What is X-ray Powder Diffraction (XRD)?

• X-ray powder diffraction (XRD) is a rapid

analytical technique primarily used for phase
identification of a crystalline material and can
provide information on unit cell dimensions.
The analyzed material is finely ground,
homogenized, and average bulk composition is
determined.
Fundamental Principles of X-ray Powder Diffraction (XRD)

• Max von Laue, in 1912, discovered that crystalline

substances act as three-dimensional diffraction gratings
for X-ray wavelengths similar to the spacing of planes in
a crystal lattice.

• X-ray diffraction is now a common technique for the

study of crystal structures and atomic spacing.

• X-ray diffraction is based on constructive interference of

monochromatic X-rays and a crystalline sample.
• These X-rays are generated by a cathode ray
tube, filtered to produce monochromatic
radiation, collimated to concentrate, and
directed toward the sample.

• The interaction of the incident rays with the

sample produces constructive interference (and
a diffracted ray) when conditions satisfy 
Bragg's Law (nλ=2d sin θ).
• This law relates the wavelength of electromagnetic
radiation to the diffraction angle and the lattice
spacing in a crystalline sample.

• These diffracted X-rays are then detected,

processed and counted. By scanning the sample
through a range of 2θangles, all possible diffraction
directions of the lattice should be attained due to
the random orientation of the powdered material.
• Conversion of the diffraction peaks to d-
spacings allows identification of the mineral
because each mineral has a set of unique d-
spacings.

• Typically, this is achieved by comparison of d-

spacings with standard reference patterns.
• All diffraction methods are based on 
generation of X-rays in an X-ray tube. These X-
rays are directed at the sample, and the
diffracted rays are collected.
• A key component of all diffraction is the angle
between the incident and diffracted rays.
Powder and single crystal diffraction vary in
instrumentation beyond this.
 X-ray Powder Diffraction (XRD) Instrumentation - How Does It
Work?

• X-ray diffractometers consist of

three basic elements: an X-ray tube,
a sample holder, and an X-ray
detector. 

• Bruker's X-ray Diffraction D8-

Discover instrument. Details X-rays
are generated in a cathode ray tube
by heating a filament to produce
electrons, accelerating the
electrons toward a target by
applying a voltage, and bombarding
the target material with electrons.
• When electrons have sufficient energy to dislodge
inner shell electrons of the target material,
characteristic X-ray spectra are produced.

• These spectra consist of several components, the

most common being Kα and Kβ. Kα consists, in part,
of Kα1 and Kα2.

• Kα1 has a slightly shorter wavelength and twice the

intensity as Kα2.
• The specific wavelengths are characteristic of the target
material (Cu, Fe, Mo, Cr).

• Filtering, by foils or crystal monochrometers, is required

to produce monochromatic X-rays needed for
diffraction.

• Kα1and Kα2 are sufficiently close in wavelength such that

a weighted average of the two is used.

• Copper is the most common target material for single-

crystal diffraction, with CuKα radiation = 1.5418Å.
• These X-rays are collimated and directed onto the sample.

• As the sample and detector are rotated, the intensity of

the reflected X-rays is recorded.

• When the geometry of the incident X-rays impinging the

sample satisfies the Bragg Equation, constructive
interference occurs and a peak in intensity occurs.

• A detector records and processes this X-ray signal and

converts the signal to a count rate which is then output to
a device such as a printer or computer monitor.
• The geometry of an X-ray diffractometer is such that
the sample rotates in the path of the collimated X-ray
beam at an angle θ while the X-ray detector is mounted
on an arm to collect the diffracted X-rays and rotates at
an angle of 2θ.

• The instrument used to maintain the angle and rotate

the sample is termed a goniometer.

• For typical powder patterns, data is collected at 2θ from

~5° to 70°, angles that are preset in the X-ray scan.
 Applications
• X-ray powder diffraction is most
widely used for the
identification of unknown
crystalline materials (e.g.
minerals, inorganic compounds).
Determination of unknown
solids is critical to studies in
geology, environmental science,
material science, engineering
and biology. Other applications
include:
• characterization of crystalline materials
• identification of fine-grained minerals such as
clays and mixed layer clays that are difficult to
determine optically.
• determination of unit cell dimensions
• measurement of sample purity
 With specialized techniques, XRD can be
used to:
o determine crystal structures using Riveted refinement
o determine of modal amounts of minerals (quantitative analysis)
o characterize thin films samples by:
=> determining lattice mismatch between film and substrate and to
inferring stress and strain
=> determining dislocation density and quality of the film by rocking curve
measurements
=> measuring superlattices in multilayered epitaxial structures
=> determining the thickness, roughness and density of the film using
glancing incidence X-ray reflectivity measurements
=> make textural measurements, such as the orientation of grains, in a
polycrystalline sample
Strengths and Limitations of X-ray Powder Diffraction (XRD)?

Strengths
o Powerful and rapid (< 20 min) technique for
identification of an unknown mineral
o In most cases, it provides an unambiguous
mineral determination
o Minimal sample preparation is required
o XRD units are widely available
o Data interpretation is relatively straight forward
Limitations
• Homogeneous and single phase material is best for identification of an
unknown.

• Must have access to a standard reference file of inorganic compounds (d-

spacings, hkls).

• Requires tenths of a gram of material which must be ground into a powder.

• For mixed materials, detection limit is ~ 2% of sample.

• For unit cell determinations, indexing of patterns for non-isometric crystal

systems is complicated

• Peak overlay may occur and worsens for high angle 'reflections'
 Sample Holders
• Various types of
sample holders are
used in XRD
depends on the type
of the sample to be
analyzed.
 Determination of an unknown requires: the material, an instrument for
grinding, and a sample holder.

• Obtain a few tenths of a gram (or more) of the material, as pure as

possible.

• Grind the sample to a fine powder, typically in a fluid to minimize

inducing extra strain (surface energy) that can offset peak positions,
and to randomize orientation.

• Powder less than ~10 μm(or 200-mesh) in size is preferred.

• Place into a sample holder or onto the sample surface: smear

uniformly onto a glass slide, assuring a flat upper surface, pack into a
sample container, sprinkle on double sticky tape.

• Typically the substrate is amorphous to avoid interference

 Data Collection, Results and Presentation

Data Collection
•  The intensity of diffracted X-rays is
continuously recorded as the sample and
detector rotate through their respective angles.

• A peak in intensity occurs when the mineral

contains lattice planes with d-spacings
appropriate to diffract X-rays at that value of θ.
• Although each peak consists of two separate
reflections (Kα1 and Kα2), at small values of 2θ the
peak locations overlap with Kα2 appearing as a
hump on the side of Kα1.

• Greater separation occurs at higher values of θ.

Typically these combined peaks are treated as one.

• The 2λ position of the diffraction peak is typically

measured as the center of the peak at 80% peak
height.
Data Reduction
• Results are commonly presented as peak positions at
2θ and X-ray counts (intensity) in the form of a table
or an x-y plot (shown above).

• Intensity (I) is either reported as peak height

intensity, that intensity above background, or as
integrated intensity, the area under the peak.

• The relative intensity is recorded as the ratio of the

peak intensity to that of the most intense peak
(relative intensity = I/I1 x 100 ).
Determination of an Unknown
• The d-spacing of each peak is then obtained by solution of
the Bragg equation for the appropriate value of λ.

• Once all d-spacings have been determined, automated

search/match routines compare the ds of the unknown to
those of known materials.

• Because each mineral has a unique set of d-spacings,

matching these d-spacings provides an identification of
the unknown sample.

• A systematic procedure is used by ordering the d-spacings

in terms of their intensity beginning with the most intense
peak.
• Files of d-spacings for hundreds of thousands of inorganic
compounds are available from the 
International Centre for Diffraction Data as the Powder
Diffraction File (PDF). Many other sites contain d-spacings
of minerals such as the 
American Mineralogist Crystal Structure Database .

• Commonly this information is an integral portion of the

software that comes with the instrumentation.

• Determination of Unit Cell DimensionsFor determination

of unit cell parameters, each reflection must be indexed to
a specific hkl.
 Literature
• Bish, DL and Post, JE, editors. 1989. Modern Powder
Diffraction. Reviews in Mienralogy, v. 20. Mineralogical
Society of America.
• Cullity, B. D. 1978. Elements of X-ray diffraction. 2nd ed.
Addison-Wesley, Reading, Mass.
• Klug, H. P., and L. E. Alexander. 1974. X-ray diffraction
procedures for polycrystalline and amorphous materials.
2nd ed. Wiley, New York.
• Moore, D. M. and R. C. Reynolds, Jr. 1997. X-Ray diffraction
and the identification and analysis of clay minerals. 2nd Ed.
Oxford University Press, New York.
Thank you !
• For BCC iron, compute (a) the interplaner
spacing and (b) the diffraction angle for (220)
set of planes. The lattice parameter for Fe is
0.2866 nm. Also assume that monochromatic
radiation having a wave length of 0.1790 nm is
used, and the order of reflection is one.