Belite

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Belite is the mineralogical name for Dicalcium Silicate, Ca2SiO4. It is a mineral present in Portland cement. It also - rarely - occurs naturally, as larnite.

Contents

Simplified Crystal Structure of Belite
Simplified Crystal Structure of Belite

The belite found in Portland cement differs in composition from simple dicalcium silicate. It is a solid solution and contains minor amounts of other oxides besides CaO and SiO2. A typical composition[1] is:

Oxide Mass %
SiO2 31.5
Al2O3 2.1
Fe2O3 0.9
CaO 63.5
MgO 0.5
SO3 0.1
Na2O 0.1
K2O 0.9
TiO2 0.2
P2O5 0.2

Based on this, the formula can be expressed as Ca1.94Mg0.02Na0.01K0.03Fe0.02Al0.07Si0.90P0.01O3.93. In practice, the composition varies with the bulk composition of the clinker, subject to certain limits. Substitution of calcium ions or orthosilicate ions requires that electric charges be kept in balance. For instance, a limited number of orthosilicate (SiO44-) ions can be replaced with sulfate (SO42-) ions, provided that for each sulfate ion, two aluminate (AlO45-) ions are also substituted.

Dicalcium silicate is stable, and is readily prepared from reactive CaO and SiO2 at 300°C. The low temperature form is γ-belite, or lime olivine. This form does not hydrate, and is avoided in cement manufacture.

As the temperature rises, it passes through several polymorphic states:

Temp°C Name Crystal
>1425 α Hexagonal
1160-1425 α'H Monoclinic
680-1160 α'L Monoclinic
500-680 β Monoclinic
<500 γ Orthorhombic

Belite is the mineral in Portland cement responsible for development of "late" strength. The other silicate, alite contributes "early" strength, due to its higher reactivity. Belite reacts with water (roughly) according to the reaction:

2Ca2SiO4 + 4H2O → 3CaO.2SiO2.3H2O + Ca(OH)2

The hydrate is referred to as the "C-S-H" phase. It grows as a mass of interlocking needles that provide the strength of the hydrated cement system. Relatively high belite reactivity is desirable in Portland cement manufacture, and the formation of the unreactive γ-form must be rigourously avoided. This is achieved by rapid cooling, forming crystals that are small, distorted and highly defective. Defects provide sites for initial water attack. Failure to cool the clinker rapidly leads to inversion of belite to the γ-form. The γ-form has a substantially different structure and density, so that inversion leads to degradation of the crystal and its surrounding matrix, and can also trigger decomposition of the neighbouring alite. This is observed macroscopically as "dusting": the clinker nodules fall to a fine dust.

Clinker Section 0.15 x 0.15 mm
Clinker Section 0.15 x 0.15 mm

The minerals in Portland cement clinker may be observed and quantified by petrographic microscopy. Clinker nodules are cut and ground to a flat, polished surface. The exposed minerals are made visible and identifiable by etching the surface. The surface can then be observed in reflected light by optical microscopy. In the example, a clinker nodule has been polished and etched with hydrogen fluoride vapour. The alite shows as brown, the belite as blue, and the melt phases as white. Electron microscopy can also be used, in which case the minerals may be identified by microprobe analysis. The preferred method to quantify the minerals accurately is X-ray diffraction on the powdered clinker, using the Rietveld analysis technique.

  1. ^ H F W Taylor, Cement Chemistry, Academic Press, 1990, ISBN 0-12-683900-X, pp 10-11
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