powder x-ray diffraction, require the use of monochromatic radiation (single wavelength x-rays).

This is because the high intensity and monochromatic nature of characteristic lines make them
ideal for XRD analysis. For Cu radiation, the K x-ray is 90 times the intensity of the
bremsstrahlung x-rays.
X-rays are a form of electromagnetic radiation of very short wavelengths in the angstrom and
nanometre region. Laue knew that X-rays had wavelengths on the order of 1. After learning
that Paul Ewald's optical theories had approximated the distance between atoms in a crystal by
the same length, Laue postulated that X-rays would diffract, by analogy to the diffraction of light
from small periodic scratches drawn on a solid surface (an optical diffraction grating).
The typical wavelength of x-rays is 1 x 10-10m (1 angstrom), whereas the wavelength of visible
light is typically 1 x 10-6m (1 m). X-rays are produced when any electrically charged particle of
sufficient kinetic energy is rapidly decelerated. Electrons are used as the particles in x-ray tubes
along with two metal electrodes. A high voltage (typically tens of thousands of volts) is
maintained across these electrodes, which draws electrons to the anode or target. X-rays are
produced at the point of impact and radiate in all directions.
A continuous spectrum is produced when electrons hit the target, which is referred to as
bremsstrahlung or German for braking radiation as it is produced by stopping electrons.
However, when the applied voltage is raised above a critical value, characteristic of the target
metal, sharp intensity maxima appear in the spectrum. These are the characteristic lines and
they are produced by exciting an electron out of its shell (only K lines are used in x-ray
diffraction due to absorption). The K lines are produced as an electron from one of the outer
shells falling into the vacancy created in the K shell, thereby emitting energy in the process as xrays.
Many techniques, including powder x-ray diffraction require the use of monochromatic radiation
(single wavelength x-rays). Hence the high intensity and monochromatic nature of characteristic
lines make them ideal for XRD analysis. For Cu radiation, the K x-ray is 90 times the intensity
of the bremsstrahlung x-rays.

X-ray spectra showing the underlying bremsstrahlung with sharp boundary at low energy
and gradual falloff at higher energies. The two peaks on the spectrum are the K and
K lines for the target metal. Note that only at sufficiently high energy does the spectrum
contain characteristic lines.

Diffraction
When a monochromatic X-ray comes into contact with a crystal lattice, interference patterns are
produced by each atom hit by the beam. Many of these patterns will interfere with each other
and cancel each other out. However, at the right distance and angle these patterns can be inphase with one another and cause constructive interference. This is known as diffraction.

This type of waveform interaction can be seen in all wave systems. The image to the right
shows a simulated wave pattern where the lattice is placed on its side and two slits are present.
The interfering wave propagation can be seen amplifying three waves. A crystal lattice can be
thought of as a source of multiple tiny slits, where the X-ray beam is acting like the waveform in
the image.

Bragg's law
In 1912 W. L. Bragg noticed there was a relationship between the
wavelength of radiation, the angle of the X-rays and the internal spacing in
the crystal, which is expressed in the form:
n = 2dsin
where n is an integer, is the wavelength of the x-rays (in our case 1.54
for a copper tube source), d is the spacing between planes in the atomic
lattice of the sample, and is the diffraction angle in degrees. This is known
as Braggs law. Although Bragg's law was used to explain the interference
pattern of X-rays scattered by crystals, diffraction has been developed to
study the structure of all states of matter with any beam, e.g., ions,
electrons, neutrons, and protons, with a wavelength similar to the distance
between the atomic or molecular structures of interest.
There are two important things to note about Braggs Law:
1. The smaller the distance d, the larger the diffraction angle .
2. The bigger the wavelength , the larger the diffraction angle .
(i.e. sin = n / 2d)
Bragg conditions of diffraction: To maintain the same path length and remain
in-phase, the x-rays must be deviated at an angle equal to the angle of
incidence (). The deviated rays combine to form a diffracted beam if they
differ in phase by a whole number of the ray wavelength ().

Schematic of Braggs law conditions. If the difference in phase between the parallel x-rays
(coloured red and green) is a whole number (n) of the wavelength (), then the 'reflected' x-rays
remain in phase and constructive interference occurs to create a diffracted beam (left above)
which can be detected by an x-ray diffractometer. If n is not a whole number of and the
reflected x-rays are out of phase, then destructive interference occurs and a diffracted beam is not
formed (right above).
Image by Cdang, available under the Creative Commons Attribution-Share Alike 3.0
Unportedlicense.
Although it doesnt play a major role in the technique of x-ray powder
diffraction we must at least mention the phenomenon of absorption of xrays. When x-rays encounter any form of matter, they are partly transmitted
and partly absorbed. The mass absorption coefficient / is a constant of
the material and is independent of its physical state. The absorption of xrays is utilized in experiments on X-ray synchrotron sources where the high
intensity of the X-ray beam is adjusted at low angles by the use of
absorbers, typically Ni foils.

Powder diffraction
Now that the effect of diffraction on a crysalline sample has been described,
it is time to discuss the core concept of this module: how diffraction of a
polycrystalline sample (usually a powder) works.
A powder pattern is like a 'spectrum' of d-spacings in the crystal structure
and is usually presented in the form of a line trace. A finely
ground crystalline powder contains a very large number of small crystals
known as crystallites, which should be oriented randomly to one another.

When this sample is placed in the path of a monochromatic X-ray beam,

diffraction will occur from planes in those crystallites, which happen to be
oriented at the correct angle to fulfill the Bragg condition. The effect of this is
that each lattice space in the crystal will give rise to a cone of diffraction.
Every cone consists of a set of closely spaced dots, each of which
represents diffraction from a single crystallite within the powder sample.

Schematic of a powder diffraction measurement. All crystal planes are accessible as

the incoming radiation is rotated.
The goal of performing X-ray diffraction on a polycrystalline sample is to
capture all possible orientations of the sample crystal structure using a
minimal amount of change in the relative orientation of the sample. This has
the benefit of requiring far less time and resources to obtain the same
information. It also allows observation of a much more diverse faimly of
types of samples. Many materials only ever appear as a residual
polycrystalline signature within another matrix, and there are difficulties in
growing crystals of sufficient dimensions for single crystal diffraction
analysis.
In order to obtain powder x-ray diffraction data in a useful format necessary
for analysis, the positions of the various diffraction cones need to be
determined. This can be achieved by using photographic film or a detector
sensitive to x-ray radiation. Both techniques allow us to determine the angle
(2, referring to Bragg's law) of the diffracted beam of the various diffraction
cones.

Limitations of powder diffraction:

Single crystal techniques utilize mathematical algorithms

and accurate peak intensities to solve structures

The 3D collection of spots and intensities of a single crystal

experiment are reduced to a 1D pattern. This causes peak overlap
and makes accurate peak intensities problematic.

Crystal symmetry is not obvious from the pattern.

Multiphase mixtures complicate the issue.

Preferred orientation leads to inaccurate peak intensities.

One improtant thing to note about powder diffraction is that sample

preparation must be done carefully and precisely to get a good result.

Output
The output from an X-ray diffraction experiment is usually presented as
a diffractogram in which the intensity of diffracted x-rays is shown as a
function of the scanning angle 2. The quality of a powder diffractogram
usually refers to two things: first, the signal to noise ratio, and second, the
resolution. They are strongly linked and often one can only be improved at
the expense of the other. It is necessary to find a reasonable compromise
for each experiment. Both machine settings and sample preparation are
important in obtaining a good quality difractogram.
An ideal output graph will consist of a series of tall thin peaks as narrow
peaks provide better analysis of the sample. The most important data to
observe in the diffraction pattern includes:

The spacing/position of the peaks

o The spacing of peaks gives information about
which crystal group the sample belongs to
o The position of peaks describes the size of the
crystal unit cell

The intensity values and shapes of the peaks

o Intensity gives information about the elements

present in the crystal

The intensity distribution as a function of the diffraction angle

The most common way to use this data to determine the properties of the
specimen is to compare its peak pattern with a large set of standard data.
Computer programs exist to do this quickly and efficiently, and can reveal
information about the sample including d-spacing, elements that are present
and crystalline phases. However, in more complicated situations the
software can't always do this all automatically. As a result, it is important to
know the basics behind interpretation of a diffractogram. This information
can be foundhere.

A sample diffractogram showing a 50/50 calcite - argonite mixture. The various peaks have been
labelled with their respective elements.

Summary of analysis cues

Peak positions show:

Crystal system

Space group symmetry

Translational symmetry

Unit cell dimensions

Qualitative phase information

Peak intensities show:

Unit cell contents

Point symmetry

Quantitative phase fractions

Peak shapes and widths show:

Crystallite size

Non-uniform microstrain

Extended defects (stacking faults, antiphase boundaries etc)