Chapter 1

Crystal Structure of Metals

 Crystal Structures of Metals
 What you have to learn from this chapter?
 Classification of Crystal Structure
 Simple Symmetry Description of Structure
 Miller Indices of Planes & Directions
 Crystallographic Planes & Directions
 The Stereographic Projection
 X-ray/Electron Diffraction
 Identification of Crystals
 Crystal Structures of Metals
 Importance of the Physical Metallurgy:

Structures

Processing Properties Applications

• Dealing with relationship between the structures & properties

of metals.
• Providing a theoretical base for understanding how structure
is controlled.
 Crystal Structures of Metals
 Classification for the Structures:
(1) Polycrystalline: an aggregate of many crystals (internal
boundaries within crystal). Chemical and structural
discontinuity.
(2) Grain: the small crystals in polycrystalline materials are
normally referred to as its grains.
(3) Macrostructure: large crystals that can be easily examined by
the naked eyes or low magnification methods.
(4) Microstructure: need high magnification methods (OM/SEM)
to examine, e.g. grains, phases, precipitates, defects, etc.
(5) Crystal structure: an orderly array of atoms in space,
preferred orientation, texture, superlattice, polycrystalline.
 Microstructural Analysis of Metals
Cast Equal-axial grain Precipitation

XRD Pole figure

TEM (SAED)
EBSD: Preferred orientation
1.1 Lattices & Unit Cells
 Lattice
• A lattice is an infinite array of evenly spaced points (points
with identical surrounding) which are all similarly situated.

• Each points are regarded as similarly situated in the rest of

the lattice appears the same, and in the same orientation
when viewed form them.
 Ideal Crystal
• Crystals are three-dimensional periodic arrangement of atoms.
• A body in which the atoms are arranged in a lattice.
(1) The atomic arrangement appears the same, and in the same
orientation, when viewed from all the lattice points.
(2) Lattice + Basis = Crystal Structure
(3) The form and orientation of the lattice in an ideal crystal is
independent of which point in the crystal is chosen as
origin.
(4) An ideal crystal is infinite in extent. Real crystals are not
only bounded, but also depart from the ideal crystals by
possessing occasional imperfections.
 Primitive Unit Cell
• It is a type of minimum-volume cell that will fill all space by
the repetition of suitable translation operation.
(1 lattice point/cell)
 Unit Cell
• The smallest group of atoms possessing the system of the
crystal which, when repeated in all directions, will develop the
crystal lattice. (non-primitive, multiply primitive unit cell)
Primitive Cell

Unit Cell
 Unit Cell
• The atom pattern which is repeated over and over again to
produce a crystal is known as the unit cell to form a space
lattice.
• All lattice points have the same environment in the same
orientation and are indistinguishable from one another.
• Any lattice point is related to any other by a simple lattice
translation.
• The simplest possibility is with one atom centered on each
lattice point; BCC & FCC metals are of this type. However, a
very large number of actual crystal structures have more than
one atom associated with a given lattice point.
 The Primitive Unit Cell is not Unique
• Such as A, B, C. In 3-D, like simple cubic structure.
 Multiply Primitive Unit Cell
• A unit cell has lattice points at the centers of its faces, or at
its body center, or occasionally at other positions, besides the
points at its corners. (like fcc, bcc, E, D, F etc.)
 Principle of Lattice Constant
• The lengths of unit cell edges: a, b, c
• The angles between the crystallographic axes: α, β, γ
• A lattice in space could be described by a translation vector:

• The sets of points for all n1, n2, n3 define a lattice.

• The number of lattice points in a unit cell (Nu) is:
 Crystalline Defects
Vacancy/Interstitial Dislocation
• Point defects:
 vacancy, interstitials (tetrahedral/octahedral sites)...
• Line defects:
 dislocations (edge/screw, loops, extended...)
• Planar defects:
 stacking fault, grain boundary, twinning...
• Volume defects:
 voids, pores, gas bubbles, cavities...

Twinning Voids/Pores
1.2 bcc, fcc and cph Structures
 The Location of All Atoms in the Unit Cell
bcc fcc
Coordination Coordination
number = 8 number = 12

Diamond structure Zinc-Blend

Combination of structure
two FCC cells

cph
Coordination
number = 12
ZnS
 Unit Cell & Body-Centered Cubic (bcc)
• 2 atoms per unit cell. Coordination number (CN) = 8.
• Typical metals with a bcc unit cell are Mo, W and a-Fe...etc.
 Choices of Unit Cells in a Lattice is not Unique

Shared by 8 unit cells

 Tetrahedral & Octahedral Interstitialcy
• Tetrahedral interstices are bounded by 4 atoms whose centers
join up to make an tetrahedron. (24 tetra. sites/bcc unit cell)
• Octahedral interstices are bounded by 6 atoms whose centers
join up to make an octahedron. (18 octa. sites/bcc unit cell)

Tetrahedral sites Octahedral sites

1.2.1 Close-Packed Structures
 Unit Cell & Face-Centered Cubic (fcc)
• 4 atoms per unit cell. Coordination number (CN) = 12.
• Typical examples of metals with an fcc unit cell include Al,
Ag, Au, Ni, g-iron…etc. Ductile & good electrical conductors.
 Tetrahedral & Octahedral Interstitials
Diagonal passes through the
center of the tetrahedral sites.
 In bcc Structure: Tetra. Size > Octa. Size
 In fcc Structure: Octa. Size > Tetra. Size
fcc Void CN Max. Value of r
fcc Tetragonal 4 0.225R
Tetrahedral interstitial
fcc Octahedral 6 0.414R
bcc Tetragonal 4 0.291R
bcc Octahedral 6 0.154R
Octahedral interstitial

bcc
• In real cases, interstitial atoms (C, N,
O...) larger than the sites, leading to
symmetric or asymmetric expansion
Tetrahedral interstitial in the lattice.

Octahedral interstitial
 Hexagonal System

Primitive unit cell

• Conventional unit cell to show hexagonal structure.
(non-primitive: 3 lattice point/unit cell)
 Close-Packed Hexagonal (cph) Lattice c
• 6 atoms per unit cell.
• Coordination number (CN) = 12. a a a
• Typical metals with a cph unit cell are Zn, Mg, Be, a-Ti...etc.
 c site
b site
a site
 Close-Packed Planes
• {111} of fcc, and (0002) basal planes of cph.
 Stacking Sequence
• Relation between fcc and cph structure
is the stacking sequence on the (111) planes.
Tetrahedral sites in cph
 Closed-Packing Sequence of fcc & cph

cph
fcc
 Faults in the Stacking
• Stacking fault (...ABCA↕CABCA...)
• Twinning (...ABCACBA...)
1.2.2 Extended Crystal Structures
 7 Crystal Systems
 14 Bravais Lattices
Triclinic

Plagioclase

Monoclinic
(P, Po)
CaSO4·2H2O
Orthorhombic
(S, Ga, Pa, U)

Chrysoberyl: BeAl2O4
Topaz: Al2SiO4(F,OH)2

Tetragonal
(In, Sn)
Zircon: ZrSiO4
Cubic

Spinel: MgAl2O4 Diamond

Trigonal
Hexagonal (B, As, Sb, Bi)

Beryl: Be3Al2(SiO3)6
Quartz: SiO2
 Lattice Constant of 7 Crystal Systems
 Crystal Symmetry
• By definition all crystals have translational symmetry, that is,
applying a lattice vector to any location leads to an equivalent
site in the structure.
• All Bravais lattice is characterized by the specification of all
operations that take the lattice into itself. These operations
result in symmetry group or space group.
(1) Translation Symmetric hierarchy
(2) Rotation (2p/n) Triclinic
Hexagonal Monoclinic
(3) Reflection (mirror plane)
(4) Inversion Cubic Orthorhombic
Trigonal Tetragonal
 Rotational Symmetry
2-fold 2 3 1 2
3-fold
2p/(p/2) = 4
4-fold 4-fold symmetry
6-fold o
5-fold? 1 90 4 4 3
2 3 4 1 2 3
180o 180o

1 4 3 2 1 4
2p/(p) = 2
Total rotation: p 2-fold symmetry
  Reflection = Rotation + Reflection
Mirror plane (m)

 Inversion = Rotation + Inversion

z z z

y y y
x x x
Rotate 180o Do a mirror reflection
along the z-axis in the x-y plane
 Symmetry of 7 Crystal Systems
Triclinic ( )
Insert a mirror (m)
Monoclinic ( )
Insert a mirror (m)
Orthorhombic ( ) 3-fold axis Cubic ( )
at diagonal
2-fold to 4-fold axis Extended along diagonal
Tetragonal ( ) Trigonal ( )
Let b = 120º
Hexagonal ( )
 Rotational Symmetry
• In a cubic unit cell:

3 tetra rotation axes 4 trial rotation axes 6 diad rotation axes

 Quasi-crystal Penrose tiling
• Quasi-crystal: a long-range ordered, non-periodic structure.
• A quasi-crystalline pattern can continuously fill all available
space, but it lacks translational symmetry (crystallographic
restriction theorem).
• Quasi-crystals are found most often in Al alloys (Al-Li-Cu,
Al-Mn-Si, Al-Ni-Co, Al-Cu-Fe, Al-Cu-V), and other
compositions (Mg-Zn-Al, Ti-Zr-Ni, Zn-Mg-Ho, Zn-Mg-Sc).

Ho-Mg-Zn
Al-Mn-Pd Mg9Zn4Al3
 Types of Quasi-crystals Icosahedron
• Polygonal quasi-crystals: have 8-fold, 10-fold, 12-fold local
symmetry (octagonal, decagonal, dodecagonal quasi-
crystals).
• Icosahedrite (Icosahedron): the only naturally occurring
quasi-crystal phase with a composition Al63Cu24Fe13, is a
mineral approved by the International Mineralogical
Association in 2010.

Face-centered Edge-centered Vertex-centered

 Plane of a Zone & the Zone Axis
• Those planes that mutually intersect along a common
direction form the zone planes, and the line of intersection is
called the zone axis.
• Zone axis: [u v w]
Zone planes: {h k l}
 Weiss Zone Law: hu + kv + wl = 0
• Zone planes contain a common direction.
• This law is true for cubic, tetragonal,
Zone planes in a crystal
orthorhombic systems and all other crystal systems.
 Plane of a Zone & the Zone Axis
• The condition for a vector [u v w] lying in a plane (h k l):
1.3 Miller Indices of Planes & Directions

 Indices for Lattice Planes

• (h k l) represents a specific plane.
• {h k l} represents all of the planes of the same form.
• Miller indices (h k l) (a/1a b/3b c/2c) = (623)
 A Set of (111) Planes
c z
y
b
x
a
 Indices for Lattice Planes
• A plane in space satisfies the equation:

• Where a, b, c are the unit length (lattice constant) of the x, y,

z axes, respectively.
• Intercepts are x = a/h, y = b/k, z = c/l
• The reciprocals of the intercepts: h/a, k/b, l/c, and the indices
of the plane is (h k l).
 z

 Indices for Lattice Directions

• To find direction of : y
Shift to to contact the origin. x

• Normalize u’, v’ w’ by the same factor to have the smallest

integers u, v, w
Direction of = [u v w]
• [h k l] represents a specific crystallographic direction.
< h k l > represents all of the directions of the same form.
• Plane normal of (h k l) is the direction of [h k l].
 Inter-planar Spacing, dhkl, for (h k l) Planes
• For (h k l) planes: = unit vector along [h k l].
z
a: lattice constant a/3l

a/3k
a/2l y
a/2k

a/l n
A a/k
x
O a/h a/2h a/3h
1.3.1 Specific Planes & Directions for cph

 Three axes (a1, a2, a3) along close-packed

direction on basal plane.
 The fourth axis is normal to basal plane, called

C axis.
 The unit of measurement along a axis is a,
C
along C axis is c.
a3
c
-a1
-a2
a2
a1 a -a3
 Theoretical c/a Ratio: 1.633
 Axial Ratios in Close-Packed Hexagonal Metals

Metal Be Mg Zn Cd Ti
c/a 1.568 1.624 1.856 1.886 1.60
 Basal Planes
• (h k w l) = (a/∞ a/∞ a/∞ c/1c) = (0001)
• It also designated as (0002) to emphasize c/2 distance of the
adjacent planes of cph.
C

Basal plane
a3
c
-a1

-a2
a2

a1
a (0002) -a3
 Prism Planes of Type I
• Plane ABCD: (h k w l) = (a/-a a/a a/∞ c/∞) =
• Plane EFGH:
• Others such as: …… C
Prism planes of type I =
a3
-a1

-a2 a2

a1
-a3
 Prism Planes of Type II
• Plane ABCD: (h k w l) = (a/a a/a a/-0.5a c/∞) =
• Plane CDEF:
• Others such as: …… C
Prism planes of type II =
a3
-a1

-a2
a2

a1
-a3
 Pyramidal Planes
• Type I, order I: ABD =
• Type I, order II: ABC =
• Type II, order I: AED = C
• Type II, order II: AEC =
a3
4-digit plane index = (h k w l)
-a1
w = –(h + k)
-a2
a2

a1
-a3
 4-Digit Miller Indices of Directions for cph
• [h k w l]: h + k = -w also holds.
= [0001], plane normal of basal plane.
• Looking on basal plane:
 Diagonal axes, type I:
 Diagonal axes, type II:

Type I Type II
1.3.2 Miller Indices for cph & Textures

 Basal Plane
• (0001) ↔ (001)
 Prism Planes
• Type I ─ ABCD: ↔ (100)
EFGH: ↔
• Type II ─ ABGH: ↔ (110)
CDEF: ↔
 Diagonal Axes
 Concepts of Isotropy & Anisotropy
• Isotropy: The properties of a material are independent of its
crystal direction. For many polycrystalline materials,
orientations of grains are random.
• Anisotropy: The properties of a material are dependent of
its crystallographic direction.
• Basically, a single crystal is not isotropy, but anisotropy.
• When the grains in a polycrystalline material are randomly
arranged, the material is expected to be isotropy.
 Concepts of Isotropy & Anisotropy
 Concepts of Isotropy and Anisotropy
• The deformation used in forming sheets (or plates) is
basically two-dimensional in character. In the sheet, we can
find a specific direction parallel to the rolling direction, and a
specific plane to be aligned parallel to the rolling plane.
• It should be noted also that anisotropy is not always
undesirable. Preferred orientations can often result in
materials with superior properties.
• Wires are formed by pulling rods through successively
smaller and smaller dies. In the case of iron, this kind of
deformation tends to align a special direction of each crystal
parallel to the wire axis.
1.4 Stereographic Projection
 Physical Meaning
• Amethod of representing the planes in a crystal “all at once”.
• The relationship (angles) between planes and directions.
• A tool to map in 2-D of crystallographic planes and directions.
• A 2-D drawing of 3-D data.
• Planes ↔ great circle, directions ↔ points.
• Great circle
 A circle of maximum diameter, if the plane passes through the
center of the sphere.
• Small circle
 A plane not passes through the center of the sphere will intersect
the sphere in a small circle.
 Physical Meaning
• The stereographic projection provides us with
such a map in the metallurgical literature.
• Represent the planes in a crystal by their normals.
 Reference Cube
• A crystal is placed at the center of a sphere.
Reference
cube

{100} planes {110} planes {111} planes

1.4.1 Stereographic Projection Methods

 Reference Sphere (Sphere of Projection)

• Place (h k l) on center of sphere, (h k l) can be interpreted by:
(1) P is intersection of with the sphere (the pole of (h k l)).
(2) Great circle of (h k l) on sphere.
 Angle between Two Planes (C1, P1 & C2, P2): f
• Great circle through P1 & P2. P1
• Divide the circle into 360º, f is determined. f
f P2
C1
f
C2
 Stereographic Projection
PG’: Gnomonic
The projection point is located at
the sphere center.

PS’: Stereographic
(Basic circle) The projection point is located at
the sphere base.
Pole of (h k l)
PO’: Orthographic
Reference (h k l) plane The projection point is located at
sphere infinity.
 Stereographic Projection of a Circle
N N Small circle on sphere

P1
Small circle in plane of
Equatorial plane O projection
of projection
P2
N
P1’

O
P2’

S S Cone of elliptical
cross-section
 Stereographic Projection of a Point
Reference
sphere
PN
: northern hemisphere

: southern hemisphere
PS

Great circle

Basic • Pole of plane :p

circle Outside basic circle (inconvenient for analysis)

• Conventionally: projected from N pole

 Pole p’ interpreted by instead of
 Stereographic Projection of Crystal Planes
• (a) The pole P to a (111) plane.
• (b) The anglebetween two poles, P, P’.
• (c) Stereographic projection of P and P’ poles to the (111) and
(001) planes, reepectively.
 3D of the Stereographic Projection

{100} poles of a cubic crystal {111} poles of a cubic crystal

 3D of the Stereographic Projection
 Alternative Method of Stereographic Projection
• The projection plane without passing through the ball center C.
 2-D Drawing of 3-D Crystallographic Features

• Directions that lie in a plane

 The Wulff Net
• A tool to measure the angular relation different operations of
planes.
• All meridians (longitude lines), including the basic circle, are
great circles.
• The equator is a great circle. All other latitude lines are small
circles.
• Angular between points representing directions in space can
be measured on the Wulff net only in the points are made to
coincide with a great circle of the net.
 The Wulff Net

Latitude line

Longitude line

• 2º interval in the Wulff net

Basic circle
 Construction of Wulff Net

Latitude line Longitude line

Sphere of
projection
A B

B C
A
C Projection paper
Basic
circle
 Construction of Wulff Net
 Rotation about an Axis in the Line of Sight
• This rotation is easily performed by merely rotating the
tracing paper, relative to the net, about the pin.
 Rotation about the North-South Axis of
Wulff Net
• Rotations of this type are accomplished by a graphical
method. The data are first plotted stereographically and then
rotated along latitude lines and re-plotted in such a manner
that each point in longitude undergoes the same change.
 Stereographic Projection of a Crystal
1.4.2 Stereographic Projection of Cubic

 Zone Planes on the Stereographic Projection

• At the zone axis of [111]:
 Zone Planes on the Stereographic Projection
• At the zone axis of [111]:

• The direction of the zone axis is perpendicular

to each normal of the planes in the same zone.
 Standard Stereographic Projections
• Pole of an important crystallographic plane (e.g., (100),
(010), (110), (111)) lies at the center of projection. z
• (100) standard projection: Basic circle
y

Pole of (110)
plane
Trace of (110)
plane
 Standard Stereographic Projections
• (100) & (111) standard stereographic projection of a cubic
crystal showing additional poles.
 Standard Stereographic Triangle
• 24 triangles (total: 48) with <100>, <110> & <111> at corners.
• The triangles are crystallographically equivalent.
e.g., single crystal tensile tests with tensile direction parallel to
a1, a2, a3  will obtain the same stress-strain curves.

• A standard stereographic triangle is frequently

adopted for the analysis (instead of the whole
stereographic projection)
 Sine Rule & Cosine Rule
• The sum of the three angles of a spherical triangle A+B+C is
not 180º.
• There are no such things as similar spherical triangles.

B a
C
c b
A
 Napier’s Rule
• It is more convenient to use special forms to deal with right
angled spherical triangles.
 Physical Meaning
• Amethod of representing the planes in a crystal “all at once”.
• The relationship (angles) between planes and directions.
• A tool to map in 2-D of crystallographic planes and directions.
• A 2-D drawing of 3-D data.
• Planes ↔ great circle, directions ↔ points.
• Great circle
 A circle of maximum diameter, if the plane passes through the
center of the sphere.
• Small circle
 A plane not passes through the center of the sphere will intersect
the sphere in a small circle.
1.5 The Relation between Stereographic
Projection and Material Analysis
 Diffraction & Tool of Characterization
• X-ray/electron diffraction
(XRD & TEM)
• Reciprocal lattice
1.5.1 X-ray Diffraction (XRD)
 Discovery of X-rays
• Wilhelm Roentgen discoverd the “invisible” X-rays
serendipitously in 1895.
• X-rays can be diffracted (scattered) by crystals to produce
interference pattern-wave-like property.
 Fundamentals
• In crystals, the separation between equally spaced parallel
atomic planes is of the order of a few Å.
• Low-voltage X-rays have wavelengths of the proper
magnitudes to be diffracted by crystal. X-rays produced by
tubes operated in the range between 20~50 kV.
• Basic principle: a wave interference phenomenon.
• Path difference (x)
• Phase difference (f)
2p

λ
 The Bragg’s Law
• Constructive interference occurred under :
Integer × Wavelength = Path differences
where n = 1, 2, 3…
l = wavelength in nm
d = interplanar distance in nm
q = incident or reflection angle
of X-ray beam
q q

d
 A Crystallographic X-Ray Tube
X-ray beam

Cooling
water

X-ray beam
 X-Ray Beam & Reflection
• The reflecting planes were assumed parallel to the crystal
surface. This is not a necessary requirement for reflection.
• White X-ray beam: It is not monochromatic but contains all
wavelengths longer than a given minimum value l0.
• As white X-ray beams strikes a crystal, many reflected beams
emerge from the crystal, each reflected beam corresponding to
a reflection from a different crystallographic plane.
• In contrast to the incident beam that is continuous in
wavelength, each reflected beam will contain only discrete
wavelengths as prescribed by the Bragg’s law.
 Continuous Spectrum
• X-rays are produced when electrons with
high kinetic energy rapidly decelerates.
• When the tube is biased at high voltage, say 30 kV, most of
the kinetic energy of the electrons striking the target is
converted into heat.
• Only less than 1% is transformed into X-rays.
• The spectrum contains characteristics X-rays associated with
the target and Bremsstrahlung X-rays (polychromatic,
continuous or white radiation).
 Characteristic X-Ray & Bragg Reflections
 d-spacing in orthogonal axes
• Assume the RMS plane is the first plane away from the
origin in a family of (h k l) planes. (orthogonal axes)
• The interplanar spacing is the length of the normal ON.
z
c
R

N
S y
O b

a M a
x
 For Cubic crystal: a = b = c

 For Tetragonal crystal: a = b ≠ c

 For Orthorhombic crystal: a ≠ b ≠ c

 Four General Diffraction Technologies
• The Laue method:
Provide crystal orientation also coarse test of crystallinity.
• The rotating crystal method:
Typically used with single crystal, rotating to bring different
diffraction plane into play.
• The Debye-Scherrer method:
Crystal identification, similar to TEM diffraction pattern for
polycrystalline sample.
• The X-ray diffractometer:
 Laue Diffraction
• The Laue X-ray diffraction methods make use of a crystal
with an orientation that is fixed with respect to a beam of
continuous X-rays.
• In the back-reflection Laue technique, the beams reflected
back in directions close to that of the incident X-ray beam
are studied.
• In the transmission Laue technique, the reflected beams that
pass through the crystal are studied.
 A Comparison of the Two Laue Diffraction
D D
2q F F
X-ray A C r1 A X-ray
C
r2
B S B
180º−2q

Transmission Laue camera Back-reflection Laue camera

A: collimator tube; B: holder; C: crystal

D: specimen-to-film distance; F: film
S: beam stop; r1, r2: distance of spot from center of film.
 A Comparison of the Two Laue Diffraction

One side of the cone of Laue
reflections is defined by the
transmitted beam. The film
intersects the cone, with the
diffraction spots generally lying
on an ellipse.
One side of the cone of Laue
reflections is defined by the
transmitted beam. The film
intersects the cone, with the
diffraction spots generally lying
on an hyperbola.
 A Comparison of the Two Laue Diffraction

Transmission Laue camera Back-reflection Laue camera

 Diffraction Path of the Laue Diffraction

 Incident/diffracted beam vs. diffracting plane normal = 90 − θ

 Incident beam, diffracted beam and diffracting plane normal
must be coplanar
 Diffraction Path of the Laue Diffraction
• Incident beam vs. plane normal = 54.7º
Diffracted beam vs. plane normal = 54.7º
• 2θ = 70.6º, θ = 35.3º
 Anisotropy & Asterism
• Both Laue transmission and back-reflection techniques can
be used to study asterism. A crystal that has been bent, or
otherwise distorted, will have curved lattice planes that act in
the manner of curved mirrors and form distorted or elongated
spots instead of small circular images of the X-ray beam.

X-ray ┴ (0001) −
X-ray ┴ (1120) The asterism, which related
to plastic deformation.
 The Rotating-Crystal Method
• In the rotating-crystal method, crystallographic planes are
brought into reflecting positions by rotating a crystal about
one of its axes while simultaneously radiating it with a beam
of monochromatic X-rays. The reflections are usually
recorded on a photographic film that surrounds the specimen.
 The Debye-Scherrer (Powder) Method
• The specimen contains not a crystal, but more than several
hundred randomly oriented crystals.
• Specimens may be either a small polycrystalline metal wire,
or a finely ground powder of the metal contained in a plastic,
cellulose or glass tube.
 The Operation of Debye-Scherrer Camera
• The angle q is the variable, the wavelength l remains constant.
• A variation of q is obtained through the presence of many
small crystals randomly oriented in space in the specimen.

Film
 Determination of Crystal Structures
• The Debye-Scherrer powder method is a powerful tool.
• Each crystalline material has its own characteristic set of
interplanar spacings and Bragg angles.
• The identification of an unknown crystalline phase in a metal
can be made by matching powder pattern Bragg angles and
reflected intensities of the unknown substance with the
proper card (JCPDS, the X-ray diffraction data index).
• Not only the Bragg angle of each important Debye-Scherrer
diffraction line, but also its relative intensity.
 JCPDS Data Index
 Debye (Powder) Camera Photographs

S
2q 
R
 X-Ray Powder Diffraction
• The X-ray diffractometer (with a beam of monochromatic X-
rays) is a device that measures the intensity of the X-ray
reflections from a crystal with an electronic device.
• A plot of intensity versus Bragg angles is obtained through a
suitable amplification system to a chart recorder.
 Ca4P2O9, TP
 a-Ca3(PO4)2, a-TCP
 b-Ca3(PO4)2, b-TCP
 CaO
 The X-Ray Diffractometry
• Phase identification:
 The X-Ray Diffractometry
• Oriented or textured samples:
 The X-Ray Diffractometry
• Crystallite size & Scherrer equation:
 The X-Ray Diffractometry
1.5.2 The Transmission Electron Microscope

 Applications of the TEM

• A very powerful technique has become available to material
scientists. It involves the use of the electron microscope to
study the internal structure of thin crystalline films or foils.
• The foils are normally only several thousand to several
hundred Å thick. The thickness is dictated by the voltage at
which the microscope is operated. The normal instrument is
rated between 100 & 400 keV.
• Plastic deformation results in unwanted structural defects in
the microstructure that are visible in the TEM image.
 Schematic Illustration of a TEM
 The Diffraction and Wavelength of Energetic
Electrons
• Assume an electron is accelerated by a potential of 100 keV.
 Give the electron a wavelength of about 0.0037 nm.
 About two orders of magnitude smaller than the average
wavelength (0.1 nm) used in X-ray diffraction.
(Typical E: 80- 400 keV, l = 0.002 ~ 0.0042 nm)

h: Planck’s constant m: electron mass

v: electron velocity E: electron energy
 Interaction of Energetic Electrons with a Lattice
• Concern with first-order diffraction (n=1), d = 0.2 nm
• The angle of incidence (reflection) of a diffracted beam:
 10-2 radians (30').
• Only those planes nearly parallel to the beam can be expected
to contribute to the resulting diffraction pattern.
 Images Formed in the TEM

Electron
Beam

Thin specimen
Direct Diffracted
beam beam
Objective lens

Aperture
Used to select the specific beams
to form image
Image of the specimen
 Bright Field & Dark Field Images
• Using the image formed either by the direct beam or by the
diffraction beam from a particular set of planes.
• Bright-field image and dark-field image are made by the
insertion of an aperture diaphragm just below objective lens.
 Bright Field & Dark Field Images

Bright Field Image Dark Field Image Lattice Image

1.5.3 Diffraction Patterns & Reciprocal Lattice

 Selected Area Diffraction (SAD)

• An interesting diffraction pattern is obtained when the
specimen is tilted.
 A zone axis is placed parallel to the microscope axis.
• When this is done, a pattern is obtained whose spots
correspond to the planes of the zone whose axis parallels the
electron beam.
 All spots correspond to planes parallel to the electron beam.
• The reason is that the small value of the Bragg angle and the
very thin thickness of the specimen, which tends to relax the
diffraction conditions.
 Electron Beam Corresponds to the Zone Axis

Stereographic projection The SAD pattern

 Ewald Construction (Ewald Sphere)
 Reciprocal Lattice
 Ewald Construction (Ewald Sphere)
• Draw the reciprocal lattice. Draw a sphere of radius 1/l with
one point on the sphere touching the origin of reciprocal
space (this is the Ewald sphere).
• Any reciprocal lattice point touching the surface of the
sphere is in the diffraction condition and the diffracted beam
will travel in the direction of the line joining the sphere
center to the surface of the sphere.
• We can rotate the crystal and hence the reciprocal lattice to
bring other reciprocal lattice point into the diffraction
condition.
 Ewald Construction (Ewald Sphere)
• Visualization of the reciprocal lattice: X-ray diffraction or
electron diffraction can be used to probe the reciprocal lattice.
 TEM: electron wavelength < 0.004 nm  very large
Ewald sphere.
 X-ray: wavelength ~ 0.1 nm  much smaller Ewald
sphere.
 SAD of Metals with Different Zone Axes

Al (fcc) Fe (bcc)
Zone axis: <110> Zone axis: <112>

Al (fcc) Ti (cph)
Zone axis: <111> Zone axis: <0001>
 SAD Patterns from Various Crystal Types

Single crystal Textured 1. Fine grained

specimen specimen 2. Amorphous
specimens
 a
L
lL

(h2+ k2 + l2)1/2
R1
R2 Radius, R
 Amorphous

Crystalline
Lattice Image

Diffraction Ring 0.5m

Dark Field

Bright Field 0.5m 0.5m Quasi-crystal