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Cement powder in a bag, ready to be mixed with aggregates and water.[1]
Cement block construction examples from the Multiplex Manufacturing Company of Toledo, Ohio, in 1905

A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel (aggregate) together. Cement mixed with fine aggregate produces mortar for masonry, or with sand and gravel, produces concrete. Concrete is the most widely used material in existence and is behind only water as the planet's most-consumed resource.[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]
Clinker nodules produced by sintering at 1450 °C

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]
Calcium oxide obtained by thermal decomposition of calcium carbonate at high temperature (above 825 °C).

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 septarianodules 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]

William Aspdin is considered the inventor of "modern" Portland cement.[30]

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]
Workers bagging cement in a factory in Scotland, 1918
The National Cement Share Company of Ethiopia's new plant in Dire Dawa

Calcium aluminate cements were patented in 1908 in France by Jules Bied for better resistance to sulfates.[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]
Components of cement:
comparison of chemical and physical characteristics[a][41][42][43]
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
  1. ^ Values shown are approximate: those of a specific material may vary.
  2. ^ ASTM C618 Class F
  3. ^ ASTM C618 Class C
  4. ^ Specific surface measurements for silica fume by nitrogen adsorption (BET) method, others by air permeability method (Blaine).

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]
Global cement production (2022)
Global cement production in 2022
Global cement capacity (2022)
Global cement capacity in 2022

In 2010, the world production of hydraulic cement was 3,300 megatonnes (3,600×10^6 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]
Global carbon emission by type to 2018
Global carbon emission by type to 2018

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 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]

Further reading

[edit]
[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia

Cement is a hydraulic binder obtained by pulverizing —nodules formed by and aluminosilicate materials such as clay at high temperatures around 1450°C—with added to regulate setting time; , the predominant variety, consists primarily of hydraulic calcium silicates. Developed in 1824 by English Joseph Aspdin, who patented it as "Portland cement" for its resemblance to natural , this material revolutionized construction by enabling durable, weather-resistant and mortars essential for , buildings, and dams worldwide. 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 of , contributing 7-8% to global anthropogenic emissions amid annual output exceeding 4 billion tons, dominated by . 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.

Chemical Foundations

Hydration Chemistry

The hydration of is an exothermic set of chemical reactions between its primary clinker phases—tricalcium silicate (C₃S), dicalcium silicate (C₂S), (C₃A), and tetracalcium aluminoferrite (C₄AF)—and water, producing (C-S-H) gel, (CH, or ), and other hydrates that interlock to form a rigid matrix responsible for strength development. 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. The process is diffusion-controlled, involving dissolution of anhydrous phases, and growth of hydrates, and pore space filling, with overall approximated but varying due to incomplete reactions and gel-like products lacking fixed compositions. 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 (amorphous, nanoscale fibers providing cohesion) and crystalline CH (hexagonal plates that fill pores but can lead to or alkali-silica reactions if excessive). This phase's high reactivity stems from its structure, dissolving to supersaturate the solution with Ca²⁺ and ions, promoting heterogeneous of C-S-H on particle surfaces.
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.
Tricalcium aluminate (C₃A, 5-10% of clinker) reacts vigorously with water, potentially causing flash set without (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 depletes, releasing heat and risking shrinkage if uncontrolled. Gypsum's role is causal: it adsorbs on C₃A surfaces, delaying hydration until ettringite forms a protective layer, enabling workability.
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. 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.

Hydraulic and Non-Hydraulic Variants

Hydraulic cements harden through a with , forming insoluble hydration products that bind aggregates into durable s and mortars, even in submerged conditions. This process, known as hydration, primarily involves the calcium silicates in the cement—tricalcium silicate (C₃S) and dicalcium silicate (C₂S)—reacting to produce (C-S-H) gel and (CH). For instance, the reaction for C₃S is approximately 2C₃S + 6H → C₃S₂H₃ + 3CH, where H denotes molecules, yielding a dense, microstructure responsible for early strength gain. These cements, exemplified by , achieve compressive strengths exceeding 20 MPa within 28 days under standard curing, enabling applications in modern infrastructure like dams and bridges. 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. 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. 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. 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 without underwater capability. 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. Hybrid formulations, like natural hydraulic limes with 5-20% clay, blend properties but classify as mildly hydraulic if they exhibit partial water-setting.

Historical Evolution

Pre-Industrial Binders and Early Uses

The earliest known use of binders resembling cement occurred during the period, with archaeological evidence from sites like in the Pre-Pottery Neolithic era (ca. 7000–6000 BCE) indicating plasters made with a limy clay binder derived from calcined mixed with aggregates. These materials served to waterproof and stabilize structures such as floors and walls, demonstrating rudimentary control over processes to produce for binding. Such binders were non-hydraulic, relying on rather than water-induced setting, and were formed by heating to approximately 800–900°C to drive off , yielding quicklime that was then slaked with to form a putty. By around 4000 BCE, had become a staple in Egyptian , applied as to the interiors and exteriors of pyramids and tombs to seal surfaces against moisture and pests. Gypsum-based binders, calcined from selenite deposits at lower temperatures (around 150–200°C), were also utilized by circa 3000 BCE for bonding blocks in structures like mastabas, offering faster setting but limited durability in wet conditions due to their non-hydraulic nature. In parallel, Mesopotamian and Indus Valley civilizations employed similar lime mortars for bricklaying and rendering, with residues analyzed from sites like showing mixtures of burnt lime, sand, and organic fibers for enhanced workability and tensile strength. 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 to form insoluble compounds. In northern , binders incorporating 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. These pre-industrial materials prioritized local resources like , , and natural pozzolans, enabling durable without high-temperature kilns, though their performance was constrained by variable purity and environmental exposure compared to later formulations.

Classical Civilizations

In , builders primarily employed as a binder for stone in temples and other structures, produced by burning to create quicklime, slaking it with , and mixing with sand. This mortar set through , reacting with atmospheric to reform , but lacked the ability to harden underwater or in wet conditions, limiting its applications compared to later innovations. Greek use of lime-based binders dates to around the 8th century BC, as evidenced in structures like the Temple of at Olympia, where it served mainly for joints and decorative rather than . The Romans advanced binder technology significantly in the 3rd to 2nd centuries BC by developing opus caementicium, a hydraulic that incorporated pozzolanic —sourced from regions like near —with slaked lime and aggregates such as broken stones or bricks. This mixture achieved hydraulic setting through pozzolanic reactions forming hydrates and other compounds, enabling curing even submerged in , as demonstrated in harbors like constructed around 20-10 BC. Architect , writing circa 15 BC in , prescribed specific proportions: one part lime to three parts for general building mortar and one to two for underwater applications, emphasizing the ash's fineness and reactivity for strength. 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. Unlike Greek , which was prone to 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. This innovation facilitated large-scale engineering feats, including the 300 km-long aqueduct (AD 38-52) and extensive road networks, marking a shift from mere binding to true composite materials in classical .

Medieval and Renaissance Developments

Following the fall of the in the , the advanced pozzolanic hydraulic cements of antiquity were largely forgotten in , leading to a reliance on non-hydraulic lime mortars produced by slaking burnt with water and mixing with . These mortars set through , absorbing CO₂ from the air to form , but lacked the water resistance of Roman concretes, limiting their use in submerged or exposed structures. Archaeological evidence from sites like 7th-century longhouses in Lyminge, , shows sporadic employment of basic concrete-like mixtures, often with lime and aggregate, though on a diminished scale compared to imperial precedents. 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. 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. 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. 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. During the (c. 1400–1600 CE), renewed scholarly interest in classical texts like Vitruvius's (1st century BCE), rediscovered in 1416, spurred experimentation with lime-based stuccos and mortars inspired by ancient descriptions of , though systematic hydraulic rediscovery awaited the . Architects such as , in constructing the 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. This era saw refined lime putty techniques, including hot-mixed limes for faster setting, applied in frescoed palaces and palazzos across , but innovations remained incremental, focusing on aesthetic finishes rather than material breakthroughs; compressive strengths hovered at 2–4 MPa, insufficient for widespread waterproofing. The period's emphasis on and antiquity bridged medieval practices to Enlightenment engineering, yet cement technology exhibited continuity in lime dominance without causal advances in clinkering or artificial hydraulics.

Industrial Revolution and Modern Portland Cement

The invention of occurred amid the '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 patented the process (British Patent No. 5022), which involved grinding and clay, mixing them into a , burning the mixture in a to form clinker, and then pulverizing it into a fine powder. This artificial cement derived its name from the hardened material's resemblance to high-quality from Dorset, , and provided superior hydraulic properties—setting underwater and resisting water penetration—compared to non-hydraulic lime mortars prevalent at the time. Aspdin established production at a works in in 1825, initially producing small quantities for local use in and early projects. Refinements by Aspdin's son, , elevated Portland cement to a more consistent and stronger product suitable for industrial-scale application. In the , 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. He established factories in from 1841 and later in at Altona and Lagerndorf starting in 1860, exporting the abroad and initiating non-British production of advanced . Concurrently, 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. 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 facilitated faster and more robust . 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. 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. 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. 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.

20th Century Advances and Global Expansion

The adoption of rotary kilns, initially developed in the late , became standard in cement production by the early , enabling continuous operation, higher throughput, and better clinker quality compared to batch shaft kilns. Refinements in kiln design, including longer lengths and improved , further increased output, with plants scaling to produce thousands of tons daily by mid-century. These mechanical advances were complemented by chemical progress, such as precise control of raw mix composition through analysis introduced in the 1940s, ensuring consistent clinker minerals like and for predictable hydration. Standardization drove quality improvements, with the American Society for Testing and Materials (ASTM) issuing its first specification for (C150) in 1904, defining chemical and physical requirements that influenced global norms. 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. 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 for enhanced durability and lower cost, though Portland remained dominant. 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. 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. 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. This growth enabled unprecedented urbanization and civil engineering feats, though it strained resources in import-dependent areas until domestic capacity caught up.

Classification and Types

Portland Cement

Portland cement is a finely ground produced by pulverizing clinker nodules, which consist primarily of hydraulic calcium silicates such as (tricalcium silicate, C3S) and (dicalcium silicate, C2S), along with smaller amounts of (C3A) and tetracalcium aluminoferrite (C4AF); (calcium sulfate) is typically added during grinding to control setting time. The clinker forms through the high-temperature of a of calcareous materials like (providing ) and argillaceous materials like clay (providing silica, alumina, and ) at approximately 1400–1500°C in a . This process yields dark grey, nodular clinker that, when ground to a fine with 3–5% , produces the hydraulic binder capable of setting and hardening through reaction with , even underwater. The material derives its name from its resemblance in color and superior durability to , a quarried on the Isle of Portland in ; it was patented on October 21, 1824, by English Joseph Aspdin, who produced it by burning and clay in a and grinding the resulting clinker. Aspdin's formulation marked a significant advancement over earlier hydraulic limes, enabling stronger, more consistent for industrial-scale . Subsequent refinements, including by Aspdin's son William in the , optimized the burning temperature and raw mix to enhance strength, establishing the modern composition where calcium silicates comprise 70–80% of the clinker minerals. 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 limits and physical properties like , setting time, and strength development. Type I serves general-purpose use where special properties are not required, suitable for most structures like pavements and buildings; Type II offers moderate resistance and lower heat of hydration for ; Type III provides high early strength for rapid ; Type IV generates low heat for large pours like ; and Type V delivers high sulfate resistance for exposure to severe sulfate environments, such as certain soils or seawaters. Variants with an "A" suffix (e.g., IA, IIA) incorporate air-entraining properties to improve freeze-thaw durability in . 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. Internationally, similar categorizations exist, though remains the foundational type comprising the majority of global production, often blended with supplementary materials in composite cements; pure (e.g., CEM I under EN 197-1) contains at least 95% clinker. Its hydraulic nature stems from the cementitious reactions where calcium silicates hydrate to form (C-S-H) gel and , providing the binding matrix responsible for concrete's exceeding 20–40 MPa at 28 days under standard curing.

Blended and Composite Cements

Blended hydraulic cements consist of clinker interground or intimately blended with supplementary cementitious materials (SCMs), such as blast-furnace slag, pozzolans, or , along with for set control. 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 (C-S-H) gel during hydration. In contrast to pure , blended variants exhibit slower early strength development but enhanced long-term performance due to the SCMs' contributions to pore refinement and reduced permeability. Common SCMs include (GGBS), which provides latent hydraulic reactivity and can comprise up to 70% in Type IS cements per ASTM C595; fly ash, a derived from 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 , an ultrafine from production used at 5-10% for high-strength applications due to its high silica content and reactivity. powder, permitted up to 15% in Type IL cements, acts as a filler and site accelerator without significant . 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 and fly ash, to optimize performance while further minimizing clinker content to as low as 35-65%. Manufacturing involves either intergrinding clinker with SCMs during final cement production or post-blending finished with SCMs, ensuring uniform distribution for consistent hydration behavior. 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. Environmentally, they lower the 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 and fuel combustion, while repurposing industrial byproducts like fly ash and reduces waste. Additional benefits include decreased heat of hydration, mitigating thermal cracking in , and enhanced workability from SCM particle shapes, though early-age strengths may require adjusted mix designs or admixtures. 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 (L up to 15%), and IT for ternary blends, with chemical limits on (≤4.5% SO3) and . European 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. These specifications ensure 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. 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.

Specialty and Alternative Cements

Specialty cements are formulated for targeted performance characteristics beyond standard , 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 , enabling faster construction timelines in repairs or precast elements. High-alumina cement, rich in calcium aluminate phases, provides rapid strength gain and resistance but requires careful curing to avoid conversion-related strength loss over time. Calcium sulfoaluminate (CSA) cements represent a specialty variant with clinker compositions emphasizing ye'elimite (C4A3S) over traditional , 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 and further optimize sulfate resistance and long-term durability, though sensitivity to content can influence performance. 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 , form a three-dimensional silicate-aluminate network without clinkering, slashing CO2 emissions by up to 80% relative to 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., ), and aggregates, though scalability remains limited by activator costs and variability in precursors. Magnesium-based cements, such as magnesium oxychloride () 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 or reduced longevity in moist environments. Other alternatives include calcined clay cements (LC3), which substitute up to 50% clinker with calcined clay and 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 and integration.

Manufacturing Process

Raw Material Extraction and Preparation

The principal raw materials for Portland cement clinker production are calcareous materials, primarily or chalk providing calcium carbonate (CaCO₃), and argillaceous materials such as clay, , or supplying silica (SiO₂), alumina (Al₂O₃), and (Fe₂O₃). Supplementary sources like , , or may be added to adjust oxide compositions if natural deposits are deficient. These materials are selected for their geochemical suitability, with typically comprising 75-90% of the mix by weight to achieve the target CaO content of 60-67% in the raw meal. 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. 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. 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. Preparation begins with primary crushing in or gyratory crushers to reduce fragments to under 100-200 mm, followed by secondary and tertiary stages using or impact crushers to achieve sizes below 25-50 mm, often incorporating screening to recycle oversize. 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. Final homogenization in vertical , with capacities up to 20,000 tonnes, employs injection or blending to achieve uniformity, targeting standard deviations below 0.5-1% for CaO, SiO₂, Al₂O₃, and Fe₂O₃ to ensure consistent clinker quality and efficiency. Automated systems monitor oxide ratios via 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. This stage is critical, as poor homogenization can increase energy use by 5-10% in the and degrade cement strength by up to 2-3 MPa.

Clinkering and Grinding

Clinkering involves heating a finely ground mixture of raw materials, primarily and clay, in a to temperatures around 1450°C, where and chemical reactions form hard, nodular clinker. This process occurs in stages: initial of up to 125°C, decomposition of clays and carbonates between 400-900°C releasing CO2, and finally clinkering in at 1300-1450°C, where calcium silicates dominate. The primary phases produced include (tricalcium silicate, C3S, approximately 65% by weight), which governs early strength development, (dicalcium silicate, C2S) for later strength, (C3A), and tetracalcium aluminoferrite (C4AF). forms via reaction of with silica at these high temperatures, with impurities aiding stabilization at lower energies. The , 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. 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 by preheating air. Optimal clinkering requires precise control of raw mix composition, such as lime saturation factor, to maximize content while minimizing free lime, which can impair cement quality. Grinding follows clinkering, where cooled clinker is interground with 3-5% and sometimes or other additives in mills or vertical roller mills to produce fine cement powder. mills, large rotating drums filled with balls, achieve particle fineness measured by Blaine air permeability, typically targeting 3000-5000 cm²/g for ordinary Portland cement, influencing hydration rate and strength. Vertical roller mills offer energy savings up to 30% over mills by combining crushing, grinding, and , though they require careful control to avoid overgrinding , which reduces reactivity. Grinding aids, such as amines or glycols, are added at 0.01-0.1% to enhance flowability and reduce , which averages 30-50 kWh per ton of cement. The resulting cement must meet standards for residue on 45 μm (below 15-20%) to ensure consistent performance.

Hydration, Setting, and Curing Mechanisms

Hydration of is an exothermic between its primary clinker phases—tricalcium silicate (C₃S, approximately 50% by weight), dicalcium silicate (C₂S, 25%), (C₃A, 10%), and tetracalcium aluminoferrite (C₄AF, 10%)—and , moderated by (5%) to control early reactivity. The process forms hydration products including (C-S-H) gel, which provides the primary binding and strength through its amorphous, nanoscale structure, and crystalline (CH, or ). C₃A reacts rapidly with and sulfate ions from to form ettringite (calcium sulfoaluminate hydrate), a needle-like that influences early stiffness, while C₄AF contributes similar but slower ferritic phases. Key reactions include the hydration of C₃S: 2Ca3SiO5+7H2O3CaO2SiO24H2O+3Ca(OH)22Ca_3SiO_5 + 7H_2O \rightarrow 3CaO \cdot 2SiO_2 \cdot 4H_2O + 3Ca(OH)_2, releasing approximately 174 kJ/mol of , and C₂S: 2Ca2SiO4+5H2O3CaO2SiO24H2O+Ca(OH)22Ca_2SiO_4 + 5H_2O \rightarrow 3CaO \cdot 2SiO_2 \cdot 4H_2O + Ca(OH)_2, with 59 kJ/mol , both yielding C-S-H and CH. 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). 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. 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. 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. Setting refers to the transition from a 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 (4-10 hours) from C₃S-driven C-S-H precipitation reducing plasticity. This stiffening arises from reduced free water and interparticle friction, not full hardening, as measured by penetration resistance or Vicat needle tests. Hardening follows as ongoing hydration densifies the microstructure, with gaining rapidly in the first 28 days (e.g., C₃S contributes ~70% of early strength) but continuing indefinitely under saturated conditions. Curing sustains hydration by maintaining moisture and temperature, preventing that halts reactions and induces microcracking; optimal curing at 20-25°C and >95% relative allows near-complete hydration, maximizing durability against chemical attack and load-bearing. Methods include wet burlap, membranes, or , with inadequate curing reducing strength by 20-50% in the first week due to incomplete C-S-H formation and increased . The process exploits coupled dissolution-precipitation kinetics, where sustained water availability promotes non-classical of C-S-H, enhancing matrix cohesion without excessive CH accumulation, which can lead to or vulnerability.

Physical and Engineering Properties

Strength and Durability Characteristics

Cement-based materials, particularly , exhibit high but relatively low tensile strength, necessitating in structural applications. 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. The water-to-cement ratio profoundly influences this property, as lower ratios reduce and enhance strength by minimizing voids in the hydrated cement paste. 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. This disparity arises from the brittle nature of the cement matrix and aggregates, leading to crack propagation under tension. The modulus of elasticity, indicating , varies with compressive strength and aggregate type, typically 20-40 GPa for normal-weight , calculated empirically as Ec ≈ 4700 √fc' MPa where fc' is compressive strength in MPa. Proper compaction and curing further optimize these mechanical properties by ensuring uniform hydration and reducing microcracks. 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. penetration resistance depends on low permeability, influenced by dense microstructure from low water-cement ratios and supplementary cementitious materials, preventing of embedded steel. , the reaction of CO2 with hydrated cement to form carbonates, reduces pH and exposes reinforcement; resistance improves with adequate and pozzolanic admixtures that refine pore structure. Other factors like aggregate quality, for freeze-thaw cycles, and minimized alkali-silica reactivity enhance longevity, with empirical tests showing reduced weight loss or strength retention under simulated exposures.
PropertyTypical RangeInfluencing FactorsTest Standard
Compressive Strength (28 days)17-55 MPaWater-cement ratio, curing durationASTM C39
Tensile Strength2-5 MPaAggregate shape, fiber additionASTM C496 (splitting)
Modulus of Elasticity20-40 GPaCompressive strength, aggregate modulusASTM C469
Sulfate ResistanceLow to high (cement type-dependent)C3A content, exposure classASTM C1012
Overall, strength and durability are interdependent, with empirical data emphasizing that suboptimal mix design or execution—such as inadequate curing—can halve expected service life despite nominal strengths.

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. Fresh cement paste exhibits non-Newtonian, thixotropic behavior, often modeled as a fluid, where the τ relates to γ̇ by τ = τ₀ + μ γ̇, with τ₀ as yield stress and μ as plastic . 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 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. Key factors influencing rheological behavior include the w/c ratio, which inversely affects both yield stress and ; 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 . Cement fineness exacerbates interparticle friction and flocculation, with finer particles (Blaine surface area >400 m²/kg) elevating by 20-50% compared to coarser ones due to higher demanding more 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 of cement, thereby improving workability without excess that compromises strength. 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. Mixing intensity and duration also modulate through shear-induced deflocculation; high-shear mixing (e.g., >100 s⁻¹ for 1-2 minutes) can lower initial 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 in the and aluminate phases, contributing to higher yield stresses in pastes with elevated C₃A content (>8%). typically employs rotational rheometers with 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 . 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.

Applications and Economic Significance

Primary Uses in Construction and Infrastructure

Cement functions primarily as the hydraulic binder in , mortar, and , 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, reacts with water to form a paste that hardens and binds aggregates such as , , or , yielding compressive strengths typically ranging from 20 to 40 MPa for general construction applications. 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. In , 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, 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 usage supports such projects, including roadways and pipelines, with the remainder allocated to buildings. Geotechnical applications, such as walls for excavation support and via cement grouting, further extend its role in foundational works. 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.

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. Per capita cement consumption correlates closely with stages of , functioning as an empirical proxy for GDP growth and infrastructural maturity, as higher usage reflects intensified 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 and since the early 2000s. The industry generates direct employment in raw material extraction, clinker production, grinding, and , while indirect jobs arise in downstream and supplier networks. In , representing about 7.6% of world output, the sector directly employs approximately 56,000 workers, with broader cement and activities supporting additional positions through value chains. In contexts like , 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 dynamics particularly aid skill-building and generation in developing regions, where cement often serve as anchors for .

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. Dermal contact with wet cement paste or dry powder poses hazards due to its high alkalinity (pH 12-13 from and hydroxides) and potential presence of (Cr(VI)) formed during high-temperature clinkering. This can cause irritant or , 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. Ocular exposure to cement dust or splashes irritates the and , potentially causing burns, abrasions, or foreign body sensations; prolonged contact risks permanent vision impairment if not flushed immediately. Additional hazards include 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 emphasizing prevention through exposure controls.

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. Eye exposure to wet cement or splashes can result in serious damage, including corneal ulceration or blindness, while dry cement dust irritates mucous membranes. Inhalation of cement dust during mixing, pouring, or finishing can irritate the , leading to symptoms such as coughing, , or chronic conditions like upon repeated exposure, particularly if respirable fractions containing silica are present. 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. In finished applications, safety risks diminish once cured, but activities like cutting or drilling generate silica-laden dust that heightens potential without controls. Hexavalent chromium (Cr(VI)), a trace component in some cements arising from raw materials or manufacturing, is a potent sensitizer causing in sensitized individuals, characterized by eczematous reactions that persist even after exposure ceases. 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. Affected individuals often experience lifelong sensitivity, underscoring the material's potential for inducing chronic occupational disorders.

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. Production remains heavily concentrated in , which accounts for over 80% of output, driven by and needs in countries like and . 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. ranks second with around 400 million metric tons annually, fueled by government infrastructure initiatives, while , , and follow as key contributors, each producing 50–90 million metric tons.
RankCountryProduction (million metric tons, approx. 2023–2024)
12,000
2400
390
470
560
690
760
855
955
1050
Data compiled from industry reports; U.S. figure from USGS estimates for portland and cement. Among companies, Chinese firms hold the largest capacities: (CNBM) exceeds 500 million metric tons annually, followed closely by at over 400 million metric tons. Globally diversified players like Ltd. (revenue leader at over $30 billion in 2023) and operate extensive networks but produce far less volume than Chinese giants, focusing on higher-value markets in and . Other notables include () and (Ireland-based, strong in the ). This concentration underscores China's state-supported industry dominance, with non-Chinese firms emphasizing efficiency and exports. Global cement demand reached approximately 4.2 billion metric tons per year as of recent estimates, with forecasts indicating modest growth to 4.7 billion metric tons by 2050 under reference scenarios, driven primarily by and development in emerging markets. Excluding , where demand is expected to peak and decline due to overcapacity and slowing construction, global consumption outside is projected to increase by 1-2% in 2025, reflecting uneven recovery amid economic variability. Market value stood at around $384 billion in 2024, with projections for a (CAGR) of about 4-5% through 2030, fueled by residential and commercial building in and , though tempered by high energy costs and regulatory pressures on emissions. Cement prices have exhibited upward trends in recent years, influenced by volatile energy inputs, with production costs rising 14% year-over-year in some regions during 2022 due to fuel and electricity expenses. In 2023, a decline in coal and petcoke prices provided temporary relief, but subsequent rebounds in energy markets—exacerbated by geopolitical tensions and supply constraints—have pushed prices higher, such as to $85 per metric ton in during Q3 2024. These fluctuations underscore the sector's sensitivity to dependency, where accounts for up to 40% of production costs, prompting some producers to explore alternative fuels amid persistent inflationary pressures. Supply chain vulnerabilities in the cement industry stem from its reliance on regionally sourced s like and clay, combined with energy-intensive kilns and extensive for bulk transport. Disruptions such as port congestion and shipping delays, intensified during the , have rippled through global trade, delaying clinker and cement shipments and amplifying overcapacity risks in high-production regions like . Rising and transportation costs further strain margins, with external factors like events and economic downturns causing volatility that mismatches fixed-capacity investments. Efforts to mitigate these factors include adopting supplementary cementitious materials (SCMs) to reduce clinker dependency and address resource scarcity, potentially expanding SCM markets to $40-60 billion by 2035. Geopolitical risks, including energy supply interruptions from conflicts, continue to highlight the need for diversified sourcing and localized production to enhance resilience, though China's dominance in capacity—over half of global totals—poses competitive distortions via exports. Overall, focuses on risk modeling to prioritize elements like and , aiming to minimize disruptions in an industry characterized by capital-intensive, low-margin operations.

Environmental and Sustainability Aspects

Emissions Profile and Process Inherent Impacts

The production of , the most common type, generates approximately 0.8 to 0.9 tons of CO₂ per ton of cement, contributing to global emissions of around 2.3 to 2.4 gigatons of CO₂ annually as of recent estimates, equivalent to roughly 6-8% of total anthropogenic CO₂ releases. These figures reflect direct emissions from , excluding downstream use or indirect factors, and have risen in absolute terms since 2015 despite some efficiency gains, driven by increasing global demand for materials. Of the total CO₂, 60-65% originates from process emissions during limestone , where (CaCO₃) decomposes at temperatures above 900°C into (CaO) and CO₂ via the reaction CaCO₃ → CaO + CO₂, releasing about 0.785 tons of CO₂ per ton of pure CaCO₃ processed (or roughly 0.51 tons per ton of clinker). This is stoichiometrically inherent to clinker formation, the core step yielding the binding agent in cement, and cannot be eliminated without substituting carbonate-based raw materials. The balance, 35-40%, stems from fuel combustion to sustain temperatures of 1,450°C or higher for clinker , predominantly using , petcoke, or other carbon-intensive fuels that oxidize to CO₂. Non-CO₂ emissions further characterize the profile, including nitrogen oxides () formed by thermal fixation of atmospheric nitrogen at high kiln temperatures (typically 200-3,000 mg/Nm³), sulfur oxides () from sulfur in fuels and raw materials (up to 3,500 mg/Nm³ for SO₂), and particulate matter (dust) from raw material grinding, handling, and kiln operations. In major producing regions like the , these have historically exceeded 500,000 tons annually for SO₂ and NOx combined, posing risks to air quality through precursors and respiratory irritants, though levels vary widely by plant technology and fuel quality. Process-inherent impacts extend beyond emissions to the thermodynamic demands of the reactions, requiring sustained high-energy inputs that favor fuels for reliability and cost, and generating alkaline dust with potential for localized and alkalinity if unmanaged. The step's fixed CO₂ yield per clinker ton—tied causally to the mineralogy of abundant feedstocks—limits mitigation to partial measures like blended cements reducing clinker content, underscoring that full avoidance demands alternative chemistries not yet scalable for applications.

Resource Use and Waste Management

Cement production requires substantial raw materials, primarily for and clay, , or for silica, alumina, and iron oxides, with typical ratios yielding about 1.5 to 1.6 metric tons of raw materials per metric ton of due to losses. Global production of 4.16 billion metric tons of in 2022 thus consumed approximately 6.56 billion metric tons of raw materials, predominantly non-renewable mineral aggregates. Energy inputs dominate resource demands, with thermal energy averaging 3 to 4 gigajoules per ton of clinker from fuels like or pet coke, and electrical energy at around 100 kilowatt-hours per ton of cement for grinding and processing. Water usage remains relatively low at 0.14 to 1.28 liters per kilogram of cement, primarily for cooling and dust suppression, though in closed-loop systems can minimize net consumption. To mitigate depletion of virgin resources, the industry incorporates alternative raw materials such as fly ash from combustion and granulated slag, which can substitute up to 30-50% of clinker in blended cements while providing pozzolanic reactivity. These substitutes, sourced from industrial byproducts, reduce limestone quarrying by diverting wastes that would otherwise require disposal; for instance, fly ash utilization in cement avoids accumulation and stabilizes through encapsulation. However, availability constraints, such as declining fresh fly ash supplies amid phase-outs, limit scalability without compromising cement performance. Waste management focuses on cement kiln dust (CKD), a fine particulate byproduct comprising 10-20% of kiln feed weight, rich in lime and alkalis but variably contaminated with sulfates and metals. Up to 50% of CKD is typically recycled internally by reintegrating it into the raw meal, recovering valuable minerals and reducing needs, while excess is stabilized for uses like soil amendment or neutralized for acidic . External recycling rates vary by ; in the U.S., beneficial reuse in cement or avoids hazardous classification under RCRA when low in , though improper landfilling risks leaching. Kilns' high temperatures enable co-processing of other as alternative fuels or raw materials, incinerating organics while incorporating inorganics, thus achieving thermal substitution rates of 20-60% in advanced facilities without elevating emissions beyond process norms. Empirical data from operational confirm that such practices lower net output by 15-30% per ton of cement compared to traditional disposal.

Technological Mitigations and Low-Carbon Innovations

Efforts to mitigate emissions in cement production focus on reducing the clinker factor, substituting fossil fuels, capturing process-derived CO2, and developing alternative cementitious materials, as these address the dual sources of emissions from fuel combustion (about 40%) and limestone (about 60%). Industry-wide, clinker substitution with supplementary cementitious materials (SCMs) such as slag, fly ash, or calcined clay has achieved up to 50% reduction in clinker content in blended cements, lowering overall CO2 intensity by 20-30% without compromising performance in many applications. For instance, increasing limestone filler to 15% in Portland-limestone cement (PLC), standardized in the U.S. since 2013, yields a 10% emissions cut per ton compared to traditional . Alternative fuels, including , municipal waste, and non-recyclable tires, have been integrated into operations to displace and petcoke, with global substitution rates reaching 20-30% in leading facilities by 2023, potentially halving fuel-related emissions where fully implemented. These fuels leverage the cement 's high temperatures (up to 1450°C) for complete and hazardous waste destruction, but their net emissions benefit depends on upstream waste processing; biogenic fractions enable negative emissions via bio-CCS. Process optimizations, such as heat recovery and AI-driven controls, further contribute 5-10% gains, as demonstrated in European plants averaging 3.3 GJ/ton clinker energy use. Novel low-carbon cements bypass traditional Portland clinker: calcium sulfoaluminate (CSA) cements, using ye'elimite as the primary phase, require less limestone and lower kiln temperatures (around 1250°C), achieving 20-30% lower process emissions than ordinary Portland cement (OPC). Geopolymer cements, alkali-activated from industrial byproducts like slag or metakaolin, eliminate clinker entirely, offering 50-80% emissions reductions while providing comparable or superior durability in alkaline environments. Belite-rich clinkers (beta-C2S dominant) reduce lime content, cutting calcination CO2 by up to 10%, though hydration kinetics require additives for standard setting times. Carbon capture, utilization, and storage (CCUS) targets process CO2 directly: post-combustion scrubbing captures 80-90% of flue gases, while oxyfuel combustion enables over 95% capture by recycling oxygen-enriched exhaust. Commercial-scale projects include ' Brevik CCS in , operational from 2024 under the program, capturing 400,000 tons CO2 annually (95% of plant emissions) for offshore storage. Holcim's GO4ZERO initiative in aims for 70% capture at a 1 million ton/year plant by 2025, integrating technology with CO2 use in aggregates. Emerging , such as plasma arc or microwave kilns powered by renewables, shows pilot potential for 100% decarbonized but faces scalability hurdles due to high demands (up to 5 GJ/ton). These innovations, while promising, require support to overcome costs estimated at $50-100/ton CO2 abated for CCUS.

Policy Debates: Regulation versus Market-Driven Progress

The cement industry's contribution to global CO2 emissions, estimated at 7-8% or approximately 2.6 gigatonnes annually, has fueled policy debates over whether stringent regulations or market-driven mechanisms best achieve decarbonization without undermining production essential for . Proponents of regulation advocate for tools like carbon pricing, systems (ETS), and mandates, arguing they internalize externalities and compel adoption of low-carbon technologies such as carbon capture, utilization, and storage (CCUS). For instance, the European Union's Emissions Trading System has applied to cement since 2005, with expansions under the package targeting a 55% emissions cut by 2030 relative to 1990 levels, supplemented by the Carbon Border Adjustment Mechanism (CBAM) implemented in 2023 to curb by taxing high-emission imports. However, empirical analyses indicate that such policies can elevate production costs by 20-40% due to CCUS requirements, potentially leading to plant closures, job losses, and to unregulated regions like , where accounts for over 50% of global capacity and faces less stringent enforcement. Critics of heavy , including industry analyses, contend that top-down mandates distort markets and hinder dynamic efficiency gains, as evidenced by modeling of U.S. cement under cap-and-trade scenarios, which predicts reduced output and if abatement costs exceed $100 per of CO2 without corresponding global coordination. Carbon has shown limited effectiveness in driving transformative change; for example, while Canada's industrial framework incentivizes reductions, cement firms report compliance costs absorbing up to 40% of potential investments in alternatives, with emissions intensity reductions often attributable to prior efficiency improvements rather than the policy itself. In contrast, market-driven progress has historically lowered emissions intensity through voluntary adoption of process optimizations, such as AI-enhanced controls at plants, which achieved a 2% emissions cut in 2024 without mandates. Market-oriented approaches emphasize demand-pull incentives and private R&D, fostering breakthroughs like novel low-carbon cements from startups such as Sublime Systems and Fortera, which use electrochemical processes or waste-derived precursors to eliminate clinker emissions, attracting over $700 million in between 2022 and 2023. These innovations demonstrate causal links between competitive pressures and technological leaps, as firms pursue cost advantages in a global market projected to demand 5 billion tonnes annually by 2050 for in developing economies. Regulatory skepticism arises from observations of policy-induced distortions, such as in , where state mandates have prompted calls for subsidies to offset viability threats to domestic plants amid rising energy costs. Ultimately, evidence suggests hybrid models—minimal regulation paired with technology-neutral pricing—may outperform prescriptive rules, as overly aggressive interventions risk inflating cement prices by 20-50% globally while failing to address process-inherent emissions without scalable alternatives.

Controversies and Balanced Perspectives

Overstated Environmental Alarmism

Cement production accounts for approximately 7-8% of global anthropogenic CO₂ emissions, a figure frequently cited in environmental discourse but often framed in isolation to amplify its perceived threat. In 2022, the industry emitted about 1.6 billion metric tons of CO₂, contributing to a total global emissions tally exceeding 37 billion metric tons from energy-related sources alone. While process emissions from represent roughly half of this total—stemming from an inherent releasing CO₂—the remainder arises from fuel , which is amenable to decarbonization via or alternative fuels. Alarmist narratives, such as equating cement's footprint to that of an independent nation rivaling the or in emissions, exaggerate its standalone culpability by neglecting that fossil fuel in energy and transport sectors dominates at over 70% of totals. Such portrayals overlook cement's foundational role in enabling low-emissions , including hydroelectric dams, nuclear facilities, and durable housing that underpin alleviation and in developing regions. Global production, led by at 718 million metric tons of CO₂ in 2023, correlates with rapid and expansion in , where emissions growth reflects essential human flourishing rather than discretionary excess. Critics argue that demonizing cement distracts from larger emitters like power, while ignoring empirical offsets: natural of absorbs a portion of emitted CO₂ over decades, though studies indicate prior estimates of this uptake—sometimes claimed to neutralize up to 20-30%—have been overstated by factors of 60% due to slower real-world kinetics in buried or sealed applications. Media and advocacy sources, including outlets like , amplify these concerns with hyperbolic language such as "tipping us into climate catastrophe," reflecting a of selective emphasis that prioritizes material-specific blame over systemic analysis—a tendency traceable to institutional biases favoring narrative-driven reporting over proportional assessment. Peer-reviewed analyses confirm the 8% benchmark but emphasize that per-unit emissions intensity has declined 20-30% since 1990 through efficiency gains, undermining claims of inexorable escalation absent intervention. This framing risks policy distortions, such as premature carbon taxes that could inflate costs in low-income areas without commensurate global benefits, as evidenced by stalled decarbonization in high-emitting regions despite regulatory pressures.

Essentiality for Human Flourishing and Infrastructure Needs

Cement serves as the primary binder in , the most widely used material globally, enabling the erection of durable structures essential to modern . In 2020, worldwide production reached approximately 14 billion cubic meters, underscoring its scale in supporting buildings, roadways, bridges, and water management systems. Without cement-based , alternatives like wood or alone would prove insufficient for the compressive loads and required in high-density urban environments or large-scale projects such as dams and reservoirs. Concrete's versatility and strength facilitate that underpins economic activity and public safety, including highways that enable efficient transportation of goods and people, reducing costs and fostering trade. For instance, bridges and tunnels withstand environmental stresses, minimizing disruptions from natural disasters compared to less resilient materials. In infrastructure, cement-lined pipes and concrete reservoirs ensure reliable supply and , preventing and supporting population health in expanding cities. These applications are particularly vital in developing regions, where cement demand correlates with rates exceeding 3-4% annually in parts of and , driving the construction of housing and utilities necessary for poverty alleviation. The indispensability of cement extends to human flourishing by enabling scalable solutions for shelter, mobility, and resource access amid global projected to reach 9.7 billion by 2050. Affordable housing accommodates urban migration, providing weather-resistant dwellings that improve living standards over traditional or thatch structures prone to failure. Moreover, reliant on cement, such as ports and power plants, supports industrialization and energy distribution, correlating with GDP per capita increases observed in cement-intensive economies like , where production surged alongside from 88% in 1981 to under 1% by 2019. This material's role in clean energy transitions—forming foundations for turbines and solar farms—further highlights its alignment with long-term prosperity, as no scalable substitute matches its cost-effectiveness and performance under load.

References

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