FASCINATING QUASICRYSTALS

MATERIALS SCIENCE
Part of & A Learner’s Guide
ENGINEERING
AN INTRODUCTORY E-BOOK
Anandh Subramaniam & Kantesh Balani
Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
http://home.iitk.ac.in/~anandh/E-book.htm

Based on atomic order quasicrystals are one of the 3 fundamental phases of matter
Where are quasicrystals in the scheme of things?

UNIVERSE STRONG
WEAK
HYPERBOLIC ELECTROMAGNETIC
EUCLIDEAN SPACE ENERGY GRAVITY
SPHERICAL
nD + t
PARTICLES FIELDS

METAL
ATOMIC NON-ATOMIC
SEMI-METAL BAND STRUCTURE
SEMI-CONDUCTOR
INSULATOR STATE / VISCOSITY

LIQUID
GAS SOLID LIQUID CRYSTALS
STRUCTURE

AMORPHOUS QUASICRYSTALS RATIONAL CRYSTALS

APPROXIMANTS
SIZE

NANO-QUASICRYSTALS NANOCRYSTALS
Let us first revise what is a crystal before defining a quasicrystal

WHAT IS A CRYSTAL?

Crystal =
Lattice (Where to repeat)
+
Motif (What to repeat)

a
=

a
+

a
2
Crystals have certain symmetries
Symmetry operators

t  Translation

R  Rotation R  Inversion R  Mirror

R  Roto-inversion

G  Glide reflection

S  Screw axis

 Takes object to the same form

 Takes object to the enantiomorphic form
 3 out of the 5 Platonic solids have the symmetries seen in the
crystalline world
i.e. the symmetries of the Icosahedron and its dual the Dodecahedron are
not found in crystals

These symmetries (rotation,

mirror, inversion) are also
expressed w.r.t. the external
shape of the crystal

Pyrite
Cube Fluorite
Rüdiger Appel, http://www.3quarks.com/GIF-Animations/PlatonicSolids/ Octahedron
HOW IS A QUASICRYSTAL DIFFERENT FROM A
CRYSTAL?
 FOUND!
THE MISSING PLATONIC SOLID

[2]

Dodecahedral
single crystal
[1] Mg-Zn-Ho

[1] I.R. Fisher et al., Phil Mag B 77 (1998) 1601

[2] Rüdiger Appel, http://www.3quarks.com/GIF-Animations/PlatonicSolids/
 QUASICRYSTALS (QC)

ORDERED PERIODIC QC ARE

ORDERED
CRYSTALS   STRUCTURES
QC   WHICH ARE
NOT
AMORPHOUS   PERIODIC
 SYMMETRY

CRYSTAL QUASICRYSTAL
t  
RC  RCQ

t  translation
  inflation QC are characterized by Inflationary
Symmetry and can have disallowed
RC  rotation2,crystallographic
3, 4, 6 crystallographic symmetries*
RCQ  RC + 5, 8, 10, 12
other

* Quasicrystals can have allowed and disallowed crystallographic symmetries

 DIMENSION OF QUASIPERIODICITY (QP)

QP/P QC can have quasiperiodicity along 1,2 or 3

dimensions
(at least one dimension should be
QP QP/P
quasiperiodic)

HIGHER DIMENSIONS
QP
QC can be thought of as crystals in higher
1  4
dimensions
2  5
(which are projected on to lower
dimensions → lose their periodicity*) 3  6

* At least in one dimension

 HOW TO CONSTRUCT A QUASICRYSTAL?

 QUASILATTICE + MOTIF
(Construction of a quasilattice followed by the decoration of the lattice by a motif)

 PROJECTION FORMALISM
 TILINGS AND COVERINGS

 CLUSTER BASED CONSTRUCTION

(local symmetry and stagewise construction are given importance)

 TRIACONTAHEDRON (45 Atoms)

 MACKAY ICOSAHEDRON (55 Atoms)
 BERGMAN CLUSTER (105 Atoms)
The Fibonacci sequence has a curious connection with quasicrystals* via the GOLDEN MEAN ()

THE FIBONACCI SEQUENCE

Fibonacci  1 1 2 3 5 8 13 21 34 ... 

Ratio  1/1 2/1 3/2 5/3 8/5 13/8 21/13 34/21 ...  = ( 1+5)/2

Where  is the root of the quadratic equation: x2 – x – 1 = 0

Convergence of Fibonacci Ratios

The ratio of
successive terms of
2.2
the Fibonacci
sequence converges to
2
the Golden Mean
1.8
Ratio

1.6

1.4

1.2

1
1 2 3 4 5 6 7 8 9 10
n

* There are many phases of quasicrystals and some are associated with other sequences and other irrational numbers
 Deflated
A
sequence

B
B A a

B A B b
Rational
Approximants B A B B A ba

Each one of these units

B A B B A B A B bab
(before we obtain the 1D
quasilattice in the limit)
can be used to get a
B A B B A B A B B A B B A babba
crystal (by repetition:
e.g. AB AB AB…or
BAB BAB BAB…)
Note: the deflated sequence is
identical to the original sequence

1-D QC
In the limit we obtain the 1D quasilattice

2D analogue of the 1D quasilattice Penrose tiling

Schematic diagram showing the structural analogue of the Fibonacci sequence leading to a 1-D QC
 PENROSE TILING The inflated tiles
can be used to
create an inflated
replica of the
original tiling

 Inflated tiling
The tiling has only one
point of global 5-fold
symmetry (the centre of
the pattern)

However if we
obtain a diffraction
pattern (FFT) of
any ‘broad’ region
in the tiling, we will
get a 10-fold
pattern!
(we get a 10-fold instead of a The tiling has regions of
5-fold because the SAD pattern local 5-fold symmetry
has inversion symmetry)
 ICOSAHEDRAL QUASILATTICE
 The icosahedral quasilattice is the 3D analogue of the Penrose tiling.
 It is quasiperiodic in all three dimensions.
 The quasilattice can be generated by projection from 6D.
 It has got a characteristic 5-fold symmetry.

5-fold [1  0]

Note the occurrence of irrational Miller

indices

3-fold [2+1  0]

2-fold [+1  1]
HOW IS A DIFFRACTION PATTERN FROM A CRYSTAL
DIFFERENT FROM THAT OF A QUASICRYSTAL?
 Let us look at the Selected Area Diffraction Pattern (SAD) from a crystal → the spots/peaks are arranged periodically

The spots are

periodically
arranged

[112]
Superlattice spots [111] [011]

SAD patterns from a BCC phase (a = 10.7 Å) in as-cast Mg4Zn94Y2 alloy showing important zones
Now let us look at the SAD pattern from a quasicrystal from the same alloy system (Mg-Zn-Y)

The spots
show
inflationary
symmetry
Explained in
the next slide
[1 1 1]
[1  0]

[0 0 1] [ 1 3+ ]

SAD patterns from as-cast Mg23Zn68Y9 showing the formation of Face Centred Icosahedral QC
DIFFRACTION PATTERN
5-fold SAD pattern
from as-cast
Mg23Zn68Y9 alloy

Note the 10-fold pattern

1  2 3 4

Successive spots are at a distance inflated by 

Inflationary symmetry
THE PROJECTION METHOD
TO
CREATE QUASILATTICES
 HIGHER DIMENSIONS ARE NEAT

E2

GAPS

S2  E3

REGULAR
PENTAGONS

Regular pentagons cannot tile E2 space

but can tile S2 space (which is SPACE FILLING
embedded in E3 space)
 For crystals  We require two basis vectors to index the diffraction pattern in 2D

For quasicrystals 
We require more than two basis vectors to index the diffraction pattern in 2D

For this SAD pattern

we require 5 basis vectors
(4 independent)
to index the diffraction pattern in 2D
 PROJECTION METHOD

QC considered a crystal in higher dimension → projection to lower dimension can give a crystal or a
quasicrystal

Additional basis vectors needed to index the diffraction pattern

2D  1D

E E||
E||  

e2 In the work presented

approximations are made
 e1 in E (i.e to )

Irrational  QC
Slope = Tan ()
Rational  RA (XAL)  x'   Cos Sin  x 
     
 y '    Sin Cos  y 
 B A B B A B A B B A B B A

1-D QC
List of quasicrystals with diverse kinds Type of QP+ Rank Metric Symmetry System First

of symmetries quasicrystal Report

Icosahedral 3D 6  m 35
_ _
AlMn Shechtman et al.

(5) 1984

3
_
Cubic 3D 6 4 3m VNiSi Feng et al
1989

3
_
Tetrahedral 3D 6 m3 AlLiCu Donnadieu
1994

Decagonal 2D 5  10/mmm AlMn Chattopadhyay et

(5) al., 1985a and

Bendersky, 1985

Dodecagonal 2D 5 3 12/mmm NiCr Ishimasa et al.

1985

Octagonal 2D 5 2 8/mmm VNiSi, Wang et al.

CrNiSi 1987
_
Pentagonal 2D 5  5m AlCuFe Bancel

(5) 1993

Hexagonal 2D 5 3 6/mmm AlCr Selke et al.

1994
_
Trigonal 1D 4 3 3m AlCuNi Chattopadhyay et
al.,
1987

Digonal 1D 4 2 222 AlCuCo He et al.

1988
Comparison of a crystal with a quasicrystal

CRYSTAL QUASICRYSTAL
Translational symmetry Inflationary symmetry

Crystallographic rotational symmetries Allowed + some disallowed rotational

symmetries
Single unit cell to generate the structure Two prototiles are required to generate the
structure
3D periodic Periodic in higher dimensions

Sharp peaks in reciprocal space with Sharp peaks in reciprocal space with
translational symmetry inflationary symmetry
Underlying metric is a rational number Irrational metric
 APPLICATIONS OF QUASICRYSTALS

 WEAR RESISTANT COATING (Al-Cu-Fe-(Cr))

 NON-STICK COATING (Al-Cu-Fe)
 THERMAL BARRIER COATING (Al-Co-Fe-Cr)
 HIGH THERMOPOWER (Al-Pd-Mn)
 IN POLYMER MATRIX COMPOSITES (Al-Cu-Fe)
 SELECTIVE SOLAR ABSORBERS (Al-Cu-Fe-(Cr))
 HYDROGEN STORAGE (Ti-Zr-Ni)
 High-resolution micrograph

SAD pattern BFI

As-cast Mg37Zn38Y25 alloy showing a 18 R modulated phase

Rational Approximants
 3.14 (=314/100) is a rational approximant to . Similarly, 1.414 is a rational approximant to
2 (to 3 decimal places).
 Rational approximants are structural analogues of such ‘number’ approximants.
 Rational approximants locally resemble the quasicrystal (to which it is an approximant), but
it is a crystal based on long range order. The higher the order of the approximant, the longer
the ‘patch’ in the structure which ‘looks like’ a quasicrystal.
As mentioned before if we two length segments (A and B) such that:
Length of A = 2 (length of B) and make the structure as below (In the  limit we get the
quasicrystal_.

 B A B B A B A B B A B B A

1-D QC
However if a we take a part of the same and repeat it to make a crystal, it is a rational approximant

B A B Repeat   B A B B A B B A B B A B 

If we take a bigger patch, it will resemble a QC more (locally) B A B B A

 B A B B A B A B B A B A B B A B A B B A 
 Rational Approximants

 A nice example of a rational approximant amongst crystal structures is the Al12W Frank-
Kasper phase.
 This phase locally has icosahedra (as in figure below), but is overall a crystal having a BCC
lattice. This crystal structure can be considered as a rational approximant to the icosahedral
quasicrystal.

Al

Motif: 12Al +W (consistent with stoichiometry)

Lattice: Body Centred Cubic

Al12W (Frank-Kasper)
Lattice parameter(s) a = 7.58 Å
Space Group Im3 (204)
Strukturbericht notation Wyckoff Site
x y z Occupancy
Pearson symbol cI26 position Symmetry

Other examples with this Al 24g m 0 0.184 0.309 1

Al12Mn, Al12Mo
structure W 2a m-3 0 0 0 1