Definition
cement |
A cement is a binder, a substance used for construction that sets, hardens, and adheres to other materials to bind
them together. Cement is seldom used on its own, but rather to bind sand and gravel (aggregate) together. Cement
mixed with fine aggregate produces mortar for masonry, or with sand and gravel, produces concrete. Cement is the
most widely used material in existence and is only behind water as the planet's most-consumed resource.
Cements used in construction are usually inorganic, often lime or calcium silicate based, and can be characterized as either hydraulic or non-hydraulic, depending on the ability of the cement to set in the presence of water.
Non-hydraulic cement does not set in wet conditions or under water. Rather, it sets as it dries and reacts with carbon dioxide in the air. It is resistant to attack by chemicals after setting.
Hydraulic cements (e.g., Portland cement) set and become adhesive due to a chemical reaction between the dry ingredients and water. The chemical reaction results in mineral hydrates that are not very water-soluble and so are quite durable in water and safe from chemical attack. This allows setting in wet conditions or under water and further protects the hardened material from chemical attack. The chemical process for hydraulic cement found by ancient Romans used volcanic ash (pozzolana) with added lime (calcium oxide).
The word "cement" can be
traced back to the Roman term opus caementicium,
used to describe masonry resembling modern concrete that was made from crushed rock with burnt lime as binder. The volcanic ash and pulverized brick supplements that were added to the burnt lime, to
obtain a hydraulic binder, were later referred to as cementum, cimentum, cäment,
and cement. In modern times, organic polymers are sometimes used as
cements in concrete.
Chemical Composition
Non-hydraulic cement, such as slaked lime (calcium oxide mixed with water), hardens by carbonation in the presence of carbon dioxide, which is naturally present in the air. First calcium oxide (lime) is produced from calcium carbonate (limestone or chalk) by calcination at temperatures above 825 °C (1,517 °F) for
about 10 hours at atmospheric pressure:
CaCO3 →
CaO + CO2
The calcium oxide is then spent (slaked)
mixing it with water to make slaked lime (calcium hydroxide):
CaO + H2O →
Ca(OH)2
Once the excess water is completely
evaporated (this process is technically called setting), the
carbonation starts:
Ca(OH)2 +
CO2 →
CaCO3 +
H2O
This reaction takes time, because
the partial pressure of carbon dioxide in the air is low. The carbonation
reaction requires that the dry cement be exposed to air, so the slaked lime is
a non-hydraulic cement and cannot be used under water. This process is called
the lime cycle.
Hydraulic cement hardens by hydration when water is added. Hydraulic
cements (such as Portland cement)
are made of a mixture of silicates and oxides, the four main components being:
Belite (2CaO·SiO2);
Alite (3CaO·SiO2);
Tricalcium aluminate (3CaO·Al2O3) (historically, and still occasionally, called 'celite');
Brownmillerite (4CaO·Al2O3·Fe2O3).
The silicates are responsible for the cement's mechanical
properties—the tricalcium aluminate and brownmillerite are essential for
formation of the liquid phase during the kiln sintering (firing). The chemistry
of these reactions is not completely clear and is still the object of research.
History
Perhaps the earliest known occurrence of cement is from
twelve million years ago. A deposit of cement was formed after an occurrence of
oil shale located adjacent to a bed of limestone burned due to natural causes.
These ancient deposits were investigated in the 1960s and 1970s.
Cement, chemically speaking, is a
product that includes lime as the primary curing ingredient, but is far from
the first material used for cementation. The Babylonians and Assyrians
used bitumen to bind together burnt brick or alabaster slabs. In Egypt stone
blocks were cemented together with a mortar made
of sand and roughly burnt gypsum (CaSO4·2H2O),
which often contained calcium carbonate (CaCO3).
Macedonians
and Romans
Lime (calcium oxide) was used on
Crete and by the ancient Greeks. There is evidence that
the Minoans of Crete used crushed potshards as an artificial pozzolan
for hydraulic cement. Nobody knows who first discovered that a combination of
hydrated non-hydraulic lime and a pozzolan produces
a hydraulic mixture (see also: Pozzolanic reaction)—but such concrete was
used by the Ancient Macedonians,
and three centuries later on a large scale by Roman engineers.
There is... a kind of powder which
from natural causes produces astonishing results. It is found in the
neighborhood of Baiae and in the country belonging
to the towns round about Mt. Vesuvius. This substance when mixed with lime and
rubble not only lends strength to buildings of other kinds, but even when piers
of it are constructed in the sea, they set hard under water.
— Marcus Vitruvius Pollio, Liber
II, De Architectura, Chapter VI "Pozzolana" Sec. 1
The Greeks used volcanic tuff from
the island of Thera as their pozzolan and the Romans used crushed volcanic ash
(activated aluminium silicates) with lime. This mixture could set under
water, increasing its resistance.[ clarification
needed ] The material was called pozzolana from
the town of Pozzuoli, west of Naples where volcanic ash was
extracted. In
the absence of pozzolanic ash, the Romans used powdered brick or pottery as a
substitute and they may have used crushed tiles for this purpose before
discovering natural sources near Rome. The huge dome of the Pantheon in Rome and the massive Baths of Caracalla are
examples of ancient structures made from these concretes, many of which still
stand. The vast system of Roman aqueducts also made extensive use of
hydraulic cement. Roman concrete was rarely used on the outside of buildings.
The normal technique was to use brick facing material as the formwork for an
infill of mortar mixed with an aggregate of broken pieces of stone,
brick, potsherds, recycled chunks of concrete, or other building rubble.
Middle Age
Any preservation of this knowledge
in literature from the Middle Ages is unknown, but medieval masons and some military engineers actively used hydraulic
cement in structures such as canals, fortresses, harbors, and shipbuilding
facilities. A mixture of lime mortar and
aggregate with brick or stone facing material was used in the Eastern Roman
Empire as well as in the West into the Gothic period. The German Rhineland continued
to use hydraulic mortar throughout the Middle Ages, having local pozzolana
deposits called trass.
16th century
Tabby is a building material
made from oyster-shell lime, sand, and whole oyster shells to form a concrete.
The Spanish introduced it to the Americas in the sixteenth century.
18th century
The technical knowledge for making hydraulic cement was
formalized by French and British engineers in the 18th century.
john smeaton |
John Smeaton made an important
contribution to the development of cements while planning the construction of
the third Eddystone Lighthouse (1755–59)
in the English Channel now known as Smeaton's Tower. He needed a
hydraulic mortar that would set and develop some strength in the twelve-hour
period between successive high tides. He performed experiments with
combinations of different limestones and additives including trass
and pozzolanas and did exhaustive market research on the available
hydraulic limes, visiting their production sites, and noted that the
"hydraulicity" of the lime was directly related to the clay content
of the limestone used to
make it. Smeaton was a civil engineer by profession, and took the
idea no further.
In the South Atlantic
seaboard of the United
States, tabby relying on the oyster-shell middens of earlier Native American populations was used in
house construction from the 1730s to the 1860s.
In Britain particularly, good quality building stone became ever
more expensive during a period of rapid growth, and it became a common practice
to construct prestige buildings from the new industrial bricks, and to finish
them with a stucco to imitate stone. Hydraulic
limes were favored for this, but the need for a fast set time encouraged the
development of new cements. Most famous was Parker's "Roman cement".
This was developed by James Parker in the 1780s, and finally patented
in 1796. It was, in fact, nothing like material used by the Romans, but was a
"natural cement" made by burning septaria – nodules that are found in
certain clay deposits, and that contain both clay minerals and calcium carbonate. The burnt nodules were
ground to a fine powder. This product, made into a mortar with sand, set in
5–15 minutes. The success of "Roman cement" led other manufacturers
to develop rival products by burning artificial hydraulic lime cements of clay and chalk. Roman cement quickly became popular but was largely
replaced by Portland cement in the 1850s.
19th century
Apparently unaware of Smeaton's
work, the same principle was identified by Frenchman Louis Vicat in
the first decade of the nineteenth century. Vicat went on to devise a method of
combining chalk and clay into an intimate mixture, and, burning this, produced
an "artificial cement" in 1817 considered the "principal
forerunner" of Portland cement and "...Edgar Dobbs of Southwark
patented a cement of this kind in 1811."
In Russia, Egor Cheliev created a
new binder by mixing lime and clay. His results were published in 1822 in his
book A Treatise on the Art to Prepare a Good Mortar published
in St. Petersburg. A few years later in 1825, he published another book, which
described various methods of making cement and concrete, and the benefits of
cement in the construction of buildings and embankments.
William Aspdin is considered
the inventor of "modern" Portland cement.
Portland
cement, the most common type of cement in
general use around the world as a basic ingredient of concrete, mortar, stucco, and non-speciality grout,
was developed in England in the mid 19th century, and
usually originates from limestone. James
Frost produced what he called "British cement" in a similar
manner around the same time, but did not obtain a patent until 1822. In
1824, Joseph Aspdin patented a similar material, which he
called Portland cement, because the render made from it was in
color similar to the prestigious Portland stone quarried on
the Isle of Portland, Dorset, England. However, Aspdins' cement was
nothing like modern Portland cement but was a first step in its development,
called a proto-Portland cement. Joseph Aspdins' son William
Aspdin had left his father's company and in his cement manufacturing
apparently accidentally produced calcium silicates in the 1840s, a
middle step in the development of Portland cement. William Aspdin's innovation
was counterintuitive for manufacturers of "artificial cements",
because they required more lime in the mix (a problem for his father), a much
higher kiln temperature (and therefore more fuel), and the resulting clinker was very hard and rapidly wore down
the millstones, which were the only available grinding technology of the
time. Manufacturing costs were therefore considerably higher, but the product
set reasonably slowly and developed strength quickly, thus opening up a market
for use in concrete. The use of concrete in construction grew rapidly from 1850
onward, and was soon the dominant use for cements. Thus Portland cement began
its predominant role. Isaac Charles Johnson further refined the
production of meso-Portland cement (middle stage of
development) and claimed he was the real father of Portland cement.
Setting time and "early
strength" are important characteristics of cements. Hydraulic limes,
"natural" cements, and "artificial" cements all rely on
their belite content for strength development. Belite
develops strength slowly. Because they were burned at temperatures below
1,250 °C (2,280 °F), they contained no alite, which is
responsible for early strength in modern cements. The first cement to
consistently contain alite was made by William Aspdin in the early 1840s: This
was what we call today "modern" Portland cement. Because of the air
of mystery with which William Aspdin surrounded his product, others (e.g., Vicat
and Johnson) have claimed precedence in this invention, but recent analysis of
both his concrete and raw cement have shown that William Aspdin's product made
at Northfleet, Kent was a true alite-based cement. However,
Aspdin's methods were "rule-of-thumb": Vicat is responsible for
establishing the chemical basis of these cements, and Johnson established the
importance of sintering the mix
in the kiln.
In the US the first large-scale use
of cement was Rosendale cement, a natural cement mined from a massive
deposit of a large dolostone rock deposit
discovered in the early 19th century near Rosendale, New York. Rosendale
cement was extremely popular for the foundation of buildings (e.g., Statue of Liberty, Capitol Building, Brooklyn Bridge) and lining water pipes.
Sorel
cement was patented in 1867 by
Frenchman Stanislas Sorel. It was stronger than Portland cement but its
poor water resistance and corrosive qualities limited its use in building
construction. The next development in the manufacture of Portland cement was
the introduction of the rotary kiln, which
produced a stronger, more homogeneous mixture and facilitated a continuous
manufacturing process.
20th century
The National Cement Share Company
of Ethiopia's new plant
in Dire Dawa.Calcium aluminate cements were
patented in 1908 in France by Jules Bied for better resistance to sulfates.
In the US, after World War One, the long curing
time of at least a month for Rosendale cement made it unpopular for
constructing highways and bridges, and many states and construction firms
turned to Portland cement. Because of the switch to Portland cement, by the end
of the 1920s only one of the 15 Rosendale cement companies had survived. But in
the early 1930s, builders discovered that, while Portland cement set faster, it
was not as durable, especially for highways—to the point that some states
stopped building highways and roads with cement. Bertrain H. Wait, an engineer
whose company had helped construct the New York City's Catskill Aqueduct,
was impressed with the durability of Rosendale cement, and came up with a blend
of both Rosendale and Portland cements that had the good attributes of both. It
was highly durable and had a much faster setting time. Wait convinced the New
York Commissioner of Highways to construct an experimental section of highway
near New Paltz, New York, using one sack of Rosendale to six sacks of
Portland cement. It was a success, and for decades the Rosendale-Portland
cement blend was used in highway and bridge construction.
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