White Cement

1. INTRODUCTION

White cement can be

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defined as a hydraulic inorganic binder which is obtained by

grinding white cement clinker with a suitable set-controlling agent. It differs from grey
cement by its colour, which is an important quality criterion. White cement is to be
classed as a luxury product, which is used mostly for aesthetic reasons, especially for
decorative purposes on visibly exposed .surfaces. Furthermore, white cement is used on
the facades of buildings in tropical countries to promote reflection of solar radiation.

Because of the limited marketing scope for white cement and because of the high specific
energy consumption demanded by its manufacture, as a rule only relatively small white
cement manufacturing plants are built. Typical production figures of such plants are in
the range of 30000 to 300000 ton of clinker per year.

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Quality control of white cement involves regulation of strength, setting, workability and
soundness; as with grey cement with the added requirement of consistent whiteness.

Aspects of this last requirement are discussed here.

Raw materials must be selected in a way that keeps any element which would colour the
clinker to a minimum. These elements are principally the first series of the transition
metals (scandium to zinc). When these elements are combined with oxygen ligands, as in
clinker, they have empty orbital available and electrons absorb energy in the visible
region electro-magnetic spectrum and are promoted to these higher available orbitals.
This absorption colours the clinker.

Selection of appropriate raw materials must be combined with avoiding contamination in

the processÿFour sources of contamination, which must be avoided arÿron from the raw
mill grinding mediÿhromium from magnesite-chrome refractories in the kilnÿnetallic
oxides in the fuel ash an(§}ie colour of the gypsum, which is ground with the clinker to
control setting.

With industrial raw materials; and processes some traces of colouring metal oxides are
inevitable and the technology of the industry must minimize their effect on the final
product whiteness.

The four means of contamination listed above are avoided by using hard forged media in
raw mills, non-use of magnesite-chrome refractories in the kilns, firing the kiln with
natural gas or oil and selection of a white or colourless gypsum.

Raw materials can be pretreated before being taken into cement making process in order
to reduce the content of colouring metals, particularly iron. The most obvious method is
to screen out the lines from the limestone as any iron bearing clay will be concentrated in
the smaller fractions.
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Cement

White

Magnetic separation of any metallic iron can also be included if considered necessary.
Chemical enrichment of kaolin (China clay) has been used by the porcelain industry to
reduce iron content but is unlikely to be economical for the cement industry.

he mineralogical composition is an important factor in controlling the whiteness of the

clinker. C3A is colourless and helps produce a white cementÿ3S is preferable to C2S
because traces of iron form solid solutions with C2S colouring the mineral. C4AF is kept
as low as possible.

The clinker mineralogy of grey cement is controlled by means of the silica and alumina
ratios and by the lime saturation factor. In white cement the alumina ratio loses its
significance because of the low iron content. The total silicate content (C3S + C2S) is
controlled by the silica ratio and the proportion of C3S to C2S by the L.S.F.

(jQ)n this basis as high an L.S.F. as possible should be used to maximize the whiteness of
the clinker, howeveiydue the lack of iron, the raw mix is inherently difficult to combine
(burn). The higher the L.S.F. , the more difficult combination becomes ancflie higher the
temperature which must be achieved in the kiln. Fuel and refractory costs rise sharply1
and there is a risk of incomplete combination. This leads to C2S and free lime replacing
C3S defeating the object of the high L.S.F. In practice there will be a maximum beyond
which it is not advisable to increase L.S.F. for a particular set of raw materials.

There is also a maximum beyond which increasing the silica ratio will reduce the
whiteness. In fact increasing silica ratio leads to replacement of C3A by C2S.

Because of the difficulty of burning white cement raw mix, mineralizers which reduce
the combustion temperature are often used. Mineralizers must not themselves contain
colouring elements and they have an important effect on clinker crystal structure. A fine
crystal structure increases diffuse reflectance and whiteness. Mineralizers containing
sulphates and chlorides should not be used as they promote the formation of large
crystals. Fluorides are the best mineralizers for any kind of cement but they have the
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added benefit with white cement of promoting a fine crystal structure due to the high
electro negativity of the fluoride ion .

As mentioned before all the elements of the first row of transition metals reduce
whiteness when they are incorporated in clinker. However, the effect is not additive when
more than one element is present. Traces of titanium can lead to an increase in whiteness
in the presence of iron; the reasons for this are complex.

A colouring effect is determined by the individual metal , metal -oxygen bond strength
and coordination number . Each metal has a certain colouring potential and this will be
higher if the metal is in a tetrahedral rather than octahedral coordination site in the
crystal. The coordination site depends on the strength of the metal oxygen bond relative
to the other metals present. The transition metal with the strongest metal -
oxygen
bonds will be in tetrahedral sites and the others in octahedral sites. Metal -oxygen bond
strengths decrease in the order Ti, V Fe , Mn , Cr. Traces of titanium are beneficial
because titanium occupies tetrahedral sites, forcing iron to octahedral sites and so
reducing the colouring effect of iron. Vanadium has the same effect on the iron,
coordination site but does not improve whiteness because vanadium is itself more
colouring than iron. Incorporation of cobalt oxide is used in the porcelain industry to
give a blue" whiteness and this has been suggested for white cement.
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Traces of colouring metals are usually a characteristic of the raw materials used and
wouldn't normally be added to the mix. The processing conditions can have a significant
effect on the product whiteness particularly in the burring and cooling of the clinker. A
reducing atmosphere in the kiln leads to iron in the 2+ oxidation state rather than the 3+ .
This lowers the iron oxygen bond strength i.e iron takes up octahedral coordination and is
less colouring. The calciualumino-ferrite (C4AF) solid solution series also is shifted to the
C()AF2 composition. This leaves more alumina available to form C3A so improving the
whiteness.
 Reducing conditions can be included by a bleaching flame directed at the clinker falling
over the nose ring of the kiln or by the main flame impinging directly on the feed. In the
latter case refractory life must suffer. Incorporation of carbon in the raw materials helps
to induce a reducing atmosphere in the kiln.

C6AF2 is the high temperature form of the alumino-ferrite solid solution. This and the
other minerals formed in the reducing atmosphere must be frozen before they have time
to re-oxidize in air. If slow cooling occurred then FeO would tend to break down C3S to
C2S and free lime hence lowering whiteness. For these reasons white cement clinker

usually is quenched in water immediately after leaving the kiln. The physical size of the
clinker nodules becomes important as large nodules retain sufficient heat in the core to
re-oxidize and small nodules will hydrate with the quenching water.

A dryer is sometimes employed after the quencher , in these cases the temperature in the
dryer must not exceed 600 °K or re-oxidation can again occur.