History of the origin of cement

Early uses
It is uncertain where it was first discovered that a combination of hydrated non-hydraulic lime and
a pozzolan produces a hydraulic mixture (see also: Pozzolanic reaction), but concrete made from
such mixtures was first used on a large scale by Roman engineers. They used both natural pozzolans
(trass or pumice) and artificial pozzolans (ground brick or pottery) in these concretes. Many excellent
examples of structures made from these concretes are still standing, notably the
huge monolithic dome of the Pantheon in Rome and the massive Baths of Caracalla. The vast system
of Roman aqueducts also made extensive use of hydraulic cement. The use of structural concrete
disappeared in medieval Europe, although weak pozzolanic concretes continued to be used as a core
fill in stone walls and columns.

Modern cement
Modern hydraulic cements began to be developed from the start of the Industrial Revolution (around
1800), driven by three main needs:

 Hydraulic render (stucco) for finishing brick buildings in wet climates.

 Hydraulic mortars for masonry construction of harbor works, etc ... , in contact with sea water.
 Development of strong concretes.

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 any 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 mixtures of clay and chalk.

John Smeaton made an important contribution to the development of cements when he was planning
the construction of the third Eddystone Lighthouse (1755-9) in the English Channel. He needed a
hydraulic mortar that would set and develop some strength in the twelve hour period between
successive high tides. He performed an 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 from which it was made. Smeaton was acivil engineer by profession, and
took the idea no further. Apparently unaware of Smeaton's work, the same principle was identified
by 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. James Frost, working in Britain, 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.

All the above products could not compete with lime/pozzolan concretes because of fast-setting (giving
insufficient time for placement) and low early strengths (requiring a delay of many weeks
before formwork could be removed). Hydraulic limes, "natural" cements, and "artificial" cements all
rely upon their belite content for strength development. Belite develops strength slowly. Because they
were burned at temperatures below 1250 °C, they contained no alite, which is responsible for early
strength in modern cements. The first cement to consistently contain alite was made by Joseph
Aspdin's son William 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 I.C. 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 atNorthfleet, 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.

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
onwards, and was soon the dominant use for cements. Thus Portland cement began its predominant
role.

Types of modern cement

Portland cement
Cement is made by heating limestone (calcium carbonate), with small quantities of other materials
(such as clay) to 1450 °C in a kiln, in a process known as calcination, whereby a molecule of carbon
dioxide is liberated from the calcium carbonate to form calcium oxide, or quicklime, which is then
blended with the other materials that have been included in the mix . The resulting hard substance,
called 'clinker', is then ground with a small amount of gypsum into a powder to make 'Ordinary
Portland Cement', the most commonly used type of cement (often referred to as OPC).

Portland cement is a basic ingredient of concrete, mortar and most non-speciality grout. The most

common use for Portland cement is in the production of concrete. Concrete is a composite material
consisting of aggregate (gravel and sand), cement, and water. As a construction material, concrete
can be cast in almost any shape desired, and once hardened, can become a structural (load bearing)
element. Portland cement may be gray or white.
Portland cement blends
Portland cement blends are often available as inter-ground mixtures from cement manufacturers, but
similar formulations are often also mixed from the ground components at the concrete mixing plant.

Portland blastfurnace cement contains up to 70 % ground granulated blast furnace slag, with the
rest Portland clinker and a little gypsum. All compositions produce high ultimate strength, but as slag
content is increased, early strength is reduced, while sulfate resistance increases and heat evolution
diminishes. Used as an economic alternative to Portland sulfate-resisting and low-heat cements.

Portland flyash cement contains up to 30 % fly ash. The fly ash is pozzolanic, so that ultimate
strength is maintained. Because fly ash addition allows a lower concrete water content, early strength
can also be maintained. Where good quality cheap fly ash is available, this can be an economic
alternative to ordinary Portland cement.

Portland pozzolan cement includes fly ash cement, since fly ash is a pozzolan, but also includes
cements made from other natural or artificial pozzolans. In countries where volcanic ashes are
available (e.g. Italy, Chile, Mexico, the Philippines) these cements are often the most common form in
use.

Portland silica fume cement. Addition of silica fume can yield exceptionally high strengths, and
cements containing 5-20 % silica fume are occasionally produced. However, silica fume is more
usually added to Portland cement at the concrete mixer.

Masonry cements are used for preparing bricklaying mortars and stuccos, and must not be used in
concrete. They are usually complex proprietary formulations containing Portland clinker and a number
of other ingredients that may include limestone, hydrated lime, air entrainers, retarders, waterproofers
and coloring agents. They are formulated to yield workable mortars that allow rapid and consistent
masonry work. Subtle variations of Masonry cement in the US are Plastic Cements and Stucco
Cements. These are designed to produce controlled bond with masonry blocks.

Expansive cements contain, in addition to Portland clinker, expansive clinkers (usually

sulfoaluminate clinkers), and are designed to offset the effects of drying shrinkage that is normally
encountered with hydraulic cements. This allows large floor slabs (up to 60 m square) to be prepared
without contraction joints.

White blended cements may be made using white clinker and white supplementary materials such
as high-purity metakaolin.

Colored cements are used for decorative purposes. In some standards, the addition of pigments to
produce "colored Portland cement" is allowed. In other standards (e.g. ASTM), pigments are not
allowed constituents of Portland cement, and colored cements are sold as "blended hydraulic
cements".
Very finely ground cements are made from mixtures of cement with sand or with slag or other
pozzolan type minerals that are extremely finely ground together. Such cements can have the same
physical characteristics as normal cement but with 50% less cement particularly due to their increased
surface area for the chemical reaction. Even with intensive grinding they can use up to 50% less
energy to fabricate than ordinary Portland cements.

Non-Portland hydraulic cements

Pozzolan-lime cements. Mixtures of ground pozzolan and lime are the cements used by the
Romans, and can be found in Roman structures still standing (e.g. the Pantheon in Rome). They
develop strength slowly, but their ultimate strength can be very high. The hydration products that
produce strength are essentially the same as those produced by Portland cement.

Slag-lime cements. Ground granulated blast furnace slag is not hydraulic on its own, but is
"activated" by addition of alkalis, most economically using lime. They are similar to pozzolan lime
cements in their properties. Only granulated slag (i.e. water-quenched, glassy slag) is effective as a
cement component.

Supersulfated cements. These contain about 80% ground granulated blast furnace slag,
15 % gypsum or anhydrite and a little Portland clinker or lime as an activator. They produce strength
by formation of ettringite, with strength growth similar to a slow Portland cement. They exhibit good
resistance to aggressive agents, including sulfate.

Calcium aluminate cements are hydraulic cements made primarily from limestone and bauxite. The

active ingredients are monocalcium aluminate CaAl2O4 (CaO · Al2O3 or CA in Cement chemist
notation, CCN) and mayenite Ca12Al14O33 (12 CaO · 7 Al2O3 , or C12A7 in CCN). Strength forms by
hydration to calcium aluminate hydrates. They are well-adapted for use in refractory (high-
temperature resistant) concretes, e.g. for furnace linings.

Calcium sulfoaluminate cements are made from clinkers that include ye'elimite (Ca4(AlO2)6SO4 or

C4A3  in Cement chemist's notation) as a primary phase. They are used in expansive cements, in
ultra-high early strength cements, and in "low-energy" cements. Hydration produces ettringite, and
specialized physical properties (such as expansion or rapid reaction) are obtained by adjustment of
the availability of calcium and sulfate ions. Their use as a low-energy alternative to Portland cement
has been pioneered in China, where several million tonnes per year are produced. Energy
requirements are lower because of the lower kiln temperatures required for reaction, and the lower
amount of limestone (which must be endothermically decarbonated) in the mix. In addition, the lower
limestone content and lower fuel consumption leads to a CO 2 emission around half that associated
with Portland clinker. However, SO2 emissions are usually significantly higher.

"Natural" cements correspond to certain cements of the pre-Portland era, produced by

burning argillaceous limestones at moderate temperatures. The level of clay components in the
limestone (around 30-35 %) is such that large amounts of belite (the low-early strength, high-late
strength mineral in Portland cement) are formed without the formation of excessive amounts of free
lime. As with any natural material, such cements have highly variable properties.

Geopolymer cements are made from mixtures of water-soluble alkali metal silicates and

aluminosilicate mineral powders such as fly ashand metakaolin.

The setting of cement

Cement sets when mixed with water by way of a complex series of hydration chemical reactions still
only partly understood. The different constituents slowly hydrate and crystallise while the interlocking
of their crystals gives to cement its strength. After the initial setting, immersion in warm water will
speed up setting. In Portland cement, gypsum is added as a compound preventing cement flash
setting. The time it takes for cement to set varies; and can take anywhere from twenty minutes for
initial set, to twenty-four hours, or more, for final set.

Environmental impacts
Cement manufacture causes environmental impacts at all stages of the process. These include
emissions of airborne pollution in the form of dust, gases, noise and vibration when operating
machinery and during blasting in quarries, and damage to countryside from quarrying. Equipment to
reduce dust emissions during quarrying and manufacture of cement is widely used, and equipment to
trap and separate exhaust gases are coming into increased use. Environmental protection also
includes the re-integration of quarries into the countryside after they have been closed down by
returning them to nature or re-cultivating them.

CO2 emissions
Cement manufacturing releases CO2 in the atmosphere both directly when calcium carbonate is
heated, producing lime and carbon dioxide, and also indirectly through the use of energy if its
production involves the emission of CO2. The cement industry is the second largest CO2 emitting
industry behind power generation. The cement industry produces about 5% of global man-made
CO2 emissions, of which 50% is from the chemical process, and 40% from burning fuel. The amount
of CO2 emitted by the cement industry is nearly 900 kg of CO2 for every 1000 kg of cement produced. 

In certain applications, lime mortar, reabsorbs the CO2 chemically released in its manufacture, and
has a lower energy requirement in production. Newly developed cement types from
Novacem and Eco-cement can absorb carbon dioxide from ambient air during hardening.

Heavy metal emissions in the air

In some circumstances, mainly depending on the origin and the composition of the raw materials
used, the high-temperature calcination process of limestone and clay minerals can release in the
atmosphere gases and dust rich in volatile heavy metals, a.o, thallium, cadmium and mercury are the
most toxic. Heavy metals (Tl, Cd, Hg, ...) are often found as trace elements in common
metal sulfides (pyrite (FeS2), zinc blende (ZnS), galena (PbS), ...) present as secondary minerals in
most of the raw materials. Environmental regulations exist in many countries to limit these emissions.

Heavy metals present in the clinker

The presence of heavy metals in the clinker arises both from the natural raw materials and from the
use of recycled by-products or alternative fuels. The high pH prevailing in the cement porewater (12.5
< pH < 13.5) limits the mobility of many heavy metals by decreasing their solubility and increasing
their sorption onto the cement mineral phases. Nickel, zinc and lead are commonly found in cement in
non-negligible concentrations.

Use of alternative fuels and by-products materials

A cement plant consumes 3 to 6 GJ of fuel per tonne of clinker produced, depending on the raw
materials and the process used. Most cement kilns today use coal and petroleum coke as primary
fuels, and to a lesser extent natural gas and fuel oil. Selected waste and by-products with recoverable
calorific value can be used as fuels in a cement kiln, replacing a portion of conventional fossil fuels,
like coal, if they meet strict specifications. Selected waste and by-products containing useful minerals
such as calcium, silica, alumina, and iron can be used as raw materials in the kiln, replacing raw
materials such as clay, shale, and limestone. Because some materials have both useful mineral
content and recoverable calorific value, the distinction between alternative fuels and raw materials is
not always clear. For example, sewage sludge has a low but significant calorific value, and burns to
give ash containing minerals useful in the clinker matrix.

Cement industry in the world

Cement output in 2004

In 2002 the world production of hydraulic cement was 1,800 million metric tons. The top three
producers were China with 704, India with 100, and the United States with 91 million metric tons for a
combined total of about half the world total by the world's three most populated states.

China
"For the past 18 years, China consistently has produced more cement than any other country in the
world. [...] (However,) China's cement export peaked in 1994 with 11 million tons shipped out and has
been in steady decline ever since. Only 5.18 million tons were exported out of China in 2002. Offered
at $34 a ton, Chinese cement is pricing itself out of the market as Thailand is asking as little as $20 for
the same quality."
In 2006 it was estimated that China manufactured 1.235 billion metric tons of cement, which was 44%
of the world total cement production.[23] "Demand for cement in China is expected to advance 5.4%
annually and exceed 1 billion metric tons in 2008, driven by slowing but healthy growth in construction
expenditures. Cement consumed in China will amount to 44% of global demand, and China will
remain the world's largest national consumer of cement by a large margin