Editing Cement (section)

==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.<ref name=MAST>{{cite web|title=The History of Concrete|url=http://matse1.matse.illinois.edu/concrete/hist.html|publisher=Dept. of Materials Science and Engineering, University of Illinois, Urbana-Champaign|access-date=8 January 2013|url-status=live|archive-url=https://web.archive.org/web/20121127052951/http://matse1.matse.illinois.edu/concrete/hist.html|archive-date=27 November 2012}}</ref>

===Alternatives to cement used in antiquity===
Cement, chemically speaking, is a product that includes [[Calcium oxide|lime]] as the primary binding ingredient, but is far from the first material used for cementation. The [[Babylonia]]ns and [[Assyria]]ns used [[bitumen]] (asphalt or [[pitch (resin)|pitch]]) to bind together burnt brick or [[alabaster]] slabs. In [[Ancient Egypt]], stone blocks were cemented together with a [[Mortar (masonry)|mortar]] made of [[sand]] and roughly burnt [[gypsum]] (CaSO<sub>4</sub> · 2H<sub>2</sub>O), which is [[plaster]] of Paris, which often contained calcium carbonate (CaCO<sub>3</sub>),<ref name="Blezard"/>

===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.<ref name="Blezard"/> Nobody knows who first discovered that a combination of [[Slaked lime|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]],<ref>Brabant, Malcolm (12 April 2011). [https://www.bbc.co.uk/news/av/world-europe-13046299/macedonians-created-cement-three-centuries-before-the-romans Macedonians created cement three centuries before the Romans] {{webarchive|url=https://web.archive.org/web/20190409224527/https://www.bbc.co.uk/news/av/world-europe-13046299/macedonians-created-cement-three-centuries-before-the-romans |date=9 April 2019 }}, ''BBC News''.</ref><ref>{{cite web|url=http://www.ashmolean.org/exhibitions/current/?timing=current&id=57&exhibitionYear=2011|title=Heracles to Alexander The Great: Treasures From The Royal Capital of Macedon, A Hellenic Kingdom in the Age of Democracy|archive-url=https://web.archive.org/web/20120117164459/http://www.ashmolean.org/exhibitions/current/?timing=current&id=57&exhibitionYear=2011|archive-date=17 January 2012|publisher=Ashmolean Museum of Art and Archaeology, University of Oxford}}</ref> and three centuries later on a large scale by [[Roman engineers]].<ref>{{Cite book|last=Hill|first=Donald|url={{google books|plainurl=y|id=oMceAgAAQBAJ|page=106}}|title=A History of Engineering in Classical and Medieval Times|date=19 November 2013|publisher=Routledge|isbn=978-1-317-76157-0|language=en|page=106}}</ref><ref>{{Cite web|url=https://www.understanding-cement.com/history.html|title=History of cement|website=www.understanding-cement.com|access-date=17 December 2018}}</ref><ref>{{Cite web|url=https://io9.gizmodo.com/how-the-ancient-romans-made-better-concrete-than-we-do-1672632593|title=How the Ancient Romans Made Better Concrete Than We Do Now|last=Trendacosta|first=Katharine|date=18 December 2014|website=Gizmodo}}</ref>

{{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 [[Tuff|volcanic tuff]] from the island of [[Thera]] as their pozzolan and the Romans used crushed [[volcanic ash]] (activated [[aluminium silicate]]s) with lime. This mixture could set under water, increasing its resistance to corrosion like rust.<ref name="Natural Pozzolan Association">{{cite web|url=https://pozzolan.org/improve-concrete.html|title=How Natural Pozzolans Improve Concrete|work=Natural Pozzolan Association|access-date=7 April 2021}}</ref> The material was called ''pozzolana'' from the town of [[Pozzuoli]], west of [[Naples]] where volcanic ash was extracted.<ref name=Ridi2010>{{Cite journal|first=Francesca|last=Ridi|title=Hydration of Cement: still a lot to be understood|journal=La Chimica & l'Industria|url=http://www.soc.chim.it/sites/default/files/chimind/pdf/2010_3_110_ca.pdf|issue=3|date=April 2010|pages=110–117|url-status=live|archive-url=https://web.archive.org/web/20151117023718/http://www.soc.chim.it/sites/default/files/chimind/pdf/2010_3_110_ca.pdf|archive-date=17 November 2015}}</ref> 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.<ref name="Blezard"/> The huge [[dome]] of the [[Pantheon, Rome|Pantheon]] in Rome and the massive [[Baths of Caracalla]] are examples of ancient structures made from these concretes, many of which still stand.<ref>{{cite web|url=http://www.chamorro.com/community/pagan/Azmar_Natural_Pozzolan.pdf|title=Pure natural pozzolan cement|access-date=12 January 2009|url-status=bot: unknown|archive-url=https://web.archive.org/web/20061018162743/http://www.chamorro.com/community/pagan/Azmar_Natural_Pozzolan.pdf|archive-date=18 October 2006}}. chamorro.com</ref><ref name="Rodgers-2018" /> The vast system of [[Roman aqueduct]]s also made extensive use of hydraulic cement.<ref>Russo, Ralph (2006) [http://www.yale.edu/ynhti/curriculum/units/2006/4/06.04.04.x.html "Aqueduct Architecture: Moving Water to the Masses in Ancient Rome"] {{webarchive|url=https://web.archive.org/web/20081012075152/http://www.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.</ref> 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 (masonry)|mortar]] mixed with an [[Construction aggregate|aggregate]] of broken pieces of stone, brick, [[Sherd|potsherds]], recycled chunks of concrete, or other building rubble.<ref name="Cowan 1975">{{cite journal|doi=10.1080/00038628.1975.9696342|title=An Historical Note on Concrete|journal=Architectural Science Review|volume=18|pages=10–13|year=1975|last1=Cowan|first1=Henry J.}}</ref>

===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.<ref>{{Cite book|last1=Cabrera|first1=J. G.|last2=Rivera-Villarreal|first2=R.|last3=Sri Ravindrarajah|first3=R.|chapter=Properties and Durability of a Pre-Columbian Lightweight Concrete |year=1997|title=SP-170: Fourth CANMET/ACI International Conference on Durability of Concrete|journal=Symposium Paper / American Concrete Institute, International Concrete Abstracts Portal|volume=170|issue=SP-170: Fourth CANMET/ACI International Conference on Durability of Concrete|pages=1215–1230|doi=10.14359/6874|isbn=9780870316692|s2cid=138768044}}</ref>

=== Middle Ages ===
Any preservation of this knowledge in literature from the [[Middle Ages]] is unknown, but medieval [[masonry|masons]] and some military engineers actively used hydraulic cement in structures such as [[canal]]s, fortresses, [[harbor]]s, and [[Shipyard|shipbuilding facilities]].<ref name="Sismondo">{{Cite book|last=Sismondo|first=Sergio|url={{google books|plainurl=y|id=LescwF8FBigC}}|title=An Introduction to Science and Technology Studies|date=20 November 2009|publisher=Wiley|isbn=978-1-4443-1512-7|language=en}}</ref><ref name="Mukerji">{{Cite book|last=Mukerji|first=Chandra|url={{google books|plainurl=y|id=fRwNRrFswv8C|page=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}}</ref> 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 architecture|Gothic period]]. The German [[Rhineland]] continued to use hydraulic mortar throughout the Middle Ages, having local pozzolana deposits called [[trass]].<ref name="Cowan 1975"/>

===16th century===
[[Tabby (cement)|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.<ref name="books.google.com"><{{Cite journal|last=Taves|first=Loren Sickels|url={{google books|plainurl=y|id=VJY1hE0W9UoC|page=5}}|page=5|title=Tabby Houses of the South Atlantic Seaboard|journal=Old-House Journal|date=27 October 2015|publisher=Active Interest Media, Inc.|language=en}}</ref>

===18th century===
The technical knowledge for making hydraulic cement was formalized by French and British engineers in the 18th century.<ref name="Sismondo"/>

[[John Smeaton]] made an important contribution to the development of cements while planning the construction of the third [[Eddystone Lighthouse]] (1755–59) in the [[English Channel]] now known as [[Smeaton's Tower]]. He needed a hydraulic mortar that would set and develop some strength in the twelve-hour period between successive high [[tide]]s. He performed experiments with combinations of different [[limestone]]s and additives including trass and [[pozzolana]]s<ref name="Blezard">{{Cite book|editor-last=Hewlett|editor-first=Peter|url={{google books|plainurl=y|id=v1JVu4iifnMC}}|title=Lea's Chemistry of Cement and Concrete|date=12 November 2003|publisher=Elsevier|isbn=978-0-08-053541-8|language=en|last=Blezard|first=Robert G.|chapter=The History of Calcareous Cements|pages=1–24}}</ref> and did 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]] used to make it. Smeaton was a civil engineer by profession, and took the idea no further.

In the [[Atlantic coastal plain|South Atlantic seaboard]] of the United States, [[Tabby (cement)|tabby]] relying on the oyster-shell [[midden]]s of earlier Native American populations was used in house construction from the 1730s to the 1860s.<ref name="books.google.com"/>

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]]".<ref>Francis, A.J. (1977) ''The Cement Industry 1796–1914: A History'', David & Charles. {{ISBN|0-7153-7386-2}}, Ch. 2.</ref> This was developed by [[James Parker (cement maker)|James Parker]] in the 1780s, and finally patented in 1796. It was, in fact, nothing like material used by the Romans, but was a "natural cement" made by burning [[Septarian concretion|septaria]] – [[Nodule (geology)|nodules]] that are found in certain clay deposits, and that contain both [[clay minerals]] and [[calcium carbonate]]. The burnt [[nodule (geology)|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 [[hydraulic lime]] cements of [[clay]] and [[chalk]].
Roman cement quickly became popular but was largely replaced by [[Portland cement]] in the 1850s.<ref name="Blezard"/>

===19th century===
Apparently unaware of [[John Smeaton|Smeaton's]] work, the same principle was identified by Frenchman [[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<ref>{{cite web|url=http://www.nationalcement.com/faq/who-discovered-cement|title=Who Discovered Cement|url-status=live|archive-url=https://web.archive.org/web/20130204131106/http://www.nationalcement.com/faq/who-discovered-cement|archive-date=4 February 2013|df=dmy-all|date=12 September 2012}}</ref> considered the "principal forerunner"<ref name="Blezard"/> of Portland cement and "...Edgar Dobbs of [[Southwark]] patented a cement of this kind in 1811."<ref name="Blezard"/>

In Russia, [[Egor Cheliev]] created a new binder by mixing lime and clay. His results were published in 1822 in his book ''A Treatise on the Art to Prepare a Good Mortar'' published in [[Saint Petersburg|St. Petersburg]]. A few years later in 1825, he published another book, which described various methods of making cement and concrete, and the benefits of cement in the construction of buildings and embankments.<ref>{{cite book|author1=Znachko-Iavorskii|author2=I. L.|title=Egor Gerasimovich Chelidze, izobretatelʹ tsementa|url=http://catalog.hathitrust.org/Record/008851841|url-status=live|archive-url=https://web.archive.org/web/20140201232847/http://catalog.hathitrust.org/Record/008851841|archive-date=1 February 2014|publisher=Sabchota Sakartvelo|year=1969}}</ref><ref>{{cite web|title=Lafarge History of Cement|url=http://cement-174.ru/stati/izobretenie.html|url-status=live|archive-url=https://web.archive.org/web/20140202101113/http://cement-174.ru/stati/izobretenie.html|archive-date=2 February 2014}}</ref>

[[File:William Aspdin Radford cyclopedia Volume 1.jpg|thumb|right|upright|[[William Aspdin]] is considered the inventor of "modern" [[Portland cement]].<ref name="William Aspdin">{{cite book|last1=Courland|first1=Robert|title=Concrete planet : the strange and fascinating story of the world's most common man-made material|date=2011|publisher=Prometheus Books|location=Amherst, N.Y.|isbn=978-1616144814|url=https://archive.org/details/isbn_9781616144814|url-access=registration|page=[https://archive.org/details/isbn_9781616144814/page/190 190]}}</ref>]]
[[Portland cement]], the most common type of cement in general use around the world as a basic ingredient of concrete, [[mortar (masonry)|mortar]], [[stucco]], and non-speciality [[grout]], was developed in England in the mid 19th century, and usually originates from [[limestone]]. [[James Frost (cement maker)|James Frost]] produced what he called "British cement" in a similar manner around the same time, but did not obtain a patent until 1822.<ref>Francis, A.J. (1977) ''The Cement Industry 1796–1914: A History'', David & Charles. {{ISBN|0-7153-7386-2}}, Ch. 5.</ref> 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]] quarried on the [[Isle of Portland]], Dorset, England. However, Aspdins' cement was nothing like modern Portland cement but was a first step in its development, called a ''proto-Portland cement''.<ref name="Blezard"/> Joseph Aspdins' son [[William Aspdin]] had left his father's company and in his cement manufacturing apparently accidentally produced [[calcium silicate]]s in the 1840s, a middle step in the development of Portland cement. 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 [[millstone]]s, which were the only available [[Grinding wheel|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. [[Isaac Charles Johnson]] further refined the production of ''meso-Portland cement'' (middle stage of development) and claimed he was the real father of Portland cement.<ref>Hahn, Thomas F. and Kemp, Emory Leland (1994). ''Cement mills along the Potomac River''. Morgantown, WV: West Virginia University Press. p. 16. {{ISBN|9781885907004}}</ref>

Setting time and "early strength" are important characteristics of cements. Hydraulic limes, "natural" cements, and "artificial" cements all rely on their [[belite]] (2 CaO · SiO<sub>2</sub>, abbreviated as C<sub>2</sub>S) content for [[Strength of materials|strength]] development. Belite develops strength slowly. Because they were burned at temperatures below {{convert|1250|C|F}}, they contained no [[alite]] (3 CaO · SiO<sub>2</sub>, abbreviated as C<sub>3</sub>S), which is responsible for early strength in modern cements. The first cement to consistently contain alite was made by William Aspdin 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 Johnson) have claimed precedence in this invention, but recent analysis<ref>{{cite book|author=Hewlett, Peter|title=Lea's Chemistry of Cement and Concrete|url={{google books|plainurl=y|id=v1JVu4iifnMC|page=1}}|year=2003|publisher=Butterworth-Heinemann|isbn=978-0-08-053541-8|page=Ch. 1|url-status=live|archive-url=https://web.archive.org/web/20151101041700/https://books.google.com/books?id=v1JVu4iifnMC|archive-date=1 November 2015}}</ref> 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 [[Cement kiln|kiln]].

In the US the first large-scale use of cement was [[Rosendale cement]], a natural cement mined from a massive deposit of [[Dolomite (rock)|dolomite]] 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]], [[United States Capitol|Capitol Building]], [[Brooklyn Bridge]]) and lining water pipes.<ref name="Natural Cement Comes Back">{{Cite web|url={{google books|plainurl=y|id=VCcDAAAAMBAJ|page=118}}|title=Natural Cement Comes Back|work=Popular Science|date=October 1941|page=118|publisher=Bonnier Corporation|language=en}}</ref>
[[Sorel cement]], or magnesia-based cement, was patented in 1867 by the Frenchman [[Stanislas Sorel]].<ref name=sorel_1867>Stanislas Sorel (1867). "[https://archive.org/details/ComptesRendusAcademieDesSciences0065/page/n103 Sur un nouveau ciment magnésien]". ''Comptes rendus hebdomadaires des séances de l'Académie des sciences'', volume 65, pages 102–104.</ref> It was stronger than Portland cement but its poor water resistance (leaching) and corrosive properties ([[pitting corrosion]] due to the presence of leachable [[chloride]] anions and the low pH (8.5–9.5) of its pore water) limited its use as reinforced concrete for building construction.<ref name="WallingProvis2016">{{cite journal|last1=Walling|first1=Sam A.|last2=Provis|first2=John L.|title=Magnesia-based cements: A journey of 150 years, and cements for the future?|journal=Chemical Reviews|volume=116|issue=7|year=2016|pages=4170–4204|issn=0009-2665|doi=10.1021/acs.chemrev.5b00463|pmid=27002788|doi-access=free}}</ref>

The next development in the manufacture of Portland cement was the introduction of the [[rotary kiln]]. It produced a [[clinker (cement)|clinker]] mixture that was both stronger, because more [[alite]] (C<sub>3</sub>S) is formed at the higher temperature it achieved (1450&nbsp;°C), and more homogeneous. Because raw material is constantly fed into a rotary kiln, it allowed a [[continuous production|continuous manufacturing process]] to replace lower capacity [[batch production]] processes.<ref name="Blezard"/>

===20th century===
[[File:Factory of National Cement Share Company.jpg|thumb|right|The National Cement Share Company of [[Ethiopia]]'s new plant in [[Dire Dawa]]]]
[[Calcium aluminate cements]] were patented in 1908 in France by Jules Bied for better resistance to sulfates.<ref>{{Cite book|url={{google books|plainurl=y|id=NAqkAgAAQBAJ|page=211}}|title=Engineering Materials Science: Properties, Uses, Degradation, Remediation|last1=McArthur|first1=H.|last2=Spalding|first2=D.|date=1 January 2004|publisher=Elsevier|isbn=9781782420491}}</ref> Also in 1908, Thomas Edison experimented with pre-cast concrete in houses in Union, N.J.<ref>{{Cite web|url=https://science.howstuffworks.com/transport/engines-equipment/cement-mixer.htm|title=How Cement Mixers Work|date=26 January 2012|website=HowStuffWorks|language=en|access-date=2 April 2020}}</ref>

In the US, after World War One, the long [[curing time]] of at least a month for [[Rosendale cement]] made it unpopular for constructing highways and bridges, and many states and construction firms turned to Portland cement. Because of the switch to Portland cement, by the end of the 1920s only one of the 15 Rosendale cement companies had survived. But in the early 1930s, builders discovered that, while Portland cement set faster, 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 helped construct the New York City's [[Catskill Aqueduct]], was impressed with the durability of Rosendale cement, and came up with a blend of both Rosendale and Portland cements that had the good attributes of both. It was highly durable and had a much faster setting time. 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 Portland cement. It was a success, and for decades the Rosendale-Portland cement blend was used in concrete highway and concrete bridge construction.<ref name="Natural Cement Comes Back"/>

Cementitious materials have been used as a nuclear waste immobilizing matrix for more than a half-century.<ref>Glasser F. (2011). Application of inorganic cements to the conditioning and immobilisation of radioactive wastes. In: Ojovan M.I. (2011). Handbook of advanced radioactive waste conditioning technologies. Woodhead, Cambridge, 512 pp.</ref> Technologies of waste cementation have been developed and deployed at industrial scale in many countries. Cementitious wasteforms require a careful selection and design process adapted to each specific type of waste to satisfy the strict waste acceptance criteria for long-term storage and disposal.<ref>Abdel Rahman R.O., Rahimov R.Z., Rahimova N.R., Ojovan M.I. (2015). Cementitious materials for nuclear waste immobilization. Wiley, Chichester 232 pp.</ref>