1.0 1.5 2.0 2.5
Cl, percent by mass of cement
Figure 4-1. Average current density versus added chloride from 100-mV
potentiostatic testing of Cement M
100.0
10.0
w/c=0.4
w/c=0.5
w/c=0.6
1.0
0.1
0.0 0.5 1.0 1.5
Figure 4-2. Average current density (log scale) versus added chloride from 100-mV
potentiostatic testing of Cement M
47
200
180
w/c=0.4
Average current density, mA/cm2 160 w/c=0.5
w/c=0.6
140
120
100
80
60
40
20
0
0.0 0.5 1.0 1.5 2.0
Acid-soluble Cl, percent by mass of cement
Figure 4-3. Average current density versus analyzed (acid-soluble) chloride from
100-mV potentiostatic testing of Cement M.
100.0
10.0
w/c=0.4
w/c=0.5
w/c=0.6
1.0
0.1
0.0 0.5 1.0
Figure 4-4. Average current density (log scale) versus analyzed (acid-soluble)
chloride from 100-mV potentiostatic testing of Cement M.
48
200
180
w/c=0.4
Average current density, mA/cm2 160 w/c=0.5
w/c=0.6
140
120
100
80
60
40
20
0
0.0 0.5 1.0 1.5
Water-soluble Cl, percent by mass of cement
Figure 4-5. Average current density versus water-soluble chloride from 100-mV
potentiostatic testing of Cement M.
100.0
10.0
w/c=0.4
w/c=0.5
w/c=0.6
1.0
0.1
0.0 0.2 0.4 0.6 0.8 1.0
Figure 4-6. Average current density (log scale) versus water-soluble chloride from
100-mV potentiostatic testing of Cement M.
49
100
10
w/c=0.4
w/c=0.5
1
0
0 0.5 1 1.5
potentiostatic testing of Cement L.
100
w/c=0.50
w/c=0.40
10
0
0 0.5 1 1.5
potentiostatic testing of Cement H.
50
100
10
w/c=0.4
w/c=0.5
1
0
0.0 0.5 1.0
Figure 4-9. Log of average current density (log scale) versus analyzed (acid
soluble) chloride from 100-mV potentiostatic testing of Cement L.
100
w/c=0.40
w/c=0.50
10
0
0.0 0.5 1.0
Figure 4-10. Average current density (log scale) versus analyzed (acid soluble)
chloride from 100-mV potentiostatic testing of Cement H.
51
100
10
w/c=0.4
w/c=0.5
1
0
0.0 0.5 1.0
100-mV potentiostatic testing of Cement L.
100
w/c=0.40
w/c=0.50
10
0
0.0 0.5 1.0
100-mV potentiostatic testing of Cement H.
52
Cement C3A
w/c L M H
0.4 7 levels Cl- 7 levels Cl- 7 levels Cl-
0.6 7 levels Cl-
Figure 4-13. Cells selected for 2-way ANOVA of w/c and C3A effects. ANOVA
carried out at each level of chloride.
Cement C3A
w/c L M H
0.6 7 levels Cl-
Figure 4-14. Cells selected for 1-way ANOVA of w/c effect. ANOVA carried out at
each level of chloride.
53
500
w/c=0.40
Potential, negative mV vs. CSE

400 w/c=0.50
w/c = 0.60
300
200
100
0
0 0.5 1 1.5 2 2.5
Figure 4-15. Potential at 35 days versus added chloride content for Cement M
concretes.
500
w/c=0.40
400 w/c=0.50
w/c = 0.60
300
200
100
0
0.0 0.5 1.0 1.5 2.0
Water soluble Cl, percent by mass of cement
Figure 4-16. Potential at 35 days versus water-soluble chloride content for Cement
M concretes.
54
500

w/c=0.40
400
w/c=0.50
300
200
100
0
0 0.5 1 1.5 2 2.5
Figure 4-17. Potential at 35 days versus added chloride content for Cement L
concretes.
500
w/c=0.40
400
w/c=0.50
300
200
100
0
0.0 0.5 1.0 1.5
L concretes.
55
300
Potential, negative mV vs. CSE w/c=0.40

w/c=0.50
200
100
0
0 0.5 1 1.5 2 2.5
Figure 4-19. Potential at 35 days versus added chloride content for Cement H
concretes.
300
w/c=0.40
w/c=0.50
200
100
0
0.0 0.5 1.0 1.5
H concretes.
56
Figure 4-21. Surface of a bar where no chloride was added to the concrete mixture
(cement M, w/c = 0.50).
Figure 4-22. Corrosion present on deformations of bar embedded in concrete cast

with cement L using 0.2% added chloride (w/c = 0.50).
57
Figure 4-23. Only small flecks of corrosion present on bar embedded in concrete
produced with cement H (w/c = 0.50) and exposed to 0.7% chloride.
Figure 4-24. Bar embedded in concrete produced with cement M (w/c = 0.50) and
exposed to 0.7% chloride. Larger areas of corrosion seen on deformations.
58
Figure 4-25. More extensive corrosion seen on bar embedded in concrete

produced with cement L (w/c = 0.50) and exposed 0.7% chloride.
Figure 4-26. Widespread corrosion on bar embedded in concrete produced with

cement M (w/c = 0.50) and exposed to 2.0% chloride. Arrow points to pit with black
corrosion nodule.
59
100

total chloride
10
water-soluble chloride
0
0.0 0.5 1.0
Figure 4-27. Average current density (log scale) versus analyzed(acid-soluble or

total) and water-soluble chloride from 100-mV potentiostatic testing of Cement M
with additional alkali.
60
100
no fly ash
Class F ash
Class C ash
10
0
0 0.5 1 1.5
Total Cl, percent by mass of cement
Figure 4-28. Average current density (log scale) versus added chloride from 100-
mV potentiostatic testing of Cement M with two fly ashes.
100
no fly ash
Class F ash
Class C ash
10
0
0.0 0.5 1.0 1.5
chloride from 100-mV potentiostatic testing of Cement M with two fly ashes.
61
100
Eau Claire siliceous (free Cl)
Average current density, µA/cm2 Thornton limestone
Cleveland limestone
10 Alton limestone
Romeoville limestone
0
0.0 0.5 1.0 1.5
chloride from100 potentiostatic testing of concretes containing various aggregates
prepared with cement M.
100
2
Average current density, µA/cm
10

1 Thornton limestone
Cleveland limestone
Alton limestone
0
0.0 0.5 1.0 1.5
chloride from100-mV potentiostatic testing of concretes containing various
aggregates prepared with cement L.
62
100
Log average current density, mA/cm2
10
Eau Claire siliceous (free

Cl)
Thornton limestone
Cleveland limestone
1
Alton limestone
0
0.0 0.5 1.0 1.5
Figure 4-32. Average current density (log scale) versus water-soluble chloride
from100-mV potentiostatic testing of concretes containing various aggregates
prepared with cement M.
100
10

Thornton limestone
1 Cleveland limestone
Alton limestone
0
0.0 0.5 1.0 1.5
100-mV potentiostatic testing of concretes containing various aggregates prepared
with cement L.
63
100
10
cement M - C 1218 mod.

1 cement L - C 1218 mod.
cement M - Soxhlet
cement L - Soxhlet
0
0.01 0.10 1.00
Figure 4-34. Average current density (log scale) versus modified C 1218 water-
soluble and Soxhlet extracted chloride from100-mV potentiostatic testing of
concretes containing chloride-doped siliceous gravel (log scale).
64
Figure 4-35. Areas of corrosion visible on a few deformations where aggregate

soaked in 25% calcium chloride solution prior to mixing (cement M, w/c = 0.50).
Figure 4-36. Areas of corrosion visible on deformations where aggregate soaked in

25% calcium solution prior to mixing. Arrow points to pit (cement L, w/c = .50).
65
Figure 4-37. Surface of rebar removed from concrete where aggregate was soaked
in 50% calcium chloride solutions prior to mixing (cement M, w/c = 0.50).
Figure 4-38. Surface of rebar removed from concrete where aggregate was soaked
in 50% calcium chloride solution prior to mixing (cement L, w/c = 0.50).
66
APPENDIX A
Table A-1a. Acid-Soluble (Total) and Water-Soluble Chloride Contents for Concretes Prepared from Cement M
Cement Water-Cement Added Chloride Acid-soluble Chloride (ASTM C 1152) Water-Soluble Chloride (ASTM C 1218)
Ratio
(% by mass of cement) (% by mass of cement) (% of added Cl) (% by mass of cement) (% of total Cl)
M 0.40 0.00 0.019 n/a 0.005 25
0.10 0.101 101 0.034 33
0.20 0.188 94 0.091 49
0.40 0.351 88 0.221 63
0.70 0.592 85 0.439 74
1.00 0.810 81 0.637 79
2.00 1.740 87 1.297 75
Average 89 Average 62
M 0.50 0.00 0.014 n/a 0.007 48
0.10 0.074 74 0.027 37
0.20 0.189 95 0.108 57
0.40 0.379 95 0.250 66
0.70 0.561 80 0.487 87
1.00 0.867 87 0.704 81
2.00 1.720 86 1.404 82
M 0.60 0.00 0.024 n/a 0.008 33
0.10 0.111 111 0.048 43
0.20 0.182 91 0.119 65
0.40 0.350 88 0.262 75
0.70 0.556 79 0.461 83
1.00 0.810 81 0.667 82
2.00 1.832 92 1.179 64
67
Table A-1B. Modified Water-Soluble and Soxhlet Extracted Chloride Contents for Concretes Prepared
from Cement M
Cement Water- Added Chloride Water-Soluble Chloride Soxhlet Extraction

Cement Ratio (ASTM C 1218-modified) (ACI 222.1-96)
(% by mass of (% by mass of (% of ASTM (% by mass of (% of ASTM
cement) cement) C 1218) cement) C 1218)
M 0.40 0.00 0.005 100 0.062 1300
0.10 0.005 14 0.077 229
0.20 0.024 26 0.043 47
0.40 0.058 26 0.106 48
0.70 0.125 29 0.159 36
1.00 0.159 25 0.275 43
2.00 0.329 25 0.290 22
M 0.50 0.00 0.007 100 0.054 800
0.10 0.007 25 0.054 200
0.20 0.034 31 0.081 75
0.40 0.081 32 0.135 54
0.70 0.176 36 0.250 51
1.00 0.244 35 0.305 43
2.00 0.468 33 0.482 34
M 0.60 0.00 0.008 100 0.056 700
0.10 0.016 33 0.087 183
0.20 0.040 33 0.262 220
0.40 0.095 36 0.159 61
0.70 0.207 45 0.413 90
1.00 0.199 30 0.214 32
2.00 0.486 41 0.295 25
68
Table A-2. Acid-Soluble (Total) and Water-Soluble Chloride Contents for Concretes Prepared from Cement L
Ratio
L 0.40 0.00 0.019 n/a 0.010 50
0.10 0.106 106 0.043 41
0.20 0.202 101 0.125 62
0.40 0.380 95 0.226 59
0.70 0.636 91 0.405 64
1.00 0.820 82 0.670 82
2.00 2.327 116 1.829 79
L 0.50 0.00 0.020 n/a 0.007 33
0.10 0.095 95 0.047 50
0.20 0.176 88 0.115 65
0.40 0.338 85 0.237 70
0.70 0.616 88 0.487 79
1.00 0.805 81 0.704 87
2.00 1.777 89 1.411 79
69
Table A-3. Acid-Soluble (Total) and Water-Soluble Chloride Contents for Concretes Prepared from Cement H
Ratio
H 0.40 0.00 0.022 n/a 0.004 20
0.10 0.091 91 0.035 38
0.20 0.191 95 0.091 48
0.40 0.351 88 0.217 62
0.70 0.625 89 0.412 66
1.00 0.926 93 0.639 69
2.00 1.822 91 1.282 70
H 0.50 0.00 0.018 n/a 0.006 33
0.10 0.113 113 0.048 42
0.20 0.214 107 0.113 53
0.40 0.339 85 0.214 63
0.70 0.542 77 0.459 85
1.00 0.900 90 0.823 91
2.00 1.824 91 1.333 73
Table A-4. Acid-Soluble (Total) and Water-Soluble Chloride Contents for Concretes Prepared from High-Alkali Cement (w/c = 0.50)
Cement Added Chloride Acid-soluble Chloride (ASTM C 1152) Water-soluble Chloride (ASTM C 1218)
M (plus added alkali*) 0.00 0.014 n/a 0.020 150
0.20 0.210 105 0.122 58
0.40 0.392 98 0.284 72
0.70 0.670 96 0.541 81
1.00 0.895 89 0.773 86
* Alkali equivalent to 1.0 percent as Na2O.
70
Table A-5. Acid-Soluble (Total) and Water-Soluble Chloride Contents for Fly Ash Concretes (w/c = 0.50).
Cement Fly Ash Added Chloride Acid-soluble Chloride (ASTM C 1152) Water-Soluble Chloride (ASTM C 1218)
M F 0.00 0.027 n/a 0.018 67
0.20 0.206 103 0.143 70
0.40 0.385 96 0.296 77
0.70 0.708 101 0.537 76
1.00 1.041 104 0.781 75
M C 0.00 0.027 n/a 0.018 67
0.20 0.225 112 0.126 56
0.40 0.404 101 0.261 64
0.70 0.657 94 0.675 103
1.00 0.928 93 0.748 81
71
Table A-6a. Acid-Soluble (Total) and Water-Soluble Chloride Contents for Aggregates and Concretes (w/c = 0.50 or 0.60).
Aggregate Aggregate Cement Acid-soluble Chloride Water-Soluble Chloride Acid-soluble Chloride Water-Soluble Chloride
Source (ASTM C 1152) (ASTM C 1218) (ASTM C 1152) (ASTM C 1218)
in Aggregate in Aggregate in Concrete in Concrete
(% by mass) (% by mass) (% by mass of cement) (% by mass of cement)
Eau Claire Siliceous M 0.197 0.184 0.564 0.394
Eau Claire Siliceous L 0.197 0.184 0.598 0.449
Eau Claire* Siliceous M 0.488 0.444 1.338 1.107
Eau Claire* Siliceous L 0.488 0.444 1.381 1.164
Thornton Limestone M 0.104 0.058 0.349 0.123
Thornton Limestone L 0.104 0.058 0.376 0.137
Cleveland Limestone M 0.114 0.059 0.508 0.185
Cleveland Limestone L 0.114 0.059 0.512 0.184
Alton Limestone M 0.006 0.004 0.017 0.007
Alton Limestone L 0.006 0.004 0.014 0.004
Romeoville Limestone M 0.085 0.029 0.269 0.055
Romeoville Limestone L 0.085 0.029 0.273 0.062
* Aggregates with added chloride
Table A-6b. Modified Water-Soluble and Soxhlet Extracted Chloride Contents for Aggregates and Concretes (w/c = 0.50 or 0.60).
Aggregate Aggregate Cement Water-Soluble Chloride Soxhlet Extracted Chloride Water-Soluble Chloride Soxhlet Extracted Chloride
Source (ASTM C 1218 modified) (ACI 222.1-96) (ASTM C 1218 modified) (ACI 222.1-96)
in Aggregate in Aggregate in Concrete in Concrete
(% by mass) (% by mass) (% by mass of cement) (% by mass of cement)
Eau Claire Siliceous M 0.165 0.024 0.116 0.014
Eau Claire Siliceous L 0.165 0.024 0.109 0.020
Eau Claire* Siliceous M 0.416 0.047 0.333 0.034
Eau Claire* Siliceous L 0.416 0.047 0.237 0.034
Thornton Limestone M 0.002 0.001 0.007 0.007
Thornton Limestone L 0.002 0.001 0.007 0.007
Cleveland Limestone M 0.002 0.001 0.007 0.007
Cleveland Limestone L 0.002 0.001 0.007 0.007
Alton Limestone M 0.000 0.001 0.007 0.007
Alton Limestone L 0.000 0.001 0.007 0.007
Romeoville Limestone M 0.001 0.001 0.007 0.007
Romeoville Limestone L 0.001 0.001 0.007 0.007
* Aggregates with added chloride
72

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PCA R&D Serial No.

Chloride Limits in Reinforced Concrete

by David A. Whiting, Peter C. Taylor, and Mohamad A. Nagi

© Portland Cement Association 2002

Chapter 5 Conclusions and Recommendations 26

CHLORIDE LIMITS IN REINFORCED

CHAPTER 1 INTRODUCTION AND SCOPE

SIGNIFICANCE AND OBJECTIVES

Task 1. Literature Review

Task 2. Laboratory Investigation

CHAPTER 2 ORIGINS OF CHLORIDE LIMITS

CHLORIDE CORROSION THRESHOLDS

content was conceived.

DEVELOPMENT OF ACI CHLORIDE LIMITS

CHAPTER 3 LABORATORY TEST PROGRAM

SCOPE AND ORGANIZATION

TEST SPECIMENS AND PROCEDURES

Long Term Exposure

Modified C 1218 extractions. As the Soxhlet procedure requires relatively expensive

CHAPTER 4 RESULTS AND DISCUSSION

SERIES 1 – PLAIN CONCRETE MIXTURES

Potentiostatic Test Results

Half Cell Potentials

SERIES 2 – EFFECTS OF CEMENT ALKALI CONTENT AND FLY ASH

Cement with Added Alkali

Fly Ash Series

SERIES 3 – AGGREGATE EFFECTS

Potentiostatic Test Results

CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS

American Concrete Institute, Corrosion of Metals in Concrete (ACI 222R-96), American

Federal Highway Administration, Washington, DC, April 1973, 103 pp.

Clear, K. C., “Time-to-Corrosion of Reinforcing Steel in Concrete Slabs,” Federal Highway

Whiting, D.A., “Permeability of Selected Concretes,” Permeability of Concrete, pp. 195-222,

Limits for water-soluble chloride ion in concrete prior to service

Type of member Limit

Table 2-2. Current Chloride Limits in ACI 318-99

Type of member Maximum water-soluble

Table 2-3. Current Limits Published* by ACI Committee 222 in 1997

Category Chloride limit for new construction

Prestressed concrete 0.08 0.06 0.06

Table 3-1. Concrete Mixture Matrix for Series 1 of Test Program.

Table 3-2. Chemical Composition of Cements used in Study.

Component Weight, percent

Alkalies (Na2O equivalent) – water-soluble – 0.12 –

Tricalcium silicate (C3S) 54 64 58

Table 3-3. Gradations and Characteristics of Eau Claire Aggregates.

Table 3-4. Chemical Composition of Fly Ashes Used in Study.

Component Weight, percent

Constituent Mixture proportions, kg/m3

Constituent Mixture proportions, kg/m3

Constituent Mixture proportions, kg/m3

w/c = 0.40 w/c = 0.50 w/c = 0.60

Constituent Mixture proportions, kg/m3

w/c = 0.40 w/c = 0.50 w/c = 0.60

Constituent Mixture proportions, kg/m3

Constituent Mixture proportions, kg/m3

w/c C3A w/c x C3A

Table 4-4. Results of 3-way ANOVA on Series 1 Data Assuming no Interactions

Chloride 21.13 0.001*

C3A 9.33 0.001*

C3A x w/c 0.54 0.58

Table 4-5a. Visual Observations of Rebar Removed from Series 1 Specimens,

Table 4-5b. Visual Observations of Rebar Removed from Series 1 Specimens,