Characterization of Construction Materials

Prof. Piyush Chaunsali

Lecture 8
Calorimetry: Introduction and types of Calorimeters – Part2

(Refer Slide Time: 00:20)

If we want to study Portland cement hydration, we want to first look into the stages of the
hydration. Many of you must have seen this, but anyway we will discuss it here. So this is the
typical rate of hydration plot for Portland cement. So what do you see? You see there are four
different stages. At one here, is the ‘Initial period’ - A. It is called heat of dissolution.

So you have this cement and you are dissolving it in water. So basically, it is nothing but heat
of wetting, and maybe some formation of products. Notice, you have very high rate of heat. It
does not mean that the amount of heat is also high. It is a rate. Any powder for an example,
even if it is non reactive, you will have this heat of wetting. But in this case you have heat of
wetting and some reactions, some dissolution, some formation of calcium silicate hydrate, for
an example.

So, you have a rapid release, a significant heat production rate, rate of heat hydration, and then
it slows down. Then you come to this part - 2. 2 is nothing but ‘Induction period’. Now you see
that the reaction has slowed down, does not mean that it has stopped, still you have a positive
rate of heat of hydration. Can anyone tell what the importance of this induction time, induction
period is?

So it is valuable to us because it gives us some time. It is also called ‘dormant period’. Why is it
happening, what is the cause for this? Right, I mean those reactions will take place, but
primarily, you have a cement particle, it is reacting and something is forming on its surface. So
imagine, you have these cement particles. Now, after some time something is formed on the
surface that acts as a barrier.

You have water, then, it acts as a barrier for some time, but after some time, this barrier breaks
down. But it gives you some time to finish your concrete for an example or maybe transport it.
So it's very important, that’s induction period. Then the reaction accelerates. It is called
‘Accelerating period’ - very important. Lot of hydration products are formed during this period.

And the peak is achieved around 12 to 14 hours. Then you see a slowdown, now this is a
deceleration why because you have formed so many products. Now, imagine, you have so
many products, now you are making it difficult. It's the diffusion control. If you want to make
this remaining cement particle react you have to go, you have to cross this barrier.

So it becomes diffusion control. So that is why you see this decelerating period. So this is again
the rate, note that it does not mean that you have a positive rate. Your total heat is increasing.
So if we have to plot, for an example, cumulative heat. The plot will be something like this, this
is total heat. So, the total heat plot you can see, after this main peak, the slope changes.

So you have this acceleration period, then your slope is changing. But still you are seeing in this
increase. It will go on. So that was this deceleration thing period was ‘D’. One more interesting
observation here is, you see something in this decelerating period here. It is shown as E. For
example, sulphate depletion peak. So you use some gypsum in your cement. Why is gypsum
used? Yes, to prevent flash set.

But when the gypsum gets consumed fully, you form mono sulphate. Your Ettringite converts
to mono sulphate. So this tells you about this sulphate depletion. It tells you that whatever
gypsum you have added is finally consumed. So it is very important, because lot of times, this
optimization of sulphate is done through strength test.
You optimize the strength - you add 1% gypsum, 2% gypsum, 3%, 4%,5% and see which one is
giving you the maximum strength. But Calorimetry can also tell you how much gypsum should
be added; you do not have to do a destructive test. So, Calorimetry is a non-destructive
technique. See the power of this measurement - tells you about lot of things, the rate, which are
the critical stages because it is very important to know.

Suppose, you want to extend this dormant period, suppose you decide that you have to transport
your concrete to 30 kilometres away, which needs at least one hour, for an example, may be
included in traffic if it is one and a half hours, so you want to use some admixtures to delay this
setting or prolong this dormant period. So what can you do? You can study; you can carry out
these experiments and see what happens, when you have these additives.

So, we will come back to it, but I am trying to draw your attention that you can get a lot of
information. So, this is the typical Portland cement hydration. Our focus will be to study this.
How can we use Isothermal Calorimetry or Adiabatic Calorimetry to understand it better.
(Refer Slide Time: 08:10)

Continuing this Portland cement hydration, suppose you have measured the heat evolved. So,
here what you see on the y axis, you have a mean heat evolved at different days right 3 days, 7
days, 28 days, 90 days, one year, 6.5 years, 13years, and you have compared different types of
cements. So here ASTM Type I, Type II, Type III, Type IV cements are there. All of you must
be familiar with this ASTM classification, right?
So you see that the Type III cement has the highest heat at all ages. Now, it is getting very
similar to Type I at later age, but at least at earlier age it has more heat. Type II is low heat
cement - moderate sulphate resistance. So, it has a little bit more C2 S, less C3 A. So you see that
this is the trend. Type IV is low heat cement. So it has more C2 S. So, the heat is less because
the reaction is slow, because you have more C2 S in the system.

So, heat evolved is directly related to the amounts of clinker phases that have reacted. You see
here, you see the difference right? That difference is because you have different phases. The
phase compositions of cements are different. Type I cement has maybe less C2 S compared to
Type IV. Type IV has more C2 S. And the heat evolved will depend on the amount of each
phase, how much C3 S you have, how much C2 S you have, because reaction is different.

Each chemical reaction is different. If it is different, then the associated heat release is also
different. So it depends on many factors such as particle size distribution. You all know that if
you make your cement finer, you make it react more. You have higher heat which is evolved,
water-cement ratio, temperature and relative humidity of curing. These all will affect your heat.
(Refer Slide Time: 10:54)

So how can we calculate heat of hydration? We know that this is our hydration curve. How can
we calculate? This is a simple calculation. The total heat of hydration can be written as
summation of the contribution of individual phases. So through Bogue formulations, you can
find out how much C3 S, C2 S, C3 A C4 AF you have in your cement.
And now in this table you see that the value of coefficients is given. So for an example, if you
want to calculate the heat of hydration at 3 day what do you do? You take the coefficient as 243
for C3 S. If you know the C3 S, suppose you have 55%, then, if you know, how much C3 S you
have C2 S, C3 A, C4 AF. So, you know this now and you just use the coefficients to calculate the
total heat of hydration. Is it clear?

Obviously, these coefficients will not be same. So, you see that coefficient changing, 7-day is
different from 28-day, 90 day, 1 year. In this study, they looked up to 13 years. So, basically,
this simple relationship can be used to calculate the heat of hydration. It is nothing but the
contribution from individual phases; also you see here enthalpy of the complete hydration. That
is very important.

So, for an example, there is a pure C 3 S phase that will release roughly around 517 kilo Joule per
kg (kJ kg-1 ). So, that is a number for pure C3 S. And similarly, obviously C2 S is slow in reacting.
So, you have around 262 kJ kg-1 , which means 1 kg of pure C2 S will give you 262 kilo Joule of
heat. These are pure phases. So you use these to finally calculate. Now, your Portland cement is
nothing but a mixture of C 3 S, C2S, C3 A, C4 AF.

Now you know the values for the pure phases and you know how much of these phases you
have. You can calculate the total heat of hydration. And also see here for C3 A. So, this value
1144 is for the reaction with gypsum to give mono sulphate, and 1672 is for the reaction with
gypsum to give Ettringite. You have these different reactions. We are not going in detail, but in
cement chemistry or any other class, you must have learnt the reactions.

C3 S reacts with water to give C-S-H (calcium silicate hydrate), same with C 2 S. Whereas, C3 A
reacts with calcium sulphate or gypsum to give AFt or Ettringite. Then AFt converts to AFm –
monosulphate.

It is good to know these enthalpy values for pure phases, because then if you know how much
of it is there, you will be able to calculate. Is it clear? Simply, you are basically breaking down
your system.
You are assuming that your cement is made of fo ur phases. And if you know the amount of
these phases and you know what the enthalpy of the complete reaction is, complete hydration of
pure phases you will be able to calculate total heat of hydration.
(Refer Slide Time: 15:31)

Moving on, now we know about the Portland cement hydration and what are the phases which
are of importance. Now we will focus on measuring. How do we measure? So we will focus on
primarily three types of calorimeters. Isothermal - as you can guess - Isothermal calorimeter is
used when you are interested in measuring heat at constant temperature. So, in isothermal, you
maintain the temperature.
Constant temperature is maintained between the samples and surrounding. So how do you do
it? You have cement hydration going on and you know that the cement hydration will release
some heat and that heat you can remove, to maintain the temperature. Obviously, when the
cement hydrates, the temperature will increase, because there is a heat.

If you can remove that heat, then you will be able to maintain. Now, you are measuring that
heat. The heat that you are removing from the system, you are measuring it. So that way you
are monitoring this process.

Adiabatic - In adiabatic, what do we do? No heat loss should occur between the sample and
surrounding. That is the ideal case, but usually, the heat loss is small and almost constant. We
will go over these techniques but right now just to understand these are different techniques.
Semi-adiabatic is similar to adiabatic, but only difference is heat loss is not constant, increases
with the rise in the temperature. The adiabatic your heat loss is small and almost constant. In
semi adiabatic, heat loss is not constant, it increases with the rise in temperature.
(Refer Slide Time: 17:29)

Coming back to isothermal calorimeter, we are maintaining the temperature and then measure
the heat. So, heat flow or heat production rate is measured here. How do you do it? You have a
reference sample also. So you have a sample, your sample (S) and you have a reference sample
(R). We will come back to it. So, reference sample without any heat production is also present.
We will pick a sample which does not release any heat and we are measuring the difference
basically.

So, the output is the difference between the sample signal and the reference signal. This is all
done to reduce the noise. Important point to keep in mind is, the heat capacity of the reference
sample (R) should be same as that of sample (S). That is very important. Heat capacity of the
reference should be same as should be same as that of your sample, but it should not release any
heat. So for an example, you can take quartz or water for an example, as a reference.

Also isothermal calorimeter can be used for the paste or mortars, because the amount is limited.
You can use typically 1-100 gram of sample, it is small. You are not talking about kgs, so that
is the also limitation of this technique. You can only use it for paste and mortar. And the
amount is up to 100 gram. So you finally get this power, thermal power (P), changing with T.
Thermal power tells you about the heat production rate.
This is a typical signal you get. We will convert it later. Come back to it. But idea is, you have a
reference and sample, you are measuring the difference between reference and sample.
Basically, how are you doing is, whatever heat is generated is sent to the heat sink, that heat
will cause some temperature difference.

You have a heat flow sensor. That temperature difference will lead to the voltage. So, you are
measuring the voltage. And now you have this sensor where you have voltage, you are also
measuring the current. Once you know the current and voltage, you can calculate the power, or
you can do it through current and resistance also, you know that.
(Refer Slide Time: 20:35)

So, thermal mass of the reference sample should always be similar to the thermal mass of target
- very important. Okay, so I will show you how to do it. Suppose, you want to make a paste,
you decide to add cement and water. That is how you make paste, right? And the heat capacity
of cement is, in this table, you can see 0.75 Joule per gram, per Kelvin (J/gm.K) and water is
4.18.

Suppose, you decide that you are using 3 gram of cement and 1.5 gram of water, so you can
calculate the thermal mass of this system - cement and water. How will you do it?
3 * 0.75 + 1.5 * 4.18 = 8.52 J/K
That is the thermal mass. Obviously, this will change right if you want to try different water -
cement ratio and other things, or if you want to add sand. But you can calculate what the
approximate thermal mass is.
So in this case, it comes out around 8.52 Joule per Kelvin (J/K). Now you want to keep this
same. So you want to calculate how much reference you have to use. So, suppose you decide to
use water, so what do you do? (suppose R is reference weight) so you know this is the thermal
mass here to get, and you know the capacity, so it gives you 2.04 grams of water. Simple
calculation to show you how to balance, because now you are sure that your reference and
sample have similar thermal mass.

Basically, heat capacities are similar, same. Now you are measuring the difference, whatever is
happening because of the reaction you are measuring the difference, because water is not going
to release any heat. You can use quartz also, a lot of times commonly used reference is quartz.
You can see here right. So, the thermal mass of a given material is calculated by multiplying the
mass of its specific heat capacities.
(Refer Slide Time: 23:13)

Now you know the about the isothermal calorimeter. Now, we will come back to semi-adiabatic
calorimeter. Semi-adiabatic calorimeter, what we said about semi adiabatic calorimeter is that,
you want to have the constant heat loss. It will be small, but constant. Ideally, you want to have
zero heat loss. So, simply put, your sample is insulated and the temperature increase is
measured. So, imagine you have the sample insulated, and because you want to prevent this
heat loss and you have embedded a sensor where you can measure the temperature (T). Now
the question is how do you do it? So, you measure the temperature, but the corrections must be
applied for the heat losses. You know that even though we have tried to make it completely
insulated, but there will be heat losses. So, those corrections you will have to apply and you
measure the temperature.
So, the typical output is this temperature versus time. But the advantage of this technique is that
you can use the large samples. Large samples like you can use mortar, concrete up to 10 kg. But
what is disadvantage? Anyway we will come back to it. See what happens you have made this
very insulated. Now what happens due to the reaction there will be heat release.

That heat release will increase the temperature and that increase in temperature will influence
your cement hydration, you understand. In the isothermal case, we are trying to maintain the
temperature; whatever heat is being released, we are removing it and measuring that heat. In
this case, we are measuring the temperature, this is the insulated system. So there will be
temperature rise that will affect your cement hydration.

Although you started at 20 ºC but then, as soon as it goes to 30, 40, 50 ºC, it will start affecting
your cement hydration. So, see the advantages and disadvantages. But the advantage is you can
look into the concrete, close to reality. If you are using concrete in any building structure, you
want to study how the concrete performs, like what is the interaction between cement and
aggregates, other things.
(Refer Slide Time: 25:42)

This is the final one, adiabatic calorimeter - similar to what we have seen. In this case also the,
we want to reduce the heat loss but how are we doing it? We are not insulating it completely,
but temperature of the sample surroundings is maintained at the same level. So, how we are
doing it? We know that your sample temperature due to the hydration will rise, but we are also
rising the temperature of the surrounding. So that there is no heat loss.
So the sample surrounding is maintained at the same level as that of sample, to prevent this heat
loss. So for that you may have to provide some additional heat. Suppose, cement is hydrating
and the temperature is going up to 40 or 50 °C, then you have to raise the temperature. So here
is the schematic of this. You see your sample, and you are measuring the temperature and what
else you have?

You have this thermal unit conditioning, this is your thermal jacket basically, surrounding it.
That is how you are maintaining the temperature right. And also you want to insulate the
sample so that there is no loss. But the idea is, you are maintaining the temperature of sample
and surrounding. It is also commonly used for mortar and concrete.
(Refer Slide Time: 27:22)

So this is the adiabatic calorimeter we have at IIT Madras. Now, you know the principle of
adiabatic calorimeter. You can see - this is the big water tank. Inside it, we have this sample
holder. This is a top view, sample holder looks like this. So, you put your concrete in this
sample holder and it is in the water bath. So, here you see it is in the water bath. So basically
you are sensing the temperature of your sample.

And also, then you have sensor in your water bath. And as you want to make sure that there is
not much difference between the sample temperature and your sample surrounding temperature,
you have a program controller. Controller minimizes the temperature difference between the
sample and the ambient.
(Refer Slide Time: 28:20)
Finally this is the last slide. We will start from here in the next lecture, but I just want to show
you. Here I am plotting temperature we are seeing temperature versus time, for three different
types of calorimeters isothermal, semi adiabatic, adiabatic. Isothermal - no brainer, why is it
same? Because we have made it same, so you see constant temperature. Semi-adiabatic you see
increase in temperature because you have this insulated system so there is no heat loss.

You have adiabatic, so you see the difference in adiabatic. Your Delta H (ΔH) is very small.
ΔH is very small, even at high temperature. So what happens with the semi adiabatic as you
raise the temperature, even if you go like 70 °C, your losses will also be higher. So that is why
you do not see and the question is why the adiabatic calorimeter gives you higher temperature
than semi, semi adiabatic. So we will start from this slide in the next lecture. Thank you.