Differential Scanning Calorimetry

Stephen Collins

Definitions
A calorimeter measures the heat into or out of a sample. A differential calorimeter measures the heat of a sample relative to a reference. A differential scanning calorimeter does all of the above and heats the sample with a linear temperature ramp. Endothermic heat flows into the sample. Exothermic heat flows out of the sample.

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DSC: The Technique

Differential Scanning Calorimetry (DSC) measures the temperatures and heat flows associated with transitions in materials as a function of time and temperature in a controlled atmosphere. These measurements provide quantitative and qualitative information about physical and chemical changes that involve endothermic or exothermic processes, or changes in heat capacity .

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Conventional DSC
Sample
Metal 1 Metal Metal 2 1

Empty
Metal 2

Sample Temperature

Reference Temperature

Temperature Difference = Heat Flow

A linear heating profile even for isothermal methods

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What can DSC measure?

Glass transitions Melting and boiling points Crystallisation time and temperature Percent crystallinity

Heats of fusion and reactions

Specific heat capacity Oxidative/thermal stability Rate and degree of cure Reaction kinetics Purity

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DSC Thermogram

Heat Flow -> exothermic

Crystallisation

Cross-Linking (Cure)

Oxidation

Glass Transition

Melting

Temperature
6

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Example DSC - PET

Sample: PET80PC20_MM1 1min Size: 23.4300 mg Method: standard dsc heat -cool-heat Comment : 5/4/06 1.5

DSC

File: C:...\DSC\Melt Mixed1\PET80PC20_MM1.001 Operator : SAC Run Date : 05-Apr-2006 15:34 Instrument : DSC Q1000 V9.4 Build 287

Tm

245.24C

1.0

Tg
Heat Flow(W/g)
0.5
79.70C(I) 75.41C 81.80C

Tc
137.58C 20.30J/g 228.80C 22.48J/g

Cycle 1

0.0

144.72C

-0.5
Exo Down

50

100

150

200

250

300
Universal V 4.2E TA Instruments

Temperature (C)

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Influence of Sample Mass

0

-2

Indium at 10C/minute Normalized Data

15mg 10mg 4.0mg 1.7mg 1.0mg 0.6mg

Onset not influenced by mass

-4 DSC Heat Flow (W/g)

-6 150 152 154

706

156 158 160 Temperature (C)

162

164

166

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Effect of Heating Rate on Indium Melting Temperature

1 0 Heat Flow (W/g) -1 -2 -3 -4 -5 154

heating rates = 2, 5, 10, 20 C/min

156

158

160 162 164 Temperature ( C)

166

168

170

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DSC: Main Sources of Errors

Calibration Contamination Sample preparation how sample is loaded into a pan

Residual solvents and moisture.

Thermal lag Heating/Cooling rates

Sample mass
Processing errors

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Sample Preparation : Shape

Keep sample as thin as possible (to minimise thermal gradients) Cover as much of the pan bottom as possible Samples should be cut rather than crushed to obtain a thin sample (better and more uniform thermal contact with pan)

99

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Other DSC Techniques

Hyper-DSC
Based on principle that high heating rates give large broad transitions. Heating rates typically 400-500oC/min Need very small sample sizes (~nanograms)

Good for:

A quick overview of new sample

Picking out minute transition

Poor for: Accuracy: transitions can be shifted by as much as 40oC Repeatabiliy: Very sensitive to thermal lag.
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Other DSC Techniques

Modulated DSC
Composite heating profile: Determines heat capacity and separates heat flow into that due to reversible and non-reversible events.
62 62

Modulate +/- 0.42 C every 40 seconds Ramp 4.00 C/min to 290.00 C

Typicaly: Heating rates: 0 - 50C

Temperature (C)

60

60

58

58

Modulation:
Period: 60 second Amplitude: +/-10C

56

56

54

54

Note that temperature is not decreasing during Modulation i.e. no cooling

52 13.0 13.5 14.0 14.5 52 15.0

Time (min)

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Modulated Temperature (C)

Modulated DSC
Benefits Increased Sensitivity for Detecting Weak (Glass) Transitions Eliminates baseline curvature and drift Increased Resolution Without Loss of Sensitivity Two heating rates (average and instantaneous) Ability to Separate Complex Thermal Events and Transitions Into Their Heat Capacity and Kinetic Components Ability to Measure Heat Capacity (Structure) Changes During Reactions and Under Isothermal Conditions Downside Slow data collection

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Example MDSC
0.00 0.00

-0.02

-0.02

-0.02

-0.04

-0.04

-0.04

Nonrev Heat Flow (W/g)

-0.06

-0.06

-0.06

-0.08

-0.08

-0.08

-0.10

-0.10

-0.10

-0.12

-0.12

-0.12

-0.14 -50
Exo Up

50

100

150

200

-0.14 250
Universal V4.2E TA Instruments

Temperature (C)

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Rev Heat Flow (W/g)

Heat Flow (W/g)

Modulated DSC
Reversible Transitions Glass Transition Melting

Non-reversible Crystallisation Curing Oxidation/degradation

Evaporation
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