X-Rays Historical Background

• X-rays were invented in the late 19 th century.

• Before that, mineralogists were studying minerals for
Lecture 8 hundreds of years & believed that minerals had
orderly and repetitive arrangement.
• They speculated about atomic arrangements &
crystal structure BUT LACKED DIRECT EVIDENCE.
• William Rontgen discovered X-rays in 1895 & this
X-Ray Diffractometer
allowed mineralogists to apply X-rays to minerals &
verify their earlier concepts.
N.V.CHALAPATHI RAO • Firm theoretical basis was established for minerals &
Centre of Advanced Study in Geology their structures only due to X-rays.
BANARAS HINDU UNIVERSITY • If we now know about the structure of thousands
VARANASI-221005 (U.P)
of minerals & understand their lattices it is only
[email protected];
http://www.nvcrao.webs.com
due to RONTGEN.

Rontgen, von Laue, Debye, Scherrer & Bragg..

Rontgen, von Laue, Debye, Scherrer & Bragg..
• They confirmed that crystals have a regular crystal structure.
• Rontgen – Physics Professor at University of Wurtzburg, Germany
• He was studying relationship between matter & force by flowing
• Paul Debye & Paul Scherrer (1912) showed that all crystals
charged particles (electrons) from a heated filament in an evacuated have a lattice & it lattices vary in their symmetry.
glass tube. • In 1913 William H. Bragg & his son William determined crystal
• Accidentally they fluoresced barium platinocyanide which is nearby. structure of ZnS using data obtained from X-Ray studies.
• He found that this radiation can penetrate a paper & even thin
• For the first time, mineralogists knew the ACTUAL LOCATIONS
metals.
of atoms WITHIN a crystal.
• He named it as X-radiation since he believed it is completely different
from light. • Linaus Pauling extended these studies (Paulings rules etc).
• Physicists started searching for an understanding of nature of X- • Earlier X-ray studies were very tedious (several years for
radiation. determining structure of a few minerals).
• Max von Laue (1911) – first applied X-rays to minerals.
• High speed computers (crystal structures – known in < a day).
• He hypothesised that atoms in minerals could lead to diffractions of X-
rays. • 1901 – Rontgen
• His students Walter Friedrich and Paul Knipping confirmed Laue • 1914 – von laue
theories in 1912 by causing X-rays to pass through ZnS & recorded the
pattern on a film. • 1955 – Both Braggs (NOBEL PRIZE in Physics for X-rays)
 What are X-rays?

• X-rays are a form of electro-magnetic radiation.

• Wavelengths of visible light is 10-6 to 10-7 meters, X-ray wave lengths are
only 10-8 to 10—12 meters.
• Long wave length X-rays grade into UV rays whereas short-wave-
length X-rays grade into Gamma rays & Cosmic rays.
• X-ray wave lengths are expressed in Angstrom units. (1Ao = 10–10 metres)
• The frequency (ν ) and wave length (λ) of electromagnetic spectrum are
inversely related. Planck’s law relates them to Energy:
• E = h ν = hc/ λ
• Where h = Planck’s constant
• C = speed of light in vacuum
• Because of their short wave length and high frequency, X-rays have
very high energy compared to visible light & other EMR.
• This enables them to penetrate many natural materials.

How are X-rays generated???

Types of X-Ray radiations
• X-rays are produced when high speed electrons strike atoms of
• Two types: any substance.
• A modern X-ray Tube contains essentially a HEATED FILAMENT
• Hard radiation – have highest energy. Used in (CATHODE) which provides a source of electrons & a METAL
manufacturing & industrial applications for checking TARGET (ANODE) placed in an EVACUATED CHAMBER.
• Cu, Mo, Ni, Co, Fe, W and Cr metals can be targets but Cu is
steel for flaws. mostly used.
• Soft radiation – X-rays of relatively low energy. • When a potential is applied, electrons move from high speed from
CATHODE to ANODE.
These are used by mineralogists & for medical
• The fast moving electrons of cathode collide with orbital electrons of
diagnosis. atoms of target and bump them temporarily into higher energy levels.
• Soft radiation is more dangerous than hard radiation, • The target atom gets into EXCITED STATE.
• Then the outer shell electrons which have higher characteristic
since instead of passing through tissues like hard X- energies than inner shells shift to vacancies in inner shells resulting in
rays, soft X-rays interact with ‘atoms’ in cells and loss of energy [ E = E outer – E inner ]
tissues and causes damage. taking the form of emitted X-ray radiation.
X-radiation is a characteristic energy and wave length for a given
• X-Ray operators take special care! element.
Lot of HEAT Is generated (always coolant water is circulated)
 X-rays vs atomic interactions X-rays & electronic shells

• If a K-shell vacancy is filled by L

shell electron, radiation is called
K α radiation.
• If a K-shell vacancy is filled by
M shell electron, radiation is
called K β radiation.
X-rays
• If L- shell vacancy is filled by
outer shell electron, radiation is
called L –series radiation.
• ATOMS of a given element emit
X-radiation of several wave
lengths , each of which is
characteristic of that element.

Out put from a X-ray tube

• Typical X-ray tubes emit Interaction of X-rays & Atoms
POLYCHROMATIC RADIATION.
• The broad WHALEBACK SHAPED • When X-rays strikes an atom, wave-like characters of
background (called WHITE or X rays causes electrons, protons & neutrons of atom
CONTINUOUS RADIATION) &
to vibrate.
• SHARP PEAKS of high intensity
(CHARACTERISTIC RADIATION). • Heavy protons & neutrons vibrate less than lighter
• They occur at different wave lengths electrons.
depending on metal of the target and
the accelerating voltage applied. • The oscillating electrons re-emit radiation called
• For most routine mineralogical studies, SECONDARY RADIATION , almost the same
Cu Kα radiation is used. Cu has frequency & wave length as incoming beam.
several characteristic wave lengths,
but for easy interpretation ONE WAVE • This process is called SCATTERING. (It is defined as
LENGTH (MONOCHROMATIC deflection of any radiation upon its interaction with
RADIATION) is used. matter).
• FILTERS or MONOCHROMATORS
(Ni, Zr, Co, Fe, Mn) of <0.1mm • It varies from element to element and varies from
thickness are used to isolate K α direction to direction.
radiation from other wave lengths.
 DIFFRACTION Diffraction by a row of atoms
• It is analogous to group of campers on a
lake bank and a canoeist in lake.
A
Just like visible light X-rays • If a stone is thrown wave front has
propagate in all directions & circular or arc shape. It loses energy
interact or INTERFERE with gradually & die out (canoeist feel a
each other. B ripple). See A
It can be CONSTRUCTIVE or • Long log (wood) is thrown, wave front is
DESTRUCTIVE. straight , more pronounced & passes
Two point sources interfere beneath the boat. See B
constructively in some • If a number of rocks are dropped in
directions (arrows) water, several wave fronts form then
& destructively in others. Dotted both constructive & destructive wave
circles are wave fronts from C fronts form & soon die out as they are
both sources. OUT OF PHASE. They are hardly noticed.
Energy is channelised in directions • When these rocks are thrown
where wave peaks coincide simultaneously, a wave front is created
because Waves add similar to that of log. Canoeist cannot
constructively. distinguish between them! They are in
THIS CHANNELING OF ENERGY phase.
IN SPECIFIC DIRECTION IS • When X-rays strike a row of atoms they
DIFFRACTION. produce a coherent wave front
D (perpendicular to row of atoms) similar to
In X-rays, intense energy
(constructive) & no X-rays that when rocks were thrown
simultaneously. (D shows atoms giving
(destructive)
identical wave fronts).

Bragg’s law • Bragg's Law refers to the simple

What causes Diffraction in minerals? equation:
n λ = 2d sinθ ……….eqn (1)
• When a beam of light or any electromagnetic radiation passes
through an aperture & falls upon a screen patterns of light and
dark bands (with monochromatic light) or coloured bands (with • The variable d is the distance between
atomic layers in a crystal,
colour light) are observed near edges of beam. This is due to
• and the variable lambda is the
interference due to wave nature of light & is known as
wavelength of the incident X-ray beam;
DIFFRACTION.
• n is an integer and is order of diffraction
• A narrow slit, regularly spaced atoms in a crystal etc can cause • In mineralogy and in conventional X-ray
diffraction. studies n=1 (first order assumed) since
• All electromagnetic radiation can be diffracted (in principle) but first-order diffraction at spacing d
for diffraction to occur, the spacing of atoms, slits etc should be occurs at same angle as second order
similar to wave length of radiation. diffraction by a set of planes spaced
twice apart & we cannot distinguish
• Atomic radii of elements (in Angstrom units) are of same them.
magnitude as wave length of X-rays since atoms in a crystal are • Atoms in xl do not diffract visible light
closely packed. since their λ are too long compared to
• Atoms in crystals therefore produce intense X-rays. atomic spacings.
 Bragg’s law What is X-Ray Diffraction Technique?
• Criteria:
• the incident angle equals and reflecting angle (to make phases coincide)
• Top beam strikes the top layer at atom z • XRD technique is essentially a non-destructive
• The second beam continues to the next layer where it is scattered by atom B. method to identify any crystalline material crystallized
• The second beam must travel the extra distance AB + BC if the two beams are under any crystal system.
to continue traveling adjacent and parallel.
• This extra distance must be an integral (n) multiple of the wavelength (λ) for It is very quick, accurate & can give semi-quantitative
the phases of the two beams to be the same:
as well as quantitative distribution of different phases
• n λ = AB +BC ….. Eqn (2) in multiphase samples.
• Recognizing d as the hypotenuse of the right triangle Abz, we can use
trigonometry to relate d and θ to the distance (AB + BC). The distance AB is Microcrystalline and cryptocrystalline minerals cannot
opposite θ so, be identified under the microscope owing to their
• AB = d sin θ ….. Eqn (3) extremely fine size and in such cases XRD would be
a very suitable method.
• Because AB = BC eq. (2) becomes,
Likewise, complex minerals and artificial phases can
• n λ = 2AB ……Eqn (4) be identified readily by this technique.
• Substituting eq. (3) in eq. (4) we have,

• n λ = 2 d sin θ ..(Eq 1)

How XRD works? Steps involved in XRD of minerals

• XRD principle: Every crystallized mineral has a unique diffraction pattern.

Therefore, a set of “d” values are unique for each mineral ( FINGER
PRINTING METHOD)

• The distance between the interatomic planes of crystal “d” are determined
either by Diffractometer method or camera method.

• APD (Automatic Peak Detection) software also available for easy and rapid
peak identification.

* Steps in XRD technique include

(i) obtaining X-ray diffraction pattern,
(ii) determining “d” values and corresponding intensities,
(iii) comparing “d”values with standard JCPDS (Joint Committee for Powder
Diffraction Studies) or ICDD (International committee for Diffraction Data)
data file for mineral identification and
iv) semi-quantitative/ quantitative evaluation of mineral /phase
abundance.
 Sample Preparation
Typical XRD Spectrum • To obtain useful powder patterns, sample must be
ground to –200 mesh size.
• Vigorous grinding has to be carried out in agate
mortar.
• In case of Diffractometer method, the fine powder is
placed onto a flat sample holder and pressed tightly.
It adheres to it.
• In case of Powder camera method, sample powder
is mixed with a drop of collodion solution (
colourless fingernail polish is fine) and rolled into a
spindle.
• The hardened spindle is mounted in powder camera.

POWDER CAMERA METHOD Powder Diffraction method

• It is only of historical interest. • Here diffraction angles are measured by a rotating goniometer
& intensity of X-rays are detected by X-ray detectors such as
• It consists of a camera called DEBYE SCHERRER camera.
scintillation counters or proportional counters.
• Small amount of sample (spindle form) is mounted in the centre
• Here, sample in fine powder form is placed and pressed tightly
of camera and encircled by a piece of photographic film.
into flat sample holder.
• The camera has an arrangement COLLIMATOR through which
• Xrays from target falls on the sample, then sample holder
X-rays are allowed to enter the camera & strike the specimen.
rotates on a horizontal axis at an angle of 2 θ.
• Diffraction takes place & leaves DARK LINES & ARCS on the
• The peak position and peak height gives 2 θ values and
film. (resemble tracks on a CD disc!)
intensities.
• 2 θ values can be determined by measuring the distance from
• From 2 θ values, ‘d’ in Amstrong units are calculated.
the centre of film to each diffracting line.
• The main advantage of this method is automated diffractometers
• Then d values can be calculated.
when connected to computers can collect and analyze a pattern
• Biggest disadvantage is a single sample takes several hours in few minutes.
to record results on film.
• Computers can produce paper copies in any scale and size.
• Film has to be developed in a dark room.
 How to INDEX a mineral?
How to Identify a mineral? • To calculate UNIT CELL dimensions from X-ray pattern, we must
determine which hkl values go with which X-Ray peaks.
• Powder patterns are NOT usually used to identify structure of a • This is called INDEXING.
mineral. • This is done by comparing the ‘unknown’ pattern to the one already
• They are used to identify a mineral (indirectly its structure). indexed & by assigning hkl values to peaks in unknown pattern.
• Obtained ‘d’ values are compared with those of already known • Garnets are cubic; so a is the only unit cell parameter to be determined.
minerals available in JCPD (Joint commission for Powder • We can derive dhkl and a from equation:
diffraction data) charts or ICDD (International commission for • a 2 = (h2 + k2 + l2) d2 (we calculate a values for each of 5 dhkl values.
Diffraction data) charts. • [Py= 11.46; Alm= 11.53; Sp = 11.62; Gr= 11.85; And= 12.05; Uv= 12.0]
• There are two methods to search data:
d values for the Similar d hkl values for Calculated
• HANAWALT METHOD: ‘d’ values are listed in decreasing order ‘unknown’ values for the ‘known’ values of a for
of ‘d’ values of their most intense peaks. garnet ‘known’ almandine unknown
• RIETVELD METHOD: List mineral names in alphabetical names almandine garnet
(Grossular)
along with their ‘d’ values.
1.583 1.540 642 11.82
• SOFTWARES are in vogue which suggest a probable name.
1.652 1.599 640 11.90
1.924 1.866 611 11.84
2.653 2.569 420 11.85
2.961 2.873 400 11.84

Single Crystal Technique

• Here X-ray patterns involve those of single homogeneous

crystals and are generally a few mm across.
• They yield more extensive data than is available from powder
patterns.
• Data obtained is useful to determine essentially all structural
information about a mineral.
• If we know composition of a mineral, from diffraction data (i) we
can how many atoms of which element are present and (ii)
where such atoms are located.
• Different methods in vogue include:
• Laue method
• Weissenberg method
• Precession method
• Rotation method