Thermal Properties

Heat capacity, Conductivity, Thermal Stresses

Prepared by: JG Caliston

1
figun_19_p781b
Chapter 19 -
figun_19_p781a

Chapter 19 -
figun_19_p781c

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?

Chapter 19 -
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
(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 usually > Cv
J  Btu 
• Heat capacity has units of  
mol ⋅ K  lb − mol ⋅ °F 
6

Chapter 19 -
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 θD
Debye temperature
(usually less than T room )
• From atomic perspective:
-- Energy is stored as atomic vibrations.
-- As temperature increases, the average energy
7
of
atomic vibrations increases. Chapter 19 -
 Atomic Vibrations
Atomic vibrations are in the form of lattice waves or phonons

Adapted from Fig. 19.1,

8
Callister & Rethwisch 8e.
Chapter 19 -
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 9

Chapter 19 -
Thermal Expansion
Materials change size when temperature
is changed
Tinitial
 initial
Tfinal > Tinitial
Tfinal
 final

∆l = l0α l ∆T = l0α l (T f − T0 )

10

Chapter 19 -
Atomic Perspective: Thermal
Expansion

Asymmetric curve: Symmetric curve:

-- increase temperature, -- increase temperature,
-- increase in interatomic -- no increase in interatomic
separation separation
-- thermal expansion -- no thermal11expansion
Adapted from Fig. 19.3, Callister & Rethwisch 8e. Chapter 19 -
Coefficient of Thermal Expansion:
Comparison -6
Material α (10 /°C)
at room T
• Polymers
Polypropylene 145-180 Polymers have larger
Polyethylene 106-198 α values because of
Polystyrene 90-150 weak secondary bonds
Teflon 126-216
• Metals • Q: Why does α
increasing α

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 12

Chapter 19 -
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 α
  = 16.5 x 10 (
−6 
C) −1

rearranging Equation 19.3b

∆ = α   0 ∆T = [16.5 x 10 −6 (1/ °C)](15 m)[ 40°C − ( −9°C)]

∆ = 0.012 m = 12 mm

13

Chapter 19 -
Thermal Conductivity
The ability of a material to transport heat.
Fourier’s Law
temperature
dT gradient
q = −k
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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Chapter 19 -
Thermal Conductivity:
Energy Transfer
Comparison
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 15
Selected values from Table 19.1, Callister & Rethwisch 8e. Chapter 19 -
table_19_01
Chapter 19 -
Prob #2 To what temperature must a cylindrical rod of tungsten 10.000 mm in diameter and
a plate of 316 stainless steel having a circular hole 9.988 mm in diameter have to be
heated for the rod to just fit into the hole? Assume that the initial temperature is 25°C.

Solution
This problem asks for us to determine the temperature to which a cylindrical
rod of tungsten 10.000 mm in diameter must be heated in order for it of just fit
into a 9.988 mm diameter circular hole in a plate of 316 stainless steel, assuming
that the initial temperature is 25°C. This requires the use of Equation 19.3a,
which is applied to the diameters of both the rod and hole. That is

d f − d0
= α l (T f − T0 )
d0

d f = d 0 1 + αl (T f −T0 )

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Chapter 19 -
 Now all we need do is to establish expressions for df (316
stainless) and df (W), set them equal to one another, and solve for
Tf. According to Table 19.1, αl(316 stainless) = 16.0 × 10-6 (ºC)-1
and αl (W) = 4.5 × 10-6 (ºC)-1. Thus

d f (316 stainless) = d f (W)

(9.988 mm) 1 + {16.0 × 10−6 (°C ) −1}(T f − 25°C ) 

= (10.000 mm) 1 + {4.5 × 10−6 (°C ) −1}(T f − 25°C ) 

Now solving for Tf gives Tf = 129.5ºC

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Chapter 19 -
Thermal Stresses
• Occur due to:
-- restrained thermal expansion/contraction
-- temperature gradients that lead to differential
dimensional changes

Thermal stress = σ
= Eα  (T0 −Tf ) = Eα  ∆T

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Chapter 19 -
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 ∆ ∆
= εthermal = α  (Tf −T0 )
Tf  room
Step 2: Compress specimen back to original length
0 ∆
−∆
σ σ εcompress = = −εthermal
  room 20
Chapter 19 -
Example Problem (cont.)
0 The thermal stress can be directly
calculated as
σ σ
σ = E(εcompress )

Noting that εcompress = -εthermal and substituting gives

σ = −E(εthermal ) = −Eα  (Tf −T0 ) = Eα  (T0 −Tf )

Rearranging and solving for Tf gives
20ºC
-172 MPa (since in compression)
σ
Tf = T0 −
 Eα 

Answer: 106ºC 100 GPa 20 x 10-6/ºC

Chapter 19 - 21
 Prob # 3. A copper wire is stretched with a stress of 70 MPa (10,000 psi) at
20°C (68°F). If the length is held constant, to what temperature must the
wire be heated to reduce the stress to 35 MPa (5000 psi)?

Solution
We want to heat the copper wire in order to reduce the stress level from 70 MPa
to 35 MPa; in doing so, we reduce the stress in the wire by 70 MPa – 35 MPa = 35
MPa, which stress will be a compressive one (i.e., σ = –35 MPa). Solving for Tf
from Equation 19.8 [and using values for E and αl of 110 GPa (Table 6.1) and 17.0
× 10-6 (°C)-1 (Table 19.1), respectively] yields

σ
T f = T0 −
Eα l

− 35 MPa
= 20°C −
(110 × 103 MPa) 17.0 × 10−6 (°C ) −1 

= 20ºC + 19ºC = 39ºC (101ºF)

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Chapter 19 -
Thermal Shock Resistance
• Occurs due to: nonuniform heating/cooling
• Ex: Assume top thin layer is rapidly cooled from T1 to T2
rapid quench
σ
tries to contract during cooling T2 Tension develops at surface
resists contraction T1
σ = −Eα  (T1 −T2 )
Temperature difference that Critical temperature difference
can be produced by cooling: for fracture (set σ = σf)
quench rate σ
(T1 − T2 ) = (T1 −T2 ) fracture = f
k  Eα 
set equal
σk
• (quench rate) for fracture = Thermal Shock Resistance (TSR) ∝ f
 Eα 
σk
• Large TSR when f is large 23
Eα  Chapter 19 -
Thermal Protection System
Re-entry T
• Application: Distribution
Space Shuttle Orbiter

reinf C-C silica tiles nylon felt, silicon rubber

(1650ºC) (400-1260ºC) coating (400ºC)
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
Shuttle Orbiter Thermal Protection System", Ceramic
• Silica tiles (400-1260ºC): Bulletin, No. 11, Nov. 1981, p. 1189.)
-- large scale application -- microstructure:
~90% porosity!
Si fibers
bonded to one
another during
heat treatment.
100 µm
Fig. 19.3W, Callister 5e. (Fig. 19.3W courtesy the Fig. 19.4W, Callister 5e. (Fig. 219.4W
24 courtesy
National Aeronautics and Space Administration.) Lockheed Aerospace Ceramics
Systems, Sunnyvale, CA.) Chapter 19 -
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
σf k
-- is proportional to
Eα 
25

Chapter 19 -