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From Wikipedia, the free encyclopedia
For other uses, see Cement (disambiguation). Not to be confused with Concrete.
Lafarge cement plant in Contes, France.
A cement is a binder, a substance that sets and hardens independently, and can bind other materials together. The word "cement" traces to theRomans, 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. 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 anaggregate to form a strong building material.
1 Chemistry 2 History of the origin of cement
2.1 Early uses 2.2 Modern cements 3.1 Portland cement 3.2 Energetically modified cement 3.3 Portland cement blends 3.4 Non-Portland hydraulic cements
3 Types of modern cement
o o o o
4 Curing (Setting) 5 Safety issues 6 Cement industry in the world
6.1 China 6.2 Africa 7.1 CO2 emissions 7.2 Heavy metal emissions in the air 7.3 Heavy metals present in the clinker 7.4 Use of alternative fuels and by-products materials
7 Environmental impacts
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8 Green cement 9 See also 10 References
Brownmillerite (4CaO·Al2O3·Fe2O3). Alite (3CaO·SiO2). the carbonation starts: Ca(OH)2 + CO2 → CaCO3 + H2O This reaction takes a significant amount of time because the partial pressure of carbon dioxide in the air is small. Calcium oxide is produced by lime calcination at temperatures above 825 °C (1. hence. 11 Further reading 12 External links Chemistry Non-hydraulic cement such as slaked limes (calcium hydroxide mixed with water). The reaction of carbonation requires the air be in contact with the dry cement. Celite (3CaO·Al2O3). harden due to the reaction of carbonation in presence of the carbon dioxide naturally present in the air. Conversely.517 °F) for about 10 hours at atmospheric pressure: CaCO3 → CaO + CO2 The calcium oxide is then spent mixing it to water to make slaked lime: CaO + H2O → Ca(OH)2 Once the water in excess from the slaked lime is completely evaporated (this process is technically called setting). for this reason the slaked lime is a non-hydraulic cement and cannot be used under water. The reactions during the setting of the cement are: (3CaO·Al2O3)2 + (x+8) H2O → 4 CaO·Al2O3·xH2O + 2 CaO·Al2O3·8H2O (3CaO·Al2O3) + 12 H2O + Ca(OH)2 → 4 CaO·Al2O3·13 H2O (4CaO·Al2O3·Fe2O3) + 7 H2O → 3 CaO·Al2O3·6H2O + CaO·Fe2O3·H2O . Hydraulic cements (such as the Portland cement) are made of a mixture of silicates and oxides. the four main components being: Belite (2CaO·SiO2). the chemistry ruling the action of the hydraulic cement is the hydration.
The chemistry of the above listed reactions is not completely clear and is still object of research. notably the huge dome of . History of the origin of cement Early uses An early version of cement made with lime. and gravel was used in Mesopotamia in the third millennium B. and later in Egypt. Many excellent examples of structures made from these concretes are still standing.And during the hardening (the chemistry of the reaction of hydration is still not completely clear): (3CaO·SiO2)2 + (x+3) H2O → 3 CaO2·SiO2·xH2O + 3 Ca(OH)2 (2CaO·SiO2)2 + (x+1) H2O → 3 CaO2·SiO2·xH2O + Ca(OH)2 The silicates are responsible of the mechanical properties of the cement. but concrete made from such mixtures was first used by the Ancient Macedonians and three centuries later 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. 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). the celite and the browmillerite are essential to allow the formation of the liquid phase during the cooking. sand.C.
Development of strong concretes. Hydraulic mortars for masonry construction of harbor works. The vast system of Roman aqueducts also made extensive use of hydraulic cement.the Pantheon in Rome and the massive Baths of Caracalla. driven by three main needs: Hydraulic cement render (stucco) for finishing brick buildings in wet climates. and to finish them with . good quality building stone became ever more expensive during a period of rapid growth. The technical knowledge of making hydraulic cement was later formalized by French and British engineers in the 18th century. and shipbuilding facilities. in contact with sea water. fortresses. etc. Modern cements Modern hydraulic cements began to be developed from the start of the Industrial Revolution (around 1800). harbors. and it became a common practice to construct prestige buildings from the new industrial bricks.. medieval masons and some military engineers maintained an active tradition of using hydraulic cement in structures such as canals. In Britain particularly. Although any preservation of this knowledge in literary sources from the Middle Ages is unknown.
He performed an exhaustive market research on the available hydraulic limes. Most famous was Parker's "Roman cement". Hydraulic limes were favored for this. The burnt nodules were ground to a fine powder. Smeaton was a civil engineer by profession. and finally patented in 1796. 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. in fact. The success of "Roman Cement" led other manufacturers to develop rival products by burning artificial mixtures of clay and chalk. and took the . and that contain both clay minerals and calcium carbonate. but the need for a fast set time encouraged the development of new cements. It was. This product. visiting their production sites. He needed a hydraulic mortar that would set and develop some strength in the twelve hour period between successive high tides. nothing like any material used by the Romans. set in 5–15 minutes. and noted that the "hydraulicity" of the lime was directly related to the clay content of the limestone from which it was made. but was a "Natural cement" made by burning septaria – nodules that are found in certain clay deposits.a stucco to imitate stone. This was developed by James Parker in the 1780s. made into a mortar with sand.
idea no further. Setting time and "early strength" are important characteristics of cements.C. the same principle was identified by Louis Vicat in the first decade of the nineteenth century. Apparently unaware of Smeaton's work. others (e. Belite develops strength slowly.. In 1824. and "artificial" cements all rely upon their belite content for strength development. produced an "artificial cement" in 1817. and. James Frost. burning this. The first cement to consistently contain alite was made by Joseph Aspdin's son William in the early 1840s. which is responsible for early strength in modern cements. working in Britain. produced what he called "British cement" in a similar manner around the same time. which he called Portland cement. This was what we call today "modern" Portland cement. Vicat and I. Vicat went on to devise a method of combining chalk and clay into an intimate mixture. they contained no alite. Because they were burned at temperatures below 1250 °C. "natural" cements. . because the render made from it was in color similar to the prestigious Portland stone.g. Johnson) have claimed precedence in this invention. Joseph Aspdin patented a similar material. Hydraulic limes. Because of the air of mystery with which William Aspdin surrounded his product. but did not obtain a patent until 1822.
Rosendale cement was extremely popular for the foundation . and Johnson established the importance of sintering the mix in the kiln. Kent was a true alitebased cement. Manufacturing costs were therefore considerably higher. Thus Portland cement began its predominant role.but recent analysis of both his concrete and raw cement have shown that William Aspdin's product made at Northfleet. and the resulting clinker was very hard and rapidly wore down the millstones. The use of concrete in construction grew rapidly from 1850 onward. William Aspdin's innovation was counterintuitive for manufacturers of "artificial cements". 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 nearRosendale. and was soon the dominant use for cements. thus opening up a market for use in concrete. New York. because they required more lime in the mix (a problem for his father). which were the only available grinding technology of the time. a much higher kiln temperature (and therefore more fuel). but the product set reasonably slowly and developed strength quickly. However. Aspdin's methods were "rule-of-thumb": Vicat is responsible for establishing the chemical basis of these cements.
was impressed with the durability of Rosendale cement. Statue of Liberty. an engineer whose company had worked on the construction of the New York Cities Catskill Aqueduct. only one had survived. and it was proved a success and for decades the Rosendale-synthetic cement blend became common use in highway and bridge construction. But in the early 1930s it was soon discovered that. while Portland cement had a faster setting time it was not as durable. to the point that some states stopped building highways and roads with cement. Wait. .g.. Capitol Building. New York. Bertrain H. Because of the switch to Portland cement. Brooklyn Bridge) and lining water pipes. Wait convinced the New York Commissioner of Highways to construct an experimental section of highway near New Paltz. especially for highways. using one sack of Rosendale to six sacks of synthetic cement.of buildings (e. 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. by the end of the 1920s of the 15 Rosendale cement companies. 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.
Portland cement may be grey or white. or quicklime. The resulting hard substance. mortar and most nonspecialty grout. whereby a molecule of carbon dioxide is liberated from the calcium carbonate to form calcium oxide.Types of modern cement Portland cement Main article: Portland cement Portland cement is by far the most common type of cement in general use around the world. in a process known as calcination. and once hardened. . called 'clinker'. and water. which is then blended with the other materials that have been included in the mix. is then ground with a small amount of gypsum into a powder to make 'Ordinary Portland Cement'. concrete can be cast in almost any shape desired. As a construction material. Portland cement is a basic ingredient of concrete. can become a structural (load bearing) element. the most commonly used type of cement (often referred to as OPC). Concrete is a composite material consisting of aggregate (gravel and sand). cement. The most common use for Portland cement is in the production of concrete. This cement is made by heating limestone (calcium carbonate) with small quantities of other materials (such as clay) to 1450 °C in a kiln.
Used as an economic alternative to Portland . performance and durability improvements. if not improved.Energetically modified cement Main article: 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"). Portland blastfurnace cement contains up to 70% ground granulated blast furnace slag. early strength is reduced. with the rest Portland clinker and a little gypsum. All compositions produce high ultimate strength. but similar formulations are often also mixed from the ground components at the concrete mixing plant. while sulfate resistance increases and heat evolution diminishes. Portland cement blends Portland cement blends are often available as inter-ground mixtures from cement producers. at a fraction of the cost of using Portland cement. The resultant concretes can have the same. This yields a high-level replacement of Portland cement in concrete with lower costs. with significant energy and carbon dioxide savings. but as slag content is increased. physical characteristics as "normal" concretes.
Mexico. and must not be used in concrete. and cements containing 5–20% silica fume are occasionally produced. Where good quality cheap fly ash is available. retarders.g. However. Because fly ash addition allows a lower concrete water content. They are usually complex proprietary formulations containing Portland clinker and a number of other ingredients that may include limestone. early strength can also be maintained. waterproofers and coloring agents. The fly ash is pozzolanic. air entrainers. Addition of silica fume can yield exceptionally high strengths. Portland flyash cement contains up to 35% fly ash. Portland pozzolan cement includes fly ash cement. Portland silica fume cement. Chile.sulfate-resisting and low-heat cements. Italy. the Philippines) these cements are often the most common form in use. silica fume is more usually added to Portland cement at the concrete mixer. but also includes cements made from other natural or artificial pozzolans. In countries where volcanic ashes are available (e. so that ultimate strength is maintained. since fly ash is a pozzolan. Masonry cements are used for preparing bricklaying mortars and stuccos. hydrated lime. They are formulated to yield workable mortars . this can be an economic alternative to ordinary Portland cement.
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.that allow rapid and consistent masonry work. Expansive cements contain. In other standards (e. Colored cements are used for decorative purposes. Subtle variations of Masonry cement in the US are Plastic Cements and Stucco Cements. White blended cements may be made using white clinker and white supplementary materials such as highpurity metakaolin. These are designed to produce controlled bond with masonry blocks.g. Even with intensive . pigments are not allowed constituents of Portland cement. 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. In some standards. This allows large floor slabs (up to 60 m square) to be prepared without contraction joints. and are designed to offset the effects of drying shrinkage that is normally encountered with hydraulic cements. ASTM). and colored cements are sold as "blended hydraulic cements". the addition of pigments to produce "colored Portland cement" is allowed. in addition to Portland clinker. expansive clinkers (usually sulfoaluminate clinkers).
Only granulated slag (i. They produce strength by formation of ettringite. The hydration products that produce strength are essentially the same as those produced by Portland cement. They are similar to pozzolan lime cements in their properties. Slag-lime cements.grinding they can use up to 50% less energy to fabricate than ordinary Portland cements. These contain about 80% ground granulated blast furnace slag. They exhibit good resistance to aggressive agents. most economically using lime. glassy slag) is effective as a cement component. the Pantheon in Rome). They develop strength slowly. Mixtures of ground pozzolan and lime are the cements used by the Romans. Ground granulated blast furnace slag is not hydraulic on its own. The active ingredients are .g. Calcium aluminate cements are hydraulic cements made primarily from limestone and bauxite. but their ultimate strength can be very high. 15% gypsum or anhydrite and a little Portland clinker or lime as an activator.e. but is "activated" by addition of alkalis. and can be found in Roman structures still standing (e. with strength growth similar to a slow Portland cement. Non-Portland hydraulic cements Pozzolan-lime cements. Supersulfated cements. water-quenched. including sulfate.
In addition. in ultra-high early strength cements. for furnace linings. CCN) and mayenite Ca12Al14O33 (12 CaO · 7 Al2O3. Calcium sulfoaluminate cements are made from clinkers that include ye'elimite (Ca4(AlO2)6SO4 or C4A3S in Cement chemist's notation) as a primary phase. They are welladapted for use in refractory (hightemperature resistant) concretes. the lower limestone content and lower fuel consumption leads to a CO2 emission around half that associated with Portland clinker. or C12A7 in CCN). and the lower amount of limestone (which must be endothermically decarbonated) in the mix. Their use as a low-energy alternative to Portland cement has been pioneered in China. "Natural" cements correspond to certain . and specialized physical properties (such as expansion or rapid reaction) are obtained by adjustment of the availability of calcium and sulfate ions. and in "low-energy" cements. SO2 emissions are usually significantly higher. e. However.g. Hydration produces ettringite.monocalcium aluminate CaAl2O4 (CaO · Al2O3 or CA in Cement chemist notation. They are used in expansive cements. Strength forms by hydration to calcium aluminate hydrates. where several million tonnes per year are produced. Energy requirements are lower because of the lower kiln temperatures required for reaction.
the interlocking of the crystals gives cement its strength. allowing a longer working time.cements of the pre-Portland era. Curing (Setting) Cement sets or cures when mixed with water which causes a series of hydration chemical reactions. produced by burning argillaceous limestones at moderate temperatures. The time it takes for cement to cure varies depending on the mixture and environmental conditions. such cements have highly variable properties. As with any natural material. initial hardening can occur in as little as twenty minutes. Maintaining a high moisture content in cement during curing increases both the speed of curing. while full cure can take over a month. high-late strength mineral in Portland cement) are formed without the formation of excessive amounts of free lime. Cement typically cures to the extent that it can . The constituents slowly hydrate and crystallize. and its final strength. Geopolymer cements are made from mixtures of water-soluble alkali metal silicates and aluminosilicate mineral powders such as fly ash andmetakaolin. Gypsum is often added to Portland cement to prevent early hardening or "flash setting". The level of clay components in the limestone (around 30–35%) is such that large amounts of belite (the lowearly strength.
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. Cement industry in the world . Similarly. As a result.be put into service within 24 hours to a week. wet cement is stronglycaustic and can easily cause severe skin burns if not promptly washed off with water. Cement users should wear protective clothing. Reducing agents are sometimes added to cement to prevent the formation of carcinogenic chromate in cement. dry cement powder in contact with mucous membranes can cause severe eye or respiratory irritation.
and USA with 63. India with 220.800. The top three producers were China with 1.Global Cement Production in 2010 Global Cement Capacity in 2010 See also: List of countries by cement production In 2010.5 million tonnes for a combined total of over half the world total by the world's three most populated states. China . For the world capacity to produce cement in 2010. and USA) accounting for just under half the world total capacity. the situation was similar with the top three states (China. India.300 million tonnes. the world production of hydraulic cement was 3.
" In 2010.235 billion tonnes of cement. which was 44% of the world total cement production.. China accounted for 1.4% annually and exceed 1 billion tonnes in 2008. Chinese cement is pricing itself out of the market as Thailand is asking as little as $20 for the same quality. Of this. Only 5. [. Africa See also: Cement in Africa Environmental impacts Cement manufacture causes environmental impacts at all stages of the process. Cement consumed in China will amount to 44% of global demand.3 billion tonnes of cement was consumed globally. it was estimated that China manufactured 1."For the past 18 years. driven by slowing but healthy growth in construction expenditures. China consistently has produced more cement than any other country in the world. and China will remain the world's largest national consumer of cement by a large margin. "Demand for cement in China is expected to advance 5.18 million tonnes were exported out of China in 2002..8 billion tonnes.) China's cement export peaked in 1994 with 11 million tonnes shipped out and has been in steady decline ever since. Offered at $34 a ton." In 2006. These include emissions of airborne pollution in the form of .] (However. 3.
This reduction in primary . In the European union the specific energy consumption for the production of cement clinker has been reduced by approximately 30% since the 1970s. 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.Cement manufacturing releases CO2 in the atmosphere both directly when calcium carbonate is heated. and damage to countryside from quarrying. The amount of CO2 emitted by the cement industry is nearly 900 kg of CO2 for every 1000 kg of cement produced. producing limeand carbon dioxide. and equipment to trap and separate exhaust gases are coming into increased use. CO2 emissions Carbon concentration in cement spans from ≈5% in cement structures to ≈8% in the case of roads in cement. and also indirectly through the use of energy if its production involves the emission of CO2.dust. Equipment to reduce dust emissions during quarrying and manufacture of cement is widely used. noise and vibration when operating machinery and during blasting in quarries. The cement industry produces about 5% of global man-made CO2 emissions. gases. of which 50% is from the chemical process. and 40% from burning fuel.
it is more economical for cement plants to be closer to the limestone quarries rather than to the consumer centers. the high-temperature calcination process of limestone and clay minerals can release in the atmosphere gases and dust rich in . Newly developed cement types from Novacem and Eco-cement can absorb carbon dioxide from ambient air during hardening. lime mortar reabsorbs the same amount of CO2 as was released in its manufacture. Heavy metal emissions in the air In some circumstances. and has a lower energy requirement in production than mainstream cement. In certain applications. to reduce the transport of heavier raw materials and to mimimize the associated costs. mainly depending on the origin and the composition of the raw materials used.energy requirements is equivalent to approximately 11 million tonnes of coal per year with corresponding benefits in reduction of CO2 emissions.  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. Use of the Kalina cycle during production can also increase energy efficiency.
.5 < pH < 13. 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 ..volatile heavy metals. Nickel. Hg. zinc and lead are commonly found in cement in nonnegligible concentrations. cement kilns are "legally allowed to pump more toxins into the air than are hazardous-waste incinerators. Heavy metals (Tl.o.) are often found as trace elements in common metal sulfides (pyrite (FeS2). . thallium. .. a. The high pH prevailing in the cement porewater (12. As of 2011 in the United States." 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. galena (PbS). Environmental regulations exist in many countries to limit these emissions.) present as secondary minerals in most of the raw materials. zinc blende (ZnS).5) limits the mobility of many heavy metals by decreasing their solubility and increasing their sorption onto the cement mineral phases. cadmium and mercury are the most toxic. Cd..
Because some materials have both useful mineral content and recoverable calorific value. For example. the distinction between alternative fuels and raw materials is not always clear. The gas residence time at high temperature in the rotary kiln is of the . and limestone. alumina. Selected waste and byproducts containing useful minerals such as calcium. replacing raw materials such as clay. shale. Most cement kilns today use coal and petroleum coke as primary fuels. like coal.the process used. replacing a portion of conventional fossil fuels. if they meet strict specifications. silica. and to a lesser extent natural gas and fuel oil. and iron can be used as raw materials in the kiln. and burns to give ash containing minerals useful in the clinker matrix. This is primarily due to the very high temperatures of the kiln gases (2000 °C in the combustion gas from the main burners and 1100 °C in the gas from the burners in the precalciner). sewage sludge has a low but significant calorific value. Selected waste and by-products with recoverable calorific value can be used as fuels in a cement kiln (referred to as co-processing). Normal operation of cement kilns provides combustion conditions which are more than adequate for the destruction of even the most difficult to destroy organic substances.
have to be safely disposed of or transformed. and energy. and even eliminating. . the production and release of damaging pollutants and greenhouse gasses. Growing environmental and incresing cost of fuels of fossil origin have resulted in many contries in sharp reduction of the resources needed to produce cement and effluents (dust and exhhust gases). together with the incineration. resulting in a more sustainable construction material. thereby reducing consumption of natural raw materials. The manufacturing process for green cement succeeds in reducing. is to date one of the two main ways to treat this solid effluent of the food industry. Due to bovine spongiform encephalopathy (BSE) crisis in the European beef industry. The production of cement kilns. particularly CO2. the use of animal-derived products to feed cattle is now severely restricted. Large quantities of waste animal meat and bone meal (MBM). 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. . water.order of 5-10 seconds and in the precalciner more than 3 seconds. also known as animal flour.
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