Cement - Britannica Online Encyclopedia PDF

1/19/23, 12:10 PM cement -- Britannica Online Encyclopedia
cement
cement,
TABLE OF CONTENTS
in
general, Introduction
adhesive Applications of cement
History of cement
cement-making process
Raw materials
substances of all kinds, but, in a narrower Manufacture of cement
sense, the binding materials used in building The major cements: composition and
and civil engineering construction. Cements of properties
this kind are finely ground powders that, when Cement testing
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
https://www.britannica.com/print/article/101833 1/13
concrete (0.2 inch) in size. Concrete is a mixture of cement, sand

or other fine aggregate, and a coarse aggregate that for 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 concrete is placed in large masses such as dams. Mortars are used 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
Eddystone Lighthouse: Sir James France, was a material obtained by burning nodules of
N. Douglass's version
clayey limestone. Soon afterward in the United States, a
similar material was obtained by burning a naturally
occurring substance called “cement rock.” These materials belong to a class known as natural
cement, allied to portland cement but more lightly burned and not of controlled composition.
The invention of portland cement usually is attributed to Joseph 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.
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
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
Hachinohe: cement factory 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 semidry processes and are so termed when the raw materials are ground
wet and fed to the kiln as a slurry, ground dry and fed as a 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
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
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.
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 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
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
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: 17 September 2022
URL: https://www.britannica.comhttps://www.britannica.com/technology/cement-building-material
Access Date: January 18, 2023

Cement - Britannica Online Encyclopedia PDF

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Cement - Britannica Online Encyclopedia PDF

Uploaded by

Copyright:

Available Formats

1/19/23, 12:10 PM cement -- Britannica Online Encyclopedia

mixed with water, set to a hard mass. Setting

concrete (0.2 inch) in size. Concrete is a mixture of cement, sand

Portland cement is a successor to a hydraulic lime that

Extraction and processing

Crushing and grinding

Types of portland cement

Another type of slag-containing cement is a supersulfated cement consisting of granulated slag

Expanding and nonshrinking cements

Frederick M. Lea The Editors of Encyclopaedia Britannica

You might also like