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Push-Pull Alloys and the Legacy of Dan Shechtman.

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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).

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Push-Pull Alloys and the Legacy of Dan Shechtman.

  1. 1. 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.
  2. 2. 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.
  3. 3. 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.
  4. 4. 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. All rights reserved.
  5. 5. 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. All rights reserved.
  6. 6. 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. All rights reserved.
  7. 7. 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.
  8. 8. 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. All rights reserved.
  9. 9. 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.
  10. 10. 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. All rights reserved.
  11. 11. 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.
  12. 12. 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. All rights reserved.
  13. 13. 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. All rights reserved.
  14. 14. Al Cu Fe ? push pull 29 sept. 2014. MRS Brazil 2014 14 Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  15. 15. 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. All rights reserved.
  16. 16. 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. All rights reserved.
  17. 17. Electron transport MRS Brazil 2014 Size of the unit cell 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. All rights reserved.
  18. 18. 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.
  19. 19. Optical conductivity MRS Brazil 2014 0 2 0 0 0 4 0 0 0 6 0 0 0 8 0 0 0 1 1 0 4 0 2 4 0 6 0 0 8 0 0 1 0 0 1 0 0 1 2 0 4 0 0 0 0 i - A l 0 % - 5 0 % 8 0 % 1 0 0 % 0 0 . 0 0 . 0 4 0 . 0 8 1 . 2 1 O s()p  t (i - 1 . c - 1 ) W a v e n - 1 ) E n e r g y 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.
  20. 20. Selective Laser Sintering MRS Brazil 2014 IR light 29 sept. 2014. 20 Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  21. 21. 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.
  22. 22. Part 2: The Legacy of Dan Shechtman 29 sept. 2014. MRS Brazil 2014 22 Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  23. 23. 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.
  24. 24. 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.
  25. 25. 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. All rights reserved.
  26. 26. Non-periodic space groups in soft matter 29 sept. 2014. MRS Brazil 2014 26 Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  27. 27. Defects as in metallic alloys 29 sept. 2014. MRS Brazil 2014 27 Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  28. 28. 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. All rights reserved.
  29. 29. Natural quasicrystal : a meterorite 29 sept. 2014. MRS Brazil 2014 29 Terrestrial origin Extraterrestrial origin Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  30. 30. Graphic arts 29 sept. 2014. MRS Brazil 2014 30 R. Lück, MPG Stuttgart Private communication Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  31. 31. Not that new! 29 sept. 2014. MRS Brazil 2014 31 Dürer (1471-1528) Kepler (1571-1630) Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  32. 32. Hans Ude Nissen c.a. 1996 29 sept. 2014. MRS Brazil 2014 32 Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  33. 33. Lu and Steinhardt: Science, 315 (2007) 1106 29 sept. 2014. MRS Brazil 2014 33 Copyright © 2014 Jean-Marie Dubois. All rights reserved.
  34. 34. 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.
  35. 35. 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. All rights reserved.
  36. 36. 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.
  37. 37. 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.
  38. 38. 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.
  39. 39. MRS Brazil 2014 29 sept. 2014. 39 Thank you for your kind attention! Copyright © 2014 Jean-Marie Dubois. All rights reserved.

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