CRYSTALLOGRAPHY

CRYSTALLOGRAPHY
Unit Cell and Lattice
Bravais Lattices
FCC, BCC, HCP
Atomic Packing Factor
Directions in a unit cell
Planes in a unit cell
Polymorphism

.(M.C. Escher)

1845: Bravais correctly predicted 14 lattice systems,

later to be called Bravais Lattices.
1912: Max von Laue demonstrated the wave nature
of X-rays, by diffraction from a crystal of
copper sulphate.
1913: Sir L. Bragg solved the structure of NaCl.

 " .

)(Crystal

) (Long Range Order , .

) , ,-
) ((.

) (.

Selenite
Gypsum
)CaSO4-2(H2O

Garnet
X3Y4(SiO4)3
Where X=Ca, Mg, Fe2+, Mn
Y=Al, Fe3+, Cr

Calcite
CaCO3

Amethyst
SiO2

 )(Lattice

- , ,
, .

)( .
.

, .
.

)(Unit Cell

-.

" , ) ,
( , .

)(110

 )(NaCl

NaCl

" .


.
-
.
" a, b, c " a1, a2, a3
,x-y-z" . , ,
) (90 ao
.

.nm

1 nm = 10 = 10-9 m
" .

7 )( ,
, :

 7 )( ,
, )(:

)(Bravais Lattices
:P )- (Primitive Unit Cell
.
:I - )- (Body Centered Cell
.
:F -/ )- (Face Centered Cell
.
:C )- (Base Centered Cell
.


14
Bravais Lattices

I F - ,
,
, FCC ,BCC:HCP -
)Body Centered Cubic - BCC (CN=8
)Face Centered Cubic - FCC (CN=12
)Hexagonal Close Packed - HCP (CN=12

Body centered cubic (BCC)

http://www.enstimac.fr/recherche/mat/Formation/CRYSTAL/html/bravais.html

Face centered cubic (FCC)

http://www.enstimac.fr/recherche/mat/Formation/CRYSTAL/html/bravais.html

a = b = c & = = 90 , = 120

.
" .

) , ,(
.

.

" .

 '

" .

HCP unit cell -

HCP = Hexagonal Close Packed

HCP
3x2 atoms per unit cell

Structures of Metallic Elements

He

H
Li

Be

Ne

Na

Mg

Al

Si

Cl

Ar

Ca

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga Ge

As

Se

Br

Kr

Rb

Sr

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

Xe

Cs

Ba

La

Hf

Ta

Re

Os

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

At

Rn

Fr

Ra

Ac

Primitive Cubic

Cubic close packing

(Face centered cubic)

Body Centered Cubic

Hexagonal close packing

BCC, FCC, HCP :

. "

. "


FCC .
,
, - .

" .

" .


- . ?!
, '' -
) (basal plane
- ] [.
.
, .
,A B C
.A
, ABABAB .ABCABC
"

.AB


,C...

" .

 FCC

" .

.AB


,A...

" .

 HCP

" .

ABCA

ABAB

-.
ABAB .HCP
ABCA .FCC

, .
" .

A B A : hexagonal close pack

A B C : cubic close pack

.HCP FCC
. "

Is FCC
A
B

C
A

A B C : cubic close pack

.- FCC
. "

ABCABC

" .

FCC

FCC

HCP ABABAB

HCP

BCC !
" .

 1
HCP
.c/a = 1.633

Top layer
Middle layer
Bottom layer
HCP

" .

JKLM

,K ,J M - .
M ,
''.MH= c/2 :
" .

 )(
JM = JK = 2R = a
R .
:JHM
(JM)2 = (JH)2 + (MH)2
(a)2 = (JH)2 + (c/2)2

JH
.JKL
" .

)(

a
3
= )cos(30
= 2
2
JH
a
3

== JH

JH:

8
= 1.633
3

C
= a

" .

(a)2 = (JH)2 + (c/2)2

2

a2 c2
a C
2
= a
+ 2 = 3 + 4
3

 )(Coordination Number
.
)(.
' ):(CN1
9 ).6 - (SC
.8 - BCC 9
) 12 - FCC 9 (.
) 12 - HCP 9 (.
" .

=

.

Askeland, D. R., The Science and Engineering of Materials, PWS Publishing Company, 3th edition, Boston (1994).

Face centered cubic (FCC)

http://www.enstimac.fr/recherche/mat/Formation/CRYSTAL/html/bravais.html

FCC

2 2r
6

9
2

2R

2 2r

10

4
7

12

11

12
CN1 = 12

. "

 )(close-packed directions
.

) (.

-
) FCC -
(.

" .

2

) (.

" .


FCC
" .

a 3
a

a 2

BCC
" .

a0 = 2 r :

4r
:FCC
2

= a0

2 a = 4r

4r
:BCC
3

= a0

3 a = 4r

" .

3
:
.1 4.9489 .1.75
.2 0.42906 nm .0.1858 nm

" .

(Atomic Packing Factor)

. "
.
:

Packing Factor =
(number of atoms / cell ) (volume of each atom )
volume of unit cell
. "

- 4 '
.FCC
4R

CN=12
Number of atoms = (6 1 + 8 1 ) = 4 atoms
2
8

4
Volume of atoms = 4 R 3
3

4R = a FCC 2 R =

a 2
4R
, a FCC =
4
2

4
4 R 3
Volume of atoms
3
APF =
=
= 0.74
Volume of unit cell ( 4R / 2 ) 3

 ' 5
.BCC
4R

a 2

CN=8

Number of atoms = (1 center atom + 8 1 ) = 2 atoms

8
4
Volume of atoms = 2 R 3
3
3
4R
= a, a BCC
4
3

= (4R ) 2 = a 2 + 2a 2 = 3a 2 R

4
2 R 3
Volume of atoms
8 3 3
3
= APF
=
=
= 0.68
Volume of unit cell ( 4R / 3 ) 3
3 64

6

HCP ) FCC
(.

6
).(2 x 3

" .

 )(
.
, .ACDE
= .

2R 3
2

= ) BC = 2 R cos(300

" .

)(
, :

2R 3
) = 6 R2 3
2

( ) Base Area = 3 CD BC = 3 (2 R

:c/a

c
= 1.633
a
)c = 1.633 a = 2 R (1.633
" .

 )(
:

= )Vcell = ( Base Area ) (c ) = 6 R 2 c 3 = (6 R 2 3) (2 R 1.633

= 12 3 (1.633) R 3
:
)(number of atoms / cell) ( volume of each atom
)( volume of unit cell

= APF

4
) (6) ( R 3
3
= 0.74
= APF
3
12 3 (1.633) R
" .

9 FCC ,0.74 74%
.
9 BCC .0.68
9 SC .0.52
FCC ,BCC BCC
.SC
.
)( , FCC
.26%
,
.
" .

Structure

a versus r

Atoms
per cell

Simple
Cubic
(SC)

a = 2r

Coordination
number

Packing
factor

Typical
metals

0.52

None

0.68

Fe, Ti, W,
Mo, Nb,
Ta, K, Na,
V, Cr

12

0.74

12

0.74

6
SC

Body
Centered
Cubic
(BCC)

a = 4r/ 3

Face
Centered
Cubic
(FCC)

a = 4r/ 2

Hexagonal
Close
Packed
(HCP)

a = 2r
c = 1.633a

2
BCC

4
FCC

2 x3
HCP

Fe, Cu, Al,

Au, Ag, Pd,
Ni, Pt
Ti, Mg, Zn,
Be, Co, Cd

Askeland, D. R., The Science and Engineering of Materials, PWS Publishing Company, 3th edition, Boston (1994).

(Density)

.
.
:

n = number of atoms per cell (dimensionless)

M = atomic mass (g/mol)
VC = volume of unit cell (m3)
NA = Avogadros number (6.0231023 1/mol)

nM
VC N A

 9
.(-Fe) BCC
:
= .2
BCC -
, :

a0 = 0.2866 nm = 2.866 1010 m

:

)M = 55.847(g / mol

" .

m3
[
]
cell

30

10 3

) = 23.54 10

a0 = (2.866 10
3

nM
=
VC N A
= 7.88 g / cm 3

" .

2 55.847 g / mol
)(23.541 10 24 cm 3 )(6.023 10 23 1 / mol

10
o

Copper has an atomic radius of 0.128 nm (1.28 A), an FCC crystal

structure, and an atomic mass of 63.5 g/mol. Compute its density.

Since the crystal structure is FCC, the number of atoms per unit cell n=4.
The unit cell volume VC for FCC is 16R3 x 2 , where the atomic radius R
is 0.128 nm.

4 63.5 g / mol
nM
=
= 8.89 g / cm 3

8
3
3
23
VC N A [16 2 (1.28 10 ) cm (6.023 10 1 / mol)

The literature value for the density of copper is 8.94 g/cm3.

11
.0.855 g/cm3 BCC
.39.09 g/mol
. )( . )(

. "


-
.x-y-z
, :

x,y,z

) (a-b-c :

x=a , y=b , z=c

b

a,b,c .

" .

= point A = origin
= point B

= point C

= point D

a
y

x
" .

)z (c

)y (b

)x (a

1
1/2

1
0

1
1/2

C
D

 " .

13
:FCC

:
;0,0,0; 1,0,0; 1,1,0; 0,1,0
, , 0
:
;0,0,1; 1,0,1; 1,1,1; 0,1,1
, , 1

:
1,,, ; 0,,, ; ,0,, ; ,1,,
" .

x
Atoms at the corners of the cube
+
Atoms at the center of each face

Directions in a Unit Cell

Directions in a unit cell are described using three integers,
in the form [a b c], obtained by subtracting the coordinates
of the base of the vector from its tip.
z

z = wc
y
x = ua
x

y = vb

. "

 ] [120
.

z = 0 :

a/2

" .

" .

][0 1 2

" .

][1 1 2

" .

][6 6 1

1
1
1
) 0,1, 1, 0, = ( 1)(1)(
3
2
6

1
) ( 1) (1) (
6

" .

1 1
)( ) ( )(1
2 2

2
1
) (1) ( )(
3
3

" .

 9 , (-1) -
.

] [0 1 0

] [ 010

] [0 2 0

] [0 1 0

9 '
) (.

] [0 2 0
] [010

] [0 1 0

" .

9
.
9
.
9 .

> < uv w

9 ),
' (.
1

etc

and
3
equivalent

1
2 equivalent

2
" .

, , .
.

]< 100 > [100], [010], [001], [010], [001 ], [ 100

" .

 .

, , .
" .
,
.
,1 -
.1
'
'.
" .

9


.
9

.

" .

][ 3 0 1

] [1 2 2

] [0 1 0

][1 0 1

] [0 1 2

] [4 1 0

][ 2 2 1

] [1 1 0
][1 0 1

] [0 1 0
" .

1
]
3

= [1 0

][ 3 0 1
" .

1
]1 1
2

[=

] [1 2 2

.
" " .
" .

) (Planes ,
.
.

.

).(hkl
.

) (h k l
" .

 .1 .
9 ,
.
.
9 , 0
).(1/

.2 .
.3 ) (.
.4 .

" .

(-1) - ( 0 2 0 ) = ( 0 2 0 ) .

.
= .

z
x ,a -
,y z
c/2
c
.c/2 -
) (1 0 2
b
y
" .

) (1 1 0 ) (1 1 0

) (1 1 1 ) (1 1 1

) (1 1 0

- .

) (1 1 1

= 1

1/1

1/1

1/1

c
)(111

b
y

" .

= 1

1/

1/1

1/1

)(110
b
y

= 2

" .

1/2

1/ 1/

1/1/2

0
z

c
)(200
b
y

" .

= 2 1 4/3

3/4

1/2

1/ 1 1/ 3/4

1/1/2

4
z

c
)(634

b
y

' '
".


.x
,
,
.
" .

" .

O -
" .

c
2

-1

= 0

-1 c/2

1/ -1 1/ 2

1/

-1

" .

 ' ' ":

" .

:A

) (1 1 1
:B

)(0 3 0
" .

-A

 :C

-
,
' .
-C

) (1 0 2

" .

.
, .
, .
, .
, .
) (0 - .
: ,
.
" .

)(0 1 1

, x y (-1) - z(1) -

)(0 1 1
z

c
b

-b
a

)(1 1 1

)(1 1 0

)( 1 0 0

.
" .

9
.
9
.
9 .

}{h k l

" .

 } {110
) (.

(1 1 0 ), (11 0 ), (1 0 1 ),
) (10 1 ), ( 0 1 1 ), ( 011
O x,y ,

,
( h k i l ) .i
:

) i = (h + k

. .
: ,
, .
" .

 ) (0001
:

] [1 0 0 ] [ 2110

u 20= 2
v 0 1 = 1
t (2 + 1) = 1
w 0
] [1 1 0 ] [1 1 2 0

b
a
)(110
](100) [110

][100

-

" .

.
.

 ] [010 4?

n
n
= 1
u = (2 0 1) =
3
3
2n
n
= 2
v = (2 1 0) =
3
3
n
n
t = (1 + 2) =
= 1
3
3
w = n(0) = 0

] [0 1 0

] [1 2 1 0

" .

.
a2
-a3

a2
2

a3
a1
2

a1

, , -1, 0

] [1 1 2 0

" .

b
a

, i :

) (1 1 0 ) (110 0

)(110
](100) [110

][100

i ( h + k ) = (1 + 1 ) = 0
) (1 0 0 ) (1 010

i ( h + k ) = (1 + 0 ) = 1
" .

:
c

a3

a2

a1

-1

1/1

1/-1

1/

1/1

-1

-1

) (1 0 1 1

" .

""

 :
c

a3

a2

a1

-1

1/2

-1

1/-1

1/-1 1/1

1/1/2

-1

-1

-1

-1

""

) (1 2 1 1

" .

.
A
a3

a2

a1

1/ 1/1

1/

1/

c
1

)(0 0 0 1

" .

B
a3

-1/2

1/ (-1/2) 1/1

-2

a2

a1

1/1

1/ 1

) (1 1 2 1

" .

C
0,0,1 :

1,0,0 :

0,0,1 1,0,0 = -1,0,1

] [1 0 1] [ 2 1 1 3
D
0,1,0 :

1,0,0 :

0,1,0 1,0,0 = -1,1,0

] [1 1 0 ] [1 1 0 0

" .



Linear and Planar APF
Linear APF =

length that passes through atom centers

length in a specific direction

Planar APF =

area occupied by atoms

total crystallographic plane area

HCP

FCC

BCC

Linear and Planar APF
- Linear Density (LD) Callister :***
, ,Planar APF - Linear APF Planar Density (PD)
- "
:Askeland & Phul

Linear density (LD) =

number of repeat distances

length in a specific direction

Planar density (PD) =

atoms per face

area of face

 .0.36151 nm
] ,[110) :( ' ') ,( ),(LD
)( ) .(LAPF
.FCC
)( :
1
1
= 2a0
= 2 0 .3 6 1 5 1
2
2
= 0 .2 5 5 6 n m
" .

)( :

2 la ttice p o in t

= L in ea r D en si t y

2 0 .3 6 1 5 1
= 3 .9 1 la ttic e p o in t s / n m

)( :
4 R
Linear
Atomic
= PFr D e n si t y
=
A
to m ic
L in ea
4R
= 1 .0
FCC
] .[110 .1

" .

 .0.35089 nm
.BCC
], [111] , [110] ,[100) :( ' ',
)( ) ,( .
?

" .

) (1 ]:[001
3a0 / 4

= r

.
FCC BCC - , .

) (2 ]:[110

" .

) (3 ]:[111

: ] [111 .
. BCC ] [111 .
" .

- 7
Calculate the linear APF of the [100] direction for BCC.

M
N

[100]

The lattice parameter, a, is the distance between the centers of

atoms M and N. In terms of atomic radius R:

a=

4R
3

The total line length intersecting circles is equal to 2R, thus:

Linear APF =

2R
4R

= 0.866

FCC
<111> -< 110> ,<100> BCC
. "

Calculate the planar APF of the (110) plane for FCC.

A

The rectangle length (AC) and width (AD) are:

AC = 4R , AD = 2R 2
A ACDF = (AC)(AD) = (4R )(2R 2 ) = 8R 2 2
One fourth of each of atoms A, C, D and F and one half of atoms B
and E reside within this rectangle, which gives a total of 2 equivalent
circles. Thus the total circle area is A c = 2R 2

Planar APF =

Ac
A ACDF

2R 2
8R 2 2

= 0.555

' '
( 0 1 0 ), ( 0 2 0 ) : -
.a0 = 0.334 nm : :

. "

) ( 0 1 0

" 4 .
= .1 :
:
atom per face 1 atom per face
=
area of face
(0.334)2

= )Planar density (010

= 8.96 atoms/nm 2 = 8.96 1014 atoms/cm 2

" .

:
) area of atoms per face (1 atom) ( r 2
= )Packing fraction (010
=
area of face
(a 0 )2

= 0.79

r2
(2r )2

)(0 2 0

.
" .

 ,BCC ,
(1 0 0 ), (1 1 0 ), (1 1 1 ) :

) (1 0 0

" 1
)
(.
" .

,BCC -:
:

4R
3

= a0

16 R 2
4R

=
3
3

)(100

2D repeat unit

4R
3

= a0

" .

)(100

 , ) (100

" .

) (1 1 0

" 2 ) ,
.(1

" .

 , .x*y

4R

x -:

z .4R

z2 x2

= )2

4R
3

= y

( (4 R )2
2

= y

4R
3

Z = 4R

x*y -:

- ):(110

" .

= x = a0

 , ,BCC
) (1 1 1
: a0 = 0.35089 nm :
z

600

) 2 co s 3 0 0

1
A = (a0 2 ) (a0
2

) (1 1 1
" ) ,1/6
3 - .(1/6 x3 = 1/2
, :

" .

X'


FCC BCC } {110} ,{100{111} -
" .

FCC

(1 0 0) plane
" .

Look down this direction

)(perpendicular to the plane

FCC
z
Look down this direction
(perpendicular to the plane)

(1 1 1) plane
. "

HCP
z

a2
a3

(0 0 0 1) plane
a1

Parallel to a1, a2 and a3 -> h = k = i = 0

Intersects at z = 1

. "

HCP
z

a2
+1 in a1

a3
-1 in a2

a1
h = 1, k = -1, i = -(1+-1) = 0 , l = 0

(1 1 0 0) plane
. "

(1 1 1) plane of FCC

y
x

(0 0 0 1) plane of HCP

SAME THING!*

a2
a3
. " a1

*Note: The difference is in the third layer.

, c

||c

" a-
b
.b

|b|cos

||b
|a|co
s

b


)(

||a

c = a b
c = a b sin = ab sin = A

/
:

a b = a b cos = ab cos

= c = x1 y1 z1

x2 y 2 z 2

) c = i( y z y z ) j (x z x z ) + k (x y x y

1 2
2 1
1 2
2 1
1 2
2 1

/:

x1 x2 + y1 y2 + z1 z 2
= arc cos
x2 + y2 + z 2 x2 + y2 + z 2
1
1
2
2
2
1

- ) (Interplanar Spacing
, ,
.
-

a0
h2 + k 2 + l 2

= d hkl

= a0 9 .
= h,k,l 9 .
= dhkl 9 .

" .


)(001
d 001 = a 0

:
a0
0 2 + 0 2 + 12
1 = a0

= d 110

)(0 0 1

= a0 /

, ,
.
" .

)(111
a0 3
3

:
" .

) (1 1 1
a0
12 + 12 + 12
a0 3
3

= 3

= d 110
= a0 /

) (1 1 0

) (1 2 0

)(0 1 0
- .
) (hkl , .

" .

) ( -
.
, ) (C , .60

60
Fullerenes
Buckyball

Polymorphs of Carbon

Polymorphism

FeFCC

T = 912 oC

Liquid
FeBCC

- Fe

CN = 12

CN = 8

PF = 0.74

PF = 0.68

rat (Room Temp.) = 0.129 nm

rat (Room Temp.) = 0.1241 nm

- Fe

rat (T=912oC) = 0.126 nm

FeBCC

)ZrO2 (cubic

T = 1400 oC

FeFCC

)ZrO2 (tetragonal

- Fe

)ZrO2 (monoclinic

.
,
, .
- , , , ,'.
,
E (diagonal) = 273 GPa
.
.
-
.
: .
" .

E (edge) = 125 GPa

-Fe

 ) (
. -.
" .