Chapter 19:

Thermal Properties

Re-entry T -- microstructure:
Distribution
~90% porosity!
Si fibers
bonded to one
another during
reinf C-C silica tiles nylon felt, silicon rubber heat treatment.
(1650ºC) (400-1260ºC) coating (400ºC) 100 mm
 Atomic Vibrations
Atomic vibrations are in the form of lattice waves or phonons
• Atoms in solid materials are constantly
vibrating at very high frequencies and with
relatively small amplitudes.: Elastic waves
or simply sound waves

• The vibrational thermal energy for a

material consists of a series
of these elastic waves, which have a
range of distributions and frequencies.

• Only certain energy values are allowed

(quantized), and a single quantum of
vibrational energy is called a phonon (a
Adapted from Fig. phonon is analogous to the quantum of
19.1, Callister &
Rethwisch 8e.
electromagnetic radiation, the photon.) .

• The thermal scattering of free electrons during electronic conduction is by these

vibrational waves, and these elastic waves also participate in the transport of energy
during thermal conduction
Source: http://www.chembio.uoguelph.ca/educmat/chm729/Phonons/cont.htm 2
 Heat Capacity
The ability of a material to absorb heat
• Quantitatively: The energy required to produce a unit rise in
temperature for one mole of a material.
energy input (J/mol)
heat capacity
(J/mol-K)
temperature change (K)

• Two ways to measure heat capacity:

Cp : Heat capacity at constant pressure.
Cv : Heat capacity at constant volume.

• Heat capacity has units of

‘The magnitude of Cp is almost always greater than Cv’ Why?

3
 Dependence of Heat Capacity on Temperature
• Heat capacity...
-- increases with temperature
-- for solids it reaches a limiting value of 3R
R = gas constant 3R Cv = constant
= 8.31 J/mol-K

Cv

Adapted from Fig. 19.2,

Callister & Rethwisch 8e.
0 T (K)
0 qD
Debye temperature
(usually less than T room )

• From atomic perspective:

-- Energy is stored as atomic vibrations and other kinds of movements
-- As temperature increases, the average energy of
atomic vibrations increases.
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 Specific Heat: Comparison
Material cp (J/kg-K)
• Polymers at room T
Polypropylene 1925 cp (specific heat): (J/kg-K)
Polyethylene 1850 Cp (heat capacity): (J/mol-K)
Polystyrene 1170
Teflon 1050
• Why is cp significantly
increasing cp

• Ceramics larger for polymers?

Magnesia (MgO) 940
Alumina (Al2O3) 775
Glass 840
• Metals
Aluminum 900
Steel 486 Selected values from Table 19.1,
Tungsten 138 Callister & Rethwisch 8e.

Gold 128
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 Thermal Expansion
Materials change size when temperature is changed
Tinitial
 initial
Tfinal > Tinitial
Tfinal
 final

linear coefficient of
thermal expansion (1/K or 1/ºC)
• In many materials, the value of v is
anisotropic; that is, it depends on the
crystallographic direction along which it is
measured.
• For materials in which the thermal
expansion is isotropic, v
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is approximately 3l
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 Thermal Expansion: Example
Ex: A copper wire 15 m long is cooled from
40 to -9ºC. How much change in length will it
experience?
• Answer: For Cu

rearranging Equation 19.3b

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 Atomic Perspective: Thermal Expansion

Harmonic
anharmonic oscillator
oscillator
Asymmetric curve: Symmetric curve:
-- increase temperature, -- increase temperature,
-- increase in interatomic separation -- no increase in interatomic separation
-- thermal expansion
-- no thermal expansion
With regard to temperature dependence, the magnitude of the coefficient
of expansion increases with rising temperature.

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 Coefficient of Thermal Expansion:
Comparison
Material a (10-6/C)
• Polymers at room T
Polypropylene 145-180 Polymers have larger
Polyethylene 106-198  values because of
Polystyrene 90-150 weak secondary bonds
Teflon 126-216
• Metals • Q: Why does a
increasing 

Aluminum 23.6 generally decrease

Steel 12 with increasing
Tungsten 4.5
bond energy?
Gold 14.2
• Ceramics
Magnesia (MgO) 13.5 Selected values from Table 19.1,
Alumina (Al2O3) 7.6 Callister & Rethwisch 8e.

Soda-lime glass 9
Silica (cryst. SiO2) 0.4
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 Thermal Conductivity
The ability of a material to transport heat.
Fourier’s Law
temperature
gradient
heat flux
(J/m2-s) thermal conductivity (J/m-K-s)

T1 T2
T2 > T1
x1 heat flux x2

• Atomic perspective: Atomic vibrations and free electrons in

hotter regions transport energy to cooler regions.

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Thermal Conductivity: Comparison
Energy Transfer
Material k (W/m-K) Mechanism
• Metals
Aluminum 247 atomic vibrations
Steel 52 and motion of free
Tungsten 178
electrons
Gold 315
• Ceramics
increasing k

Magnesia (MgO) 38
Alumina (Al2O3) 39 atomic vibrations
Soda-lime glass 1.7
Silica (cryst. SiO2) 1.4
• Polymers
Polypropylene 0.12
Polyethylene 0.46-0.50 vibration/rotation of
Polystyrene 0.13 chain molecules
Teflon 0.25
Selected values from Table 19.1, Callister & Rethwisch 8e. 12
 Thermal conductivity versus
fig_19_04
composition for copper–zinc
alloys. • Where kl and ke represent the
lattice vibration and electron
thermal conductivities, respectively;

• Phonons moves from high- to low

temperature regions of a body.

• Free or conducting electrons

moves from hot region (high kinetic
energy) of the specimen to colder
areas
• Some of this kinetic energy is transferred to the atoms themselves (as
vibrational energy) as a consequence of collisions with phonons or other
imperfections (scattering centers) in the crystal.

• The relative contribution of ke to the total thermal conductivity increases with

increasing free electron concentrations, since more electrons are available to
participate in this heat transference process.
• Since free electrons are responsible for both electrical and
thermal conduction in pure metals, theoretical treatments
suggest that the two conductivities should be related according
to the Wiedemann–Franz law.

• ratio of the electronic contribution of the thermal conductivity (κ)

to the electrical conductivity (σ) of a metal is proportional to
the temperature (T)

The theoretical value of L, should be independent of temperature

and the same for all metals if the heat energy is transported
entirely by free electrons.
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 • phonons are primarily
fig_19_05 responsible for thermal
conduction in ceramics.
ke<<kl

• The scattering of lattice

vibrations becomes
more pronounced with
rising temperature .

• the conductivity begins

to increase at higher
temperatures, which is
due to radiant heat
transfer:
significant quantities of infrared radiant heat may be transported
through a transparent ceramic material. The efficiency of this
process increases with temperature.
Radiation, energy transfer across a system boundary due to a T,
by the mechanism of photon emission or electromagnetic wave
emission.

Thermal Stresses
• Occur due to:
-- restrained thermal expansion/contraction
-- temperature gradients that lead to differential

dimensional changes
Thermal stress 

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 Example Problem
-- A brass rod is stress-free at room temperature (20ºC).
-- It is heated up, but prevented from lengthening.
-- At what temperature does the stress reach -172 MPa?
Solution:
T0 Original conditions
room
Step 1: Assume unconstrained thermal expansion
room D
Tf
Step 2: Compress specimen back to original length
room D
 

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 Example Problem (cont.)
0 The thermal stress can be directly
calculated as
 

Noting that compress = -thermal and substituting gives

Rearranging and solving for Tf gives

20ºC
-172 MPa (since in compression)

Answer: 106ºC 100 GPa 20 x 10-6/ºC

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 Thermal Shock Resistance
• Occurs due to: nonuniform heating/cooling
• Ex: Assume top thin layer is rapidly cooled from T1 to T2
rapid quench
s
tries to contract during cooling T2 Tension develops at surface
resists contraction T1

Temperature difference that Critical temperature difference

can be produced by cooling: for fracture (set s = sf)

set equal

• Large TSR when is large

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 Summary
The thermal properties of materials include:
• Heat capacity:
-- energy required to increase a mole of material by a unit T
-- energy is stored as atomic vibrations
• Coefficient of thermal expansion:
-- the size of a material changes with a change in temperature
-- polymers have the largest values
• Thermal conductivity:
-- the ability of a material to transport heat
-- metals have the largest values
• Thermal shock resistance:
-- the ability of a material to be rapidly cooled and not fracture

-- is proportional to

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