Portland cement

A pallet with Portland cement

Blue Circle Southern Cement works near Berrima, New South Wales, Australia.

Portland cement is the most common type of cement in general use around the world, because it is a basic ingredient of concrete, mortar, stucco and most non-specialty grout. It is a fine powder produced by grinding Portland cement clinker (more than 90%), a limited amount of calcium sulfate which controls the set time, and up to 5% minor constituents (as allowed by various standards).

As defined by the European Standard EN197.1, "Portland cement clinker is a hydraulic material which shall consist of at least two-thirds by mass of calcium silicates (3CaO.SiO₂ and 2CaO.SiO₂), the remainder consisting of aluminium- and iron-containing clinker phases and other compounds. The ratio of CaO to SiO₂ shall not be less than 2.0. The magnesium content (MgO) shall not exceed 5.0% by mass." (The last two requirements were already set out in the German Standard, issued in 1909).

Portland cement clinker is made by heating, in a kiln, a homogeneous mixture of raw materials to a sintering temperature, which is about 1450 °C for modern cements. The aluminium oxide and iron oxide are present as a flux and contribute little to the strength. For special cements, such as Low Heat (LH) and Sulfate Resistant (SR) types, it is necessary to limit the amount of tricalcium aluminate (3CaO.Al₂O₃) formed. The major raw material for the clinker-making is usually limestone (CaCO₃) mixed with a second material containing clay as source of alumino-silicate. Normally, an impure limestone which contains clay or SiO₂ is used. The CaCO₃ content of these limestones can be as low as 80%. Second raw materials (materials in the rawmix other than limestone) depend on the purity of the limestone. Some of the second raw materials used are: clay, shale, sand, iron ore, bauxite, fly ash and slag. When a cement kiln is fired by coal, the ash of the coal acts as a secondary raw material.

History

Portland was developed from cements (or correctly hydraulic limes) made in Britain in the early part of the nineteenth century, and its name is derived from its similarity to Portland stone, a type of building stone that was quarried on the Isle of Portland in Dorset, England.

Joseph Aspdin, a British bricklayer, in 1824 was granted a patent for a process of making a cement which he called Portland cement. His cement was an artificial hydraulic lime similar in properties to the material known as "Roman Cement" (patented in 1796 by James Parker) and his process was similar to that patented in 1822 and used since 1811 by James Frost who called his cement "British Cement". The name "Portland cement" is also recorded in a directory published in 1823 being associated with a William Lockwood and possibly others.

Aspdin's son William in 1843 made an improved version of this cement and he initially called it "Patent Portland cement" although he had no patent. In 1848 William Aspdin further improved his cement and in 1853 moved to Germany where he was involved in cement making. Many people have claimed to have made the first Portland cement in the modern sense, but it is generally accepted that it was first manufactured by William Aspdin at Northfleet, England in about 1842. The German Government issued a standard on Portland cement in 1878.

Production

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TXI cement plant, Midlothian, Texas

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Schematic explanation of Portland cement production

There are three fundamental stages in the production of Portland cement:

1. Preparation of the raw mixture
2. Production of the clinker
3. Preparation of the cement

The chemistry of cement is very complex, so cement chemist notation was invented to simplify the formula of common oxides found in cement. This reflects the fact that most of the elements are present in their highest oxidation state, and chemical analyses of cement are expressed as mass percent of these notional oxides.

Rawmix preparation

Main article: Rawmill

A limestone prehomogenization pile being built by a boom stacker

A completed limestone prehomogenization pile

The raw materials for Portland cement production are a mixture (as fine powder in the 'Dry process' or in the form of a slurry in the 'Wet process') of minerals containing calcium oxide, silicon oxide, aluminium oxide, ferric oxide, and magnesium oxide. The raw materials are usually quarried from local rock, which in some places is already practically the desired composition and in other places requires the addition of clay and limestone, as well as iron ore, bauxite or recycled materials. The individual raw materials are first crushed, typically to below 50 mm. In many plants, some or all of the raw materials are then roughly blended in a "prehomogenization pile." The raw materials are next ground together in a rawmill. Silos of individual raw materials are arranged over the feed conveyor belt. Accurately controlled proportions of each material are delivered onto the belt by weigh-feeders. Passing into the rawmill, the mixture is ground to rawmix. The fineness of rawmix is specified in terms of the size of the largest particles, and is usually controlled so that there are less than 5%-15% by mass of particles exceeding 90 μm in diameter. It is important that the rawmix contains no large particles in order to complete the chemical reactions in the kiln, and to ensure the mix is chemically homogenous. In the case of a dry process, the rawmill also dries the raw materials, usually by passing hot exhaust gases from the kiln through the mill, so that the rawmix emerges as a fine powder. This is conveyed to the blending system by conveyor belt or by a powder pump. In the case of wet process, water is added to the rawmill feed, and the mill product is a slurry with moisture content usually in the range 25-45% by mass. This slurry is conveyed to the blending system by conventional liquid pumps.

Rawmix blending

The rawmix is formulated to a very tight chemical specification. Typically, the content of individual components in the rawmix must be controlled within 0.1% or better. Calcium and silicon are present in order to form the strength-producing calcium silicates. Aluminium and iron are used in order to produce liquid ("flux") in the kiln burning zone. The liquid acts as a solvent for the silicate-forming reactions, and allows these to occur at an economically low temperature. Insufficient aluminium and iron lead to difficult burning of the clinker, while excessive amounts lead to low strength due to dilution of the silicates by aluminates and ferrites. Very small changes in calcium content lead to large changes in the ratio of alite to belite in the clinker, and to corresponding changes in the cement's strength-growth characteristics. The relative amounts of each oxide are therefore kept constant in order to maintain steady conditions in the kiln, and to maintain constant product properties. In practice, the rawmix is controlled by frequent chemical analysis (hourly by X-Ray fluorescence analysis, or every three minutes by prompt gamma neutron activation analysis). The analysis data is used to make automatic adjustments to raw material feed rates. Remaining chemical variation is minimized by passing the raw mix through a blending system that homogenizes up to a day's supply of rawmix (15,000 tonnes in the case of a large kiln).

Formation of clinker

Main article: Cement kiln

Precalciner kiln

Typical clinker nodules

The raw mixture is heated in a cement kiln, a slowly rotating and sloped cylinder, with temperatures increasing over the length of the cylinder up to a peak temperature of 1400-1450 °C. A complex succession of chemical reactions take place (see cement kiln) as the temperature rises. The peak temperature is regulated so that the product contains sintered but not fused lumps. Sintering consists of the melting of 25-30% of the mass of the material. The resulting liquid draws the remaining solid particles together by surface tension, and acts as a solvent for the final chemical reaction in which alite is formed. Too low a temperature causes insufficient sintering and incomplete reaction, but too high a temperature results in a molten mass or glass, destruction of the kiln lining, and waste of fuel. When all goes to plan, the resulting material is clinker. On cooling, it is conveyed to storage. Some effort is usually made to blend the clinker, because although the chemistry of the rawmix may have been tightly controlled, the kiln process potentially introduces new sources of chemical variability. The clinker can be stored for a number of years before use. Prolonged exposure to water decreases the reactivity of cement produced from weathered clinker.

The enthalpy of formation of clinker from calcium carbonate and clay minerals is ~1700 kJ/kg. However, because of heat loss during production, actual values can be much higher. The high energy requirements and the release of significant amounts of carbon dioxide makes cement production a concern for global warming. See "Environmental effects" below.

Cement grinding

Main article: Cement mill

A 10 MW cement mill, producing cement at 270 tonnes per hour

In order to achieve the desired setting qualities in the finished product, a quantity (2-8%, but typically 5%) of calcium sulfate (usually gypsum or anhydrite) is added to the clinker and the mixture is finely ground to form the finished cement powder. This is achieved in a cement mill. The grinding process is controlled to obtain a powder with a broad particle size range, in which typically 15% by mass consists of particles below 5 μm diameter, and 5% of particles above 45 μm. The measure of fineness usually used is the "specific surface", which is the total particle surface area of a unit mass of cement. The rate of initial reaction (up to 24 hours) of the cement on addition of water is directly proportional to the specific surface. Typical values are 320-380 m²·kg^-1 for general purpose cements, and 450-650 m²·kg^-1 for "rapid hardening" cements. The cement is conveyed by belt or powder pump to a silo for storage. Cement plants normally have sufficient silo space for 1-20 weeks production, depending upon local demand cycles. The cement is delivered to end-users either in bags or as bulk powder blown from a pressure vehicle into the customer's silo. In developed countries, 80% or more of cement is delivered in bulk, and many cement plants have no bag-packing facility. In poor countries, bags are the normal mode of delivery.

Typical constituents of Portland clinker
Cement industry style notation under CCN

Clinker	CCN	Mass%
Tricalcium silicate (CaO)3.SiO2	C3S	45-75%
Dicalcium silicate (CaO)2.SiO2	C2S	7-32%
Tricalcium aluminate (CaO)3.Al2O3	C3A	0-13%
Tetracalcium aluminoferrite (CaO)4.Al2O3.Fe2O3	C4AF	0-18%
Gypsum CaSO4 · 2 H2O		2-10%

Typical constituents of and Portland cement
Cement industry style notation under CCN

Cement	CCN	Mass%
Calcium oxide, CaO	C	61-67%
Silicon oxide, SiO2	S	19-23%
Aluminium oxide, Al2O3	A	2.5-6%
Ferric oxide, Fe2O3	F	0-6%
Sulfate		1.5-4.5%

An alternative fabrication technique EMC Energetically modified cement uses very finely ground cements that are made from mixtures of cement with sand or with slag or other pozzolan type minerals which are extremely finely ground together. Such cements can have the same physical characteristics as normal cement but with 50% less cement particularly due to their increased surface area for the chemical reaction. Even with intensive grinding they can use up to 50% less energy to fabricate than ordinary Portland cements.

Chemical composition of EMC (50/50 OPC/FA - Fly Ash)

Compound	OPC %	FA %	EMC %
CaO	62.4	15	40.9
SiO2	17.8	49.4	33.2
Al2O3	4.0	19.6	6.3
Fe2O3	3.9	5.2	4.1
SO3	3.2	0.8	1.6
Na2O	<0.1	0.3	0.1
K2O	0.3	1.2	1.2
Insolubles	0.5	51.3	21.6

Use

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Decorative use of Portland cement panels on London’s Grosvenor estate

The most common use for Portland cement is in the production of concrete. Concrete is a composite material consisting of aggregate (gravel and sand), cement, and water. As a construction material, concrete can be cast in almost any shape desired, and once hardened, can become a structural (load bearing) element. Users may be involved in the factory production of pre-cast units, such as panels, beams, road furniture, or may make cast-in-situ concrete such as building superstructures, roads, dams. These may be supplied with concrete mixed on site, or may be provided with "ready-mixed" concrete made at permanent mixing sites. Portland cement is also used in mortars (with sand and water only) for plasters and screeds, and in grouts (cement/water mixes squeezed into gaps to consolidate foundations, road-beds, etc).

Types

General

There are different standards for classification of Portland cement. The two major standards are the ASTM C150 used primarily in the U.S. and European EN-197. EN 197 cement types CEM I, II, III, IV, and V do not correspond to the similarly-named cement types in ASTM C 150.

ASTM C150

There are five types of Portland cements with variations of the first three according to ASTM C150.

Type I Portland cement is known as common or general purpose cement. It is generally assumed unless another type is specified. It is commonly used for general construction especially when making precast and precast-prestressed concrete that is not to be in contact with soils or ground water. The typical compound compositions of this type are:

55% (C₃S), 19% (C₂S), 10% (C₃A), 7% (C₄AF), 2.8% MgO, 2.9% (SO₃), 1.0% Ignition loss, and 1.0% free CaO.

A limitation on the composition is that the (C₃A) shall not exceed fifteen percent.

Type II is intended to have moderate sulfate resistance with or without moderate heat of hydration. This type of cement costs about the same as Type I. Its typical compound composition is:

51% (C₃S), 24% (C₂S), 6% (C₃A), 11% (C₄AF), 2.9% MgO, 2.5% (SO₃), 0.8% Ignition loss, and 1.0% free CaO.

A limitation on the composition is that the (C₃A) shall not exceed eight percent which reduces its vulnerability to sulfates. This type is for general construction that is exposed to moderate sulfate attack and is meant for use when concrete is in contact with soils and ground water especially in the western United States due to the high sulfur content of the soil. Because of similar price to that of Type I, Type II is much used as a general purpose cement, and the majority of Portland cement sold in North America meets this specification.

Note: Cement meeting (among others) the specifications for Type I and II has become commonly available on the world market.

Type III is has relatively high early strength. Its typical compound composition is:

57% (C₃S), 19% (C₂S), 10% (C₃A), 7% (C₄AF), 3.0% MgO, 3.1% (SO₃), 0.9% Ignition loss, and 1.3% free CaO.

This cement is similar to Type I, but ground finer. Some manufacturers make a separate clinker with higher C₃S and/or C₃A content, but this is increasingly rare, and the general purpose clinker is usually used, ground to a specific surface typically 50-80% higher. The gypsum level may also be increased a small amount. This gives the concrete using this type of cement a three day compressive strength equal to the seven day compressive strength of types I and II. Its seven day compressive strength is almost equal to types I and II 28 day compressive strengths. The only downside is that the six month strength of type III is the same or slightly less than that of types I and II. Therefore the long-term strength is sacrificed a little. It is usually used for precast concrete manufacture, where high 1-day strength allows fast turnover of molds. It may also be used in emergency construction and repairs and construction of machine bases and gate installations.

Type IV Portland cement is generally known for its low heat of hydration. Its typical compound composition is:

28% (C₃S), 49% (C₂S), 4% (C₃A), 12% (C₄AF), 1.8% MgO, 1.9% (SO₃), 0.9% Ignition loss, and 0.8% free CaO.

The percentages of (C₂S) and (C₄AF) are relatively high and (C₃S) and (C₃A) are relatively low. A limitation on this type is that the maximum percentage of (C₃A) is seven, and the maximum percentage of (C₃S) is thirty-five. This causes the heat given off by the hydration reaction to develop at a slower rate. However, as a consequence the strength of the concrete develops slowly. After one or two years the strength is higher than the other types after full curing. This cement is used for very large concrete structures, such as dams, which have a low surface to volume ratio. This type of cement is generally not stocked by manufacturers but some might consider a large special order. This type of cement has not been made for many years, because Portland-pozzolan cements and ground granulated blast furnace slag addition offer a cheaper and more reliable alternative.

Type V is used where sulfate resistance is important. Its typical compound composition is:

38% (C₃S), 43% (C₂S), 4% (C₃A), 9% (C₄AF), 1.9% MgO, 1.8% (SO₃), 0.9% Ignition loss, and 0.8% free CaO.

This cement has a very low (C₃A) composition which accounts for its high sulfate resistance. The maximum content of (C₃A) allowed is five percent for Type V Portland cement. Another limitation is that the (C₄AF) + 2(C₃A) composition cannot exceed twenty percent. This type is used in concrete that is to be exposed to alkali soil and ground water sulfates which react with (C₃A) causing disruptive expansion. It is unavailable in many places although its use is common in the western United States and Canada. As with Type IV, Type V Portland cement has mainly been supplanted by the use of ordinary cement with added ground granulated blast furnace slag or tertiary blended cements containing slag and fly ash.

Types Ia, IIa, and IIIa have the same composition as types I, II, and III. The only difference is that in Ia, IIa, and IIIa an air-entraining agent is ground into the mix. The air-entrainment must meet the minimum and maximum optional specification found in the ASTM manual. These types are only available in the eastern United States and Canada but can only be found on a limited basis. They are a poor approach to air-entrainment which improves resistance to freezing under low temperatures.

EN 197

EN 197-1 defines 5 classes of common cement that comprise Portland cement as a main constituent. These classes differ from the ASTM classes.

I	Portland cement	Comprising Portland cement and up to 5% of minor additional constituents
II	Portland-composite cement	Portland cement and up to 35% of other single constituents
III	Blastfurnace cement	Portland cement and higher percentages of blastfurnace slag
IV	Pozzolanic cement	Portland cement and up to 55% of pozzolanic constituents
V	Composite cement	Portland cement, blastfurnace slag and pozzolana or fly ash

Constituents that are permitted in Portland-composite cements are blastfurnace slag, silica fume, natural and industrial pozzolans, silicious and calcareous fly ash, burnt shale and limestone.

White Portland cement

Main article: White Portland cement

White Portland cement differs physically from the gray form only in its color, and as such can fall into many of the above categories (e.g. ASTM Type I, II and/or III). However, its manufacture is significantly different from that of the gray product, and is treated separately.

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Sampling fast set concrete made from Portland cement

Safety

When cement is mixed with water a highly alkaline solution (pH ~13) is produced by the dissolution of calcium, sodium and potassium hydroxides. Gloves, goggles and a filter mask should be used for protection. Hands should be washed after contact. Cement can cause serious burns if contact is prolonged or if skin is not washed promptly. Once the cement hydrates, the hardened mass can be safely touched without gloves.

In Scandinavia, France and the UK, the level of chromium(VI), which is thought to be toxic and a major skin irritant, may not exceed 2 ppm (parts per million).

Environmental effects

Portland cement manufacture can cause 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, consumption of large quantities of fuel during manufacture, release of CO₂ from the raw materials during manufacture, 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.

Epidemiologic Notes and Reports Sulfur Dioxide Exposure in Portland Cement Plants, from the Centers for Disease Control, states "Workers at Portland cement facilities, particularly those burning fuel containing sulfur, should be aware of the acute and chronic effects of exposure to SO₂ [sulfur dioxide], and peak and full-shift concentrations of SO₂ should be periodically measured."

— 

"The Arizona Department of Environmental Quality was informed this week that the Arizona Portland Cement Co. failed a second round of testing for emissions of hazardous air pollutants at the company's Rillito plant near Tucson. The latest round of testing, performed in January 2003 by the company, is designed to ensure that the facility complies with federal standards governing the emissions of dioxins and furans, which are byproducts of the manufacturing process." Cement Reviews' "Environmental News" web page details case after case of environmental problems with cement manufacturing.

An independent research effort of AEA Technology to identify critical issues for the cement industry today concluded the most important environment, health and safety performance issues facing the cement industry are atmospheric releases (including greenhouse gas emissions, dioxin, NO_x, SO₂, and particulates), accidents and worker exposure to dust.

The CO₂ associated with Portland cement manufacture falls into 3 categories:

• CO₂ derived from decarbonation of limestone,
• CO₂ from kiln fuel combustion,
• CO₂ produced by vehicles in cement plants and distribution.

Source 1 is fairly constant: minimum around 0.47 kg CO₂ per kg of cement, maximum 0.54, typical value around 0.50 world-wide. Source 2 varies with plant efficiency: efficient precalciner plant 0.24 kg CO₂ per kg cement, low-efficiency wet process as high as 0.65, typical modern practices (e.g UK) averaging around 0.30. Source 3 is almost insignificant at 0.002-0.005. So typical total CO₂ is around 0.80 kg CO₂ per kg finished cement. This leaves aside the CO₂ associated with electric power consumption, since this varies according to the local generation type and efficiency. Typical electrical energy consumption is of the order of 90-150 kWh per tonne cement, equivalent to 0.09-0.15 kg CO₂ per kg finished cement if the electricity is coal-generated.

Overall, with nuclear- or hydroelectric power and efficient manufacturing, CO₂ generation can be as little as 0.7 kg per kg cement, but can be as high as twice this amount. The thrust of innovation for the future is to reduce sources 1 and 2 by modification of the chemistry of cement, by the use of wastes, and by adopting more efficient processes. Although cement manufacturing is clearly a very large CO₂ emitter, concrete (of which cement makes up about 15%) compares quite favorably with other building systems in this regard.

Cement plants used for waste disposal or processing

Used tires being fed to a pair of cement kilns

Due to the high temperatures inside cement kilns, combined with the oxidizing (oxygen-rich) atmosphere and long residence times, cement kilns have been used as a processing option for various types of waste streams. The waste streams often contain combustible material which allows the substitution of part of the fossil fuel normally used in the process.

Waste materials used in cement kilns as a fuel supplement:

• Car and truck tires - steel belts are easily tolerated in the kilns
• Waste solvents and lubricants
• Hazardous waste - cement kilns completely destroy hazardous organic compounds
• Meat and bone meal - slaughterhouse waste due to bovine spongiform encephalopathy contamination concerns
• Waste plastics
• Sewage sludge
• Rice hulls
• Sugarcane waste
• Used wooden railroad ties (railway sleepers)

Portland cement manufacture also has the potential to remove industrial byproducts from the waste-stream, effectively sequestering some environmentally damaging wastes. These include:

• Slag
• Fly ash (from power plants)
• Silica fume (from steel mills)
• Synthetic gypsum (from desulfurisation)

There are significant pollution problems from using toxic waste as a fuel in cement kilns. As the quantity of toxic fuel use is quite often kept below local regulatatory requirements by blending, most kilns use significantly less stringent air pollution control devices than other industrial or waste burning incinerators. This significantly increases local air pollution and has on occassions led to produce from surrounding farms being considered unfit for human consumption due to high levels of heavy metals, pcbs, dioxins, etc.

See also

• Lime mortar
• Mortar (masonry)
• Rosendale cement
• White Portland cement
• Calcium Silicate Hydrate

External links

• World Production of Hydraulic Cement, by Country
• PCA - The Portland Cement Association
• Alpha The Guaranteed Portland Cement Company: 1917 Trade Literature from Smithsonian Institution Libraries
• Cement Sustainability Initiative
• A cracking alternative to cement
• What is the Difference Between Cement, Portland Cement & Concrete?
• Aerial views of the world's largest concentration of cement manufacturing capacity, Saraburi Province, Thailand, at 14.6325°N 101.0771°E / 14.6325; 101.0771
• Fountain, Henry (March 30, 2009). "Concrete Is Remixed With Environment in Mind". The New York Times. Retrieved 2009-03-30.

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