4 PORTLAND CEMENT

Portland cement is the chief ingredient in cement paste - Major Topics on this Page
the binding agent in portland cement concrete (PCC). It is a
hydraulic cement that, when combined with water, hardens 4.1 Background
into a solid mass. Interspersed in an aggregate matrix it 4.2 Manufacturing
forms PCC. As a material, portland cement has been used
for well over 175 years and, from an empirical perspective, 4.3 Chemical Properties
its behavior is well-understood. Chemically, however, 4.4 Types of Portland Cement
portland cement is a complex substance whose mechanisms
4.5 Physical Properties
and interactions have yet to be fully defined. ASTM C 125
and the Portland Cement Association (PCA) provide the 4.6 Summary
following precise definitions:

hydraulic cement An inorganic material or a mixture of inorganic materials that sets

and develops strength by chemical reaction with water by
formation of hydrates and is capable of doing so under water.

portland cement A hydraulic cement composed primarily of hydraulic calcium

silicates.

4.1 Background
Although the use of cements (both hydraulic and non-hydraulic)
goes back many thousands of years (to ancient Egyptian times at
least), the first occurrence of "portland cement" came about in the
19th century. In 1824, Joseph Aspdin, a Leeds mason took out a
patent on a hydraulic cement that he coined "Portland" cement
(Mindess and Young, 1981). He named the cement because it
produced a concrete that resembled the color of the natural
limestone quarried on the Isle of Portland, a peninsula in the
English Channel (see Figure 3.43 and 3.44). Since then, the name Figure 3.43: Portland,
"portland cement" has stuck and is written in all lower case England
because it is now recognized as a trade name for a type of material
and not a specific reference to Portland, England.

Today, portland cement is the most widely used building material

in the world with about 1.56 billion tonnes (1.72 billion tons)
produced each year. Annual global production of portland cement
concrete hovers around 3.8 million cubic meters (5 billion cubic
yards) per year (Cement Association of Canada, 2001). In the
U.S., rigid pavements are the largest single use of portland cement
and portland cement concrete (ACPA, 2002).

This section covers the following topics:

Portland cement manufacturing

The chemical constituents and properties of portland

cement

Types of portland cements

The physical properties of portland cement

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 Figure 3:44: Limestone at
the Portland Bill near
4.2 Manufacturing Weymouth

Although there are several variations of commercially manufactured portland cement, they each
share many of the same basic raw materials and chemical components. The chief chemical
components of portland cement are calcium, silica, alumina and iron. Calcium is derived from
limestone, marl or chalk, while silica, alumina and iron come from the sands, clays and iron ore
sources. Other raw materials may include shale, shells and industrial byproducts such as mill
scale (Ash Grove Cement Company, 2000).

The basic manufacturing process heats these materials in a kiln to about 1400 to 1600 °C (2600 -
3000°F) - the temperature range in which the two materials interact chemically to form calcium
silicates (Mindess and Young, 1981). This heated substance, called "clinker" is usually in the form of
small gray-black pellets about 12.5 mm (0.5 inches) in diameter. Clinker is then cooled and
pulverized into a fine powder that almost completely passes through a 0.075 mm (No. 200) sieve
and fortified with a small amount of gypsum. The result is portland cement. The Portland Cement
Association (PCA) has an excellent interactive illustration of this process on their website.

4.3 Chemical Properties

Portland cements can be characterized by their chemical composition although they rarely are for
pavement applications. However, it is a portland cement's chemical properties that determine its
physical properties and how it cures. Therefore, a basic understanding of portland cement chemistry
can help one understand how and why it behaves as it does. This section briefly describes the basic
chemical composition of a typical portland cement and how it hydrates.

4.3.1 Basic Composition

Table 3.12 and Figure 3.45 show the main chemical compound constituents of portland cement.

Table 3.12: Main Constituents in a Typical Portland Cement (Mindess and Young, 1981)

Chemical Name Chemical Formula Shorthand Notation Percent by Weight

Tricalcium Silicate 3CaO⋅SiO2 C3 S 50
Dicalcium Silicate 2CaO⋅SiO2 C2 S 25
Tricalcium Aluminate 3CaO⋅Al2O3 C3 A 12
Tetracalcium Aluminoferrite 4CaO⋅Al2O3⋅Fe2O3 C4AF 8
Gypsum CaSO4⋅H2O CSH2 3.5

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 Figure 3.45: Typical Oxide Composition of a General-Purpose Portland Cement
(Mindess and Young, 1981)

4.3.2 Hydration

When portland cement is mixed with water its chemical compound constituents undergo a series of
chemical reactions that cause it to harden (or set). These chemical reactions all involve the addition
of water to the basic chemical compounds listed in Table 3.12. This chemical reaction with water is
called "hydration". Each one of these reactions occurs at a different time and rate. Together, the
results of these reactions determine how portland cement hardens and gains strength.

Tricalcium silicate (C3S). Hydrates and hardens rapidly and is largely responsible for initial
set and early strength. Portland cements with higher percentages of C 3S will exhibit higher
early strength.

Dicalcium silicate (C2S). Hydrates and hardens slowly and is largely responsible for
strength increases beyond one week.

Tricalcium aluminate (C 3A). Hydrates and hardens the quickest. Liberates a large amount
of heat almost immediately and contributes somewhat to early strength. Gypsum is added
to portland cement to retard C3A hydration. Without gypsum, C 3A hydration would cause
portland cement to set almost immediately after adding water.

Tetracalcium aluminoferrite (C4AF). Hydrates rapidly but contributes very little to

strength. Its use allows lower kiln temperatures in portland cement manufacturing. Most
portland cement color effects are due to C4AF.

Figure 3.46 shows rates of heat evolution, which give an approximate idea of hydration times and
when a typical portland cement initially sets.

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 Figure 3.46: Rate of Heat Evolution During Hydration of a Typical Portland Cement

The result of the two silicate hydrations is the formation of a calcium silicate hydrate (often written
C-S-H because of is variable stoichiometry). C-S-H makes up about 1/2 - 2/3 the volume of the
hydrated paste (water + cement) and therefore dominates its behavior (Mindess and Young, 1981).

4.4 Types of Portland Cement

Knowing the basic characteristics of portland cement's constituent chemical compounds, it is possible
to modify its properties by adjusting the amounts of each compound. In the U.S., AASHTO M 85 and
ASTM C 150, Standard Specification for Portland Cement, recognize eight basic types of portland
cement concrete (see Table 3.13). There are also many other types of blended and proprietary
cements that are not mentioned here.

WSDOT Portland Cement Specifications

WSDOT specifies that portland cement shall conform to the requirements for
Types I, II or III cement as listed in AASHTO M 85. Type II cement shall
additionally meet the requirements for setting time by the Vicat method.

Table 3.13: ASTM Types of Portland Cement

Type Name Purpose

I Normal General-purpose cement suitable for most purposes.

IA Normal-Air Entraining An air-entraining modification of Type I.

Moderate Sulfate Used as a precaution against moderate sulfate attack. It will

II
Resistance usually generate less heat at a slower rate than Type I cement.

Moderate Sulfate
IIA Resistance- An air-entraining modification of Type II.
Air Entraining

Used when high early strength is needed. It is has more C3S

III High Early Strength than Type I cement and has been ground finer to provide a
higher surface-to-volume ratio, both of which speed hydration.

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 Strength gain is double that of Type I cement in the first 24
hours.

High Early Strength-

IIIA An air-entraining modification of Type III.
Air Entraining

Used when hydration heat must be minimized in large volume

IV Low Heat of Hydration applications such as gravity dams. Contains about half the C3S
and C3A and double the C2S of Type I cement.

Used as a precaution against severe sulfate action - principally

High Sulfate where soils or groundwaters have a high sulfate content. It
V
Resistance gains strength at a slower rate than Type I cement. High sulfate
resistance is attributable to low C3A content.

4.5 Physical Properties

Portland cements are commonly characterized by their physical properties for quality control
purposes. Their physical properties can be used to classify and compare portland cements. The
challenge in physical property characterization is to develop physical tests that can satisfactorily
characterize key parameters. This section, taken largely from the PCA (1988), describes the more
common U.S. portland cement physical tests. Specification values, where given, are taken from
ASTM C 150, Standard Specification for Portland Cement.

Keep in mind that these tests are, in general, performed on "neat" cement pastes - that is, they only
include portland cement and water. Neat cement pastes are typically difficult to handle and test and
thus they introduce more variability into the results. Cements may also perform differently when
used in a "mortar" (cement + water + sand). Over time, mortar tests have been found to provide a
better indication of cement quality and thus, tests on neat cement pastes are typically used only for
research purposes (Mindess and Young, 1981). However, if the sand is not carefully specified in a
mortar test, the results may not be transferable.

4.5.1 Fineness

Fineness, or particle size of portland cement affects hydration rate and thus the rate of strength
gain. The smaller the particle size, the greater the surface area-to-volume ratio, and thus, the more
area available for water-cement interaction per unit volume. The effects of greater fineness on
strength are generally seen during the first seven days (PCA, 1988).

Fineness can be measured by several methods:

AASHTO T 98 and ASTM C 115: Fineness of Portland Cement by the Turbidimeter.

AASHTO T 128 and ASTM C 184: Fineness of Hydraulic Cement by the 150-µm (No. 100)
and 75-µm (No. 200) Sieves

AASHTO T 153 and ASTM C 204: Fineness of Hydraulic Cement by Air Permeability
Apparatus

AASHTO T 192 and ASTM C 430: Fineness of Hydraulic Cement by the 45-µm (No. 325)
Sieve

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4.5.2 Soundness

When referring to portland cement, "soundness" refers to the ability of a hardened cement paste
to retain its volume after setting without delayed destructive expansion (PCA, 1988). This
destructive expansion is caused by excessive amounts of free lime (CaO) or magnesia (MgO).
Most portland cement specifications limit magnesia content and expansion. The typical
expansion test places a small sample of cement paste into an autoclave (a high pressure steam
vessel). The autoclave is slowly brought to 2.03 MPa (295 psi) then kept at that pressure for 3
hours. The autoclave is then slowly brought back to room temperature and atmospheric
pressure. The change in specimen length due to its time in the autoclave is measured and
reported as a percentage. ASTM C 150, Standard Specification for Portland Cement specifies a
maximum autoclave expansion of 0.80 percent for all portland cement types.

The standard autoclave expansion test is:

AASHTO T 107 and ASTM C 151: Autoclave Expansion of Portland Cement

4.5.3 Setting Time

Cement paste setting time is affected by a number of items including: cement fineness,
water-cement ratio, chemical content (especially gypsum content) and admixtures. Setting tests are
used to characterize how a particular cement paste sets. For construction purposes, the initial set
must not be too soon and the final set must not be too late. Additionally, setting times can give
some indication of whether or not a cement is undergoing normal hydration (PCA, 1988). Normally,
two setting times are defined (Mindess and Young, 1981):

1. Initial set. Occurs when the paste begins to stiffen considerably.

2. Final set. Occurs when the cement has hardened to the point at which it can sustain some
load.

These particular times are just arbitrary points used to characterize cement, they do not have any
fundamental chemical significance. Both common setting time tests, the Vicat needle and the
Gillmore needle, define initial set and final set based on the time at which a needle of particular size
and weight either penetrates a cement paste sample to a given depth or fails to penetrate a cement
paste sample. The Vicat needle test is more common and tends to give shorter times than the
Gillmore needle test. Table 3.14 shows ASTM C 150 specified set times.

Table 3.14: ASTM C 150 Specified Set Times by Test Method

Test Method Set Type Time Specification

Initial ≥ 45 minutes
Vicat
Final ≤ 375 minutes
Initial ≥ 60 minutes
Gillmore
Final ≤ 600 minutes

The standard setting time tests are:

AASHTO T 131 and ASTM C 191: Time of Setting of Hydraulic Cement by Vicat Needle

AASHTO T 154: Time of Setting of Hydraulic Cement by Gillmore Needles

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 ASTM C 266: Time of Setting of Hydraulic-Cement Paste by Gillmore Needles

4.5.4 Strength

Cement paste strength is typically defined in three ways: compressive, tensile and flexural. These
strengths can be affected by a number of items including: water-cement ratio, cement-fine
aggregate ratio, type and grading of fine aggregate, manner of mixing and molding specimens,
curing conditions, size and shape of specimen, moisture content at time of test, loading conditions
and age (Mindess and Young, 1981). Since cement gains strength over time, the time at which a
strength test is to be conducted must be specified. Typically times are 1 day (for high early strength
cement), 3 days, 7 days, 28 days and 90 days (for low heat of hydration cement). When considering
cement paste strength tests, there are two items to consider:

Cement mortar strength is not directly related to concrete strength. Cement paste
strength is typically used as a quality control measure.

Strength tests are done on cement mortars (cement + water + sand) and not on cement
pastes.

4.5.4.1 Compressive Strength

The most common strength test, compressive strength, is carried out on a 50 mm (2-inch) cement
mortar test specimen. The test specimen is subjected to a compressive load (usually from a
hydraulic machine) until failure. This loading sequence must take no less than 20 seconds and no
more than 80 seconds. Table 3.15 shows ASTM C 150 compressive strength specifications.

Table 3.15: ASTM C 150 Portland Cement Mortar Compressive Strength Specifications in
MPa (psi)

Portland Cement Type

Curing Time
I IA II IIA III IIIA IV V
12.4 10.0
1 day - - - - - -
(1800) (1450)
12.4 10.0 10.3 8.3 24.1 19.3 8.3
3 days -
(1800) (1450) (1500) (1200) (3500) (2800) (1200)
19.3 15.5 17.2 13.8 6.9 15.2
7 days - --
(2800) (2250) (2500) (2000) (1000) (2200)
17.2 20.7
28 days - - - - - -
(2500) (3000)
Note: Type II and IIA requirements can be lowered if either an optional heat of hydration or chemical
limit on the sum of C 3S and C3A is specified

The standard cement mortar compressive strength test is:

AASHTO T 106 and ASTM C 109: Compressive Strength of Hydraulic Cement Mortars (Using
50-mm or 2-in. Cube Specimens)

ASTM C 349: Compressive Strength of Hydraulic Cement Mortars (Using Portions of Prisms
Broken in Flexure)

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4.5.4.2 Tensile Strength

Although still specified by ASTM, the direct tension test does not provide any useful insight into the
concrete-making properties of cements. It persists as a specified test because in the early years of
cement manufacture, it used to be the most common test since it was difficult to find machines that
could compress a cement sample to failure.

4.5.4.3 Flexural Strength

Flexural strength (actually a measure of tensile strength in bending) is carried out on a 40 x 40 x

160 mm (1.57-inch x 1.57-inch x 6.30-inch) cement mortar beam. The beam is then loaded at its
center point until failure.

The standard cement mortar flexural strength test is:

ASTM C 348: Flexural Strength of Hydraulic Cement Mortars

4.5.5 Specific Gravity Test

Specific gravity is normally used in mixture proportioning calculations. The specific gravity of
portland cement is generally around 3.15 while the specific gravity of portland-blast-furnace-slag
and portland-pozzolan cements may have specific gravities near 2.90 (PCA, 1988).

The standard specific gravity test is:

AASHTO T 133 and ASTM C 188: Density of Hydraulic Cement

4.5.6 Heat of Hydration

The heat of hydration is the heat generated when water and portland cement react. Heat of
hydration is most influenced by the proportion of C3S and C3A in the cement, but is also influenced
by water-cement ratio, fineness and curing temperature. As each one of these factors is increased,
heat of hydration increases. In large mass concrete structures such as gravity dams, hydration heat
is produced significantly faster than it can be dissipated (especially in the center of large concrete
masses), which can create high temperatures in the center of these large concrete masses that, in
turn, may cause undesirable stresses as the concrete cools to ambient temperature. Conversely, the
heat of hydration can help maintain favorable curing temperatures during winter (PCA, 1988).

The standard heat of hydration test is:

ASTM C 186: Heat of Hydration of Hydraulic Cement

4.5.7 Loss on Ignition

Loss on ignition is calculated by heating up a cement sample to 900 - 1000 °C (1650 - 1830°F) until a
constant weight is obtained. The weight loss of the sample due to heating is then determined. A high loss on ignition can

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indicate prehydration and carbonation, which may be caused by improper and prolonged storage or adulteration during
transport or transfer (PCA, 1988).

The standard loss on ignition test is contained in:

AASHTO T 105 and ASTM C 114: Chemical Analysis of Hydraulic Cement

4.6 Summary
Portland cement, the chief ingredient in cement paste, is the most widely used building material in
the world. In the presence of water, the chemical compounds within portland cement hydrate
causing hardening and strength gain. Portland cement can be specified based on its chemical
composition and other various physical characteristics that affect its behavior. ASTM specifies eight
basic types of portland cement concrete. Tests to characterize portland cement, such as fineness,
soundness, setting time and strength are useful in quality control and specifications but should not
be substituted for tests on PCC.

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