High Performance Magnesium Diboride (Mgb ) Superconductors
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High Performance Magnesium Diboride (MgB2) Superconductors: Towards the Prospect for Commercialization M.S.A. Hossain (ARC DECRA Fellow) The Australian National University– 16/04/2014 Research Programs at ISEM/AIIM Faculty . Applied Superconductivity Group • Bulk • Wire • Tape • Cable • Thin Film . Energy Storage Group . Spintronics and Electronic Materials Group . Thin Film Technology Group . Terahertz Science, Solid State Physics Group . Nanostructure Materials Group . Advanced Photovoltaic Materials Group ISEM Performance Profile highlight ISEM Team: 40 research staff (12 ARC fellows) and more than 80 PhD Seven research program centred on energy and electronics Electrification Program leader in Automotive CRC 2020 More than 50% citations in Li ion battery and superconductivity from ISEM in Australia ISEM is ranked at first place in magnesium diboride supercondcutors and eighth place in Li ion battery research in terms of outputs since 2001 105 PhD graduates widely spread across five continents since 1994 50 ARC fellowship awards to ISEM since 1995 80 ARC projects since 2000 12% publications, 15% ARC funding and 24% citations of UoW are from ISEM $80m for building & $20m for facilities for research infrastructure Member of CoE, ANFF and Flagship Bao Steel Joint Centre with other 3 Universities; Network with more than 50 institutions world-wide Strong links with more than 10 industry partners ERA assessment ranked at 5 for materials engineering, materials chemistry, physical chemistry and interdisciplinary engineering of UOW Superconductivity? Applications • Making a good superconducting product is a formidable interdisciplinary problem Wire cost Wire performance Engineering Cryogenics MgB2 Very simple crystal structure Very high current densities Polycristalline materials observed in films carry large currents Moderately high Tc Tc of 39K Factor of 10 larger than in bulks; room for large improvement in wires still available from R&D MgB2 presents very Good mechanical properties Potentially high critical field 60 1.2 promising features Sample No. 1 Sample No. 2 50 thin film 1.1 dirty limit [T] bulk dirty 1.0 2 c2 40 limit 1 0.9 wire SiC 30 doped 3 Low cost – low weight 0.8 5 20 0.7 MgB2 precursors: 8 6 (ZeroStrain) External 10 Upper critical field H c 0.6 150 €/Kg today /I 7 c clean limit I 0.5 4.2K(Liq.T He) 0 4T Tape Surface 4 0 5 10 15 20 25 30 35 40 Soldered to SUS304 Rig 0.4 MgB2 mass density: Temperature [K] -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 3 External Strain (%) 2.5 kg/dm Larger than 60 Tesla at low T Current situation • Superconductivity is a wonderful phenomenon, but its today’s applications are still confined to MRI-NMR, R&D, current leads and ‘big physics’ • 2G HTS material is expected to modify soon this scenario, but its complexity and limitation is currently delaying its positive effect on the industrial market of superconductivity • What can we expect more from MgB2? • MgB2 is technologically and economically viable conductor than LTs and HTS, HTS > MgB2 > LTS • Soaring He price is a serious threat to LTS i. e. NbTi (11 K), NBSn3 (18 K) • Cryogen-free operation can be easily achievable in the temperature range of 10-20 K. • More than 20 years of efforts did not reduce the production cost of HTS i.e YBCO (93K), BSSCO (110 K) even if it operates at liquid N2 • MgB2 is of particular interest because of its • low material cost, • simple crystalline structure, • ease of manufacture • larger coherence length • lower anisotropy Which make MgB2 competitive with HTS. The MgB2 superconductor, therefore, has significant potential for industrial applications. Superconducting wires presently available on the market NbTi Nb3Sn MgB2 Bscco YBCO Wire type Tc (K) 9 K 18 K 39 K 108 K 90 K Bc2 (T) 10 T 28 T <70 T >100 T >100 T Operation in LN2 NO NO NO < 1T <2T Ductile compound YES NO NO NO NO Flexible wires YES NO YES YES YES Superconducting splices YES YES YES NO NO Low cost YES ≈YES YES NO Not yet Possible applications ∗ Transportation ∗ Maglev trains ∗ Medical ∗ MRI imagers ∗ Energy ∗ Wind turbine ∗ Superconducting Magnets ∗ Josephson Devices ∗ Power transmission ∗ Fault-current limiters ∗ Electric motors ∗ Fusion 19 Fusion P.I.T. In/Ex-situ method Possible routes: Commercial MgB2 MgB2 High energy ball + Commercial precursors B Mg MgB2 milling Home made boron B O 2 3 B + Mg MgB2 Doped Doped Doped boron B + dopant + Mg B MgB2 HyperTech CTFF for MgB2 CONTINUOUS TUBE FORMING AND FILLING (CTFF) Internal Mg Diffusion IMD B powder + dopant Mg Rod Tube MgB2 wire fabrication Fabrication Advantages Disadvantages process Higher layer Jc Brittle IMD Better connectivity Hollow in middle solid structure Lower Jc PIT Less connectivity Multi layer sheaths Fast fabrication speed Lower Jc CTFF solid structure Less connectivity Suitable for longer length (1) Mg reacts with melting B2O3 to form MgO Sintering range (2) MgB2 formation (3) Curie temp. of bare Fe (4) Fe2B formation between bare Fe and MgB2 MgB2 conductors from various designs: Both High field and low field performance is crucial for various magnet application: Many research has been successfully done to improve high field properties by carbon doping but low field performance is still poor..(refs…) How to improve low field properties: Reduction of porosity ? by improving fabrication process..?? mechanical deformation..?? Enhancement of both low and high field Jc Enhancement of low field Jc is due to the reduction of porosity Enhancement of high field Jc is due to the defects by C-doping NPG Asia Materials (2011) SiC – US Patent (2009) Malic acid – (European Patent 2011) Chemical doping—the most effective means for enhancing Jc, Hc2 and Hirr in MgB2 1. SiC: SX Dou et al APL (2002), PRL (2007) 2. C: Soltanian et al Physica C (2003); YW Ma et al and Dresden group and Wisconsin Group, APL(2005-2008) 3. CNT: SX Dou et al APL (2003) 4. Carbohydrate: SH Zhou et al. Adv. Mater (2007), JH Kim, Hossain et al. APL (2006) 5. Hydrocarbon: NIMS group, APL (2005) 6. Graphene: X Xu et al SUST (2010), 7. Graphene oxide: KS de Silver et al Scripter Mater (2011) Nano doping in MgB2 – significant breakthrough Jc : Malic acid doped MgB2 wire Nano SiC doped MgB2 wire Dou et al PRL 98 (2007)97002; Kim et al APL 89 (2006) 142505; U.S. Patent, 7,838,645 (2010) European patent Dual Reaction Model Application “Dual Reaction Model: Parent compound formation and doping reaction takes place at the same time” --Explain, classify and predict dopants that follow the dual reaction mechanism S.X. Dou et al. Phys Rev. Lett. 98, 097002 (2007) Low field enhancement: 3D X-ray Tomogram Analysis: Voids are removed significantly after doping with malic acid using chemical solution route boron vacancies => stacking faults => lattice distortion within the MgB2 grains => increase the impurity scattering rate => enhances the upper critical field and high field critical current density. Undoped C-doped a-axis: 3.0832 3.0758 c-axis: 3.5221 3.5237 Binary MgB2 : Applying Pressures from 4 sides on square wires. 0 GPa 2 GPa Binary 18-filament MgB2 wire: CHPD applied A. B. 0 GPa 1.5 GPa Binary MgB2 : Higher mass density due to volume contraction Jc vs. B at 4.2, 20 and 25 K for 18-filament binary MgB2 wires densified at 1.5 Gpa on short and15cm long samples Hossain et al, SUST (2011) MgB2 wires, doped with 10 wt.% C4H6O5 5 2 NbTi: Jc = 1 x 10 A/cm at 8T/4.2K compression 5 C4H6O5 additive 10 600 °C/4hrs 12.9 T ) 13.4 T 2 104 ( A/cm c Square Wire (0 GPa) J // 3 J (2 GPa) Almost 10 c ⊥ // isotropic J (2 GPa) ⊥ c behavior 102 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 B (T) Hossain MSA, Supercond. Sci. Technol. 22 (2009) 095004 (8pp) OSU measurement: MgB2 wires, after 1.8 Gpa, Alloyed with 10 wt.% C4H6O5 At 20K, Jc = 10^4 A/cm2 at >7T!!! 106 René Flükiger-1.8 GPa- edge on 10 K 12.5 15.0 K 17.5 K 5 20.0 K 10 22.5 K 25.0 K , A/cm2 27.5 K c J 30.0 K 32.5 K 104 103 Critical Current, Current, Critical 102 0 2 4 6 8 10 12 14 Magnetic Field, B, T CHPD improves the homogeneity of Jc in the s/c layer 80 60 2 10 2 70 j = 0.06 A/cm j = 0.06 A/cm 50 j = 0.30 A/cm2 j = 0.30 A/cm2 60 2 8 non-densified 2 j = 0.60 A/cm 40 j = 0.60 A/cm 2 2 50 j = 1.20 A/cm densified j = 1.20 A/cm 6 40 30 cm] cm] cm] cm] cm] µΩ µΩ µΩ µΩ µΩ 30 V/cm] [ [ [ [ [ p = 0 GPa 20 p = 2 GPa µ 4 ρ ρ ρ ρ ρ 20 E [ T = 30 K 10 T = 30 K 10 2 T = 4.2 K 0 0 0 1 2 03 4 5 0 1 2 3 4 5 MgB2 - 650C/1h B [T] 2000 3000 4000 5000 MgB60002 - 650C/1h7000 8000 B [T] J [A/cm2] … as a consequence, also the n value of I-V curve is increased n-factor improves in both binary and alloyed MgB2 sample after CHPD: First test on densification of longer wire lengths (1 meter) by means of an automatic press/release/advance mechanism CHPD IMD (NIMS Group, 2009) and Modıfıed IMD (OSU Group, 2012) 2nd Generation MgB2 wires with world record Je… Issues???? Issues involved in IMD Very high densed MgB2 layer with high Jc But: 1.