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cement

cement, in TABLE OF CONTENTS

general,
adhesive Introduction

substances Applications of cement

of all kinds, History of cement
but, in a
Raw materials
narrower
cement-making process Manufacture of cement
sense, the
binding The major cements: composition and
The cement-making process, from
properties
crushing and grinding of raw materials
materials, through roasting of the Cement testing
used in
ground and mixed ingredients, to final
cooling and storing of the finished building
product. and civil
engineering construction. Cements of this kind are finely ground
powders that, when mixed with water, set to a hard mass. Setting and hardening result from hydration, which is a
chemical combination of the cement compounds with water that yields submicroscopic crystals or a gel-like
material with a high surface area. Because of their hydrating properties, constructional cements, which will even
set and harden under water, are often called hydraulic cements. The most important of these is portland cement.

This article surveys the historical development of cement, its manufacture from raw materials, its composition
and properties, and the testing of those properties. The focus is on portland cement, but attention also is given to
other types, such as slag-containing cement and high-alumina cement. Construction cements share certain
chemical constituents and processing techniques with ceramic products such as brick and tile, abrasives, and
refractories. For detailed description of one of the principal applications of cement, see the article building
construction.

Applications of cement
Cements may be used alone (i.e., “neat,” as grouting materials), but
the normal use is in mortar and concrete in which the cement is
mixed with inert material known as aggregate. Mortar is cement
mixed with sand or crushed stone that must be less than
approximately 5 mm (0.2 inch) in size. Concrete is a mixture of
cement, sand or other fine aggregate, and a coarse aggregate that for
concrete most purposes is up to 19 to 25 mm (0.75 to 1 inch) in size, but the
coarse aggregate may also be as large as 150 mm (6 inches) when

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Pouring concrete for the foundation of concrete is placed in large masses such as dams. Mortars are used
a house.
for binding bricks, blocks, and stone in walls or as surface
renderings. Concrete is used for a large variety of constructional purposes. Mixtures of soil and portland cement
are used as a base for roads. Portland cement also is used in the manufacture of bricks, tiles, shingles, pipes,
beams, railroad ties, and various extruded products. The products are prefabricated in factories and supplied ready
for installation.

The manufacture of cement is extremely widespread, as concrete is the most widely used of all construction
materials in the world today.
History of cement
The origin of hydraulic cements goes back to ancient Greece and Rome. The materials used were lime and a
volcanic ash that slowly reacted with it in the presence of water to form a hard mass. This formed the cementing
material of the Roman mortars and concretes of more than 2,000 years ago and of subsequent construction work
in western Europe. Volcanic ash mined near what is now the city of Pozzuoli, Italy, was particularly rich in
essential aluminosilicate minerals, giving rise to the classic pozzolana cement of the Roman era. To this day the
term pozzolana, or pozzolan, refers either to the cement itself or to any finely divided aluminosilicate that reacts
with lime in water to form cement. (The term cement, meanwhile, derives from the Latin word caementum, which
meant stone chippings such as were used in Roman mortar—not the binding material itself.)

Portland cement is a successor to a hydraulic lime that was first

developed by John Smeaton in 1756 when he was called in to erect
the Eddystone Lighthouse off the coast of Plymouth, Devon,
England. The next development, taking place about 1800 in England
and France, was a material obtained by burning nodules of clayey
limestone. Soon afterward in the United States, a similar material
Eddystone Lighthouse: Sir James was obtained by burning a naturally occurring substance called
N. Douglass's version
“cement rock.” These materials belong to a class known as natural
Sir James N. Douglass's Eddystone cement, allied to portland cement but more lightly burned and not of
Lighthouse, Plymouth, England,
controlled composition.
photochrome print, c. 1890–1900. The
remnants of John Smeaton's
The invention of portland cement usually is attributed to Joseph
lighthouse are at left.
Aspdin of Leeds, Yorkshire, England, who in 1824 took out a patent
for a material that was produced from a synthetic mixture of limestone and clay. He called the product “portland
cement” because of a fancied resemblance of the material, when set, to portland stone, a limestone used for
building in England. Aspdin’s product may well have been too lightly burned to be a true portland cement, and
the real prototype was perhaps that produced by Isaac Charles Johnson in southeastern England about 1850. The
manufacture of portland cement rapidly spread to other European countries and North America. During the 20th
century, cement manufacture spread worldwide. By 2019 China and India had become the world leaders in
cement production, followed by Vietnam, the United States, and Egypt.

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Raw materials
Composition
Portland cement consists essentially of compounds of lime (calcium oxide, CaO) mixed with silica (silicon
dioxide, SiO2) and alumina (aluminum oxide, Al2O3). The lime is obtained from a calcareous (lime-containing)
raw material, and the other oxides are derived from an argillaceous (clayey) material. Additional raw materials
such as silica sand, iron oxide (Fe2O3), and bauxite—containing hydrated aluminum, Al(OH)3—may be used in
smaller quantities to get the desired composition.

The commonest calcareous raw materials are limestone and chalk, but others, such as coral or shell deposits, also
are used. Clays, shales, slates, and estuarine muds are the common argillaceous raw materials. Marl, a compact
calcareous clay, and cement rock contain both the calcareous and argillaceous components in proportions that
sometimes approximate cement compositions. Another raw material is blast-furnace slag, which consists mainly
of lime, silica, and alumina and is mixed with a calcareous material of high lime content. Kaolin, a white clay that
contains little iron oxide, is used as the argillaceous component for white portland cement. Industrial wastes, such
as fly ash and calcium carbonate from chemical manufacture, are other possible raw materials, but their use is
small compared with that of the natural materials.

The magnesia (magnesium oxide, MgO) content of raw materials must be low because the permissible limit in
portland cement is 4 to 5 percent. Other impurities in raw materials that must be strictly limited are fluorine
compounds, phosphates, metal oxides and sulfides, and excessive alkalies.

Another essential raw material is gypsum, some 5 percent of which is added to the burned cement clinker during
grinding to control the setting time of the cement. Portland cement also can be made in a combined process with
sulfuric acid using calcium sulfate or anhydrite in place of calcium carbonate. The sulfur dioxide produced in the
flue gases on burning is converted to sulfuric acid by normal processes.

Extraction and processing

Raw materials employed in the manufacture of cement are extracted by quarrying in the case of hard rocks such
as limestones, slates, and some shales, with the aid of blasting when necessary. Some deposits are mined by
underground methods. Softer rocks such as chalk and clay can be dug directly by excavators.

The excavated materials are transported to the crushing plant by trucks, railway freight cars, conveyor belts, or
ropeways. They also can be transported in a wet state or slurry by pipeline. In regions where limestones of
sufficiently high lime content are not available, some process of beneficiation can be used. Froth flotation will
remove excess silica or alumina and so upgrade the limestone, but it is a costly process and is used only when
unavoidable.

Manufacture of cement
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There are four stages in the manufacture of portland cement: (1)

crushing and grinding the raw materials, (2) blending the materials
in the correct proportions, (3) burning the prepared mix in a kiln, and
(4) grinding the burned product, known as “clinker,” together with
some 5 percent of gypsum (to control the time of set of the cement).
The three processes of manufacture are known as the wet, dry, and
Hachinohe: cement factory semidry processes and are so termed when the raw materials are
Cement factory, Hachinohe, Aomori ground wet and fed to the kiln as a slurry, ground dry and fed as a
prefecture, Japan. dry powder, or ground dry and then moistened to form nodules that
are fed to the kiln.

It is estimated that around 4–8 percent of the world’s carbon dioxide (CO2) emissions come from the manufacture
of cement, making it a major contributor to global warming. Some of the solutions to these greenhouse gas
emissions are common to other sectors, such as increasing the energy efficiency of cement plants, replacing fossil
fuels with renewable energy, and capturing and storing the CO2 that is emitted. In addition, given that a
significant portion of the emissions are an intrinsic part of the production of clinker, novel cements and alternate
formulations that reduce the need for clinker are an important area of focus.

Crushing and grinding

All except soft materials are first crushed, often in two stages, and then ground, usually in a rotating, cylindrical
ball, or tube mills containing a charge of steel grinding balls. This grinding is done wet or dry, depending on the
process in use, but for dry grinding the raw materials first may need to be dried in cylindrical, rotary dryers.

Soft materials are broken down by vigorous stirring with water in wash mills, producing a fine slurry, which is
passed through screens to remove oversize particles.

Blending
A first approximation of the chemical composition required for a particular cement is obtained by selective
quarrying and control of the raw material fed to the crushing and grinding plant. Finer control is obtained by
drawing material from two or more batches containing raw mixes of slightly different composition. In the dry
process these mixes are stored in silos; slurry tanks are used in the wet process. Thorough mixing of the dry
materials in the silos is ensured by agitation and vigorous circulation induced by compressed air. In the wet
process the slurry tanks are stirred by mechanical means or compressed air or both. The slurry, which contains 35
to 45 percent water, is sometimes filtered, reducing the water content to 20 to 30 percent, and the filter cake is
then fed to the kiln. This reduces the fuel consumption for burning.

Burning

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The earliest kilns in which cement was burned in batches were bottle kilns, followed by chamber kilns and then
by continuous shaft kilns. The shaft kiln in a modernized form is still used in some countries, but the dominant
means of burning is the rotary kiln. These kilns—up to 200 metres (660 feet) long and six metres in diameter in
wet process plants but shorter for the dry process—consist of a steel, cylindrical shell lined with refractory
materials. They rotate slowly on an axis that is inclined a few degrees to the horizontal. The raw material feed,
introduced at the upper end, moves slowly down the kiln to the lower, or firing, end. The fuel for firing may be
pulverized coal, oil, or natural gas injected through a pipe. The temperature at the firing end ranges from about
1,350 to 1,550 °C (2,460 to 2,820 °F), depending on the raw materials being burned. Some form of heat
exchanger is commonly incorporated at the back end of the kiln to increase heat transfer to the incoming raw
materials and so reduce the heat lost in the waste gases. The burned product emerges from the kiln as small
nodules of clinker. These pass into coolers, where the heat is transferred to incoming air and the product cooled.
The clinker may be immediately ground to cement or stored in stockpiles for later use.

In the semidry process the raw materials, in the form of nodules containing 10 to 15 percent water, are fed onto a
traveling chain grate before passing to the shorter rotary kiln. Hot gases coming from the kiln are sucked through
the raw nodules on the grate, preheating the nodules.

Dust emission from cement kilns can be a serious nuisance. In populated areas it is usual and often compulsory to
fit cyclone arrestors, bag-filter systems, or electrostatic dust precipitators between the kiln exit and the chimney
stack. More than 50 percent of the emissions from cement production are intrinsically linked to the production of
clinker and are a by-product of the chemical reaction that drives the current process. There is potential to blend
clinker with alternative materials to reduce the need for clinker itself and thus help reduce the climate impacts of
the cement-making process.

Modern cement plants are equipped with elaborate instrumentation for control of the burning process. Raw
materials in some plants are sampled automatically, and a computer calculates and controls the raw mix
composition. The largest rotary kilns have outputs exceeding 5,000 tons per day.

Grinding
The clinker and the required amount of gypsum are ground to a fine powder in horizontal mills similar to those
used for grinding the raw materials. The material may pass straight through the mill (open-circuit grinding), or
coarser material may be separated from the ground product and returned to the mill for further grinding (closed-
circuit grinding). Sometimes a small amount of a grinding aid is added to the feed material. For air-entraining
cements (discussed in the following section) the addition of an air-entraining agent is similarly made.

Finished cement is pumped pneumatically to storage silos from which it is drawn for packing in paper bags or for
dispatch in bulk containers.
The major cements: composition and properties
Portland cement
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Chemical composition
Portland cement is made up of four main compounds: tricalcium silicate (3CaO · SiO2), dicalcium silicate (2CaO
· SiO2), tricalcium aluminate (3CaO · Al2O3), and a tetra-calcium aluminoferrite (4CaO · Al2O3Fe2O3). In an
abbreviated notation differing from the normal atomic symbols, these compounds are designated as C3S, C2S,
C3A, and C4AF, where C stands for calcium oxide (lime), S for silica, A for alumina, and F for iron oxide. Small
amounts of uncombined lime and magnesia also are present, along with alkalies and minor amounts of other
elements.

Hydration
The most important hydraulic constituents are the calcium silicates, C2S and C3S. Upon mixing with water, the
calcium silicates react with water molecules to form calcium silicate hydrate (3CaO · 2SiO2 · 3H2O) and calcium
hydroxide (Ca[OH]2). These compounds are given the shorthand notations C–S–H (represented by the average
formula C3S2H3) and CH, and the hydration reaction can be crudely represented by the following reactions:
2C3S + 6H = C3S2H3 + 3CH 2C2S + 4H = C3S2H3 + CH During the initial stage of hydration, the parent
compounds dissolve, and the dissolution of their chemical bonds generates a significant amount of heat. Then, for
reasons that are not fully understood, hydration comes to a stop. This quiescent, or dormant, period is extremely
important in the placement of concrete. Without a dormant period there would be no cement trucks; pouring
would have to be done immediately upon mixing.

Following the dormant period (which can last several hours), the cement begins to harden, as CH and C–S–H are
produced. This is the cementitious material that binds cement and concrete together. As hydration proceeds, water
and cement are continuously consumed. Fortunately, the C–S–H and CH products occupy almost the same
volume as the original cement and water; volume is approximately conserved, and shrinkage is manageable.

Although the formulas above treat C–S–H as a specific stoichiometry, with the formula C3S2H3, it does not at all
form an ordered structure of uniform composition. C–S–H is actually an amorphous gel with a highly variable
stoichiometry. The ratio of C to S, for example, can range from 1:1 to 2:1, depending on mix design and curing
conditions.

Structural properties
The strength developed by portland cement depends on its composition and the fineness to which it is ground.
The C3S is mainly responsible for the strength developed in the first week of hardening and the C2S for the
subsequent increase in strength. The alumina and iron compounds that are present only in lesser amounts make
little direct contribution to strength.

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Set cement and concrete can suffer deterioration from attack by some natural or artificial chemical agents. The
alumina compound is the most vulnerable to chemical attack in soils containing sulfate salts or in seawater, while
the iron compound and the two calcium silicates are more resistant. Calcium hydroxide released during the
hydration of the calcium silicates is also vulnerable to attack. Because cement liberates heat when it hydrates,
concrete placed in large masses, as in dams, can cause the temperature inside the mass to rise as much as 40 °C
(70 °F) above the outside temperature. Subsequent cooling can be a cause of cracking. The highest heat of
hydration is shown by C3A, followed in descending order by C3S, C4AF, and C2S.

Types of portland cement

Five types of portland cement are standardized in the United States by the American Society for Testing and
Materials (ASTM): ordinary (Type I), modified (Type II), high-early-strength (Type III), low-heat (Type IV), and
sulfate-resistant (Type V). In other countries Type II is omitted, and Type III is called rapid-hardening. Type V is
known in some European countries as Ferrari cement.

There also are various other special types of portland cement. Coloured cements are made by grinding 5 to 10
percent of suitable pigments with white or ordinary gray portland cement. Air-entraining cements are made by the
addition on grinding of a small amount, about 0.05 percent, of an organic agent that causes the entrainment of
very fine air bubbles in a concrete. This increases the resistance of the concrete to freeze-thaw damage in cold
climates. The air-entraining agent can alternatively be added as a separate ingredient to the mix when making the
concrete.

Low-alkali cements are portland cements with a total content of alkalies not above 0.6 percent. These are used in
concrete made with certain types of aggregates that contain a form of silica that reacts with alkalies to cause an
expansion that can disrupt a concrete.

Masonry cements are used primarily for mortar. They consist of a mixture of portland cement and ground
limestone or other filler together with an air-entraining agent or a water-repellent additive. Waterproof cement is
the name given to a portland cement to which a water-repellent agent has been added. Hydrophobic cement is
obtained by grinding portland cement clinker with a film-forming substance such as oleic acid in order to reduce
the rate of deterioration when the cement is stored under unfavourable conditions.

Oil-well cements are used for cementing work in the drilling of oil wells where they are subject to high
temperatures and pressures. They usually consist of portland or pozzolanic cement (see below) with special
organic retarders to prevent the cement from setting too quickly.

Slag cements
The granulated slag made by the rapid chilling of suitable molten slags from blast furnaces forms the basis of
another group of constructional cements. A mixture of portland cement and granulated slag, containing up to 65
percent slag, is known in the English-speaking countries as portland blast-furnace (slag) cement. The German

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Eisenportlandzement and Hochofenzement contain up to 40 and 85 percent slag, respectively. Mixtures in other
proportions are found in French-speaking countries under such names as ciment portland de fer, ciment
métallurgique mixte, ciment de haut fourneau, and ciment de liatier au clinker. Properties of these slag cements
are broadly similar to those of portland cement, but they have a lower lime content and a higher silica and
alumina content. Those with the higher slag content have an increased resistance to chemical attack.

Another type of slag-containing cement is a supersulfated cement consisting of granulated slag mixed with 10 to
15 percent hard-burned gypsum or anhydrite (natural anhydrous calcium sulfate) and a few percent of portland
cement. The strength properties of supersulfated cement are similar to those of portland cement, but it has an
increased resistance to many forms of chemical attack. Pozzolanic cements are mixtures of portland cement and a
pozzolanic material that may be either natural or artificial. The natural pozzolanas are mainly materials of
volcanic origin but include some diatomaceous earths. Artificial materials include fly ash, burned clays, and
shales. Pozzolanas are materials that, though not cementitious in themselves, contain silica (and alumina) in a
reactive form able to combine with lime in the presence of water to form compounds with cementitious
properties. Mixtures of lime and pozzolana still find some application but largely have been superseded by the
modern pozzolanic cement. Hydration of the portland cement fraction releases the lime required to combine with
the pozzolana.

High-alumina cement
High-alumina cement is a rapid-hardening cement made by fusing at 1,500 to 1,600 °C (2,730 to 2,910 °F) a
mixture of bauxite and limestone in a reverberatory or electric furnace or in a rotary kiln. It also can be made by
sintering at about 1,250 °C (2,280 °F). Suitable bauxites contain 50 to 60 percent alumina, up to 25 percent iron
oxide, not more than 5 percent silica, and 10 to 30 percent water of hydration. The limestone must contain only
small amounts of silica and magnesia. The cement contains 35 to 40 percent lime, 40 to 50 percent alumina, up to
15 percent iron oxides, and preferably not more than about 6 percent silica. The principal cementing compound is
calcium aluminate (CaO · Al2O3).

High-alumina cement gains a high proportion of its ultimate strength within 24 hours and has a high resistance to
chemical attack. It also can be used in refractory linings for furnaces. A white form of the cement, containing
minimal proportions of iron oxide and silica, has outstanding refractory properties.

Expanding and nonshrinking cements

Expanding and nonshrinking cements expand slightly on hydration, thus offsetting the small contraction that
occurs when fresh concrete dries for the first time. Expanding cements were first produced in France about 1945.
The American type is a mixture of portland cement and an expansive agent made by clinkering a mix of chalk,
bauxite, and gypsum.

Gypsum plasters

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Gypsum plasters are used for plastering, the manufacture of plaster boards and slabs, and in one form of floor-
surfacing material. These gypsum cements are mainly produced by heating natural gypsum (calcium sulfate
dihydrate, CaSO4 · 2H2O) and dehydrating it to give calcium sulfate hemihydrate (CaSO4 · 1/2H2O) or
anhydrous (water-free) calcium sulfate. Gypsum and anhydrite obtained as by-products in chemical manufacture
also are used as raw materials.

The hemihydrate, known as plaster of Paris, sets within a few minutes on mixing with water; for building
purposes a retarding agent, normally keratin, a protein, is added. The anhydrous calcium sulfate plasters are
slower-setting, and often another sulfate salt is added in small amounts as an accelerator. Flooring plaster,
originally known by its German title of Estrich Gips, is of the anhydrous type.
Cement testing
Various tests to which cements must conform are laid down in national cement specifications to control the
fineness, soundness, setting time, and strength of the cement. These tests are described in turn below.

Fineness
Fineness was long controlled by sieve tests, but more sophisticated methods are now largely used. The most
common method, used both for control of the grinding process and for testing the finished cement, measures the
surface area per unit weight of the cement by a determination of the rate of passage of air through a bed of the
cement. Other methods depend on measuring the particle size distribution by the rate of sedimentation of the
cement in kerosene or by elutriation (separation) in an airstream.

Soundness
After it has set, a cement must not undergo any appreciable expansion, which could disrupt a mortar or concrete.
This property of soundness is tested by subjecting the set cement to boiling in water or to high-pressure steam.
Unsoundness can arise from the presence in the cement of too much free magnesia or hard-burned free lime.

Setting time
The setting and hardening of a cement is a continuous process, but two points are distinguished for test purposes.
The initial setting time is the interval between the mixing of the cement with water and the time when the mix has
lost plasticity, stiffening to a certain degree. It marks roughly the end of the period when the wet mix can be
molded into shape. The final setting time is the point at which the set cement has acquired a sufficient firmness to
resist a certain defined pressure. Most specifications require an initial minimum setting time at ordinary
temperatures of about 45 minutes and a final setting time no more than 10 to 12 hours.

Strength

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The tests that measure the rate at which a cement develops strength are usually made on a mortar commonly
composed of one part cement to three parts sand, by weight, mixed with a defined quantity of water. Tensile tests
on briquettes, shaped like a figure eight thickened at the centre, were formerly used but have been replaced or
supplemented by compressive tests on cubical specimens or transverse tests on prisms. The American Society for
Testing and Materials (ASTM) specification requires tensile tests on a 1:3 cement-sand mortar and compressive
tests on a 1:2.75 mortar. The British Standards Institution (BSI) gives as alternatives a compressive test on a 1:3
mortar or on a concrete specimen. An international method issued by the International Organization for
Standardization (ISO) requires a transverse test on a 1:3 cement-sand mortar prism, followed by a compressive
test on the two halves of the prism that remain after it has been broken in bending. Many European countries have
adopted this method. In all these tests the size grading of the sand, and usually its source, is specified.

In the testing of most cements, a minimum strength at 3 and 7 days and sometimes 28 days is specified, but for
rapid-hardening portland cement a test at 1 day also is sometimes required. For high-alumina cement, tests are
required at 1 and 3 days.

Strength requirements laid down in different countries are not directly comparable because of the differences in
test methods. In actual construction, to check the strength of a concrete, compressive tests are made on cylinders
or cubes made from the concrete being placed.

Frederick M. Lea The Editors of Encyclopaedia Britannica

Citation Information
Article Title: cement
Website Name: Encyclopaedia Britannica
Publisher: Encyclopaedia Britannica, Inc.
Date Published: 13 May 2024
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