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cement
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{{Short description|Hydraulic binder used in the composition of mortar and concrete}}{{Other uses}}{{Use dmy dates|date=January 2019}}(File:USMC-110806-M-IX060-148.jpg|thumb|Cement powder, here conditioned{{clarification needed|date=April 2024}} in bag, ready to be mixed with aggregates and water. Dispersing dry cement dust in the air should be avoided to prevent health issues.WEB, Draeger: Guide for selection and use of filtering devices,www.draeger.com/Library/Content/ab-selection-guide-fl-9045782-en-1502-3.pdf, 22 May 2020, Draeger, live,web.archive.org/web/20200522143702/https://www.draeger.com/Library/Content/ab-selection-guide-fl-9045782-en-1502-3.pdf, 22 May 2020, 22 May 2020, )(File:Year book - photo flashes showing Toledo’s phenomenal progress, thriving industries and wonderful resources - DPLA - ac95c5ef8efd2394c21e2b6edcd01d94 (page 94) (cropped).jpg|thumb|right|Cement block construction examples from the Multiplex Manufacturing Company of Toledo, Ohio, in 1905)A cement is a binder, a chemical 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. Concrete is the most widely used material in existence and is behind only water as the planet’s most-consumed resource.NEWS,www.bbc.com/news/science-environment-46455844, The massive CO2 emitter you may not know about, Rodgers, Lucy, 17 December 2018, BBC News, 17 December 2018, Cements used in construction are usually inorganic, often lime or calcium silicate based, which can be characterized as hydraulic or the less common non-hydraulic, depending on the ability of the cement to set in the presence of water (see hydraulic and non-hydraulic lime plaster).Hydraulic cements (e.g., Portland cement) set and become adhesive through a chemical reaction between the dry ingredients and water. The chemical reaction results in mineral hydrates that are not very water-soluble. This allows setting in wet conditions or under water and further protects the hardened material from chemical attack. The chemical process for hydraulic cement was found by ancient Romans who used volcanic ash (pozzolana) with added lime (calcium oxide).Non-hydraulic cement (less common) 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.The word “cement” can be traced back to the Ancient Roman term , 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 , , cäment, and cement. In modern times, organic polymers are sometimes used as cements in concrete.World production of cement is about 4.4 billion tonnes per year (2021, estimation),WEB, Cement,pubs.usgs.gov/periodicals/mcs2022/mcs2022-cement.pdf, 2023-09-26, United States Geological Survey (USGS), of which about half is made in China, followed by India and Vietnam.The cement production process is responsible for nearly 8% (2018) of global {{CO2}} emissions, which includes heating raw materials in a cement kiln by fuel combustion and resulting release of {{CO2}} stored in the calcium carbonate (calcination process). Its hydrated products, such as concrete, gradually reabsorb substantial amounts of atmospheric {{CO2}} (carbonation process) compensating near 30% of initial {{CO2}} emissions, as estimations suggest.JOURNAL, Cao, Zhi, Myers, Rupert J., Lupton, Richard C., Duan, Huabo, Sacchi, Romain, Zhou, Nan, Reed Miller, T., Cullen, Jonathan M., Ge, Quansheng, Liu, Gang, 2020-07-29, The sponge effect and carbon emission mitigation potentials of the global cement cycle, Nature Communications, en, 11, 1, 3777, 10.1038/s41467-020-17583-w, 32728073, 7392754, 2020NatCo..11.3777C, 2041-1723, free,

Chemistry

Cement materials can be classified into two distinct categories: hydraulic cements and non-hydraulic cements according to their respective setting and hardening mechanisms. Hydraulic cement setting and hardening involves hydration reactions and therefore requires water, while non-hydraulic cements only react with a gas and can directly set under air.

Hydraulic cement

File:LDClinkerScaled.jpg|thumb|Clinker nodules produced by sintering at 1450 Â°C]]By far the most common type of cement is hydraulic cement, which hardens by hydration of the clinker minerals when water is added. Hydraulic cements (such as Portland cement) are made of a mixture of silicates and oxides, the four main mineral phases of the clinker, abbreviated in the cement chemist notation, being:
C3S: alite (3CaO·SiO2); C2S: belite (2CaO·SiO2); C3A: tricalcium aluminate (3CaO·Al2O3) (historically, and still occasionally, called celite); C4AF: brownmillerite (4CaO·Al2O3·Fe2O3).
The silicates are responsible for the cement’s mechanical properties — the tricalcium aluminate and brownmillerite are essential for the formation of the liquid phase during the sintering (firing) process of clinker at high temperature in the kiln. The chemistry of these reactions is not completely clear and is still the object of research.WEB,cee.mit.edu/cee-in-focus/2011/spring/cement-structure,cee.mit.edu/cee-in-focus/2011/spring/cement-structure," title="web.archive.org/web/20130221105202cee.mit.edu/cee-in-focus/2011/spring/cement-structure,">web.archive.org/web/20130221105202cee.mit.edu/cee-in-focus/2011/spring/cement-structure, dead, Cement’s basic molecular structure finally decoded (MIT, 2009), 21 February 2013, First, the limestone (calcium carbonate) is burned to remove its carbon, producing lime (calcium oxide) in what is known as a calcination reaction. This single chemical reaction is a major emitter of global carbon dioxide emissions.WEB, EPA Overview of Greenhouse Gases, 23 December 2015,www.epa.gov/ghgemissions/overview-greenhouse-gases,
CaCO3 -> CaO + CO2
The lime reacts with silicon dioxide to produce dicalcium silicate and tricalcium silicate.
2CaO + SiO2 -> 2CaO.SiO2 3CaO + SiO2 -> 3CaO.SiO2
The lime also reacts with aluminium oxide to form tricalcium aluminate.
3CaO + Al2O3 -> 3CaO.Al2O3
In the last step, calcium oxide, aluminium oxide, and ferric oxide react together to form brownmillerite.
4CaO + Al2O3 + Fe2O3 -> 4CaO.Al2O3.Fe2O3

Non-hydraulic cement

File:Calcium oxide powder.JPG|thumb|Calcium oxide obtained by thermal decomposition of calcium carbonatecalcium carbonateA less common form of cement is non-hydraulic cement, such as slaked lime (calcium oxide mixed with water), which hardens by carbonation in contact with carbon dioxide, which is present in the air (~ 412 vol. ppm ≃ 0.04 vol. %). First calcium oxide (lime) is produced from calcium carbonate (limestone or chalk) by calcination at temperatures above 825 Â°C (1,517 Â°F) for about 10 hours at atmospheric pressure:
CaCO3 -> CaO + CO2
The calcium oxide is then spent (slaked) by 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 is slow, because the partial pressure of carbon dioxide in the air is low (~ 0.4 millibar). 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.

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 by natural causes. These ancient deposits were investigated in the 1960s and 1970s.WEB, The History of Concrete,matse1.matse.illinois.edu/concrete/hist.html, Dept. of Materials Science and Engineering, University of Illinois, Urbana-Champaign, 8 January 2013, live,matse1.matse.illinois.edu/concrete/hist.html," title="web.archive.org/web/20121127052951matse1.matse.illinois.edu/concrete/hist.html,">web.archive.org/web/20121127052951matse1.matse.illinois.edu/concrete/hist.html, 27 November 2012,

Alternatives to cement used in antiquity

Cement, chemically speaking, is a product that includes lime as the primary binding 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 Ancient Egypt, stone blocks were cemented together with a mortar made of sand and roughly burnt gypsum (CaSO4 · 2H2O), which is Plaster of Paris, which often contained calcium carbonate (CaCO3),

Ancient Greece and Rome

Lime (calcium oxide) was used on Crete and by the Ancient Greeks. There is evidence that the Minoans of Crete used crushed potsherds 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 Greeks, specifically the Ancient Macedonians,Brabant, Malcolm (12 April 2011). Macedonians created cement three centuries before the Romans {{webarchive|url=https://web.archive.org/web/20190409224527www.bbc.co.uk/news/av/world-europe-13046299/macedonians-created-cement-three-centuries-before-the-romans |date=9 April 2019 }}, BBC News.Heracles to Alexander The Great: Treasures From The Royal Capital of Macedon, A Hellenic Kingdom in the Age of Democracy {{webarchive|url=https://web.archive.org/web/20120117164459www.ashmolean.org/exhibitions/current/?timing=current&id=57&exhibitionYear=2011 |date=17 January 2012 }}, Ashmolean Museum of Art and Archaeology, University of Oxford and three centuries later on a large scale by Roman engineers.Hill, Donald (1984). A History of Engineering in Classical and Medieval Times, Routledge, p. 106, {{ISBN|0415152917}}.WEB,www.understanding-cement.com/history.html, History of cement, www.understanding-cement.com, 17 December 2018, WEB,io9.gizmodo.com/how-the-ancient-romans-made-better-concrete-than-we-do-1672632593, How the Ancient Romans Made Better Concrete Than We Do Now, Trendacosta, Katharine, 18 December 2014, Gizmodo, {{Blockquote|text=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 Mount 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 underwater.|author=Marcus Vitruvius Pollio|source=Liber II, De Architectura, Chapter VI “Pozzolana” Sec. 1|title=}}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 to corrosion like rust.WEB,pozzolan.org/improve-concrete.html, How Natural Pozzolans Improve Concrete, Natural Pozzolan Association, 2021-04-07, The material was called pozzolana from the town of Pozzuoli, west of Naples where volcanic ash was extracted.JOURNAL, Francesca, Ridi, Hydration of Cement: still a lot to be understood, La Chimica & l’Industria,www.soc.chim.it/sites/default/files/chimind/pdf/2010_3_110_ca.pdf, 3, April 2010, 110–117, live,www.soc.chim.it/sites/default/files/chimind/pdf/2010_3_110_ca.pdf," title="web.archive.org/web/20151117023718www.soc.chim.it/sites/default/files/chimind/pdf/2010_3_110_ca.pdf,">web.archive.org/web/20151117023718www.soc.chim.it/sites/default/files/chimind/pdf/2010_3_110_ca.pdf, 17 November 2015, 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.WEB,www.chamorro.com/community/pagan/Azmar_Natural_Pozzolan.pdf, Pure natural pozzolan cement, 12 January 2009, bot: unknown,www.chamorro.com/community/pagan/Azmar_Natural_Pozzolan.pdf," title="web.archive.org/web/20061018162743www.chamorro.com/community/pagan/Azmar_Natural_Pozzolan.pdf,">web.archive.org/web/20061018162743www.chamorro.com/community/pagan/Azmar_Natural_Pozzolan.pdf, 18 October 2006, . chamorro.com The vast system of Roman aqueducts also made extensive use of hydraulic cement.Russo, Ralph (2006) “Aqueduct Architecture: Moving Water to the Masses in Ancient Rome” {{webarchive|url=https://web.archive.org/web/20081012075152www.yale.edu/ynhti/curriculum/units/2006/4/06.04.04.x.html |date=12 October 2008 }}, in Math in the Beauty and Realization of Architecture, Vol. IV, Curriculum Units by Fellows of the Yale-New Haven Teachers Institute 1978–2012, Yale-New Haven Teachers Institute. 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.JOURNAL, 10.1080/00038628.1975.9696342, An Historical Note on Concrete, Architectural Science Review, 18, 10–13, 1975, Cowan, Henry J.,

Mesoamerica

Lightweight concrete was designed and used for the construction of structural elements by the pre-Columbian builders who lived in a very advanced civilisation in El Tajin near Mexico City, in Mexico. A detailed study of the composition of the aggregate and binder show that the aggregate was pumice and the binder was a pozzolanic cement made with volcanic ash and lime.JOURNAL, Properties and Durability of a Pre-Columbian Lightweight Concrete, G. Cabrera., R. Rivera-Villarreal., R. Sri Ravindrarajah, 1997, 170, 1215–1230, 10.14359/6874, Symposium Paper / American Concrete Institute, International Concrete Abstracts Portal, 9780870316692, 138768044,

Middle Ages

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.BOOK, Sismondo, Sergio, {{google books, y, LescwF8FBigC, |title=An Introduction to Science and Technology Studies |date=2009-11-20 |publisher=Wiley |isbn=978-1-4443-1512-7 |language=en}}BOOK, Mukerji, Chandra, {{google books, y, fRwNRrFswv8C, 121, |title=Impossible Engineering: Technology and Territoriality on the Canal Du Midi |date=2009 |page=121|publisher=Princeton University Press |isbn=978-0-691-14032-2 |language=en}} 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.

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