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Plenary lecture of the XIII SBPMat (Brazilian MRS) meeting, given on September 29th by Jean-Marie Dubois (Institut Jean Lamour, Nancy, France).
Citation preview
Push-Pull Alloys
and the
Legacy of Dan Shechtman
Jean-Marie Dubois
Institut Jean Lamour
CNRS and Université de Lorraine
Nancy, France
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
Part 1
Push-Pull Alloys:
- Penrose tiling
- The discovery of non-periodic crystals
- A new paradigm in crystallography
- Push-Pull Alloys
- Complex metallic alloys (CMAs)
- One (essential) property of CMAs
- A typical application of a specific CMA
29 sept. 2014. MRS Brazil 2014 2 Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
MRS Brazil 2014
Tiling 2D-space, like the floor of your kitchen
An integer number of
tiles around each
vertex:
No void, no overlap.
1/6 of 2p: 6 tiles
1/4 of 2p: 4 tiles
1/3 of 2p: 3 tiles
29 sept. 2014. 3 Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
Tiling a floor may not be that simple!
29 sept. 2014. MRS Brazil 2014 4
= 2(p- p /5)/2 = 4p/5 = 144°
1
Copyright © 2014 Jean-Marie Dubois.
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The final result and its variety
29 sept. 2014. MRS Brazil 2014 5
This logical problem
was solved in 1974
by Sir Roger
Penrose.
Copyright © 2014 Jean-Marie Dubois.
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THE discovery in 1982
29 sept. 2014. MRS Brazil 2014 6
Same point group symmetry as that
of the icosahedron or of the
pentagonal dodecahedron
Danny Shechtman,
Technion, Haifa
Copyright © 2014 Jean-Marie Dubois.
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Two main types of quasicrystals
Icosahedral:
Aperiodic in 3D
Quasiperiodic planes stacked periodically
Decagonal:
Aperiodic in 2D,
Periodic in 1D
29 sept. 2014. 7 MRS Brazil 2014
Courtesy: P. A. Thiel, Ames Labs, USA.
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
Where are the atoms?
L
L
L
L
L
L
L
L
S
S
S
S
L LS
S L
L
LS
LSL
LSLLS
LSLLSLSL
…LSLLSLSLLSLLS…
Non-periodic if :
Num(L)/Num(S) =
=(1+5)/2 ≈ 1.618…
etc.
Courtesy : N. Takanura et al., NRIM, Japan
Although it is not periodic, the sequence of (red) planes is
fully determined by an non-ambiguous algorithm: there is
no disorder!
The same holds true for any other plane.
As a consequence, diffraction patterns show sharp
diffraction spots, like periodic crystals do.
Copyright © 2014 Jean-Marie Dubois.
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5-fold, 8-fold, 10-fold and 12-fold
29 sept. 2014. MRS Brazil 2014 9
All this implies a change of
paradigm: sharp diffraction spots do
not mean periodicity, but long range
order!
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
29 sept. 2014. MRS Brazil 2014 10
Nobel Prize for Chemistry in 2011
… for having forced the
scientific community to
change its paradigm
about crystals …
Copyright © 2014 Jean-Marie Dubois.
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Typical examples of quasicrystal-forming alloys
29 sept. 2014. MRS Brazil 2014 11
Al-Cu-Fe
Al-Pd-Mn
Al-Cu-Ta
Al-Ni-Co
Al-Ni-Cu
Al-Li-Cu
Al-Mg-Zn
Ti-Zr-Ni
Ag-In-Yb
Au-Sn-Yb
Mg-Cd-Yb
Hf-Mg-Zn
…
Cd-RE & Cd-Ca: the only known so far binary QCs
Immiscible
elements
or
Weakly
interacting
species
Pd Cu
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
29 sept. 2014. MRS Brazil 2014 12
CMAs in the Al-Cu-Fe system
Al62.5Cu25Fe12.5
-Al70Cu20Fe10
q-Al2Cu etc.
Cu & Fe form no
compounds
Copyright © 2014 Jean-Marie Dubois.
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Large size approximants
29 sept. 2014. MRS Brazil 2014 13 Lei et al., Phil. Mag. 88-4 (2008) 279.
Quiquandon et al., JPCM 8
(1996) 2487
N=154
N≈2750 N≈300
N≈6125 Ω = 60-65 at/nm3
Copyright © 2014 Jean-Marie Dubois.
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Al
Cu Fe
?
push
pull
29 sept. 2014. MRS Brazil 2014 14 Copyright © 2014 Jean-Marie Dubois.
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B C
A
push
Phase diagram of Push-Pull Alloy systems
immiscible
repulsive
A complexity amplifier
29 sept. 2014. MRS Brazil 2014 15 Copyright © 2014 Jean-Marie Dubois.
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To summarize at this stage
29 sept. 2014. MRS Brazil 2014 16
Complexity: natural logarithm of Nunit cell or bC=Ln(Nuc)
∞ bC
Ln(2) 5 54
B2 CsCl type
Intermetallics Complex metallic alloys
1 atom gram
10
Largest Al-based
PERIODIC CMA
known so far
Icosahedral
quasicrystals
Copyright © 2014 Jean-Marie Dubois.
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Electron transport
MRS Brazil 2014
Siz
e o
f th
e u
nit c
ell
Conductivity:
Einstein type: n(EF)-1
Conductivity:
Mott type: n(EF)-2
Belin-Ferré, Klanjšek, Jagličić, Dolinšek, Dubois, J. Phys. Cond. Matter (2005) 6911.
29 sept. 2014. 17
Complexity determines the
type of conductivity
Copyright © 2014 Jean-Marie Dubois.
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An example of Self-Organised Criticality?
MRS Brazil 2014 29 sept. 2014. 18
Slope = - 1 Slope = 0
4,0
6,0
8,0
10,0
12,0
14,0
0,0 10,0 20,0 30,0 40,0 50,0 60,0 bC
Ln s
Earthquakes in California
are another example of
SOC: the frequency of
occurrence of an
earthquake of magnitude
Am is f(m)/A if f(m) is the
frequency of earthquakes
of magnitude m.
Copyright © 2014 Jean-Marie Dubois. All rights reserved.
Optical conductivity
MRS Brazil 2014
0
2 0 0 0
4 0 0 0
6 0 0 0
8 0 0 0
1 1 04
0 2 0 04 0 06 0 08 0 01 0 0 01 2 0 01 4 0 0
i - A l - C u - F e - B0 % - A l - C r - F e5 0 % - A l - C r - F e8 0 % - A l - C r - F e1 0 0 % - A l - C r - F e
0 0 . 0 40 . 0 80 . 1 20 . 1 6O
pt
ic
al
c
on
du
ct
iv
it
y
s(
)
(
-1
.c
m-
1)
W a v e n u m b e r ( c m- 1
)
E n e r g y ( e V )
2000
4000
6000
8000
10000
g-Al-Cr-Fe
O1-Al-Cr-Fe
Ico-Al-Cu-Fe-B
Drude peak
No Drude peak
V. Demange et al. PRB 6-14 (2002) 144205 1.
High IR light
absorption 29 sept. 2014. 19
Copyright © 2014 Jean-Marie Dubois. All rights reserved.
Selective Laser Sintering
MRS Brazil 2014
IR light
29 sept. 2014. 20 Copyright © 2014 Jean-Marie Dubois.
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A new, commercial technology based on CMAs
MRS Brazil 2014
Approx. 20 cm Polyamide-matrix
composite
reinforced by
atomized
Al-Cu-Fe-B
icosahedral
particules, which
was assembled
by Selective Laser
Sintering.
Used for a
Formula I race car
by Renault.
S. Kenzari & V. Fournée, French Patent n°2950826
(2009), PCT n° WO2011/039469 (2011).
29 sept. 2014. 21 Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
Part 2: The Legacy of Dan Shechtman
29 sept. 2014. MRS Brazil 2014 22 Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
29 sept. 2014. MRS Brazil 2014 23
Part 2
The Legacy of Dan Shechtman:
- Soft-quasicrystals
- Quasiperiodic waves in hydrodynamics
- Quasicrystals in oxides
- Quasiperiodic cold atoms traps
- Quasiperiodic ensembles of microscopic particles
- Natural quasicrystal
- Quasiperiodic patterns in medieval islamic art
- Conclusion: What else?
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
29 sept. 2014. MRS Brazil 2014 24
Part 2, revised
The Legacy of Dan Shechtman:
- Soft-quasicrystals
- Quasiperiodic waves in hydrodynamics
- Quasicrystals in oxides
- Quasiperiodic cold atoms traps
- Quasiperiodic ensembles of microscopic particles
- Natural quasicrystal
- Quasiperiodic patterns in medieval islamic art
- Conclusion: What else?
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
Soft quasicrystals
29 sept. 2014. MRS Brazil 2014 25
Zeng et al., Nature 428 (2004) 157
Miscellar phases in
- lyotropic systems
- block co-polymers
- thermotropic liquid crystals
X: weakly binding group
Copyright © 2014 Jean-Marie Dubois.
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Non-periodic space groups in soft matter
29 sept. 2014. MRS Brazil 2014 26
Copyright © 2014 Jean-Marie Dubois. All rights reserved.
Defects as in metallic alloys
29 sept. 2014. MRS Brazil 2014 27 Copyright © 2014 Jean-Marie Dubois.
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A natural quasicrystal
29 sept. 2014. MRS Brazil 2014 28
L. Bindi P.J. Steinhardt
See: L. Bindi et al.,
Science, 324 (2009) 1306
Copyright © 2014 Jean-Marie Dubois.
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Natural quasicrystal : a meterorite
29 sept. 2014. MRS Brazil 2014 29
Terrestrial origin
Extraterrestrial origin
Copyright © 2014 Jean-Marie Dubois.
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Graphic arts
29 sept. 2014. MRS Brazil 2014 30
R. Lück, MPG Stuttgart
Private communication
Copyright © 2014 Jean-Marie Dubois. All rights reserved.
Not that new!
29 sept. 2014. MRS Brazil 2014 31
Dürer (1471-1528)
Kepler (1571-1630)
Copyright © 2014 Jean-Marie Dubois.
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Hans Ude Nissen c.a. 1996
29 sept. 2014. MRS Brazil 2014 32 Copyright © 2014 Jean-Marie Dubois.
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Lu and Steinhardt: Science, 315 (2007) 1106
29 sept. 2014. MRS Brazil 2014 33
Copyright © 2014 Jean-Marie Dubois. All rights reserved.
Conclusion: What else?
29 sept. 2014. MRS Brazil 2014 34
A never ending story!
See for instance: hydrogen-bonded quasicrystals (Wasio et al.,
Nature 507 (6 March 2014) 86) in ferrocenecarboxylic acid.
20.5nm x 20.5 nm 11 nm x 10 nm Copyright © 2014 Jean-Marie Dubois. All rights reserved.
Templating artificially nanostructured materials
29 sept. 2014. MRS Brazil 2014 35
Fournée et al.,
ACS Nano 8-4 (2014) 3646
Just one example: C60 balls ordered on an aperiodic surface
Copyright © 2014 Jean-Marie Dubois.
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Shechtman's legacy is …
29 sept. 2014. MRS Brazil 2014 36
A change of paradigm
AND
A full range of new discoveries, of unprecedented
physics and chemistry of materials, of (???).
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
MRS Brazil 2014
Acknowledgements
Special thanks go to my great friend,
Prof. Dr Severino Jackson Guedes de Lima,
29 sept. 2014. 37
who dedicated his life-long career
to his University and to the Rapid
Solidification Laboratory, for his
invitation to this five-star
conference, for the performance
the whole of his group has
achieved in bringing it to, and
managing it in, Joao Pessoa and
for the beautiful talks and events all
of us will enjoy this week. Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
29 sept. 2014. MRS Brazil 2014 38
And thanks to my sponsors:
Thank you to all those who worked hard to make this
conference a reality, especially to the Chairlady,
Prof. Dr Iêda Maria Garcia dos Santos.
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.
MRS Brazil 2014 29 sept. 2014. 39
Thank you for your
kind attention!
Copyright © 2014 Jean-Marie Dubois.
All rights reserved.