Calorimetry and scanning

thermal measurements
R W McCallum
Ames Laboratory
And
Materials Science and Engineering
 Types of thermal analysis
• Semi Adiabatic Specific Heat
• DTA differential thermal analysis (rt to 1650 C)
• DSC Differential Scanning Calorimetry (rt to 750 C)
• Heat flux DSC (rt to 1650 C), (-150 to 900 C)
• TGA thermal gravimetric analysis (rt – 1500 C)
• STA simultaneous thermal analysis (rt – 1500 C)
• TMA
– thermo mechanical analysis
– Thermo magnetic analysis
• Dilatometry ( thermal expansion )
– (rt to 1650 C), (-150 to 900 C)
 Differential Calorimeter
heater power adjusted for equal temperature both samples
(power compensated)

Isothermal shield

Thermometer Thermometer

Reference
Sample Sample
Heater Heater
 DSC
3500 500

Gas 450
3000

400
2500
Reference
Liquid
Temperature ( C )

350
Fe
2000
300

1500 Fe
250
Reference Constant Power
Fe Sample Power Varaible
1000
200

500 Fe 150

0 100
Time
Differential Thermal Analysis

Furnace

Thermometer Thermometer

Reference
Sample Sample
Differential Heat Flux Calorimeter

Furnace

Thermometer Thermometer

Reference
Sample Sample
Calibrated link
Melting
curve
Netzsch DSC 404 C Pegasus®
 1500
Hypothetical Phase Diagrams
1300
Temperature

1100
60% 75% 80%
35% 45%
liquid
liquid
900
liquid

700 liquid
liquid

500
0 20 40 60 80 100
 1500
Hypothetical Phase Diagrams
1300
Temperature

1100
60% 75% 80%
35% 45%
liquid
liquid
900
liquid

700 liquid
liquid

500
0 20 40 60 80 100

Nonequilibrium Melting
Nonequilibrium Solidification

Initial Melting
80%

550 650 750 850 950 1050

Temperature (C)
liquidus

solidus
liquidus

solidus
 liquidus

solidus
Composition Composition
of solid of liquid
 liquidus

Fraction of liquid =
a/(a+b)

Fraction of solid =
b/(a+b)

a b

solidus
Composition Composition
of solid of liquid
 1.2

1
liquidus

0.8
Fraction Liquid

0.6
solidus

0.4

0.2

0
Temperature
 1.2

1
liquidus

0.8
Fraction Liquid (F)

dF/dT
0.6
solidus

0.4

0.2

0
Temperature
 liquidus

Fraction of liquid =
a/(a+b)

Fraction of solid =
b/(a+b)

a b

solidus
Composition Composition
of solid of liquid
 1500
Hypothetical Phase Diagrams
1300
Temperature

1100
60% 75% 80%
35% 45%
liquid
liquid
900
liquid

700 liquid
liquid

500
0 20 40 60 80 100

initial 75%

550 650 750 850 950 1050

 1500
Hypothetical Phase Diagrams
1300
Temperature

1100
60% 75% 80%
35% 45%
liquid
liquid
900
liquid

700 liquid
liquid

500
0 20 40 60 80
delta T 100

initial
60%

550 650 750 850 950 1050

 1500
Hypothetical Phase Diagrams
1300
Temperature

1100
60% 75% 80%
35% 45%
liquid
liquid
900
liquid

700 liquid
liquid

500
0 20 40 60 80 100

initial
45%

550 650 750 850 950 1050

 1500
Hypothetical Phase Diagrams
1300
Temperature

1100
60% 75% 80%
35% 45%
liquid
liquid
900
liquid

700 liquid
liquid

500
0 20 40 60 80 100

initial
35%

550 650 750 850 950 1050

Phase transition

From Wikipedia,
 Phase Transition
• At phase-transition
point
– the two phases have
identical free Gl El-TSl+pVl
energies
– equally likely to exist.
Llh=(Sh-Sl)T

Free Energy
• Below the phase- High Temperature
transition point Phase

– Low temperature Phase Transition

phase is more stable
state of the two. Gh Eh-TSh+pVh
• Above the phase- Low Temperature
transition point Phase

– High temperature Temperature (K)

phase is more stable
state of the two.
 Types of phase transitions
• first-order phase transitions
– involve a latent heat
• system either absorbs or releases a fixed (and typically
large) amount of energy.
• the temperature of the system will stay constant as
heat is added or released.
– "mixed-phase regimes“
• in which some parts of the system have completed the
transition and others have not.
– a pot of boiling water:
» turbulent mixture of water and water vapor bubbles.
 Ehrenfest's classification of phase
transitions
• phase transitions labeled by the lowest derivative of the free
energy that is discontinuous at the transition.
• First-order phase transitions
– exhibit a discontinuity in the first derivative of the free energy with a
thermodynamic variable.
– solid/liquid/gas transitions are first-order transitions
• because they involve a discontinuous change in density (which is the first
derivative of the free energy with respect to chemical potential.)
• Second-order phase transitions
– continuous in the first derivative
– exhibit discontinuity in a second derivative of the free energy.
• example, the ferromagnetic phase transition in materials such as Fe,
– magnetization ( the first derivative of the free energy with the applied magnetic field
strength), increases continuously from zero as the temperature is lowered below Tc
– magnetic susceptibility (the second derivative of the free energy with the field) changes
discontinuously.
International Union of Pure and Applied Chemistry.
first-order phase transition
A transition in which the molar Gibbs energies or molar Helmholtz energies
of the two phases (or chemical potentials of all components in the two
phases) are equal at the transition temperature, but their first derivatives
with respect to temperature and pressure (for example, specific enthalpy
of transition and specific volume) are discontinuous at the transition point,
as for two dissimilar phases that coexist and that can be transformed into
one another by a change in a field variable such as pressure, temperature,
magnetic or electric field.
Example:
The transition on heating CsCl to 752 K at which it changes from the
low-temperature, CsCl-type structure to the high-temperature NaCl-type
structure.
Synonymous with discontinuous phase transition.
1994, 66, 583
IUPAC Compendium of Chemical Terminology 2nd Edition (1997)
second-order transition
A transition in which a crystal structure
undergoes a continuous change and in which
the first derivatives of the Gibbs energies (or
chemical potentials) are continuous but the
second derivatives with respect to
temperature and pressure (i.e. heat capacity,
thermal expansion, compressibility) are
discontinuous. Example: The order-disorder
transition in metal alloys, for example, CuZn.
Synonymous with continuous transition.
 NIST Recommended Practice Guide
Special Publication 960-15
• DTA and Heat-flux DSC Measurements of Alloy
Melting and Freezing
– W. J. Boettinger, U. R. Kattner, K.-W. Moon
• Metallurgy Division
• Materials Science and Engineering Laboratory,
• National Institute of Standards and Technology
– J. H. Perepezko
• Department of Materials Science and Engineering,
• University of Wisconsin - Madison
– Special Publications
– November 2006
– U.S. Department of Commerce
 Terms and definitions

• ASTM E473, "Standard Terminology Relating to

Thermal Analysis," is a compilation of definitions
of terms used in other ASTM documents on all
thermal analysis methods including techniques
besides DTA and HF-DSC.
• ASTM E1142, "Terminology Relating to
Thermophysical Properties," is a compilation of
definitions of terms used in other ASTM
documents that involve the measurement of
thermophysical properties in general.
 ASTM Practice Standards
• ASTM E967, "Practice for Temperature Calibration of DSC and DTA,"
presents simple recipes for calibration for fixed mass and heating
rate using two pure materials to obtain a linear correction for
conversion of measured temperature to actual temperature. The
onset temperature extracted from the melting peak is determined
by the extrapolation method, see section 2.4.3. For some ♦DTA and
Heat-flux DSC Measurements 5 materials the standard suggests
using the peak for calibration, a method not recommended for
metals.
• ASTM E968, "Standard Practice for Heat Flow Calibration of DSC,"
uses sapphire as heat capacity standard. The method is described in
section 2.4.4.
• ASTM E2253, "Standard Method for Enthalpy Measurement
Validation of Differential Scanning Calorimeters," presents a
method using three small masses to determine the detection limit
of DTA/DSC.
 ASTM Practice Standards
• ASTM E928, "Standard Test Method for Determining Purity by DSC,”
employs comparison of the shape of the melting peak of an impure
sample to the shape for a high purity sample to determine the
concentration of the impurity. The method uses the "1/F plot"
which examines the down slope of the melting peak.
• ASTM E794, "Standard Test Method for Melting and Crystallization
Temperatures by Thermal Analysis," employs the extrapolated
onset determination method.
• ASTM E793, "Standard Test Method for Enthalpies of Fusion and
Crystallization by DSC," uses area on signal vs. time plot for
comparison to known heats of fusion of pure materials.
• ASTM E1269, "Standard Test Method for Determining Specific Heat
Capacity by DSC," uses sapphire or aluminum as a standard.