Differential Scanning Calorimetry (DSC)

Prapared By Amira A-K. AlTikriti St. # 201127015

Difinition
DSC is a thermo analytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference (reference solution is usually the same buffer used in the preparation of the sample solution) is measured as a function of temperature. Both sample and reference are maintained at nearly the same temperature throughout the experiment.

In simple words: DSC is a technique used to study what happens to polymers when they're heated.

Mechanism of DSC experiment

The first step would be to heat our polymer in the DSC device.

There are two pans. In one pan (the sample pan), we put the polymer sample. The other one is the reference pan.
Then the computer turns on the heaters, which will heat the two pans at a specific rate about 10oC per minute. The computer makes absolutely sure that the heating the rate stays exactly the same throughout the experiment. But more importantly, computer makes sure that the two separate pans, with their two separate heaters, heat at the same rate as each other, because the polymer sample means there is extra material in the sample pan. Having extra material means that it will take more heat to keep the temperature of the sample pan increasing at the same rate as the reference pan. So the heater underneath the sample pan has to work harder than the heater underneath the reference pan. It has to put out more heat.

By measuring just how much more heat it has to put out is what we measure in a DSC experiment.

To do DSC measurements and get the results

On the x-axis we plot the temperature. On the y-axis we plot difference in heat output of the two heaters at a given temperature.

Heat capacity "Cp"

Heat capacity is the measurable physical quantity that characterizes the amount of heat required to change a substance's temperature by a given amount. i.e. When we put a certain amount of heat into a polymer, its temperature will go up by a certain amount, and the amount of heat it takes to get a certain temperature increase

Heat capacity "Cp"

From DSC plot we can calculate the Heat capacity "Cp" of the polymer that we used as a sample

Glass Transition Temperature ( )

When we heat the polymer a little more, after Tcapacity, plot will shift upward suddenly! This means we're now getting more heat flow.

The Glass Transition is the reversible change of the amorphous region of a polymer to a viscous or rubbery condition. The Glass Transition Temperature ( ) is a temperature taken to represent the temperature range over which the glass transition takes place.

( )
Effect of the side chain (Sample) on ( ) -H -36C -CH3 -12C -CH2(CH3) 64 C6H5 100 Cyclohexyl 120

Effect of Polymer Backbone on the Tg For -O-(CH2)n n=2 -41 n=3 -78 n=4 -84

Crystallization
Above the glass transition, And when the polymer reachs the right temperature, it will has gained enough energy to move into very ordered arrangements, which is called crystals.

-When polymers fall into these crystalline arrangements, they give off heat. -Because the polymer gives off heat when it crystallizes, we call crystallization: an exothermic transition.

Melting
If we keep heating the polymer past its "Tc", we'll reach another thermal transition, called melting. When we reach the "Tm", the polymer must start to absorb heat, its crystals begin to fall apart, the chains come out of their ordered arrangements, and begin to move around freely.

Because we have to add energy to the polymer to make it melt, we call melting an endothermic transition.

Tm
Effect of Polymer Type on Melting Class Structur Polyolefins Polyamides Polyesters Sulfides -CH -CH -CH -NH-C(O)-CH -CH -O-C(O)-CH -Ph-SMelting Range 85 - 174C 190 - 265C 220 - 270C 300 - 360C

Effect of Molecular Weight on Melting Formula Mole. Wt. "g/mol" C12H26 170 C24H50 339 C30H62 423 C35H72 493

Tm -10 54 66 75

Total heat flow: The sum of all thermal events in the sample.

-We saw a step in the plot when the polymer was heated past its glass transition temperature. Then we saw a big dip when the polymer reached its crystallization temperature. Then finally we saw a big peak when the polymer reached its melting temperature. -Because there is a change in heat capacity, but there is no latent heat involved with the glass transition, we call the glass transition a second order transition. -Transitions like melting and crystallization, which do have latent heats, are called first order transitions.

Total heat flow

- The crystallization dip and the melting peak will only show up for polymers that can form crystals. But completely amorphous polymers won't show any crystallization, or any melting either. -DSC can tell us how much of a polymer is crystalline and how much is amorphous. Because many polymers contain both amorphous and crystalline material. But how much of each? DSC can tell us.

Calculation from DSC plot

The first thing we have to do is measure the area of the big peak we have for the melting of the polymer. Our plot is a plot of heat flow per gram of material, versus temperature.

= Hm*

we can make it simpler

Now we have a number of joules per gram. But because we know the mass of the sample, so we can make it simpler.

Up to here, we just calculated the total heat given off when the polymer melted "Hm", total, If we do the same calculation for our dip that we got on the DSC plot for the crystallization of the polymer, we can get the total heat absorbed during the crystallization "Hc", total

H' is the heat given off by that part of the polymer sample which was already in the crystalline state before we heated the polymer above the "Tc".

Now we want to know how much of the polymer was crystalled before we induced more of it to become crystalline. So, we have to divide H' by the specific heat of melting, Hm* , to get the answer in grams, which we'll call "mc".

Then If we divide this number by the weight of our sample, mtotal, we get the fraction of the sample that was crystalline, and then of course, the percent crystallinity

Applications of DSC technique

The technique is widely used across a range of applications, both as a routine quality test and as a research tool. Polymers DSC is used widely for examining polymers to check their composition. Melting points and glass transition temperatures for most polymers are available from standard compilations The percentage crystallinity of a polymer can be found from the crystallization peak of the DSC graph since the heat of fusion can be calculated from the area under an absorption peak.

Liquid crystals DSC is used in the study of liquid crystals. As some forms of matter go from solid to liquid they go through a third state, which displays properties of both phases. This anisotropic liquid is known as a liquid crystalline state. Oxidative stability Using Differential scanning calorimetry to study the stability to oxidation of samples generally requires an airtight sample chamber.
Such analysis can be used to determine the stability and optimum storage conditions for a material or compound.

Food science In food science research, DSC is used in conjunction with other thermal analytical techniques to determine water dynamics.

Drug analysis DSC is widely used in the pharmaceutical and polymer industries. In the pharmaceutical industry it is necessary to have wellcharacterized drug compounds in order to define processing parameters. For instance, if it is necessary to deliver a drug in the amorphous form, it is desirable to process the drug at temperatures below those at which crystallization can occur.

Metals In recent decades this technology has been involved in the study of metallic materials. Low melting materials such as solder are easily examined for example.

References
1-Differential scanning calorimetry studies on coal. 1. Pyrolysis in an inert atmosphere. Available online 11 August 2003 http://www.sciencedirect.com/science/article/pii/0016236176900 727 2- Modulated differential scanning calorimetry http://www.springerlink.com/content/w7p2nt8g844xh236 3-A Book / Riesen R., Widmann G. and Truttmann R., Alternating thermal analysis techniques.(1996) 4-http://www.microcal.com/technology/dsc.asp 5-http://www1.chm.colostate.edu/Files/CIFDSC/dsc2000.pdf

Thank You