4 Cement
4 Cement
4 Cement
materials used in building 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.
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 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 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 the early 21st century, China and India had become the world leaders in cement production,
followed by the United States, Brazil, Turkey, and Iran.
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.
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.
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 +
3CH2C2S + 4H = C3S2H3 + CHDuring 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 unfavorable 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 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.
The strength of rapid hardening cement at the 3 days is similar to 7 days strength of OPC with
the same water-cement ratio. Thus, advantage of this cement is that formwork can be removed
earlier which increases the rate of construction and decreases cost of construction by saving
formwork cost.
Rapid hardening cement is used in prefabricated concrete construction, road works, etc.
9. White Cement
It is prepared from raw materials free from Iron oxide and is a type of ordinary portland cement
which is white in color. It is costlier and is used for architectural purposes such as precast curtain
wall and facing panels, terrazzo surface etc. and for interior and exterior decorative work like
external renderings of buildings, facing slabs, floorings, ornamental concrete products, paths of
gardens, swimming pools etc.