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Thermal Analysis
Thermal Analysis
INTRODUCTION:
THERMAL ANALYSIS: A number of physical and chemical effects can be produced
by temperature changes, and methods for characterizing these alterations upon heating or
cooling a sample material are referred to as thermal analysis.
The physical and chemical changes a sample undergoes when heated, are characteristic of the
material being examined. By measuring the temperature at which such reactions occur and
the heat involved in the reaction, the compounds present in the material can be characterized.
The majority of known inorganic compounds have been so characterized. The physical and
chemical changes that take place when unknown sample is heated provide the information
that enables the identification of the material. These changes also indicate the temperature at
which the material in question ceases to be stable under normal conditions.
Common methods of thermal analysis are DSC, DTA, TGA, and TMA.
vs temperature
9 Electrical conductivity Electrometer or Current(I) or I or R vs
(EC) Bridget Resistance(R) temperature
THERMAL EVENTS:
DSC is most often used thermal analysis method, primarily because of its speed, simplicity
and availability.
PRINCIPLE:
The difference in heat supplied to the sample, and the reference material per unit time
is recorded and plotted as dH/dt vs the average temperature to which the sample and
reference to be raised.
COVENTIONAL DSC:
OUTPUT OF DSC:
Glass Transition
Thermogram
Step in ther mogram
Tr ansi ti on from
disordered soli d to
dH/dt, mJ/s
Tem perature, K
Crystallization Melting
Thermogram Thermogram
Sharp positive peak Negative peak on
Disordered to ordered thermogram
transition Crystallization Ordered to disordered
dH/dt, mJ/s
Melting
Material can crystallize!
dH/dt, mJ/s
transition
Observed in glassy Tm, melting temperature
solids, e.g., polymers
Tc
Tc, crystallization
NB: melting happens Tm
temperature
to crystalline polymers;
glassing happens to
Temperature, K amorphous polymers
Temperature, K
Principle:
The introduction of a controlled heat leak between the sample and reference holders enabled
a quantitative measurement of energy changes to be made. Heat flux can be measured
directly if a sample is surrounded by a thermopile.
The peak area is related to the enthalpy change by a calibration factor which is partially
temperature dependent.
Sample holder: sample and reference holders are connected by a low resistance heat flow
path. The material with which the sample holder is made may be aluminium, stainless steel,
platinum.
Sensors: temperature sensors are thermocouples.
Furnace: same block is used for sample and reference.
Temperature controller: temperature difference between sample and reference is measured.
A metallic disc made of constantan alloy is the primary means of heat transfer. Sample and
reference sit on raised constantan discs.
Differential heat flow to sample and reference is measured by thermocouples which are
connected in series, located at the junction of constantan disc and chromel wafers.
With this, it is possible to achieve heating or cooling rates of 100 0 c /min to 00 c /min
(isothermal).
It needs mathematical equations to get the heat flow.
S no ASPECT DS C DTA
nd
4 It can be observed with a It is not observed
2 order phase
sample of 200mg
transition
INSTRUMENTATION:
This instrument works on the temperature control of two similar specimen holders
SAMPLE PREPARATION:
It is possible to use materials which creep, froth or boil if sealed sample sample containers
are used to ensure no damage occurs to the sample holder assembly.
Accurately weighed samples (approx 3 to 20 mg) are encapsulated in the metal pans of high
thermal conductivity.
Small pans of inert treated materials (aluminium, platinum, stainless steel) are used.
Pan configurations may be open, pinhole or hermetically sealed. Same pan material and
configuration for both sample and reference.
Material should entirely cover the bottom of the pan to ensure thermal contact. Avoid
overfilling of the pan to minimize the thermal lag from the bulk of the material to the sensor.
Small sample masses and low heating rates improve resolution but at the expense of
sensitivity.
DONOT DECOMPOSE THE SAMPLES IN DSC CELL
SAMPLE SHAPE:
Cut the sample to uniform shape, do not crush the sample.
If the sample to be taken is pellet, cross section is to be taken.
If the sample material is powder then, it is spread uniformly over the bottom of the sample
pan.
USING SAMPLE PRESS:
When using crimped pans, the pans should not be over crimped.
The bottom of the pans should remain flat, even after crimping.
When using hermetic pans, a little more pressure is required to crimp the pans.
Hermetic pans are sealed by forming a cold wield on the aluminium pans.
SAMPLE SIZE:
Smaller samples will increase the resolution but will decrease the sensitivity.
Larger samples will decrease the resolution but will increase the sensitivity.
Sample size depends on the type of material being measured
If the sample is –
Extremely reactive in nature – very small samples (<1 mg) are to be taken.
REFERENCE MATERIALS:
An inert material like α-alumina is generally used.
Empty pan can also be used, if the sample weight is small.
With higher sample weights it is necessary to use a reference material, because the total
weight of the sample and its container should be approximately the same as the total weight
of the reference and its container. The reference material should be selected so that it
possesses similar thermal characteristics to the sample.
The most widely used reference material is α-alumina, which must be of analytical reagent
quality. Before use, α-alumina should be recalcined and stored over magnesium perchlorate
in a dessicator.
Kieselguhr is another reference material normally used when the sample has a fibrous nature.
If there is an appreciable difference between the thermal characteristics of the sample and
reference materials, or if values of ∆T are large, then dilution of the sample with the reference
substance is sensible practice. Dilution may be accomplished by thoroughly mixing suitable
proportions of sample and reference material.
PURGE GASES:
Sample may react with air and may oxidize or burn. The problem is overcomed by using inert
gases.
Inert gases are used to control moisture in the surrounding atmosphere. Commonly used inert
gases are nitrogen, helium, argon etc.
Inert gases should ensure even heating and helps to sweep away the off gases that might be
released during sublimation or decomposition.
Nitrogen:
It is the most commonly used inert gas.
It increases the sensitivity of the experiment.
Typical flow rate is 50 ml/min.
Helium:
It has high thermal conductivity.
It increases the resolution of the peaks.
• Heating/Cooling rates
• Sample mass
• Processing errors
MODULATED DSC:
It is introduced in 1993and also developed by TA instruments. It uses heat flux DSC design
but a different furnace heating profile.
62 62
60 60
56 56
54 54
Benefits
APPLICATIONS:
1) Determination of crystallinity in a polymer:
DSC evaluation can be used to measure amount of crystallinity in the sample. Let the heat of
crystallization be Hc and total heat given off during melting be Ht.
H=Ht-Hc……(1)
where H is the heat given off by that part of polymer, which was already in crystalline state.
Now by dividing H by Hc (specific heat of melting)
Where Hc is the amount of heat given off when 1gm of polymer is melted.
H/Hc=joules/joules/gram=Mc grams
This is total amount of polymer that was crystalline below Tc, crystallization temperature.
So % crystallinity in polymer sample=Mc/Mt *100
Where Mt is total mass of sample taken.
The determination of purity by means of DSC is based on the assumption that impurities
depress the melting point of pure material according to the eutectic phase diagram behavior.
It is well known that the higher the concentration of impurity present in the sample, the lower
its melting point and broader its melting range. The obtained by DSC includes the complete
melting curve and the latent heat of fusion (∆Hf) of the sample. The interpretation of the DSC
chamber, hence the solidification process is very rapid & results in the first instance in
spherical or near sphere particles.
Consequently spray drying may result profound changes to the physical properties of the
material compared to the unprocessed solid form, both in terms of morphology & lattice
structure. In particular spray dried products may be partially or completely amorphous or
alternatively may result in the generation of a range of polymorphic forms.
Ex: spray drying of phenobarbitone from ethanolic solution.
Digitoxin (90); diacetylmide camycin (91) & thiazide diuretics (92).
In particular, spray dried products may be partially or completely amorphous or,
alternatively, may result in the generation of a range of polymorphic forms.
Example of the latter include a study on the spray drying of phenobarbitone from ethanolic
solution, reporting the generation of a material that showed characteristics of the Form 111
polymorph after processing in contrast to the commercially available Form 11.
However, the majority of DSC studies on spray-dried systems have focused on the generation
of amorphous material from the process. DSC can be used to study the number and
temperature range of polymorphs, since each polymorphic transition causes an energy change
that may be detected by DSC.
4) 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 or mesomorphous state. Using DSC, it
is possible to observe the small energy changes that occur as matter transitions from a solid to
a liquid crystal and from a liquid crystal to an isotropic liquid.
CONCLUSION
Differential scanning calorimetry is extremely versatile and able to address a wide
variety of analytical problems.
It is often used in conjunction with TG to obtain better results.
Widespread study of thermal properties on an extensive range of sample types can be
done.
REFERENCES
K.Sravya, pharmaceutics, NCOP Page 19
DIFFERENTIAL SCANNING CALORIMETRY
CONTENTS
S NO TOPIC PAGE NO
1 Introduction 1
2 Principle 4
3 Output of DSC 7
4 Types of DSC 8
5 Comparison of DSC and DTA 10
6 Instrumentation 11
7 Factors affecting Thermogram 14
8 MDSC 15
9 Applications 16
10 Conclusion 19
11 References 20