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APPLICATIONS OF DTA & DSC

Application of the DTA/DSC methods are very wide and can be divided
into two categories:

(a) Measurement of physical (b) Measurement of chemical reaction:


properties changes:
 dehydration
 melting  decomposition
 crystal phase changes  polymer curing
 changes in the conditions of  glass formation
liquid and liquid crystal  oxidation reaction
 changes in the physical
properties of polymer
 phase diagram
 heat capacity
 glass transition
 thermal conductivity
 diffusivity
 emissivity

Lecture 7 Application DTA & DSC 01 1


AP
PLI
CA
a) Determination of Changes in Physical Properties T IO
NS
O FD
TA
Melting and ∆ Hfusion of Materials & DS
C
 Determination of melting point may be easier by using a simple apparatus, but
determination of ∆ H of a fusion process is more complicated.
 Although DTA may give the value of melting point (Tm) accurately, the ∆ H need to
be determined by using a DSC method.

∆ H = K ∫∆ T dt = K . (peak area)

Figure 7.1 DSC peak for the melting of pure indium


(Source: Haines: F_3.11)

Lecture 7 Application DTA & DSC 01 2


AP
PLI
CA
T IO
NS
O FD
CRYSTAL PHASE TRANSITION TA
& DS
C

The crystal shapes of a material may influence some properties of the material,
such as solubility, density and the electrical properties.

a) Polymorphic : materials that have more than two shapes of crystal.

b) Enantiotropic : shapes system of a material that are stable in certain


range of temperature and have specific transition
temperature.

c) Monotropic : only one shape of the crystal is stable throughout the


temperature range, while the other shapes are meta-
stable. The shapes that are less stable tend to transform
into the more stable shapes.

Lecture 7 Application DTA & DSC 01 3


APPL
I CATI
ONS
Potassium Nitrate, KNO3 (Haines: F 3.12) OF D
TA &
DSC

Heating - phase II to phase I at 128 oC Cooling - the exothermic peak at 120 oC with
and ∆ H = 5.0 kJ/mole ∆ H = -2.5 kJ/mole
- melting of phase I at 334 oC - formation of another phase
with ∆ H = 10 kJ/mole (phase III)
- at lower temperature, it slowly
returns to phase II

Figure 7.2
DSC curve for
potassium nitrate
(4 mg, 5 K/min,
nitrogen)
(Source: Haines: F
3.12)

Lecture 7 Application DTA & DSC 01 4


AP
PLI
CA
Ammonium Nitrate, NH4NO3 (Haines: Figure 3.13) TIO
N OF
DTA
& DS
It is widely used as components of fertilizers and explosives C

Transition from phase IV


(rhombic II) to phase III Explosion of NH4NO3 at a
(rhombic I) produces an temperature around 200
endothermic peak at 40 oC o
C as shown by a large
exothermic reaction
Transition from
phase III to phase
II (tetragonal) with
a small
endothermic peak
at 80 oC Figure 7.3
DTA curve for ammonium nitrate
(Source: Haines: F 3.13)

Melting at 170 oC
Transition from phase II to
phase I (cubic) at 120 oC

Lecture 7 Application DTA & DSC 01 5


POLYMORPHISM IN FOODS

Polymorphism is important in Example:


food because it influences Glycerides (glycerol esters) :
the properties of the food CH2OH.CHOH.CH2OH
materials in terms of:
which show three phases:
 Solubility β shape – the most stable with the highest
 Physiological activities melting point
 Stability β ’ shape – a meta-stable shape
 Bioavailability α shape – the most unstable shape with
the lowest melting point
The DSC is widely used in
the study of polymorphism If the liquid is cooled to a temperature several
changes in the mixtures of degrees above the melting point of α shape and
fats in confectionery and the then allowed to remain at the same temperature
characterization of fats and for sometime until crystallization takes place, the
oils. β ’ shape will be formed.

Heating of β ’ shape will produce a partial melting of β ’ shape, followed


by conversion to β shape and melting of β shape as shown by the
dotted line (Figure 7.4)

Lecture 7 Application DTA & DSC 01 6


If the liquid is cooled to a temperature
several degrees above the melting point of
Solid line: first heating α shape and then allowed to remain at the
same temperature for sometime until
crystallization takes place, the β ’ shape
Conversion and will be formed.
crystalization of
β polymorph that Dotted line: second heating
is stable at 60 oC from 57 oC

Melting of α
shape at 54 oC
Melting of
β shape
at 73 oC
Heating of β ’ shape will produce a partial melting
of β ’ shape, followed by conversion to β shape
and melting of β shape as shown by the dotted
line

Figure 7.4 DSC curve of trystearin (gliceryl trystearate) : 4.3 mg, 5 K/min, nitrogen
(Source: Haines: F 3.14)

Lecture 7 Application DTA & DSC 01 7


Polymorphisme in Pharmaceutical Materials

Norfloxacin : Full characterization would require the use of DSC


the derivative of and other analytical instrumentation such as TG,
4-quinolone XRD and spectroscopy
carboxylic acid
 Two forms of norfloxacin: form A
and form B
 They show different anti-microbe
activities
 Obtained from different sources

The form B  Transformation of Form B (to form


experienced A) is not seen when heating is
transition (to Form repeated showing that the
A) at 195.6 ± 0.2 oC material is monotropic.
with ∆ H = 20 J/g
(varies with the Figure 7.5 DSC curve for the two
heating rate)
forms of polymorphic norfloxasin (10
The Form A melts at K/min, nitrogen (Haines: F 3.15)
219.5 ± 0.2 oC with ∆ H
= 115 J/g

Lecture 7 Application DTA & DSC 01 8


Transition of Liquid Crystals:
Liquid crystals:
Digital Display...Liquid Crystal Display
The molecules have:
rod-like structure
polar end groups
highest order in the solid form
various degrees of order in the liquid form:
 various smectic phase, having plane like order
 nematic phase, having rod-like order
 cholesteric phase, these are the twisted nematic
 Isotropic phase, these are liquid of complete disorder

 For the order changes in the liquid crystal transition, a greater entropy change is
observed if disorder increased
 Since ∆ S = ∆ H / T the enthalpy change, ∆ H is greater if a large change of
order takes place

Lecture 7 Application DTA & DSC 01 9


Nematic liquid → True liquid

 The first transition at 119 oC has a large ∆ H because


the material is transformed from a high order crystal
phase into a disorder nematic liquid phase
 The second (smaller) transition takes place at 135 oC
when the material changes into a true liquid.

Nematic crystal → Nematic liquid

Figure 7.6 DSC curve for p-azoxianisol (15 mg, 16 K/min,


static atmosphere) (Source: Haines: F 3.16)

p-azoxianisol: CH3.C6H4.N=NO.C6H4.OCH3
Lecture 7 Application DTA & DSC 01 10
 When all crystal phases have been
A. High order solid crystal phase at below 100 oC
B. Peaks indicate the smectic phase changes formed and the material is cooled down to
between 120 - 205 oC 80 oC, two exothermic peaks are
C. Stable nematic liquid crystal above 205 oC observed between 110 - 80 oC.
 These are changes from the nematic
liquid crystal phase to the smectic and
from the smectic to the high order solid
phase

A
B C
Solid
crystals

Figure 7.7 The DSC curve for N,N’-bis(4-octyloxibenzilydene)-p-phenylene diamine


(OOBPD) (9 mg, 10 K/min, nitrogen) (Source: Haines: F 3.17)
Lecture 7 Application DTA & DSC 01 11
PHASE DIAGRAM

When more than one chemical components can co-exist


 the thermodynamic will become complicated, and
 the melting behaviour will become more complex.

The cooling curve


 Plot of T versus time for a mixture while it is being cooled from its melting
temperature
 It is the traditional method in the investigation of changes in a mixture of
phases.

DTA/DSC
 It gives a lot of information about the sample
 The process is much faster than the traditional method
 The sample size is smaller than the traditional method provided that
heating is carried out at a very slow rate (less than 10 K/min)

Lecture 7 Application DTA & DSC 01 12


Figure 7.8
EUTHECTIC POINT Euthectic phase diagram
(Source: Haines: F 3.18)

 When a pure solid A, completely


insoluble in the pure solid B, the
presence of B reduces the
freezing point of A, producing a
diagram as shown in Figure 7.8.
 The lowest temperature where
the liquid phase can exist is
known as euthectic point, TE.

 Below the euthectic point various


mixture of crystals A and B can
be found

 When the temperature gets higher than PQR (Figure 7.8), the mixture begins to melt and an
endothermic DSC peak is obtained, the size of which depends on the amount of the crystal that
is melting at that temperature
 If the euthectic composition is closer to the composition of Q, the TE peak will become larger
 The mixture will slowly and continuously melt until it reaches the liquid line of UQW (Figure 7.8)
where the last fraction will melt. This is shown as the last peak in the thermogram.

Lecture 7 Application DTA & DSC 01 13


If A and B have a very similar structure, for example, cube shape crystal, they will
form solid solution, where the crystal structures mix and there is an apparent
intermediate crystal lattice between the structure A and the structure B.

This will produce a phase diagram as shown in Figure 7.9 or Figure 7.10.

Figure 7.9
Phase diagram of a
series of solid solution
(Source: Haines F 3.19)

Lecture 7 Application DTA & DSC 01 14


Figure 7.10 Phase diagram for a partially miscible system of
solid α and solid β (Source: Haines F 3.20)

Lecture 7 Application DTA & DSC 01 15


Euthectic system produces two DTA peaks
Figure 7.11
An overlap of the
euthectic phase
U diagrams and the
W DTA curves
(Source: Haines F 3.21)

When the temperature gets


higher than PQR (Figure
7.8), the mixture begins to
melt and an endothermic
DSC peak is obtained, the
P Q R size of which depends on
the amount of the crystal
that is melting at that
temperature

The mixture will slowly and continuously melt


If the euthectic composition is closer until it reaches the liquid line of UQW (Figure
to the composition of Q, the TE peak 7.8) where the last fraction will melt. This is
will become larger shown as the last peak in the thermogram.

Lecture 7 Application DTA & DSC 01 16


Solid solution system produces single broad DTA peaks

Figure 7.12
An overlap of solid solution
phase diagram and the DTA
curves (Source: Haines F 3.22)

 A partially miscible system (Figure 7.10) produces both DTA thermograms (two peaks
and single broad peak)
 The phase diagram becomes more complicated when components are interacting to each
other.
 The DSC/DTA systems have been widely used for the study of phase diagrams for metals,
liquid crystal and pharmaceutical materials.
Lecture 7 Application DTA & DSC 01 17
COMPATIBILITY OF PHARMACEUTICAL MIXTURES

 Compatibility refers to situation where  If the drug reacts with the diluent
two components of a pharmaceutical component, the shape of the
dose can be mixed without any mixture thermogram would be
interaction to each other as long as the different from both the original
shelf life duration of the dose has not respective thermograms.
expired.

 Each pharmaceutical dose normally  This means that any changes or


contains a drug active component appearance of new characteristics
together with other inactive materials of the thermogram curve would
as the diluent, binder or dispersant. indicate that there is some
Any chemical or physical interaction interaction between the mixtures
between these components will affect (Figure 7.13).
the pharmaceutical properties of the
mixture.
 E.g.: mixture of stearic acid with
pheniciline shows similar changes
obtained by DSC method and
stability test for 8 weeks at 50 oC.

Lecture 7 Application DTA & DSC 01 18


Figure 7.13
DTA thermograms of
materials compatibility
(Source: Haines F 3.23)

Mixture of glycerides show euthectic behaviour, but this behaviour changes


in the presence of ketoprophene.

Lecture 7 Application DTA & DSC 01 19


 Sometimes alteration in the
treatment of the materials may
change the mixture stability as
shown by the mixture of the drug
trimethoprim (TMP) with the liquid
diluent consisting of the cross-
linked polyvinylpirolidone (PVP-XL):
 shows thermogram
characteristics similar to
those of the original
 shows different thermogram
characteristics when the
mixture is ground.

Figure 7.14
The DSC curve for
(a) PVP-XL,
(b) TMP,
(c) physical mixture of 75 % PVP-XL / 25 %
TMP,
(d) ground mixture 75 % PVP-XL / 25 %
TMP
(Source: Haines F 3.24)

Lecture 7 Application DTA & DSC 01 20


PHASE CHANGES IN THE THERMOPLASTIC POLYMERS

Polymers that melt before


they decompose might be: (B)
 transformed into crystals
completely or
 retained as amorphous
inhomogeneous solid or
 a glass

When heated, the changes of


glass like polymer into a plastic (A)
like polymer can be seen
through an increase in the heat (C)
capacity (A). This process is
called Glass Transition.

The polymer molecules can now


move more freely and rearranged
again to become a tidier crystal Figure 7.15
structure. This process is exothermic The DSC curve to show changes in poly(ethylene
(B). terefthalate), PET, (10 mg, 10 K/min, nitrogen)
(Source: Haines F 3.25)
Finally, the polymer melts within a wide
range of temperature to become liquid (C).

Lecture 7 Application DTA & DSC 01 21


Some polymers show multiple endothermic melting processes, meaning that the
relevant portion of the sample had crystallized at different temperatures during the
previous heat treatment applied to the sample

Polymer samples normally do not perfectly crystallize simultaneously.


The percentage of crystallization can be determined by comparison of the
thermogram peak area of the sample with that of a polymer standard of known
crystality.

Area of the sample melting peak x (% standard)


% crystallization =
Area of the standard melting peak

The components of a polymer blend might be melting at different temperatures and


these could be use to determine each of the components, qualitatively as well as
quantitatively.

Lecture 7 Application DTA & DSC 01 22


DETERMINATION OF HEAT CAPACITY

Heat Capacity (Cp,s J/K) is defined as


the amount of heat required to raise Cp,s = (∂qs / ∂T)p
the temperature of a body by 1 K.
Cp,s = K . Δy / (dT/dt)
Heat Capacity is an important
parameter in the industrial polymers,
insulators and construction materials Where K = the calorimetric sensitivity,
determined by calibration

In a DSC system, the y-axis is Calibration is normally carried out using


calibrated as the integration of the sapphire, i.e. pure crystal of Al2O3 of known
supplied heat, or the Δenergy or
Heat Capacity.
(dΔq/dt). Since heating (dT/dt) is at a
constant rate, deviation from the y-
axix baseline without the sample Larger deviation from the baseline is
divided by the rate of heating will give observed when heating rate (dT/dt) is
the difference in the heat capacity of increased.
the sample.

Lecture 7 Application DTA & DSC 01 23


Heat capacity of sapphire (Al2O3) at
445 K is 0.997 J/(K g). Using data
from Figure 7.16, determine the
heat capacity (Cp) of polyethylene
(PE). Heating rate is 20 oC/min.

Cp (sapphire) = 0.997 x 133.6 x 10-3


= 0.1332 J/K
Δy (sapphire) = 75.0 mm
Cp (sapphire) = (K x 75)/20
= 0.1332
Hence, K = 3.552 x 10-2 J/(min mm)
For PE: Δy = 34 mm
Therefore,
Cp(PE) = (3.552 x 10-2 x 34) / 20
= 0.0604 J/K
PE mass = 23.14 mg
Cp(PE) = 23.14 x 0.0604
= 2.609 J/(K g)

Figure 7.16 DSC curve for the measurement of


heat capacity of a polyethylene (PE) melt (Source:
Haines: F 3.26) Lecture 7 Application DTA & DSC 01 24
GLASS TRANSITION TEMPERATURE
When a materiaql is heated, a small increase in
At temperatures below the glass volume and energy until Tg is reached where the
transition, Tg, the polymer polymer chain becomes more mobile and the
molecules do not have enough polymer behaves like plastics or rubber.
energy to rotate or rearrange.
Further heating leads to the crystallization and
Materials under this condition is
melting processes
like glass and brittle.
Direct cooling from the melting will
Figure 7.17 cause some portion of the polymer to
The energy transition scheme crystallize at temperature Tm.
for materials undergoing glass
formation (Source: Haines: F 3.27) At Tg, the heat capacity increased due to
increase mobility of the polymer chain.
Hence, ΔCp and the expansion of the
sample appears to increase.
Tg is phenomenon that depends on time.
Polymer may slowly changes in shape
(distort) at lower temperature and
appears brittle under a sudden bent.
Although Tg can be determined under
certain range of equilibrium temperature,
the value depends on the heating and
cooling rate used in the DSC system.

Lecture 7 Application DTA & DSC 01 25


Figure 7.18 The DSC curves to show glass transition of several polymers (20 mg,
10 K/min, nitrogen). PVC = poly(vynil chloride), PS = polystirene, EP = cured epoxy
resin, PC = polycarbonate (Source: Haines: F 3.28).

Lecture 7 Application DTA & DSC 01 26


A sample that has been cooled at a
low cooling rate (0.1 K/min)
undergoes Tg at 80 oC. If the
sample is, then heated up at a high
heating rate (20 K/min), it will not
under glass transition until the
temperature reaches 85 oC. This
means that the sample must have
absorbed more energy to become
rubber-like material. As a result, an
Glass transition with
endotherm is observed overlapping
an endothermic with the glass transition step as
phenomenon shown in Figure 7.19.

While the rate of heating and cooling must


be stated, Tg also depends on the :
• molecular weight
Figure 7.19 The DSC curve for polystyrene • degree of cure
that has been cooled at the rate of 0.2 K/min • amount of plastisizer
and then heated up at a rate of 5 K/min
(Source: Haines F 3.29)

Lecture 7 Application DTA & DSC 01 27


NEASUREMENT OF PURITY Assumption: two effective components that will produce an
euthectic phase (Figure 7.20). When A is not pure and
Purity test is very important in the contains a small amount of impurity, B (xB mol %), the van’t
industry such as pesticides, pure Hoff equation shows that the freezing point will reduce from
organics and metals,. T0,A for pure A to Tm, the melting temperature of the mixture.
Although the mole fraction of B is small and
ΔT = (T0,A – Tm) = (RT 20,A / ΔHfus,A ) . xB ΔT is also very small the DSC curve of
impure material is broader than the pure
sample due to gradual melting of the impurity
concerned.
The phase line can be considered almost linear and a
similar triangle can be constructed as shown in Figure 7.20.
Since melting starts from the euthectic point, the line
PQR can be divided into solid : liquid ratio as follows:
Liquid fraction / solid fraction = PQ / QR or Melting fraction, F = PQ / QR
From the similar triangle concept, a ration on the y-axis is obtained:
F = (T0,A – T) / (T0,A – Tm) = (T0,A – T) / ΔT
Replace into the van’t Hoff eqn.: (T0,A – T) = (1/F) . (RT 20,A / ΔHfus,A ) . xB

Rearranged: T = T0,A - (1/F) . (RT 20,A / ΔHfus,A ) . xB The plot of temperature


versus (1/F) will
produce a straight line
with the slope, b
Figure 7.20 The portion of the depends on xB, T0,A
Euthectic Phase diagram that is close and ΔHfus,A .
to the Pure A (Source: Haines: F 3.30) Lecture 7 Application DTA & DSC 01 28
The effect of thermal lag on
the temperature, T can be
corrected in two ways:

1. Using the software of the DSC system, or


2. Using the measurement of the DSC peak for pure indium (Figure 7.21)

Figure 7.21 DSC peak for the melting of pure indium


(Source: Haines: F_3.11)

Lecture 7 Application DTA & DSC 01 29


From the DSC curve (Figure 7.22) The eqn. F = a/A should give a straight line.
that was obtained using the However, non-linear relationship is obtained due
lowest heating rate, the ΔHfus,A to several factors:
and T0,A can be estimated and the
portion of the sample that has
melted at the temperature T oC is 1. disregard of any pre-melting factor prior to
obtained from the ratio of the area the measurement of the peak area;
a (up to the temperature T oC) 2. non-equilibrium conditions, due to the
divided by the area of the peak, A. dynamic of heating;
3. the formation of solid solution.
The melted fraction, F = a/A

Correction for these factors may be


carried out in two ways:

a) Using an addition factor, da, or


Figure 7.22
DSC curve for an
b) Removal of non-equilibrium effects
impure material showing
the measurement of the
by using discrete steps of heating
related area and melting
temperature correction
(Source: Haines: F 3.31)

Lecture 7 Application DTA & DSC 01 30


Correction for factors leading towards non-linear relationship of the
equation F = a/A:

a) Using an addition factor, da b) Removal of non-equilibrium effects by


using discrete steps of heating
F´ = (a + da) / (A + da)
 If the heating steps of less than 1 K is used and
and the system is then allowed to achieve an
ΔHfus,A = K . (A + da) equilibrium, peaks of equal areas will be formed
until melting begins to take place.
This can be related to the  The peak size will increase until the melting has
corrected van’t Hoff equation for been completed.
the solid solution
 The total sum of the peak areas, after correction
ΔT ´ = (1 – k) · (RT 20,A / ΔHfus,A ) . xB for the heat capacity, will give the value of a and
A.

where k = the distribution


constant in the solid
solution

Lecture 7 Application DTA & DSC 01 31


Example:

A sample of pesticide (MW = 365) is melted in a DSC system at the rate of


1 K/min and the results are as follows:

A = 10.5 cm2

K = 10.0 mJ/cm2

T (K) a (cm2) F
427 1.78 0.170
428 2.31 0.220
429 3.21 0.306
430 4.58 0.436
431 6.33 0.603

Calculate the values of T0,A , ΔHfus,A , xB

Lecture 7 Application DTA & DSC 01 32


The plot of T versus 1/F produces curves that meet/cross on the axis at T
= 434 K (Figure 7.23)

Figure 7.23
Plot of T (K) versus 1/F and the
corrected 1/F.
(a) without correction,
(b) 5 % correction,
(c) 10 % correction,
(d) 19 % correction.
(Source: Haines: F 3.32 )

Lecture 7 Application DTA & DSC 01 33


The data can be treated as follows:

1. Continue to add small amount of 2. The plot of (1/(T – T)) versus F


0,A
a and A until a straight line is
the slope = k
obtained
If the equation is rearranged, it is found that
The consecutive additions of 0.5 cm to2 the plot of 1/(T0,A – T) versus F gives a straight
the area results in the best straight line line with the slope of (ΔH / RT20,A ) / xB and the
when the correction is about 2.0 cm2 intersection is related to the correction of k. If
and this give a total sum of corrected T0,A = 434 K, then xB = 0.028 and the purity is
areas to 12.5 cm2, and the corrected 97.2 %.
ΔH to 15.2 kJ/mole and the slope –2.2
which gives the value of xB = 2.1 mole
% (97.9 % A purity)

3. Carry out regression analysis to the curve

This is the best method which will give the


correction factors of 0.163 and the purity of 97.9 %.

Lecture 7 Application DTA & DSC 01 34