Point of view

Why Chemistry
Matters in Concrete
BY VAGN C. JOHANSEN, WALDEMAR A. KLEMM, AND PETER C. TAYLOR

hy does chemistry matter? It matters because

chemistry controls the life span of concrete.
Chemistry explains why cement hardens and the interaction between cement and its environment. We will
discuss the basic inorganic chemistry of cement and
concrete under service conditions. Of course, there are
other types of chemical processes that occur when
mixing concrete, such as arcane aspects of organic
chemistry and surface chemistry. These are left out, not
because these subjects are unimportant, but because
they are not the main focus of this article.

Chemistry and concrete

The first principle to understand is that, in a broad
sense, concrete is thermodynamically unstable. When
cement paste is exposed to the earths atmosphere, it
begins to deteriorate, which is a form of chemical
corrosion. The paste will react to exposure to acid rain
or just the normal amount of carbon dioxide in the air.
This reaction causes surfaces to etch and carbonate, and
then, the calcium silicate hydrates that give concrete its
strength will be converted back to calcium carbonate,
silica gel, and alumina gel.
This is one aspect of chemistry, but chemistry is not
only thermodynamics, it is also kinetics. In other words,
concrete has the potential to change, but how fast will
that happen? Concrete made carefully with the right
materials in the proper proportions, and developing the
optimum microstructure by adequate curing, can last for
many hundreds, or even thousands, of years. An example
of this is the Pantheon in Rome, expertly constructed with
a pozzolanic Roman Cement, which so far has lasted for
over 2000 years.
When Joseph Aspdin patented his Portland Cement
in 1824, it was titled An Improvement in the Modes of
Producing Artificial Stone. Concrete was considered to
be artificial stone having the appearance, strength, and
durability of the real thing. Some of the early concrete
The opinions expressed in this point of view article may
not necessarily be those of the American Concrete Institute.
Reader comment is invited.

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structures made with Aspdins cement still stand today,

none the worse for wear.
The important point is that concrete (the system of
cement paste binding together aggregate particles into
an artificial stone body) is inherently reactive and, given
its particular individual structure and exposure conditions,
that reactivity will result in either excellent durability or
poor durability. In both the long and short terms, it is the
chemistry that makes the difference in concrete permanence. Examples of typical exposure agents that affect
durability are:
Moisture and ground water;
Temperature cycles;
Deicing salts;
Marine environment; and
Carbon dioxide and acidic air pollutants
(NOx and SOx ).
Depending upon the composition of the concrete and
the exposure conditions, a variety of possible chemical
reactions may deteriorate concrete. Sometimes, however, the enemy is not some outside element, but rather,
the seeds of destruction may be innocently contained
within the concrete itself.
Moisture, or water, plays the most important role in
the setting, strength development, and eventual deterioration of concrete. Portland cement hardens because of
a chemical process called hydration. This means that the
silicate and aluminate minerals in portland cement react
and combine with water to produce the glue that holds
together the aggregate that we call concrete. Furthermore, in a more general fashion, these cements are called
hydraulic cements. Hydraulic simply means the
capability to harden under water. Portland cement is
only one type of hydraulic cement, and it should be
noted that C 1157-00, the ASTM performance specification for cement, is called the Standard Performance
Specification for Hydraulic Cement, and includes both
portland and blended types.
As Duff Abrams emphasized in his seminal paper
Design of Concrete Mixtures, however, presented at the
December 1918 meeting of the Portland Cement Association and then published as the Lewis Institute Bulletin 1,
the water-cement ratio (w/c) dictates the strength of

concrete. Although the size and grading of the aggregate

and the quantity of cement influence the quantity of water
required to produce a workable mixture, the amount of
water in a mixture controls the concretes strength. Therefore, one should use the smallest quantity of water that
will produce plastic, or workable, concrete. Water may,
depending upon the quality and nature of the aggregate
used and the concrete curing history, trigger such other
deleterious events as alkali-silica reactivity (ASR) or delayed
ettringite formation (DEF). Water may also function as
a transport medium for potentially aggressive species,
such as sulfate, to enter the system. These chemical
reactions will be covered in greater detail further in
this article.
Temperature affects the rate of chemical reactions,
and a general rule of thumb is that a chemical reaction
rate doubles for every 10 C increase in temperature.
Thus, temperature influences the rate of both concrete
setting and hardening. Additionally, cycles in temperature may result in freezing-and-thawing distress if the
concrete lacks sufficient air entrainment. Curing concrete
above certain critical temperatures may lead to the
expansion and cracking associated with DEF.
Several external environmental factors may initiate
destructive chemical reactions in concrete, particularly
concrete with a more open porosity (due to an elevated
w/c). Some of these factors include chloride-containing
deicing salts used to treat roadways in winter, salt spray
or tidal exposure to seawater, and sulfate-containing
soil or ground water. Chlorides can slowly diffuse into
concrete and, in the presence of moisture and oxygen,
will initiate corrosion of reinforcing steel. The oxidation
of iron to produce iron oxide is a chemical process
that yields a large volume of oxidation product that
not only structurally weakens the metal, but also produces
internal localized pressure that can cause severe
cracking of the concrete cover. Once cracking begins,
more of the concrete surface is exposed to further
chemical attack.
A vulnerable part of the concrete is the cement
paste. Although concrete is composed of 10 to 15%
by mass of portland cement, it becomes the focus of
aggressive outside chemical agents like atmospheric
carbon dioxide (CO2 ) and acidic gases that dissolve in
moisture to produce acid rain. Cement paste is highly
alkaline, with a pH greater than 12.5. This high pH is
due to the presence of the calcium hydroxide hydration
products and the lesser amounts of alkali (sodium and
potassium) salts. Under ideal carbonation conditions
(50 to 70% relative humidity and an exposed paste
surface), the hydrated lime (calcium hydroxide) constituent reacts with CO2 to form calcium carbonate, which
is the same mineral as calcite or limestone. As this
process slowly progresses, perhaps even at rates of only
a millimeter or less per year, the pH is gradually lowered
and a finely crystalline calcium carbonate replaces the
hydration products.
Acid rain is aggressive and can more rapidly etch and
corrode exposed surfaces, eventually destroying the
hydrated cement minerals that provide strength and

durability. One example of this destructive behavior is

the limestone obelisk in New York Citys Central Park. It
had survived thousands of years in the Egyptian desert,
remaining in almost pristine condition, but now after
only decades of exposure to acidic gases in the citys
atmosphere, the hieroglyphic inscriptions have all but
disappeared from view. Although limestone isnt concrete,
the overall effects of acid rain are quite similar.
During the design of a concrete mixture, chemistry
must be considered. For instance, if the concrete is
placed where it may be exposed to aggressive environments such as chlorides or sulfates, a different ASTM
cement type will be selected. Type I is ordinary portland
cement, whereas Type II cement provides moderate
resistance to sulfate attack, and Type V cement provides
much greater resistance to sulfates. There are now
many ASTM standard specifications, ASTM standard test
methods, ACI guidelines, and other recommendations for
the engineering professional on how to design concrete
mixtures, and all of these are based upon fundamental
knowledge of the chemistry of cement and concrete
(Weaver 1978).
During the past 10 to 20 years, field experience has
shown that not only mixture design, but also the curing
of concrete is very important. Curing, of course, is the
process that provides sufficient moisture and thermal
energy to promote the hydration process. Curing
conditions control strength development and thermal
cracking; therefore, they have a significant impact on
the durability of concrete. A recent example of the
importance of curing and temperature control is concrete
degradation from DEF. As will be discussed later, ettringite
formation is a normal and useful event as portland cement
begins to set. If its formation is greatly delayed (days or
months after concrete hardening), however, it can cause
serious durability problems.

The chemical reactions of cement

Portland cement contains calcium silicates and calcium
aluminates formed by a sequence of thermal and chemical
processes, including decomposition of limestone; reaction
with other quarried materials such as clay, iron ore, and
sand; partial fusion of these ingredients; and finally, the
formation of hard, rounded nodules called clinker. All of
this occurs at temperatures reaching about 1450 C in
a cement plants rotary kiln. After cooling, the clinker
is ground together with approximately 5% gypsum
(calcium sulfate dihydrate) to a flourlike fineness,
producing the final product, portland cement (Kosmatka
and Panarese 1994).
At this stage, we will review some elementary cement
chemistry. The present knowledge of the chemical
composition of portland cement and what happens to it
when it is mixed with water was first disclosed in 1887
by the French chemist Henry Le Chatelier (1905). In his
doctoral thesis, he correctly identified the major cement
minerals as tricalcium silicate, dicalcium silicate, and
tricalcium aluminate. In 1915, scientists at the Geophysical Laboratory in Washington, D.C., were studying
the high-temperature phase relationships of the ternary

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system CaO-SiO2-Al2O 3. Among the mineral phases

investigated were, of course, tricalcium silicate,
dicalcium silicate, and tricalcium aluminate. In the
process of publishing the complex triangle-shaped
phase diagram, certain simplifying abbreviations for
the chemical compositions of each mineral phase were
invented. For example, tricalcium silicate, Ca3 SiO5, could
also be written as the combined sequence of the two
oxides, such as 3CaOSiO2. The investigators, Rankin and
Wright, then used the shorthand notation of CaO = C;
SiO2 = S; and Al2O3 = A. Accordingly, 3CaOSiO2 could be
written as C3S. In similar fashion, dicalcium silicate,
2CaOSiO2, became C2S, and tricalcium aluminate,
3CaOAl2O3, became C3 A (Bogue and Steinour 1961).
This notation was so convenient and useful that, in
future publications over the following years, a shorthand
notation for other oxides was similarly introduced. Thus,
Fe2O3 = F; MgO = M; H2O = H; Na2O = N; and K 2O = K. The
additional S problem of sulfur trioxide, SO3, was simply
resolved by indicating it as (S-bar). Other names for
cement minerals or their hydrates concurrently entered
the language and are commonly used today. For approximately 100 years, the tricalcium silicate and dicalcium
silicate minerals, in their somewhat impure composition
as they crystallize in clinker, have been called alite and
belite, respectively. Others are called by their equivalent
mineralogical name, such as periclase for MgO crystals
in cement, portlandite for calcium hydroxide (CH in
shorthand notation), and ettringite for the calcium
aluminosilicate hydrate (C3A3C32H). The formula for
ettringite in cement chemists notation appears to be
complicated, but it is simplified compared to a conventional
chemical formula, {Ca6[Al(OH)6 ]224H 2O}(3SO4 )(2H2O).

Normal hydration reactions

The most rapid reaction that occurs when mixing
cement and water is the hydration of tricalcium aluminate
(C3 A). Entirely by itself, C3A and water will quickly form
calcium aluminate hydrates such as C4 AH13 and C2 AH8.
This can occur so rapidly that the concrete may stiffen
within minutes and become entirely unworkable because
of the heat emitted. This condition is called flash set.
In the nineteenth century, when cement developed
strength slowly because it was coarsely ground and
imperfectly reacted, flash set was not a problem. Eventually, with the introduction of rotary kilns, a more
scientific proportioning of raw material ingredients, and
much finer clinker grinding, the addition of gypsum
(CH2 ) to the cement eliminated flash-setting problems.
Chemically the C3 A, the gypsum, and the water would
form a protective coating of calcium sulfoaluminate
hydrate (ettringite) over the exposed tricalcium aluminate
surfaces that would remain for several hours. The C3 A
hydration reactivates as the initial setting begins,
consuming the sulfate and forming more ettringite. If
the portland cement is an ASTM Type I, however, it
probably contains over 8% C3 A, which is a much greater
percentage than the sulfate present. When all of the sulfate
has been combined into ettringite, the excess C3 A
continues to hydrate, and then begins to remove sulfate
from some of the ettringite (trisulfate) to form another

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stable calcium sulfoaluminate compound called the

monosulfate, C3 AC H12 (Eq. (1) and (2)). A fourth
major mineral in cement, the iron-containing ferrite
phase, or tetracalcium aluminoferrite (C4 AF) also hydrates,
although much more slowly, to form chemically similar
trisulfate and monosulfate compounds, in which iron
(Fe2O 3 ) replaces a portion of the aluminum (Al2O 3 )
(Steinour, 1958). Cement chemists generically call these
the AFt (aluminate-ferrite-trisubstituted) and AFm
(aluminate-ferrite-monosubstituted) phases, respectively.
C3 A + 3C H2 + 26H C6 A 3 H32 (ettringite)

(1)

2C3 A + C6 A 3 H32 + 4H 3C4 A H12

(monosulfoaluminate)

(2)

The major strength development of concrete, however, results from the hydration of the calcium silicate
phases (C3S and C2S). Both of these calcium silicates
combine with water to form the gel-like calcium silicate
hydrate, or C-S-H (Eq. (3) and (4)).
2C3 S + 6H C-S-H + 3CH

(3)

2C2 S + 4H C-S-H + CH

(4)

Cement paste microstructure

When concrete hardens due to hydration of the cement
paste portion, the total volume of the hydration products
is smaller than the original volume of portland cement
and water. As a result of these hydration reactions and
the decrease in paste volume, a system of capillary pores
is created (Fig. 1). This porosity in concrete governs its
degree of susceptibility to various chemical factors having
a profound influence on its durability.
The reactions of greatest interest in the cement paste
are those between the components of the pore solution,
and the solid phases present, which are the original cement
minerals, their hydration products and, possibly, susceptible aggregate surfaces, in the case of ASR. This means
that, as time passes, some of the solid phases dissolve and
new phases precipitate. The transport in solution of the
various substances participating in the reactions controls
the rate at which the chemical reactions take place.
In order for water to be available, it has to be able to
enter the concrete and move through the paste structure,
where it becomes part of the pore solution within the
capillary pore system. The pore solution contains various
chemical compounds that have dissolved from solid
materials. These are primarily hydroxyl ions (OH) and
alkali ions (K+ and Na+), as well as lesser amounts of
calcium, silicate, aluminate, and sulfate ions. Ions from
external sources, such as deicing salts, may include
sodium and chloride. This is the point where the importance of the paste microstructure, in the form of the
capillary pore system, is evident. If cracks in the aggregate are disregarded, only the paste will take part in the
transport of reactive ions into a concrete system. In such
a system, there are three possibilities for water movement:
Through the capillary system;
Through the hydration products (primarily C-S-H
gel); and
Through cracks in the paste structure.

If the concrete is moisture-saturated, the pore solution

will fill both the capillary pore system and the cracks in
the paste. The connectivity of these systems is critical
in controlling how far and how fast solutions can move
into the concrete. For concrete produced with a w/c
of 0.6 and higher, the capillary system will be continuous
(percolating system), and aggressive reactants will easily
move through the concrete mass. With decreasing w/c,
however, the pore system becomes isolated into smaller
and smaller unconnected clusters of pores. These small
clusters close to the surface may become saturated with
solution and dissolved reactants. Any further movement
through the paste has to occur through the C-S-H gel or
through the hydration products.
The rate of liquid transport through the C-S-H phase
is on the order of 1000 times slower than that occurring
through the capillary pores. Therefore, even if the capillary
pores account for only 1% of the total transport cross
section, they will still provide 90% of the solution transport.
Any chemical reactions that depend solely on transport
through C-S-H are negligible for all practical purposes.
If liquid-filled cracks are present, the movement of a
solution will be proportional to the number and size of
cracks. Additionally, cracks will also provide shortcuts
between pore clusters and thereby expose deeper layers
of concrete to the penetrating solution. With sufficient
cracking, the cracks themselves may form a connected
system percolating the concrete and allowing dissolved
reactants to move into the system more quickly.
The most common type of chemical attack on concrete
results from exposure to soils or ground water containing
elevated sulfate contents. This malady is a common
occurrence in the western United States, and has been
known for many years. Production of ASTM Type II and
Type V cements is particularly intended to provide
resistance to deleterious sulfate exposure. The mechanism
of sulfate attack is relatively simple. If cement contains
an elevated amount of C3A, a substantial amount of the
calcium monosulfoaluminate (AFm) phase will form during
hydration. This substance is reactive, and if additional
sulfate from an outside source such as soil or ground
water penetrates the concrete, the monosulfate will readily
react with it and convert back to the AFt phase, or
ettringite. The conversion of the monosulfate phase into
ettringite will result in a significant volumetric increase
and be disruptive to the concrete. If this is allowed to
continue, the concrete will eventually be destroyed.
Concrete made at a high w/c and subjected to sodium
sulfate-containing ground water can be damaged by
another mechanism. Studies conducted in California have
shown that, even with the use of ASTM Type II and Type V
cement types, if water is able to percolate through the
concrete, the wetting and drying on the surfaces exposed
to air result in serious deterioration. Damage is mainly
from the repeated crystallization of alkali sulfates and
carbonates during the drying cycles (Stark 1989).

Chemistry and cracking

Cracks in concrete may develop for physical reasons
such as drying shrinkage or mechanical loading. Local
chemical reactions in the concrete, however, may also

Water

Capillary
pores

Gel

Unhydrated cement
Unhydrated cement

Fig. 1: Relative volumes of cement, water, and hydration products

before (left) and after (right) hydration

result in expansion, a buildup of internal pressure, and

then cracking. Concrete is a brittle material and therefore can only expand to a limited degree before cracking.
In broad terms, the observed expansion is equal to the
sum of the crack widths. It is not possible to determine
the cause of expansion and cracking from the appearance
of the crack pattern on the surface of the concrete. Interior
concrete samples must be examined microscopically,
chemically, or both, to determine the root cause of the
internal expansion. In field concrete exposed to the
elements, there are two basic modes of expansion:
The aggregate can expand relative to the cement
paste; and
The cement paste can expand relative to the aggregate.
It follows from physical considerations that, in a
composite system consisting of expanding particles in a
matrix, cracks are formed in the matrix radiating away
from the particles. Expansion of particles in a hardened
paste, such as aggregate particles undergoing ASR, causes
the particles to crack and the crack to extend outward
into the surrounding paste. A particle cracking, when
expanded from the surface, is actually a fairly common
experience. When ice cubes are dropped into a drink and
a familiar crackling sound is heardthat is the sound of
the ice being heated on the outside, expanding, and then
cracking. The expansion at the surface causes the inner
part of the particle to be under tensile stress, and it
cracks from the inside outward.
Shrinkage of cement paste is a common phenomenon
related to hydration, and from a cracking point of view,
is equivalent to the expansion of aggregate particles.
Consider, however, what would happen if the paste
actually expands relative to the aggregate particles. When
cement paste expands relative to the aggregate particles,
as it has in DEF, gaps open up around the particles. This
concept is actually a little counterintuitive, in that one
might expect the expanding paste to actually crush the
particle rather than create a gap around it. This is similar
to the question of whether a hole that has been drilled
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deterioration mechanism. Reactions

related to sulfate are a group of
reactions that involve only the
cement paste. DEF reactions that are
associated with concrete exposure
to high temperatures during curing,
in systems containing normal(a)
sulfate-content cements, have been
a hot button topic of discussion
(b)
(c)
for some time. DEF results from
Fig. 2: Expansion mind experimenta) a matrix containing aggregate particles;
a chemical reaction, or sets of
b) the whole system is expanded by 20%; and c) the aggregate particles are returned to
reactions, that are still not well
their original size, leaving voids around them
understood at the present time,
but the diagnosis is relatively
simple; deterioration results from paste expansion in
through a piece of metal will become smaller or larger
the affected concrete.
in diameter as the metal is heated and expands.
In DEF-affected concrete, the AFt phase, or ettringite,
One way to understand the phenomenon is to consider
is
usually
observed. But ettringite in concrete is not
concrete made with aggregate that does not expand, and
conduct the following imaginary experiment (Fig. 2). First, unique to DEF. Ettringite is a normal hydration product
formed by the chemical reaction between the aluminate
assume that the concrete, including both paste and
phases of cement, water, and calcium sulfate (gypsum),
aggregate, expands, say 20%, in all directions. There is no
as mentioned previously. The formation of ettringite
distortion, no cracking, and the concrete is just somewhat
takes place in the paste and is uniformly distributed.
larger. Next, since the aggregate particles were not expanding,
Within mature concrete exposed to moist conditions,
shrink them back to their original size. What has happened?
ettringite is usually found in pores and cracks. This is
The particles now rattle around in holes that are 20%
not an indication of damage, but rather the result of
larger than the individual particles. Thus, gaps have
a normal recrystallization process known as Ostwald
actually formed around the aggregate particles and,
ripening. This means that small crystals have a higher
furthermore, these gaps are proportional to particle size.
solubility than large crystals, and when concrete become
Alkali-silica reactivity
water-saturated to a certain degree, the small crystals
The chemical reaction called ASR takes place between
within the paste dissolve in the pore liquid and subsethe highly alkaline (very high pH) pore solution and
quently recrystallize as larger crystals in any available
reactive siliceous portions of some aggregate particles.
spaces, such as cracks and pores. Ostwald ripening is
The large amount of hydroxyl (OH) ions present in the
a general chemical principle, and calcium hydroxide
pore solution, due to a high alkali concentration (potassium
crystallization behaves in a similar fashion.
and sodium), dissolve the reactive silica on the aggregate
Regarding DEF, however, a high concrete temperature
surfaces to form an alkali silicate gel. Although any form
at an early age is a very important parameter. At certain
of silica can react with alkali hydroxides in theory, it is
temperatures, generally above 70 C, and more frequently
the siliceous rocks such as opal, greywacke, some chert,
above 80 C, ettringite becomes unstable because its
and glassy volcanic materials that appear to be the most
solubility increases. This temperature is strongly depenreactive. Reactive siliceous aggregates will form alkalident upon the alkali content and other compositional
silica gel starting at the surface of the aggregate and moving
factors of the cement that are less well understood.
inwards. Tensile stresses build up during the reaction,
Where the components of the ettringite go after its
causing the aggregate particles and the surrounding
decomposition is not clear. Portions of ettringite may
paste to crack. In severe cases, the cracks will interbe consumed by the C-S-H or may stay in solution. This
connect and lead to weakening of the concrete. The
issue is the subject of much scientific research and
weakening is only due to the cracks; the paste between
discussion at present (Tennis et al. 1999). What is clear,
the cracks maintains its composition and strength.
however, is that the chemistry matters, even if we do
Denser polycrystalline rocks, such as granites, will react
not fully understand the precise sequence of reactions.
much more slowly. The chemical reaction will occur at
One sign of paste expansion is the presence of voids
those heterogeneous areas of grain boundaries. In such
or cracks around the aggregate particles, as explained
cases, only a minimal degree of reaction may be needed
previously. Usually, ettringite fills these gaps. There are also
to cause cracking, but only meager amounts of gel will
examples of paste expansion showing empty gaps, however.
form. In ASR distress, since each internal fracture in concrete
The following is one possible explanation of the
creates an empty space, the alkali-silica reaction causes
observed paste expansion related to DEF, in which
corresponding incremental volume increases (Helmuth
sulfate dissolved in the pore liquid reacts with the
1993). The resulting visual evidence of the reaction is the
anhydrous and hydrated aluminate particles in the
map cracking observed on the concrete surface.
hardened cement paste. Johansen and Thaulow (1999)
Paste expansion
discussed this previously. Hardened paste, mortar, and
ASR is an example of a chemical reaction in which
heat-treated as well as normally cured concrete are all
the aggregate portion of the concrete plays a role in the
places where one can find unhydrated clinker particles

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in various amounts. As mentioned previously, above

certain temperatures ettringite is unstable, and the
primary hydrated aluminate phase is the calcium
monosulfoaluminate (AFm). Therefore, after cooling to
room temperature following heat treatment, concrete
will contain anhydrous aluminate particles, anhydrous
aluminate particles with AFm, and AFm phases. During
the passage of time and moist curing of such concrete,
these particles will continue to react with sulfate in the
pore solution. Both ettringite and AFm phases form,
depending upon the composition of the pore solution.
The sulfate, liberated from the C-S-H that had initially
absorbed it during the heat treatment, maintains the
sulfate concentration of the pore solution.
The hardened paste confines the reacting particles
and the volume of the AFm and ettringite (AFt) formed
will result in development of localized pressure. Crystals
under pressure have a higher solubility than what they
would have when not under pressure. When more and
more AFm and AFt phases are formed on the reacting
particles, the pressure will increase and, therefore, so
will their solubility. If the solubility increases to a level
corresponding with the actual concentration in the pore
solution, the crystal growth stops and the pressure will
act locally on the particle and its surroundings. In this
way, the reacting particle can act as a local pressure
center. This will cause stress to build up in the surrounding
paste as sort of a sphere of influence around the particle.
If the pressure created is larger than the tensile strength
of the paste, the paste will crack or yield. If the reacting
particles are sufficiently close to each other, mass volumetric expansion will result.

Conclusion
Returning to the original question, why does chemistry
matter? The answer can be summarized as follows:
chemistry matters because concrete composition and
performance are based upon a variety of chemical
reactions that range from the original setting and
hardening of the portland cement constituent to the
eventual desired engineering properties. The durability
of concrete depends on chemical processes developing
out of cement and aggregate compositional factors,
curing conditions, and exposure to a variety of environmental effects. The chemical reactions that occur
during the hydration of the clinker minerals determine
the concrete microstructure. The hardened concrete
is chemically reactive given the right conditions, as
shown in the examples. Therefore, it is essential to
design concrete mixtures properly and erect structures
in a way to control or adequately compensate for
chemical reactivity.

References
Bogue, R. H. and Steinour, H. H., Origin of the Special Chemical
Symbols Used by Cement Chemists, Journal of the PCA Research &
Development Laboratories, V. 3, No. 3, Sept. 1961, pp. 20-21.
Helmuth, R., Alkali-Silica Reactivity: An Overview of Research,
SHRP-C-342, Strategic Highway Research Program, National Research
Council, Washington, D.C., 1993.
Johansen, V. and Thaulow, N., Heat Curing and Late Formation of

Ettringite, Ettringite: The Sometimes Host of Destruction, SP-177,

B. Erlin, ed., American Concrete Institute, Farmington Hills, Mich.,
1999, pp. 47-64.
Kosmatka, S. H. and Panarese, W. C., Design and Control of
Concrete Mixtures, PCA Engineering Bulletin EB001.13T, Portland
Cement Association, Skokie, Ill., 1994.
Le Chatelier, H., Experimental Researches on the Constitution of
Hydraulic Mortars, Translated by J. L. Mack, McGraw Publishing Co.,
New York, N.Y., 1905.
Stark, D., Durability of Concrete in Sulfate-Rich Soils, PCA
Research and Development Bulletin RD097, Portland Cement
Association, Skokie, Ill., 1989.
Steinour, H. H., The Setting of Portland Cement: A Review of
Theory, Performance and Control, PCA Research Department
Bulletin 98, Portland Cement Association, Chicago, Ill., Nov. 1958.
Tennis, P. D.; Bhattacharja, S.; Klemm, W. A.; and Miller, F. M.,
Assessing the Distribution of Sulfate in Portland Cement and
Clinker and Its Influence on Expansion in Mortar, Cement, Concrete,
and Aggregates, V. 21, No. 2, Dec. 1999, pp. 212-216.
Weaver, W. S., Committee C-1 on CementSeventy-Five Years of
Achievement, Cement StandardsEvolution and Trends, ASTM STP
663, P. K. Mehta, ed., American Society for Testing and Materials,
Philadelphia, Pa., 1978, pp. 3-15.
Received and reviewed under Institute publication policies.

an
sen is a Senior
ACI member Vagn C. Joh
Johan
ansen
Principal at Construction Technology
Laboratories (CTL), Inc. He has more than
20 years of experience with cement
chemistry and cement manufacture, and
10 years of experience with concrete
materials and durability-related work.
Previously, he worked in Denmark for Idorn
Consult, and with F.L. Smith & Co.

W al
dem
ar A
emm is an Affiliated
aldem
demar
A.. Kl
Klemm
Consultant with CTL, Inc. He has 30 years
of experience with the U.S. cement industry
in plant process, chemistry, research, and
developmental activities. He has authored
numerous technical reports and scientific
papers on clinkering chemistry, cement
hydration, admixture research, cement
manufacturing, and environmental
problems. He is a member of ASTM.
er C. Ta ylor has been
ACI member P et
eter
at CTL, Inc., since 1997, and is a Senior
Engineer. He is a graduate in Civil
Engineering from the University of Cape
Town, South Africa, and has 18 years
experience in consulting and research. He
is a member of ACI Committees 232, Fly
Ash and Natural Pozzolans in Concrete,
and 236, Material Science of Concrete.
Concrete international

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