Material Science:

The thermal and optical

Outline:

The characteristic of thermal

The characteristic of Optical

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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?
* Callister et al., Chapter
19, page 782
3

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.
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 usually > Cv
J
Btu

mol K lb mol F
4

Dependence of Heat Capacity on

Temperature
Heat capacity...
-- increases with temperature
-- for solids it reaches a limiting value of 3R
Cv = constant

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

T (K)

Adapted from Fig. 19.2,

Callister & Rethwisch 8e.

Debye temperature
(usually less than T room )

From atomic perspective:

-- Energy is stored as atomic vibrations.
-- As temperature increases, the average energy of
atomic vibrations increases.

Atomic Vibrations
Atomic vibrations are in the form of lattice waves
or phonons

Adapted from Fig. 19.1, Callister & Rethwisch 8e.

Specific Heat: Comparison

increasing cp

cp (J/kg-K)
Material
at room T
Polymers
cp (specific heat): (J/kg-K)
1925
Polypropylene
1850
Polyethylene
Cp (heat capacity): (J/mol-K)
1170
Polystyrene
1050
Teflon
Ceramics
Magnesia (MgO)
Alumina (Al2O3)
Glass

940
775
840

Metals
Aluminum
Steel
Tungsten
Gold

900
486
138
128

Why is cp
significantly
larger for polymers?

Selected values from Table 19.1,

Callister & Rethwisch 8e.

Thermal Expansion
Materials change size when temperature is
changed
Tinitial

initial

Tfinal

final

final

initial

Tfinal > Tinitial

l (Tfinal Tinitial)

initial

linear coefficient of
thermal expansion (1/K or 1/C)

Atomic Perspective: Thermal Expansion

Asymmetric curve:
-- increase temperature,
-- increase in interatomic
separation
-- thermal expansion

Symmetric curve:
-- increase temperature,
-- no increase in interatomic
separation
-- no thermal expansion

Adapted from Fig. 19.3, Callister & Rethwisch 8e.

Coefficient of Thermal Expansion:

Comparison
Material

increasing

Polymers
Polypropylene
Polyethylene
Polystyrene
Teflon

a (10-6/C)
at room T

Metals
Aluminum
Steel
Tungsten
Gold
Ceramics
Magnesia (MgO)
Alumina (Al2O3)
Soda-lime glass
Silica (cryst. SiO2)

145-180
106-198
90-150
126-216
23.6
12
4.5
14.2
13.5
7.6
9
0.4

Polymers have larger

values because of
weak secondary bonds
Q: Why does a
generally decrease
with increasing
bond energy?

Selected values from Table 19.1,

Callister & Rethwisch 8e.

10

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 ( o C) 1

Rearranging Equation 19.3b

0 T
[16.5 x 10 6 (1 / C)](15 m)[40 C ( 9 C)]
0.012 m 12 mm
11

Thermal Conductivity
The ability of a material to transport heat.

heat flux
(J/m2-s)

Fouriers
Law
dT
q k
dx

temperature
gradient

thermal conductivity (J/m-K-s)

T2

T1
x1

heat flux

x2

T2 > T1

Atomic perspective: Atomic vibrations and free

electrons in
hotter regions transport energy to cooler regions.

12

increasing k

Thermal Conductivity:
Energy Transfer
Comparison
Material
k (W/m-K)
Mechanism
Metals
Aluminum
Steel
Tungsten
Gold
Ceramics
Magnesia (MgO)
Alumina (Al2O3)
Soda-lime glass
Silica (cryst. SiO2)
Polymers
Polypropylene
Polyethylene
Polystyrene
Teflon

247
52
178
315
38
39
1.7
1.4

atomic vibrations
and motion of free
electrons

atomic vibrations

0.12
0.46-0.50 vibration/rotation
of chain
0.13
molecules
0.25

Selected values from Table 19.1, Callister & Rethwisch 8e.

13

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

Thermal stress

E (T0 Tf ) E T
Modulus
of
elasticity

Linear coefficient of thermal

expansion from table 19.1
14

Example:
A brass rod is to be used in an application
requiring its ends to be held rigid. If the rod is
stress free at room temperature [ 20oC (293 K)],
what is the maximum temperature to which the
rod may be heated without exceeding a
compressive stress of 172 MPa? Assume a
modulus of elasticity of 100 GPa for brass

Linear coefficient of thermal

expansion from table 19.1, is
20 x 10-6 (oC)-1

Modulus
of
elasticity
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Example Problem
-- A brass rod is stress-free at room temperature (20C).
-- It is heated up, but prevented from lengthening.
-- At what temperature does the stress reach -172 MPa?
Solution:
T0

Original conditions

Step 1: Assume unconstrained thermal expansion

0

Tf

thermal (Tf T0 )
room

Step 2: Compress specimen back to original length

0

compress

thermal
room
16

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
20C

Tf T0

Answer: 106C

100 GPa

-172 MPa (since in compression)

E
20 x 10-6/C
17

Thermal Shock Resistance

Occurs due to: nonuniform heating/cooling
Ex: Assume top thin layer is rapidly cooled from T1 to T2
rapid quench

T2
tries to contract during cooling

Tension develops at surface

T1

resists contraction

E (T1 T2 )

Temperature difference that

can be produced by cooling:

(T1 T2 )

quench rate
k

Critical temperature difference

for fracture (set s = sf)

(T1 T2 ) fracture

f
E

set equal
(quench rate) for

fracture

Large TSR when

k
Thermal Shock Resistance (TSR) f

f k
is large
E

18

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
-- is proportional to f k
E
19

Optical Properties
ISSUES TO ADDRESS...
What phenomena occur when light is shined on a material?
What determines the characteristic colors of materials?
Why are some materials transparent and others are
translucent or opaque?
How does a laser operate?

* Callister et al., Chapter

21, page 840
20

Optical Properties
Light has both particulate and wavelike characteristics
Photon - a quantum unit of light

hc
E h

E energy of a photon
wavelength
of radiation

frequency of radiation
h Planck s constant (6.62 x 10 34 J s)
c speed of light in a vacuum (3.00 x 108 m/s)
21

Refraction
Transmitted light distorts electron clouds.
no
transmitted
light

transmitted
light

electron
cloud
distorts

The velocity of light in a material is lower than in a

vacuum.
n = index of
refraction

c (velocity of light in vacuum)

v (velocity of light in medium)

-- Adding large ions (e.g., lead) to glass

decreases the speed of light in the glass.
-- Light can be bent as it passes through a
transparent prism

Material

Typical glasses ca. 1.5 -1.7

Plastics
1.3 -1.6
PbO (Litharge)
2.67
Diamond
2.41
Selected values from Table 21.1,
Callister & Rethwisch 8e.

22

Total Internal Reflectance

n2 < n1

n1 sin 2

n2 sin 1

n2

n1

= incident angle

= refracted angle

= critical angle

exists when 2 = 90

For 1 > c light is internally reflected

Fiber optic cables are clad in low n material so that light

will experience total internal reflectance and not escape
from the optical fiber.

23

Example: Diamond in
What is the critical angle for light passing
air
c

from diamond (n1 = 2.41) into air (n2 = 1)?

1 c
2 90
Rearranging the equation n1 sin 2

n2 sin 1

n2
n2
sin 1 sin c sin(90 )
n1
n1
Substitution gives
1
sin c
c 24.5o
2.41

Solution: At the critical

angle,
and

24

Light Interactions with Solids

Incident light is reflected, absorbed, scattered, and/or
transmitted: I I I I I
0

Reflected: IR

Absorbed: IA
Transmitted: IT

Incident: I0

Scattered: IS

Optical classification of materials:

Transparent

Translucent
Opaque

single
crystal

polycrystalli
ne dense

Adapted from Fig. 21.10,

Callister 6e. (Fig. 21.10 is by
J. Telford, with specimen
preparation by P.A. Lessing.)

polycrystallin
e porous
25

Concept
check:
Distinguish between materials that are
opaque, translucent, and transparent in
terms of their appearance and light
transmittance

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Optical Properties of Metals:

Absorption
Absorption of photons by electron transitions:
Energy of electron
unfilled states

n
o
t
ho
p
nt
e
h
d
i
y
g
Inc
r
ne
e
of
Plancks constant
(6.63 x 10-34 J/s)

freq.
of
incident
light

E = h required!

filled states
Adapted from Fig. 21.4(a),
Callister & Rethwisch 8e.

Unfilled electron states are adjacent to filled states

Near-surface electrons absorb visible light.
27

Light Absorption
The amount of light absorbed by a material is calculated
using Beers Law

IT I 0e

= absorption coefficient, cm-1

= sample thickness, cm
I 0 = incident light intensity

IT

= transmitted light intensity

Rearranging and taking the natural log of both sides of

the equation leads to

IT
ln
I 0
28

Example 21.1
The fraction of nonreflected light that is
transmitted through a 200-mm thickness of glass
is 0.98. calculate the absorption coefficient of
this material

IT I 0e

IT
ln
I 0

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Reflection of Light for Metals

Electron transition from an excited state
produces a photon.
Energy of electron

IR
photon emitted
from metal
surface

unfilled states
conducting electron
Electron transition
filled states

Adapted from Fig. 21.4(b),

Callister & Rethwisch 8e.

30

Reflection of Light for Metals

(cotd)

Reflectivity = IR /I0 is between 0.90 and 0.95.

Metal surfaces appear shiny
Most of absorbed light is reflected at the same
wavelength
Small fraction of light may be absorbed
Color of reflected light depends on wavelength
distribution
Example: The metals copper and gold absorb
light in blue and green => reflected light has
gold color
31

Reflection
I0 = intensities of incident
beams
IR = Intensities of reflected
beams
If the light is normal(or
perpendicular) to the
interface, then:
n1 and n2 are the indices of
refraction of the two media
When light is transmitted from vacuum or air into a
solid, then

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Reflectivity of Nonmetals

For normal incidence and light passing into a

solid having an index of refraction n:

n 12
R reflectivity
n 1
Example: For Diamond n = 2.41

2.41 1
R
0.17
2.41 1
17% of light is reflected
33

Problem:
The index of refraction of corundum (Al2O3) is
anisotropic. Suppose that visible light is
passing from one grain to another of different
crystallographic orientation and at normal
incidence to the grain boundary. Calculate the
reflectivity at the boundary if the indices of
refraction for the two grains are 10.12 and 8.25
in the direction of light propagation

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Transmission
(eq. 21.19)

Inciden
t beam,
Io

Reflected
beam, IR = IoR

Problem#
Derive
Equation
21.19, starting from
other expressions
given in the chapter

Transmitted
beam

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Scattering of Light in Polymers

For highly amorphous and pore-free polymers

Little or no scattering
These materials are transparent
Semicrystalline polymers
Different indices of refraction for amorphous and
crystalline regions
Scattering of light at boundaries
Highly crystalline polymers may be opaque
Examples:
Polystyrene (amorphous) clear and transparent
Low-density polyethylene milk cartons opaque
36

Selected Light Absorption in

Semiconductors
Absorption of light of frequency by by electron transition
occurs if
hn > Egap
Examples of photon
energies:
blue light: h = 3.1 eV
red light: h = 1.8 eV

Energy of electron
unfilled states

Egap
incident photon
energy hn

filled states
Adapted from Fig. 21.5(a),
Callister & Rethwisch 8e.

If Egap < 1.8 eV, all light absorbed; material is opaque (e.g., Si, GaAs)
If Egap > 3.1 eV, no light absorption; material is transparent and
colorless (e.g., diamond)
If 1.8 eV < Egap < 3.1 eV, partial light absorption; material is colored
37

Computations of Minimum
Wavelength Absorbed
(a) What is the minimum wavelength absorbed by
Ge, for which Eg = 0.67 eV?
Solution:

hc
(6.63 x 10 34 Js)(3 x 108 m/s)
Ge (min)

E g (Ge)
(0.67 eV)(1.60 x 10 19 J/eV)
Ge (min) 1.86 x 10 -6 m 1.86 m

(b) Redoing
this computation for Si which has a band
gap
of 1.1 eV (min) 1.13 m
Si

Note: the presence of donor and/or acceptor states allows for

light absorption
at other wavelengths.

38

Luminescence

Luminescence reemission of light by a material

Material absorbs light at one frequency and reemits it at

another (lower) frequency.
Trapped (donor/acceptor) states introduced by
impurities/ defects
Conduction band

Eg

Eemission

If residence time in trapped state

is relatively long (> 10-8 s)
-- phosphorescence

For short residence times (< 10-8

s)
-- fluorescence
activator
level
Example: Toys that glow in the
Valence band
dark. Charge toys by exposing
them to light. Reemission of
39
light over time

trapped
states

Photoluminescence
Hg atom

UV light
electrode

electrode

Arc between electrodes excites electrons in mercury atoms in the

lamp to higher energy levels.
As electron falls back into their ground states, UV light is emitted
e.g., suntan lamp
Inside surface of tube lined with material that absorbs UV and
reemits visible light
E.g., Ca F P O
10 2 6 24 with 20% of F replaced by Cl
Adjust color by doping with metal cations
Sb3+
blue
Mn2+ orange-red
40

Cathodoluminescence

Used in cathode-ray tube devices (e.g., TVs, computer monitors)

Inside of tube is coated with a phosphor material
Phosphor material bombarded with electrons
Electrons in phosphor atoms excited to higher state
Photon (visible light) emitted as electrons drop back into
ground states
Color of emitted light (i.e., photon wavelength) depends on
composition of phosphor
ZnS (Ag+ & Cl-)
blue
(Zn, Cd) S + (Cu++Al3+) green
Y2O2S + 3% Eu
red
Note: light emitted is random in phase & direction
i.e., is noncoherent
41

The LASER

The laser generates light waves that are in phase

(coherent) and that travel parallel to one another
LASER
Light
Amplification by
Stimulated
Emission of
Radiation

Operation of laser involves a population inversion of

energy states process
42

Operation of the Ruby Laser

pump electrons in the lasing material to

excited states
e.g., by flash lamp (incoherent light).

Fig. 21.13, Callister & Rethwisch 8e.

Direct electron decay transitions produce incoherent

43

Semiconductor Laser Applications

Compact disk (CD) player

Use red light
High resolution DVD players
Use blue light
Blue light is a shorter wavelength than red light
so it produces higher storage density
Communications using optical fibers
Fibers often tuned to a specific frequency
Banks of semiconductor lasers are used as flash
lamps to pump other lasers
44

Other Applications of Optical

Phenomena

New materials must be developed to make new &

improved optical devices.
Organic Light Emitting Diodes (OLEDs)
More than one color available from a single
diode
Also sources of white light (multicolor)

Fig. 21.12, Callister & Rethwisch 8e.

(Reproduced by arrangement with
Silicon Chip magazine.)

45

Other Applications - Solar Cells

p-n junction:
P-doped Si
conductance
Si
electron
Si P Si
Si

Operation:
-- incident photon of light produces elec.-hole
pair.
-- typical potential of 0.5 V produced across
junction
creation of
-- current increases w/light
intensity.
hole-electron
light

n-type Si
p-n junction
p-type Si

n-type Si
p-n junction
p-type Si

pair

- +
+ + +

Solar powered weather station:

Si

hole
Si

Si

Si
B-doped Si

polycrystalline Si
Los Alamos High School weather
station (photo courtesy
P.M. Anderson)
46

Optical Fibers (cont.)

fibers have diameters of 125 m or less

plastic cladding 60 m thick is applied to fibers

Fig. 21.20, Callister &

Rethwisch 8e.

47

SUMMARY
Light radiation impinging on a material may be reflected
from, absorbed within, and/or transmitted through
Light transmission characteristics:
-- transparent, translucent, opaque
Optical properties of metals:
-- opaque and highly reflective due to electron energy band
structure.
Optical properties of non-Metals:
-- for Egap < 1.8 eV, absorption of all wavelengths of light
radiation
-- for Egap > 3.1 eV, no absorption of visible light radiation
-- for 1.8 eV < Egap < 3.1 eV, absorption of some range of
light
radiation wavelengths
-- color determined by wavelength distribution of
transmitted light
Other important optical applications/devices:

48