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.
heat capacity (J/mol-K)

dQ C= dT

energy input (J/mol) 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
+ Cv Solid state physics MA Wahab, hal. 300) Chapter 19 - 2

Heat Capacity vs T
• Heat capacity...
-- increases with temperature -- reaches a limiting value of 3R
3R gas constant = 8.31 J/mol-K Cv = constant

Cv
0

0

θD

T (K)

Adapted from Fig. 19.2, Callister 7e.

• Atomic view:

Debye temperature (usually less than T room )

-- 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
c p (J/kg-K) material at room T • Polymers 1925 Polypropylene c p : (J/kg-K) 1850 Polyethylene Cp : (J/mol-K) 1170 Polystyrene 1050 Teflon • Why is cp significantly • Ceramics larger for polymers? Magnesia (MgO) 940 Alumina (Al2 O3 ) 775 Glass 840 • Metals Aluminum Steel Tungsten Gold 900 486 138 128

increasing c p

Selected values from Table 19.1, Callister 7e.

Chapter 19 - 6

Thermal Expansion
• Materials change size when heating.

Lfinal − Linitial = α(Tfinal − Tinitial ) Linitial
coefficient of thermal expansion (1/K or 1/°C)

L init L final

Tinit Tfinal

• Atomic view: Mean bond length increases with T.
Bond energy Bond length (r)
Adapted from Fig. 19.3(a), Callister 7e. (Fig. 19.3(a) adapted from R.M. Rose, L.A. Shepard, and J. Wulff, The Structure and Properties of Materials, Vol. 4, Electronic Properties, John Wiley and Sons, Inc., 1966.)

increasing T

T5 T1

r(T1) r(T5)

bond energy vs bond length curve is “asymmetric”
Chapter 19 - 7

Thermal Expansion: Comparison
Material
• Polymers Polypropylene Polyethylene Polystyrene Teflon • Metals Aluminum Steel Tungsten Gold • Ceramics Magnesia (MgO) Alumina (Al2O3) Soda-lime glass Silica (cryst. SiO2)

α  (10-6 /K)
at room T
145-180 106-198 90-150 126-216 23.6 12 4.5 14.2 13.5 7.6 9 0.4
Chapter 19 - 8

Polymers have smaller α  because of weak secondary bonds

• Q: Why does α generally decrease with increasing bond energy?

Selected values from Table 19.1, Callister 7e.

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

α  = 16.5 x 10 −6 (  C)−1

rearranging Eqn 19.3b
∆ = α o ∆T = [16.5 x 10 −6 (1/ °C)](15 m) ( 40°C − ( −9°C)) ∆ = 0.012 m

Chapter 19 - 9

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

T1 x1
heat flux

T2 > T1 x2

• Atomic view: Atomic vibrations in hotter region carry
energy (vibrations) to cooler regions.

Chapter 19 - 10

Thermal Conductivity: Comparison
• Metals

Material
Aluminum Steel Tungsten Gold

k (W/m-K)
247 52 178 315 38 39 1.7 1.4

Energy Transfer
By vibration of atoms and motion of electrons By vibration of atoms

increasing k

• Ceramics
Magnesia (MgO) Alumina (Al2O3) Soda-lime glass Silica (cryst. SiO2)

• Polymers
Polypropylene Polyethylene Polystyrene Teflon

By vibration/ 0.12 0.46-0.50 rotation of chain molecules 0.13 0.25
Chapter 19 - 11

Selected values from Table 19.1, Callister 7e.

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 (20°C). -- It is heated up, but prevented from lengthening. -- At what T does the stress reach -172 MPa?
T room L room

∆L T

∆L = ε thermal = α(T − Troom ) Lroom
100GPa 20 x 10-6 /°C

σ ε = thermal ) = (T − ) E(− − Eα Troom
compressive σ keeps ∆ L = 0
-172 MPa

Answer: 106°C

20°C
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 resists contraction

T2 T1

σ

Tension develops at surface

σ = −Eα(T1 − T2 )
Critical temperature difference for fracture (set σ = σ f)

Temperature difference that can be produced by cooling:

(T1 − T2 ) =

quench rate k

(T1 − T2 )fracture =

σf Eα

set equal

σf k • Result: (quench rate) for fracture ∝ Eα • Large thermal shock resistance when

σf k is large. Eα

Chapter 19 - 13

Thermal Protection System
• Application:
Space Shuttle Orbiter
Re-entry T Distribution

• Silica tiles (400-1260°C):
--large scale application

Chapter-opening photograph, Chapter 23, Callister 5e (courtesy of the National Aeronautics and Space Administration.)

reinf C-C silica tiles (1650°C) (400-1260°C)

nylon felt, silicon rubber 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.)

--microstructure:
~90% porosity! Si fibers bonded to one another during heat treatment.

100 µ m
Fig. 19.3W, Callister 5e. (Fig. 19.3W courtesy the National Aeronautics and Space Administration.)

Fig. 19.4W, Callister 5e. (Fig. 219.4W courtesy Lockheed Aerospace Ceramics Chapter 19 - 14 Systems, Sunnyvale, CA.)

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 σ f k/Eα .
Chapter 19 - 15

ANNOUNCEMENTS
Reading: Core Problems: Self-help Problems:

Chapter 19 - 16

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