CE 512: REINFORCED CONCRETE DESIGN

Lecture No. 03
HYDRAULIC CEMENTS
By Sir E. Anacta

3.1— LECTURE OBJECTIVES 3.4— PORTLAND CEMENT

After this lecture, you will be able to: 3.4.1 Definition.

1. Classify and distinguish hydraulic and non-hydraulic ASTM C 150 defines Portland cement as a hydraulic
cements; cement produced by pulverizing clinkers consisting
essentially of hydraulic calcium silicates, and a small
2. Characterize Portland Cement; amount of one or more forms of calcium sulfate as an
interground addition. Clinkers
3. Recognize special types of hydraulic cements; and are 5- to 25-mm-diameter nodules of a sintered material
4. Recognize trends in cement specifications. that is produced when a raw mixture of predetermined
composition is heated to high temperatures.

3.2— INTRODUCTION 3.4.2 Manufacturing Process

Hydraulic or water-resisting cements consist essentially of Since calcium silicates are the primary constituents of
Portland cement and its several modifications. To Portland cement, the raw material for the production of
understand the properties of Portland cement, it is helpful cement must provide calcium and silica in suitable forms
to acquire some familiarity with its manufacturing process, and proportions. Naturally occurring calcium carbonate
chemical and mineralogical composition, and reactivity of materials such as limestone, chalk, marl, and sea-shells
the constituent compounds such as calcium silicates and are the common industrial sources of calcium, but clay or
calcium aluminates. Furthermore, properties of concrete dolomite (CaCO3 MgCO3) are usually present as
containing Portland cement develop as a result of chemical impurities. Clays and shales, rather than quartz, are the
reactions between the Portland cement compounds and preferred sources of additional silica in the raw-mix for
water, because the hydration reactions are accompanied making calcium silicates because quartzitic silica does not
by changes in matter and energy. react easily with lime.

In this lecture the composition and characteristics of the

principal compounds of Portland cement are described.
Hydration reactions of the aluminate compounds with their
influence on setting behavior of cement, and of silicate
compounds with their influence on strength development
are fully discussed. The relationship between the chemistry
of reactions and physical aspects of setting and hardening
of Portland cements is explained. Classification of Portland
cement types and cement specifications are also reviewed.
Portland cements do not completely satisfy the needs of
the concrete construction industry. Special cements have
been developed to fill those needs. The compositions, (a)
hydration characteristics, and important properties of
pozzolan cements, blast-furnace slag cements, expansive
cements, rapid setting and hardening cements, white and
colored cements, oil-well cements, and calcium aluminate
cements are described. Finally, trends in cement
specifications in Europe and North America are reviewed.

3.3— HYDRAULIC AND NONHYDRAULIC CEMENTS

3.3.1 Chemistry of Gypsum and Lime Cements (b)

Cements that not only harden by reacting with water but Figure 3.1 Chemistry of gypsum and lime cements:
also form a water resistant product are called hydraulic (a) production of gypsum cement, and hydration
cements. The cements derived from the calcination of reaction;
gypsum or calcium carbonates are nonhydraulic because (b) production of lime cements, and hydration
their products of hydration are not resistant to water. The reactions both with and without pozzolans.
chemistry underlying the gypsum and lime cements is
illustrated in Fig. 3.1. Lime mortars that were used in Crystallization of gypsum needles from a hydrated
ancient structures built by Greeks and Romans were gypsum-cement is the cause of setting and hardening.
rendered hydraulic by the addition of pozzolanic materials, Gypsum is not stable in water; therefore, the gypsum
which reacted with lime to produce a water-resistant, cement is nonhydraulic. Hydrated lime, Ca(OH)2 is also not
cementitious product. stable in water. However, it can slowly carbonate in air to
form a stable product (CaCO3). When a pozzolan (reactive
Compared to gypsum and lime cements, Portland cement silica) is present in the system, the calcium silicate
and its various modifications are the principal cements hydrates formed as a result of the reaction between lime
used today for making structural concrete. Portland cement and pozzolan are stable in water.
and modified Portland cements are hydraulic cements
because they do not require the addition of a pozzolanic
material to develop water-resisting properties.
Clay minerals contain alumina (Al2O3), iron oxide (Fe2O3), cement industry to compute the compound composition of
and alkalies. The presence of aluminum, iron and Portland cement from the oxide analysis by using a set of
magnesium ions, and alkalies in the raw mix has a equations which were originally developed by R.H. Bogue.
mineralizing effect on the formation of calcium silicates; Direct determination of the compound composition, which
that is, they facilitate the formation of the calcium silicate at requires special equipment and skill (Fig. 3.2), is not
considerably lower temperatures than would otherwise be necessary for routine quality control.
possible. Therefore, when sufficient amounts of iron and
alumina minerals are not present in the primary raw Table 3.1 Oxide Analyses of Portland Cement
materials, these are purposely incorporated into the raw
mix through addition of secondary materials such as
bauxite and iron ore. As a result, besides the calcium
silicate compounds, the Portland cement clinker also
contains aluminates and aluminoferrites of calcium.

To facilitate the formation of the desired compounds in

Portland cement clinker it is necessary to homogenize the
raw-mix before heat treatment. That is why the materials
are subjected to a series of crushing, grinding, and
blending operations. From chemical analyses of the
stockpiled materials, their individual proportions are
Table 3.2 Oxide Analyses of Different Portland Cements
determined by the compound composition desired in the
clinker; the proportioned raw materials are usually Cement No.
interground in all or roller mills to particles below 75 m.
Oxide 1 2 3 4 5
In the wet process of cement manufacture, the grinding
and homogenization of the raw mix is carried out in the
form of a slurry containing 30 to 40 percent water. Modern
cement plants favor the dry process, which is more energy
efficient than the wet process because the water in the
slurry must be evaporated before clinkering. For the
clinkering operation, the dry-process kilns equipped with
multi-stage suspension preheaters, which permit efficient
heat exchange between hot gases and the raw-mix,
require a fossil-fuel energy input on the order of 800
kcal/kg ofclinker compared to about 1400 kcal/kg for the
wet process kilns. Figure 3.3 shows a simplified flow
diagram of the dry process for Portland cement
manufacture; an aerial view of a modern cement plant is
shown in Fig. 3.4.

The chemical reactions taking place in the cement kiln may

be expressed as follows:

Limestone  CaO + CO2 (a)

Clay  SiO2 + Al2O3 + Fe2O3

3CaO  Al2O3
3CaO  SiO2
Clay + Limestone 
2CaO  SiO2
4CaO  Al2O3  Fe2O3

The final operation in the Portland cement manufacturing

process consists of pulverizing the clinker to an average
particle between 10 and 15 m. The operation is carried out
in ball mills, also called finish mills. Approximately 5
percent gypsum or calcium sulfate is usually interground
with clinker in order to control
the early setting and hardening behavior of the cement, as
will be discussed.
(b)
3.4.3 Chemical Composition
Figure 3.2
(a) Photomicrograph of a polished clinker specimen
Although Portland cement consists essentially of various
by reflected light microscopy; (b) X-ray diffraction
compounds of calcium, the results of routine chemical
pattern of a powdered clinker specimen.
analysis are reported in terms of oxides of the elements
present. Also, it is customary to express the individual
Two methods are commonly used for direct quantitative
oxides and clinker compounds by using the abbreviations
analysis of Portland cement clinker. The first method
shown in Table 3.1.
involves reflected-light microscopy of polished and etched
sections, followed by a point count of areas occupied by
Since properties of Portland cement are related to the
the various compounds. Typically, C3S appears as
compound composition, it is difficult to draw any
hexagonal-plate crystals, C2S as rounded grains with
conclusions from the cement oxide analyses, such as
twinning bands, and C3A and C4AF as interstitial phases.
those shown in Table 3.2. It is a common practice in the
The second method which is also applicable to pulverized
cements, involves X-ray diffraction of powder specimens. estimate of the compound is made by using these curves
Calibration curves based on known mixtures of pure and the intensity ratios between a selected diffraction peak
compounds and an internal standard are required; an of the compound and the internal standard.

Figure 3.3 Flow diagram of the dry process for Portland cement manufacture.

A major step in the process is the clinkering operation carried out in a rotary kiln, which consists of an inclined steel
cylinder lined with refractory bricks. The preheated and partially calcined raw mix enters at the higher end of the
continuously rotating kiln and is transported to the lower end at a rate controlled by the slope and the speed of the kiln
rotation. Pulverized coal, oil, or a fuel gas is injected at the lower end in the burning zone, where temperatures on the
order of 1450 to 1550 C may be reached and the chemical reactions involving the formation of Portland cement
compounds are completed.

Figure 3.4 Aerial view of the Ash Grove Cement (West) Portland cement plant at Durkee, Oregon.

An aerial photograph of the Ash Grove Cement (West) dry process plant located near Durkee, Oregon, is shown. This
500,000 tonne/year plant, which in 1979 replaced a 200,000 tonne/year wet process plant, contains a 4.35 by 66 m long
rotary kiln equipped with a four-stage suspension preheater. The preheater exhaust gases go to an electrostatic
precipitator designed for an emission efficiency of 99.93 percent. All process loops are monitored and controlled with a
2000 microprocessor-based distributed control system utilizing fuzzy logic.
3.4.4 Determination of the Compound Composition aluminum, iron, potassium, sodium, and sulfur ions.
from Chemical Analysis The impure forms of C3S and C2S are known as alite
and belite, respectively.
The Bogue equations for estimating the theoretical or the
potential compound composition of Portland cement are as Although three main crystalline forms of alitetriclinic,
follows: monoclinic, and trigonalhave been detected in
industrial cements, these forms are a slight distortion of
%C3S = 4071C – 7.600S – 6.718A (3-1) an ideal C3S pseudostructure built from SiO4
– 1.430F – 2.850S tetrahedra, calcium ions, and oxygen ions (Fig. 3.4a).
1
According to Lea, a notable feature of the ionic
%C2S = 2867S – 0.7544C3S (3-2) packing is that the coordination of oxygen ions around
the calcium is irregular so that the oxygen ions are
%C3A = 2650A – 1.692F (3-3) concentrated on one side of each of the calcium ion.
This arrangement leaves large structural holes, which
%C4AF = 3.043F – 7.600S (3-4) account for the high lattice
energy and reactivity.
The equations are applicable to Portland cements with an
A/F ratio 0.64 or higher; should the ratio be less than 0.64 Similarly, the structure of belite in industrial cements is
another set of equations apply, which are included in irregular, but the interstitial holes thus formed are much
ASTM C 150. smaller, and this makes belite far less reactive than
alite. By way of contrast, another crystallographic form
Even small differences in the oxide analyses of two of dicalcium silicate, namely, C2S, has a regularly
cements can result in large differences in their compound coordinated structure (Fig. 3.4b) thus rendering this
composition. The Bogue equations assume that the compound nonreactive.
chemical reactions of formation of clinker compounds have
proceeded to completion, and that the presence of
impurities such as MgO and alkalies can be ignored. Both
assumptions are not valid; hence in some cases the
computed compound compositions, especially the amounts
of C3A and C4AF in cement, are known to deviate
considerably from the actual compound composition
determined directly. This is why the computed compound
composition is also referred to as the potential compound
composition. Because properties of Portland cement are
influenced by the proportion and the type of the
compounds present, the Bogue equations serve a useful
purpose by offering an easy method of providing a first
estimate of the compound composition of Portland cement
from oxide analysis.

3.4.5 Crystal Structure and Reactivity of the

Compounds
(a)
The chemical composition of the compounds present in
industrial Portland cements is not exactly what is
expressed by the commonly used formulas, C3S, C2S, C3A,
and C4AF. This is because at the high temperatures
prevalent during clinker formation the elements present in
the system, including the impurities such as magnesium,
sodium, potassium, and sulfur, are able to enter into solid
solutions with each of the major compounds of the cement
in clinker. Very small amounts of impurities in solid solution
may not significantly alter the crystal structure and
reactivity of a compound, but larger amounts can do so.

Besides the particle size and the temperature of hydration,

the reactivity of the Portland cement compounds with water
is influenced by their crystal structure. Under the high-
temperature and nonequilibrium conditions of the cement
kiln, and with a variety of cations present, the crystal
structures formed are far from perfect. The structural
imperfections thus produced explain why the cement
compounds are unstable in an aqueous environment. In
fact, differences between the reactivity of two compounds (b)
having a similar chemical composition can only be
explained from the degree of their structural instability. It is Figure 3.4 Crystal structures of (a) 3CaO-SiO2 (b)
beyond the scope of this book to discuss in detail the
– 2CaO-SiO2. Part (a) shows a vertical section of
highly complex crystal structures of cement compounds;
the bottom layer of the pseudo structure of 3CaO-
however, essential features that account for differences in
SiO2 through the long diagonal of the cell. Only the
the reactivity are described next.
oxygen atoms in the symmetry plane are shown
as plain circles. 1, 2, and 3 are sections of SiO 4
Cacium Silicates. Tricalcium silicate (C3S) and beta-
tetrahedron. Calcium atoms are labeled. In (b),
dicalcium silicate (C2S) are the two hydraulic silicates silicon atoms are not shown; they occur at the
commonly found in industrial Portland cement clinkers. center of the silica tetrahedra.
Both invariably contain small amounts of magnesium,
The irregular coordination of the oxygen ions around Alkali and Sulfate Compounds.
calcium leaves large voids, which account for the high
reactivity of C3S. On the other hand, -C2S has a regularly The alkalies (sodium and potassium) in Portland
coordinate structure and is, therefore, nonreactive. cement clinker are derived mainly from the clay
components present in the raw mix and coal; their total
Calcium Aluminate and Ferroaluminate. amount, expressed as Na2O equivalent (Na2O
+0.64K2O), may range from 0.3 to 1.5 percent. The
Several hydraulic calcium aluminates can occur in the sulfates in a cement kiln generally originate from fuel.
CaO-Al2O3 system; however, the tricalcium aluminate Depending on the amount of sulfate available, soluble
(C3A) is the principal aluminate compound in Portland double-sulfates of alkalies such as langbeinite (2CS 
cement clinker. Calcium ferrites are not found in S) and aphthitalite (3NS  S) are known to be present
normal Portland cement clinker; instead, calcium in Portland cement clinker. Their presence has a
ferroaluminates which belong to the C2A-C2F ferrite significant influence on the early hydration reactions of
solid solution (Fss) series are formed, and the most the cement.
common compound corresponds approximately to the
equimolecular composition, C4AF. Similar to the When sufficient sulfate is not present in the kiln
calcium silicates, in industrial clinkers both C3A and system, the alkalies are preferentially taken up by C 3A
C4AF contain significant amounts of magnesium, and C2S, which may then be modified to compositions
sodium, potassium, and silica in their crystal structure. of the type NC8A3 and KC23S12, respectively.
The crystal structure of pure C3A is cubic; however, Sometimes large amounts of sulfate in the form of
both C4AF and C3A contain large amounts of alkalies gypsum are purposely added to the raw mix either for
and are therefore orthorhombic. The crystal structures lowering the burning temperature or for modification of
are very complex but are characterized by large the C3A phase to C4A3S, which is an important
structural holes that account for high reactivity. constituent of certain types of cements that will be
described later.
Magnesium Oxide and Calcium Oxide.
In ordinary Portland cement the source of most of the
The source of magnesium oxide in cement is usually sulfate (expressed as SO3) is calcium sulfate in one of
dolomite, which is present as an impurity in most its several possible forms, added to the clinker during
limestones. A part of the total magnesium oxide in grinding. The main purpose of this additive is to retard
Portland cement clinker (i.e., up to 2 percent) may the quick-setting tendency of ground Portland clinker,
enter into solid solution with the various compounds attributable to the highly reactive C3A phase. Calcium
described above; however, the rest occurs as sulfate can occur as gypsum (CaSO 4  2H2O), plaster
crystalline MgO, also called periclase. Hydration of of Paris or hemihydrate (CaSO4  1/2H2O), and
periclase to magnesium hydroxide is a slow and anhydrite (CaSO4). Compared to clinker compounds,
expansive reaction that, under certain conditions, can gypsum, the principal form of calcium sulfate, dissolves
cause unsoundness (i.e., cracking and pop-outs in rather quickly in water. Hemihydrate is even more
cement-based products). soluble than gypsum and is invariably present in
cements due to decomposition of gypsum during the
Uncombined or free calcium oxide is rarely present in finish grinding operation.
significant amounts in modern Portland cements.
Improper proportioning of raw materials, inadequate 6.2.5 Fineness
grinding and homogenization of the raw mix, and
insufficient temperature or hold time in the kiln burning In addition to the compound composition, the fineness of
zone are among the principal factors that account for cement also affects its reactivity with water. Generally, the
the presence of free or crystalline calcium oxide in finer the cement, the more rapidly it will react. For a given
Portland cement clinker. Like MgO, the crystalline CaO compound composition the rate of reactivity and hence the
that has been exposed to high temperature in the strength development can be enhanced by finer grinding of
cement kiln hydrates slowly and the hydration reaction cement; however, the cost of grinding and the heat evolved
is capable of causing unsoundness in cement-based on hydration set some limits on the fineness.
products.
For quality control purposes in the cement industry, the
Both MgO and CaO form cubic structures, with each fineness is easily determined as the residue on standard
magnesium or calcium ion surrounded by six oxygens sieves such as No. 200 mesh (75 m) and No. 325 mesh
2+
in a regular octahedron. The size of the Mg ion is (45 m). It is generally agreed that cement particles larger
such that, in the MgO structure, the oxygen ions are in than 45 m are slow to hydrate and those larger than 75 m
2+
close contact and the Mg ions are well packed in the may never hydrate completely.
interstices. However, in the case of the CaO structure,
2+
due to the much larger size of the Ca ion, the oxygen However, an estimate of the relative rates of reactivity of
2+
ions are forced apart so that the Ca ions are not well cements with similar compound composition cannot be
packed. Consequently, the crystalline MgO formed made without knowing the complete particle size
from a high-temperature (>1,400C) melt in a Portland distribution. As the determination of particle size
cement kiln is much less reactive with water than the distribution is either cumbersome or requires expensive
crystalline CaO formed under the same temperature equipment, it is a common practice in the industry to obtain
conditions. This is the reason why under ordinary a relative measure of the particle size distribution from
curing temperatures the presence of a significant surface area analysis of the cement by the Blaine Air
quantity of crystalline CaO in Portland cement may Permeability Method (ASTM C 204). Typical data on
cause unsoundness in cement-based products, particle size distribution and Blaine surface area for two
whereas a similar amount of crystalline MgO may samples of industrially produced Portland cements are
prove harmless. shown in Fig. 3.5.
 Since Portland cement is composed of a heterogeneous
mixture of several compounds, the hydration process
consists of simultaneously occurring reactions of the
anhydrous compounds with water. All the compounds,
however, do not hydrate at the same rate. The aluminates
are known to hydrate at a much faster rate than the
silicates. In fact, the stiffening (loss of consistency) and
setting (solidification) characteristics of a Portland cement
paste, are largely determined by the hydration reactions
involving the aluminates.

The silicates, which make up about 75 percent of ordinary

Portland cement, play a dominant role in determining the
hardening (rate of strength development) characteristics.
For the purpose of obtaining a clear understanding of the
chemical and physical changes during the hydration of
Portland cement, it is desirable to discuss separately the
Figure 3.5 Typical particle size distribution data from hydration reactions of aluminates and silicates.
ASTM Type I and III Portland cement samples.

3.5— HYDRATION OF PORTLAND CEMENT

3.5.1 Significance

Anhydrous Portland cement cannot bind sand and rock; it

acquires the adhesive property only when mixed with
water. This is because the chemical reaction of cement
with water, commonly referred to as the hydration of
cement, yields products that possess setting and
2
hardening characteristics. Brunauer and Copeland aptly
described the significance of Portland cement hydration to
concrete technology:

The chemistry of concrete is essentially the

chemistry of the reaction between Portland
cement and water. . . . In any chemical reaction
the main features of interest are the changes in
matter, the changes in energy, and the speed of
the reaction. These three aspects of a reaction
have great practical importance for the user of
Portland cement. Knowledge of the substances
formed when Portland cement reacts is important
because the cement itself is not a cementing
material; its hydration products have the
cementing action. Knowledge of the amount of
heat released is important because the heat is
sometimes a help and sometimes a hindrance. . . .
Knowledge of reaction speed is important because
it determines the time of setting and hardening.
The initial reaction must be slow enough to enable
the concrete to be poured into place. On the other
hand, after the concrete has been placed rapid
2
hardening is often desirable.

3.5.2 Mechanism of Hydration

Two mechanisms of hydration of Portland cement have

been proposed. The through-solution hydration involves
dissolution of anhydrous compounds into their ionic
constituents, formation of hydrates in the solution and, due
to their low solubility, eventual precipitation of the hydrates
from the supersaturated solution. Thus the through-solution
mechanism envisages complete reorganization of the
constituents of the original compounds during the hydration
of cement. According to the other proposed mechanism,
called the topochemical or solid-state hydration of cement,
the reactions take place directly at the surface of the
anhydrous cement compounds without the compounds
going into solution. From electron microscopic studies of
hydrating cement pastes (Fig. 3.6), it appears that the Figure 3.6 Scanning electron micrograph of a fractured
through-solution mechanism is dominant in the early specimen of a 3-day-old Portland cement paste.
stages of cement hydration. At later ages, when the ionic
mobility in the solution becomes restricted, the hydration of Calcium hydroxide crystals are massive, C-S-H crystals
residual cement particle may occur by solid-state reactions. are poorly crystalline and show a fibrous morphology.
 C3Aand C4AF, ettringite becomes unstable and is gradually
3.5.3 Hydration of Aluminates converted into the monosulfate phase, which is the final
product of hydration of Portland cements containing more
The reaction of C3A with water is immediate. Crystalline than 5 percent C3A:
hydrates, such as C3AH6, C4AH19, and C2AH8, are formed
quickly, with liberation of a large amount of heat of C6A S 3 H32 + 2C3A + 22H  3C4A S 3 H18 (3-7)
hydration. Unless the rapid hydration of C3A is slowed
down by some method, Portland cement cannot be used
Since the aluminate-to-sulfate balance in the solution
for most construction applications. This task is generally
phase of a hydrated Portland cement paste primarily
accomplished by the addition of gypsum. Therefore, for
determines whether the setting behavior is normal or not,
practical purposes, it is not the hydration reactions of C3A
various setting phenomena affected by an imbalance in the
alone but the hydration reactions of C3A in the presence of
A/S ratio, which have practical significance in the concrete
gypsum which are important.
construction practice, are illustrated by Fig. 3.7, and are
discussed below:
From the standpoint of hydration of Portland cement, it is
also convenient to discuss the hydration reactions of C3A
Case I. When the rates of availability of the aluminate
and ferroaluminate together because when the latter reacts
ions
with water in the presence of sulfate, the products formed
and the sulfate ions to the solution phase are low, the
are structurally similar to those formed from the hydration
cement paste will remain workable for about 45 min;
of C3A. For instance, depending on the sulfate
thereafter it will start stiffening as the water-filled space
concentration, the hydration of C4AF produces either
begins to get filled with ettringite crystals. Most so-
C6A(F) S 3 H32 or C4A(F) S 3 H18, which, in spite of called normal-setting Portland cements belong to this
differences in chemical composition, have crystal category. The paste becomes less workable between 1
structures that are similar to ettringite and low sulfate, and 2 h after the addition of water, and may begin to
respectively. However, the part played by the solidify within 2 to 3 h.
ferroaluminate compound in the early setting and
hardening reactions of the Portland cement paste depends Case II. When the rates of availability of the aluminate
mainly on its chemical composition and temperature of ions and the sulfate ions to the solution phase are high,
formation. Generally, the reactivity of the ferrite phase is large amount of ettringite form rapidly and cause a
somewhat slower than C3A, but it increases with increasing considerable loss of consistency in 10 to 45 min, with
alumina content and with decreasing temperature of solidification of the paste between 1 and 2 h. Freshly
formation during the clinkering process. In any case, it may produced high-C3A cements containing more than
be noted that the hydration reaction of the aluminates normal amounts of alkali sulfates or calcium sulfate
described below are applicable to both the C 3A phase and hemihydrate are generally characterized by this type of
the ferrite phase in Portland cement although, for the sake behavior.
of simplicity, only C3A is discussed.
Case III. When the amount of reactive C3Ais high but
Several theories have been postulated to explain the the soluble sulfate present is less than required for
mechanism of retardation of C3A by gypsum. According to normal retardation, hexagonal-plate crystals of
one theory, since gypsum and alkalies go into solution monosulfate and calcium aluminate hydrates form
quickly, the solubility of C3A is depressed in the presence quickly and in large amounts causing the cement paste
of hydroxyl, alkali, and sulfate ions. Depending on the to set in less than 45 min after the addition of water.
concentration of aluminate and sulfate ions in the solution, This phenomenon is known as quick set.
the precipitating crystalline product is either
calcium aluminate trisulfate hydrate or the calcium Case IV. When little or no gypsum has been added to
aluminate monosulfate hydrate. In solutions saturated with a ground Portland cement clinker, the hydration of C3A
calcium and hydroxyl ions, the former crystallizes as short is rapid and the hexagonal-plate calcium aluminate
prismatic needles and is also referred to as high-sulfate or hydrates start forming in large amounts soon after the
by its mineralogical name, ettringite. The monosulfate is addition of water, causing almost an instantaneous set.
also called low-sulfate and crystallizes as thin hexagonal This phenomenon, known as flash set, is associated
plates. The relevant chemical reactions may be expressed with large heat evolution and poor ultimate strength.
as follows:
Case V. When the C3A in cement is of low reactivity,
Ettringite: as is the case in partially hydrated or carbonated
cements which have been improperly stored, and at
– 2– 2+
[AlO4] + 3[SO4] + 6[Ca} + aq. the same time a large amount of calcium sulfate
hemihydrate is present in the cement, the solution
 C6A S 3 H32 (3-5) phase will contain a low concentration of aluminate
ions but will quickly become supersaturated with
Monosulfate: respect to calcium and sulfate ions. This situation will
lead to the rapid formation of large crystals of gypsum
– 2– 2+
[AlO4] + [SO4] + 4[Ca} + aq. with a corresponding loss of consistency. The
phenomenon, called false set, is not associated with
 C4A S H18 (3-6) large heat evolution and can be remedied by vigorous
mixing of the cement paste with or without additional
Ettringite is usually the first hydrate to crystallize because water.
of the high sulfate/aluminate ratio in the solution phase
during the first hour of hydration. In normally retarded Although gypsum is added to cement to serve as a
Portland cements, which contain 5 to 6 percent gypsum, retarder, what is known as the optimum gypsum content of
the precipitation of ettringite contributes to stiffening (loss cement is generally determined from standard tests which
of consistency), setting (solidification of the paste), and show maximum cement strength and minimum shrinkage
early strength development. Later, after the depletion of at given ages of hydration. As discussed next, the sulfate
sulfate when the concentration of aluminate ions in the ions contributed to the solution phase by gypsum have a
solution goes up again due to renewed hydration of retarding effect on the hydration of the aluminate
compounds but an accelerating effect on the hydration of aluminates, a side effect is the acceleration of alite
the silicates that are the principal compounds in Portland hydration without which the industrial cements would
cement. Therefore, depending on the composition of a harden at a slower rate.
cement, a specific gypsum content is indicated for optimum
performance of the cement. 3.5.4 Hydration of Silicates

Research has shown that, unlike the suppression of The hydration of C3S and C2S in Portland cement
solubility of the aluminate compounds, the solubility of the produces a family of calcium silicate hydrates which are
calcium silicate compounds is actually increased in the structurally similar but vary widely in calcium/silica ratio
presence of sulfate ions in the solution phase. Typical data and the content of chemically combined water. Since the
on the effect of gypsum addition on the strength structure determines the properties, the compositional
development rate of pure alite cements are shown in Table differences among the calcium silicate hydrates have a
6.3. In conclusion, although the primary purpose of little effect on their physical characteristics.
gypsum in Portland cement is to retard the hydration of

Figure 3.7 Influence of the Aluminate/Sulfate Ratio in the Solution Phase on

Setting Characteristics of Portland Cement Pastes.

The microstructure and properties of calcium silicate Table 3.3 Accelerating Effect of Gypsum on Setting Time,
hydrates formed in Portland cement pastes were described Heat of Hydration and Strength of Alite.
in Lect. No. 2. In general, the material is poorly crystalline
and forms a porous solid which exhibits characteristics of a
rigid gel. In the literature, this gel has sometimes been
referred to as tobermorite gel, after a naturally occurring
mineral of seemingly similar structure. The use of this
name is no longer favored because the similarity in crystal
structures is rather poor. Also, since the chemical
composition of the calcium silicate hydrates in hydrating
Portland cement pastes varies with the water-cement ratio,
temperature, and age of hydration, it has become rather
customary to refer to these hydrates simply as C-S-H, a
notation that does not imply a fixed chemical composition.
On complete hydration the approximate composition of the
material may be assumed as C3S2H3; this composition is
therefore used for stoichiometric calculations. *
Alite cement made by grinding a laboratory preparation of high-
2
purity monoclinic alite to fineness 330 m /kg Blaine. An industrial
The stoichiometric reactions for fully hydrated C3S and C2S Portland cement meeting the requirements of both ASTM Types I
pastes can therefore be expressed as 2
and II, and a fineness of 330 m /g Blaine, was included for
reference purposes.
2C3S + 6H  C3S2H3 + 3CH (3-8) +
ASTM Methods C 266, C 186, and C 109 were used for
determination of setting time, heat of hydration, and compressive
2C2S + 4H  C3S2H3 + CH (3-9) strength, respectively.

In addition to the fact that similar reaction products are

formed on hydration of both the tricalcium silicate and the
dicalcium silicate present in Portland cement, the following
points should be noted.
First, stoichiometric calculations show that the C 3S
hydration would produce 61 percent C3S2H3 and 39
percent calcium hydroxide, whereas the C2S hydration
would produce 82 percent C3S2H3 and 18 percent calcium
hydroxide. As the high specific surface area and,
consequently, the adhesive property of the hydrated
cement paste are essentially due to the formation of the
calcium silicate hydrate, it is to be expected that the
ultimate strength of a high-C3S Portland cement would be
lower than a high-C2S cement. This, indeed, is confirmed
by the data from several research investigations.

Second, if the durability of a hardened cement paste to

acidic and sulfate waters is reduced due to the presence of
calcium hydroxide, it may be expected that a cement
containing a high proportion of C2S will be more durable to
acidic and sulfate environments compared to a cement
containing a high proportion of C3S. This conclusion is also
generally confirmed by laboratory and field experience. Figure 3.8. Heat liberation rate of a Portland cement
From the standpoint of durability to chemical attacks, some paste during setting and early hardening period.
cement standards attempt to limit the maximum
permissible C3S in cement, others recommend the use of
pozzolans in order to remove the excess calcium hydroxide This initial heat evolution ceases quickly (descending
from the hydrated cement paste. Third, it can be calculated portion of peak A) when the solubility of aluminates is
from the above stoichiometric equations that C3S and C2S depressed in the presence of sulfate in the solution. The
require 24 and 21 percent water, respectively, for complete next heat evolution cycle, culminating in the second peak
hydration. after about 4 to 8 h of hydration for most Portland cements,
represents the heat of formation of ettringite (ascending
The stoichiometric equations of C3S and C2S hydration do portion of peak B). Researchers believe that the heat
not tell anything about the reaction rates. From the evolution period includes some heat of solution due to C3S
standpoint of instability of the crystal structure described and heat of formation of C-S-H. The paste of a properly
earlier and the heat of hydration data given below, it is retarded cement will retain much of its plasticity before the
apparent that C3S would hydrate at a faster rate than C2S. commencement of this heat cycle and will stiffen and show
In the presence of gypsum, C3S in fine particles of cement the initial set (beginning of solidification) before reaching
begins to hydrate within an hour of the addition of water to the apex at B, which corresponds to the final set (complete
cement, and thus contributes to the final time of set and the solidification and beginning of hardening).
early strength of a hydrated cement paste. The relatively
quicker rate of C3S hydration in finely ground Portland From analysis of the heat of hydration data on a large
4
cements has become an important factor in the production number of cements, Verbeck and Foster computed the
of high-early-strength Portland cements as will be relative rates of heat evolution due to the four principal
discussed later. compounds of Portland cement (Table 3.4).

3.5.5 Heat of Hydration Table 3.4. Heat of Hydration of Portland

Cement Compounds
The compounds of Portland cement are nonequilibrium
products of high temperature reactions and are therefore in
a high-energy state. When a cement is hydrated, the
compounds react with water to acquire stable, low-energy
states and the process is accompanied by the release of
energy in the form of heat. In other words, the hydration
reactions of Portland cement compounds are exothermic.
The significance of heat of cement hydration in concrete
technology is manifold. The heat of hydration can
sometimes be a hindrance (e.g., mass concrete Since the heat of hydration of cement is an additive
structures), and at other times a help (e.g., winter property, it can be predicted from an expression of the
concreting when ambient temperatures may be too low to type:
provide the activation energy for hydration reactions).
H = aA + bB + cC + dD (3-10)
The total amount of heat liberated and the rates of heat
liberation from hydration of the individual compounds can where H represents the heat of hydration at a given age
be used as indices of their reactivity. As discussed below, and under given conditions; A, B, C, and D are the
the data from heat of hydration studies can be used for percentage contents of C3S, C2S, C3A, and C4AF present
characterizing the setting and hardening behavior of in the cement; and a, b, c, and d are coefficients
cements, and for predicting the temperature rise. representing the contribution of 1 percent of the
corresponding compound to the heat of hydration. The
3
By using a conduction calorimeter, Lerch recorded the values of the coefficients will be different for the various
rate of heat evolution from cement pastes during the ages of hydration.
setting and early hardening period. A typical plot of the
data is shown in Fig. 3.8. For a typical Portland cement, it appears that
approximately 50 percent of the potential heat is liberated
In general, on mixing cement with water, a rapid heat within the first 3 days, and 70 percent within the first 7 days
evolution (ascending portion of peak A) lasting a few of hydration. Type I Portland cements meeting ASTM C150
minutes occurs. This probably represents the heat of Standard Specification generally produce 330 to 370 kJ/kg
solution of aluminates and sulfates. (80 to 90 cal/g) in 7 days.
ASTM C150 contains standard specifications for a low-heat 3.5.7 Effect of Cement Characteristics on Strength and
Portland cement (Type IV) and a moderate-heat Portland Heat of Hydration
cement (modified Type II) with 7-day heat of hydration
limits of 250 kJ/kg (60 cal/g), and 290 kJ/kg (70 cal/g), Since the rates of reactivity of individual Portland cement
respectively. Such Portland cements are no longer readily compounds with water vary considerably, it is possible to
available. Hydraulic cements meeting similar heat of change the strength development characteristics of
hydration requirements, that is, a Type LH (low-heat) cements simply by altering the compound composition. For
cement and a Type MH (moderate-heat) cement can now instance, the early strengths at 3, 7, and 28 days would be
be marketed under a performance specification (ASTM C high if the cement contains relatively large amounts of C 3S
1157) that does not restrict the composition or the and C3A; and the early strength would be low if the cement
constituents of the cement. Blended Portland cements contains a larger proportion of C2S. Also, from theoretical
containing large proportions of pozzolans or slags can considerations (Eqs. (6-8 and 6-9), the ultimate strength of
readily satisfy the performance limits specified by ASTM C a high-C2S cement should be greater than that of a low-
1157. C2S cement. Laboratory studies confirm this (Fig. 3.9a).
Also, as the compound composition of the cement affects
3.5.6 Physical Aspects of the Setting and Hardening the heat of hydration, it is to be expected that cements
Process containing high C2S will not only exhibit slow hardening but
also less heat production (Fig. 3.9b).
The chemical aspects of the hydration reactions of
Portland cement compounds have already been discussed. The rates of strength development and heat evolution can
For application to the concrete construction practice it is also be controlled by controlling the fineness of cement.
desirable to review the physical aspects, such as stiffening, For instance, with a given compound composition, by
setting, and hardening, which are different manifestations making a change in the surface area of the cement from
2
of the ongoing hydration process. 300 to 500 m /kg Blaine, it was possible to increase the 1-,
3-, and 7-day compressive strengths of the cement mortar
Stiffening is the loss of consistency by the plastic cement by about 50 to 100 percent, 30 to 60 percent, and 15 to 40
paste, and is associated with the slump loss phenomenon percent , respectively. Typical data on the influence of
in concrete. It is the free water in a cement paste that is fineness on strength are shown in Fig. 3.9c.
responsible for its plasticity. The gradual loss of free water
from the system as a result of the formation of hydration
products, surface adsorption by poorly crystalline products
such as ettringite and C-S-H, and evaporation causes the
paste to stiffen and, finally, to set and harden.

The term setting refers to the solidification of the plastic

cement paste. The beginning of solidification, called the
initial set, marks the point in time when the paste has
become unworkable. Accordingly, concrete placement,
compaction, and finishing operations are difficult beyond
this stage. The paste does not solidify suddenly; it requires
considerable time to become fully rigid. The time marks the
final set, which should not be too long in order to avoid
delays in the construction process. Almost universally, the
initial and the final setting times are determined by the
(a)
Vicat apparatus, which measures the resistance of a
cement paste of a standard consistency to the penetration
of a needle under a total load of 300 g. The initial set is an
arbitrary time in the setting process which is said to have
been reached when the needle is no longer able to pierce
a 40-mm-deep cement paste pat to approximately 5 to 7
mm from the bottom. The final set is said to be reached
when the needle makes an impression on the surface of
the paste but does not penetrate. ASTM C 150, Standard
Specification for Portland Cement, requires the initial
setting time to be not less than 45 min, and the final setting
time to be not more than 375 min, as determined by the
Vicat Needle (ASTM C 191).

At the final set, Portland cement paste has little or no

strength because it represents only the beginning of the
hydration of C3S, the principal compound present. Once
the C3S hydration starts, the reaction continues rapidly for
several weeks. The progressive filling of void spaces in the
paste with reaction products results in a decrease of
porosity and permeability, and an increase in strength. In
concrete technology, the phenomenon of strength gain with
time is called hardening. Figure 3.9 shows a graphic
presentation of the relation between the chemistry of the
hydration process of a normal Portland cement paste and
the physical phenomena of gradual stiffening, setting, and
hardening with a corresponding decrease of porosity and
permeability.
 (b)

(c)

Figure 3.9 (a) Influence of cement composition (b)

on strength; (b) influence of cement composition
on heat of hydration; (c) influence of cement
fineness on strength.

(c)

Figure 3.10 Influence of compound composition, fineness,

and hydration temperature on heat development in
cement pastes. (0.4 water-cement ratio).
(a) Both the rate and the total amount of heat developed
during the hydration of cement are influenced by the
compound composition, fineness, and temperature of
hydration.

Figure 3.11. (a) Typical rates of formation of hydration products in an ordinary Portland cement paste;
(b) influence of formation of hydration products on setting time, porosity, permeability, and strength of cement paste.
3.6— TYPES OF PORTLAND CEMENT Type IIIA. Air-entraining Type III cement.
Type IV. For use when a low heat of hydration is
A summary of the main characteristics of the principal desired. As C3S and C3A produce high heats of
compounds in Portland cement is shown in Table 3.5. hydration, and C2S produces much less heat, the
From the knowledge of relative rates of reactivity and specification calls for maximum limits of 35 and 7
products of hydration of the individual compounds it is percent on C3S and C3A, respectively, and requires a
possible to design cements with special characteristics minimum of 40 percent C2S.
such as high early strength, low or moderate heat of Type V. For use when high sulfate resistance is
hydration, and high or moderate sulfate resistance. desired. The specification calls for a maximum limit of
Accordingly, ASTM C 150, Standard Specification for 5 percent on C3A to be applied when the sulfate
Portland Cement, covers the following eight types of expansion test is not required.
Portland cement:
It should be noted that the hydration product of cements
Type I. For use when the special properties specified with more than 5 percent potential C3A, as calculated by
for any other type are not required. No limits are Bogue equations, contains monosulfate hydrate which is
imposed on any of the four principal compounds. unstable when exposed to a sulfate solution. Ettringite is
the stable product in a sulfate environment, and conversion
Type IA. Air-entraining Type I cement, where air of the monosulfate to ettringite is generally associated with
entrainment is desired (e.g., for making frost-resisting expansion and cracking.
concrete).
Although ASTM C 150 covers the production and use of
Type II. For general use, especially when moderate air-entraining Portland cements, concrete producers prefer
sulfate resistance is desired. The C3A content of the cements without entrained air because the application of
cement is limited to a maximum of 8 percent. Also, an air-entraining admixtures during concrete manufacture
additional maximum limit of 58 percent of the sum of offers better control for obtaining the desired amount and
C3S and C3A applies when a moderate heat of distribution of air in the product. Consequently, there is little
hydration is desired and test data for the heat of demand for the air-entrained cements. Similarly, low heat
hydration are not available. Portland cement is no longer made in the United States
because the use of mineral admixtures in concrete offers,
Type IIA. Air-entraining Type II cement, where air in general, a less expensive way to control the temperature
entrainment is desired. rise. It may be noted that more than 90 percent of the
hydraulic cements produced in the country are ASTM Type
Type III. For use when high early strength is desired. I and Type II Portland cements, approximately 3 percent
To ensure that the high strength is not due mainly to are ASTM Type III Portland cement, and the rest are
the hydration products of C3A, the specification limits special cements such as oil-well cement. The setting and
the C3A content of the cement to a maximum of 15 hardening characteristics, fineness, and compound
percent. It may be noted from Fig. 3.11 that generally composition of ASTM Type I and Type II cements are very
the high early strength of the Type III Portland cement similar except that the latter has a maximum 8 percent limit
is partly due to the higher specific surface that is on the C3A content. ASTM Type III is similar in compound
2
approximately 500 m /kg Blaine, instead of 330 to 400 composition to ASTM Type I except that the former is more
2
m /kg typical for Type I Portland cement. finely ground in order to achieve higher strength at early
ages. Typical compound compositions of the commonly
available Portland cements are shown in Table 3.6.

Table 3.5 Typical Compound Composition of Various Types of Portland Cement Compound composition range

Table 3.6 Principal Compounds of Portland Cement and their Characteristics

Important features of the physical requirements according result of their energy saving and clinker saving potential.
to ASTM C 150, with reference to methods of testing, are Also, in certain respects, the blended cements perform
summarized in Table 3.7. The test methods and better than Portland cement. Presently, the production of
specifications are useful mainly for the purpose of quality blended Portland-limestone cements, slag cements, and
control of cement; they must not be used to predict pozzolan cements in Europe and Asia has exceeded the
properties of concrete which, among other factors, are production of pure Portland cements. In the United States
greatly influenced by the water-cement ratio, curing the production of blended cements is still in infancy;
temperature, and cement-admixture interactions. For however, there is a growing interest to use pozzolanic
instance, compared to the standard test conditions, the (e.g., fly ash) and cementitious materials (e.g., ground
time of set of a cement will increase with increasing water- blast-furnace slag) as mineral admixtures in concrete. The
cement ratio, and will decrease with increase in the curing composition and properties of pozzolanic and cementitious
temperature. materials are described in Lecture No. 8.

Many cement standards of the world are similar to ASTM C ASTM C 595, Standard Specification for Blended Hydraulic
150 but vary in minor details. For example, some cement Cements, covers eight classes of cements, but commercial
standards do not differentiate between the ASTM Types I production is limited to Portland blast furnace slag cement
and II Portland cements. Also, most cement standards do (Type IS), and Portland pozzolan cement (Type IP).
not favor the ASTM C 151 autoclave expansion test and According to the Specification, Type IS cement shall
the C 150 soundness specification, because the hydration consist of an intimate and uniform blend of Portland
behavior of Portland cement is considerably distorted cement and fine granulated blast-furnace slag in which the
under the autoclaving conditions, and because a slag constituent is between 25 and 70 percent of the mass
correlation has never been demonstrated between the of Portland blast-furnace slag cement. Blast-furnace slag is
maximum permissible expansion according to the test and a nonmetallic product consisting essentially of silicates and
5
the soundness of cement in service. Instead, the Le aluminosilicates of calcium and other bases; granulated
Châtelier’s test, which involves exposure of a cement paste slag is the glassy or noncrystalline product which is formed
to boiling water (not autoclaving conditions), is preferred. when molten blast-furnace slag is rapidly chilled, as by
immersion in water. Type IP cement shall consist of an
intimate and uniform blend of Portland cement (or Portland
3.7—SPECIAL HYDRAULIC CEMENTS blast-furnace slag cement), and fine pozzolan in which the
pozzolan content is between 15 and 40 percent of the
3.7.1 Classification and Nomenclature mass of the total cement. A pozzolan is defined as a
siliceous or siliceous and aluminous material, which in itself
Portland cements do not satisfy all the needs of the possesses little or no cementing property but will, in a
concrete industry; therefore, special cements have been finely divided form and in the presence of moisture,
developed to meet certain needs. Compared to Portland chemically react with calcium hydroxide at ordinary
cement, their volume is small, however structural temperatures to form compounds possessing cementitious
engineers should be familiar with special cements and their properties.
unique characteristics.
Compared to pozzolans, finely ground granulated blast-
With one notable exception, the special hydraulic cements furnace slag is self-cementing; that is, it does not require
may be considered as modified Portland cements in the calcium hydroxide to form cementitious products such as
sense that they are made either by altering the compound C-S-H. However, when granulated blast-furnace slag
composition of Portland cement clinker, or by blending hydrates by itself, the amount of cementitious products
certain additives with formed and the rates of formation are insufficient for the
use of the material by itself for structural applications.
Portland cement, or by doing both. A clear classification of When used in combination with Portland cement, the
the special cements is difficult; however, in the American hydration of slag is accelerated due to the presence of
practice the use of the term blended Portland cement is calcium hydroxide and gypsum. During the hydration of
confined to blends of Portland cements with either rapidly Type IS cement, some calcium hydroxide produced by the
cooled blast-furnace slag or pozzolanic material such as fly Portland cement component is consumed by the slag
ash. component of the cement. Due to general similarity in the
hydration reaction and microstructure of the hardened
Other special cements are generally classified under the Type IS and Type IP cement pastes, it is desirable to
term modified Portland cement because they are made by discuss the hydration characteristics and properties of the
modification of the compound composition of Portland two types of cement together.
cement clinker. The hydraulic calcium silicates, C3S and
C2S, continue to be the primary cementitious constituents; 3.7.3 The Pozzolanic Reaction and its Significance.
only the aluminate and the ferrite phases are suitably
altered to obtain the desired properties. With respect to the main C-S-H forming reaction, a
comparison between Portland cement and Portland-
The exception to the blended and modified Portland pozzolan cement is useful for the purpose of understanding
cements is the calcium aluminate cement, which does not the reasons for differences in their behavior:
derive its cementing property from the presence of
hydraulic calcium silicates. Noteworthy special cements, Portland Cement:
their compositions, and major applications are summarized
in Table 3.8. Important features, hydration characteristic f a st
and properties of the cements listed in the table, are C3S + H    C-S-H + CH (3-11)
discussed next.
Portland-Pozzolan Cement:
3.7.2 Blended Portland Cements
sl ow
Pozzolan + CH + H    C-S-H (3-12)
Cost saving was probably the original reason for the
development of blended Portland cements. However, the
impetus to rapid growth in the production of blended
cements in many countries in Europe and Asia came as a
Table 3.7 Principal Physical Requirements and Essential Features of ASTM Test Methods for Portland Cement

*
The 3-day and the 7-day minimum compressive strength shall be 6.0 MPa (1000 psi) and 11.7 MPa
(1700 psi), respectively, when the optional heat of hydration or the chemical limits on the sum of C3S
and C3A are specified.
+
When specifically requested, minimum 28-day strength values for Types I and II cements shall be
27.6 MPa (4000 psi).

The reaction between a pozzolan and calcium hydroxide is

called the pozzolanic reaction. The technical advantage of
using pozzolan cements and slag cements is derived
mainly from three features of the pozzolanic reaction. First,
the reaction is slow; therefore, the rates of heat liberation
and strength development will be accordingly slow.
Second, the reaction is lime-consuming instead of lime
producing, which has an important bearing on the durability
of the hydrated paste in acidic environments. Third, pore
size distribution studies of hydrated IP and IS cements
have shown that the reaction products are very efficient in
filling up capillary spaces, thus improving the strength and
impermeability of the system. Pore size distribution data of
Portland pozzolan cements containing a Greek pozzolan
(Santorini earth) are shown in Fig. 3.12, and a
diagrammatic representation of the pore refinement Figure 3.12 Diagrammatic representation of
process associated with the pozzolanic reaction is shown well-hydrated cement pastes made with a
in Fig. 3.12. In addition to contributing reactive silica, slags Portland pozzolan cement. Compared to a
and pozzolans also contribute reactive alumina, which, in Portland cement paste (see Fig. 2.6 for
the presence of calcium hydroxide and sulfate ions in the identification of the phases present) it is shown
system, also forms cementitious products such as C 4AH13, here that, as a result of the pozzolanic reaction,
AFt, and AFm. Properties of Types IP and IS vary widely the capillary voids are either eliminated or
depending on the curing conditions and the proportions as reduced in size, and crystals of calcium
well as physical-chemical characteristics of the constituent hydroxide are replaced with additional C-S-H of
materials present. The properties described below may a lower density.
therefore be considered as indicative of a general trend.
 Table 3.8 Special Hydraulic Cements: Their Composition and Uses

On the basis of scanning electron microscopic and pore- 3.7.4 Heat of Hydration.
size distribution studies of hydrated cement pastes both
with and without a pozzolan, it is possible to conclude that Figure 3.13 shows the effect of increasing amounts of
there are two physical effects of the chemical reaction pozzolan on the heat of hydration of Portland-pozzolan
between the pozzolanic particles and calcium hydroxide: (i) cements. Type IS cements containing more than 50
pore-size refinement and (ii) grain-size refinement. The percent slag show approximately 60 cal/g heat of hydration
formation of secondary hydration products (mainly calcium at 7 days, which is comparable to 30 percent pozzolan
silicate hydrates) around the pozzolan particles tends to fill cements.
the large capillary voids with a microporous, low-density
material. The process of transformation of a system
containing large capillary voids into a microporous product
containing numerous fine pores is referred to as pore-size
refinement. Also, nucleation of calcium hydroxide around
the fine and well distributed particles of pozzolan will have
the effect of replacing the large and oriented crystals of
calcium hydroxide with numerous, small, and less oriented
crystals plus poorly crystalline reaction products. The
process of transformation of a system containing large
grains of a component into a product containing smaller
grains is referred to as grainsize refinement. Both the pore
size and the grain-size refinement processes strengthen
the cement paste.

From the standpoint of impermeability and durability the

effects of the pozzolanic reaction are probably more
important in concrete than in the hydrated cement paste.
As discussed in Lecture No. 5, the permeability of concrete Figure 3.13 Effect of substituting an Italian natural
is generally much higher than the permeability of cement pozzolan on the heat of hydration of Portland
paste because of microcracks in the cement paste- cement.
aggregate interfacial transition zone.
3.7.5 Strength Development. pastes of cements containing 30 mass percent of a Greek
volcanic ash. Also, a 1-year-old paste of the reference
Figure 14 shows strength development rates up to 30 days Portland cement contained 20 percent calcium hydroxide,
in cements containing 10, 20, or 30 percent pozzolan, and whereas there was only 8.4 percent calcium hydroxide in a
Figure 15 shows strength development rates up to 1 year similarly hydrated paste of the cement containing 30 mass
days in cements containing 10, 20, or 30 percent pozzolan. percent of the Greek pozzolan.
In general, pozzolan cements are somewhat slower than
slag cements in developing strength; whereas the slag in
Type IS cements usually makes a significant contribution to
the 7-day strength, a Type IP cement containing an
ordinary pozzolan shows strength gain from the pozzolanic
constituent only after 7 days of hydration. When
adequately reactive materials are used in moderate
proportion (e.g., 15 to 30 percent pozzolan or 25 to 50
percent slag), and moist curing is available for long
periods, the ultimate strengths of Types IP and IS cements
are higher than the strength of the reference Portland
cement without the blending materials. This is because of
the pore refinement associated with the pozzolanic
reaction and the increase in C-S-H and other hydration
products at the expense of calcium hydroxide.

Figure 3.15 Strength of blended cement

containing a pozzolan

Type IS cements behave in a similar manner. Figure 3.17

shows the effect of increasing the slag content on the
amount of calcium hydroxide in Portland blast-furnace slag
cements at 3 and 28 day after hydration. At about 60
percent slag content, the amount of calcium hydroxide
becomes so low that even slags containing large amounts
of reactive alumina can be safely used to make sulfate-
resisting cements. It may be recalled (see Lecture No. 5)
that the rate of sulfate attack depends on the permeability,
and the amount of calcium hydroxide and reactive alumina
phases present. Some high-alumina slags and fly ashes
tend to increase the content of calcium aluminate hydrates
Figure 3.14 Effect of s and monosulfate (which are vulnerable to sulfate attack) in
the hydrated cement paste. Because the presence of
3.7.6 Durability significant amounts of calcium hydroxide in the system is
necessary for the ettringite-related expansion to occur,
Compared to Portland cement, the superior durability of both laboratory and field experience show that IS cements
Type IP cement to sulfate and acidic environments is due containing 60 to 70 percent or more slag are highly
to the combined effect of higher impermeability, and lower resistant to sulfate attack, irrespective of the C 3A content of
calcium hydroxide content of the hydrated cement paste Portland cement and the reactive alumina content of the
(Fig. 3.16). In one investigation it was found that, slag.
compared to Portland cement, the depth of penetration of
water was reduced by about 50 percent in 1-year-old

Figure 3.16 Changes in pore size distribution of cement pastes with varying pozzolan content.

In a laboratory investigation Portland pozzolan cements containing 10, 20, or 30 weight percent of a Greek
natural mineral pozzolan were hydrated at a given water-cement ratio, and the pore size distributions were
determined at 28, 90, and 365 days by mercury penetration porosimetry. With 20 or 30 percent pozzolan content,
no large pores (> 0.1 m) were found in the pastes cured for 1 year. Water permeability tests showed that these
cement pastes were much more impermeable than the reference Portland cement paste.
 sulfoaluminate-type clinker is a modified Portland cement
clinker containing significant amounts of C4A3S and C S

Figure 3.17 Effect of curing age on the calcium

hydroxide content of a cement-sand mortar made
with a Portland-pozzolan cement.
Figure 3.18 Influence of pozzolan on
In the case of Portland-pozzolan cement the reduction of alkali-aggregate expansion.
calcium hydroxide in the hydrated cement paste, which is
due to both the dilution effect and the pozzolanic reaction, in addition to the principal cementitious compounds such
is one reason that concrete made from such cements as C3S and C2S. To achieve a better control of expansion
tends to show superior resistance to sulfate and acidic in industrial expansive cements, it is customary to blend a
environments. Initially, with curing the calcium hydroxide suitable proportion of the sulfoaluminate clinker with
content of the cement increases due to hydration of the normal Portland cement clinker.
Portland cement present; however, later it begins to drop
with the progress of the pozzolanic reaction. Depending on Type K expansive cement used in the U.S. construction
curing conditions, Portland-pozzolan cement products practice is covered by ASTM Standard C 845. ASTM C
contain higher calcium hydroxide because the reactive 845 covers two other expansive hydraulic cements which
pozzolan content may range between 20 to 30 percent in a also derive their expansion characteristic from ettringite but
cement containing 40% pozzolan. are not produced in the United States. The cements differ
from the Type K cement and from each other with respect
In regard to the deleterious expansion associated with the to the source of aluminate ions for ettringite formation.
alkali-aggregate reaction, combinations of high-alkali Type M expansive cement is a mixture of Portland cement,
Portland cement with pozzolan or slag are generally known calcium aluminate cement (with CA is the principal
to produce durable products (Fig. 3.18). Sometimes the compound), and calcium sulfate. Type S expansive cement
alkali content of pozzolans and slags are high, but if the is composed of a very high C3A Portland cement
alkali-containing mineral is not soluble in the high-pH approximately 20 percent C3A) and large amounts of
environment of Portland-cement concrete, the high-alkali calcium sulfate. The stoichiometry of the expansive
content of the blended cement generally does not cause reactions in the three cements can be expressed as
any problem. follows:

3.7.7 Expansive Cements Type K:

Expansive cements are hydraulic cements which, unlike C4A3S + 8 C S + 6CH + 90H
Portland cement, expand during the early hydration period  3C6AS3H3 2 (3-13)
after setting. Large expansion occurring in an unrestrained
cement paste can cause cracking; however, if the
expansion is properly restrained, its magnitude will be Type M:
reduced and a prestress will develop. CA + 3 C S + 2CH + 30H
When the magnitude of expansion is small such that the  C6AS3H3 2 (3-14)
prestress developed in concrete is on the order of 15 to
100 psi (0.1 to 0.7 MPa), which is usually adequate to Type S:
offset the tensile stress from restrained drying shrinkage,
the cement is known as shrinkage compensating. Cements C3A + 3 C S + 32H  C6AS3H3 2 (3-15)
of this type have proved very useful for making crack-free
pavements and slabs. When the magnitude of expansion is The CH in the above reactions is provided by the Portland
large enough to produce prestress levels on the order of cement hydration although Type K clinker generally contain
1000 psi (6.9 MPa), the cement is called self-stressing and some free CaO. Initially developed by the Onoda Cement
can be used for the production of chemically prestressed Company of Japan, the expansive Portland cement
concrete elements. deriving its expansion from hard-burnt CaO is called Type
O expansive cement.
Formation of ettringite and hydration of hard-burnt CaO are
the two phenomena known to cement chemists that can Compared to Portland cements, the ettringite-forming
cause disruptive expansion in concrete (Lecture No. 5). expansive cements are quick setting and prone to suffer
Both phenomena have been harnessed to produce rapid slump loss. However, they show excellent workability.
expansive cements. The cement produced by grinding a These properties can be anticipated from the large
sulfoaluminate-type clinker is called Type K expansive amounts of ettringite formed and the water-imbibing
cement. Developed originally by Alexander Klein of the characteristic of the ettringite. Other properties of
University of California at Berkeley in the 1960s, the
expansive cement concretes are similar to Portland cement In the precast concrete industry, quick turnover of forms is
concrete except durability to sulfate attack. Type K an economic necessity. Rapid setting and hardening
shrinkage-compensating cements made with blending cements should have a considerable appeal to the
ASTM Type II or Type V Portland cement show excellent construction industry because under normal curing
durability to sulfate attack because they contain little temperatures (i.e., without steam curing) they are capable
reactive alumina or monosulfate after hydration. Types M of developing compressive strengths of 15 and 25 MPa
and S cement products usually contain significant amounts within 8 and 24 h, respectively, with about 50 MPa ultimate
of compounds that are vulnerable to sulfate attack and strength. A belite-ferrite-sulfoaluminate type cement with a
therefore are not recommended for use in sulfate potential compound composition of 50 percent C 2S, 30
environments. A review of the properties percent C4A3S and C4AF, and 20 percent C S gave 15.6,
and applications of expansive cement concrete is included
28.3, 35.7, and 54 MPa compressive strength at 8-h, 1-d,
in Lecture No. 12.
7-d, and 120-day, respectively. This is truly an energy-
saving cement because the clinker formation temperature
3.7.8 Rapid Setting and Hardening Cements
was 250C lower than the temperatures normally used for
7
Portland cement clinker manufacture.
It may be noted that ASTM Type III cement is rapid
hardening (i.e., high early strength) but not rapid setting
3.7.9 White and Colored Cements
because the initial and final setting times of the cement are
generally similar to Type I Portland cement. For
The universally gray color of Portland cement products
applications such as emergency repair of leaking joints and
limits an architect’s opportunity for creating surfaces with
shotcreting, hydraulic cements are needed that not only
aesthetic appeal. A white cement, with exposed-aggregate
are rapid hardening but also rapid setting. Setting times as
finish, can be useful in creating desired aesthetic effects.
low as 10 minutes can be achieved by using mixtures of
Furthermore, by adding appropriate pigments, white
either Portland cement and plaster of Paris (CaSO4  ½
cement can be used as a base for producing cements with
H2O) or Portland cement and calcium aluminate cement.
varying colors.
The durability and ultimate strength of the hardened
product are generally low.
White cement is produced by pulverizing a white Portland-
cement clinker. The gray color of ordinary Portland-cement
During the 1970s, a new generation of cements were
clinker is generally due to the presence of iron. Thus by
developed which derive rapid setting and hardening
lowering the iron content of clinker, light-colored cements
characteristics from ettringite formation. After the initial
can be produced. When the total iron in clinker
rapid hardening period, these cements continue to harden
corresponds to less than 0.5 percent Fe2O3, and the iron is
subsequently at a normal rate due to the formation of C-S-
held in the reduced Fe2O3 state, the clinker is usually white
H from hydraulic calcium silicates.
(see the story below). These conditions are achieved in
cement manufacturing by using iron-free clay and
Regulated-set cement, also called Jet cement in Japan, is
carbonate rock as raw materials, special ball mills, with
manufactured under patents issued to the U.S. Portland
ceramic liners and balls for grinding the raw mix, and clean
Cement Association. Using a modified Portland cement
fuel such as oil or gas for production of clinker under a
clinker containing mainly alite and a calcium
reducing environment in the high temperature zone of the
fluoroaluminate (11CaO  7Al2O3  CaF2), a suitable cement rotary kiln. Consequently, white cements are
proportion of the clinker is blended with normal Portland approximately three times as expensive as conventional
cement clinker and calcium sulfate so that the final cement Portland cement.
contains 20 to 25 percent of the fluoroaluminate compound
and about 10 to 15 percent calcium sulfate. The cement is Colored cements fall into two groups; most are derived
generally very fast setting (2 to 5 min setting time) but the from the addition of a pigment to white cement, but some
setting time can be retarded by using citric acid, sodium are produced from clinkers having the corresponding
sulfate, calcium hydroxide, and other retarders. colors. A buff-colored cement marketed in the United
States under the name warm tone cement is produced
The high reactivity of the cement is confirmed by the high from the clinker made from a Portland cement raw mix
heat of hydration (100 to 110 cal/g at 3 days), and over containing a higher iron content (approximately 5 percent
1000 psi (6.9 MPa) compressive strength (ASTM C 109 Fe2O3) than normal, and processed under reducing
mortar) at 1 h after hydration. The ultimate strength and conditions.
other physical properties of the cement are comparable to
those of Portland cement except that due to the high For producing colored cements with pigment, it should be
content of the reactive aluminate, the sulfate resistance is noted that not all the pigments that are used in the paint
poor. Studies at the concrete laboratory of the U.S. Army industry are suitable for making colored cements. To be
Engineer Waterways Experiment Station6 have shown that suitable, a pigment should not be detrimental to the setting,
the high heat of hydration of the regulated-set cement can hardening, and durability characteristics of Portland
help produce concrete with adequate strength even when cement, and should produce durable color when exposed
the concrete is placed and cured at temperatures as low as to light and weather. Red, yellow, brown, or black cements
15F (–9.5C). can be produced by intergrinding 5 to 10 weight percent
iron-oxide pigments of the corresponding color with a white
In addition to regulated set cements, two other modified clinker. Green and blue-colored cements can be made by
Portland cements derive their rapid setting and hardening using chromium oxide and cobalt blue, respectively.
characteristics from the formation of large amounts of
ettringite during the early hydration period. With the very 3.7.10 Calcium Aluminate Cement
high-early-strength (VHE) cement, C4A3S is the main
source of aluminate for the ettringite formation whereas Compared to Portland cement, calcium aluminate cement
with high-iron cement (HIC) both C4A3S and a reactive (CAC) possesses many unique properties, such as high
early strength, ability to harden even under low
C4AF provide the aluminate ions. Although there are temperature conditions, and superior durability to sulfate
certain basic differences in their composition, both cement attack. However, several structural failures due to gradual
types exhibit setting time and strength development rates strength loss with concrete containing
that are suitable for emergency repair jobs and for
application to precast and prestressed concrete products.
CAC have been instrumental in limiting the use of this
cement for structural applications. In most countries, now
CAC is used mainly for making castable refractory lining for
high-temperature furnaces.

According to ASTM C 219 definitions, calcium aluminate

cement is the product obtained by pulverizing calcium
aluminate cement clinker; the clinker is a partially fused or
a completely fused product consisting of hydraulic calcium
aluminates. Thus unlike Portland and modified Portland
cements, in which C3S and C2S are the principal cementing
compounds, CAC contains monocalcium aluminate (CA)
as the principal cementing compound with C12A7, CA,
C2AS,  C2S, and Fss as minor compounds. Typically, the
chemical analysis of ordinary CAC corresponds to
approximately 40 percent Al2O3 and some cements contain
even higher alumina content (50 to 80 percent); therefore,
this cement is also called high-alumina cement (HAC).
Bauxite, a hydrated alumina mineral, is the commonly used
Figure 3.19 (a) Strength development rates for various
source of alumina in raw materials for the manufacture of
cements at normal temperature; (b) effect of low
CAC. Most bauxite ores contain considerable amount of
curing-temperatures on the strength of high-alumina
iron as an impurity that accounts for the 10 to 17 percent
cement concrete.
iron (expressed as Fe2O3) usually present in ordinary CAC.
This is why, unlike Portland cement clinker, the CAC
Calcium aluminate or high-alumina cements are able to
clinker is in the form of a completely fused melt that
develop very high strengths in relatively short periods of
requires a specially designed furnace. This is also the
time. Unlike portland cements, they can develop high
reason why in France and Germany the cement is called strengths even at lower than normal temperatures.
ciment fondu and tonerdeschmelz zement, respectively.
CAH10 and C2AH8 phases tend to convert to the cubic
CAC cements meant for making very high-temperature
C3AH6. As a consequence of the CAH10–C3AH6
furnace lining, contain very low iron and silica, and can be
conversion, a hardened CAC paste would show more than
made by sintering in a rotary kiln. Like Portland cement,
50 percent reduction in the volume of solids, which causes
the properties of CAC are dependent on the hydration
an increase in porosity (Fig. 3.20a) and a loss in strength
characteristics of the cement and the microstructure of the
associated with this phenomenon (Fig. 3.20b).
hydrated cement paste. The principal cement compound is
CA which usually ranges between 50 and 60 percent.
Although CAC products have setting times comparable to
ordinary Portland cement, the rate of strength development
at early ages is quite high due to the high reactivity of CA.
Within 24 h of hydration, the strength of a normally cured
CAC concrete can attain values equal to or exceeding the
7-day strength of ordinary Portland cement (Fig. 3.19a).
Also, the strength gain characteristic under subzero curing
condition (Fig. 3.19b) is much better than with Portland
cement; hence the material is quite attractive for cold
weather applications. It may be noted that the rate of heat
liberation from a freshly hydrated CAC can be as high as 9
cal/g per hour, which is about three times the rate with
high-early strength Portland cement.

The composition of the hydration products shows a time-

temperature dependency; the low-temperature hydration
product (CAH10) is thermodynamically unstable, especially
in warm and humid storage conditions, under which a more
stable compound, C3AH6, is formed (see the equation on
page 246). Laboratory and field experience with CAC
concrete show that on prolonged storage the hexagonal

Figure 3.20 Scanning electron micrograph of a partially

converted calcium aluminate cement system; (b)
influence of water-cement ratio on the long time
strength of calcium aluminate cement concretes.
Calcium aluminate cement concretes are generally not that prescribe their blending constituents, their proportions
recommended for structural use. This is because the and physical characteristics.
principal hydration product, CAH10, is unstable under
ordinary conditions. It gradually transforms into a stable Although national standards are constantly under review, it
phase, C3AH6, which has a cubic structure and is denser. seems that the customary minor revisions are no longer
The CAH10-to-C3AH6 conversion is associated with a large sufficient to meet the needs of a rapidly changing world. As
increase in porosity and therefore a corresponding a result, worldwide, the standards specifications for cement
decrease in strength. are undergoing fundamental change that is reflected by
recent developments in Europe and North America, as
Formerly, it was assumed that the strength-loss problem in described below.
concrete could be ignored when low water-cement ratios In 1992, all member states of the European Union decided
were used, and the height of casting was limited to reduce to establish a single market for their products. As cement is
the temperature rise due to heat of hydration. The data in one of their most important construction products, the
Fig. 6.20b show that this may not be the case. The real harmonization of the national standards was a formidable
problem is not that the residual strength is inadequate for task which was accomplished in April 2002 with the release
structural purposes but that, as a result of the increase in of EN 197 - a single standard to replace earlier standards
porosity, the resistance to atmospheric carbonation and to and certification codes for all types of Portland and
corrosion of the embedded steel in concrete is reduced. blended-Portland cements throughout Europe. EN 197-1
From hydration reaction of CAC, it may be noted that there outlines the specification requirements for 27 different
is no calcium hydroxide in the hydration product; this cements that are classified into five main cement types,
feature also distinguishes CAC from Portland cement and described as follows:
is the reason why CAC concrete shows excellent
resistance to acidic environments (4 to 6 pH), seawater, 1. CEM I covers traditional Portland cements
and sulfate waters. As discussed below, the absence of comprising at least 95 percent Portland-cement clinker
calcium hydroxide in hydrated CAC is also beneficial for and up to 5 percent additional constituents (such as
the use of the material for making high-temperature gypsum).
concrete.
2. CEM II covers 19 varieties of blended Portland
In practice, the use of Portland cement for concrete cements containing at least 65 percent Portland-
exposed to high temperature is rather limited to about cement clinker. A letter notation identifies the blending
500C, because at higher temperatures the free CaO constituents that include blast furnace slag, siliceous
formed on decomposition of calcium hydroxide would fly ash, calcareous fly ash, natural uncalcined
cause the concrete to become unsound on exposure to pozzolan, natural calcined pozzolan, burnt shale,
moist air or water. Not only does CAC not produce any limestone, and silica fume. Each cement type is
calcium hydroxide on hydration but also, at temperatures available either with 6 to 20 percent or 21 to 35 percent
above 1000C, CAC is capable of developing a ceramic of the blending constituent by mass except the silica-
bond, which is as strong as the original hydraulic bond. fume cements, which shall contain 6 to 10 percent
The green or the unfired strength of the CAC concrete silica fume.
drops considerably during the first-heating cycle due to the
CAH10-to-C3AH6 conversion phenomenon. With a high 3. CEM III covers three varieties of blended Portland-
cement content of the concrete, however, the green slag cements containing more than 35 percent
strength may be adequate to prevent damage until the granulated blastfurnace slag, namely 36 to 65 percent,
strength increases again due to the development of the 66 to 80 percent, and 81 to 95 percent slag.
ceramic bond (Fig. 3.21).
4. CEM IV covers two Portland-pozzolan cements
containing 11 to 35 percent or 36 to 55 percent
pozzolan.

5. CEM V covers two composite Portland cements

containing either 36 to 60 percent or 61 to 80 percent
of a mixture of blending components, namely, blast-
furnace slag, fly ash, and other pozzolans.

EN 197-1 also provides six strength grades according to

which the cements may be manufactured for marketing.
Besides the three customary strength grades, 32.5, 42.5,
and 52.5 (minimum 28-day compressive strength, MPa), a
cement may also be classified as a rapid-hardening or
normal-hardening on the basis of its early strength
characteristics.

The American Society of Testing Materials provides for

eight types of Portland cements (covered by ASTM
Standard C 150) and eight types of blended Portland
cements (covered by ASTM Standard C 595), which
Figure 3.21 Effect of temperature rise on strength of
contain restrictions on chemical composition, physical
calcium aluminate cement concretes.
properties, and characteristics as well as proportion of
blending materials. As with CEM II of EN197, ASTM
cement specifications are being amended to permit the use
3.8— TRENDS IN CEMENT SPECIFICATIONS
of limestone as a blending material in blended Portland
cements. Due to the cumbersome, prescriptive,
Most countries in the world produce a variety of hydraulic
requirements hardly any blended cements meeting the
cements according to their national standards. Usually,
ASTM C 595 requirements are being manufactured in the
there are separate specifications governing Portland
United States. Instead, blending materials are added at the
cements and different types of blended Portland cements
ready-mixed concrete batching plant to produce concrete
mixtures meeting certain performance standards. With References.
regard to the ASTM Standard C 150 covering Portland
cements, a 1998 survey of the U.S. cement manufacturers 1. Lea, F.M. The Chemistry of Cement and Concrete,
conducted by the Portland Cement Association shows that, Chemical Publishing Company, I New York, pp. 317–
in general, the cement industry is making only one type of 337,1971.
cement-clinker which meets the requirements of the Type I, 2. Brunauer, S., and L.E. Copeland, The Chemistry of
II, and III cements, except that in the case of Type II Concrete, Sci. Am., April 1964.
cement, the C3A content is somewhat lower than 8 percent. 3. Lerch, W., Proceedings of the American Society for
With all three cement types, the mean compound Testing and Materials, Vol. 46, p. 1252, 1946.
composition was 56 percent C3S and 17 percent C2S. The 4. Verbeck, G.J., and C.W. Foster, Proceedings of the
mean Blaine fineness for Type I and II cements was 380 American Society for Testing and Materials, Vol. 50, p.
2 2
m /kg, whereas it was 547 m /kg for the Type III cement. 1235, 1950.
5. Mehta, P.K., ASTM STP 663, pp. 35–60, 1978.
In 1992, a performance-based standard for blended 6. Hoff, G.C., B.J. Houston, and F.H. Sayler, U.S. Army
hydraulic cements, C 1157, was issued by ASTM. Unlike, Engineer Waterway Experiment Station, Vicksburg,
ASTM C 595, this specification contains no restrictions MS, Miscellaneous Paper C-75-5, 1975.
whatsoever on the composition of blended cements or the 7. Mehta, P.K., World Cement Technology, pp. 166–
proportion of their constituents. Also, there are no 177, May 1980.
requirements on the physical-chemical properties of the 8. Tennis, P.D., Concr. Tech. Today, Vol. 20, No. 2,
constituents. In 1998, ASTM C 1157 was amended to Portland Cement Association, August 1999.
include Portland cements. Thus, this is a performance-
based cement standard that covers all hydraulic cements. ///Prepared by Sir Anacta..
ASTM C 1157 classifies cements by type based on specific
performance requirements such as general use, high-early
strength, resistance to attack by sulfates, and heat of
hydration. The six cement types conforming to this
specification, along with some of the key requirements are
as follows:

1. Type GU—General Use Hydraulic Cement.

Minimum compressive strength 10 and 17 MPa at age
3 and 7 days, respectively.

2. Type HE—High Early Strength. Minimum

compressive strength 10 and 17 MPa at age 1 and 3
days, respectively.

3. Type MS—Moderate Sulfate Resistance. 0.1

percent maximum expansion in 6 months with mortar
bars immersed in a standard sulfate solution (ASTM C
1012)

4. Type HS—High Sulfate Resistance. 0.05 percent

maximum expansion in 6 months with mortar bars
immersed in a standard sulfate solution (ASTM C
1012)

5. Type MH—Moderate Heat of Hydration. 290 kJ/kg

(70 cal/g) max., heat of hydration in 7 days

6. Type LH—Low Heat of Hydration. 250 kJ/kg (60

cal/g) max., heat of hydration in 7 days

The performance-based cement standards, like ASTM C

1157, are expected to play a major part in the future
development of multi-component hydraulic cements
containing large amounts of industrial by-products and a
correspondingly small proportion of Portland cement
clinker. The manufacturing process for Portland cement
clinker is not only energy-intensive but also produces large
amounts of CO2, which is a primary greenhouse gas.
Therefore, in the future it is expected that the use of pure
Portland cement would be limited to special applications
whereas performance-based blended Portland cements
with low Portland clinker content will find increasing use for
all types of concrete construction.