1. Artificial pinning in films, melt- textured and MgB 2 Adrian Crisan School of Metallurgy and Materials, University of Birmingham, UK and National Institute of Materials Physics, Bucharest, Romania

2. CONTENTS Motivation YBCO (REBCO) films and coated conductors MgB 2 Melt-textured 123

3. Motivation Energy efficient devices and equipment (magnets, motors, transformers, power lines) High Tc superconductors Low cost, High critical current Losses (dissipation): Movement of flux lines (Lorenz force, Thermal fluctuations) Solution: blocking flux lines (pinning) on various types of defects, natural and/or artificial Nanoengineered pinning centres

4. YBCO(REBCO) films and coated conductors YBCO films (Coated Conductors) have many types of natural pinning centres (i.e., they may occur naturally during growth process However, for many foreseen applications, especially in high magnetic fields, critical current still need improvement, hence larger F P, hence ARTIFICIAL PINNING CENTRES S.R. Foltyn et al, Nat Mater 6/9 (2007) 631.

5. Substrate decoration 1 2 4 3 5 1- substrate; 2- nanodots; 3- SC film; 4- columnar defects; 5- dislocations 2001 – A. C. and H. Ihara, Jap. Patent #3622147, EU and USA; A. C. et al. APL 79, 4547 (2001), APL 80, 3566 (2002), IEEE Trans. Appl. Supercond. 13, 3726 (2003); M. Ionescu,…, and A.C. J. Phys. D: Appl. Phys. 37, 1824 (2004)

6. Quasi-superlattices (quasi-multilayers) 2002 – A. C., seminar AIST (unpublished) 2004 – T. Haugan et al, (USAFRL), Nature, 430, 867 2005 – B. Holzapfel group (Dresden) J. Appl. Phys. 98, 123906.

7. Nanostructured targets (secondary phase nano-inclusions)

8. Materials used up to now on Tl-based films, YBCO, ErBCO substrate decoration: Ag – AIST Tsukuba (A. C.), Univ. Wollongong Australia (Ionescu, Dou, A. C.); MgO - AIST Japan (Badica and A. C.); Y 2 O 3 – CREST Japan (Matsumoto), Barcelona (Puig, Obradors), Dresda (Holzapfel); Ce 2 O 3 – AIST Tsukuba (Nie, Yamasaki); Ir – USA Univ. and Nat. Lab. consortium.; Au, Pd, LaNiO 3 – Univ. Birmingham (A. C.) quasi-superlattices approach: Y 2 BaCuO 5 – USAFR, Wright-Patterson (Houghan); Y 2 O 3 – USAFR, Dresda ; YSZ; BaTMO 3 (TM = transition metal = Ir, Ti, Zr, Hf); TM – Dresda; Au, Ag, Pd, LNO, PrBCO, ns-YBCO - Univ. Birmingham (A. C.) impurity addition to targets: BaZrO 3 – many groups (Cambridge & Los Alamos, ORNL, CREST-Japan, Univ. Birmingham & Univ. Turku Finland, etc..); BaNb 2 O 6,BaSnO 3 – CREST Japan (Matsumoto); RE 3 TaO 7 (RE = rare earth = Er, Gd, Yb); - Univ. Cambridge & Los Alamos (J. McManus-Driscoll); double-perovskites YBa 2 NbO 6 (Cambridge) Gd 2 Ba 4 CuWO y – Univ. Birmingham & Cambridge (A. C.); combination of two-three types of impurities

9. Dimensionality and strength of PCs

10. Pinning centres in films obtained by PLD

12. Substrate decoration Distribution of the Ag nano particles deposited at 400 o C by 15 laser pulses

13. Field dependence of critical current density at 77.3 K of pure YBCO film (open squares) and of the film grown on substrate decorated with 15 laser pulses substrate (full circles).

14. Columnar growth of YBCO on Ag Nanodots YBCO STO AFM-side view- of YBCO grown on (from left to right): Au nanodots decorated substrate, Ag nanodots decorated substrate and on bare substrate.

15. Ag/YBCO quasi-multilayer films

16. Y2O3Y2O3 HRTEM showing the Cu-O planes and a large Y 2 O 3 precipitate

17. Cross-sectional TEM image, showing c-axis correlated defects, arrow indicates c-axis. Mis-orientation in the boundary area

18. High-resolution cross-sectional TEM image of the substrate-film boundary. A nano-particle can be seen near the substrate High-resolution cross-sectional TEM image of the substrate-film boundary.

19. Columnar structure formed from the substrate Columnar structure

20. Nanoscale particles

21. a) STEM image and element mapping of b) O2, c) Ba, d) Ag, e) Cu, f) Y

22. PBCO/YBCO quasi-multilayer films

23. High-resolution TEM image of PBCO/YBCO multilayer near the film substrate interface, arrow and circle point to a PBCO nano-particle. A grain boundary along the c-axis.

24. Mis-orientated grain observed in the cross section TEM image. Defects in the middle of the film

25. BZO-doped YBCO and multilayer architectures of BZO-doped YBCO films BZO nano-particles in the YBCO matrix of the film deposited at 780 o C High resolution of cross section TEM image of the film deposited at low temperature, BZO nano- particles are visible, and marked by circles.

26. Cross section TEM image of BZO-doped YBCO film deposited at 800 o C, clearly visible columnar structures (nano-rods) along the c-axis are formed Formation of Cu-O nano-particle found in the YBCO matrix of the film Cu-O

27. EDX mapping of the BZO-doped YBCO film using STEM mode, a) STEM image, b) mapping of Ba, c) mapping of Cu, d) mapping of O, e) mapping of Y and f) mapping of Zr

28. Cross section TEM image of BZO- doped YBCO film near the substrate, arrow shows the c-axis of YBCO Formation of BZO nano-rods in the mildle area of the film, arrow shows c-axis

29. Short and long nano-rods grows together inside the YBCO matrix, along the c-axis. The BZO nano-rods started growing from the STO substrate, along the c-axis (arrow)

30. Some of the nano-rods are long, larger than the cross section of the image, arrow indicates c-axis Stacking fault found in high resolution TEM image

31. 15Ag/BZO-doped YBCO multilayer architecture Cross section image of (15Ag/1 μm BZO- doped YBCO)x2, arrow shows c direction BZO nano-rods and nanoparticles in the YBCO matrix

32. Co-existence of Y2O3 (circle) and Cu rich phase (rectangular) and/or BZO phase. Defects caused by CuO2 and/or BZO phase observed in the middle area of the film.

33. A cross section TEM image near the STO substrate, arrow show the c-axis of YBCO A distorted area near the STO substrate, the c-axis is indicated by arrow

34. BZO nanoparticles and nano-rods BZO nano-rods entangled with columns of YBCO due to Ag-induced columnar growth

35. 1.5 μm BZO doped YBCO / 30 nm STO/ 1.5 μm BZO doped YBCO on Ag decorated (15 pulses) STO substrates

36. Pinning in MgB 2 MgB 2 wires are produced by various variants of Powder-In-Tube (PIT) process Increase of H c2 and J c using nanophase additions in the precursors in the initial stage Carbon doping: amorphous, nano-diamond, carbon nanotubes Ta, Ti, Zr impurity atoms used for absorbtion of H, to form e.g., ZrH 2, preventing the formation of harmful MgH 2 impurity

37. Addition of nano-Silicon Best doping: SiC nanoparticles (up to 13-14 mol%) - B-rich phase - Mg 2 Si secondary phase - O- and Si- containing matrix Silicon oil liquid precursor - Si formed Mg 2 Si - C substitutes B sites Many other substitutions tried

38. Melt-textured REBa 2 Cu 3 O 7 Elemental 123: YBa 2 Cu 3 O 7, NdBa 2 Cu 3 O 7 Mixed ternary light rare earth LRE–Ba 2 Cu 3 O y (LRE = Nd, Eu, Sm, Gd) compounds (NEG-123, NSG-123, SEG-123) have twice irreversibility line (critical current density). All these elements tend to sit on both the rare earth- and Ba-sites in the matrix and to form so called LRE/Ba solid solution. Moreover, one can vary the LRE elemental ratio. Due to differences in the LRE ion sizes, the LRE ratio variation, especially in ternary composites can affect the local tensions in the matrix and contribute to the pinning performance. Microstructure observations clarified that one can create nanoscale arrays in these materials and dramatically improve pinning at high magnetic fields

39. Besides, the melt-process technology enables introduction of non-superconducting secondary phase particles, RE 2 BaCuO 5 RE-211 that were found to enhance pinning at low magnetic fields. ZrO 2 ball milling of LRE-211 particles led to nanoscale 211 phase Such particles (in the size of 70–150 nm) not only survived the melt-texturing process but also further reduced their size up to 20–50 nm. Micro-chemical analysis identified these defects as Zr-rich ZrBaCuO and (NEG, Zr) BaCuO ones

40. The effect of Zr in the particles size diminution stacks obviously in the chemical inertia of Zr in the superconductor matrix Creating nanoscale particles based on some other inert elements, like MgO or adding fine Y 2 Ba 4 CuZrO y particles to RE-123 confirmed validity of this hypothesis. Use of the initial powder composed of the nano- sized REBa 2 CuZrO y particles and 35 mol% of sub- micron Gd-211 precipitates led to the super- current density around 270 kA/cm 2 at 77 K.

41. nanoparticles from the same chemical group, namely Mo, and Nb: MoO 3 and Nb 2 O 5 Other family of nanoscale inclusions (RE) 2 Ba 4 CuMO y (where RE = Y, Sm, Gd, Nd, and M = Nb, Ta, W, Mo, Zr, Hf, Ag, Sb, Sn, Bi) were shown to improve drastically the properties of melt- textured 123