So welcome to the third video in this introductory module series.

In this module, we are

going to talk about how we can lower the environmental impact of cementitious materials
by replacing part of the Portland cement clinker with other cementitious materials.

So classically, cement has been clinker which is ground with a small addition of calcium
sulfate, normally referred to as gypsum, to produce cement. And this is what we call
Ordinary Portland Cement, O.P.C. or Plain Portland Cement.

50 years ago this made up practically all the cement produced but nowadays the vast
majority of cement produced also contain what are known as supplementary cementitious
materials or SCMs

Now what are these SCMs? Some examples are limestone which comes from the quarry.
Fly ash which comes from burning coal to produce electricity. Slag which comes from blast
furnaces where iron ore is is reduced to iron. And natural pozzolans which are found in
nature and finally calcined clays.

Now these are often bright products a waste from other industry
and their availability will vary considerably from place to place. If we look at the overall
level of substitution of SCMs in cements around the world, we can see in this graph here
that just three materials make up the overwhelming majority of the substitutes, namely
limestone slag and fly ash.

Secondly we can see that while a few years ago the level of substitution was increasing,
for the last five or six years it has remained almost static.

Now before we look at the reasons for this let's look at these different SCMs in a bit more
detail.

So first we have limestone. This comes through from the same quarry where limestone is
excavated for producing the clinker, but the important thing here is because it doesn't
pass through the kiln it doesn't lose it CO2.

It is typically interground with the cement during milling and we find that if we have small
levels of addition up to about five percent it actually enhances the properties
and this is due to the fact that a small amount of the limestone does react with the
aluminate phases and also because the fine limestone particles enhance the nucleation of
the CSH and give a denser microstructure.

Now we don't actually need to use high quality limestone, although this is often required
in standards.
The second material is blast furnace slag. This schematic here shows that we have iron
which comes from the iron ore
and slag is the material which is used to help the separation of the iron from the
impurities in the iron ore.
This material is liquid in the blast furnace and then it is poured off.
And depending on the cooling, we can either have crystalline material which really can
only be used as aggregate,
which is air-cooled slag. We can also make expanded slag which can be used as
lightweight aggregate
but what we are really interested in is when we quench this slag which is what is known as
granulation,
and by this very fast cooling with water, then we produce amorphous phases
and these amorphous phases can then dissolve in water and react like the cement grains.
And here we see a picture of the slag, we can see these angular grains. They are made up
about 90% percent or more
are amorphous material. And then this is ground
and the break up of this glass gives these sharp irregular glassy materials. This has a very
high calcium oxide
content
and produces what is called a latent hydraulic material. Because of the high calcium
content then we can replace very
high amounts of clinker in cement. Typical replacement levels are in the range from 30-
70% percent.
Now the problem with slag is that the growth in availability of slag has been not as fast as
the growth in availability of cement.
So at present, the annual production of slag is only around eight percent of the production
of clinker
and this proportion is unlikely to increase because we are producing more or more iron
and steel from recycled materials
and this means there is less slag available from blast furnaces.
Next we move to fly ash
and as I have said, this is the incombustible material which is in the coal. What happens is
that during the
burning of the coal, little droplets of water form, these droplets then are carried in the
flue gas
and subsequently recovered by electrostatic precipitation to avoid their dispersion into
the atmosphere.
Now because they are very small, they cool quite quickly
and this quick cooling again leads to the formation of amorphous or glassy material.
So we have much lower proportion of amorphous material. We typically find the that the
core of these
grains is crystalline, because of this reason and the chemical composition where it
contains less calcium,
this is less reactive than the slag
and the typical levels of addition we can make are up to around thirty percent. Now the
other problem with fly ash
is that it is a very heterogeneous material. In this micrograph here we can see the
different grey levels indicate the
different chemical composition and on the right here we have made a chemical mapping
of that fly ash
and the different colours indicate different chemical compositions. So what you can really
see is that the chemical
composition varies considerably from place to place and this makes it quite tricky to
determine how fly ashes react
and means that one fly ash can behave quite differently from another fly ash.
So in this series of slides, we can look at
the availability of these SCMs compared to Portland cement. So this red bar shows the
amount of Portland cement produced
in the world today, just over four billion tonnes.
And if we look at these common replacement materials, slag and fly ash, we see that the
amounts available are much
lower than the amount of Portland cement.
So slag, we have about eight percent compared to portland cement
and the vast majority of this is already used either blended with cement or added at the
concrete stage.
When we come to fly ash, overall we have a somewhat higher amount but because of that
variability, the amount that can be
used with cement is quite a bit lower.
And these two materials together make up only around fifteen percent of the amount of
Portland cement produced today.
Now people have looked for other materials that can be blended in. The other material we
have is
limestone, we have talked about earlier and there is effectively unlimited amount of this
material available.
But the problem is that we can't have very high amounts without diluting the properties of
the cement.
And generally if we have additions above about ten percent or so then the strength
and other properties of the cement tends to decrease. Now people have looked at other
materials to use as SCMs which we
see now here on the top. We see natural pozzolan.
The amounts used today are really quite small. This could perhaps be increased,
but nevertheless, geographically, the distribution of natural pozzolan is very uneven.
People have considered vegetable ashes, so notably the ash produced by burning rice
husks can be an active
addition in cementitious materials.
But the amounts available are really quite small
and there are a lot of other problems with these vegetable ashes such that they are only
produced seasonally, they
tend to be produced in rural areas where the big demand for cement is in urban areas
and currently many of these
agricultural waste are used as fertilizers so if they are taken off the land, they may lead to
a problem of soil
fertility.
People have talked about waste glass, but really we see that the amounts of this are very,
very small
and of course it is much, much better to recycle waste glass into new bottles.
And finally of course silica fume which is a very high performance additive widely used to
produce high performance
concrete but the amounts available are really very very small.
So what else can we have? Now what we really
see is that there is only one material that is available in the kind of quantities we really
need
and this is calcined clay. And the amounts of calcined clay really are virtually unlimited.
So to summarize that, what we see is that there is no magic solution. Blended cements
with SCMs will be the best
solution for sustainable cement for the forseeable future. The traditional SCMs
we have are only about fifteen percent compared to the amount of cement we produce
and the only material available in viable quantities apart from these is calcined clay.
And even more interesting is the use a combination of calcined clay with limestone which
we will talk about in another
video of this module.
So this material, this material with that combination of calcined clay and limestone is what
we call limestone calcined clay cement
or LC3.
So before summarizing this, I just want to say a short word about alkali activated materials
or geopolymers.
The low availability of slag is the main reason why alkali activated materials will not
contribute
significantly to lowering global CO2 emissions. All the formulations of alkali activated
which harden at ambient temperature
contained today contain mainly slag.
And as we have seen the availability of slag is really very low. So if slag is diverted from
use in cement blends
and concrete
to be used in alkali activated materials, then we may be able to say that these alkali
activated materials have a
lower CO2 emissions, but globally the emissions of other concrete will increase
and in fact what we need to consider is also the CO2 emissions of the alkali activator.
And for these two reasons, the CO2 emissions may be increased at a global level.
And in fact there are very few countries which have really abundant supplies of slag which
would favour the use of alkali
activated materials, so one exception in this case is Japan. OK so let's summarize what we
have seen in this lecture.
In this lecture we have seen that supplementary cementitious materials are an effective
way to reduce the amount of
clinker in cement or in concrete
and hence to reduce CO2 emissions. Over the past few decades, the average level of
substitution has increased to
around twenty percent and this is made up mainly of slag, fly ash and limestone.
Further progress in this respect is mainly limited by the availability of these SCMs
and this limited availability is also the main reason that alkali activated materials cannot
have a really significant
impact on lowering overall emissions from cementitious materials.
What we have seen is that the only other material available in the kind of quantities we
need
is clay which is active when calcined and this is particularly interesting
when used in combination of limestone. So in the next lecture we are going to look in
detail at the use of calcined clays for
cement and concrete. So thank you for listening and I hope to see you next time.

So welcome to video number four in this introductory module. And in this video we are
going to talk about LC3
or limestone calcined clay cement. So what is limestone calcined clay cement?
This is actually a family of cements and often we talk about LC-350 or LC-365. The figure in
this case refers to the clinker content.
So here we see on the left, we see the composition of ordinary Portland cement where we
have about 95% clinker,
and 5% addition of calcium sulfate or gypsum.
When we have typical Portland pozzolanic cements as shown here, we will have about
70% clinker and about 30% pozzolan,
which can be typically something like fly ash but can also be calcined clay.
And usually because of the reactivity of these pozzolanic additions, 30% is the maximum
level of addition we find in practice.
However, what is very special about the LC3 family, is now instead of adding just calcined
clay on it is own,
we add calcined clay together with limestone.
And what we find is that we can add an extra 15% of limestone, we can remove 15% more
of the clinker,
and we can get the same performance as in the pozzolanic case here.
So on the right here we see some strength results for LC3-50. You see that one day the
strength is somewhat lower than it was for the ordinary portland cement,
But already by only 7 days, the strength of the LC3-50 system has surpassed that of the
ordinary portland cement
and it is still higher at 28 days.
So this is quite remarkable because it means that for only 50% of the clinker, we have the
same performance.
This also means we have about 30% less CO2. We get as I said similar strength.
And in some respect, we have quite a big improvement in the properties, particularly in
respect to chloride penetration and to alkali silica reaction.
So in this module, what we are going to talk about is what types of clays can be used,
how they can be calcined
and where we can find the kind of suitable clays in the world today.
So what we see in this slide here are the crystal structures of the basic clay types.
All the clays are layer structures, so here we see the layers, and these layers are alumino-
silicate layers.
So we see the orange dots represent the silicon atoms which are found in little tetrahedra.
So in a little cage of oxygens. And the green atoms represent the aluminium, which are
found in octahedral cages of oxygen.
Now the two materials on the left here, the illites and the montmorillonites are called 2:1
clays.
What these means is that we have two silicate layers here, and here we have sandwiched
the aluminium layer in the middle.
And the difference between illites and montmorillonites is mainly in terms of the ions that
are found between the layers
and the montmorillonite usually has alkali ions and more water between the layers.
And finally on the right here, we have the kaolinite structure, and the kaolinitic clays are
what is called 1:1 clays
and this means in the layers we have one layer of silicate and one layer of aluminate.
In this slide here, what we see is the thermal decomposition of the different clay types.
And we can see that these have a thermal decomposition in different ranges.
What do these peaks represent? They represent the amount of heat that is absorbed by
the material as it is heated up
And this heat is absorbed due to the loss of hydroxide from the structure which is called
dehydroxilation.
And we can see that these different clay types have dehydroxilation in different
temperature ranges.
The clearest dehydroxilation is this one here for the kaolinite which occurs between about
450 and 650 degrees.
And this signature provides a very good way of determining how much kaolinite you have
in any clay you may want to investigate.
All you do is to make this kind of thermal decomposition.
You can even quite simply do it by heating your material in two different ovens
one at say 400 and one at 700
and looking at the weight loss between these two temperatures.
Of course as you can see there will be a small interference if you have also some illite in
your sample.
But these kind of effects can be determined by looking at something like an x-ray
diffraction diagram.
If we look in the electron micrograph, we can see this layered clay structure,
we can see that the clay is made up of little platelets. Here we see the raw clay before
dehydroxilation,
here we see the clay after dehydroxilation. Basically at this level in the SEM you dont see
any change in the morphology, it appears to be very similar.
We have to use other techniques to really see what is happening within the crystal
structure.
And particularly useful in this regard is solid state NMR,
when we study 27 aluminium ion. So nuclear magnetic resonance, or NMR,
is a technique that can be used to look at the local environment of a particular species.
So we see for the two 2:1 clays, illites and montmorillonites, that as we heat these
materials, we get a
transition of the aluminium from the octahedral coordination in the raw clay. Octahedron
has six apexes
so this is also called a six coordination to a tetrahedral coordination or a four fold
coordination.
What is quite clearly different in the kaolinitic clays is that as well as the shift from
octahedral coordination to
tetrahedral coordination, we see quite clearly the emergence of this five fold coordinated
site and this five fold
coordinated site is the indicative of a disordered
or semi-amorphous sight, which is what means that it is easier for it for react.
So this is a very important difference between what happens in thermal decomposition
between the 2:1 clays
and the 1:1 kaolinitic clays. The 1:1
kaolinitic alays had this disordered aluminium which is then the
atoms that can go on and react without cementitious materials. Here we see the
appearance of these
calcined clays depending on the other materials that are present in the clay, the colour of
the clay can change over the whole
spectrum from white to reddish colour if there is a lot of iron oxides present.
You can actually control the colour that comes out in the end by the
conditions of oxidation and reduction in the kiln. OK in this slide here, what we see is the
pozzolanic reaction, all of
these different clay types in cement. So the pozzolanic reaction basically involves the
reaction of the pozzolan,
the calcined clay in this case, with calcium hydroxide that comes from the cement.
And this code here, K stands for kaolinitic, I stands for illitic,
M for montmorillonite clays. And as references we have got the plain OPC and the plain
OPC
with just an inert filler which in this case was quartz.
So we can see how the different clays react by looking at their consumption of calcium
hydroxide relative to the amount
of the cement, the clinker based cement, OPC.
And in most cases, we see that the amount of calcium hydroxide produced is actually
somewhat higher than the reference
which is this curve in black, which is the plain Portland cement.
And the amount of calcium hydroxide is somewhat higher purely due to a filler effect as in
this grey curve here, where
the fact that you have a dilution of the cement by the clay gives a bit more room for the
cement to react so it
produces a bit more calcium hydroxide.
In sharp contrast, we see the kaolinitic clays here we have much lower calcium hydroxide
contents, this calcium
hydroxide content gets lower and lower with time and this is a typical
signature of the pozzolanic reaction of the calcined clay.
Even in very early ages we can see the calcium hydroxide content is very much reduced
compared to the Portland cement reference.
Finally we perhaps want to look at this montmorillonitic clay here which does seem to
show some reaction at later ages.
What should be the optimum temperature for the calcination? In this graph, here we see
for a particular clay
that has been calcined at different temperatures, how the strength varies over time. So
the different temperatures
we have used are the plain raw clay with no calcination at all, 600,700,750,800
850.
And the raw clay, it is just reacting as a filler, so you see the strength development is really
quite poor. The calcined
clays even from three days are giving a very significant increase which is indicative of their
reaction.
And we see by seven days that for this particular clay which contained about forty percent
kaolinite,
for the optimum calcination temperatures, this strength is surpassing that of the Portland
cement. We see
that the strength is increasing from 600 to 700 to 750. 800 is about the same
and by the time we get to 850 then we see in this particular case the strength is going
down.
And this is what we have observed in most cases that the optimum calcination
temperature is in this range, 750
to 800. It may be somewhat lower if you have small contents of calcite in the clay.
Instead of having to do this series of strength tests,
what we see on the right is the results of a reactivity test which we will talk about later in
the
series and here we can use much smaller amounts of clay and study the heat evolution in
what is called a calorimeter
but we can see the same trend, we can see the raw material has no reactivity, at 600 we
get modest reaction
this increases through
700, 750, 800
and then by 850 there is a clear decrease in reactivity. Now why do we have this decrease
in reactivity? We can
see that in this series here, this is the clay calcined at 600. We can see these agglomerates
of these tiny
clay platelets. Again we can see these agglomerates at 800 and now
when we go at higher temperatures, in this case we have gone right up to 925, we now
can see that we
no longer see the individual platelets but we see these kind of
glassy looking grains
and what happens is we have had a small amount of liquid phase forming which actually
sinters these clay particles together.
And if we have this happening, then we will get a very strong decrease in reactivity.
So the critical question now is what grade of clay do we need to be able to make these LC3
materials?
So at EPFL here, we have studied a wide range of clays from around the world. These clays
had different origins, some came from
Latin America some from India, other parts of Asia etc, even from Europe and the fineness
of this clay,
the production method of the clay, the minor phases that were present in addition to clay,
all of these
vary quite widely between the different materials.
If they weren't calcined, we have calcined these clays
and then we use them in the LC3-50 system and measure their strength in the European
mortar bar test.
And what we see quite clearly here is that we get a very clear correlation between the
calcined kaolinite content, that is
the amount of kaoline which was in the original clay that had been broken down during
the calcination, between the
calcined kaolinite content
and the compressive strength development. So we have different curves here for the
different ages for one day, for seven
days, three days, for seven days twenty eight days, ninety days.
And in addition to this strong correlation with the calcined kaolinite content, we have
indicated here by this dotted line,
we have indicated the reference strength of the plain Portland cement. So you can see the
three days if you have a
kaolinite content of over eighty percent, you can meet the same strength as your ordinary
Portland cement. Whereas if you are prepared
to wait a bit longer, to about seven days, then if you have a kaolinite content of between
forty
and fifty percent, you will get a similar strength to your ordinary Portland cement.
So this is very important because it means for this LC3
system, we don't need to use very high purity clays. High purity clays notably used to
produce metakaolin have to
have very strong requirements for colour, for purity etc.,
which makes them very expensive. Whereas these kind of clays which contain much lower
amounts of kaolinite, only
say forty/fifty percent, are generally waste materials which are consequently much
cheaper.
So the kind of clays we want to use are very widely distributed around the Earth.
And this is a soil map which gives an indication of what kind of clays you are likely to find
below the surface
and it is a rather simplistic
representation
but we can be quite sure that in all the regions where we have this yellow colour or this
pink colour, there we will
certainly have abundant clays
and we see that this is really very very widely available in the central equatorial
subtropical region, going through
China, Southeast Asia, India, Africa and Latin America.
And in fact we have seen in India where we have made much more detailed studies that
suitable clays are not confined
only to these yellow and pink regions
but we actually have very large amounts of suitable clays, for example in this region of
India, in Gujarat and
Rajasthan, which on this soil map would appear
not to be so suitable. So the main message here is that the kind of clays we need are
incredibly abundant
throughout the world, the reserves are virtually unlimited. These are just the countries in
the equatorial subtropical
regions where the growth in demand for cement is strongest.
And in many of these countries, what we can find is that the suitable clays are currently
stockpiled as waste.
So this picture comes from a quarry in India. This is a quarry where they are extracting
high purity clay for
producing metakaolin which is then used for ceramics or in the paper industry
and this huge mountain here is just waste. This is material which has too low quality for
exploitation at the present
time, but this waste here is a very suitable quality for blending with cement.
And we have taken those kind of waste materials, we have made full scale trial
productions. This just shows a couple of
houses produced from these productions. This one in Cuba here. This one in India. All the
materials, the
concrete blocks, the render, here the roof tiles etc, these are all produced with LC3
material.
And they were actually produced, they could be produced by totally unskilled workers in
the same factories without
special training, just purely with a one to one replacement, taking one bag of the
cement that was used before either OPC
or pozzolanic cement with fly ash and replacing that with LC3.
And in this case in India we made a more detailed calculation of the CO2 savings
and we could calculate that about seven tons of CO2 were saved just in this one single
house by using LC3
materials compared to the existing materials. So let's look at what we have seen in this
module.
What we have seen is how we can use a combination of calcined clay with limestones to
go to much higher levels of
substitution than is typical in pozzolanic cements. We have seen that it is really the
kaolinitic clays which have
the potential to give these high pozzolanic activity after calcination.
And this high pozzolanic activity results from their one to one structure which means we
get poorly
organized alumina after calcination.
The optimum temperature for the calcination is in this range 750 to 850. If we go to higher
temperatures then
we may get sintering, a loss of surface and reactivity. If we look at the performance in
mortars
and concretes we see that if we have got more than about forty percent kaoline, this can
be very suitable for use in LC3
blends, even in a mixed system you can get a similar strength after about seven days
and we are sure you could get even better earlier strength by optimizing the grinding
parameters.
These kind of clays, with forty percent
or more kaolinite, are very widely available around the world, particularly in the regions
where the growth in
demand for cement is highest. And we have made trial productions of LC3
in both Cuba and India.
So this short video completes the introductory module. I hope that you will be interested
to come back
and listen to the module on hydration which follows this.