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MTE 583 MTE 583 Advanced Structure of Materials Advanced Structure of Materials MTE 583 MTE 583 - - Advanced

d Structure of Materials Advanced Structure of Materials


Class 13
Crystallography and Crystal Structures continued
Suggested Reading
M. DeGraef and M.E. McHenry, Structure of Materials, Cambridge (2007). Ch. 8, pp. 181-197;
Ch 10 230 252) Ch. 10, pp. 230-252)
Ch. 1 C. Kittel, Introduction to Solid State Physics, 3
rd
Edition, Wiley (1956).
Excerpt from ASM Metals Handbook.
Chs. 1 and 3 S.M. Allen and E.L. Thomas, The Structure of Materials, Wiley (1999).
Ch 3 d4 R Till C l dC l S Wil (2006)
102
Chs. 3 and 4 R. Tilley, Crystals and Crystal Structures, Wiley (2006).
Symmetry Operators Symmetry Operators
All motions that allowa pattern to be transformed from All motions that allow a pattern to be transformed from
an initial position to a final position such that the initial
and final patterns are indistinguishable.
1. Translation*
2 Reflection
All crystals exhibit
translational symmetry.
2. Reflection
3. Rotation
4. Inversion (center of symmetry)
Any other symmetry elements
must be consistent with
translational symmetry of the
5. Roto-inversion (inversion axis)
lattice
These are compound
symmetry operators
6. Roto-reflection
7. Glide (translation + reflection)
8 Screw(rotation +translation)
symmetry operators
(combinations of 1-4)
103
8. Screw (rotation + translation)
Other Symmetry Operators Other Symmetry Operators
Translations interact with symmetry operators 1-6.
Results in the final two symmetry operators.
7. Glide Plane = Mirror Plane + Translation
a b c n d
8. Screw Axis = Rotation Axis + Translation
2
11
3
1
, 3
2
4 4 4 4
1
, 4
2
, 4
3
6
1
, 6
2
, 6
3
, 6
4
, 6
5
104
7. Glide Planes 7. Glide Planes
Combine reflection and translation
Spacing btw. Lattice points
A
A
A
Mirror plane
(Glide plane)
Glide direction
Nomenclature for glide planes

Glide Direction Glide Magnitude Designation
<100> axislength a b or c <100> axis length a, b, or c
<110> face diagonal n
<110> face diagonal d

When going from a space group to the parent point group, all as, bs,
105
g g p g p p p g p, , ,
cs, ns, and ds are converted back into ms.
8. Screw Axes 8. Screw Axes
P
Combine rotation
and translation
foldof rotation(2 3 4 or 6); eachrotation=2 /
m
nt mP
n n t
=
=
n
P
(i.e., corresponds to the spacing btween lattice points)
fold of rotation (2, 3, 4, or 6); each rotation =2 /
unit translation parallel to screw axis
n n
P
t =
=
P
( )
pitch of screw axis /
#
t t m n P
m
= = (

= of cells/steps back to starting position
P
n-fold rotation followed by a translation parallel to
the rotation axis P by a vector t =mP/n.
P
106
Adapted from L.V. Azaroff, Introduction to Solids,
McGraw-Hill, New York, 1960, p. 22.
( ) ( )
2
2
4
m
m
t P P
n
=
= =
n 4
( ) ( )
4 n
The operation of a 4
2
screw axis
parallel to the z direction; (a) atom A
at z =0isrotatedcounter clockwise
P
t
t
90
at z 0 is rotated counter clockwise
by 90; (b) the atom is translated
parallel to a by a distance of t =2P/4,
i.e. P/2, to create atom B; (c) atom B
t
90
is rotated counter clockwise by 90
and translated parallel to z by a
distance of t =2P/4, i.e. P/2, to give
C (d) C i P h
t
atom C; (d) atom C is at z =P, the
lattice repeat, and thus is repeated at z
=0; (e) repeat of the symmetry
operationproducesatomDat z =P/2
t
90
R Tilley Crystals and Crystal Structures Wiley Hoboken NJ 2006 p 95
operation produces atom D at z P/2.
Repeat of the symmetry operation on
atom D brings everything back into
coincidence, a requirement for
90
Final Configuration
107
R. Tilley, Crystals and Crystal Structures, Wiley, Hoboken, NJ , 2006, p. 95
symmetry; (f) a standard
crystallographic depiction of a 4
2
screw axis viewed along the axis.
These can be difficult to visualize. A nice, but inverted
visualization is provided on page 133 of Allen & Thomas.
Come see me if youd like a copy.
Space Groups Space Groups
Combineall geometrical symmetryoperationsthat Combine all geometrical symmetry operations that
take a 3-dimensional periodic object into itself.
Describesthe entiresymmetryof the crystal (internal
andexternal). and external).
Describehowall symmetryelementsaredistributed Describe how all symmetry elements are distributed
in space.
There are 17 space groups in 2D
108
There are 230 space groups in 3D
109
R. Tilley, Crystals and Crystal Structures, J ohn Wiley & Sons, Hoboken, NJ , 2006
Symmetry operators must leave every
lattice point unchanged (identical)
22--D example D example
Type Lattice
with
symmetry elements
lattice point unchanged (identical).
Form for symmetry symbols
Primary Secondary Tertiary Primary Secondary Tertiary
e.g., 2mm, 6mm, etc.
Consider the oblique lattice
2mm
q
180
a
b
Symmetry requires a 2-fold rotation axis
(i.e., diad) at the center of the cell.
Therefore, diads must be present on each
lattice point.
R. Tilley,
Crystals
and
Crystal
Structures
J h
There will be implied diads centered on cell
sides.
110
, J ohn
Wiley &
Sons,
Hoboken,
NJ , 2006
Point
Summary of what was presented on the previous page
symmetry
Implied
symmetry
111
M. DeGraef and M.E. McHenry, Structure of Materials, Cambridge University Press (2007) p. 233
Now, consider the rectangular
Symmetry of 2 Symmetry of 2- -D plane lattices D plane lattices Symmetry of 2 Symmetry of 2- -D plane lattices D plane lattices
Type Lattice
with
symmetry elements
o , co s de t e ecta gua
primitive lattice
180
a
b
2mm
a
2mm
As before, symmetry requirements
dictate that diads lie at the center of
the cell, at each lattice point, AND in the cell, at each lattice point, AND in
the center of the cell sides.
Newto this lattice is the presence of New to this lattice is the presence of
mirror symmetry along the cell edges
which necessitates the addition of
parallel mirrors half way along each
112
parallel mirrors half way along each
cell edge.
R. Tilley, Crystals and Crystal Structures, J ohn Wiley &
Sons, Hoboken, NJ , 2006
Point
symmetry
See this site for high resolution diagrams and tables
http://img.chem.ucl.ac.uk/sgp/mainmenu.htm
Implied
symmetry
Implied
mirrors
113
M. DeGraef and M.E. McHenry, Structure of Materials, Cambridge University Press (2007) p. 237
Point
symmetry
Implied mirrors
Implied
t
114
M. DeGraef and M.E. McHenry, Structure of Materials, Cambridge University Press (2007) p. 234
symmetry
Form/Order of Symmetry Symbols Form/Order of Symmetry Symbols
22--DD
Order of Hermann-Mauguin symbols for point groups:
Primary Secondary Tertiary
Lattice Primary Secondary Tertiary
Crystallographic position
y y y
Oblique, Rotation point --- ---
Retangular, , oc Rotation point [10] [01]
Square, Rotationpoint [10] [01] [11] [11]
mp
op
tp = = Square, Rotation point [10] [01] [11] [11]
Hexagonal, Rotation point [10]
tp
hp [01] [11] [11] [12] [21] = = = =
Example
2 m m
115
primary 2-fold rotation axis mirror to [10] mirror to [01]
Ten plane point groups (2D) without an asymmetric object Ten plane point groups (2D) without an asymmetric object
1 2 3 4 6 1 2 3 4 6 m
2mm 3m 6mm 4mm
116
Ten plane point groups (2D) with an asymmetric object Ten plane point groups (2D) with an asymmetric object
1 2 3 4 6 1 2 3 4 6 m
m
2mm 3m 6mm 4mm
m
m
m
m
m
m
m
m
m
m
m
m
m
117
m
m
Symmetry of 2 Symmetry of 2- -D plane lattices D plane lattices Symmetry of 2 Symmetry of 2- -D plane lattices D plane lattices
When all of the translations for the five plane lattices are
combined with the symmetry elements found in the 10
point groups plus glide lines, 17 plane groups are found.
Glide lines are 2 D Glide lines are 2-D
equivalents of the 3-D
glide planes we
introduced earlier.
Fi 3 8 Th l d ( ) th l l tti (b) th tt f db ddi th tif f i t Figure 3.8 The plane groups pm and cm: (a) the plane lattice op; (b) the pattern formed by adding the motif of point
group m to the lattice in (a), representing the plane group pm; (c) the plane lattice oc; (d) the pattern formed by adding
the motif of plane group m to the lattice in (c), representative of plane group cm. Mirror lines are heavy and glide lines in
(d) are heavy dashed. From R. Tilley, Crystals and Crystal Structures, J ohn Wiley & Sons, Hoboken, NJ , 2006.
17 2 17 2--D plane groups D plane groups 17 2 17 2--D plane groups D plane groups
119
R. Tilley, Crystals and Crystal Structures, J ohn Wiley & Sons, Hoboken, NJ , 2006
17 2 17 2--D plane groups D plane groups 17 2 17 2--D plane groups D plane groups
120
R. Tilley, Crystals and Crystal Structures, J ohn Wiley & Sons, Hoboken, NJ , 2006
Higher-order? Higher-order?
The maximum degree of symmetry that a crystal
can possess is defined by the lattice. can possess is defined by the lattice.
A crystal can have lower symmetry than the A crystal can have lower symmetry than the
lattice:
Square Lattice 4mm (see next page)
Allowed motif symmetry 4 and 4mm
Square + 4mm Square + 4mm
Can we put a motif with 4mm symmetry on a square lattice?
4mm
Unit cell Primitive: p
P i t t f tif 4 Point symmetry of motif: 4mm
Space or Plane group: p4mm
Symmetry in 3 Symmetry in 3--D D Symmetry in 3 Symmetry in 3--D D
Howcan we describe 3-D How can we describe 3 D
objects in terms of symmetry?
Hermann-Mauguin symbols for
point groups.
Primary Secondary Tertiary
There is a specific order that we
use to assign symbols. This is
provided on the next slide.
Detailed descriptions of the point
groups for the tetrahedron and
123
groups for the tetrahedron and
octahedron are provided after
the table of symbols.
R. Tilley, Crystals and Crystal Structures,
J ohn Wiley & Sons, Hoboken, NJ , 2006
Form/Order of Symmetry Symbols Form/Order of Symmetry Symbols
33--DD
Form/Order of Symmetry Symbols Form/Order of Symmetry Symbols
33--DD
Lattice Primary Secondary Tertiary
Crystallographic Position
Triclinic --- --- ---
Monoclinic [010], unique axis --- ---
[001], unique axis --- ---
b
c
Orthorhombic [100] [010] [001]
Tetagonal [001] [100],[010]
[110],[110]
Trigonal Rhombohedral axes [111]
[110] [011] [101]
Trigonal, Rhombohedral axes [111]
[110],[011],[101]
Trigonal, Hexagonal axes [001]
[100],[010],[110]
Hexagonal [001]
[100],[010],[110] [110],[120],[210]
Cubic [100],[010],[001]
[111],[111],[111],[111] [110],[110],[011],[011]
[101],[101]
124
In 3 In 3--D we formulate symbols just like 2 D we formulate symbols just like 2--D! D!
SPACE GROUPS SPACE GROUPS
[We often use short notation. A few are shown below] [We often use short notation. A few are shown below]
Triclinic space groups:
P1and P1
Monoclinic space groups: (we consider only a few examples)
Short symbols: P2 P2
1
P2/m C2/c
Complete symbols: P 121 P 12
1
1 P 12/m 1 C 12/c 1
Note from the last page
that we use one symbol
for monoclinic anyway
Complete symbols P 1 2 1 P 1 2
1
1 P 1 2/m 1 C 1 2/c 1
S t l i b i i
The same convention is used for
O th h bi
Symmetry along: a axis b axis c axis
Orthorhombic space groups:
Short symbols: P222
1
Pma2 Pban Cmmm
Complete symbols: P222
1
Pma2 P 2/b 2/a 2/n C 2/m 2/m 2/m
More on this later.
125
Synopsis of relationships between crystal systems, Bravais
lattices, point groups, and space groups
7 Crystal Systems
Rotation
Reflection
Inversion
Add points &
centering
32 Point Groups 14 Bravais Lattices
Screw
Applies to lattice Applies to motif on
lattice point
Screw
Glide
126
230 Space Groups
43m
Point group for a regular
43m
tetrahedron
43m
Point group for a regular
octahedron
127
R. Tilley, Crystals and Crystal Structures, J ohn Wiley & Sons, Hoboken, NJ , 2006
R. Tilley, Crystals and Crystal R. Tilley, Crystals and Crystal
Structures, J ohn Wiley & Sons,
Hoboken, NJ , 2006
128
R. Tilley, Crystals and Crystal Structures, J ohn
129
R. Tilley, Crystals and Crystal Structures, J ohn
Wiley & Sons, Hoboken, NJ , 2006
Symmetry of the Cubic Symmetry of the Cubic PP--Lattice Lattice Symmetry of the Cubic Symmetry of the Cubic PP--Lattice Lattice
4 3 2
Letter
symbol
P m m
|
+ + +
100 111 110
+ + +
Primary Secondary Tertiary
130
Adapted from W. Borchardt-Ott, Crystallography, 2
nd
Edition, Springer, Berlin, Germany, 1995, p. 99
Galena (PbS) Galena (PbS)
4 3 2
F 3
m m
m m
http://crystal-cure.com/pics/galena.jpg
http://www.minservice.com/cartshop3/catalog/FERR0240 galena p.jpg p p g _g _pjpg
http://en.wikipedia.org/wiki/File:Galena-unit-cell-3D-ionic.png
Crystal Forms Crystal Forms Crystal Forms Crystal Forms
132
Adapted from W. Borchardt-Ott, Crystallography, 2
nd
Edition, Springer, Berlin, Germany, 1995, p. 124
230 Space Groups 230 Space Groups
Describe complete symmetry of a crystal
(internal and external). (internal and external).
230 possible combinations 230 possible combinations.
Thus there are 230 possible crystal structures! Thus, there are 230 possible crystal structures!
All possibilities can be found in the International All possibilities can be found in the International
Tables for Crystallography.
133
Summary of Crystallography Summary of Crystallography
ID KNOWTHIS!
7 Crystal Systems
Based on the number of self consistent combinations of rotation axis in 3D-defines basic P
units cells.
ID KNOW THIS!
14 Bravais Lattices
Arrangements of lattice points consistent with the above combinations of rotation axes i.e.
some unit cells can also be F, I or C centered.
32 Point Groups p
Combinations of symmetry elements acting through a point - each belongs to a crystal class.
Describes macroscopic shape of ideal crystals.
Describes symmetry of properties such as thermal expansion, elastic modulus, refractive
index and conductivity. y
230 Space Groups
Point group symmetry plus translational symmetry e.g. screw axes and glide planes each
belongs to a crystal structure.
Not all of the space groups are of equal importance and many of them have no examples of p g p q p y p
real crystals at all.
About 70% of the elements belong to the space groups Fm3m, Im3m, Fd3m, F43m and
6
3
/mmc. Over 60% of organic and inorganic crystals belong to space groups P2
1
/c, C2/c, P2
1
,
P1, Pbca, P2
1
2
1
2
1
.
134
, ,
1 1 1