Introduction to

Powder X-Ray
Diffraction
 What is X-ray diffraction?
X-ray diffraction is the use of characteristic radiation determine
repeated distances between atoms in 3-dimensionally ordered
atomic structures.

What does any of that mean?

 Why X-rays?
X-rays are useful for diffraction because their wavelengths are similar in
magnitude to the distances between atoms in crystalline materials, also
known as d-spacings.

Crystalline materials are materials with three-dimensionally ordered

structures.

In nature, crystalline structures are expressed as minerals. Many materials

used in industries like structural engineering, aerospace engineering, and
pharmaceuticals are man-made crystalline solids.
 The Electromagnetic Spectrum
• Radiation of photons from a source
• We break this continuous spectrum into sections based on
wavelength/frequency/energy
• As you increase wavelength, you decrease frequency and
energy
λ=c/ƒ
Where λ is the wavelength
(angstroms), ƒ is the frequency
(hertz), and c is the speed of light
(meters per second)

E=hƒ
Where E is the energy (joules), ƒ is the
frequency (hertz), and h is Planck’s
constant (joule seconds)
 Production of X-rays
We run a current
through a tungsten
filament (cathode)
in a vacuum,
causing it to give off
electrons. These
electrons strike a
metal target
(anode) and are
absorbed. The
anode then gives
off X-rays, both Characteristic X-rays are quantized and have a specific
characteristic and wavelength dependent upon the anode material (Cu, Co, Cr,
continuous. etc.).

Continuous radiation has a range of wavelengths and is not

specific to the material of the anode.
As the voltage is increased, the intensity of both the characteristic and
the Brehmsstrahlung radiation increase, but the wavelengths of the
characteristic X-rays do not change!
Note: find a better image
 X-Ray Beam Focus
Cathode Spot Focus
• Cathode is perpendicular to anode
• Small beam footprint
• Used primarily in residual

Sample
stress/retained austenite and Laue
X-ray beam X-ray diffraction
Anode

Cathode

Line Focus
• Cathode is parallel to anode

Sample
• Larger beam footprint
• Used primarily in powder X-ray
diffraction X-ray beam
Anode
 Continuous Radiation
• Broad spectrum of radiation
• Caused by rapid deceleration of electrons when they
encounter the electric fields of the anode atoms
• The energy (and thus the wavelength) of the radiation
produced by this process depend upon how much energy the
electron lost during interaction
• An electron can lose any amount of energy UP TO the total
amount of energy it had, resulting in a CONTINUOUS
SPECTRUM of radiation
• This radiation is called “Bremsstrahlung” or braking radiation
 Characteristic radiation
• Radiation produced by electrons (from the tungsten filament) colliding
with electrons in the atoms of the anode with sufficient energy to eject
them from their nuclei, creating a vacancy in the electron shell of the
atom
• When a vacancy is created, a higher energy electron (from a higher
energy shell) drops down to fill the vacancy
• The drop to a lower energy shell forces the electron to release it’s extra
energy in the form of a photon (X-ray!)
• This X-ray has a frequency, wavelength, and energy directly related to
the loss in energy caused by dropping to a lower shell
 Radiation Sources (Anodes)
Powder X-ray diffractometers typically employ Cu radiation, but other
anodes are more useful depending on the experiment you’d like to run.

With iron-rich samples, for example, Cu radiation isn’t optimal because it

causes iron to fluoresce excessively, which results in higher background.
This can make identifying peaks and their positions difficult.

For materials with large d-spacing, such as clay minerals or mesoporous

silica, radiations with longer wavelengths may be advantageous.
 How do X-rays interact with matter?
X-rays interact with electrons  therefore, they interact with all matter!

There are four ways that X-rays can interact with matter:
1. Absorption: “capture” of X-rays by matter that mostly produces heat
2. Atomic scattering, incoherent: X-rays lose energy when they encounter an
atom and emit it as photons (with energy equal to the amount lost due to
deceleration)
3. Atomic scattering, coherent: X-rays eject an electron from an atom in the
sample, causing another electron to take it’s place and emit an X-ray of
the same wavelength in a different direction
4. Transmission: X-rays pass through the sample without interaction

“Attenuation” refers to all absorption and scattering processes.

 Linear and Mass Absorption Coefficients

All materials interact with X-rays. The degree to which they

interact with X-rays is determined by the composition and
the density of the material. 𝐼 = 𝐼0 𝑒 −(μ/ρ)ρt
This is represented by the linear absorption coefficient, or μ.
I = Transmitted beam intensity
I0 = incident beam intensity
However, it is much more useful to discuss materials in μ = linear absorption coefficient
terms of composition independent of density, so the mass ρ = density
coefficient, or μ/ρ, is used (where ρ = density). μ/ρ = mass absorption coefficient
t = thickness of material
μ/ρ values are also dependent upon the wavelength of the
radiation being emitted.
 What about mixtures?
Often the materials we analyze are not simple, single-
component samples. If your sample is a mixture, then the mass
absorption coefficient is calculated by:

𝑖=𝑛
μ = ෍(μ ) 𝑤
ൗρ ൗρ 𝑖
𝑖=1
Where 𝑤𝑖 is the weight fraction of the constituent element.
 X-ray Diffraction
Now that we know how X-rays interact with matter, let’s discuss
how this interaction can produce diffraction, and how that can
help us identify materials!

X-ray diffraction is the product of scattering and interference.

But what does that mean?
 Scattering
Scattering, as mentioned earlier, is the change in direction of a
photon due to collision with electrons.

In some cases (incoherent scattering), this results in a change in

energy of the photon.

With coherent scattering there is no change in energy of the

incident photon. This is what results in diffraction.
 Interference
When waves overlap, they interfere with one
another.

If the waves are perfectly IN PHASE, they

constructively interfere. The amplitude of the
resulting wave will be equal to the sum of the
amplitudes of the constituent waves.

If the waves are perfectly OUT OF PHASE, there

will be destructive interference, resulting in a
wave with an amplitude equal to the difference of
the amplitudes of the constituent waves.

Diffraction occurs when scattered photons of the

same wavelength constructively interfere with
each other.
Bragg’s Law
Imagine a set of lattice planes within a crystalline material
(see left).

Each plane is parallel to the others, and they are separated

from each other by a repeated distance (d).

Incident X-rays strike the material at an angle (θ).

X-rays scattered from the second plane travel farther than

those scattered from the first plane (shown in red).

Using some simple trigonometry, we can see that the extra

distance is equal to 2d sin θ.

If the extra distance traveled by the wave scattered from the

second plane is equal to the wavelength (or a multiple of the
wavelength) of the radiation being used, then the two waves
will constructively interfere with each other.

This allows you to relate wavelength to atomic distances in

crystalline materials using Bragg’s Law.
 Coherent Scattering
We can discuss scattering at three different scales:
1. Scattering by an individual electron
2. Scattering by a single atom (groups of electrons)
3. Scattering by groups of atoms (crystalline solids)
 Coherent Scattering by an Individual Electron
Scattering by a single electron can be described by the following
equation:
2
𝐼0 𝑒 2 1 + cos 2 (2θ)
𝐼= 2
𝑟 𝑚𝑒 𝐶 2 2
Where:
I = transmitted beam intensity
I0 = incident beam intensity
e = charge of an electron
C = speed of light in a vacuum
r = distance between electron and detector
2θ = scattering angle
me = mass of electron
 Coherent Scattering by a Single Atom
Scattering from an atom with multiple electrons begins to show
evidence of interference.

If scattering occurs in the forward direction, all scattered waves

will be in phase and the resulting summed wave will have an
amplitude equal to the amplitude of an X-ray scattered by a single
electron multiplied by the total number of electrons.

However, when the scattering angle is not equal to the incident

beam angle, X-rays scattered by electrons at different distances
from the detector will not be in phase due to differences in path
length.

As the angle of the incident beam increases, destructive

interference between X-rays emitted from electrons at different
locations around the atom will be significant. This will cause
intensities to decrease as you go to higher angles.

This brings us to the atomic scattering factor…

 Atomic Scattering Factor
• Also called the form factor
• Dependent upon the scattering angle and the way electrons are distributed
about the nucleus (essentially the number of electrons in the atom, Z)

amplitude of wave scattered by the atom

ƒ=
amplitude of a wave scattered by a single electron

θ 2
ƒ 0
sin θΤλ = σ4i=1 ai ∙ e−bi sin ൗλ +c

So, at an angle of 0˚ 2θ, the scattering factor is equivalent to the number of

electrons in the atom. As the angle increases, the value of ƒ decreases.
 Debye-Waller Factor
In the real world, other factors play a role in attenuation of the
X-rays. The scattering power of an atom is weakened by thermal
vibrations, and this effect can be quantified by the Debye-Waller
factor, B:
2
−B sinθൗλ
ƒB = ƒ ∙ e
And B can be related to atomic vibrations by:

B = 8π2 U 2
 Multiplicity Factor
In many crystal structures there are related reflections
that have the same d-spacing.
(100) (010) (001)
Take, for example, a cubic structure  multiple related
reflections that are essentially equivalent:
1. (100)
2. (010)
3. (001)
4. (-100)
(- (0- (00-
5. (0-10) 100) 1)
10)
6. (00-1)

Because these reflections are equivalent, they result in d-

spacings that are also equivalent. In order to account for
this when calculating intensity, we must incorporate a
multiplicity factor. In this case, M = 6.
 Lorentz Polarization Factor
Lorentz Factor Polarization Factor
The intensity of a diffraction peak is θ- The incident beam (before diffraction) is
dependent. This dependence is caused by unpolarized.
multiple factors:
• The maximum intensity of a diffraction peak
will depend on the angular range over which Once scattering has occurred the
a significant number of X-rays will be
diffracted in the direction of the detector scattered beam (after diffraction) is
(I α 1Τsin 2θ) polarized and all of the diffracted waves
• The portion of the diffraction cone are polarized in the same direction.
intersecting the detector will depend on the
diffraction angle and the detector
(I α 1Τsin 2θ)
• Because our samples will be polycrystalline The intensity of the diffracted, polarized
powders and not single crystals, the number (1+cos−1 2θ)ൗ
beam is θ-dependent (I α 2)
of crystallites that satisfy Bragg’s Law at any
angle will be dependent on the number of
crystallites oriented at or near that angle
(I α 1Τcos 2θ)
 Lorentz Polarization Factor
These two components combine to form the Lorentz Polarization
Factor, or LP, which is used as a correction when calculating
integrated intensities (more on this a bit later):

(1 + cos −1 2θ)ൗ
2൙
LP = sin θ sin 2θ
 Coherent Scattering from a Unit Cell

Because atoms in a crystalline structure are arranged in a periodic fashion,

scattering of X-rays is limited to circumstances in which Bragg’s Law is
satisfied.

Scattered waves from the atoms within the unit cell interfere with scattered
waves from atoms within adjacent unit cells, creating the diffraction pattern.
 Structure Factor
Scattering from a unit cell in a crystal structure is described by
the structure factor, or F, which is defined as the sum of the
amplitudes of the X-rays scattered by all of the atoms in the unit
cell.

This value is NOT the same as the sum of electrons in the unit
cell because not all of the X-rays scattered by the electrons in the
unit cell are perfectly in-phase.
 Calculating the Intensity of a Diffraction Peak

λ3 e2 M(hkl) 2 1 + cos 2 2θ cos 2 2θm vα

I hkl α = I0 2 2 F(hkl)
64πr me c Vα sin2 θ cos θ μ
(hkl) s

But what does all this mean?

 λ3 e2 M(hkl) 2 1 + cos 2 2θ cos 2 2θm vα
I hkl α = I0 2 2 F(hkl)
64πr me c Vα sin2 θ cos θ μ
(hkl) s
This portion is a constant for the instrument being used and incorporates
the wavelength of the radiation from the anode and the radius of the
goniometer.
 λ3 e2 M(hkl) 2 1 + cos 2 2θ cos 2 2θm vα
I hkl α = I0 2 2 F(hkl)
64πr me c Vα sin2 θ cos θ μ
(hkl) s
This portion is a constant defined by the radius of an electron.
 λ3 e2 M(hkl) 2 1 + cos 2 2θ cos 2 2θm vα
I hkl α = I0 2 2 F(hkl)
64πr me c Vα sin2 θ cos θ μ
(hkl) s
This section includes the multiplicity and structure factors, as well as the
unit cell volume, for the crystallographic plane (hkl) of phase α that
produces the peak in question.

(The multiplicity factor accounts for reflections with the same d-spacing)
 λ3 e2 M(hkl) 2 1 + cos 2 2θ cos 2 2θm vα
I hkl α = I0 2 2 F(hkl)
64πr me c Vα sin2 θ cos θ μ
(hkl) s
This section incorporates the effects of the Lorenz factor and polarization
effect.
 λ3 e2 M(hkl) 2 1 + cos 2 2θ cos 2 2θm vα
I hkl α = I0 2 2 F(hkl)
64πr me c Vα sin2 θ cos θ μ
(hkl) s
This portion contains the volume fraction (v) and the linear absorption
coefficient (μ) of phase α.
 Final Review
• X-rays interact with electrons, so they interact with all matter
• X-ray diffraction is a technique that uses characteristic radiation that
is scattered coherently by electrons to determine repeated distances
between atoms in crystalline materials
• This process is governed by Bragg’s Law and coherent scattering at
the level of:
– Individual electrons
– Atoms (groups of electrons)
– Unit cells (crystalline structures made up of atoms)
• Scattering and interference give rise to diffraction and diffraction
peaks, the intensity of which are governed by a multi-component
equation