The role of calcium
chloride in concrete
The king of accelerators is not yet dethroned for occasional crimes
Editor’s Note:
Bernard Erlin and William G. Hime, Er-
lin-Hime Associates, Northbrook, Illi-
nois wrote the sections of this article
that pertain to corrosion as well as the
information that appears in the box.
The remainder was prepared by the
staff of Concrete Construction.
hen the manufacturers
W
of an admixture inves-
tigated the usage of
their recently devel-
oped accelerator they were sur-
prised to find that it was being used
most in Arizona and Fl o ri d a — t h e
two hottest states in the country.
The investigators, like many others,
had tended to associate accelera-
tors uniquely with winter concret-
ing but this is far from being their
only use. In addition to cold weath-
er applications accelerators are
used to increase rapidity of form
t u rn over, as well as the rate of de-
velopment of handling strength in
precasting operations.
Although acceleration can be ac-
complished by increasing concrete
temperature, this procedure is sel-
dom practical or economical under
field conditions. Instead, accelera-
tion is characteristically accom-
plished by use of additional cement
or a high early strength cement, or a
chemical admixture, or some com-
bination of these. Calcium chloride
is the admixture most likely to be
used, or an admixture in which cal-
cium chloride is a major ingredient.
Calcium chloride offers many ad-
vantages that make it popular as a
concrete accelerator. It causes a
substantial increase in early
strengths and it speeds rate of set. It
is readily available. It dissolves easi-
ly in water. Its behavior with most
ingredients of concrete and under a
wide variety of conditions has been
studied and reported over a long
span of years, and its effects have
been generally understood though
in recent years increasing evidence
has accumulated that calcium chlo-
ride or other source of chloride ions
can cause serious problems in con-
c re t e. This article attempts to put
findings in this area in perspective
even though, as in many areas of
concrete technology, there are wide
divergencies of opinion
Calcium chloride changes the
rate of hydration. By changing
something this fundamental calci-
um chloride is bound to have far-
reaching effects in both the plastic
and hardened states. Its effect on
rate of set and compressive strength
development are understandably
paramount in the minds of users
who employ it primarily to affect
these pro p e rt i e s. But users should
also be aware of the effects calcium
chloride has on other major charac-
teristics of concrete.
Workability
Although calcium chloride in
amounts of 2 percent * or more im-
proves workability slightly it does
not plasticize concrete much even
at large dosages. In the usual 1 to 2
percent range it typically reduces
the water needed for a given slump
only about 1 percent. It is best to as-
sume that calcium chloride has no
significant effect on workability and
water demand.
* In this article all discussions of percentage
quantities of calcium chloride refer to percent cal-
cium chloride dihydrate (flake) by weight of port-
land cement. (See discussion in box.)
Setting time
So many factors (brand of ce-
ment, water-cement ratio, other ad-
mixtures employed and type of mix)
affect setting time that it is impossi-
ble to give specific data on how
much this will be shortened with
the use of calcium chloride. Yet it
can be said in general that if a given
concrete under constant ambient
conditions at about 70 degrees F(1)+
required 3 hours to develop initial
set, the addition of 2 percent calci-
um chloride would typically reduce
this time to 1 hour. Similarly, if an-
other concrete achieved final set in
6 hours under the same conditions
the addition of the same amount of
calcium chloride could develop fi-
nal set in about 2 hours. At lower
temperatures the effect of calcium
chloride is even more pronounced.
The early compressive strength of a
given mix is not likely to be in-
creased in proportion to the accel-
eration of setting time by the use of
calcium chloride.
Calcium chloride accelerates
slow-setting portland cements
more efficiently than faster-setting
cements and thus narrows the gap
between setting times of va ri o u s
brands of cement.
Rate of settlement
By speeding initial set calcium
chloride reduces settlement (or
bleeding) in the plastic condition.
The addition of 2 percent calcium
chloride can cut initial settlement
in half (Figure 1). This effect can be
used to advantage in filling hori-
zontal holes or under hori zo n t a l
surfaces.
+ Numbers in parentheses are references to the
metric equivalents listed with this article.
 HOW MUCH IS
TWO PERCENT?
Although calcium chloride has
been used in concrete for several
decades it is surprising that many
statements about its concentra-
tion in concrete are either ambigu-
ous or erroneous. Phrases such
as “two percent in concrete” still
appear occasionally in such widely
read publications as Concrete
Construction and the ACI Journal.
Fortunately, the industry under-
stands that what is meant is “2
percent by weight of cement,” but
it is reasonable to assume that er-
rors have sometimes been made
in the amounts used because of
this carelessness in language.
Which salt is the real calcium
chloride?
There is a further ambiguity, of
more general significance, in the
Compressive strength
Calcium chloride substantially in-
creases early compressive strengths
and sometimes causes modest in-
creases as late as several years after
placement. Occasionally, howe ve r,
concrete with calcium chloride be-
gins to exhibit a lessening in rate of
c o m p re s s i ve strength gain when
compared with ordinary concrete at
an age as early as 7 days. This can re-
sult in a lower compressive strength
than with ordinary concrete at 28
days to 3 months. It does not mean
there has been a re t ro g ression in
strength but only a tapering off of
strength gain.
Figure 2 illustrates acceleration
improvements in strength up to 28
days for mixes made with four types
of cement mixed and moist cured at
70 degrees F.(1) Cement contents
were approximately 545 pounds(2)
per cubic yard and the water-ce-
ment ratio 0.55. Calcium chloride
content was 2 percent.
Concrete containing calcium
chloride, if subjected to freezing 1 to
3 days after hardening, ultimately
develops higher strength than plain
concrete undergoing the same
treatment. This is because the
greater early strength buildup has
term “calcium chloride.” Chemical
dictionaries define this to be CaCI2
. 2H20, the dihydrate of calcium
chloride, which is commonly called
“flake” and is the type used in
ready mixed concrete and by most
researchers. But calcium chloride
is sometimes interpreted to mean
the anhydrous salt, CaCI2.
The commonly imposed 2 per-
cent limit could designate differ-
ent amounts of active ingredient,
depending on which salt is meant.
A calculation based on chemical
composition shows that 2 percent
of dihydrate is equivalent to only
1.51 percent of anhydrous calci-
um chloride. If, on the other hand,
it were found that 2 percent of the
anhydrous salt could be tolerated,
then 2.65 percent could be per-
mitted if dihydrate, or flake, calci-
um chloride were used. The 1.51
and 2.65 could be rounded to 1.5
and 2.75 percent, respectively.
Figure 1. Calcium chloride
reduces the settlement of
concrete. These data were
obtained on mixes made with
Type II cement at a water-
cement ratio of 0.51.
provided greater resistance to crack-
ing during freezing.
Calcium chloride is more effec-
tive in increasing compressive
strength at 1 to 3 days in rich mixes
than in lean ones. At later ages the
increases, in psi, are about the same
for various cement contents.
Other properties
Many other properties of con-
crete are affected to various degrees
by calcium chloride. A general guide
is provided in Table I. Further details
may be found in the classic paper by
Shideler. +
Because of differences in de-
gree of purity, actual chloride con-
tents of commercial calcium chlo-
ride might be lower than indicated
by these calculations but not
enough to change the calculations
much. ASTM D 98, “Standard
Specification for Calcium Chlo-
ride,” requires that Type I (regular
flake calcium chloride) have a min-
imum calcium chloride content of
77.0 percent and Type II (concen-
trated—as distinguished from reg-
ular — flake, pellet or other granu-
lar calcium chloride) have a
minimum of 94.0 percent.
It is time for specific language
in publications and specifications.
We suggest that the phrase “per-
cent calcium chloride dihydrate
(flake calcium chloride) by weight
of portland cement” be used
whenever reference is made to
amounts for concretes.
Corrosion
When corrosion of steel occurs in
concrete, chloride is almost always
present. Thus, it is regrettable that
in discussing the role of calcium
chloride in corrosion in concrete
ACI committees and others fre-
quently quote the classic review of
Shideler + as a primary re f e re n c e.
Although this review is extensive it
does not provide data that reflect
the tremendous effect of chloride
on corrosion of steel in concrete;
++ J.J. Shideler, “Calcium Chloride in Concrete,”
ACI Journal, March 1952, pages 537-560.
 vents (or slows) corrosion. Unless
large amounts of chloride are pre-
sent, the basicity factor usually wins
out, at least during the re l a t i ve l y
short haul of 20 to 30 years. Howev-
er, concrete slowly carbonates upon
exposure to air (inward from the
surfaces) and this carbonation de-
stroys the basicity of concrete. The
prognosis is bleak when that basici-
ty is lowered and water and oxygen
penetrate to the level of the steel.
The results can be disastrous if chlo-
rides are present.
Fortunately the carbonation of
concrete proceeds at a slow rate.
Howe ve r, past experience may be
misleading in suggesting that long-
time corrosion is not a problem.
Figure 2. Calcium chloride increases the compressive strength up to ages of New results imply that exposed re-
28 days or more for concretes made with all types of portland cement. Data inforced concrete made with chlo-
shown here represent mixes made with four types using about 545 pounds
ride admixtures may eventually be
of cement per cubic yard (323 kilograms per cubic metre) at a water-cement
ratio of 0.55. subject to failure. In fact, such an
epoch may have begun.
Our work involves post-mortem
studies of distressed concretes and
we are often asked to diagnose
TABLE I.
causes of corrosion. The studies
How calcium chloride affects various other properties of concrete
include direct evaluation of the
Property Approximate change concrete by petrographic methods
Heat of hydration at 1 day 30 percent increasea such as interpretative microscopy,
Tensile strength at 28 days Slight decrease other instrumental methods, and
chemical analyses. We feel that the
Flexural strength at 7 days 10 percent increaseb
p re vention of potential failures
Flexural strength at 28 days 0 to 15 percent decreaseb
requires publicity of present and
Volume change 0 to 15 percent increase
past failures. We believe that the
Watertightness Improved at early age; no improvement later following examples from our expe-
Cavitation Surface loss reduced by half rience illustrate the more important
Efflorescence Appearance hastened factors involved.
Sulfate resistance Aggravatedc
Alkali-silica reaction Increased up to 100 percentd Variable concentration a factor
Discoloration Trowel burns in flatwork, or mottled effecte in corrosion
One factor that has not been
a After about 11⁄2 days it decreases
widely publicized but merits major
b Depending on curing conditions, amount of calcium chloride, and the brand, type and amount of
cement used emphasis is that the chloride con-
c But not with Type V cement and adequate air content centration often varies in different
d But little effect if proper precautions taken to use pozzolan and low-alkali cement portions of a reinforced concrete
e Depending on material selection, proportioning, mixing, placing, finishing, curing. Mottled effect s t ru c t u re. An illustration of the ef-
develops in concrete that is not moist cured, producing light spots on dark background with ce-
ment of low alkali content or dark spots on light background with cement of high alkali content. fect of such a variation in causing
the corrosion of concrete columns is
given in Example 3 below. The prac-
tice of varying the calcium chloride
rather it concludes that chlorides We now know that chloride great- content of concrete of a single struc-
have a minimal effect. Unfortunate- ly increases the likelihood of corro- ture because of changes in ambient
ly, published research information sion. We also know that, under con- t e m p e ra t u res (daily, weekly or
at the time of his review did not pro- ditions where moisture penetrates monthly) can be dangerous and
vide a complete understanding of to the steel, only the chemical basic- should not be permitted when con-
mechanisms of corrosion. ity of portland cement paste pre- tinuity of steel exists.
Six case histories of corrosion TABLE II. General comparison of effects of inorganic and organic materi-
als sometimes used to accelerate setting time or strength development
Example 1. Precast reinforced
beams Material Effect of
acceleration of Strength
Exposure: Ceiling elements setting time development

Chloride content: 1.6 percent**

ALUMINATES
After 4 years of service, cracks oc- Sodium or potassium Rapid
curred over and in line with rein-
CARBONATES
forcing steel near bottom corners of
Ammonium Less rapid than
beams. Concrete cover over the steel sodium or potassium
was nominally 3⁄4 inch.(3) Spalling of Magnesium hydroxy
the concrete cover and severe corro- (hydromagnesite) Accelerates a
sion of the steel were prominent. Sodium or potassium Rapid
Primary causes: Chloride, inade- CHLORIDES
quate concrete cover over steel, car- Aluminum Considerable
bonation. Barium Slight
Magnesium Considerable
Sodium Small, variable b
Example 2. Precast pre- Strontium Slight
stressed concrete beams
HYDROXIDES
Sodium or potassium Some
Exposure: Floor slab elements in an
area of prolonged high humidity NITRITES
Chloride content: 0.8 percent Sodium Slight Decreases

SILICATES
After 10 years of service loss of Sodium or potassium Rapid
concrete cover over the steel
and corrosion of the steel were THIOSULFATES
prominent. Concrete cover over the Calcium Better than Sodium Decreases
steel was from 3⁄8 to 1⁄2 inch. (4) Sodium Some Less decrease
than calcium
Primary causes: Chloride, grossly
inadequate concrete cover over the TRIETHANOLAMINE
steel, carbonation. 0.025 percent by
weight cement Appreciable Increases early
strength. Decreases
or does not affect
Example 3. Cast-in-place 28-day strength
reinforced columns of a 0.06 percent by
multistory building weight cement Retards c Retards

Exposure: Outside columns directly CALCIUM FORMATE Less efficient than Increases 7-day and
exposed to Midwest ambient condi- calcium chloride 28-day strengths but
tions not as much as calcium chloride

FORMALDEHYDE Mild In amounts of 0.07

Chloride content of individual
percent or more,
columns: Variable from 1.5 percent markedly reduces
to essentially no chloride, the higher 28-day strength
chloride being in the bottom eleva-
tions of the columns

a Magnesium carbonate, however, retards

After three years of service crack-
ing over and in line with reinforcing b Depending on the brand or type of cement
steel was prominent in only the c Hence, beware of overdosage
chloride-containing portions of the
columns. Cover over the steel in
s e ve ral instances was 1 inch(5) and
in other instances 31⁄2 inches.(6)
Primary causes: Differential chlo-
ride content, concentration cells.
Example 4. Precast thin rein-
forced roofing planks
Exposure: High ceiling of a manu-
facturing building
Chloride content: 0.5 percent
Cover over steel: 3⁄8 to 1⁄2 inch(4)
After fifty years of service the con-
crete cover over the reinforcing steel
suddenly began to span as a result
of the corrosion of the steel. Primary
causes: Old age, carbonation, chlo-
ride, inadequate concrete cover over
steel.
Example 5. Cast-in-place rein-
forced concrete columns and
floor slabs
Exposure: Interior and exterior con-
ditions, the latter in a mild, non-
freezing, high humidity area
Chloride content: 6 percent
After less than one year of service,
extensive cracking over and in line
with the steel, spalling of the con-
crete cover over the steel, severe
corrosion of the steel, and droplets
of hydrochloric acid having a pH of
2.2 were prominent.
Primary cause: Grossly high chlo-
ride content.
Example 6. Interior steel door
jambs filled with portland
cement mortar and inset in
concrete
Exposure: Inside doorways of a
building
Chloride content: 1.4 percent
Within 1 year after construction
the steel jambs were eaten through
in many areas and moderately cor-
roded in others. The locations of
s e ve rest deterioration were associ-
ated with areas where the mortar
had not intimately contacted the
steel.
Primary causes: Chloride, oxygen
concentration cells, carbonation.
Summary comments on
corrosion
The examples above summarize
only the highlights of several situa-
tions. The investigations included
site surveys and detailed laboratory
studies of the quality and composi-
tion of each concrete, alterations in
the original concrete during its ex-
posure, and manifestations of the
corrosion. The use of analytical data
for evaluating and interpreting the
factors contributing to deterioration
is mandatory if suitable and effec-
tive refurbishing is to be done.
Our studies on corrosion of steel
in concrete have pointedly revealed:
• More than 99 percent of corrosion
problems are chloride related.
• A prominent relationship exists
between corrosion and the
amount of concrete cover.
• An increasingly apparent factor
which is being recognized and will
become more prominent is old age
(particularly where cover over steel
is thin) because of carbonation
and attendant pH reduction of
concrete flanking the steel.
• Effective renovation of damaged
s t ru c t u res must be based upon a
knowledge of the specific factors
causing the corrosion.
Other accelerators
It has been known for many years
that a number of materials other
than calcium chloride catalyze ce-
ment hydration. Yet for one reason
or another most have failed to pro-
vide the combination of advantages
that has kept calcium chloride in the
forefront for decades.
Manufacturers of water-reducing
admixtures have long studied this
subject. Since all materials used as
the active ingredient for reducing
water have the common character-
istic that they retard concrete set as
well, many formulations of water re-
ducing admixtures incorporate cal-
cium chloride to counteract set re-
tardation. Manufacturers of such
products are naturally interested in
finding a nonchloride accelerator to
render their normal water reducing
admixtures suitable for all types of
concrete applications.
Some of the many materials that
have been studied for their acceler-
ation of setting time and strength
gain are listed in Table II. Such prod-
ucts as triethanolamine and calci-
um formate have perhaps been
used more extensively as accelera-
tors than others, but so far none of
these appears to have had suffi-
ciently attractive properties to de-
velop a large market. (In addition to
the effect on setting time and
strength, cost, solubility, develop-
ment of disagreeable odors, effect
on durability, and safety in use are
factors that may affect their value.)
Usually the use of such special ac-
celerators is practically limited to
such applications as pre s t re s s e d
concrete where acceleration is
needed but where the presence of
chloride ions must be minimized or
eliminated. Nonchloride accelera-
tors are also being used (sometimes
blended with calcium chloride) in
some water-reducing admixtures to
counteract their retarding tenden-
cies.
At this stage, howe ve r, when con-
sideration is given to all the pluses
and minuses, for the great majority
of concrete construction where its
use is allowable the most practical
accelerator for concrete is calcium
chloride, warts and all.
Metric equivalents
(1) 21 degrees C
(2) 323 kilograms per cubic meter
(3) 19 millimetres
(4) 10 to 13 millimetres
(5) 25 millimetres
(6) 90 millimetres
PUBLICATION #C760057
Copyright © 1976, The Aberdeen Group
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