FASCINATING QUASICRYSTALS

Part of

MATERIALS SCIENCE
Guide
& AALearners
Learners 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
HYPERBOLIC
EUCLIDEAN
SPHERICAL

STRONG
WEAK
ELECTROMAGNETIC

ENERGY

SPACE

GRAVITY

nD + t

FIELDS

PARTICLES
METAL
SEMI-METAL

BAND STRUCTURE

NON-ATOMIC

ATOMIC

SEMI-CONDUCTOR

INSULATOR

STATE / VISCOSITY

GAS

SOLID

LIQUID
CRYSTALS

LIQUID

STRUCTURE

AMORPHOUS

QUASICRYSTALS

RATIONAL
APPROXIMANTS

CRYSTALS

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
2

Crystals have certain symmetries

Symmetry operators

t Translation

R Rotation

R Inversion

R Roto-inversion
G Glide reflection
S Screw axis

Takes object to the same form

Takes object to the enantiomorphic form

R Mirror

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
Rdiger Appel, http://www.3quarks.com/GIF-Animations/PlatonicSolids/

Fluorite
Octahedron

HOW IS A QUASICRYSTAL DIFFERENT FROM A

CRYSTAL?

FOUND!
THE MISSING PLATONIC SOLID

[2]
Dodecahedral
single crystal
[1]

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

[2] Rdiger Appel,
Appel http://www.3quarks.com/GIF-Animations/PlatonicSolids/

Mg-Zn-Ho

QUASICRYSTALS (QC)
ORDERED

PERIODIC

QC

AMORPHOUS

CRYSTALS

QC ARE
ORDERED
STRUCTURES
WHICH ARE
NOT
PERIODIC

SYMMETRY

CRYSTAL

QUASICRYSTAL

RC

RCQ

translation

inflation

RC

rotation2,crystallographic
3, 4, 6

RCQ

8, 10, 12
RC + 5,
other

* Quasicrystals can have allowed and disallowed crystallographic symmetries

QC are characterized by Inflationary

Symmetry and can have disallowed
crystallographic symmetries*

DIMENSION OF QUASIPERIODICITY (QP)

QP/P

QP

QP/P

QC can have quasiperiodicity along 1,2 or 3

dimensions
(at least one dimension should be
quasiperiodic)

HIGHER DIMENSIONS
QP
QC can be thought of as crystals in higher
dimensions
(which are projected on to lower
dimensions lose their periodicity*)

* At least in one dimension

XAL

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

Ratio

1/1 2/1 3/2 5/3 8/5

...

13

21

34

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
the Fibonacci
sequence converges to
the Golden Mean

2.2
2
Ratio

1.8
1.6
1.4
1.2
1
1

10

n
* There are many phases of quasicrystals and some are associated with other sequences and other irrational numbers

Deflated
sequence

A
B
B
B
Rational
Approximants
Each one of these units
(before we obtain the 1D
quasilattice in the limit)
can be used to get a
crystal (by repetition:
e.g. AB AB ABor
BAB BAB BAB)

B
B
B

B B

B B

B B
A

ba

B B

B
A

bab
B B

babba

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
5-fold because the SAD pattern
has inversion symmetry)

The tiling has regions of

local 5-fold 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 ) 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 0]

[1 1 1]

[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

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
embedded in E3 space)

SPACE FILLING

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

ow
d
n
Wi

E||

e2

e1

E||

In the work presented

approximations are made
in E (i.e to )

Irrational QC
Slope = Tan ()
Rational RA (XAL)

x' Cos

y ' Sin

Sin

Cos

x

y

B B

B B

1-D QC

B B

List of quasicrystals with diverse kinds

of symmetries

Type of

QP+

Rank

Metric

Symmetry

System

quasicrystal
Icosahedral

Report
3D

_ _

m 35

AlMn

3D

Shechtman et al.
1984

(5)
Cubic

First

4 3m

VNiSi

Feng et al
1989

Tetrahedral

3D

m3

AlLiCu

Donnadieu
1994

Decagonal

2D

10/mmm

AlMn

Chattopadhyay et
al., 1985a and

(5)

Bendersky, 1985
Dodecagonal

2D

12/mmm

NiCr

Ishimasa et al.
1985

Octagonal

Pentagonal

2D

2D

8/mmm

5m

VNiSi,

Wang et al.

CrNiSi

1987

AlCuFe

Bancel
1993

(5)
Hexagonal

2D

6/mmm

AlCr

Selke et al.
1994

Trigonal

1D

3m

AlCuNi

Chattopadhyay et
al.,
1987

Digonal

1D

222

AlCuCo

He et al.
1988

Comparison of a crystal with a quasicrystal

CRYSTAL

QUASICRYSTAL

Translational symmetry

Inflationary symmetry

Crystallographic rotational symmetries

3D periodic

Allowed + some disallowed rotational

symmetries
Two prototiles are required to generate the
structure
Periodic in higher dimensions

Sharp peaks in reciprocal space with

translational symmetry

Sharp peaks in reciprocal space with

inflationary symmetry

Underlying metric is a rational number

Irrational metric

Single unit cell to generate the structure

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