Course Code: MSE 255

Lecture Six

Principles of Materials Science II

Dr. Emmanuel Kwesi Arthur

Department of Materials Engineering,
Kwame Nkrumah University of Science and Technology,
Kumasi, Ghana

Email: ekarthur2005@yahoo.com
Phone #: +233541710532
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©2017
 Part Three

Thermal Properties of Materials

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 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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 Thermal properties
 Thermal Property – Response of material to application of heat
 Manifestation – Rise in temperature and change in dimension.
 Temperature rise – Heat absorption
 Heat capacity is the ability of a material to absorb heat
 Heat capacity, C, is defined as the amount of energy required to produce a
unit temperature rise
 (J/mol-K or cal/mol-K), q is energy, T is temperature.
 Specific heat, C, is heat capacity per unit mass (J/kg-K or cal/g-K)
 Constant pressure or constant volume heat capacity, Cp and Cv respectively.

Heat capacity
• atomic vibrations, phonons
• temperature dependence
• contribution of electrons
Thermal expansion
• connection to anharmonicity of interatomic potential
• linear and volume coefficients of thermal expansion

Thermal conductivity
• heat transport by phonons and electrons
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 Heat capacity
 The heat capacity, C, of a system is the ratio of the heat
added to the system, or withdrawn from the system, to the
resultant change in the temperature:

 This definition is only valid in the absence of phase transitions

 Usually C is given as specific heat capacity, c, per gram or per mol
 Heat capacity can be measured under conditions of constant temperature or
constant volume. Thus, two distinct heat capacities can be defined:

CP is always greater than CV - Why?

Hint: The difference between CP and Cv is very small for solids and liquids,
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but large for gases.
 Heat capacity
 Heat capacity is a measure of the ability of the material to
absorb thermal energy.
 Thermal energy = kinetic energy of atomic motions +
potential energy of distortion of interatomic bonds.

 The higher is T, the large is the mean

atomic velocity and the amplitude of
atomic vibrations = larger thermal
energy

 Vibrations of individual atoms in solids are not independent from each

other. The coupling of atomic vibrations of adjacent atoms results in waves
of atomic displacements. Each wave is characterized by its wavelength and
frequency. For a wave of a given frequency ν, there is the smallest
“quantum” of vibrational energy, hν, called phonon.
 Thus, the thermal energy is the energy of all phonons (or all vibrational
waves) present in the crystal at a given temperature.
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 Heat Capacity: Comparison

• Why is cp significantly
larger for polymers?

Selected values from Table 19.1, Callister 6e.

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 Thermal Expansion
 Materials expand when heated and contract when cooled

where l0 is the initial length atT0, lf is the final length atTf

is the linear coefficient of thermal expansion

Similarly, the volume change with T can be described as

where αV is the volume coefficient of thermal expansion

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 For isotropic materials and small expansions, αV ≈ 3αl

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 Example
 A steel rod is to be used with its ends held rigid. What
is the maximum temperature the rod can be heated to
without the compressive stress in it exceeding 180
MPa. Elastic modulus of the rod E = 190 GPa.

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 Thermal Expansion: Example

Ex: A copper wire 15 m long is cooled from 40 to -9°C.

How much change in length will it experience?

• Answer: For Cu   16.5 x 106 ( C)1

rearranging Equation

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

  0.012 m  12 mm

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 Example Problem
-- A brass rod is stress-free at room temperature (20°C).
-- 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  
 thermal   (Tf T0 )
Tf room

Step 2: Compress specimen back to original length

0 
 
  compress   thermal
room
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 Example Problem (cont.)
0 The thermal stress can be directly
calculated as
 
  E(compress )

Noting that compress = -thermal and substituting gives

  E(thermal )  E
 (Tf T0 )  E (T0 Tf )

Rearranging and solving for Tf gives

 20ºC
-172 MPa (since in compression)

Tf  T0 
E

Answer: 106°C 100 GPa 20 x 10-6/°C

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 Physical Origin of Thermal Expansion

Rising temperature
results in the increase of
the average amplitude of
atomic vibrations. For an
anharmonic potential,
this corresponds to the
increase in the average
value of interatomic
separation, i.e. thermal
expansion.

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 Physical Origin of Thermal Expansion

Thermal expansion is related to the asymmetric (anharmonic) shape of

interatomic potential. If the interatomic potential is symmetric (harmonic), the
average value of interatomic separation does not change, i.e. no thermal
expansion.
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 Coefficient of Thermal Expansion: Comparison

Material a (10-6/C)
at room T
• Polymers
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
Alumina (Al2O3) 7.6
Soda-lime glass 9
Silica (cryst. SiO2) 0.4
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Thermal Expansion of Various Materials

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 Thermal Expansion of Various Materials

 The stronger the interatomic bonding (deeper the potential

energy curve), the smaller is the thermal expansion.
 The values of αl and αV are increasing with rising T

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 Implications and Applications of Thermal Expansion

Railway tracks are

built from steel rails
laid with a gap
between the ends

Thermostats based on bimetal strips made of two metals

with different coefficient of thermal expansion:

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 Thermal Conductivity
• General: The ability of a material to transfer heat.
• Quantitative:
temperature
dT gradient
q  k
heat flux dx
(J/m2-s) thermal conductivity (J/m-K-s)

• Atomic view: Atomic vibrations in hotter region carry

energy (vibrations) to cooler regions.

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 Thermal Conductivity
If there is a temperature gradient, heat will flow from higher to
lower temperature region. This is Thermal conduction. The ability of a
material to transfer the heat is the Thermal conductivity, k.

where q is the heat flux (amount of thermal energy flowing

through a unit area per unit time) and dT/dx is the
temperature gradient, and k is the coefficient of thermal
conductivity, often called simply thermal conductivity.

Units: q [W/m2], k [W/(m K)]

Note the similarity to the Fick’s first law for atomic diffusion: the diffusion
flux is proportional to the concentration gradient:

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Non-steady state heat flow and atomic diffusion are described
by the same equation:

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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
Magnesia (MgO) 38
increasing k

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
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 Ex: Thermal Stress
• Occurs due to:
--uneven heating/cooling
--mismatch in thermal expansion.
• Example Problem 17.1, p. 724, Callister 2e.
--A brass rod is stress-free at room temperature (20C).
--It is heated up, but prevented from lengthening.
--At what T does the stress reach -172MPa?

L L
T   thermal  (T  Troom )
L room
100GPa 20 x 10-6 /C
  E( thermal )  E(T  Troom )

-172MPa 20C
Answer: 106C
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 Conduction Mechanism
 Atoms vibrate about their equilibrium positions with high
frequency and low amplitudes. Amplitude increases with rise in
temperature.
 The vibrations of adjacent atoms are coupled due to atomic
bonding and this leads to generation of elastic waves which move
through the lattice at the velocity of sound and thus carries the
heat.
 Each quantum of the wave is known as phonon.

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 Mechanisms of heat conduction
Heat is transferred by phonons (lattice vibration waves) and
electrons. The thermal conductivity of a material is defined by
combined contribution of these two mechanisms:

where kl and ke are the lattice and electronic thermal conductivities.

 Lattice conductivity: Transfer of thermal energy phonons

 Electron conductivity: Free (conduction band) electrons equilibrate with
lattice vibrations in hot regions, migrate to colder regions and transfer a part
of their thermal energy back to the lattice by scattering on phonons.

 The electron contribution is dominant in metals and absent in insulators.

 Since free electrons are responsible for both electrical and thermal
conduction in metals, the two conductivities are related to each other by the
Wiedemann-Franz law:

where σ is the electrical conductivity

26 and L is a constant
  Free electrons gain kinetic energy in the hotter region and
move towards the colder region thus transferring the heat.
 Therefore, thermal conductivity k = kl (lattice) + ke (electron)
 Since a large number free valence electrons are available in
metals, the electron mechanism is much more efficient. This
imparts great thermal conductivity that metals are known for.
 Thermal and electrical conductivities in metals are related by
Wiedemann–Franz law: L= k/σT, L is a constant, σ is electrical
conductivity.
 Ceramics do not have free electrons as all electrons are
tightly bound in the atomic bonds and hence, are poor
conductors of heat.
 Polymers conduct heat by vibrational and rotational motion of
chain molecules and hence, are poor conductors of heat.

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 Effect of alloying on heat conduction in metals
The same factors that affect the electrical conductivity also
affect thermal conductivity in metals. E.g., adding impurities
introduces scattering centers for conduction band electrons and
reduce k.

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 Heat conduction in nonmetallic materials

In insulators and semiconductors the heat transfer is by

phonons and, generally, is lower than in metals. It is sensitive to
structure:
 glasses and amorphous ceramics have lower k compared to the
crystalline ones (phonon scattering is more effective in
irregular or disordered materials).
 Thermal conductivity decreases with porosity (e.g. foamed
polystyrene is used for drinking cups).
 Thermal conductivity of polymers depends on the degree of
crystallinity – highly crystalline polymer has higher k

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 Thermal Conductivity
 Thermal conductivity of ceramics generally decreases with
increasing temperature due to phonon scattering.
 At very high temperature it increases again due to change in heat
transfer mode from conduction to radiation.

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Temperature dependence of thermal conductivity

 Thermal
conductivity tend to
decrease with
increasing
temperature (more
efficient scattering
of heat carriers on
lattice vibrations),
but can exhibit
complex non-
monotonous
behavior.

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 Thermal conductivity of various materials at RT

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 Thermal stresses
can be generated due to restrained thermal
expansion/contraction or temperature gradients that lead
to differential dimensional changes in different part of
the solid body.
• can result in plastic deformation or fracture.

In a rod with restrained axial deformation: σ = E αl ΔT

where E is the elastic modulus, αl is the linear coefficient
of thermal expansion and ΔT is the temperature change.

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 Stresses from temperature gradient

Rapid heating can result in strong temperature gradients

=> confinement of expansion by colder parts of the
sample.
The same for cooling – tensile stresses can be introduced
in a surface region of rapidly cooled piece of material.

Thermal stresses can cause plastic deformation (in

ductile materials) or fracture (in brittle materials). The
ability of material to withstand thermal stresses due to
the rapid cooling/heating is called thermal shock
resistance.

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 Thermal Shock
 Thermal stresses might cause fracture in brittle materials
like ceramics due to rapid heating or cooling if the
expansion/contraction is restrained. This is known as thermal
shock.
 The ability of material to withstand such shocks is known as
thermal shock resistance (TSR)
Shock resistance parameter for brittle materials (ceramics):

where σf is fracture strength of the material

 Thermal shock can be prevented by controlling the external

conditions like lowering heating and cooling rates and
controlling the thermal/mechanical parameters such as CTE
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and fracture stress as per the equation above.
 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   E (T1 T2 )
Temperature difference that Critical temperature difference
can be produced by cooling: for fracture (set s = sf)
quench rate f
(T1  T2 )   (T1 T2 ) fracture 
k E
set equal
f k
• (quench rate) for  Thermal Shock Resistance (
T SR) 
fracture  E
f k
37 • Large TSR when is large
E 37
 Thermal Protection System
• Application:
Re-entry T
Space Shuttle Orbiter Distribution

reinf C-C silica tiles nylon felt, silicon rubber

(1650°C) (400-1260°C) coating (400°C)
(400-1260C):
• Silica tiles
-- large scale application -- microstructure:
~90% porosity!
Si fibers
bonded to one
another during
heat treatment.
100 mm

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 Restrained thermal expansion: Example problem
A brass rod is restrained but stress-free at RT (20ºC). Young’s
modulus of brass is 100 GPa, αl = 20×10-6 1/°C
At what temperature does the stress reach -172 MPa?

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 Summary
 Make sure you understand language and concepts:
 anharmonic potential
 atomic vibrations, phonons
 electron heat conductivity
 electronic contribution to heat capacity
 heat capacity, CP vs. CV
 lattice heat conductivity
 linear coefficient of thermal expansion
 specific heat capacity
 thermal conductivity
 thermal expansion
 thermal stresses
 thermal shock resistance
 volume coefficients of thermal expansion
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1. What is heat capacity? What is specific heat?
2. Briefly explain the mechanism of heat conduction in solids?
3. What is phonon?
4. Why do metals have good thermal conductivity?
5. Why are ceramics poor conductors of heat?
6. What is the origin of thermal expansion in solids?
7. Why thermal expansion of ceramics is much lower compared to metals?
8. What kind of stresses will be developed if the ends of a solid are
constrained while (i) heating (ii) while cooling?
9. Is it possible to have zero or negative thermal expansion?
10. What causes thermal shock?
11. What is thermal shock resistance? How can it be improved?
12. A brass rod is to be used with its ends held rigid. What is the
maximum temperature the rod can be heated to from
room temp without the compressive stress in it exceeding 172 MPa.
Elastic modulus of brass E = 100 GPa and αl = 20 x 10-6
13. A 0.35 m long brass rod is heated from 15 to 85oC with its ends held
rigid. Find out the magnitude and type of stress developed if it was free
of stress at 15 oC. Elastic modulus of brass is 100 GPa and α of brass is
20 x 10-6/oC 41
  QUESTIONS

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