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Cement
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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.[2]
Cements used in construction are usually inorganic, often lime- or calcium silicate-based, and are either hydraulic or less commonly 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 opus caementicium, used to describe masonry resembling modern concrete that was made from crushed rock with burnt lime as binder.[3] The volcanic ash and pulverized brick supplements that were added to the burnt lime, to obtain a hydraulic binder, were later referred to as cementum, cimentum, 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),[4][5] of which about half is made in China, followed by India and Vietnam.[4][6]
The cement production process is responsible for nearly 8% (2018) of global CO2 emissions,[5] which includes heating raw materials in a cement kiln by fuel combustion and release of CO2 stored in the calcium carbonate (calcination process). Its hydrated products, such as concrete, gradually reabsorb atmospheric CO2 (carbonation process), compensating for approximately 30% of the initial CO2 emissions.[7]
Chemistry
[edit]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
[edit]
By far the most common type of cement is hydraulic cement, which hardens by hydration (when water is added) of the clinker minerals. 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.[8]
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.[9]
- 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
[edit]A 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 °C (1,517 °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
[edit]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.[10]
Alternatives to cement used in antiquity
[edit]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 (asphalt or pitch) 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),[11]
Ancient Greece and Rome
[edit]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.[11] 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,[12][13] and three centuries later on a large scale by Roman engineers.[14][15][16]
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.
— Marcus Vitruvius Pollio, Liber II, De Architectura, Chapter VI "Pozzolana" Sec. 1
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.[17] The material was called pozzolana from the town of Pozzuoli, west of Naples where volcanic ash was extracted.[18] 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.[11] 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.[19][2] The vast system of Roman aqueducts also made extensive use of hydraulic cement.[20] 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.[21]
Mesoamerica
[edit]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.[22]
Middle Ages
[edit]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.[23][24] 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.[21]
16th century
[edit]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.[25]
18th century
[edit]The technical knowledge for making hydraulic cement was formalized by French and British engineers in the 18th century.[23]
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 tides. He performed experiments with combinations of different limestones and additives including trass and pozzolanas[11] 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 South Atlantic seaboard of the United States, tabby relying on the oyster-shell middens of earlier Native American populations was used in house construction from the 1730s to the 1860s.[25]
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".[26] This was developed by 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 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 hydraulic lime cements of clay and chalk. Roman cement quickly became popular but was largely replaced by Portland cement in the 1850s.[11]
19th century
[edit]Apparently unaware of 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[27] considered the "principal forerunner"[11] of Portland cement and "...Edgar Dobbs of Southwark patented a cement of this kind in 1811."[11]
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 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.[28][29]

Portland cement, the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-speciality grout, was developed in England in the mid 19th century, and usually originates from limestone. James Frost produced what he called "British cement" in a similar manner around the same time, but did not obtain a patent until 1822.[31] 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.[11] Joseph Aspdins' son William Aspdin had left his father's company and in his cement manufacturing apparently accidentally produced calcium silicates 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 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. 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.[32]
Setting time and "early strength" are important characteristics of cements. Hydraulic limes, "natural" cements, and "artificial" cements all rely on their belite (2 CaO · SiO2, abbreviated as C2S) content for strength development. Belite develops strength slowly. Because they were burned at temperatures below 1,250 °C (2,280 °F), they contained no alite (3 CaO · SiO2, abbreviated as C3S), 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[33] 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 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, Capitol Building, Brooklyn Bridge) and lining water pipes.[34] Sorel cement, or magnesia-based cement, was patented in 1867 by the Frenchman Stanislas Sorel.[35] 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.[36]
The next development in the manufacture of Portland cement was the introduction of the rotary kiln. It produced a clinker mixture that was both stronger, because more alite (C3S) is formed at the higher temperature it achieved (1450 °C), and more homogeneous. Because raw material is constantly fed into a rotary kiln, it allowed a continuous manufacturing process to replace lower capacity batch production processes.[11]
20th century
[edit]

Calcium aluminate cements were patented in 1908 in France by Jules Bied for better resistance to sulfates.[37] Also in 1908, Thomas Edison experimented with pre-cast concrete in houses in Union, N.J.[38]
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.[34]
Cementitious materials have been used as a nuclear waste immobilizing matrix for more than a half-century.[39] 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.[40]
Types
[edit]| Property | Portland cement |
Siliceous[b] fly ash |
Calcareous[c] fly ash |
Slag cement |
Silica fume | |
|---|---|---|---|---|---|---|
Proportion by mass (%)
|
SiO2 | 21.9 | 52 | 35 | 35 | 85–97 |
| Al2O3 | 6.9 | 23 | 18 | 12 | — | |
| Fe2O3 | 3 | 11 | 6 | 1 | — | |
| CaO | 63 | 5 | 21 | 40 | < 1 | |
| MgO | 2.5 | — | — | — | — | |
| SO3 | 1.7 | — | — | — | — | |
| Specific surface (m2/kg)[d] | 370 | 420 | 420 | 400 | 15,000 – 30,000 | |
| Specific gravity | 3.15 | 2.38 | 2.65 | 2.94 | 2.22 | |
| General purpose | Primary binder | Cement replacement | Cement replacement | Cement replacement | Property enhancer | |
| ||||||
Modern development of hydraulic cement began with 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
Modern cements are often Portland cement or Portland cement blends, but other cement blends are used in some industrial settings.
Portland cement
[edit]Portland cement, a form of hydraulic cement, is by far the most common type of cement in general use around the world. This cement is made by heating limestone (calcium carbonate) with other materials (such as clay) to 1,450 °C (2,640 °F) in a kiln, in a process known as calcination that liberates a molecule of carbon dioxide from the calcium carbonate to form calcium oxide, or quicklime, which then chemically combines with the other materials in the mix to form calcium silicates and other cementitious compounds. The resulting hard substance, called 'clinker', is then ground with a small amount of gypsum (CaSO4·2H2O) 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 to make concrete. Portland cement may be grey or white.
Portland cement blend
[edit]Portland cement blends are often available as inter-ground mixtures from cement producers, but similar formulations are often also mixed from the ground components at the concrete mixing plant.
Portland blast-furnace slag cement, or blast furnace cement (ASTM C595 and EN 197-1 nomenclature respectively), contains up to 95% ground granulated blast furnace slag, with the rest Portland clinker and a little gypsum. All compositions produce high ultimate strength, but as slag content is increased, early strength is reduced, while sulfate resistance increases and heat evolution diminishes. Used as an economic alternative to Portland sulfate-resisting and low-heat cements.
Portland-fly ash cement contains up to 40% fly ash under ASTM standards (ASTM C595), or 35% under EN standards (EN 197–1). The fly ash is pozzolanic, so that ultimate strength is maintained. Because fly ash addition allows a lower concrete water content, early strength can also be maintained. Where good quality cheap fly ash is available, this can be an economic alternative to ordinary Portland cement.[44]
Portland pozzolan cement includes fly ash cement, since fly ash is a pozzolan, but also includes cements made from other natural or artificial pozzolans. In countries where volcanic ashes are available (e.g., Italy, Chile, Mexico, the Philippines), these cements are often the most common form in use. The maximum replacement ratios are generally defined as for Portland-fly ash cement.
Portland silica fume cement. Addition of silica fume can yield exceptionally high strengths, and cements containing 5–20% silica fume are occasionally produced, with 10% being the maximum allowed addition under EN 197–1. However, silica fume is more usually added to Portland cement at the concrete mixer.[45]
Masonry cements are used for preparing bricklaying mortars and stuccos, and must not be used in concrete. They are usually complex proprietary formulations containing Portland clinker and a number of other ingredients that may include limestone, hydrated lime, air entrainers, retarders, waterproofers, and coloring agents. They are formulated to yield workable mortars that allow rapid and consistent masonry work. Subtle variations of masonry cement in North America are plastic cements and stucco cements. These are designed to produce a controlled bond with masonry blocks.
Expansive cements contain, in addition to Portland clinker, expansive clinkers (usually sulfoaluminate clinkers), and are designed to offset the effects of drying shrinkage normally encountered in hydraulic cements. This cement can make concrete for floor slabs (up to 60 m square) without contraction joints.
White blended cements may be made using white clinker (containing little or no iron) and white supplementary materials such as high-purity metakaolin. Colored cements serve decorative purposes. Some standards allow the addition of pigments to produce colored Portland cement. Other standards (e.g., ASTM) do not allow pigments in Portland cement, and colored cements are sold as blended hydraulic cements.
Very finely ground cements are cement mixed with sand or with slag or other pozzolan type minerals that are extremely finely ground together. Such cements can have the same physical characteristics as normal cement but with 50% less cement, particularly because there is more surface area for the chemical reaction. Even with intensive grinding they can use up to 50% less energy (and thus less carbon emissions) to fabricate than ordinary Portland cements.[46]
Other
[edit]Pozzolan-lime cements are mixtures of ground pozzolan and lime. These are the cements the Romans used, and are present in surviving Roman structures like the Pantheon in Rome. They develop strength slowly, but their ultimate strength can be very high. The hydration products that produce strength are essentially the same as those in Portland cement.
Slag-lime cements—ground granulated blast-furnace slag—are not hydraulic on their own, but are "activated" by addition of alkalis, most economically using lime. They are similar to pozzolan lime cements in their properties. Only granulated slag (i.e., water-quenched, glassy slag) is effective as a cement component.
Supersulfated cements contain about 80% ground granulated blast furnace slag, 15% gypsum or anhydrite and a little Portland clinker or lime as an activator. They produce strength by formation of ettringite, with strength growth similar to a slow Portland cement. They exhibit good resistance to aggressive agents, including sulfate.
Calcium aluminate cements are hydraulic cements made primarily from limestone and bauxite. The active ingredients are monocalcium aluminate CaAl2O4 (CaO · Al2O3 or CA in cement chemist notation, CCN) and mayenite Ca12Al14O33 (12 CaO · 7 Al2O3, or C12A7 in CCN). Strength forms by hydration to calcium aluminate hydrates. They are well-adapted for use in refractory (high-temperature resistant) concretes, e.g., for furnace linings.
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 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.[47][48] 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 CO
2 emission around half that associated with Portland clinker. However, SO2 emissions are usually significantly higher.
"Natural" cements corresponding to certain cements of the pre-Portland era, are 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.
Polymer cements are made from organic chemicals that polymerise. Producers often use thermoset materials. While they are often significantly more expensive, they can give a water proof material that has useful tensile strength.
Sorel cement is a hard, durable cement made by combining magnesium oxide and a magnesium chloride solution
Fiber mesh cement or fiber reinforced concrete is cement that is made up of fibrous materials like synthetic fibers, glass fibers, natural fibers, and steel fibers. This type of mesh is distributed evenly throughout the wet concrete. The purpose of fiber mesh is to reduce water loss from the concrete as well as enhance its structural integrity.[49] When used in plasters, fiber mesh increases cohesiveness, tensile strength, impact resistance, and to reduce shrinkage; ultimately, the main purpose of these combined properties is to reduce cracking.[50]
Electric cement is proposed to be made by recycling cement from demolition wastes in an electric arc furnace as part of a steelmaking process. The recycled cement is intended to be used to replace part or all of the lime used in steelmaking, resulting in a slag-like material that is similar in mineralogy to Portland cement, eliminating most of the associated carbon emissions.[51]
Setting, hardening and curing
[edit]Cement starts to set when mixed with water, which causes a series of hydration chemical reactions. The constituents slowly hydrate and the mineral hydrates solidify and harden. The interlocking of the hydrates gives cement its strength. Contrary to popular belief, hydraulic cement does not set by drying out — proper curing requires maintaining the appropriate moisture content necessary for the hydration reactions during the setting and the hardening processes. If hydraulic cements dry out during the curing phase, the resulting product can be insufficiently hydrated and significantly weakened. A minimum temperature of 5 °C is recommended, and no more than 30 °C.[52] The concrete at young age must be protected against water evaporation due to direct insolation, elevated temperature, low relative humidity and wind.
The interfacial transition zone (ITZ) is a region of the cement paste around the aggregate particles in concrete. In the zone, a gradual transition in the microstructural features occurs.[53] This zone can be up to 35 micrometer wide.[54]: 351 Other studies have shown that the width can be up to 50 micrometer. The average content of unreacted clinker phase decreases and porosity decreases towards the aggregate surface. Similarly, the content of ettringite increases in ITZ. [54]: 352
Safety issues
[edit]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 (pH = 13.5) 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. Some trace elements, such as chromium, from impurities naturally present in the raw materials used to produce cement may cause allergic dermatitis.[55] Reducing agents such as ferrous sulfate (FeSO4) are often added to cement to convert the carcinogenic hexavalent chromate (CrO42−) into trivalent chromium (Cr3+), a less toxic chemical species. Cement users need also to wear appropriate gloves and protective clothing.[56]
Cement industry in the world
[edit]

In 2010, the world production of hydraulic cement was 3,300 megatonnes (3,600×106 short tons). The top three producers were China with 1,800, India with 220, and the United States with 63.5 million tonnes for a total of over half the world total by the world's three most populated states.[57]
For the world capacity to produce cement in 2010, the situation was similar with the top three states (China, India, and the US) accounting for just under half the world total capacity.[58]
Over 2011 and 2012, global consumption continued to climb, rising to 3585 Mt in 2011 and 3736 Mt in 2012, while annual growth rates eased to 8.3% and 4.2%, respectively.
China, representing an increasing share of world cement consumption, remains the main engine of global growth. By 2012, Chinese demand was recorded at 2160 Mt, representing 58% of world consumption. Annual growth rates, which reached 16% in 2010, appear to have softened, slowing to 5–6% over 2011 and 2012, as China's economy targets a more sustainable growth rate.
Outside of China, worldwide consumption climbed by 4.4% to 1462 Mt in 2010, 5% to 1535 Mt in 2011, and finally 2.7% to 1576 Mt in 2012.
Iran is now the 3rd largest cement producer in the world and has increased its output by over 10% from 2008 to 2011.[59] Because of climbing energy costs in Pakistan and other major cement-producing countries, Iran is in a unique position as a trading partner, utilizing its own surplus petroleum to power clinker plants. Now a top producer in the Middle-East, Iran is further increasing its dominant position in local markets and abroad.[60]
The performance in North America and Europe over the 2010–12 period contrasted strikingly with that of China, as the 2008 financial crisis evolved into a sovereign debt crisis for many economies in this region[clarification needed] and recession. Cement consumption levels for this region fell by 1.9% in 2010 to 445 Mt, recovered by 4.9% in 2011, then dipped again by 1.1% in 2012.
The performance in the rest of the world, which includes many emerging economies in Asia, Africa and Latin America and representing some 1020 Mt cement demand in 2010, was positive and more than offset the declines in North America and Europe. Annual consumption growth was recorded at 7.4% in 2010, moderating to 5.1% and 4.3% in 2011 and 2012, respectively.
As at year-end 2012, the global cement industry consisted of 5673 cement production facilities, including both integrated and grinding, of which 3900 were located in China and 1773 in the rest of the world.
Total cement capacity worldwide was recorded at 5245 Mt in 2012, with 2950 Mt located in China and 2295 Mt in the rest of the world.[6]
China
[edit]"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."[61]
In 2006, it was estimated that China manufactured 1.235 billion tonnes of cement, which was 44% of the world total cement production.[62] "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."[63]
In 2010, 3.3 billion tonnes of cement was consumed globally. Of this, China accounted for 1.8 billion tonnes.[64]
Environmental impacts
[edit]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.
CO
2 emissions
[edit]
Carbon concentration in cement spans from ≈5% in cement structures to ≈8% in the case of roads in cement.[65] Cement manufacturing releases CO2 in the atmosphere both directly when calcium carbonate is heated, producing lime and carbon dioxide,[66][67] and also indirectly through the use of energy if its production involves the emission of CO
2. The cement industry produces about 10% of global human-made CO
2 emissions, of which 60% is from the chemical process, and 40% from burning fuel.[68] A Chatham House study from 2018 estimates that the 4 billion tonnes of cement produced annually account for 8% of worldwide CO
2 emissions.[5]
Nearly 900 kg of CO
2 are emitted for every 1000 kg of Portland cement produced. In the European Union, the specific energy consumption for the production of cement clinker has been reduced by approximately 30% since the 1970s. This reduction in primary energy requirements is equivalent to approximately 11 million tonnes of coal per year with corresponding benefits in reduction of CO
2 emissions. This accounts for approximately 5% of anthropogenic CO
2.[69]
The majority of carbon dioxide emissions in the manufacture of Portland cement (approximately 60%) are produced from the chemical decomposition of limestone to lime, an ingredient in Portland cement clinker. These emissions may be reduced by lowering the clinker content of cement. They can also be reduced by alternative fabrication methods such as the intergrinding cement with sand or with slag or other pozzolan type minerals to a very fine powder.[70]
To reduce the transport of heavier raw materials and to minimize the associated costs, it is more economical to build cement plants closer to the limestone quarries rather than to the consumer centers.[71]
As of 2025[update] carbon capture and storage is emerging as a way to decarbonise cement production. French company Air Liquide was granted EU funding for two CCS projects in Kujawy (Poland)and the K6 Program aimed at producing the first carbon neutral cement in Europe in Lumbres, France. The projects are expected to start operation between by 2028 and capture 18.1 MtCO2 emissions over a decade.[72]
CO
2 absorption
[edit]Hydrated products of Portland cement, such as concrete and mortars, slowly reabsorb atmospheric CO2 gas, which has been released during calcination in a kiln. This natural process, reversed to calcination, is called carbonation.[73] As it depends on CO2 diffusion into the bulk of concrete, its rate depends on many parameters, such as environmental conditions and surface area exposed to the atmosphere.[74][75] Carbonation is particularly significant at the latter stages of the concrete life - after demolition and crushing of the debris. It is estimated that nearly 30% of atmospheric CO
2 generated by cement production is reabsorbed during the life-cycle of cement products.[75]
Carbonation process is considered as a mechanism of concrete degradation. It reduces pH of concrete that promotes reinforcement steel corrosion.[73] However, as the product of Ca(OH)2 carbonation, CaCO3, occupies a greater volume, porosity of concrete reduces. This increases strength and hardness of concrete.[76]
There are proposals to reduce carbon footprint of hydraulic cement by adopting non-hydraulic cement, lime mortar, for certain applications. It reabsorbs some of the CO
2 during hardening, and has a lower energy requirement in production than Portland cement.[77]
A few other attempts to increase absorption of carbon dioxide include cements based on magnesium (Sorel cement).[78][79][80]
Heavy metal emissions in the air
[edit]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, e.g. thallium,[81] cadmium and mercury are the most toxic. Heavy metals (Tl, Cd, Hg, ...) and also selenium 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."[82]
Heavy metals present in the clinker
[edit]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. Chromium may also directly arise as natural impurity from the raw materials or as secondary contamination from the abrasion of hard chromium steel alloys used in the ball mills when the clinker is ground. As chromate (CrO42−) is toxic and may cause severe skin allergies at trace concentration, it is sometimes reduced into trivalent Cr(III) by addition of ferrous sulfate (FeSO4).
Use of alternative fuels and by-products materials
[edit]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.[83] Scrap automobile and truck tires are useful in cement manufacturing as they have high calorific value and the iron embedded in tires is useful as a feed stock.[84]: p. 27
Clinker is manufactured by heating raw materials inside the main burner of a kiln to a temperature of 1,450 °C. The flame reaches temperatures of 1,800 °C. The material remains at 1,200 °C for 12–15 seconds at 1,800 °C or sometimes for 5–8 seconds (also referred to as residence time). These characteristics of a clinker kiln offer numerous benefits and they ensure a complete destruction of organic compounds, a total neutralization of acid gases, sulphur oxides and hydrogen chloride. Furthermore, heavy metal traces are embedded in the clinker structure and no by-products, such as ash or residues, are produced.[85]
The EU cement industry already uses more than 40% fuels derived from waste and biomass in supplying the thermal energy to the grey clinker making process. Although the choice for this so-called alternative fuels (AF) is typically cost driven, other factors are becoming more important. Use of alternative fuels provides benefits for both society and the company: CO
2-emissions are lower than with fossil fuels, waste can be co-processed in an efficient and sustainable manner and the demand for certain virgin materials can be reduced. Yet there are large differences in the share of alternative fuels used between the European Union (EU) member states. The societal benefits could be improved if more member states increase their alternative fuels share. The Ecofys study[86] assessed the barriers and opportunities for further uptake of alternative fuels in 14 EU member states. The Ecofys study found that local factors constrain the market potential to a much larger extent than the technical and economic feasibility of the cement industry itself.
Reduced-footprint cement
[edit]Growing environmental concerns and the increasing cost of fossil fuels have resulted, in many countries, in a sharp reduction of the resources needed to produce cement, as well as effluents (dust and exhaust gases).[87] Reduced-footprint cement is a cementitious material that meets or exceeds the functional performance capabilities of Portland cement. Various techniques are under development. One is geopolymer cement, which incorporates recycled materials, thereby reducing consumption of raw materials, water, and energy. Another approach is to reduce or eliminate the production and release of damaging pollutants and greenhouse gasses, particularly CO
2.[88] Recycling old cement in electric arc furnaces is another approach.[89] Also, a team at the University of Edinburgh has developed the 'DUPE' process based on the microbial activity of Sporosarcina pasteurii, a bacterium precipitating calcium carbonate, which, when mixed with sand and urine, can produce mortar blocks with a compressive strength 70% of that of concrete.[90] An overview of climate-friendly methods for cement production can be found here.[91]
See also
[edit]References
[edit]- ^ "Draeger: Guide for selection and use of filtering devices" (PDF). Draeger. 22 May 2020. Archived (PDF) from the original on 22 May 2020. Retrieved 22 May 2020.
- ^ a b Rodgers, Lucy (17 December 2018). "The massive CO
2 emitter you may not know about". BBC News. Retrieved 17 December 2018. - ^ Cement Analyst, Milan A (2015), Lancaster, Lynne C. (ed.), "Opus Caementicium", Innovative Vaulting in the Architecture of the Roman Empire: 1st to 4th Centuries CE, Cambridge: Cambridge University Press, pp. 19–38, ISBN 978-1-107-05935-1, retrieved 7 March 2025
- ^ a b "Cement" (PDF). United States Geological Survey (USGS). Retrieved 26 September 2023.
- ^ a b c "Making Concrete Change: Innovation in Low-carbon Cement and Concrete". Chatham House. 13 June 2018. Archived from the original on 19 December 2018. Retrieved 17 December 2018.
- ^ a b Hargreaves, David (March 2013). "The Global Cement Report 10th Edition" (PDF). International Cement Review. Archived (PDF) from the original on 26 November 2013.
- ^ Cao, Zhi; Myers, Rupert J.; Lupton, Richard C.; Duan, Huabo; Sacchi, Romain; Zhou, Nan; Reed Miller, T.; Cullen, Jonathan M.; Ge, Quansheng; Liu, Gang (29 July 2020). "The sponge effect and carbon emission mitigation potentials of the global cement cycle". Nature Communications. 11 (1): 3777. Bibcode:2020NatCo..11.3777C. doi:10.1038/s41467-020-17583-w. ISSN 2041-1723. PMC 7392754. PMID 32728073.
- ^ "Cement's basic molecular structure finally decoded (MIT, 2009)". Archived from the original on 21 February 2013.
- ^ "EPA Overview of Greenhouse Gases". 23 December 2015.
- ^ "The History of Concrete". Dept. of Materials Science and Engineering, University of Illinois, Urbana-Champaign. Archived from the original on 27 November 2012. Retrieved 8 January 2013.
- ^ a b c d e f g h i Blezard, Robert G. (12 November 2003). "The History of Calcareous Cements". In Hewlett, Peter (ed.). Lea's Chemistry of Cement and Concrete. Elsevier. pp. 1–24. ISBN 978-0-08-053541-8.
- ^ Brabant, Malcolm (12 April 2011). Macedonians created cement three centuries before the Romans , BBC News.
- ^ "Heracles to Alexander The Great: Treasures From The Royal Capital of Macedon, A Hellenic Kingdom in the Age of Democracy". Ashmolean Museum of Art and Archaeology, University of Oxford. Archived from the original on 17 January 2012.
- ^ Hill, Donald (19 November 2013). A History of Engineering in Classical and Medieval Times. Routledge. p. 106. ISBN 978-1-317-76157-0.
- ^ "History of cement". www.understanding-cement.com. Retrieved 17 December 2018.
- ^ Trendacosta, Katharine (18 December 2014). "How the Ancient Romans Made Better Concrete Than We Do Now". Gizmodo.
- ^ "How Natural Pozzolans Improve Concrete". Natural Pozzolan Association. Retrieved 7 April 2021.
- ^ Ridi, Francesca (April 2010). "Hydration of Cement: still a lot to be understood" (PDF). La Chimica & l'Industria (3): 110–117. Archived (PDF) from the original on 17 November 2015.
- ^ "Pure natural pozzolan cement" (PDF). Archived from the original on 18 October 2006. Retrieved 12 January 2009.
{{cite web}}: CS1 maint: bot: original URL status unknown (link). chamorro.com - ^ Russo, Ralph (2006) "Aqueduct Architecture: Moving Water to the Masses in Ancient Rome" Archived 12 October 2008 at the Wayback Machine, 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.
- ^ a b Cowan, Henry J. (1975). "An Historical Note on Concrete". Architectural Science Review. 18: 10–13. doi:10.1080/00038628.1975.9696342.
- ^ Cabrera, J. G.; Rivera-Villarreal, R.; Sri Ravindrarajah, R. (1997). "Properties and Durability of a Pre-Columbian Lightweight Concrete". SP-170: Fourth CANMET/ACI International Conference on Durability of Concrete. Vol. 170. pp. 1215–1230. doi:10.14359/6874. ISBN 9780870316692. S2CID 138768044.
- ^ a b Sismondo, Sergio (20 November 2009). An Introduction to Science and Technology Studies. Wiley. ISBN 978-1-4443-1512-7.
- ^ Mukerji, Chandra (2009). Impossible Engineering: Technology and Territoriality on the Canal Du Midi. Princeton University Press. p. 121. ISBN 978-0-691-14032-2.
- ^ a b <Taves, Loren Sickels (27 October 2015). "Tabby Houses of the South Atlantic Seaboard". Old-House Journal. Active Interest Media, Inc.: 5.
- ^ Francis, A.J. (1977) The Cement Industry 1796–1914: A History, David & Charles. ISBN 0-7153-7386-2, Ch. 2.
- ^ "Who Discovered Cement". 12 September 2012. Archived from the original on 4 February 2013.
- ^ Znachko-Iavorskii; I. L. (1969). Egor Gerasimovich Chelidze, izobretatelʹ tsementa. Sabchota Sakartvelo. Archived from the original on 1 February 2014.
- ^ "Lafarge History of Cement". Archived from the original on 2 February 2014.
- ^ Courland, Robert (2011). Concrete planet : the strange and fascinating story of the world's most common man-made material. Amherst, N.Y.: Prometheus Books. p. 190. ISBN 978-1616144814.
- ^ Francis, A.J. (1977) The Cement Industry 1796–1914: A History, David & Charles. ISBN 0-7153-7386-2, Ch. 5.
- ^ Hahn, Thomas F. and Kemp, Emory Leland (1994). Cement mills along the Potomac River. Morgantown, WV: West Virginia University Press. p. 16. ISBN 9781885907004
- ^ Hewlett, Peter (2003). Lea's Chemistry of Cement and Concrete. Butterworth-Heinemann. p. Ch. 1. ISBN 978-0-08-053541-8. Archived from the original on 1 November 2015.
- ^ a b "Natural Cement Comes Back". Popular Science. Bonnier Corporation. October 1941. p. 118.
- ^ Stanislas Sorel (1867). "Sur un nouveau ciment magnésien". Comptes rendus hebdomadaires des séances de l'Académie des sciences, volume 65, pages 102–104.
- ^ Walling, Sam A.; Provis, John L. (2016). "Magnesia-based cements: A journey of 150 years, and cements for the future?". Chemical Reviews. 116 (7): 4170–4204. doi:10.1021/acs.chemrev.5b00463. ISSN 0009-2665. PMID 27002788.
- ^ McArthur, H.; Spalding, D. (1 January 2004). Engineering Materials Science: Properties, Uses, Degradation, Remediation. Elsevier. ISBN 9781782420491.
- ^ "How Cement Mixers Work". HowStuffWorks. 26 January 2012. Retrieved 2 April 2020.
- ^ 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.
- ^ Abdel Rahman R.O., Rahimov R.Z., Rahimova N.R., Ojovan M.I. (2015). Cementitious materials for nuclear waste immobilization. Wiley, Chichester 232 pp.
- ^ Holland, Terence C. (2005). "Silica Fume User's Manual" (PDF). Silica Fume Association and United States Department of Transportation Federal Highway Administration Technical Report FHWA-IF-05-016. Retrieved 31 October 2014.
- ^ Kosmatka, S.; Kerkhoff, B.; Panerese, W. (2002). Design and Control of Concrete Mixtures (14 ed.). Portland Cement Association, Skokie, Illinois.
- ^ Gamble, William. "Cement, Mortar, and Concrete". In Baumeister; Avallone; Baumeister (eds.). Mark's Handbook for Mechanical Engineers (Eighth ed.). McGraw Hill. Section 6, page 177.
- ^ U.S. Federal Highway Administration. "Fly Ash". Archived from the original on 21 June 2007. Retrieved 24 January 2007.
- ^ U.S. Federal Highway Administration. "Silica Fume". Archived from the original on 22 January 2007. Retrieved 24 January 2007.
- ^ Justnes, Harald; Elfgren, Lennart; Ronin, Vladimir (2005). "Mechanism for performance of energetically modified cement versus corresponding blended cement" (PDF). Cement and Concrete Research. 35 (2): 315–323. doi:10.1016/j.cemconres.2004.05.022. Archived from the original (PDF) on 10 July 2011.
- ^ Bye, G.C. (1999). Portland Cement. 2nd Ed., Thomas Telford. pp. 206–208. ISBN 0-7277-2766-4
- ^ Zhang, Liang; Su, Muzhen; Wang, Yanmou (1999). "Development of the use of sulfo- and ferroaluminate cements in China". Advances in Cement Research. 11: 15–21. doi:10.1680/adcr.1999.11.1.15.
- ^ Munsell, Faith (31 December 2019). "Concrete mesh: When to use fiber mesh or wire mesh | Port Aggregates". Port Aggregates. Retrieved 19 September 2022.
- ^ "Plaster / Stucco Manual" (PDF). Cement.org. 2003. p. 13. Retrieved 12 April 2021.
- ^ Barnard, Michael (30 May 2024). "Many Green Cement Roads Lead Through Electric Arc Steel Furnaces". CleanTechnica. Retrieved 11 June 2024.
- ^ "Using cement based products during winter months". sovchem.co.uk. 29 May 2018. Archived from the original on 29 May 2018.
- ^ a b Scrivener, K.L., Crumbie, A.K., and Laugesen P. (2004). "The Interfacial Transition Zone (ITZ) between cement paste and aggregate in concrete." Interface Science, 12 (4), 411–421. doi: 10.1023/B:INTS.0000042339.92990.4c.
- ^ a b c H. F. W. Taylor, Cement chemistry, 2nd ed. London: T. Telford, 1997.
- ^ "Construction Information Sheet No 26 (revision2)" (PDF). hse.gov.uk. Archived (PDF) from the original on 4 June 2011. Retrieved 15 February 2011.
- ^ "CIS26 – cement" (PDF). Archived from the original (PDF) on 4 June 2011. Retrieved 5 May 2011.
- ^ United States Geological Survey. "USGS Mineral Program Cement Report. (Jan 2011)" (PDF). Archived (PDF) from the original on 8 October 2011.
- ^ Edwards, P; McCaffrey, R. Global Cement Directory 2010. PRo Publications Archived 3 January 2014 at the Wayback Machine. Epsom, UK, 2010.
- ^ "Pakistan loses Afghan cement market share to Iran". International Cement Revie. 20 August 2012. Archived from the original on 22 September 2013. Retrieved 2 November 2024.
- ^ ICR Newsroom. Pakistan loses Afghan cement market share to Iran Archived 22 September 2013 at the Wayback Machine. Retrieved 19 November 2013.
- ^ Yan, Li Yong (7 January 2004) China's way forward paved in cement, Asia Times
- ^ "China now no. 1 in CO emissions; USA in second position: more info". NEAA. 19 June 2007. Archived from the original on 3 July 2007.
- ^ "China's cement demand to top 1 billion tonnes in 2008". CementAmericas. November 2004. Archived from the original on 27 April 2009.
- ^ "Uses of Coal and Cement". World Coal Association. Archived from the original on 8 August 2011.
- ^ Scalenghe, R.; Malucelli, F.; Ungaro, F.; Perazzone, L.; Filippi, N.; Edwards, A.C. (2011). "Influence of 150 years of land use on anthropogenic and natural carbon stocks in Emilia-Romagna Region (Italy)". Environmental Science & Technology. 45 (12): 5112–5117. Bibcode:2011EnST...45.5112S. doi:10.1021/es1039437. PMID 21609007.
- ^ "EIA – Emissions of Greenhouse Gases in the U.S. 2006-Carbon Dioxide Emissions". US Department of Energy. Archived from the original on 23 May 2011.
- ^ Matar, W.; Elshurafa, A. M. (2017). "Striking a balance between profit and carbon dioxide emissions in the Saudi cement industry". International Journal of Greenhouse Gas Control. 61: 111–123. Bibcode:2017IJGGC..61..111M. doi:10.1016/j.ijggc.2017.03.031.
- ^ "Trends in global CO
2 emissions: 2014 Report" (PDF). PBL Netherlands Environmental Assessment Agency & European Commission Joint Research Centre. 2014. Archived from the original (PDF) on 14 October 2016. - ^
Mahasenan, Natesan; Smith, Steve; Humphreysm Kenneth; Kaya, Y. (2003). "The Cement Industry and Global Climate Change: Current and Potential Future Cement Industry CO
2 Emissions". Greenhouse Gas Control Technologies – 6th International Conference. Oxford: Pergamon. pp. 995–1000. ISBN 978-0-08-044276-1. - ^ "Blended Cement". Science Direct. 2015. Retrieved 7 April 2021.
- ^ Chandak, Shobhit. "Report on cement industry in India". scribd. Archived from the original on 22 February 2012. Retrieved 21 July 2011.
- ^ "Cement".
- ^ a b Pade, Claus; Guimaraes, Maria (1 September 2007). "The CO2 uptake of concrete in a 100 year perspective". Cement and Concrete Research. 37 (9): 1348–1356. doi:10.1016/j.cemconres.2007.06.009. ISSN 0008-8846.
- ^ Xi, Fengming; Davis, Steven J.; Ciais, Philippe; Crawford-Brown, Douglas; Guan, Dabo; Pade, Claus; Shi, Tiemao; Syddall, Mark; Lv, Jie; Ji, Lanzhu; Bing, Longfei; Wang, Jiaoyue; Wei, Wei; Yang, Keun-Hyeok; Lagerblad, Björn (December 2016). "Substantial global carbon uptake by cement carbonation". Nature Geoscience. 9 (12): 880–883. Bibcode:2016NatGe...9..880X. doi:10.1038/ngeo2840. ISSN 1752-0908.
- ^ a b Cao, Zhi; Myers, Rupert J.; Lupton, Richard C.; Duan, Huabo; Sacchi, Romain; Zhou, Nan; Reed Miller, T.; Cullen, Jonathan M.; Ge, Quansheng; Liu, Gang (29 July 2020). "The sponge effect and carbon emission mitigation potentials of the global cement cycle". Nature Communications. 11 (1): 3777. Bibcode:2020NatCo..11.3777C. doi:10.1038/s41467-020-17583-w. hdl:10044/1/81385. ISSN 2041-1723. PMC 7392754. PMID 32728073.
- ^ Kim, Jin-Keun; Kim, Chin-Yong; Yi, Seong-Tae; Lee, Yun (1 February 2009). "Effect of carbonation on the rebound number and compressive strength of concrete". Cement and Concrete Composites. 31 (2): 139–144. doi:10.1016/j.cemconcomp.2008.10.001. ISSN 0958-9465.
- ^ Kent, Douglas (22 October 2007). "Response: Lime is a much greener option than cement, says Douglas Kent". The Guardian. ISSN 0261-3077. Retrieved 22 January 2020.
- ^ "Novacem's 'carbon negative cement'". The American Ceramic Society. 9 March 2011. Retrieved 26 September 2023.
- ^ "Novacem". imperialinnovations.co.uk. Archived from the original on 3 August 2009.
- ^ Jha, Alok (31 December 2008). "Revealed: The cement that eats carbon dioxide". The Guardian. London. Archived from the original on 6 August 2013. Retrieved 28 April 2010.
- ^ "Factsheet on: Thallium" (PDF). Archived from the original (PDF) on 11 January 2012. Retrieved 15 September 2009.
- ^ Berkes, Howard (10 November 2011). "EPA Regulations Give Kilns Permission To Pollute : NPR". NPR.org. Archived from the original on 17 November 2011. Retrieved 17 November 2011.
- ^ "Guidelines for the selection and use of fuels and raw materials in the cement manufacturing process" (PDF). World Business Council for Sustainable Development. 1 June 2005. Archived from the original (PDF) on 10 September 2008.
- ^ "Increasing the use of alternative fuels at cement plants: International best practice" (PDF). International Finance Corporation, World Bank Group. 2017.
- ^ "Cement, concrete & the circular economy" (PDF). cembureau.eu. Archived from the original (PDF) on 12 November 2018.
- ^ de Beer, Jeroen et al. (2017) Status and prospects of co-processing of waste in EU cement plants Archived 30 December 2020 at the Wayback Machine. ECOFYS study.
- ^ "Alternative fuels in cement manufacture – CEMBUREAU brochure, 1997" (PDF). Archived from the original (PDF) on 2 October 2013.
- ^ "Engineers develop cement with 97 percent smaller carbon dioxide and energy footprint – DrexelNow". DrexelNow. 20 February 2012. Archived from the original on 18 December 2015. Retrieved 16 January 2016.
- ^ "How to make low-carbon concrete from old cement". The Economist. ISSN 0013-0613. Retrieved 27 April 2023.
- ^ Monks, Kieron (22 May 2014). "Would you live in a house made of sand and bacteria? It's a surprisingly good idea". CNN. Archived from the original on 20 July 2014. Retrieved 20 July 2014.
- ^ "Top-Innovationen 2020: Zement lässt sich auch klimafreundlich produzieren". www.spektrum.de (in German). Retrieved 28 December 2020.
Further reading
[edit]- Taylor, Harry F. W. (1997). Cement Chemistry. Thomas Telford. ISBN 978-0-7277-2592-9.
- Peter Hewlett; Martin Liska (2019). Lea's Chemistry of Cement and Concrete. Butterworth-Heinemann. ISBN 978-0-08-100795-2.
- Aitcin, Pierre-Claude (2000). "Cements of yesterday and today: Concrete of tomorrow". Cement and Concrete Research. 30 (9): 1349–1359. doi:10.1016/S0008-8846(00)00365-3.
- van Oss, Hendrik G.; Padovani, Amy C. (2002). "Cement manufacture and the environment, Part I: Chemistry and Technology". Journal of Industrial Ecology. 6 (1): 89–105. Bibcode:2002JInEc...6...89O. doi:10.1162/108819802320971650. S2CID 96660377.
- van Oss, Hendrik G.; Padovani, Amy C. (2003). "Cement manufacture and the environment, Part II: Environmental challenges and opportunities" (PDF). Journal of Industrial Ecology. 7 (1): 93–126. Bibcode:2003JInEc...7...93O. CiteSeerX 10.1.1.469.2404. doi:10.1162/108819803766729212. S2CID 44083686. Archived from the original on 22 September 2017. Retrieved 24 October 2017.
- Deolalkar, S. P. (2016). Designing green cement plants. Amsterdam: Butterworth-Heinemann. ISBN 9780128034354. OCLC 919920182.
- Friedrich W. Locher: Cement : Principles of production and use, Düsseldorf, Germany: Verlag Bau + Technik GmbH, 2006, ISBN 3-7640-0420-7
- Javed I. Bhatty, F. MacGregor Miller, Steven H. Kosmatka; editors: Innovations in Portland Cement Manufacturing, SP400, Portland Cement Association, Skokie, Illinois, U.S., 2004, ISBN 0-89312-234-3
- "Why cement emissions matter for climate change" Archived 21 March 2019 at the Wayback Machine Carbon Brief 2018
- Neville, A.M. (1996). Properties of concrete. Fourth and final edition standards. Pearson, Prentice Hall. ISBN 978-0-582-23070-5. OCLC 33837400.
- Taylor, H.F.W. (1990). Cement chemistry. Academic Press. p. 475. ISBN 978-0-12-683900-5.
- Ulm, Franz-Josef; Roland J.-M. Pellenq; Akihiro Kushima; Rouzbeh Shahsavari; Krystyn J. Van Vliet; Markus J. Buehler; Sidney Yip (2009). "A realistic molecular model of cement hydrates". Proceedings of the National Academy of Sciences. 106 (38): 16102–16107. Bibcode:2009PNAS..10616102P. doi:10.1073/pnas.0902180106. PMC 2739865. PMID 19805265.
External links
[edit]- . Encyclopædia Britannica. Vol. 5 (11th ed.). 1911.
- usgs.gov (Mineral Commodity Summaries 2025): Cement
Cement
View on GrokipediaCement is a hydraulic binder obtained by pulverizing clinker—nodules formed by sintering limestone and aluminosilicate materials such as clay at high temperatures around 1450°C—with added gypsum to regulate setting time; Portland cement, the predominant variety, consists primarily of hydraulic calcium silicates.[1][2] Developed in 1824 by English bricklayer Joseph Aspdin, who patented it as "Portland cement" for its resemblance to natural Portland stone, this material revolutionized construction by enabling durable, weather-resistant concretes and mortars essential for infrastructure, buildings, and dams worldwide.[3] The production process, centered on clinker formation in rotary kilns, demands substantial energy and raw materials, yielding approximately 0.6 tons of CO2 per ton of cement from both fuel combustion and inherent calcination of limestone, contributing 7-8% to global anthropogenic emissions amid annual output exceeding 4 billion tons, dominated by Asia.[4][5][6] Despite its foundational role in modern civilization, the industry's emissions profile underscores challenges in decarbonization, with innovations like alternative clinkers and carbon capture under exploration to mitigate environmental impacts without compromising performance.[7]
Chemical Foundations
Hydration Chemistry
The hydration of Portland cement is an exothermic set of chemical reactions between its primary clinker phases—tricalcium silicate (C₃S), dicalcium silicate (C₂S), tricalcium aluminate (C₃A), and tetracalcium aluminoferrite (C₄AF)—and water, producing calcium silicate hydrate (C-S-H) gel, calcium hydroxide (CH, or portlandite), and other hydrates that interlock to form a rigid matrix responsible for strength development.[8] These reactions occur progressively, with C₃S and C₂S contributing the bulk of mechanical properties through C-S-H formation, while C₃A and C₄AF influence setting time and early rigidity but generate significant heat.[9] The process is diffusion-controlled, involving dissolution of anhydrous phases, nucleation and growth of hydrates, and pore space filling, with overall stoichiometry approximated but varying due to incomplete reactions and gel-like products lacking fixed compositions.[8] Tricalcium silicate (C₃S, typically 50-70% of clinker) hydrates rapidly, accounting for initial heat evolution and early strength (within hours to days), via the simplified reaction:2(3CaO·SiO₂) + 6H₂O → 3CaO·2SiO₂·3H₂O + 3Ca(OH)₂,
yielding C-S-H gel (amorphous, nanoscale fibers providing cohesion) and crystalline CH (hexagonal plates that fill pores but can lead to efflorescence or alkali-silica reactions if excessive).[8][9] This phase's high reactivity stems from its orthosilicate structure, dissolving to supersaturate the solution with Ca²⁺ and silicate ions, promoting heterogeneous nucleation of C-S-H on particle surfaces.[8] Dicalcium silicate (C₂S, 15-30% of clinker) hydrates more slowly than C₃S, contributing to later-age strength (beyond 7 days) through a parallel mechanism:
2(2CaO·SiO₂) + 4H₂O → 3CaO·2SiO₂·3H₂O + Ca(OH)₂,
producing similar C-S-H and CH but at reduced rates due to lower solubility and reactivity, with hydration extending over months and enhancing durability via denser microstructure.[8][9] Tricalcium aluminate (C₃A, 5-10% of clinker) reacts vigorously with water, potentially causing flash set without gypsum (calcium sulfate dihydrate, ~5% added), forming ettringite initially:
C₃A + 3(CaSO₄·2H₂O) + 26H₂O → C₃A·3CaSO₄·32H₂O,
a needle-like expansive phase that controls early stiffening; subsequent conversion to monosulfate (C₃A·CaSO₄·12H₂O) occurs as sulfate depletes, releasing heat and risking shrinkage if uncontrolled.[8][9] Gypsum's role is causal: it adsorbs on C₃A surfaces, delaying hydration until ettringite forms a protective layer, enabling workability.[9] Tetracalcium aluminoferrite (C₄AF, 5-15% of clinker) hydrates slowest among major phases, forming iron-substituted ettringite and hydrated ferrite phases analogous to C₃A products but with Fe³⁺ incorporation, contributing minimally to strength while imparting cement's gray color via Fe oxides; its reaction rate decreases with gypsum presence and generates less heat than C₃A.[9] Overall hydration kinetics follow C₃A > C₃S > C₄AF > C₂S, influenced by factors like particle fineness, water-to-cement ratio (optimal ~0.4 for percolation), and temperature, with incomplete hydration in mature pastes leaving ~20-30% unreacted clinker.[9][8]
Hydraulic and Non-Hydraulic Variants
Hydraulic cements harden through a chemical reaction with water, forming insoluble hydration products that bind aggregates into durable concretes and mortars, even in submerged conditions.[10] This process, known as hydration, primarily involves the calcium silicates in the cement—tricalcium silicate (C₃S) and dicalcium silicate (C₂S)—reacting to produce calcium silicate hydrate (C-S-H) gel and calcium hydroxide (CH).[11] For instance, the reaction for C₃S is approximately 2C₃S + 6H → C₃S₂H₃ + 3CH, where H denotes water molecules, yielding a dense, interlocking microstructure responsible for early strength gain.[8] These cements, exemplified by Portland cement, achieve compressive strengths exceeding 20 MPa within 28 days under standard curing, enabling applications in modern infrastructure like dams and bridges.[12] In contrast, non-hydraulic cements, such as high-calcium lime (from pure limestone calcined to CaO and slaked to Ca(OH)₂), do not set or harden in the presence of water alone but require exposure to air for carbonation.[13] Carbonation occurs via the reaction Ca(OH)₂ + CO₂ → CaCO₃ + H₂O, where atmospheric carbon dioxide diffuses into the lime paste, recrystallizing calcium carbonate that provides binding but at a slower rate, often taking weeks to months for full depth penetration limited to a few millimeters initially.[14] This results in softer, more flexible mortars with lower compressive strengths, typically under 2 MPa, suited for breathable historic restorations rather than load-bearing submerged structures.[15] Non-hydraulic variants remain porous and vapor-permeable, allowing moisture escape and reducing salt efflorescence risks in traditional masonry, unlike the denser, less permeable hydraulic types. The distinction arises from composition: hydraulic cements contain reactive aluminosilicates (e.g., from clay impurities or clinker grinding) that form water-resistant gels, whereas pure non-hydraulic limes lack these, relying on reversible slaking and irreversible carbonation without underwater capability.[16] Empirical tests, such as ASTM standards, confirm hydraulic cements maintain integrity in wet environments, while non-hydraulic ones weaken or dissolve, dictating their use—hydraulic for aggressive exposures, non-hydraulic for internal, dry-curing scenarios.[10] Hybrid formulations, like natural hydraulic limes with 5-20% clay, blend properties but classify as mildly hydraulic if they exhibit partial water-setting.[17]Historical Evolution
Pre-Industrial Binders and Early Uses
The earliest known use of binders resembling cement occurred during the Neolithic period, with archaeological evidence from sites like Jericho in the Pre-Pottery Neolithic era (ca. 7000–6000 BCE) indicating plasters made with a limy clay binder derived from calcined limestone mixed with aggregates.[18] These materials served to waterproof and stabilize structures such as floors and walls, demonstrating rudimentary control over calcination processes to produce calcium oxide for binding.[19] Such binders were non-hydraulic, relying on carbonation rather than water-induced setting, and were formed by heating limestone to approximately 800–900°C to drive off carbon dioxide, yielding quicklime that was then slaked with water to form a putty.[20] By around 4000 BCE, lime mortar had become a staple in Egyptian construction, applied as plaster to the interiors and exteriors of pyramids and tombs to seal surfaces against moisture and pests.[21] Gypsum-based binders, calcined from selenite deposits at lower temperatures (around 150–200°C), were also utilized by Egyptians circa 3000 BCE for bonding limestone blocks in structures like mastabas, offering faster setting but limited durability in wet conditions due to their non-hydraulic nature.[22] In parallel, Mesopotamian and Indus Valley civilizations employed similar lime mortars for bricklaying and rendering, with residues analyzed from sites like Mohenjo-Daro showing mixtures of burnt lime, sand, and organic fibers for enhanced workability and tensile strength.[23] Early hydraulic binders emerged sporadically before widespread classical adoption, as evidenced by Neolithic experiments combining lime with volcanic ashes or clays to impart water-resistant setting via pozzolanic reactions, where silica and alumina in the additives react with calcium hydroxide to form insoluble compounds.[19] In northern China, binders incorporating glutinous rice starch—fermented and mixed with lime—produced glutenous mortars used from circa 2000 BCE for pagodas, tombs, and city walls, achieving compressive strengths up to 10 MPa through polysaccharide crosslinking that improved adhesion and flexibility.[24] These pre-industrial materials prioritized local resources like limestone, gypsum, and natural pozzolans, enabling durable masonry without high-temperature kilns, though their performance was constrained by variable purity and environmental exposure compared to later formulations.[20]Classical Civilizations
In ancient Greece, builders primarily employed non-hydraulic lime mortar as a binder for stone masonry in temples and other structures, produced by burning limestone to create quicklime, slaking it with water, and mixing with sand.[25] This mortar set through carbonation, reacting with atmospheric carbon dioxide to reform calcium carbonate, but lacked the ability to harden underwater or in wet conditions, limiting its applications compared to later innovations.[26] Greek use of lime-based binders dates to around the 8th century BC, as evidenced in structures like the Temple of Hera at Olympia, where it served mainly for joints and decorative stucco rather than mass concrete.[27] The Romans advanced binder technology significantly in the 3rd to 2nd centuries BC by developing opus caementicium, a hydraulic concrete that incorporated pozzolanic volcanic ash—sourced from regions like Pozzuoli near Naples—with slaked lime and aggregates such as broken stones or bricks.[28] This mixture achieved hydraulic setting through pozzolanic reactions forming calcium silicate hydrates and other compounds, enabling curing even submerged in seawater, as demonstrated in harbors like Caesarea Maritima constructed around 20-10 BC.[29] Architect Vitruvius, writing circa 15 BC in De Architectura, prescribed specific proportions: one part lime to three parts pozzolana for general building mortar and one to two for underwater applications, emphasizing the ash's fineness and reactivity for strength.[30] Roman concrete's durability stemmed from its chemical composition, including lime clasts that enabled self-healing by reacting with water to fill cracks, a property confirmed in analyses of surviving structures like the Pantheon (completed AD 126) and aqueducts enduring over 2,000 years.[31] Unlike Greek lime mortar, which was prone to erosion in moist environments, Roman formulations resisted seismic activity and marine exposure due to the pozzolanic ash's aluminosilicate content forming robust C-A-S-H gels.[32] This innovation facilitated large-scale engineering feats, including the 300 km-long Aqua Claudia aqueduct (AD 38-52) and extensive road networks, marking a shift from mere binding to true composite materials in classical construction.[33]Medieval and Renaissance Developments
Following the fall of the Roman Empire in the 5th century, the advanced pozzolanic hydraulic cements of antiquity were largely forgotten in Western Europe, leading to a reliance on non-hydraulic lime mortars produced by slaking burnt limestone with water and mixing with sand.[34] These mortars set through carbonation, absorbing CO₂ from the air to form calcium carbonate, but lacked the water resistance of Roman concretes, limiting their use in submerged or exposed structures.[35] Archaeological evidence from sites like 7th-century longhouses in Lyminge, England, shows sporadic employment of basic concrete-like mixtures, often with lime and aggregate, though on a diminished scale compared to imperial precedents.[36] In medieval Europe (c. 500–1500 CE), mortar compositions varied regionally, with binders incorporating organic additives such as animal blood, hair, or casein to enhance adhesion and durability, though these did not confer hydraulic properties.[37] Hydraulic variants emerged where natural pozzolans like volcanic ash or crushed ceramics were available, as in parts of Italy or the Rhineland, mimicking Roman techniques through reactive silica-alumina reactions with lime in wet conditions; for instance, mortars in 12th–13th-century Gothic cathedrals, such as those at Chartres (built 1194–1220), employed lime-sand mixes occasionally augmented with brick dust for improved strength.[38] Lime production involved calcining limestone at temperatures around 900–1000°C in periodic kilns, yielding quicklime that was slaked into putty for storage, a process documented in monastic records and enabling large-scale ecclesiastical construction despite material inconsistencies.[39] Overall, technological stagnation prevailed, with mortar quality declining from Roman standards due to lost empirical knowledge and decentralized production, as evidenced by variable compressive strengths (typically 1–5 MPa) in surviving structures.[40] During the Renaissance (c. 1400–1600 CE), renewed scholarly interest in classical texts like Vitruvius's De Architectura (1st century BCE), rediscovered in 1416, spurred experimentation with lime-based stuccos and mortars inspired by ancient descriptions of pozzolana, though systematic hydraulic rediscovery awaited the 18th century.[27] Architects such as Filippo Brunelleschi, in constructing the Florence Cathedral dome (completed 1436), utilized high-lime mortars with sand and lightweight aggregates like cork for scaffolding-free vaults, prioritizing workability over hydraulic durability in dry-set applications.[41] This era saw refined lime putty techniques, including hot-mixed limes for faster setting, applied in frescoed palaces and palazzos across Italy, but innovations remained incremental, focusing on aesthetic finishes rather than material breakthroughs; compressive strengths hovered at 2–4 MPa, insufficient for widespread waterproofing.[23] The period's emphasis on humanism and antiquity bridged medieval practices to Enlightenment engineering, yet cement technology exhibited continuity in lime dominance without causal advances in clinkering or artificial hydraulics.[42]Industrial Revolution and Modern Portland Cement
The invention of Portland cement occurred amid the Industrial Revolution's demand for durable construction materials to support expanding infrastructure such as railways, canals, and urban buildings. On October 21, 1824, British bricklayer Joseph Aspdin of Leeds patented the process (British Patent No. 5022), which involved grinding limestone and clay, mixing them into a slurry, burning the mixture in a kiln to form clinker, and then pulverizing it into a fine powder.[43][44] This artificial cement derived its name from the hardened material's resemblance to high-quality Portland stone from Dorset, England, and provided superior hydraulic properties—setting underwater and resisting water penetration—compared to non-hydraulic lime mortars prevalent at the time.[45][3] Aspdin established production at a works in Wakefield in 1825, initially producing small quantities for local use in masonry and early engineering projects.[46] Refinements by Aspdin's son, William, elevated Portland cement to a more consistent and stronger product suitable for industrial-scale application. In the 1840s, William developed a formulation involving higher kiln temperatures, yielding clinker with significant alite content (an impure tricalcium silicate phase responsible for early strength development), which marked a key step toward modern compositions.[3][47] He established factories in London from 1841 and later in Germany at Altona and Lagerndorf starting in 1860, exporting the technology abroad and initiating non-British production of advanced Portland cement.[48][49] Concurrently, Isaac Johnson's 1845 process of firing chalk and clay at intense heat further improved quality, enabling broader adoption in infrastructure like small bridges, pipes, and sculptures by the 1850s.[3] These advancements aligned with surging needs for reliable binders in Britain's canal systems, railway viaducts, and iron-framed structures, where Portland cement's ability to bond aggregates into high-strength concrete facilitated faster and more robust construction.[47][3] Technological and standardization progress in the late 19th and early 20th centuries solidified Portland cement's role as the cornerstone of modern construction. The introduction of the rotary kiln in the 1870s–1880s, pioneered by figures like Friedrich Ransome, allowed continuous high-temperature burning and vastly increased output efficiency over batch kilns.[50] Quality consistency advanced through early standards, including the Association of German Cement Manufacturers' 1878 specification and the American Society for Testing and Materials' (ASTM) first cement standard in 1904, which defined chemical and physical requirements for Portland cement types.[51] By the 20th century, ordinary Portland cement (OPC)—refined to contain optimized proportions of clinker minerals like alite, belite, aluminate, and ferrite—dominated global production, underpinning concrete for skyscrapers, dams, highways, and mass housing.[3][47] These developments transformed cement from a niche binder into a ubiquitous material, with annual global output exceeding 4 billion tons by the 21st century, though early formulations sometimes suffered from variability due to inconsistent raw materials and firing.[52]20th Century Advances and Global Expansion
The adoption of rotary kilns, initially developed in the late 19th century, became standard in cement production by the early 1900s, enabling continuous operation, higher throughput, and better clinker quality compared to batch shaft kilns.[53] Refinements in kiln design, including longer lengths and improved fuel efficiency, further increased output, with plants scaling to produce thousands of tons daily by mid-century.[54] These mechanical advances were complemented by chemical progress, such as precise control of raw mix composition through X-ray fluorescence analysis introduced in the 1940s, ensuring consistent clinker minerals like alite and belite for predictable hydration.[55] Standardization drove quality improvements, with the American Society for Testing and Materials (ASTM) issuing its first specification for Portland cement (C150) in 1904, defining chemical and physical requirements that influenced global norms.[51] This evolved into multiple types by the 1930s-1950s: Type III for rapid-hardening applications in precast elements, Type IV low-heat for massive structures like dams to minimize thermal cracking, and Type V for sulfate resistance in harsh soils.[56] [57] Post-World War II innovations included suspension preheaters in kilns (1950s onward), reducing energy use by recovering waste heat, and early blended cements incorporating fly ash or slag for enhanced durability and lower cost, though Portland remained dominant.[55] Global cement production surged from about 50 million metric tons in 1928 to 132 million metric tons by 1950, driven by wartime demands and reconstruction.[58] By 2000, output exceeded 1.6 billion metric tons annually, reflecting expansion into developing regions; the United States led early in the century with over 80 million tons by 1950, but shares shifted to Europe, Japan, and emerging Asia amid infrastructure booms like U.S. interstates (1956 onward) and Soviet industrialization.[12] [59] Local industries proliferated worldwide, with rotary kiln plants established in India (1910s), China (scaling post-1949), and Latin America, supported by technology transfers that prioritized raw material proximity to cut transport costs and emissions.[60] This growth enabled unprecedented urbanization and civil engineering feats, though it strained resources in import-dependent areas until domestic capacity caught up.[38]Classification and Types
Portland Cement
Portland cement is a finely ground powder produced by pulverizing clinker nodules, which consist primarily of hydraulic calcium silicates such as alite (tricalcium silicate, C3S) and belite (dicalcium silicate, C2S), along with smaller amounts of tricalcium aluminate (C3A) and tetracalcium aluminoferrite (C4AF); gypsum (calcium sulfate) is typically added during grinding to control setting time.[1][61] The clinker forms through the high-temperature sintering of a mixture of calcareous materials like limestone (providing calcium oxide) and argillaceous materials like clay (providing silica, alumina, and iron oxide) at approximately 1400–1500°C in a rotary kiln.[61][62] This process yields dark grey, nodular clinker that, when ground to a fine powder with 3–5% gypsum, produces the hydraulic binder capable of setting and hardening through reaction with water, even underwater.[2] The material derives its name from its resemblance in color and superior durability to Portland stone, a limestone quarried on the Isle of Portland in England; it was patented on October 21, 1824, by English bricklayer Joseph Aspdin, who produced it by burning limestone and clay in a kiln and grinding the resulting clinker. Aspdin's formulation marked a significant advancement over earlier hydraulic limes, enabling stronger, more consistent concrete for industrial-scale construction.[63] Subsequent refinements, including by Aspdin's son William in the 1840s, optimized the burning temperature and raw mix to enhance strength, establishing the modern composition where calcium silicates comprise 70–80% of the clinker minerals.[64] Portland cement types are classified primarily by performance specifications to suit specific applications, with the American Society for Testing and Materials (ASTM) standard C150/C150M outlining eight variants based on chemical composition limits and physical properties like fineness, setting time, and strength development.[65] Type I serves general-purpose use where special properties are not required, suitable for most concrete structures like pavements and buildings; Type II offers moderate sulfate resistance and lower heat of hydration for mass concrete; Type III provides high early strength for rapid construction; Type IV generates low heat for large pours like dams; and Type V delivers high sulfate resistance for exposure to severe sulfate environments, such as certain soils or seawaters.[65][66] Variants with an "A" suffix (e.g., IA, IIA) incorporate air-entraining properties to improve freeze-thaw durability in concrete.[65] These classifications ensure compositional controls, such as limiting C3A content in sulfate-resistant types to below 5% for Type V, verified through chemical analysis and performance testing.[67] Internationally, similar categorizations exist, though Portland cement remains the foundational type comprising the majority of global production, often blended with supplementary materials in composite cements; pure Portland cement (e.g., CEM I under European standard EN 197-1) contains at least 95% clinker.[68] Its hydraulic nature stems from the cementitious reactions where calcium silicates hydrate to form calcium silicate hydrate (C-S-H) gel and calcium hydroxide, providing the binding matrix responsible for concrete's compressive strength exceeding 20–40 MPa at 28 days under standard curing.[64]Blended and Composite Cements
Blended hydraulic cements consist of Portland cement clinker interground or intimately blended with supplementary cementitious materials (SCMs), such as blast-furnace slag, pozzolans, or limestone, along with gypsum for set control.[69] These materials partially replace clinker, which constitutes 60-95% of the blend depending on the type, to achieve hydraulic properties through pozzolanic or latent hydraulic reactions that form additional calcium silicate hydrate (C-S-H) gel during hydration.[70] In contrast to pure Portland cement, blended variants exhibit slower early strength development but enhanced long-term performance due to the SCMs' contributions to pore refinement and reduced permeability.[71] Common SCMs include ground granulated blast-furnace slag (GGBS), which provides latent hydraulic reactivity and can comprise up to 70% in Type IS cements per ASTM C595; fly ash, a pozzolan derived from coal combustion classified as Class F (low calcium, siliceous) or Class C (high calcium, self-cementing), typically limited to 15-30% in Type IP cements; and silica fume, an ultrafine pozzolan from silicon production used at 5-10% for high-strength applications due to its high silica content and reactivity.[10] Limestone powder, permitted up to 15% in Type IL cements, acts as a filler and nucleation site accelerator without significant pozzolanic activity.[72] Composite cements, often synonymous with multi-component blends in standards like EN 197-1 (CEM II/M or CEM V), incorporate two or more SCMs, such as slag and fly ash, to optimize performance while further minimizing clinker content to as low as 35-65%.[73] Manufacturing involves either intergrinding clinker with SCMs during final cement production or post-blending finished Portland cement with SCMs, ensuring uniform distribution for consistent hydration behavior.[74] Mechanically, blended cements yield concrete with comparable or superior 28-day compressive strengths to Portland cement equivalents, often exceeding 40 MPa, alongside improved sulfate resistance and reduced alkali-silica reactivity due to denser microstructures from SCM reactions.[71] Environmentally, they lower the carbon footprint by 10-30% compared to ordinary Portland cement, as each ton of replaced clinker avoids approximately 0.8-1.0 tons of CO2 emissions from calcination and fuel combustion, while repurposing industrial byproducts like fly ash and slag reduces landfill waste.[75] [76] Additional benefits include decreased heat of hydration, mitigating thermal cracking in mass concrete, and enhanced workability from SCM particle shapes, though early-age strengths may require adjusted mix designs or admixtures.[71] Global standards govern composition and performance: ASTM C595/C595M classifies blended cements into types like IS(X) for slag (S up to 70%), IP(X) for pozzolans (P up to 50%), IL for limestone (L up to 15%), and IT for ternary blends, with chemical limits on sulfate (≤4.5% SO3) and loss on ignition.[69] European Standard EN 197-1 defines 27 cement types, with blended categories (CEM II-V) allowing SCMs up to 65% total, emphasizing strength classes from 32.5 to 52.5 MPa.[73] These specifications ensure durability metrics, such as ≤10% strength reduction after 6 months of sulfate exposure, while performance-based options like ASTM C1157 prioritize tested outcomes over prescriptive limits.[72] Adoption has grown, with blended cements comprising over 50% of U.S. production by 2020, driven by sustainability mandates and SCM availability, though reliance on coal-derived fly ash poses challenges amid energy transitions.[75]Specialty and Alternative Cements
Specialty cements are formulated for targeted performance characteristics beyond standard Portland cement, such as accelerated setting, enhanced durability in harsh environments, or resistance to chemical attack. Rapid-hardening cement, produced by finer grinding of clinker or adjusting composition for higher tricalcium silicate content, achieves compressive strengths of up to 25 MPa within 3 days, compared to 15-20 MPa for ordinary Portland cement, enabling faster construction timelines in repairs or precast elements.[77][78] High-alumina cement, rich in calcium aluminate phases, provides rapid strength gain and sulfate resistance but requires careful curing to avoid conversion-related strength loss over time.[79] Calcium sulfoaluminate (CSA) cements represent a specialty variant with clinker compositions emphasizing ye'elimite (C4A3S) over traditional alite, yielding lower kiln temperatures (around 1250°C versus 1450°C for Portland) and reduced CO2 emissions by 20-30% during production. These cements hydrate quickly via ettringite formation, attaining high early strengths (up to 40 MPa at 1 day) and exhibiting low shrinkage, making them suitable for shrinkage-sensitive applications like bridge deck repairs or tunneling. Blends with gypsum and limestone further optimize sulfate resistance and long-term durability, though sensitivity to alkali content can influence performance.[80][81][82] Alternative cements diverge from Portland-based systems by employing non-limestone-derived binders or waste-derived precursors, prioritizing reduced environmental impact. Geopolymer cements, synthesized through alkali activation of aluminosilicate sources like fly ash or metakaolin, form a three-dimensional silicate-aluminate network without clinkering, slashing CO2 emissions by up to 80% relative to Portland cement while offering superior acid resistance and fire endurance (retaining strength beyond 1000°C). Their composition typically includes 40-70% source material, 5-10% alkaline activator (e.g., sodium silicate), and aggregates, though scalability remains limited by activator costs and variability in precursors.[83][84][85] Magnesium-based cements, such as magnesium oxychloride (Sorel cement) or magnesium phosphate types, react dead-burned magnesia with chlorides or phosphates to form non-hydraulic or chemically bound matrices with rapid setting (under 1 hour) and high bond strength to aggregates. These achieve compressive strengths exceeding 50 MPa and resist freeze-thaw cycles better than Portland in some formulations, with applications in flooring or rapid repairs, but they demand precise water ratios to prevent efflorescence or reduced longevity in moist environments.[86][87][88] Other alternatives include limestone calcined clay cements (LC3), which substitute up to 50% clinker with calcined clay and limestone for 30-40% lower emissions while maintaining comparable strength via pozzolanic reactions, though adoption hinges on clay quality and processing energy. These formulations underscore a shift toward resource-efficient binders, verified through lifecycle analyses showing net decarbonization potential when sourced locally, yet challenges persist in standardization and supply chain integration.[89][90]Manufacturing Process
Raw Material Extraction and Preparation
The principal raw materials for Portland cement clinker production are calcareous materials, primarily limestone or chalk providing calcium carbonate (CaCO₃), and argillaceous materials such as clay, shale, or marl supplying silica (SiO₂), alumina (Al₂O₃), and iron oxide (Fe₂O₃).[2][91] Supplementary sources like sand, iron ore, or bauxite may be added to adjust oxide compositions if natural deposits are deficient.[2] These materials are selected for their geochemical suitability, with limestone typically comprising 75-90% of the mix by weight to achieve the target CaO content of 60-67% in the raw meal.[91][92] Extraction occurs mainly through open-pit quarrying, where overburden is removed to access deposits, followed by drilling blast holes 3-5 meters deep, loading them with ammonium nitrate-fuel oil (ANFO) explosives, and detonating to fragment the rock into manageable sizes of 0.5-1 meter.[93][94] For limestone, blasting yields are optimized to minimize fines and oversize, with overburden ratios often below 1:1 in dedicated cement quarries; softer clays or marls may use non-explosive methods like ripping with dozers or hydraulic excavators to reduce dust and vibration.[95][96] Fragmented material is loaded into haul trucks—typically 40-100 tonne capacity—and transported to processing plants, sometimes several kilometers away, with annual quarry outputs exceeding 1 million tonnes for large facilities.[2][97] Preparation begins with primary crushing in jaw or gyratory crushers to reduce fragments to under 100-200 mm, followed by secondary and tertiary stages using cone or impact crushers to achieve sizes below 25-50 mm, often incorporating screening to recycle oversize.[2][98] The crushed materials are pre-blended in stockpiles or circular storage beds using stacker-reclaimers to average compositions and mitigate quarry variability, then fed to raw mills—ball, vertical roller, or tube mills—for fine grinding to a Blaine surface area of 3000-3500 cm²/g, yielding a powdery raw meal with 15-20% moisture in wet processes or dried to under 1% in dry processes.[99][100] Final homogenization in vertical silos, with capacities up to 20,000 tonnes, employs compressed air injection or gravity blending to achieve uniformity, targeting standard deviations below 0.5-1% for CaO, SiO₂, Al₂O₃, and Fe₂O₃ to ensure consistent clinker quality and kiln efficiency.[101][102] Automated systems monitor oxide ratios via X-ray fluorescence analysis of samples, adjusting feeds in real-time to maintain the lime saturation factor (LSF) at 90-95%, silica modulus (SM) at 2.0-2.5, and alumina modulus (AM) at 1.8-2.5.[99][92] This stage is critical, as poor homogenization can increase energy use by 5-10% in the kiln and degrade cement strength by up to 2-3 MPa.[102]Clinkering and Grinding
Clinkering involves heating a finely ground mixture of raw materials, primarily limestone and clay, in a rotary kiln to temperatures around 1450°C, where partial melting and chemical reactions form hard, nodular clinker.[103] This process occurs in stages: initial evaporation of water up to 125°C, decomposition of clays and carbonates between 400-900°C releasing CO2, and finally clinkering in the burning zone at 1300-1450°C, where calcium silicates dominate.[104] The primary phases produced include alite (tricalcium silicate, C3S, approximately 65% by weight), which governs early strength development, belite (dicalcium silicate, C2S) for later strength, tricalcium aluminate (C3A), and tetracalcium aluminoferrite (C4AF).[105] Alite forms via reaction of calcium oxide with silica at these high temperatures, with impurities aiding stabilization at lower energies.[106] The rotary kiln, typically 3-5 meters in diameter and up to 200 meters long, rotates slowly while a countercurrent flow of hot gases heats the raw meal, forming molten liquid phases that bind solid particles into clinker nodules 3-25 mm in diameter.[107] Upon exiting the kiln, clinker is rapidly cooled to 100-200°C in grate or planetary coolers to preserve reactive phases, with heat recovery improving efficiency by preheating combustion air.[108] Optimal clinkering requires precise control of raw mix composition, such as lime saturation factor, to maximize alite content while minimizing free lime, which can impair cement quality.[109] Grinding follows clinkering, where cooled clinker is interground with 3-5% gypsum and sometimes limestone or other additives in ball mills or vertical roller mills to produce fine cement powder.[110] Ball mills, large rotating drums filled with steel balls, achieve particle fineness measured by Blaine air permeability, typically targeting 3000-5000 cm²/g for ordinary Portland cement, influencing hydration rate and strength.[111] Vertical roller mills offer energy savings up to 30% over ball mills by combining crushing, grinding, and drying, though they require careful control to avoid overgrinding alite, which reduces reactivity.[112] Grinding aids, such as amines or glycols, are added at 0.01-0.1% to enhance flowability and reduce energy consumption, which averages 30-50 kWh per ton of cement.[113] The resulting cement must meet standards for residue on 45 μm sieve (below 15-20%) to ensure consistent performance.[114]Hydration, Setting, and Curing Mechanisms
Hydration of Portland cement is an exothermic chemical reaction between its primary clinker phases—tricalcium silicate (C₃S, approximately 50% by weight), dicalcium silicate (C₂S, 25%), tricalcium aluminate (C₃A, 10%), and tetracalcium aluminoferrite (C₄AF, 10%)—and water, moderated by gypsum (5%) to control early reactivity.[11] The process forms hydration products including calcium silicate hydrate (C-S-H) gel, which provides the primary binding and strength through its amorphous, nanoscale structure, and crystalline calcium hydroxide (CH, or portlandite).[9] C₃A reacts rapidly with water and sulfate ions from gypsum to form ettringite (calcium sulfoaluminate hydrate), a needle-like crystal that influences early stiffness, while C₄AF contributes similar but slower ferritic phases.[8] Key reactions include the hydration of C₃S: , releasing approximately 174 kJ/mol of heat, and C₂S: , with 59 kJ/mol heat, both yielding C-S-H and CH.[11] These silicates dominate long-term strength, as C-S-H forms a dense, interlocking gel network that fills pores and binds aggregates, whereas CH contributes less to strength but maintains alkalinity (pH >12).[115] The reactions are diffusion-controlled after initial dissolution, with water penetrating protective C-S-H layers on cement grains, leading to progressive pore refinement and reduced permeability over time.[116] The hydration process unfolds in distinct stages: an initial rapid hydrolysis phase (minutes) with fast dissolution and heat release; a dormant (induction) period (1-3 hours) where supersaturation forms a transient barrier, allowing workability; an acceleration phase driven by nucleation and growth of C-S-H and ettringite; a deceleration phase limited by diffusion through product layers; and a slow steady-state phase extending years if moisture persists.[11] Crystalline defects in C₃S grains enhance early dissolution rates via etch pit formation, increasing reactive surface area, while factors like water-to-cement ratio (optimal 0.35-0.6) determine product density and final strength.[115] Setting refers to the transition from a fluid paste to a rigid state, with initial set occurring during the acceleration phase (typically 2-4 hours) due to ettringite needle growth from C₃A hydration interlocking particles, and final set (4-10 hours) from C₃S-driven C-S-H precipitation reducing plasticity.[8] This stiffening arises from reduced free water and interparticle friction, not full hardening, as measured by penetration resistance or Vicat needle tests.[116] Hardening follows as ongoing hydration densifies the microstructure, with compressive strength gaining rapidly in the first 28 days (e.g., C₃S contributes ~70% of early strength) but continuing indefinitely under saturated conditions.[9] Curing sustains hydration by maintaining moisture and temperature, preventing desiccation that halts reactions and induces microcracking; optimal curing at 20-25°C and >95% relative humidity allows near-complete hydration, maximizing durability against chemical attack and load-bearing.[11] Methods include wet burlap, membranes, or steam, with inadequate curing reducing strength by 20-50% in the first week due to incomplete C-S-H formation and increased porosity.[115] The process exploits coupled dissolution-precipitation kinetics, where sustained water availability promotes non-classical nucleation of C-S-H, enhancing matrix cohesion without excessive CH accumulation, which can lead to efflorescence or sulfate vulnerability.[116]Physical and Engineering Properties
Strength and Durability Characteristics
Cement-based materials, particularly Portland cement concrete, exhibit high compressive strength but relatively low tensile strength, necessitating reinforcement in structural applications. Compressive strength is typically measured on cylindrical specimens according to ASTM C39, with standard 28-day values ranging from 17 MPa (2500 psi) for residential applications to over 28 MPa (4000 psi) for commercial structures, and higher for specialized uses.[117][118] The water-to-cement ratio profoundly influences this property, as lower ratios reduce porosity and enhance strength by minimizing voids in the hydrated cement paste.[119][120] Tensile strength of concrete is approximately 8-15% of its compressive strength, often assessed via splitting tensile tests or modulus of rupture, with values around 2.5-5.0 MPa for typical mixes.[121] This disparity arises from the brittle nature of the cement matrix and aggregates, leading to crack propagation under tension. The modulus of elasticity, indicating stiffness, varies with compressive strength and aggregate type, typically 20-40 GPa for normal-weight concrete, calculated empirically as Ec ≈ 4700 √fc' MPa where fc' is compressive strength in MPa.[122][123] Proper compaction and curing further optimize these mechanical properties by ensuring uniform hydration and reducing microcracks.[124] Durability refers to the ability of cement concrete to resist degradation from environmental exposures, including chemical attacks and physical weathering. Key mechanisms include sulfate resistance, where Type II or V Portland cements limit expansion from ettringite formation, achieving minimum strengths like 21 MPa at 7 days for Type V.[67] Chloride penetration resistance depends on low permeability, influenced by dense microstructure from low water-cement ratios and supplementary cementitious materials, preventing corrosion of embedded steel.[125] Carbonation, the reaction of CO2 with hydrated cement to form carbonates, reduces pH and exposes reinforcement; resistance improves with adequate concrete cover and pozzolanic admixtures that refine pore structure.[126] Other factors like aggregate quality, air entrainment for freeze-thaw cycles, and minimized alkali-silica reactivity enhance longevity, with empirical tests showing reduced weight loss or strength retention under simulated exposures.[127][128]| Property | Typical Range | Influencing Factors | Test Standard |
|---|---|---|---|
| Compressive Strength (28 days) | 17-55 MPa | Water-cement ratio, curing duration | ASTM C39[118] |
| Tensile Strength | 2-5 MPa | Aggregate shape, fiber addition | ASTM C496 (splitting) |
| Modulus of Elasticity | 20-40 GPa | Compressive strength, aggregate modulus | ASTM C469 |
| Sulfate Resistance | Low to high (cement type-dependent) | C3A content, exposure class | ASTM C1012 |
Workability and Rheological Behavior
Workability of cement paste refers to its ease of flow and deformation under applied stress, which directly influences the handling, placement, and compaction of fresh concrete mixtures. In cementitious systems, workability is governed by the paste's rheological properties, primarily characterized by yield stress—the minimum shear stress required to initiate flow—and plastic viscosity, the resistance to flow once motion begins. These properties determine the paste's ability to fill formwork without excessive segregation or bleeding, with optimal workability achieved when yield stress is low enough for flow but sufficient to prevent settlement of aggregates in concrete.[131][132] Fresh cement paste exhibits non-Newtonian, thixotropic behavior, often modeled as a Bingham plastic fluid, where the shear stress τ relates to shear rate γ̇ by τ = τ₀ + μ γ̇, with τ₀ as yield stress and μ as plastic viscosity. For more complex flows, the Herschel-Bulkley model extends this to account for shear-thinning (pseudoplasticity), incorporating a flow index n < 1: τ = τ₀ + K γ̇ⁿ, where K is the consistency index. Thixotropy manifests as a reversible structural breakdown under shear—reducing viscosity during mixing—and rebuild-up at rest due to flocculation of cement particles and early hydration products like ettringite and C-S-H gel. This time-dependent structural build-up increases yield stress over minutes to hours, typically by 10-50 Pa in the first 30-60 minutes post-mixing for ordinary Portland cement pastes at water-to-cement ratios (w/c) of 0.3-0.5.[133][134][132] Key factors influencing rheological behavior include the w/c ratio, which inversely affects both yield stress and viscosity; for instance, increasing w/c from 0.3 to 0.4 can reduce yield stress by up to 70% by enhancing particle dispersion and lubrication via free water. Cement fineness exacerbates interparticle friction and flocculation, with finer particles (Blaine surface area >400 m²/kg) elevating viscosity by 20-50% compared to coarser ones due to higher specific surface area demanding more water adsorption. Chemical admixtures, such as polycarboxylate-based superplasticizers, adsorb onto particle surfaces to provide electrostatic and steric repulsion, slashing yield stress by factors of 5-10 at dosages of 0.1-0.5% by mass of cement, thereby improving workability without excess water that compromises strength. Temperature rises accelerate hydration kinetics, boosting yield stress buildup rates by 2-3 times per 10°C increase, as seen in pastes at 20°C versus 30°C.[131][135][136] Mixing intensity and duration also modulate rheology through shear-induced deflocculation; high-shear mixing (e.g., >100 s⁻¹ for 1-2 minutes) can lower initial viscosity by 30-40% by breaking agglomerates, though excessive shearing may entrain air voids that stiffen the paste. Particle packing and colloidal interactions, driven by calcium ions from dissolution, promote edge-to-face flocculation in the calcium silicate and aluminate phases, contributing to higher yield stresses in pastes with elevated C₃A content (>8%). Measurement typically employs rotational rheometers with coaxial cylinders or vane geometries to capture these properties, accounting for wall-slip effects via roughened surfaces, with protocols like those in ASTM C1911 standardizing preconditioning to minimize artifacts from thixotropy. Poor workability, evidenced by yield stresses exceeding 100-200 Pa, correlates with placement difficulties and increased energy demands for pumping, underscoring the need for rheological optimization in mix design.[137][138][131]Applications and Economic Significance
Primary Uses in Construction and Infrastructure
Cement functions primarily as the hydraulic binder in concrete, mortar, and grout, enabling the formation of rigid, durable composites essential for structural integrity in buildings and infrastructure. In concrete production, which consumes over 90% of global cement output, portland cement reacts with water to form a paste that hardens and binds aggregates such as sand, gravel, or crushed stone, yielding compressive strengths typically ranging from 20 to 40 MPa for general construction applications.[139][140] This material underpins residential and commercial buildings through elements like foundations, slabs, beams, columns, and precast components, where its ability to withstand tensile stresses when reinforced with steel rebar supports load-bearing demands.[141] In infrastructure, concrete incorporating cement is deployed for pavements, highways, bridges, tunnels, dams, and water conveyance systems, leveraging its resistance to weathering, abrasion, and chemical attack. For instance, roller-compacted concrete variants are used in heavy-duty pavements and dam facings due to their high density and rapid strength gain, while high-performance mixes enable slender bridge girders with spans exceeding 100 meters. Approximately half of global concrete usage supports such infrastructure projects, including roadways and water supply pipelines, with the remainder allocated to buildings.[142][143] Geotechnical applications, such as slurry walls for excavation support and soil stabilization via cement grouting, further extend its role in foundational infrastructure works.[142] Mortar, comprising cement, sand, and water, serves as an adhesive for masonry units like bricks and concrete blocks in walls and partitions, providing shear strength and weather resistance without the need for formwork. Grout, a fluid cement-sand-water mixture, fills voids in precast elements, anchors bolts in rock formations for bridge piers, and seals joints in tile or segmental linings, ensuring monolithic behavior under dynamic loads. These secondary but critical uses complement concrete's dominance, with cement's hydration properties—forming calcium silicate hydrates that interlock particles—underpinning the long-term durability observed in structures enduring decades of service.[139][144]Role in Economic Development and Employment
Cement serves as a foundational material for infrastructure and construction projects that underpin economic expansion, including transportation networks, housing, and industrial facilities. These investments generate multiplier effects, where initial expenditures on cement-intensive works stimulate further economic activity through linked sectors like manufacturing and services. In developing economies, the establishment of domestic cement production capacities has historically reduced reliance on imports, promoted industrialization, and bolstered national economic resilience by enabling large-scale building programs aligned with population growth and urbanization.[145][146] Per capita cement consumption correlates closely with stages of economic development, functioning as an empirical proxy for GDP growth and infrastructural maturity, as higher usage reflects intensified construction activity during industrialization phases. The global cement market reached a value of $384.67 billion in 2024, with production volumes exceeding 4 billion metric tons annually, predominantly in emerging markets where demand surges accompany rapid economic transformation, as seen in China and India since the early 2000s.[147][148][149] The industry generates direct employment in raw material extraction, clinker production, grinding, and logistics, while indirect jobs arise in downstream construction and supplier networks. In Europe, representing about 7.6% of world output, the sector directly employs approximately 56,000 workers, with broader cement and concrete activities supporting additional positions through value chains. In contexts like India, economic multipliers from cement operations reach 4.16 times output, extending job impacts to ancillary industries and contributing to workforce absorption in labor-surplus economies. These employment dynamics particularly aid skill-building and income generation in developing regions, where cement plants often serve as anchors for regional development.[150][151]Health, Safety, and Handling
Occupational Hazards
Workers in cement manufacturing face significant respiratory risks from inhaling fine particulate dust generated during raw material crushing, clinkering, grinding, and packaging processes. This dust often contains respirable crystalline silica (quartz), a byproduct of limestone and other aggregates, which can penetrate deep into the lungs and trigger inflammation leading to silicosis—an irreversible fibrotic lung disease characterized by scarring and reduced lung function. Chronic exposure has been linked to increased incidence of lung cancer, chronic obstructive pulmonary disease (COPD), and other pneumoconioses, with studies indicating elevated standardized incidence ratios (SIR) for lung cancer among exposed cohorts, though confounding factors like smoking may contribute.[152][153][154] Dermal contact with wet cement paste or dry powder poses hazards due to its high alkalinity (pH 12-13 from calcium oxide and hydroxides) and potential presence of hexavalent chromium (Cr(VI)) formed during high-temperature clinkering. This can cause irritant or allergic contact dermatitis, manifesting as burns, ulcers, or chronic eczema, particularly on hands and forearms; sensitization affects up to 10-15% of workers handling cement without barriers. Acute exposure may result in chemical burns resembling thermal injuries.[155][156] Ocular exposure to cement dust or splashes irritates the cornea and conjunctiva, potentially causing burns, abrasions, or foreign body sensations; prolonged contact risks permanent vision impairment if not flushed immediately. Additional hazards include noise-induced hearing loss from grinding mills and crushers exceeding 85 dB(A), and musculoskeletal strains from heavy lifting of bags (typically 40-50 kg), though these are more general to industrial settings than cement-specific. Overall cancer risks show modest elevations in some epidemiological reviews, but evidence attributes primary causality to silica rather than cement per se, with no effective cure for advanced silicosis emphasizing prevention through exposure controls.[154][157][158]Material Safety in Use
Wet Portland cement, with a pH typically ranging from 12 to 13, poses risks of severe chemical burns upon prolonged skin contact, as the alkaline solution formed by mixing with water reacts with moisture on the skin or clothing to cause caustic irritation or ulceration.[159][160] Eye exposure to wet cement or splashes can result in serious damage, including corneal ulceration or blindness, while dry cement dust irritates mucous membranes.[161][162] Inhalation of cement dust during mixing, pouring, or finishing concrete can irritate the respiratory tract, leading to symptoms such as coughing, shortness of breath, or chronic conditions like bronchitis upon repeated exposure, particularly if respirable fractions containing silica are present.[163][154] Occupational exposure limits established by OSHA include 15 mg/m³ for total dust and 5 mg/m³ for respirable dust over an 8-hour period to mitigate these effects.[164] In finished concrete applications, safety risks diminish once cured, but activities like cutting or drilling generate silica-laden dust that heightens silicosis potential without controls.[165] Hexavalent chromium (Cr(VI)), a trace component in some cements arising from raw materials or manufacturing, is a potent sensitizer causing allergic contact dermatitis in sensitized individuals, characterized by eczematous reactions that persist even after exposure ceases.[166][167] This condition affects up to 10% of construction workers in high-exposure settings historically, though reduction techniques like ferrous sulfate addition have lowered Cr(VI) levels in regulated markets, decreasing incidence rates post-implementation.[168][169] Affected individuals often experience lifelong sensitivity, underscoring the material's potential for inducing chronic occupational skin disorders.[170]Global Industry Dynamics
Production Statistics and Major Producers
Global cement production totaled approximately 4.1 billion metric tons in 2024, reflecting a slight increase from 4.0 billion metric tons in 2023 amid steady demand in developing regions.[171] [172] Production remains heavily concentrated in Asia, which accounts for over 80% of output, driven by urbanization and infrastructure needs in countries like China and India.[173] China leads as the dominant producer, outputting nearly 2.0 billion metric tons in 2024—about half of the global total—though it has reduced capacity in recent years to address overproduction and environmental pressures.[174] [175] India ranks second with around 400 million metric tons annually, fueled by government infrastructure initiatives, while Vietnam, Indonesia, and Turkey follow as key contributors, each producing 50–90 million metric tons.[176] [177]| Rank | Country | Production (million metric tons, approx. 2023–2024) |
|---|---|---|
| 1 | China | 2,000 |
| 2 | India | 400 |
| 3 | Vietnam | 90 |
| 4 | Indonesia | 70 |
| 5 | Turkey | 60 |
| 6 | United States | 90 |
| 7 | Brazil | 60 |
| 8 | Egypt | 55 |
| 9 | Russia | 55 |
| 10 | Saudi Arabia | 50 |