SUBJECT: APPLIED CHEMISTRY DEPARTMENT: MECHANICAL ENGINEERING

CEMENT

Lafarge cement plant in Contes, France.

In the most general sense of the word, a cement is a binder, a substance that sets and
hardens independently, and can bind other materials together. The word "cement" traces
to the Romans, who used the term opus caementicium to describe masonry resembling
modern concrete that was made from crushed rock with burnt lime as binder. The volcanic
ash and pulverized brick additives that were added to the burnt lime to obtain a hydraulic
binder were later referred to as cementum, cimentum, cäment, and cement.

Cement used in construction is characterized as hydraulic or non-hydraulic. Hydraulic

cements (e.g., Portland cement) harden because of hydration, chemical reactions that occur
independently of the mixture's water content; they can harden even underwater or when
constantly exposed to wet weather. The chemical reaction that results when the anhydrous
cement powder is mixed with water produces hydrates that are not water-soluble. Non-
hydraulic cements (e.g. gypsum plaster) must be kept dry in order to retain their strength.

The most important use of cement is the production of mortar and concrete—the bonding
of natural or artificial aggregates to form a strong building material that is durable in the
face of normal environmental effects.

Concrete should not be confused with cement, because the term cement refers to the
material used to bind the aggregate materials of concrete. Concrete is a combination of a
cement and aggregate.

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SUBJECT: APPLIED CHEMISTRY DEPARTMENT: MECHANICAL ENGINEERING

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 by the Ancient Macedonians[1][2] and three
centuries later on a large scale by Roman engineers.[3] 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 dome of the Pantheon in Rome and the massive Baths of Caracalla.[4] The
vast system of Roman aqueducts also made extensive use of hydraulic cement.

Although any preservation of this knowledge in literary sources from the Middle Ages is
unknown, medieval masons and some military engineers maintained an active tradition of
using hydraulic cement in structures such as canals, fortresses, harbors, and shipbuilding
facilities. The technical knowledge of making hydraulic cement was later formalized by
French and British engineers in the 18th century.

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

 Hydraulic cement 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".[8] 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.

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SUBJECT: APPLIED CHEMISTRY DEPARTMENT: MECHANICAL ENGINEERING
Setting time and "early strength" are important characteristics of cements. 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 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. But its long curing time of at least a month made it unpopular after
World War One in the construction of highways and bridges and many states and
construction firms turned to the use of Portland cement. Because of the switch to Portland
cement, by the end of the 1920s of the 15 Rosendale cement companies, only one had
survived. But in the early 1930s it was soon discovered that Portland cement while it had a
faster setting time was not as durable, especially for highways, to the point that some states
stopped building highways and roads with cement. An engineer, Bertrain H. Wait, whose
company had worked on the construction of the New York Cities Catskill Aqueduct, and
was impressed with the durability of Rosendale cement, came up with a blend of both
Rosendale and synthetic cements which has the good attributes of both: it was highly
durable and had a much faster setting time. Mr. Wait convinced the New York
Commissioner of Highways to construct an experimental section highway near New Paltz,
New York, of one sack of Rosendale to six sacks of synthetic cement, and it was proved a
success and for decades hence the Rosendale-synthetic cement blend became common use
in highway and bridge construction.[11]

Types of modern cement

Portland cement
Portland cement is not a trade name and neither does it refer to a geographical
place of origin. It was first made in Britain in the early 19th century and it gained
it's name from some products being made with it that looked like Portland Stone.
An Expensive and desirable building material of the time.
It is the most common form of cement used world wide and it dries to a light grey
colour. It is durable an versatile and it is forgiving of sloppy construction practises.
The main ingredient of Porland cement is Limestone which is an abundant rock that
is mined and quarried around the world.

Sustainable and Factory-made cements.

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There is currently a push from the European nations towards these types of cement
that use a lower proportion of clinker in the manufacturing process. They are said d
to be greener and to leave a smaller carbon footprint.

Sulfate-Resisting Cements
I once did a job renovating a building that suffered from catastrophic concrete
cancer. 20mm rebars were literally rusting and cracking and lifting out of floor
slabs so badly that you could trip over them. The reason was that it was in a salt
water environment. Similarly I have done repair work in sewerage pumping stations
that were affected by the chlorine that was used in them. The answer was to use a
sulphate resisting cement type that contains a high content of iron oxide. Other
types contain a proportion of fly ash in their make up.

Hydraulic Cement
A cement type that is capable of setting and hardening under water.

Refractory Cement
Calcium-aluminate cement, suitable for use at high temperatures. Used in kilns,
furnaces and the like.

Rapid Hardening Portland Cements

Rapid setting cements are composed of standard Portland cement that is generally
ground finer. They may also contain materials such as calcium aluminate or calcium
sulfoaluminate.
Because they gain heat quickly they are used in some cases where cold weather is a
factor, but for the most part they are used in precasting factories where a fast turn
around of moulds or formwork is needed.

Keene's Cement
A finely ground high density anhydrous plaster mix. Made mostly from calcined or
dead-burned gypsum.

White cement
This is a type of Portland cement made from usually pure chalk and white clay
(kaolin). It also may contain some iron oxides and manganese oxides. It is dearer
than standard grey cement. White cement is used for decorative work or decorative
toppings like terrazzo. It also makes for brighter colours when ochres and dyes are
used.
Some manufacturers also do varying grades between the standard grey and the
white but they can hardly be said to be different cement types.

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SUBJECT: APPLIED CHEMISTRY DEPARTMENT: MECHANICAL ENGINEERING

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.[17][18] 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 CO2 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 ash and metakaolin.

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SUBJECT: APPLIED CHEMISTRY DEPARTMENT: MECHANICAL ENGINEERING

Curing (Setting)
Cement sets or cures when mixed with water which causes a series of hydration chemical
reactions. The constituents slowly hydrate and crystallize; the interlocking of the crystals
gives cement its strength. Maintaining a high moisture content in cement during curing
increases both the speed of curing, and its final strength. Gypsum is often added to
Portland cement to prevent early hardening or "flash setting", allowing a longer working
time. The time it takes for cement to cure varies depending on the mixture and
environmental conditions; initial hardening can occur in as little as twenty minutes, while
full cure can take over a month. Cement typically cures to the extent that it can be put into
service within 24 hours to a week.

Safety issues
Bags of cement routinely have health and safety warnings printed on them because not
only is cement highly alkaline, but the setting process is exothermic. As a result, wet cement
is strongly caustic and can easily cause severe skin burns if not promptly washed off with
water. Similarly, dry cement powder in contact with mucous membranes can cause severe
eye or respiratory irritation. Cement users should wear protective clothing.[19][20][21]

Global Cement Capacity in 2010

In 2010 the world production of hydraulic cement was 3,300 million tonnes. The top three
producers were China with 1,800, India with 220 and USA with 63.5 million tonnes for a
combined total of over half the world total by the world's three most populated states.[22]

For the world capacity to produce cement in 2010 the situation was similar with the top
three states (China, India and USA) accounting for just under half the world total capacity.
[23]

China

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"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
tonnes shipped out and has been in steady decline ever since. Only 5.18 million tonnes 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."[24]

In 2006 it was estimated that China manufactured 1.235 billion tonnes of cement, which
was 44% of the world total cement production.[25] "Demand for cement in China is
expected to advance 5.4% annually and exceed 1 billion tonnes 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."[26]

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,[28] and also indirectly through the
use of energy if its production involves the emission of CO2. 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.[29] The amount of CO2 emitted by the cement industry is nearly
900 kg of CO2 for every 1000 kg of cement produced. [30] The high proportion of carbon
dioxide produced in the chemical reaction leads to large decrease in mass in the conversion
from limestone to cement. So, to reduce the transport of heavier raw materials and to
mimimize the associated costs, it is more economical for cement plants to be closer to the
limestone quarries rather than to the consumer centers.[31]

In certain applications, lime mortar, reabsorbs the same amount of CO2 as was released in
its manufacture, and has a lower energy requirement in production than mainstream
cement. Newly developed cement types from Novacem[32] and Eco-cement can absorb
carbon dioxide from ambient air during hardening.[33] Use of the Kalina cycle during
production can also increase energy efficiency.

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