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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 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  MSE-227
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 Dependence of Heat Capacity on
• Heat capacity... Temperature
-- increases with temperature
-- for solids it reaches a limiting value of 3R

R = gas constant 3R Cv = constant

= 8.31 J/mol-K

Cv

0 T (K)
0 D
Debye temperature
(usually less than T room )
• From atomic perspective:
-- Energy is stored as atomic vibrations.
-- As temperature increases, the average energy of
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atomic vibrations increases. 3
 Atomic Vibrations
Atomic vibrations are in the form of lattice waves or phonons

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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
Tungsten 138
Gold 128
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 Thermal Expansion
Materials change size when temperature
is changed
Tinitial
 initial
Tfinal > Tinitial
Tfinal
 final

final  initial
 α(Tfinal  Tinitial )
initial
linear coefficient of
thermal expansion (1/K or 1/°C)

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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
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 Coefficient of Thermal Expansion:
Comparison
Material  (10-6/C)
• Polymers at room T
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 
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 Conductivity
The ability of a material to transport heat.
Fourier’s Law
temperature
dT
q  k gradient
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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 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 MSE-227
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 Thermal Stresses
• Occur due to:
-- restrained thermal expansion/contraction
-- temperature gradients that lead to differential

dimensional changes

Thermal stress 

 E  (T0 Tf )  E T



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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   E  (T1 T2 )

Temperature difference that Critical temperature difference
can be produced by cooling: for fracture (set  = f)
quench rate 
(T1  T2 )   (T1 T2 ) fracture  f
k  E 
set equal
k
• (quench rate) for fracture  Thermal

Shock Resistance (TSR)  f
 E 
k
• Large TSR when f is large MSE-227
E 
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 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)

• Silica tiles (400-1260C):

-- large scale application -- microstructure:
~90% porosity!
Si fibers
bonded to one
another during
heat treatment.
100 m
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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
f k
-- is proportional to
E 

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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?
6  1
• Answer: For Cu 
  16.5 x 10 ( C)

rearranging Equation 17.3b

   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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