Blended cements: The myths and realities

Prepared by STAR LIME & ADMIXTURES for STAREX customers as an information

document only.
History
Evidence of the first blended cements dates back to Roman times, when volcanic ash was used in
a crude blend with slaked lime to give the user a product that developed higher early strength
than the usual slaked lime as well as significant durability. Evidence of this can be seen in the
Aqueducts and the Colosseum in Rome. The area in Italy where the volcanic ash was discovered
is called Pozzuola, hence the term for a reactive substance being called a pozzolan.
Some academics have assumed that the Roman Empire discovered the process of cement
manufacturing, which was lost with the decline of this empire and rediscovered in the nineteenth
century in Britain. In truth, it is more likely that the lime the Romans calcined (burnt) for the
purpose of slaking approached an argillaceous lime in chemical composition and hence hadto be
milled rather than naturally slaked. When mixed in the normal manner with water, this product
showed large early strengths and was probably the first cement made.
How cement is made: A crash course
Cement is made in by intergrinding a blend of limestone and various other products to achieve a
chemical composition that is roughly the following:
Calcium oxide - 64%
Silica - 21%
Alumina - 7%
Iron - 3%
Other - 5%
This blended raw material is heated in a rotary kiln to a temperature of about 1450C. At this
temperature, it undergoes a solid-state reaction where various crystals are formed. The main
cementing crystal is called tri-calcium silicate. As theword indicates, it is a combination of three
parts calcium and one part silica.
The content of tri-calcium silicate in cement should approach 70% by mass of cement.
The tri-calcium silicate delivers all early strength to the cement user. By early strengthwe mean
the strength developed between one hour and seven days after placement of the concrete. Most
other products used in cement and blended cements only start delivering performance to the user
after seven days.
During the high temperature reaction, a small amount of the product becomes liquid; this is a
result of the alumina and iron, which is included in the raw material. Essentially, these products
are required as fluxing agents, which reduce the reaction temperature, reduce coal consumption
and increase kiln life.
The liquid phase causes the cement to roll into little pebbles called clinker, in much the same
way as small balls of clay will form when water is added to clay in a rotating pot. This clinker is
milled in a ball mill with a specific addition of gypsum to control the rate of set.
At this point the manufacturer has made pure ordinary Portland cement.
While all this sounds quite simple, significant moneys are expended on quality control and the
erection of plant. The average cement plant produces in excess of five hundred thousand tons of
cement per year and costs in excess of fifty million dollars.
Blended cements
Initially, manufacturers found that they could increase the fineness of the cement they were
making by increasing the milling time. This yielded cement that would give the user much higher
early strengths. The manufacturer would then add an inert product (limestone) to the cement,
which would result in a reduction of the cement strength to the original levels. The result would
be an increase in output for the cement manufacturer, which yielded more profit. These products
are called cement extenders.
Over time and with the advent of more scientific methods of technical evaluation of products, it
was found that certain products, when provided with an alkaline activator, would, over time,
display cementitious properties. An alkaline activator is normally a result of slaked lime being
added to the mixing water, in the same way as when cement is added to water, the alkalinity of
the water increases significantly. These products are called pozzolans.
Pozzolans
For ease of reference, only pozzolans found in Southern Africa will be discussed.
The products known as pozzolans are:
Ground granulated blast furnace slag
Pulverised fuel ash (fly ash)
Natural pozzolans
Granulated Blast Furnace slag is made by hypercooling the molten slag from a furnace which
produces slag of an acceptable chemical composition . The term hyper-cooling normally refers to
normalization from a high temperature of about one thousand five hundred degrees Celsius to
ambient temperature in seconds. The result of this is that the product does not take on a
crystalline form but becomes a glass. This glass is milled to the same fineness as cement. Once it
is milled it is referred to as milled granulated blast furnace slag.
Pulverised Fuel Ash is made by very fine grinding of coal at power stations. This coal is fed
into the steam-generating boilers. After ignition at about one thousand eight hundred degrees
Celsius the ash that is left is molten. When the ash comes into contact with the air stream that
transports it to the precipitators or bag filters, it hyper-cools and turns into a glass. This ash is in
very fine form and normally has less than 2 % carbon. The ash is captured by the precipitator and
transferred to a hopper from where it is sold.
Natural pozzolans are formed by volcanic larvae resulting from pyroclastic events. The final
product is hypercooled by the action of the larvae being thrown into the air where it cools rapidly
below a certain threshold temperature . This product is primarily glass but does have crystalline
phases . The chemical range of these products is quite large but is characterized by a high Sio2
content.The natural pozzolan which occurs in this countryis known as a Zeolite.
What do these products do?
The mode of action of these products (how they work) is not very well known. There exists an
expert in every industry - the truth is that we have lots of theories but not much hard evidence.
We do know the following:
All these products in the presence of an alkaline activator develop strength. This is termed as
Pozzolanicity.
When blended in specific proportions with cement, these products enhance the quality of the
cement.
When blended in specific proportions with cement, the blended cement generally achieves
higher final strength than pure cement.
Pozzolanicity essentially means that, when added to cement, the pozzolan will take advantage of
the increased alkalinity that the cement imparts on the water to contribute to the strength of the
cement product. While the cement contributes to early age strengths (one hour to seven days),
the pozzolan will contribute largely to later age strengths (seven to fifty six days).
Enhanced quality : Pozzolans improve the resistance cement has to destructive agents. The
main destructive agents to cement are chlorides and sulphates. Pozzolans work by reducing the
rate at which these destructive agents ingress into the cement and hence increase the life of
cement products. As an example: most mass concrete pours (bridges, central cores of buildings)
are required to have pozzolans blended with the cement. When reference is made to time of
ingress, the normal time frame without pozzolans is approximately fifty years, while with
pozzolans added, the life of a structure could be seventy-five years. An application where the
utilization of pozzolans is critical is in the use of mass concrete pours. In these instances the heat
of hydration, if allowed to increase abovea certain level, causes cracking. The use of pozzolans
reduces hydration heat and consequently reduces hydration cracking or eradicates it completely.
Pozzolans also improve the soundness of cements by reducing the expansion of the concrete .
Expansion of concrete results from the presence of magnesium oxide and and calcium oxide (
free) in the cement , the addition of pozzolans results in a decrease of the quantity of magnesium
oxide and free lime which results in a reduction of expansion. Alkali aggregate reaction is a
phenomenon that results from the reaction of the the alkalis ( Na2O, k2O) that are resident in the
cement and the silica which is found in the aggregates. The resulting gel which is formed causes
unsoundness in some cases but mostly results in leaching of salts from the concrete which is
unsightly. The use of pozzolanas reduces the overall content of alkalis present in the cement and
as a consequence reduces the amount of gel formed.
Strength : At early ages, as a result of the slow reactiontime of the pozzolans to the alkalinity
delivered by the hydrating cement, the strengths of blended cements will be below those of pure
cements. As the pozzolans start to react, the cement gains in strength and the ultimate strength
will generally be higher than pure cement.
Environmental: For every ton of cement that is produced approximately four hundred and forty
kilogrammes of carbon dioxide is emitted, this results from the conversion of calcium carbonate
to calcium oxide.The use of fly ash or slag results in a net reduction of the amount of cement
used and a corresponding reduction in the amount of carbon dioxide emitted. The consistent
requirement of the ash distributor to maintain the level of carbon in ash to below five percent
will ensure that theash producer achieves increased burning efficiency and results in increased
life of ash dams.
Commercial: In the past the major benefit has always been that the net cost of the cement has
been reduced and this has always been the argument for the use of pozzolans. The ratification
and adoption of the Kyoto protocol with regard to carbon dioxide emissions has made the use of
pozzolans a requirement and in some countries the use of pozzolans is legislated for
environmental protection and structural longevity . The demand for pozzolan is steadily
increasing worldwide and is being viewed as a resource rather than as a waste material. In the
African context the cost of erection of new cement production facilities can be deferredthrough
the increased use of pozzolans and hence demand for pozzolans is rising .
Technical: fly ash.
The problem with all pozzolans made as a by-product of a process( steel production, power
generation) is the critical requirement for the producer to implement rigid process controls to
ensure the final product complies with a specific range of specifications. In the case of fly ash it
is crucial that the carbon content is maintained consistently below five per cent. The primary
reasons being that carbon is very fine and tends to increase the water demand of the final
concrete ( which results in strength loss) and carbon increases the setting time of the cement. The
secondary reason is that high carbon is a tell tale indicator of incomplete combustion which
results in excessive free lime and sulphur di-oxide in the final ash. The combination of these two
products under cementing conditions causes expansive gypsum to be formed which will result in
structural unsoundness.
Specifications:
1: LOI always below 5%2: Free CAO always below 3%3: Fineness 90% below 75 micron.
Technical: Slag
The original reason for the granulation of blastfurnace slag was to enable the steel producer to
manage the waste product dumps for long periods without the risk of the slag decrepitating. The
discovery of the value of the slag as a cement extender required the steel producer to manage the
quality of the slag. The main requirement is the glass content and the granulation temperature. A
high glass content is an indication of reactivity , a low granulation temperature will result in a
low glass content but will also change the colour of the slag . There is a standard requirement
that CaO, SiO2 ,Al2O3 ,MgO are present in specific ratio.
Specifications
1: Glass count More than 66%2: (CaO +MgO+Al2O3) / SiO2 greater than 1
Technical : Zeolite ( natural pozzolan)
Development still ongoing.