Tricalcium aluminate

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Tricalcium aluminate

Names

Other names

aluminate, C3A

Identifiers

CAS Number  12042-78-3

 161063-05-4
 3D model (JSmol)  Interactive image

ECHA InfoCard 100.031.744

EC Number  234-932-6

PubChem CID  92043201

CompTox  DTXSID6051223
Dashboard (EPA)

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InChI

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SMILES

Properties

Chemical formula Ca3Al2O6, or 3CaO·Al2O3

Molar mass 270.193 g/mol

Density 3.064 g/cm3

Melting point 1,542 °C (2,808 °F; 1,815 K) (decomposes)

Hazards

GHS labelling:

Pictograms

Signal word Warning

Hazard statements H319

Precautionary P264, P280, P305+P351+P338, P313

statements

Except where otherwise noted, data are given for materials in

their standard state (at 25 °C [77 °F], 100 kPa).
verify (what is ?)

Infobox references

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 Portland
cement.
Properties[edit]
Pure tricalcium aluminate is formed when the appropriate proportions of finely
divided calcium oxide and aluminium oxide are heated together above 1300 °C. The
pure form is cubic, with unit cell dimension 1.5263 nm[1] and has density 3064 kg·m−3. It
melts with decomposition at 1542 °C. The unit cell contains 8 cyclic Al6O1818− anions,
which can be considered to consist of 6 corner sharing AlO4 tetrahedra.[2] The structure
of pure liquid tricalcium aluminate contains mostly AlO4 tetrahedra in an infinite network,
with a slightly higher concentration of bridging oxygens than expected from the
composition and around 10% unconnected AlO4 monomers and Al2O7 dimers.[3]
In Portland cement clinker, tricalcium aluminate occurs as an "interstitial phase",
crystallizing from the melt. Its presence in clinker is solely due to the need to obtain
liquid at the peak kiln processing temperature (1400–1450 °C), facilitating the formation
of the desired silicate phases. Apart from this benefit, its effects on cement properties
are mostly undesirable. It forms an impure solid solution phase, with 15-20% of the
aluminium atoms replaced by silicon and iron, and with variable amounts of alkali metal
atoms replacing calcium, depending upon the availability of alkali oxides in the melt.
The impure form has at least four polymorphs:

Alkali % m/m Designation Crystal

0–1.0 CI Cubic

1.0-2.4 CII Cubic

3.7-4.6 O Orthorhombic

4.6-5.7 M Monoclinic

Typical chemical compositions are:

Mass % Mass %
Oxide
Cubic Orthorhombic

SiO2 3.7 4.3

Al2O3 31.3 28.9

Fe2O3 5.1 6.6

CaO 56.6 53.9

MgO 1.4 1.2

Na2O 1.0 0.6

K2O 0.7 4.0

TiO2 0.2 0.5

Effect on cement properties[edit]

In keeping with its high basicity, tricalcium aluminate reacts most strongly with water of
all the calcium aluminates, and it is also the most reactive of the Portland clinker
phases. Its hydration to phases of the form Ca2AlO3(OH) · n H2O leads to the
phenomenon of "flash set" (instantaneous set), and a large amount of heat is
generated. To avoid this, Portland-type cements include a small addition of calcium
sulfate (typically 4-8%). Sulfate ions in solution lead to the formation of an insoluble
layer of ettringite (3CaO • Al2O3 • 3CaSO4 · 32 H2O over the surface of the aluminate
crystals, passivating them. The aluminate then reacts slowly to form AFm phases of
general composition 3CaO • Al2O3 • CaSO4 · 12 H2O. These hydrates contribute little to
strength development.
Tricalcium aluminate is associated with three important effects that can reduce the
durability of concrete:

 heat release, which can cause spontaneous overheating in large masses of

concrete. Where necessary, tricalcium aluminate levels are reduced to
control this effect.
 sulfate attack, in which sulfate solutions to which the concrete is exposed
react with the AFm phases to form ettringite. This reaction is expansive, and
can disrupt mature concrete. Where concrete is to be placed in contact with,
for example, sulfate-laden ground waters, either a "sulfate-resisting" cement
(with low levels of tricalcium aluminate) is used, or slag is added to the
cement or to the concrete mix. The slag contributes sufficient aluminium to
suppress formation of ettringite.
 delayed ettringite formation, where concrete is cured at temperatures above
the decomposition temperature of ettringite (about 65 °C). On cooling,
expansive ettringite formation takes place.
Because they are even more basic, the alkali-loaded polymorphs are correspondingly
more reactive. Appreciable amounts (>1%) in cement make set control difficult, and the
cement becomes excessively hygroscopic. The cement powder flowability is reduced,
and air-set lumps tend to form. They withdraw water from gypsum on storage of the
cement, leading to false set. For this reason, their formation is avoided wherever
possible. It is more energetically favorable for sodium and potassium to form sulfates
and chlorides in the kiln, but if insufficient sulfate ion is present, any surplus alkalis
congregate in the aluminate phase. The feed and fuel in the kiln system are preferably
controlled chemically to keep the sulfate and alkalis in balance. However, this
stoichiometry is only maintained if there is substantial surplus oxygen in the kiln
atmosphere: if "reducing conditions" set in, then sulfur is lost as SO 2, and reactive
aluminates start to form. This is readily monitored by tracking the clinker sulfate level on
an hour-to-hour basis.
Hydration steps[edit]
Water reacts instantly with tricalcium aluminate. Hydration likely begins already during
grinding of cement clinker due to residual humidity and dehydration of gypsum
additives. Initial contact with water causes protonation of single bonded oxygen atoms
on aluminate rings and leads to the formation of calcium hydroxide.[4] The next steps in
the sequence of the hydration reaction involve the generated hydroxide ions as strong
nucleophiles, which fully hydrolyze the ring structure in combination with water.