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Chapter 19:

Thermal Properties

ISSUES TO ADDRESS...
How does a material respond to heat?
How do we define and measure...
-- heat capacity
-- coefficient of thermal expansion
-- thermal conductivity
-- thermal shock resistance

How do ceramics, metals, and polymers rank?

Chapter 19 - 1
Heat Capacity
General: The ability of a material to absorb heat.
Quantitative: The energy required to increase the
temperature of the material.
energy input (J/mol)
heat capacity dQ
(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.
Cp > Cv
J
Specific heat has typical units of
kg K

Chapter 19 - 2
Heat Capacity vs T
Heat capacity...
-- increases with temperature
-- reaches a limiting value of 3R

3R Cv = constant
gas constant
= 8.31 J/mol-K

Adapted from Fig. 19.2,


Callister 7e.
0 T (K)
0 qD
Debye temperature
(usually less than T room )
Atomic view:
-- Energy is stored as atomic vibrations.
-- As T goes up, so does the avg. energy of atomic vibr.
Chapter 19 - 3
Energy Storage
How is the energy stored?
Phonons thermal waves - vibrational modes

Adapted from Fig. 19.1,


Callister 7e.
Chapter 19 - 4
Energy Storage
Other small contributions to energy storage
Electron energy levels
Dominate for ceramics & plastics
Energy storage in vibrational modes

Adapted from Fig. 19.3,


Callister 7e. Chapter 19 - 5
Heat Capacity: Comparison
material c p (J/kg-K)
Polymers at room T
Polypropylene 1925 c p : (J/kg-K)
Polyethylene 1850 Cp : (J/mol-K)
Polystyrene 1170
Teflon 1050
Why is cp significantly
Ceramics
larger for polymers?
increasing c p

Magnesia (MgO) 940


Alumina (Al2 O3 ) 775
Glass 840
Metals
Aluminum 900
Steel 486
Tungsten 138 Selected values from Table 19.1, Callister 7e.
Gold 128

Chapter 19 - 6
Thermal Expansion
Materials change size when heating.
Lfinal Linitial Tinit
(Tfinal Tinitial ) L init
Linitial Tfinal
coefficient of L final
thermal expansion (1/K or 1/C)

Atomic view: Mean bond length increases with T.


Bond energy
Adapted from Fig. 19.3(a), Callister 7e.
r(T1)
r(T5)

(Fig. 19.3(a) adapted from R.M. Rose,


L.A. Shepard, and J. Wulff, The
Bond length (r) Structure and Properties of Materials,
Vol. 4, Electronic Properties, John
increasing T

Wiley and Sons, Inc., 1966.)


T5
bond energy vs bond length
curve is asymmetric
T1
Chapter 19 - 7
Thermal Expansion: Comparison
Material (10-6/K)
Polymers
at room T
Polypropylene 145-180 Polymers have smaller
Polyethylene 106-198
Polystyrene 90-150 because of weak
Teflon 126-216 secondary bonds
Metals Q: Why does
Aluminum 23.6
Steel 12
generally decrease
Tungsten 4.5 with increasing
Gold 14.2 bond energy?
Ceramics
Magnesia (MgO) 13.5
Alumina (Al2O3) 7.6
Soda-lime glass 9
Silica (cryst. SiO2) 0.4
Selected values from Table 19.1, Callister 7e.
Chapter 19 - 8
Thermal Expansion: Example
Ex: A copper wire 15 m long is cooled from
40 to -9C. How much change in length will it
experience?
Answer: For Cu 16.5 x 10 6 ( C)1
rearranging Eqn 19.3b

o T [16.5 x 10 6 (1/ C)](15 m) ( 40C ( 9C))

0.012 m

Chapter 19 - 9
Thermal Conductivity

General: The ability of a material to transfer heat.


Quantitative: temperature
dT
q k gradient Fouriers Law
heat flux dx
(J/m2-s) thermal conductivity (J/m-K-s)

T1 T2 > T1
x1 heat flux x2

Atomic view: Atomic vibrations in hotter region carry


energy (vibrations) to cooler regions.

Chapter 19 - 10
Thermal Conductivity: Comparison
Material k (W/m-K) Energy Transfer
Metals
Aluminum 247 By vibration of
Steel 52 atoms and
Tungsten 178 motion of
Gold 315 electrons
increasing k

Ceramics
Magnesia (MgO) 38
Alumina (Al2O3) 39 By vibration of
Soda-lime glass 1.7 atoms
Silica (cryst. SiO2) 1.4
Polymers
Polypropylene 0.12 By vibration/
Polyethylene 0.46-0.50 rotation of chain
Polystyrene 0.13 molecules
Teflon 0.25
Selected values from Table 19.1, Callister 7e.
Chapter 19 - 11
Thermal Stress
Occurs due to:
-- uneven heating/cooling
-- mismatch in thermal expansion.
Example Problem 19.1, Callister 7e.
-- 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 -172 MPa?
T room
L
L room L thermal (T Troom )
T Lroom
100GPa 20 x 10-6 /C
E(thermal ) E(T Troom )
compressive keeps L = 0
-172 MPa 20C
Answer: 106C
Chapter 19 - 12
Thermal Shock Resistance
Occurs due to: uneven 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 = f)
quench rate f
(T1 T2 ) (T1 T2 )f racture
k E
set equal
f k
Result: (quench rate) f or f racture
E
f k
Large thermal shock resistance when is large.
E
Chapter 19 - 13
Thermal Protection System
Re-entry T
Application: Distribution
Space Shuttle Orbiter

reinf C-C silica tiles nylon felt, silicon rubber


(1650C) (400-1260C) coating (400C)
Chapter-opening photograph, Chapter 23, Callister 5e
(courtesy of the National Aeronautics and Space Fig. 19.2W, Callister 6e. (Fig. 19.2W adapted from L.J.
Administration.) Korb, C.A. Morant, R.M. Calland, and C.S. Thatcher, "The

Silica tiles (400-1260C):


Shuttle Orbiter Thermal Protection System", Ceramic
Bulletin, No. 11, Nov. 1981, p. 1189.)
--large scale application --microstructure:
~90% porosity!
Si fibers
bonded to one
another during
heat treatment.
100 mm
Fig. 19.3W, Callister 5e. (Fig. 19.3W courtesy the Fig. 19.4W, Callister 5e. (Fig. 219.4W courtesy
National Aeronautics and Space Administration.) Lockheed Aerospace Ceramics
Systems, Sunnyvale, CA.) Chapter 19 - 14
Summary
A material responds to heat by:
-- increased vibrational energy
-- redistribution of this energy to achieve thermal equil.
Heat capacity:
-- energy required to increase a unit mass by a unit T.
-- polymers have the largest values.
Coefficient of thermal expansion:
-- the stress-free strain induced by heating by a unit T.
-- polymers have the largest values.
Thermal conductivity:
-- the ability of a material to transfer heat.
-- metals have the largest values.
Thermal shock resistance:
-- the ability of a material to be rapidly cooled and not
crack. Maximize f k/E.
Chapter 19 - 15

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