X-RAY DIFFRACTION BASICS

Rocks, sediments, and precipitates are examples of geologic materials that are composed of
minerals. Minerals are chemical compounds composed of various molecules, often forming a
crystalline structure.

Numerous analytical techniques are used to characterize these materials. One of these
methods, X-ray powder diffraction (XRD), is an instrumental technique that is used to identify
minerals, as well as other crystalline materials. In many geologic investigations, XRD
complements other mineralogical methods, including optical light microscopy, electron
microprobe microscopy, and scanning electron microscopy.

XRD provides a fast and reliable tool for routine mineral identification. XRD is particularly
useful for identifying fine-grained minerals and mixtures or intergrowths of minerals, which
may not lend themselves to analysis by other techniques. Petrophysicists use XRD values to
help calibrate mineral volume calculations derived from well log data. While XRD analysis
gives quantitative volume fractions of minerals in a sample, these samples are small and can
be high graded intentionally or accidentally. The important result is WHICH minerals are
present, with less emphasis on QUANTITY of each mineral.

XRD can provide additional information beyond basic identification. If the sample is a mixture,
XRD data can be analyzed to determine the proportion of the different minerals present. Other
information obtained can include the degree of crystallinity of the minerals present, possible
deviations of the minerals from their ideal compositions (presence of element substitutions
and solid solutions), the structural state of the minerals (which can be used to deduce
temperatures and pressures of formation), and the degree of hydration for minerals that
contain water in their structure.

Some mineralogical samples analyzed by XRD are too fine grained to be identified by optical
light microscopy. XRD does not, however, provide the quantitative compositional data
obtained by the electron microprobe or the textural and qualitative compositional data
obtained by the scanning electron microscope.

The three-dimensional structure of non-amorphous materials, such as minerals, is defined by

regular, repeating planes of atoms that form a crystal lattice. When a focused X-ray beam
interacts with these planes of atoms, part of the beam is transmitted, part is absorbed by the
sample, part is refracted and scattered, and part is diffracted. Diffraction of an X-ray beam by a
crystalline solid is analogous to diffraction of light by droplets of water, producing the familiar
rainbow. X-rays are diffracted by each mineral differently, depending on what atoms make up
the crystal lattice and how these atoms are arranged.

XRD has a wide range of applications in geology, material science, environmental science,
chemistry, forensic science, and the pharmaceutical industry, among others. At the U.S.
Geological Survey, researchers use XRD to characterize geologic materials from a wide variety
of settings; below are just a few examples.

X-rays are electromagnetic radiation similar to light, but with a much shorter wavelength. They
are produced when electrically charged particles of sufficient energy are decelerated. In an X-
ray tube, the high voltage maintained across the electrodes draws electrons toward a metal
target (the anode). X-rays are produced at the point of impact, and radiate in all directions.
Tubes with copper targets, which produce their strongest characteristic radiation at a
wavelength of about 1.5 angstroms, are commonly used for geological applications.

These X-rays are collimated and directed onto the sample, which has been ground to a fine
powder (typically to produce particle sizes of less than 10 microns). A detector detects the X-
ray signal; the signal is then processed either by a microprocessor or electronically,
converting the signal to a count rate. Changing the angle between the X-ray source, the
sample, and the detector at a controlled rate between preset limits creates an X-ray scan, or
spectrograph.
 Incident X-Rays are diffracted by the layers of atoms in a crystalline material.

If an incident X-ray beam encounters a crystal

lattice, general scattering occurs. Although
most scattering interferes with itself and is
eliminated (destructive interference), diffraction
occurs when scattering in a certain direction is
in phase with scattered rays from other atomic
planes. Under this condition the reflections
combine to form new enhanced wave fronts
that mutually reinforce each other (constructive
interference). The relation by which diffraction
occurs is known as the Bragg law or equation. Because each crystalline material has a
characteristic atomic structure, it will diffract X-rays in a unique characteristic pattern.
 Basic concept of an X-Ray Diffractometer

The basic geometry of an X-ray diffractometer involves a source of monochromatic radiation

and an X-ray detector situated on the circumference of a graduated circle centered on the
powder specimen. Divergent slits, located between the X-ray source and the specimen, and
divergent slits, located between the specimen and the detector, limit scattered (non-diffracted)
radiation, reduce background noise, and collimate the radiation. The detector and specimen
holder are mechanically coupled with a goniometer so that a rotation of the detector through
2x degrees occurs in conjunction with the rotation of the specimen through x degrees, a fixed
2:1 ratio.

A curved-crystal monochromator containing a graphite crystal is normally used to ensure that

the detected radiation is monochromatic. When positioned properly just in front of the
detector, only the K-alpha radiation is directed into the detector, and the K-beta radiation,
because it is diffracted at a slightly different angle, is directed away. The signals from the
detector are filtered by pulse-height analysis, scaled to measurable proportions, and sent to a
linear ratemeter for conversion into a continuous current. Common output devices include
strip-chart recorders, printers, and computer monitors.
Peaks found on the spectra must have a high enough signal to be discriminated from the
background noise. In addition, it is necessary to have secondary peaks that are used to
confirm the primary peak as belonging to the particular mineral species in question. As a
result, there are practical limitations to the minimum detectability of minerals in the sample.
Some minerals may simply be reported as having trace amounts.

Sample spectrograph in an artificial mixture

 Detail of an XRD spectrograph of a quartz sample

Sample spectrograph in some real rocks

X-RAY DIFFRACTION ANALYSIS METHODS

Source: Calgary Rock and Materials Services Inc

X-Ray Diffractometry (XRD) is a very useful tool to the geologist, in that it has the capability of
positively identifying crystalline materials. XRD can be used as a stand-alone method, or used
in conjunction with other tools to provide a comprehensive, integrated approach to petrologic
evaluation.

Major uses of XRD data in petrophysical analysis are: mineral identification, quantitative
mineral fractions, quantitative clay fractions , and by inference, clay volume and clay / silt ratio.
These are used to help calibrate lithology calculations from standard log analysis models. Clay
/ silt ratio is helpful in calibrating shaly sand analysis and in assessing shale gas prospects.

Clay volumes from XRD represent the dry clay mineral only and do not include intraparticle
porosity or bound water. Samples used in XRD are very tiny (less than a cubic centimeter)
compared to the volume measured by a log, so large statistical variations may be expected.
XRD has been used in the oil and gas industry as a routine analysis technique since the early
1960s when cost effective commercial units were introduced to the marketplace. Use of the
technique has become commonplace due to its low cost and availability.

Sample quality can vary considerably, depending on whether it is a whole rock sample,
cuttings or corrosion sample. Homogeneity of the samples can vary considerably as well. A
uniform, massive sandstone with well distributed clays and cements will present the least
problem while partially cemented sandstones and variable lithology carbonates and cuttings
samples represent the most challenging samples.

It is recommended that a minimum sample size be in the range of 5 to 10 grams. For normal
sample preparation, a 1 gram sample is needed for bulk powder analysis, while 5 grams are
needed for clay separates analysis.

Normal sampling of bulk samples is accomplished by drying the sample at 60 °C overnight,

then fracturing a portion of the bulk rock for use in the pulverizing mill. Samples are normally
ground for 20 minutes in the mill until a homogenous powder is obtained. If specified by the
client, samples can be crushed then quartered until a representative amount is obtained. This
quartered sample is then pulverized until homogeneous. The powder is then packed in a
powder mount, against glass, to provide a stable surface for analysis. This will destroy the
sample for analysis by most other testing techniques.

Special cases would include selection of specific parts of a rock for analysis, for example,
mineral nodules of interest.

Cuttings can be analyzed as well. Usually a minimal amount of sample is available for analysis,
and as a result, hand grinding and packing into a micro powder holder is required. As little as 1
or 2 cuttings can be analyzed in this fashion.

The bulk powder holder is then placed into the X-Ray Diffractometer apparatus and the sample
is typically scanned from 4 to 60 degrees 2θ (two theta) to produce the spectrum. A copper
source tube is used to provide the incident beam of monochromatic X-rays.

For clay samples, a 5 gram sample is required in order to get good results from the clay
separates. Rock portions are first of all, disaggregated using an agate mortar and pestle with a
calgon solution. Suspended clays, silt and sand are then transferred to a glass tube, topped up
with calgon solution, agitated and then centrifuged for the appropriate amount of time at given
centrifuge speeds to drop out the coarse fraction. The suspended portion is decanted into a
clean centrifuge tube, and this is spun at high speed to settle the fine fraction of material.

Some labs choose to utilize the less than 5 micron fraction (<5μ) for clay analysis, while others
may utilize the <2μ or <1μ fraction. The reason for this is that significant amounts of kaolinite
may be settled out of the clay suspension if other than the 5 micron fraction size is used.
Kaolinite particles can typically have sizes of 10 - 20 microns. If other than the <5μ fraction is
desired, clients should specify what value they want. After settling of the clays, the majority of
the supernatant liquid is poured off, and the settled clays are homogenized.

A small amount of the clay suspension is then smeared on to a glass slide, and allowed to air
dry. The slide is then placed into the goniometer and run typically from 2 to 35 degrees 2θ. The
slide will then be removed and placed in a container with glycol vapours at elevated
temperature in order to expand sensitive clays. This provides a diagnostic for particular clay
types as well as providing an indication of whether or not the clays will be fresh-water
sensitive. Heating of samples, on occasion, may be necessary to delineate clay species.
Sensitivity to ionic substitution (Na+, Mg++, K+ and Ca++) can also be completed as a special
analysis.
It should be noted that the term clay analysis in this case refers to sample particle size, and not
necessarily mineralogy. As a result, clay results will include such minerals as quartz,
feldspars, carbonates and potentially even heavy minerals such as pyrite. If true clay species
alone are needed, then recalculation excluding non-clay species will be required. It should be
kept in mind that size fractions of non-clay types may be important, particularly where
microcrystalline minerals are present, or where dissolution of minerals is or has taken place.
Often, these species will show up in the clay trace.

X-RAY DIFFRACTION RESULTS

Final results from an X-Ray diffraction analysis include printed spectra, digital spectra images,
and spreadsheets of tabular data.

The spectrum at right shows a sample of

quartz used as a standard. Virtually all of the
peaks seen in the spectrum are attributed to
the quartz. Exceptions include a peak at 33.1
degrees 2θ (pyrite) and one at 44.7 degrees 2θ
(iron). The pyrite is part of the sample while the
iron is from secondary emissions from the
metal parts of the instrument itself.

The peak with highest amplitude for a

particular mineral is the primary peak. Other
secondary peaks are present for most
minerals. Identification is based on comparing
the peak positions to standard samples with
known mineralogy.

Some databases contain more than 100,000

samples and software is used to find logical
matches to the measured spectrum. Interference between peaks from different minerals
sometimes forces the analyst to use secondary or tertiary peaks to aid in identification.
Unlikely matches are eliminated by human interpretation and a unique result can usually be
obtained.

The amplitude of the peaks is used, with scale factors, to estimate the fraction of each mineral
present in a sample, illustrated in the example XRD shown below.

In the illustration below, the spectra show the peak shifting that occurs in a sample containing
abundant smectite. The blue spectrum is the air-dried run while the green spectrum is the
glycolated run. Substitution of interlayer water molecules with larger radii glycol molecules
expands the interlayer distances causing the shift of peaks in those species which are
susceptible to expansion. Note the shift of the main peak at about 7 degrees to just over 5
degrees 2θ. The fact that the peak at about 7 degrees (air-dried) is strongly broadened
indicates multiple species of clays or disordering of clay layers. Illite-smectite layers are
indicated. A very sharp peak and placement toward 6 degrees 2θ would indicate pure smectite.
 Interpreted output tables are provided for the
client’s use. Pertinent data includes both
weight fraction as well as volume fractions for
mineral species. Note the calculated grain
density at the bottom.

Most sandstones are not pure quartz. This is

easy to see on modern logs with PE curves
that read well above 1.8. XRD can resolve
which minerals are present. In the example
below the sand is composed of 71 % quartz,
9% ankerite (an iron rich dolomite), 10%
apatite (a phosphate mineral), and 10% pyrite
(iron di-sulphide or fool's gold).

Note that the grain density is 3.15 gm/cc,

considerably higher than pure quartz. As an
exercise, you might want to calculate the
corresponding PE value from a volume
weighted summation of the four PE values of
the minerals. See Mineral Properties Table.

Example XRD Listings

 XRD Analysis of a sandstone sample. The calculated grain density is obtained by multiplying
the individual mineral weight fraction by their respective densities and adding them together:
0.63 * 2.65 + 0.09 * 3.04 + 0.10 * 3.20 + 0.17 * 5.00 = 3.113
This is slightly lower than the value on the table due too rounding erroes on the printout.
Summary XRD table for shale intervals within the sandstone in previous table

Summary XRD table for clean radioactive sandstone

THIS PAGE
XRD Basics
XRD Analysis Methods
XRD Results

THIS CHAPTER
 Water Chemistry Analysis
Core Analysis Basics
Coring and Core Porosity
Core Saturation
Core Permeability
Wettability
Capillary Pressure
Relative Permeability
Rock Compressibility
Electrical Properties A,M,N
X-Ray Diffraction (XRD)
X-Ray Fluorescence (XRF)
Infra-Red (FTIR)
Thin Section Petrography
Averaging Core Data
Core Analysis Lab Manual

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