Lecture of January 21

ENGR 4680U
Nuclear Materials
Topics I
1. Structure of Crystalline Solids
2. Solidification and Defects
3. Alloys and Phase Diagrams
Atoms in the Crystals
Want to give the position of atoms
Want to describe directions
Want to describe planes of atoms

Atom Position
Miller indices - directions
[specific direction]

<family of directions>
The bar indicates a
negative direction
Bracket Convention
specific Family or
of a class
direction [ ] < >

plane ( ) { }
Specific vs Family
~Directions~
<111> family of directions is
the following 8 specific directions:

[111], [111], [111], [111], [111], [111], [111], [111]

Specific vs Family
~Planes~
{100} family of planes is
the following 6 specific planes:

(100), (010), (001), (100), (010), (001),

Indices of planes are h,k and l, the inverse of the intercepts on the a,b,
and c axes respectively (0 for axis parallel to the plane, 1/)
Miller indices - planes
Body-centred Cubic
Body-centred Cubic
Inverse
of
intercepts
Face-centred Cubic
] 20 1 1 [
] 0 1 2 1 [
] 3 1 2 1 [
] 0001 [
] 00 1 1 [
cph Crystal Structure
Note that for
cph structures
there is also a
4 coordinate
system as well
Angle Between Directions
given two directions [uvw] and [uvw]
angle between them is
let D be the vector of [uvw] and
D is the vector of [uvw]
so:
cos D D D D u
' '
=
Angle Between Directions
or



Note: this only applies to a cubic system
See handout for other systems
cos
cos
D D D D
D D
D D
u
u
' '
=
'

=
'
( ) ( ) ( ) ( ) ( ) ( )
2 2 2 2 2 2
cos
uu vv ww
u v w u v w
u
' ' '
+ +
=
' ' '
+ + + +
Braggs Law
2d
hkl
sinu = n
Braggs Law
2d
hkl
sinu = n
Incident Beam
Reflected Beam
2u
d
Neutron vs X-ray Diffraction
Neutrons interact with nucleus while X-rays
interact with electron cloud
Neutrons penetrating; X-rays absorbed near
surface
Neutrons can probe bulk properties
References
R.E. Reed-Hill, Physical Metallurgy Principles, 2
nd

Edition, PWS-Kent Publishing Co., (1973), Chapter 4.
D.A. Porter and K.E. Easterling, Phase Transformations
in Metals and Alloys, 2
nd
Edition, Stanley Thornes
(Publishers) Ltd., Chapter 3
J.F. Shackelford, Introduction to Materials Science for
Engineers, 3
rd
Edition, Macmillan Publishing
Co.,(1992).
Polycrystalline Zr
Magnification is: 350X
Solid Solutions

Liquid Solutions

Solid Solutions
Hume-Rothery rules for solid solution formation:
less than about 15% difference in atomic radii
the same crystal structure
similar electronegativity values
same valence

all 4 rules must be satisfied; if any rule violated only
partial solubility possible
Solid Solutions

Substitutional Solid Solution

Solid Solutions

Interstitial Solid Solution

Interstitial Solid Solution

Point Defects
1. Vacancy
2. Self interstitial
3. Interstitial impurity
4. Substitutional impurity
under tension
5. Substitutional impurity
under compression



Two Types of Point Defects
Schottky (German) defect involves a pair of
oppositely charged ion vacancies

Frenkel (Russian) defect is a vacancy-
interstitialcy combination
Two Types of Point Defects

self-interstitial
atom (SIA)
Point Defects in Crystals
vacancy solute atoms
substitutional
interstitial
Thermal Production of Defects
for many processes, the process rate rises
exponentially with temperature
diffusivity of elements in metal alloys
rate of creep deformation
electrical conductivity
Diffusion in Solids

General Equation
Arrhenius (Swedish) Equation



where:
C is a preexponential constant; Q is the activation energy;
R is the universal gas constant; T is the absolute temperature


k is Boltzmanns constant; q = Q/N
A
kT
q
RT
Q
Ce rate
T
1
R
Q
C ln ) rate ln(
Ce rate

=
=
=
General Equation

Interstitial Diffusion
Interstitial Diffusion
jump frequency
flux to left/right
net flux
jump distance
diffusion coefficient units of m
2
s
-1
concentration gradient
( )
x
C
D J
x
C
6
1
J J J
n
6
1
J
n
6
1
J
i
i i
i
2
i i i i
2 i i
1 i i
c
c
=
c
c
I = =
I =
I =
o

Interstitial Jump Frequency

Interstitial Diffusion
entropy/enthalpy of migration
vibration frequency
number of available sites
jump distance
kT
H
D D
kT
H
k
S
z
mi
i i i i
mi mi
i i i
A
= I =
A

A
= I
exp
6
1
exp exp
0
2
o
v

Theoretical vs Observed Yield
For Mg single crystal
Slip Lines
Side View Front View
Atoms on the Slip Plane
Initial Position
At the Saddle Point
Shear is ~0.5
at saddle point
Forces to cause coordinated shear were calculated
G
shear modulus
3 orders of
magnitude too large
shear strain
6
2
2 2
sin
G
a
b G
G
b
x
b
x
m
m m
~

~
=
~ =
t
t
t
t
t
t
t t
Slip Systems
At low temperatures / high stresses: Deformation of crystals
occurs exclusively by slip of lattice planes
Slip system is characterized by:
slip plane normal
slip direction
slip vector (a lattice vector in the slip direction)
often: slip planes are most densely packed lattice planes
slip directions are most densely packed lattice directions
n
s
Slip Systems
Slip Systems
Shear in close packed direction
easy
Shear in nonclose packed direction
harder
Slip Systems
slip frequency occurs on the most closely
packed planes, and almost invariably in the
most closely packed direction:
fcc <110>,{111}
bcc <111>,{110}
hcp <1120>,{0002} and also {1010}

Driving Force for Slip
Tensile stress, o = F/A
Resolved shear stress t
R
in
slip system
t
R
= o cos cos |

n
s

|
F
F
A
Driving Force for Slip
t
R
= 0 if = 90
o
or | = 90
o

n
s

F
F
A
normal
perpendicular
|
Driving Force for Slip
t
R
= max when = | = 45
o

n
s

F
F
A
|

How does slip occur?
Note: slip is not a simultaneous breaking of
all bonds
Involves the motion of defects- dislocations
Dislocations
Edge dislocation
Screw dislocation
The presence of defects (dislocations,
vacancies, etc.) explains the discrepancy
between the computed (i.e., theoretical)
and real yield stress.
Edge Dislocation
Edge Dislocation
Edge Dislocation
Movement of an ED
Movement of an ED
Movement of an ED
Movement of an ED
Side view of edge dislocation
Dislocation Climb
An example of positive climb
Burgers Vector
Characterizes a dislocation
Results from a mismatch in the closed
circuit around a dislocation
Burgers Circuits
Edge Dislocation Screw Dislocation
Burgers Vector
dislocation
Burgers vector
Dislocations
Edge dislocation
line is perpendicular to Burgers vector
Positive moves right; negative moves left
Screw dislocation:
line is parallel to Burgers vector
Screw Dislocation
Screw Dislocation
Left Hand Screw Dislocation
Screw Dislocation
Right Hand Screw Dislocation

References
R.E. Reed-Hill, Physical Metallurgy Principles, 2
nd

Edition, PWS-Kent Publishing Co., (1973), Chapter 4.
D.A. Porter and K.E. Easterling, Phase Transformations
in Metals and Alloys, 2
nd
Edition, Stanley Thornes
(Publishers) Ltd., Chapter 3
J.F. Shackelford, Introduction to Materials Science for
Engineers, 3
rd
Edition, Macmillan Publishing
Co.,(1992).
Gibbs Phase Rule
P + F = C + 2
P represents # of phases
F represents # of degrees of freedom
C represents # of components
2 (limiting state variables: 1 for temperature, 1
for pressure)
Police Force = Cops + 2 Vehicles
Definitions
Phase homogeneous region
chemically and structurally homogeneous
Component distinct chemical substance from
which phase is formed
Degrees of Freedom number of independent
variables available to the system
Reduction of State Variables
If pressure is fixed P + F = C + 1

If temperature is fixed P + F = C + 1

If both fixed P + F = C
Unary Phase Diagrams
Water
Unary Phase Diagrams
Iron
Binary Phase Diagrams

Partial Binary Diagram for Pd-Rh
X
Rh
0.0 0.2 0.4 0.6 0.8 1.0
Pd Rh
1 atm
T
e
m
p
e
r
a
t
u
r
e

(
K
)

1500
2000
2500
1500
2000
2500
Liquid
Solid solution (fcc)
2236
1827
2200
Liquid + fcc
Solidus
Liquidus
Cu-Ni Binary

A ssessed Cu - N i p h ase di agr am . L i qui dus and sol i dus ar e obt ai ned f r om t he ex per i m ent al dat a of
[71Bas], [71Fee], and [71Sch]. T he l ow - t em per at ur e por t i on of t he di agr am i s obt ai ned f r om
t her m ody nam i c m odel i ng.
Rh-Pd
Rh Pd X
Pd
0.0 0.2 0.6 0.8 1.0
500
1000
1500
2000
2500
3000
500
1000
1500
2000
2500
3000
T
e
m
p
e
r
a
t
u
r
e

(
K
)

2236.4
1827.1
Rh (fcc) + Pd (fcc)
0.4
1182.8
0.45
Liquid
Solid (fcc)
Phase Assemblage

Typical Microstructural Evolution

Terminal Solid Solutions

Typical Microstructural Evolution

Binary Eutectic Phase Diagram
Typical Microstructural Evolution


Peritectic Phase Diagram for Pd-Ru
Liquid
Pd (fcc)
Pd (fcc) + Ru (cph)
Ru
(cph)
o
c
o + c
Liquid +
c
Liquid +
o
0.0 0.2 0.4 0.6 0.8 1.0
500
1000
1500
2000
2500
3000
500
1000
1500
2000
2500
3000
2607.0
1827.1
1866.4
Pd Ru X
Ru
T
e
m
p
e
r
a
t
u
r
e

(
K
)

0.923
0.185
0.10
Eutectic and Eutectoid

Fe-C

A ssessed F e- C p h ase di agr am .
Eutectic and Eutectoid

Typical Microstructural Evolution