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200px, Typical clinker nodules 200px, Hot clinker Cement clinker is a solid material produced in the manufacture of
Portland cement Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-specialty grout. It was developed from other types of hydraulic lime in England in the early 19th c ...
as an intermediary product. Clinker occurs as lumps or nodules, usually to in diameter. It is produced by
sintering Clinker nodules produced by sintering Sintering or frittage is the process of compacting and forming a solid mass of material by pressure or heat without melting it to the point of liquefaction. Sintering happens as part of a manufacturing ...
(fusing together without melting to the point of liquefaction)
limestone Limestone ( calcium carbonate ) is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals calcite and aragonite, which are different crystal forms of . Limestone forms whe ...
and
aluminosilicate Aluminosilicate minerals ( IMA symbol: Als) are minerals composed of aluminium, silicon, and oxygen, plus countercations. They are a major component of kaolin and other clay minerals. Andalusite, kyanite, and sillimanite are naturall ...
materials such as
clay Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4). Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...
during the
cement kiln Cement kilns are used for the pyroprocessing stage of manufacture of portland and other types of hydraulic cement, in which calcium carbonate reacts with silica-bearing minerals to form a mixture of calcium silicates. Over a billion tonnes of ...
stage.


Composition and preparation

The Portland clinker essentially consists of four mineral phases: two calcium silicates,
alite Alite is an impure form of tricalcium silicate, , sometimes formulated as ( in cement chemist notation), typically with 3-4% of substituent oxides. It is the major, and characteristic, phase in Portland cement. The name was given by Törnebohm i ...
(Ca3Si) and
belite Belite is an industrial mineral important in Portland cement manufacture. Its main constituent is dicalcium silicate, Ca2SiO4, sometimes formulated as 2 CaO · SiO2 (C2S in cement chemist notation). Etymology The name was given by Törnebohm in ...
(Ca2Si), along with
tricalcium aluminate Tricalcium aluminate Ca3Al2O6, often formulated as 3CaO·Al2O3 to highlight the proportions of the oxides from which it is made, is the most basic of the calcium aluminates. It does not occur in nature, but is an important mineral phase in Port ...
(Ca3Al) and calcium aluminoferrite (Ca4AlFe). These main mineral phases are produced by heating at high temperature
clays Clay is a type of fine-grained natural soil material containing clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4). Clays develop plasticity when wet, due to a molecular film of water surrounding the clay par ...
and
limestone Limestone ( calcium carbonate ) is a type of carbonate sedimentary rock which is the main source of the material lime. It is composed mostly of the minerals calcite and aragonite, which are different crystal forms of . Limestone forms whe ...
.
Portland cement Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-specialty grout. It was developed from other types of hydraulic lime in England in the early 19th c ...
clinker is made by heating a homogeneous mixture of raw materials in a
rotary kiln A rotary kiln is a pyroprocessing device used to raise materials to a high temperature (calcination) in a continuous process. Materials produced using rotary kilns include: * Cement * Lime * Refractories * Metakaolin * Titanium dioxide * Al ...
at high temperature. The products of the chemical reaction aggregate together at their sintering temperature, about . Aluminium oxide and iron oxide are present only as a flux to reduce the sintering temperature and contribute little to the cement
strength Strength may refer to: Physical strength *Physical strength, as in people or animals * Hysterical strength, extreme strength occurring when people are in life-and-death situations *Superhuman strength, great physical strength far above human c ...
. For special cements, such as ''low heat'' (LH) and ''sulfate resistant'' (SR) types, it is necessary to limit the amount of
tricalcium aluminate Tricalcium aluminate Ca3Al2O6, often formulated as 3CaO·Al2O3 to highlight the proportions of the oxides from which it is made, is the most basic of the calcium aluminates. It does not occur in nature, but is an important mineral phase in Port ...
formed. The major raw material for the clinker-making is usually limestone mixed with a second material containing clay as a source of alumino-silicate. An impure limestone containing clay or
silicon dioxide Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is one ...
(SiO2) can be used. The calcium carbonate (CaCO3) content of these limestones can be as low as 80% by weight. The second raw material (materials in the
rawmix Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-specialty grout. It was developed from other types of hydraulic lime in England in the early 19th cen ...
other than limestone) depend on the purity of the limestone. Some of the second raw materials used are: clay,
shale Shale is a fine-grained, clastic sedimentary rock formed from mud that is a mix of flakes of clay minerals (hydrous aluminium phyllosilicates, e.g. kaolin, Al2 Si2 O5( OH)4) and tiny fragments (silt-sized particles) of other minerals, especial ...
,
sand Sand is a granular material composed of finely divided mineral particles. Sand has various compositions but is defined by its grain size. Sand grains are smaller than gravel and coarser than silt. Sand can also refer to a textural class of s ...
,
iron ore Iron ores are rocks and minerals from which metallic iron can be economically extracted. The ores are usually rich in iron oxides and vary in color from dark grey, bright yellow, or deep purple to rusty red. The iron is usually found in the fo ...
,
bauxite Bauxite is a sedimentary rock with a relatively high aluminium content. It is the world's main source of aluminium and gallium. Bauxite consists mostly of the aluminium minerals gibbsite (Al(OH)3), boehmite (γ-AlO(OH)) and diaspore (α-AlO ...
, fly ash and
slag Slag is a by-product of smelting (pyrometallurgical) ores and used metals. Broadly, it can be classified as ferrous (by-products of processing iron and steel), ferroalloy (by-product of ferroalloy production) or non-ferrous/base metals (by-prod ...
. The clinker and its hydration reactions are characterized and studied in detail by many techniques, including
calorimetry In chemistry and thermodynamics, calorimetry () is the science or act of measuring changes in ''state variables'' of a body for the purpose of deriving the heat transfer associated with changes of its state due, for example, to chemical reac ...
,
strength Strength may refer to: Physical strength *Physical strength, as in people or animals * Hysterical strength, extreme strength occurring when people are in life-and-death situations *Superhuman strength, great physical strength far above human c ...
development, X-ray diffraction, scanning electron microscope and atomic force microscopy.


Uses

Portland cement clinker (abbreviated k in the European norms) is ground to a fine powder and used as the binder in many cement products. A small amount of
gypsum Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, blackboard or sidewalk chalk, and drywall. ...
(less than 5 wt.%) must be added to avoid the flash setting of the
tricalcium aluminate Tricalcium aluminate Ca3Al2O6, often formulated as 3CaO·Al2O3 to highlight the proportions of the oxides from which it is made, is the most basic of the calcium aluminates. It does not occur in nature, but is an important mineral phase in Port ...
(Ca3Al2O6), the most reactive mineral phase (exothermic hydration reaction) in Portland clinker. It may also be combined with other active ingredients or cement additions to produce other types of cement including, following the European EN 197-1 standard:European cement standard EN 197-1 Cement – Part 1: “Composition, specifications and conformity criteria for common cements” which defines 27 distinct common cement products and their constituents. * CEM I: pure Portland clinker (Ordinary Portland Cement, OPC) * CEM II: composite cements with a limited addition of limestone filler or blast furnace slag (BFS) * CEM III: BFS-OPC blastfurnace cements * CEM IV:
pozzolanic Pozzolans are a broad class of siliceous and aluminous materials which, in themselves, possess little or no cementitious value but which will, in finely divided form and in the presence of water, react chemically with calcium hydroxide (Ca(OH)2) ...
cements * CEM V: composite cements (with large additions of BFS, fly ashes, or
silica fume Silica fume, also known as microsilica, (CAS number 69012-64-2, EINECS number 273-761-1) is an amorphous (non-crystalline) polymorph of silicon dioxide, silica. It is an ultrafine powder collected as a by-product of the silicon and ferrosilicon a ...
) Clinker is one of the ingredients of an artificial rock called Pulhamite after its inventor. Other ingredients were Portland cement and sand. Pulhamite can be extremely convincing and was popular in creating natural looking rock gardens in the nineteenth century. Clinker, if stored in dry conditions, can be kept for several months without appreciable loss of quality. Because of this, and because it can be easily handled by ordinary mineral handling equipment, clinker is internationally traded in large quantities. Cement manufacturers purchasing clinker usually grind it as an addition to their own clinker at their cement plants. Manufacturers also ship clinker to grinding plants in areas where cement-making raw materials are not available.


Clinker grinding aids

Gypsum is added to clinker primarily as an additive preventing the flash settings of the cement, but it is also very effective to facilitate the
grinding Grind is the cross-sectional shape of a blade. Grind, grinds, or grinding may also refer to: Grinding action * Grinding (abrasive cutting), a method of crafting * Grinding (dance), suggestive club dancing * Grinding (video gaming), repetitive and ...
of clinker by preventing agglomeration and coating of the powder at the surface of balls and
mill Mill may refer to: Science and technology * * Mill (grinding) * Milling (machining) * Millwork * Textile mill * Steel mill, a factory for the manufacture of steel * List of types of mill * Mill, the arithmetic unit of the Analytical Engine early ...
wall. Organic compounds are also often added as grinding aids to avoid powder agglomeration.
Triethanolamine Triethanolamine, or TEA is a viscous organic compound that is both a tertiary amine and a triol. A triol is a molecule with three alcohol groups. Approximately 150,000 tonnes were produced in 1999. It is a colourless compound although samples m ...
(TEA) is commonly used at 0.1 wt. % and has proved to be very effective. Other additives are sometimes used, such as
ethylene glycol Ethylene glycol (IUPAC name: ethane-1,2-diol) is an organic compound (a vicinal diol) with the formula . It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odo ...
,
oleic acid Oleic acid is a fatty acid that occurs naturally in various animal and vegetable fats and oils. It is an odorless, colorless oil, although commercial samples may be yellowish. In chemical terms, oleic acid is classified as a monounsaturated omega ...
, and dodecyl-benzene sulfonate.


Clinker minerals hydration

Upon addition of water, clinker minerals react to form different types of hydrates and "set"(harden) as the hydrated cement paste becomes
concrete Concrete is a composite material composed of fine and coarse aggregate bonded together with a fluid cement (cement paste) that hardens (cures) over time. Concrete is the second-most-used substance in the world after water, and is the most wi ...
. The
calcium silicate hydrate Calcium silicate hydrate (or C-S-H) is the main product of the hydration of Portland cement and is primarily responsible for the strength in cement based materials (e.g. concrete). Preparation When water is added to cement, each of the compounds ...
s (C-S-H) (hydrates of
alite Alite is an impure form of tricalcium silicate, , sometimes formulated as ( in cement chemist notation), typically with 3-4% of substituent oxides. It is the major, and characteristic, phase in Portland cement. The name was given by Törnebohm i ...
and
belite Belite is an industrial mineral important in Portland cement manufacture. Its main constituent is dicalcium silicate, Ca2SiO4, sometimes formulated as 2 CaO · SiO2 (C2S in cement chemist notation). Etymology The name was given by Törnebohm in ...
minerals) represent the main "glue" components of the concrete. After initial setting the concrete continues to harden and to develop its
mechanical strength The field of strength of materials, also called mechanics of materials, typically refers to various methods of calculating the stresses and strains in structural members, such as beams, columns, and shafts. The methods employed to predict the re ...
. The first 28 days are the most critical for the hardening. The concrete does not dry but one says that it sets and hardens. The cement is a hydraulic binder whose hydration requires water. It can perfectly set under water. Water is essential to its hardening and water losses must be avoided at the young age to avoid the development of cracks. The step protecting young concrete against
desiccation Desiccation () is the state of extreme dryness, or the process of extreme drying. A desiccant is a hygroscopic (attracts and holds water) substance that induces or sustains such a state in its local vicinity in a moderately sealed container. ...
by water evaporation is the curing.


Contribution to global warming

, cement production contributed about 8% of all carbon emissions worldwide, contributing substantially to
global warming In common usage, climate change describes global warming—the ongoing increase in global average temperature—and its effects on Earth's climate system. Climate change in a broader sense also includes previous long-term changes to E ...
. Most of those emissions were produced in the clinker manufacturing process.{{Cite news, url=https://www.bbc.com/news/science-environment-46455844, title=The massive CO2 emitter you may not know about, last=Rodgers, first=Lucy, date=2018-12-17, work=BBC News, access-date=2018-12-17, language=en-GB


See also

*
Environmental impact of concrete The environmental impact of concrete, its manufacture and applications, are complex, driven in part by direct impacts of construction and infrastructure, as well as by CO2 emissions; between 4-8% of total global CO2 emissions come from concrete. Ma ...


References

Cement Concrete Limestone Climate forcing