TRACK CEMENT CHEMISTRY TO HELP PREDICT PERFORMANCE

Ignoring the mill certificate that comes with your cement means losing out onvaluable
information. Often, producers overlook this useful document because they are not
familiar with the terminology. Understanding mill certificate information does not require
an advanced degree in chemistry - just some basic knowledge of the composition of
cement and terms used to describe it.

Portland cement is manufactured using naturally occurring raw materials combined in a

controlled manner, processed in a kiln into clinker, and then ground to the appropriate
size in grinding mills.

Raw materials used in the manufacture of Portland cement may include limestone, marl,
iron ore, clay, shale, sand, and in some cases, industrial by-products.

Because a large range of raw materials is used in the manufacture of Portland cement, the
resulting product has a complex chemistry.

In fact, a chemical analysis of Portland cement identifies 12 oxides and determines their
weight percentages. These values may be reported on the mill certificate.

However, cement chemists have developed a system of quantifying four principle

components in portland cement based on the oxides present. The calculations are based
on a system developed by R.H. Bogue. Therefore, the calculated composition is often
referred to as the "Bogue Compounds."

Of the four Bogue compounds, tricalcium silicate (C 3S) in cement chemist notation) is
typically the most abundant. In Type I, II and III portland cement,C 3S will be more than
50% of the total compounds present. C3S hydrates and hardens quickly, and consequently,
influences concrete's setting time and early age strength significantly. Most strength
gained from C3S occurs in the first four weeks.

Early strength development of C3S is accompanied by generation of heat. Therefore,

when control of heat of hydration is important, such as in Type IV cement, the amount of
C3S will be reduced.

Dicalcium silicate (C2S), the second most abundant compound in Portland cement,
develops strength more slowly than C3S. Most of its strength is contributed after four
weeks. It also produces less heat upon hydration than C3S. These factors make higher
percentages of C2S important in cements used to produce concrete when early age
strength is not as important as controlling heat generation. In typical portland cement,
C2S will be between 20% and 50% of the total compounds.

Tricalcium aluminate (C3A) plays a major role in the characteristics of fresh concrete. It
starts the hydration process quickly upon exposure to water and generates much heat
during the first few days. It also contributes to the very early age strength of one to three
days. But it may somewhat reduce advanced age strength. High early-strength cement,
Type III, will have higher concentrations of C3A, often between 10% and 15%.

Cements with low percentages of a C 3A often will require changes in the amount of
gypsum added and may also affect chemical admixture dosage levels. To a large degree,
gypsum is added to cement to slow the rate of hydration of C 3A and to prevent too rapid
of setting.

The final Bogue compound, tetracalcium aluminoferrite (C4AF) is primarily a result of

materials used in the cement manufacturing process to lower the temperatures required in
the kilns. C4AF hydrates rapidly, but contributes little actual strength. Perhaps its most
significant effect on concrete is its influence on color. Higher concentrations of C 4AF will
result in darker color concretes. In white cement the percentage of C 4AF is kept low,
often about 1% to 2%.

In addition to the Bogue compounds, two other values reported on a mill certificate are
important to consider. The total alkalies (sometimes referred to as total equivalent
alkalies) will help determine if the cement may be used with aggregates that are
potentially reactive with alkalies. Cement with alkali levels below 0.6% are considered
low-alkali cements and may be suitable for use with some reactive aggregates. Sulfate
level (S03) can be important in controlling initial and final set time of concrete and
performance with chemical admixtures.

Making a habit of reviewing cement mill certification reports can be an informative and
important tool in your overall quality control program. Likely, by tracking the changes in
cement chemistry you will be able to predict their influence on the performance of your
product. Remember, the cement mill certification can and should be used to do more than
just show that the cement meets relevant specifications.

 The identification of the major compounds of cement is

largely based on Bogues equations and hence it is called
Bogues Compounds.

Alite: C3S, or tricalcium silicate

Belite: C2S, or dicalcium silicate
Aluminate phase: C3A, or tricalcium aluminate
Ferrite phase: C4AF, or tetracalcium aluminoferrite
C3A has the fastest hydration rate in cement, and begins to react with water
extremely rapidly to form calcium aluminate hydrate if there is no sulfate in solution.
This can cause flash set (immediate and permanent stiffening). In the presence of
plenty supply of sulfate, the hydration of C3A is to form ettringite, and the ettringite
produced creates a diffusion barrier around C3A to prevent further hydration of C3A,
and hence the hydration of C3A is proceeded at a controlled rate allowing cement
hydration to have dormant period. Ettringite is a stable hydration product only while
there is an ample supply of sulfate available. If the concentration in solution drops,
then ettringite becomes unstable and converts to monosulfoaluminate. This barrier
of Ettriginte is broken down during the conversion to monosulfate and allows C3A to
react rapidly again.
C3A increases rate of hydration of C3S. C3A gives flash set in absence of gypsum

Portland Pozzolana Cement (PPC) contains up to 35% fly ash. The fly ash is
pozzolanic, so that ultimate strength is maintained. Because fly ash addition allows a
lower concrete water content, early strength can also be maintained. Where good
quality cheap fly ash is available, this can be an economic alternative to ordinary
Portland cement. As a rule, Portland Pozolana Cements gain strength slowly and
therefore require curing over a comparatively long period, but the long term strength
is high shows that similar behaviour occurs where the pozzolana replaces part of
cement, but the long-term strength depends on the level of replacement.
Portland Slag Cement (PSC) contains up to 70% ground granulated blast furnace
slag, with the rest Portland clinker and a little gypsum. All compositions produce high
ultimate strength, but as slag content is increased, early strength is reduced, while
sulfate resistance increases and heat evolution diminishes. Used as an economic
alternative to Portland sulfate-resisting and low-heat cements. The hydration of slag
is initiated when lime liberated in the hydration of Portland Cement provides the
correct alkalinity; subsequent hydration does not depend on lime. Typical uses are in
mass concrete because of lower heat of hydration and in sea-water construction
because of a better sulphate resistance (due to a lower C3A content)than with
ordinary Portland cement. Slag with a low alkali content can also be used with an
aggregate suspected of alkali reactivity.
Suitability of various types of cement: A. 33 grade OPC: It is used for normal grade
of concrete upto M-20, plastering, flooring, grouting of cable ducts in PSC works etc.
The fineness should be between 225 and 280. B. 43 grade OPC: It is the most
widely used general purpose cement. For concrete grades upto M-30, precast
elements. For marine structures but C3A should be between 5 - 8%. C. 53 grade
OPC: For concrete grade higher than M-30, PSC works, bridge, roads, multistoried
buildings etc. For use in cold weather concreting. For marine structures but C3A
should be between 5 - 8%. D. Portland Slag Cement (PSC) i.e. OPC + granulated slag:
It gives low heat of hydration. The slag should be more than 50% and upto 70%. It is
used for ; Marine and off shore structures- very high chloride and sulphate
resistant. Sewage disposal treatments works Water treatment plants
Constructions which are expected to be attacked by dissolved chlorides and sulphate
ions. Should be mainly used for all future structures.
Special grade cement (43-S and 53-S): Special Grade Cement is manufactured as per
specification laid down by BIS IS 8112 & 12269. It is a very finely ground cement
with high C3S content designed to develop high early strength required for
manufacture of concrete sleeper for Indian Railways. This cement can also be used
with advantage for other applications where high strength concrete is required. This
cement can be used for prestressed concrete elements, high rise buildings, high
strength concrete etc.