# 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.

Cements used in construction can be characterized as being either hydraulic or non-hydraulic. Hydraulic cements (e.g., Portland cement) harden because of hydration, a chemical reaction between the anhydrous cement powder and water. Thus, they can harden underwater or when constantly exposed to wet weather. The chemical reaction results in hydrates that are not very water-soluble and so are quite durable in water. Non-hydraulic cements do not harden underwater; for example, slaked limes harden by reaction with atmospheric carbon dioxide.[1]

The most important uses of cement are as an ingredient in the production of mortar in masonry, and of concrete, a combination of cement and an aggregate to form a strong building material.

## Chemistry

Non-hydraulic cement such as slaked limes (calcium hydroxide mixed with water), harden due to the reaction of carbonation in presence of the carbon dioxyde naturally present in the air. Calcium oxyde is produced by lime calcination at temperatures above 825 °C (1,517 °F) for about 10 hours at atmospheric pressure:

$CaCO_3 \rightarrow CaO + CO_2$

The calcium oxyde is then spent mixing it to water to make slaked lime:

$CaO + H_2O \rightarrow Ca(OH)_2$

Once the water in excess from the slaked lime is completely evaporated (this process is technically called setting), the carbonation starts:

$Ca(OH)_2 + CO_2 \rightarrow CaCO_3 + H_2O$

This reaction take a significant amount of time, because the partial pressure of carbon dioxyde in the air is small. The reaction of carbonation requires the air to be in contact with the dry cement hence for this reason the slaked lime is a non-hydraulic cement and cannot be used under water.

Conversely, the chemistry ruling the action of the hydraulic cement is the hydration. Hydraulic cements (such as the Portland cement) are made of a mixture of silicates and oxydes, the four main components being:

Belite (2CaO.SiO2);
Alite (3CaO.SiO2);
Celite (3CaO.Al2O3);
Brownmillerite (4CaO.Al2O3.Fe2O3).

The reactions during the setting of the cement are:

$(3 \ CaO \cdot Al_2O_3)_2 + (x+8)H_2O \rightarrow 4 \ CaO \cdot Al_2O_3 \cdot xH_2O + 2 \ CaO \cdot Al_2O_3 \cdot 8 \ H_2O$
$3 \ CaO \cdot Al_2O_3 + 12 \ H_2O + Ca(OH)_2 \rightarrow 4 \ CaO \cdot Al_2O_3 \cdot 13 \ H_2O$
$4 \ CaO \cdot Al_2O_3 \cdot Fe_2O_3 + 7 \ H_2O \rightarrow 3 \ CaO \cdot Al_2O_3 \cdot 6 \ H_2O + CaO \cdot Fe_2O_3 \cdot H_2O$

And during the hardening (the chemistry o fthe reaction of hydration is still not completely clear):

$(3 \ CaO \cdot SiO_2)_2 + (x+3)H_2O \rightarrow 3 \ CaO2 \cdot SiO_2 \cdot xH_2O + 3 \ Ca(OH)_2$
$(2 \ CaO \cdot SiO_2)_2+ (x+1)H_2O \rightarrow 3 \ CaO2 \cdot SiO_2 \cdot xH_2O + Ca(OH)_2$

The silicates are responsible of the mechanical properties of the cement, the celite and the browmillerite are essential to allow the formation of the liquid phase during the cooking.

## History of the origin of cement

### Early uses

An early version of cement made with lime, sand, and gravel was used in Mesopotamia in the third millennium B.C. and later in Egypt. 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[2][3] and three centuries later on a large scale by Roman engineers.[4] 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.[5] The vast system of Roman aqueducts also made extensive use of hydraulic cement.[6]

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.[7][8] The technical knowledge of making hydraulic cement was later formalized by French and British engineers in the 18th century.[7]

### Modern cements

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".[9] 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 a civil 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.[10] James Frost,[11] 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.

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[12] 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.

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.

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, while Portland cement had a faster setting time 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 worked on the construction of the New York Cities Catskill Aqueduct, was impressed with the durability of Rosendale cement, and came up with a blend of both Rosendale and synthetic cements which had 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 of highway near New Paltz, New York, using one sack of Rosendale to six sacks of synthetic cement, and it was proved a success and for decades the Rosendale-synthetic cement blend became common use in highway and bridge construction.[13]

## 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-specialty 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 grey or white.

### Energetically modified cement

The grinding process to produce Energetically modified cement (EMC) yields materials made from pozzolanic minerals that have been treated using a patented milling process ("EMC Activation").[14] This yields a high-level replacement of Portland cement in concrete with lower costs, performance and durability improvements, with significant energy and carbon dioxide savings.[15] The resultant concretes can have the same, if not improved, physical characteristics as "normal" concretes, at a fraction of the cost of using Portland cement.[16]

## 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.[24][25][26]

## Cement industry in the world

Global Cement Production in 2010
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.[27]

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.[28]

### 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 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."[29]

In 2006, it was estimated that China manufactured 1.235 billion tonnes of cement, which was 44% of the world total cement production.[30] "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."[31]

In 2010, 3.3 billion tonnes of cement was consumed globally. Of this, China accounted for 1.8 billion tonnes.[32]

## 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

Carbon concentration in cement spans from ≈5% in cement structures to ≈8% in the case of roads in cement.[33] Cement manufacturing releases CO2 in the atmosphere both directly when calcium carbonate is heated, producing lime and carbon dioxide,[34] 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.[35] The amount of CO2 emitted by the cement industry is nearly 900 kg of CO2 for every 1000 kg of cement produced. [36] 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.[37]

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[38] and Eco-cement can absorb carbon dioxide from ambient air during hardening.[39] Use of the Kalina cycle during production can also increase energy efficiency.

### 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,[40] 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. As of 2011 in the United States, cement kilns are "legally allowed to pump more toxins into the air than are hazardous-waste incinerators."[41]

### 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 (referred to as co-processing), 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.[42]

## Green cement

Green cement is a cementitious material that meets or exceeds the functional performance capabilities of ordinary Portland cement by incorporating and optimizing recycled materials, thereby reducing consumption of natural raw materials, water, and energy, resulting in a more sustainable construction material.

The manufacturing process for green cement succeeds in reducing, and even eliminating, the production and release of damaging pollutants and greenhouse gasses, particularly CO2.

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