Differential Scanning Calorimetry

What is a DSC?
What is DSC?
Differential: measurement of the difference in heat flow from sample and reference side Scanning: the common operation mode is to run temperature or time scans

Calorimeter: instrument to measure heat or heat flow.

Heat flow: a transmitted power measured in mW

DSC working principle

Ice Ts Hot Plate

Air Tr

Heat the hot plate from -20 C to 30 C, What will happen to the ice? How do Ts and Tr react? How do the Ts and Tr relate to each other?
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DSC working principle

Temperature

Tr Ts

Tf

T =Ts-Tr 0

Time

DSC raw signal -0.5 Time or Tr

3

Tf

DSC working principle

T =Ts-Tr 0 -0.5 DSC raw signal,

Time or Tr

=T/Rth
Rth, thermal resistence of the system

Heat flow (mW) 0 -10 Tf

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DSC signal, Time or Tr Peak integral !

Baseline slope
Heat flow (mW)

= m cp
Where,

0
Initial deflection

-10 Time or Tr

m is the sample mass cp is the specific heat capacity of the sample is the heating rate

A normal DSC curve is not horizontal, its baseline shows a slope.

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ICTA and Anti-ICTA

ICTAC (International Confederation for Thermal Analysis and Calorimetry) Direction of DSC signal
ICTA (T=Ts-Tr) endothermic downwards, exothermic upwards.

mW 0

-10

-20

120
      

130

140

150

160

170

C
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Anti-ICTA ( T=Tr-Ts) endothermic upwards, exothermic downwards.



Endothermic and exothermic effects

Endothermic:
When the sample absorbs energy, the enthalpy change is said to be endothermic. Processes such as melting and vaporization are endothermic.

Exothermic:
When the sample releases energy, the process is said to be exothermic. Processes such as crystallization and oxidation are exothermic.

Exothermic effect
Temperature

Tr Ts

T =Ts-Tr

Time DSC raw signal

0 Time or Tr
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Schematic DSC curve of a polymer

exo 6 3 endo 4 5

Heat flow

Temperature

1. initial startup deflection; 2. glass transition; 3. crystallization; 4. melting; 5. vaporization; 6. decomposition.

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What is melting and crystallization?

Melting of Indium: 156.6 C, -28.6 J/g (endothermic)

crystalline

amorphous

Crystallization of Indium: 153.5 C, +28.6 J/g (exothermic)

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Melting and Crystallization with DSC

^exo
mW

prod 1

13. 03.2006 13:58:29

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In: 6.18 mg 10 K/min

Integral 194.27 mJ normalized 28.57 Jg^-1 Onset 153.43 C

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Integral -193.95 mJ normalized -28.52 Jg^-1 Onset 156.58 C

-10

140

145

150

155

160

165

MSG2006: Marco
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TA Re SW 9. 01 S TAR

How to evaluate melting peaks

Pure materials: - onset (independent of heating rate) - Hf baseline: line, integral tangential Impure materials: - peak temperature (depends on ) - Hf baseline: line, tangential right - purity analysis for eutectic systems (based on curve shape analysis) Polymers - peak temperature (depends on and m) - Hf baseline: line, spline, integral tangential
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What is glass transition?

Glassy state Glass transition Rubbery state

amorphous solid, rigid, brittle

liquid (non polymers) rubber like (polymers)

Glass transition is cooperative molecular movement.

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The glass transition with DSC

cp

1 dH cp = m dT
Temperature

= m cp

exotherm

Temperature
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Chemical reaction
A chemical reaction is a process that one or more substances (reactants) are converted to one or more new chemical substances (products) with different properties. e.g. oxidation, decomposition, polymerization etc.

Chemical reactions always involve a change in energy. Depending on whether the energy is absorbed or released during the process, they can be endothermic or exothermic.

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Chemical reaction

Homogeneous decomposition of dibenzoyl peroxide; peak temperature and peak shape depend on heating rate; peak area is independent of heating rate.
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Where to use DSC?

Polymers Pharmaceuticals Chemicals Food Cosmetics

Materials Additives Plasticizers Impurities Fillers

Material Properties

Processing Thermal treatment Mechanical stressing Shaping Storage and use

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DSC
Resolution and Sensitivity Multiple Thermocouples increase sensitivity and reduce noise For Best Resolution: Low signal time constant e.g 1.7 s (20- L Al crucible, N2 gas) High baseline stability using chemically resistant ceramic substrate and relatively inert silver furnace
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Sensor technology

Temperature gradients on the sensor lead to baseline deviation from zero

TSR

T0

A single sensor temperature (T0) is measured. Inhomogeneous temperature distribution of the sensor is not considered.

TS0 TR0

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Sensor technology
TS S R

TS TS0

TR TR0

Inner ring of thermocouples measure TR and TS Outer ring measures sensor temperatures at reference and samples sides, TS0 and TR0 Thermocouples act as thermal resistence, R.
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Sensor technology
TS S R

S0 =
R0 =

N i =1
N i =1

TS ,i TS 0 ,i Ri
TR ,i TR 0 ,i Ri

TS TS0

TR TR0

dq = S 0 R0 dt

Heat flow on the sample and reference sides are separately measured N is the number of thermocouples (TC) per ring.
FRS5 sensor (56 TC): N = 14
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HSS7 sensor (120 TC): N = 30

Noise and sensitivity

Lysozyme dissolved in 0.1 M HCl/glycine buffer at pH = 3 Heating rate 3 K/min Sample Mass around 105 mg

Step 0.69 uW

1.7 % Lysozyme 100 uW 5 uW

0.1 % Lysozyme

Peak Height 137 uW

Peak Height 6.5 uW

60 50 60 70 80 90 C 18

65 20

70 22

75 24

80

C min

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Noise and sensitivity

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Resolution

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Signal time constant

How long does the system take to equilibrate? How fast does the signal come back to the baseline? Small Signal better resolution

Signal = RthCs,

Cs = Cpan+ Csample+ Csensor

FRS5 sensor (Rth 0.04 K/mW) & Al40 l (50 mg) Cpan Csample (10 mg, 1.5 J/gK) Csensor 50 mJ/K 15 mJ/K 10 mJ/K => Signal 3 s

FRS5 sensor (Rth 0.04 K/mW) & Al20 l (20 mg) Cpan 20 mJ/K
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=> Signal 1.8 s

Signal time constant

How to improve Signal?
Cs can be strongly influenced by the choice of the pan. Recommendations for better resolution:
-> Al20 ul pan instead of Al40 ul pan -> Al pans instead of alumina pans

Cs can be reduced by using smaller sample size Signal can be further decreased by using He as purge gas.
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Cooling behavior
250 200 150

Air cooled Intracooler Liquid nitrogen

Temperature [ C]

100 50 0 -50 -100 -150 0 5 10 15 20 25

Time [min]

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