MSE203

Structure and Characterization of

Materials
L-2
10-1-17, Tuesday

Natural Crystals

https://s-media-cacheak0.pinimg.com/originals/ee/99/29/ee992930e52f7f65456328acd19a
327b.jpg

 Crystals: The word "crystal" comes from the Ancient Greeks

crustallos, or phonetically kroos'-tal-los = cold + drop, who
used the word crystal to refer to the mineral quartz, meaning
both ice and rock crystal, that is cold and hard.

Crystallography
The science that deals with the shapes and structures of
crystals.
In its origins, Crystallography was dedicated exclusively to the
study and description of the external appearance
(morphology) of crystals, mainly minerals.

Few historical events

The German Johannes Kepler (1571-1630) was surprised by
the fact that snowflakes landing on his coat always showed
perfect six-cornered symmetry and never showed five of
seven corners. He explained his observations in terms of the
particle packings, as oranges show in the picture below.

 The Danish scientist Niels Stensen

(1638-1686) and French mineralogist
Jean-Baptiste Louis Rom de l'Isle
(1736-1790), established the law of
constancy of angles between faces of
different crystal specimens of the
same species based on the
observation of crystal morphologies

Ren Just Hay (1743-1822), another

French mineralogist, concluded that
the crystals were made by the
ordered stacking of small bricks, or
unit cells, all of them identical.

While the features of crystals were being studied

During the nineteenth century, the mathematical systematization

of symmetry concepts governing the repetition of motifs around a point, as
the petals of a flower around its axis, or the repetition of patterns by
translation, gave rise to the establishment of some mathematical concepts
such as:
the so-called point groups, i.e., groups of symmetry elements (symmetry
axes, mirror planes, etc.) passing through the center of a body, and
the concept of lattice, i.e., the repetition rules by which objects or motifs
are repeated by translation in an ordered manner (for example, the
drawings in a wallpaper).
In 1830, the German physician Johann Friedrich Christian Hessel (1796-1872),
using the previous deductions of Ren Just Hay (1743-1822), and after
demonstrating that rotation axes can only be of orders 2, 3, 4 and 6, showed
that the different possible morphologies of crystals can be combined to give
exactly 32 different combinations of symmetry elements (the 32 point groups,
also known as crystal classes).
In 1848 the French physicist Auguste Bravais (1811-1863) discovered that in
the three-dimensional space, periodic repetitions by translation can only be
made in 14 different modes (the so-called 14 Bravais lattices), as they must to
be compatible with the 32 crystal classes.

The discovery that transformed the field of crystallography:

The discovery of X-rays by Wilhelm Conrad Rntgen (18451923) in the late 19th century completely transformed the old
field of Crystallography, which previously studied the
morphology of crystals, mainly minerals.
In 1901 won the highest scientific award, the
first Nobel Prize in Physics.

X-ray Crystallography
If Rntgen's discovery was important for the development of
Crystallography, it was especially due to the experiment
conducted in 1912 by Max von Laue (1879-1960), which led to
the conclusion that crystals have a regular internal structure.

Nobel Prize in Physics in 1914

Laue showed in 1912 that X-rays are electromagnetic waves and that crystals have a regular
internal structure.

 In the same year of Laue's experiment, William Henry Bragg

(1862-1942) and his son William Lawrence Bragg (1890-1971)
realized that if atoms inside crystals diffract X-rays and give
rise to a diffraction pattern, this pattern should contain
enough information to extract the relative positions of atoms
in the crystal, that is to go backwards and retrace the path of
diffraction.

They were able to determine

the atomic structure of simple
materials such as sodium
chloride (common salt) or the
mineral blend (zinc sulfide).
Father and son shared the Nobel Prize for Physics
in 1915 for demonstrating the usefulness of the
phenomenon discovered by von Laue in studying
the internal structure of crystals.

 Structural knowledge obtained by Crystallography allows us to

produce materials with predesigned properties, from catalyst
for a chemical reaction of industrial interest, up to toothpaste,
vitro ceramic plates, extremely hard materials for surgery, or
certain aircraft components.

Only after the molecular structure of

penicillin was unambiguously determined
by crystallography, chemists could start
the synthesis of this compound, thus
saving millions of lives.

thanks to Crystallography we discovered the

DNA secrets, the genetic code.

 Crystallography has become one of the most important

disciplines for many branches of science, especially for
Mineralogy, Physics, Chemistry, Materials Science, Biology and
Biomedicine.
This was recently recognized by the United Nations, declaring
2014 International Year of Crystallography, and celebrating
the centenary of the birth of modern Crystallography...

Crystallography has been (and still remains) one of the most

multidisciplinary sciences that links together frontier areas of research
and has, directly or indirectly, produced the largest number of Nobel
Laureates throughout history, up to now 29 Prizes for 48 Laureates...
http://www.xtal.iqfr.csic.es/Cristalografia/index-en.html

Crystalline State

Symmetry

http://haezn.deviantart.com/art/Symmetry-in-Nature-94003079

http://agatelady.blogspot.in/2012/01/what-is-snowflake.html

http://www.treknature.com/gallery/photo256103.htm

Symmetry
An object
or event

Transformation
under the
application of
an operation

Identical object
or event

Then
Object or the event is symmetric with respect to that
operation/transformation

Q) So what symmetry operations did you recognize in the pictures on previous

slides ?

 Symmetry

SYMMETRY OPERATION

Why do I need to talk about symmetry and symmetry operators?

If the object, collection of objects, crystal etc. (which is under consideration) has some symmetry then
the whole need not be described, but only a part can be described along with the symmetry operators.
For example consider a square (as below). An infinite tiling of squares can be thought of as a single
square repeated in x and y directions Further one half of the square with a mirror plane (mirror line
in 2D) can give the whole square. Or a quarter of a square with two mirror planes or a diagonal
half of the quarter with three mirror planes. (note: mirror planes in 2D are lines)
Consider an infinite pattern made of squares

This can be thought of as

a single square repeated
in x and y directions

Else one could have considered a quarter of the object along with a 4-fold rotation operation (with symbol and
which rotates space by 90).
Now imagine that the 1/8th triangle had a 1000 atoms in it- we will have to give the coordinates of a 7000
atoms less!

Hence, we use the language of symmetry to be terse in

our description (i.e. to supply minimum information)

Symmetry properties of a crystalline solid tell a lot of information

about the directional properties of that solid.
Properties that are directionally dependent include:
Hardness (e.g., kyanite)
Thermal conductivity
Electrical conductivity
Thermal expansion
Diffusion of ions through a crystal
External form of crystal
Dissolutiuon rates
Diffraction of X-rays
Speed of light or optical properties.

Symmetry operations (in 2D Space)

Putting the observations about the symmetry of an object in
mathematical language.
So what symmetry operations did you recognize in the pictures
on previous slides ?

 Rotational
Symmetries

 Rotational Symmetry

Motif

+
Motif

+
Motif
(What to
repeat)

Symmetry
operation
(How to
repeat)

 Mirror Symmetry:

Enantiomers

 Reflection or Mirror Symmetry

 Point symmetry
In rotation and mirror there is at least on point which is
not at all affected by the operations.

Plane Point-Groups
Combination of Rotation and Reflection Operation

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