Crystal Morphology

Remember:
Space groups for atom symmetry Point groups for crystal face symmetry

Crystal Faces = limiting surfaces of growth

Depends in part on shape of building units & physical cond. (T, P, matrix, nature & flow direction of solutions, etc.)

Crystal Morphology
Observation:
The frequency with which a given face in a crystal is observed is proportional to the density of lattice nodes along that plane

Crystal Morphology
Observation:
The frequency with which a given face in a crystal is observed is proportional to the density of lattice nodes along that plane

Crystal Morphology
Because faces have direct relationship to the internal structure, they must have a direct and consistent angular relationship to each other

Crystal Morphology
Nicholas Steno (1669): Law of Constancy of Interfacial Angles

120o

120o

120o

Quartz
120o 120o 120o

120o

Crystal Morphology
Diff planes have diff atomic environments

Crystal Morphology
Crystal symmetry conforms to 32 point groups 32 crystal classes in 6 crystal systems Crystal faces act just as our homework: symmetry about the center of the crystal so the point groups and the crystal classes are the same
Crystal System Triclinic Monoclinic Orthorhombic Tetragonal Hexagonal No Center 1 2, 2 (= m) 222, 2mm 4, 4, 422, 4mm, 42m 3, 32, 3m 6, 6, 622, 6mm, 62m Isometric 23, 432, 43m Center 1 2/m 2/m 2/m 2/m 4/m, 4/m 2/m 2/m 3, 3 2/m 6/m, 6/m 2/m 2/m 2/m 3, 4/m 3 2/m

Crystal Morphology
Crystal Axes: generally taken as parallel to the edges (intersections) of prominent crystal faces b a

Crystal Morphology
Crystal Axes: generally taken as parallel to the edges (intersections) of prominent crystal faces

The more faces the better prism faces & quartz c-axis, halite cube, etc.
We must also keep symmetry in mind: c = 6-fold in hexagonal

With x-ray crystallography we can determine the internal structure and the unit cell directly and accurately
The crystallographic axes determined by XRD and by the face method nearly always coincide This is not coincidence!!

Crystal Morphology
How do we keep track of the faces of a crystal?

Crystal Morphology
How do we keep track of the faces of a crystal?
Remember, face sizes may vary, but angles can't

Note: interfacial angle = the angle between the faces measured like this

120o

120o

120o

120o 120o

120o

120o

Crystal Morphology
How do we keep track of the faces of a crystal?

Remember, face sizes may vary, but angles can't

Thus it's the orientation & angles that are the best source of our indexing Miller Index is the accepted indexing method It uses the relative intercepts of the face in question with the crystal axes

Crystal Morphology
Given the following crystal:
2-D view looking down c a b a

Crystal Morphology
Given the following crystal:

How reference faces? a face? b face? -a and -b faces?

Crystal Morphology
Suppose we get another crystal of the same mineral with 2 other sets of faces: How do we reference them?
b w x y

a z

Miller Index uses the relative intercepts of the faces with the axes

Pick a reference face that intersects both axes

Which one?
b w x y x b

y a
z

Which one? Either x or y. The choice is arbitrary. Just pick one. Suppose we pick x
b w x y x b

y a
z

MI process is very structured (cook book)

a
unknown face (y) reference face (x) b invert

b 1 1 1 1

c 1 1

1 2 2 1

clear of fractions x

y
(2 1 0)

Miller index of face y using x as the a-b reference face

a

What is the Miller Index of the reference face?

a
unknown face (x) reference face (x) b invert

b 1 1 1 1

c 1 1

1 1 1 1

clear of fractions x
(1 1 0)

1
Miller index of the reference face is always 1 - 1

y
(2 1 0)

What if we pick y as the reference. What is the MI of x?

a
unknown face (x) reference face (y) b invert

b 1 1 1 1

c 1 1

2 1 1 2

clear of fractions x
(1 2 0)

2
Miller index of the reference face is always 1 - 1

y
(1 1 0)

Which choice is correct?

1) x = (1 1 0)

y = (2 1 0)
2) x = (1 2 0) y = (1 1 0)
x

The choice is arbitrary

y

What is the difference?

a

What is the difference?

unit cell shape if y = (1 1 0)

unit cell shape if x = (1 1 0)

a x b y a y x

axial ratio = a/b = 0.80

axial ratio = a/b = 1.60

The technique above requires that we graph each face A simpler (?) way is to use trigonometry

b w

Measure the interfacial angles

x
148o

? y ?

interfacial angles 141o

y a z a

The technique above requires that we graph each face A simpler (?) way is to use trigonometry

b b w x
148o 58o

tan 39 = a/b = 0.801 tan 58 = a/b = 1.600

x

y
141o

39o

y a z a

What are the Miller Indices of all the faces if we choose x as the reference?

Face Z?

b w

(1 1 0)
(2 1 0) a z

The Miller Indices of face z using x as the reference

a
unknown face (z) reference face (x) b w

b 1 1

c 1 1

1 1 1 1

invert (1 1 0) (2 1 0)
clear of fractions

(1 0 0) a z

Miller index of face z using x (or any face) as the reference face

Can you index the rest?

(1 1 0)

(2 1 0)
(1 0 0) a

b (0 1 0) (1 1 0) (2 1 0) (1 1 0)

(2 1 0)
(1 0 0) a

(1 0 0)

(2 1 0)

(2 1 0) (0 1 0) (1 1 0)

(1 1 0)

3-D Miller Indices (an unusually complex example) a

c

b 2 4

c 2 3

unknown face (XYZ) reference face (ABC)

C

2 1

invert
Z

1 2

4 2

3 2

clear of fractions
A X O Y B a b

(1

3)

Miller index of face XYZ using ABC as the reference face

Demonstrate MI on cardboard cube model

We can get the a:b:c axial ratios from the chosen (111) face
We can also determine the true unit cell by XRD and of course determine the a:b:c axial ratios from it

If the unit face is correctly selected, the ratios should be the same
If not, will be off by some multiple - i.e. picked (211) and called it (111) Best to change it Mineralogy texts listed axial ratios long before XRD

We had to change some after XRD developed

Form = a set of symmetrically equivalent faces braces indicate a form {210}

b (0 1) (1 1)

(1 1)
(2 1) (1 0) (2 1) (1 1)

(2 1)
(1 0) a

(2 1)
(0 1) (1 1)

Form = a set of symmetrically equivalent faces braces indicate a form {210}

Multiplicity of a form depends on symmetry {100} in monoclinic, orthorhombic, tetragonal, isometric

Form = a set of symmetrically equivalent faces braces indicate a form {210} F. 2.36 in your text (p. 49-52)
pinacoid prism pyramid dipryamid

related by a mirror or a 2-fold axis

related by n-fold axis or mirrors

Form = a set of symmetrically equivalent faces braces indicate a form {210}

Quartz = 2 forms: Hexagonal prism (m = 6) Hexagonal dipyramid (m = 12)

Isometric forms include

Cube Octahedron
_ 111 __ 111

111 _ 111

Dodecahedron
101 011

_
110 _ 101 110 _ 011

Octahedron to Cube to Dodecahedron

Click on image to run animation

All three combined:

001

011 _ 111 101 111

_ 110 100 110

010

__ 111 _ 101

_ 111

_ 011

Zone
Any group of faces || a common axis Use of h k l as variables for a, b, c intercepts (h k 0) = [001] If the MIs of 2 non-parallel faces are added, the result = MI of a face between them & in the same zone

BUT doesn't say which face

(010)

(110)?

Which??
(110)? (100)

BUT doesn't say which face

(010) (110) (210) (010) (110)?

Which??
(100) (110)? (010) (100) (120) (110)

Either is OK
(100)