Chapter 19:

Thermal Properties

ISSUES TO ADDRESS...
• How do materials respond to the application of heat?
• How do we define and measure...
-- heat capacity?
-- thermal expansion?
-- thermal conductivity?
-- thermal shock resistance?

• How do the thermal properties of ceramics, metals,

and polymers differ?

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 Atomic Vibrations
Atomic vibrations are in the form of lattice waves or phonons

Adapted from Fig. 19.1,

Callister & Rethwisch 8e.

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3
 Lattice dynamics above T=0
•Crystal lattices at zero temperature posses long range order –
translational symmetry (e.g., generates sharp diffraction pattern, Bloch
states, …).
•At T>0 ions vibrate with an amplitude that depends on temperature

•– because of lattice symmetries, thermal vibrations can be analyzed in

terms of collective motion of ions which can be populated and excited
just like electrons
•Thermal lattice vibrations are responsible for:

→ Thermal conductivity of insulators is due to

dispersive lattice vibrations (e.g., thermal
conductivity of diamond is 6 times larger than that of
metallic copper).

4
 Phonons
• Packets of sound found present in the lattice as it vibrates
• Unlike static lattice model , which deals with average positions
of atoms in a crystal, lattice dynamics extends the concept of
crystal lattice to an array of atoms with finite masses that are
capable of motion.
• This motion is not random but is a superposition of vibrations of
atoms around their equilibrium sites due to the interaction with
neighbor atoms.
• A collective vibration of atoms in the crystal forms a wave of
allowed wavelength and amplitude.
• Just as light is a wave motion that is considered as composed of
particles called photons, we can think of the normal modes of
vibration in a solid as being particle-like.
• Quantum of lattice vibration is called the phonon.

• unlike electrons, phonons are bosons (no Pauli principle, phonon number
is not conserved).
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In the same way that the energy of the electromagnetic
radiation is quantized in the form of photons so the energy
of the elastic waves, or sound waves, inside a solid
medium can be considered to be quantized in the form of
phonons.

The energy of a phonon of frequency  is again  and,

because the phonons have integral angular momentum,
the assembly of phonons in the solid may again treated as
a boson gas.
To illustrate this point, we may
consider the Hamiltonian of a classical
solid composed of N atoms whose
positions in space specified by the
coordinates (x1, x2,.…., x3N).
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 If N atoms make up the lattice, and the spring constant
between the atoms is C, then we can write an equation for
the force when the atoms are displaced:
d 2x
F  ma  m 2  Cx
dt
or
d 2 xs
m 2  C  xs 1  xs 1  2 xs 
dt  C
   2 1  cos( ka)
2

Using a position/time dependence  m

of exp(it) and solving, we get the where
relationship between wave number k n
and frequency w: k , n  1,2,...N
Na
Solid is a periodic array of mass points, there are
constraints on both the minimum and maximum
wavelength associated with a vibrational mode.
 Acoustic and Optical Phonons
• Acoustic phonons occur when wave numbers are small
(i.e. long wavelengths) and correspond to sound
transmission in crystals.
• Acoustic phonons vary depending on whether they are
longitudinal or transverse

• "Optical phonons," which arise in crystals that have more

than one atom in the unit cell.
• They are called "optical" because in ionic crystals are
excited very easily by light (by infrared radiation in NaCl).
• The positive and negative ions vibrate to create a time-
varying dipole moment.
• Optical phonons that interact in this way with light are
called infrared active.
10
11
Transverse optical mode for
diatomic chain

Transverse acoustical mode for

diatomic chain

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 Phonons
f
Hooke’s law: Vibration frequency   M
f = force
constant, M = mass
Test for phonon effects by using isotopes with different mass, for example in
super-conductivity, where electron pairs are formed by the electron-phonon
interaction.

modes
 Transverse
modes

(Oscillating Dipole)

r
 Planck Distribution
specific application of the Bose-Einstein distribution

 Max Planck – first to come up

with the idea of quantum
energy
 worked to explain blackbody
radiation
 empty cavity at temperature
T, with which the photons
are in equilibrium
Planck Distribution
 Planck Distribution

number of phonons in
energy level n

total number of phonons

all possible energy levels 0, 1, 2, etc.

 Planck Distribution

 n  n   nhf

  n / kT  n  / kT
Fraction of N n e e small as n gets large

Phonons      
at energy n N n
0
e 
  n / kT

0

e
0
 n  / kT
a constant
 Planck Distribution
average
occupied
energy
level

  
1 1 1

n 0
x 
n

1  x
 e 
n 0
n

1  e
 e
n 0
 n  / k BT

1  e   / k BT


    n n    1 

x
 nx nx x  
nn
 xx  x   
n 0 x nn00   x  1  x  1  x 2
Active Noise Cancelling

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 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 dQ Q= m * C * T
(J/mol-K) C=
dT temperature change (K)

• Two ways to measure heat capacity:

Cp : Heat capacity at constant pressure.
Cv : Heat capacity at constant volume.
J  Btu 
• Heat capacity has units of  
mol  K  lb  mol  F 

Specific heat capacity: … one gram ... 21

 Molar Thermal Energy of a Solid
• Dulong-Petit Law (1819): Observation
• Equipartition Theorem of Classical Stat
Mech: The Thermal Average Energy for
each degree of freedom is (½) kT
• Assume that each atom has 6 degrees of
freedom: 3 translational & 3 vibrational, the
Thermal Average Energy (per mole) of the
vibrating solid is:

1 
E  N A 6  kT   3RT R  NA k
2 
 The Molar Vibrational Heat Capacity
• Using this approximation, the Thermal Average
Energy (per mole) of the vibrating solid is:
1 
E  N A 6  kT   3RT
2 
• By definition, the Heat Capacity of a substance
at Constant Volume is

E 
CV    CV  3R
T V

In agreement with Dulong & Petit!

 Measured Molar Heat Capacities
• Measurements on many solids have shown that their
Heat Capacities are strongly temperature dependent
& that the Dulong-Petit result Cv = 3R is only valid
at high temperatures. C = 3R
v
Classical vs Experiment

3R Cv = constant

0 T (K)
q

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 Einstein Model
 1907-Einstein developed first reasonably
satisfactory theory of specific heat capacity
for a solid
 assumed a crystal lattice structure comprising
N atoms that are treated as an assembly of
3N one-dimensional oscillators
 approximated all atoms vibrating at the same
frequency (unrealistic, but makes things
easier)
 Einstein Model of a Vibrating Solid
extended Planck’s quantum ideas to solids:
• He proposed that energies of lattice vibrations in a solid
are quantized simple harmonic oscillators. He proposed the
following model for the lattice vibrations in a solid:
• Each vibrational mode is an independent oscillator
• Each mode vibrates in 3-dimensions
• Each vibrational mode is a quantized oscillator with energy:

En  n , n  0,1, 2,...
  hf
or
En = (n + ½ )ħ

3NA distinguishable
 Einstein Model

average
energy
per oscillator

We have 3N such oscillators, so the total energy is

Einstein model

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Einstein Model: CV for Diamond
Einstein, Annalen der Physik 22 (4), 180 (1907)
The Debye Model Vibrating Solids

• Vibrating atoms interact strongly with one another

• Normal modes of vibration with its own frequency
 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

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.
-- As temperature increases, the average energy of
atomic vibrations increases.
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Heat capacity of electrons?

33
 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
increasing cp

• Ceramics
Magnesia (MgO) 940
Alumina (Al2O3) 775
Glass 840
• Metals
Aluminum 900
Steel 486
Tungsten 138
Gold 128
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35
 Thermal Expansion
Materials change size when temperature is changed
Expand/contract
Tinitial
 initial
Tfinal > Tinitial
Tfinal
 final

ℓ final - ℓ initial
= a ℓ (Tfinal -Tinitial )
ℓ initial
linear coefficient of
thermal expansion (1/K or 1/ºC)

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Water

37
 Hot vs cold water

Mpemba effect is named after Erasto Batholomeo

Mpemba (b.1950) who discovered it in 1963. (Tanzania,
secondary school) 38
 Atomic Perspective: Thermal
Expansion

Asymmetric curve: Symmetric curve:

-- increase temperature, -- increase temperature,
-- increase in interatomic -- no increase in interatomic
separation separation
-- thermal expansion -- no thermal expansion
Adapted from Fig. 19.3, Callister & Rethwisch 8e. 39
 Coefficient of Thermal Expansion:
Comparison
Material a (10-6/C)
at room T
• Polymers
Polypropylene 145-180 Polymers have larger
Polyethylene 106-198 a values because of
Polystyrene 90-150 weak secondary bonds
Teflon 126-216
• Metals • Q: Why does a
increasing a

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 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

  a   0 T  [16.5 x 10 6 (1/ C)](15 m)[ 40C  ( 9C)]

  0.012 m  12 mm

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The linear coefficient of thermal expansion
(CTE) of iron changes abruptly at temperatures
where a phase transformation occurs.
The relationship between the linear coefficient of thermal
expansion and the melting temperature in metals. Higher
melting point metals tend to expand to a lesser degree.

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.
 Challenger

https://www.youtube.com/results?search_query=feynman+challenger
44
 Thermal Protection System
Re-entry T
Space Shuttle Atlantis Distribution

reinf C-C silica tiles nylon felt, silicon rubber

(1650°C) (400-1260°C) coating (400°C)
Fig. 19.2W, Callister 6e. (Fig. 19.2W adapted from L.J. Korb, C.A. Morant, R.M. Calland,
and C.S. Thatcher, "The Shuttle Orbiter Thermal Protection System", Ceramic Bulletin, No.
11, Nov. 1981, p. 1189.)

• Silica tiles (400-1260C):

-- large scale application -- microstructure:
~90% porosity!
Si fibers
bonded to one
another during
heat treatment.
100 mm

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 Thermal Conductivity
The ability of a material to transport heat.
Fourier’s Law
temperature
dT
q = -k gradient Steady heat flow
heat flux dx
(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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 Lorentz Constant
Lorentz constant relates electrical and thermal
conductivity.
The Lorentz constant is proportional to the ratio of
the thermal conductivity to the electrical
conductivity: L = k/σT (Widemann-Franz Law)
For example, if the electrical conductivity of
aluminum is 3.8 x107/ Ωm, estimate it's thermal
conductivity (Lorentz constant).
Thermal conductivity: k = σLT = LT/ρ; (T = 293K)
Given k = 245 W/m K
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.
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 Aerogel Properties
• Aerogel types: Carbon, Silica, Alumina
• Other typical “extreme” properties of silica aerogel materials
are:
• Aerogels have the lowest thermal conductivity values of any
solid
• Aerogels are exceptional reflectors of audible sound, making
excellent barrier materials; aerogels have very low sound
velocity through structure (~100 m/s)
• Aerogels can be exotic energy absorbers, showing capability to
capture high velocity dust particles in space that would
penetrate thick steel
• High internal surface areas (up to 1500 m2/g)
• Ultra-low refractive index values for a solid (1.025), approaching
that for air
• Ultra-low dielectric constants for a solid (can be < 1.1)
http://www.aspenaerogels.com/features/morphology.html
http://en.wikipedia.org/wiki/Aerogel
49
 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
0
Step 1: Assume unconstrained thermal expansion
0 
Tf
Step 2: Compress specimen back to original length
0 
 

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 Example Problem (cont.)
0 The thermal stress can be directly
calculated as
 
s = E(ecompress )
Noting that compress = -thermal and substituting gives

s = -E(ethermal ) = -Ea ℓ (Tf -T0 ) = Ea ℓ (T0 -Tf )

Rearranging and solving for Tf gives

20ºC
-172 MPa (since in compression)
s
Tf = T0 -
Ea ℓ

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

tries to contract during cooling T2 Tension develops at surface
resists contraction T1 s = -Ea ℓ (T1 -T2 )
Temperature difference that Critical temperature difference
can be produced by cooling: for fracture (set  = f)
quench rate sf
(T1 - T2 ) = (T1 -T2 ) fracture =
k Ea ℓ
set equal
sf k
• (quench rate)for fracture = Thermal Shock Resistance (TSR) µ
Ea ℓ
sf k
• Large TSR when is large
Ea ℓ
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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
sk
-- is proportional to f
Ea ℓ

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 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

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