IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
Recent progress of REBCO HTS bulk
Xin YAO
DtfPhi&AtDept. of Physics & Astronomy, Shanggg,hai Jiao Tong Univ.
1 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
RE in La Nd Sm Eu Gd Dy Ho Y Er Yb
(RE)Ba2Cu3O7 Melting point 1068 1085 1060 1046 1040 1010 1005 1005 990 960 (± 5oC)
---- 95 93.5 93 92.5 92 92 92 92 92
Tc (K) PO2 PO2 PO2 PO2 air air air air air
Jc @77K; 1T ---- 40-50 40-50 50-60 20-30 xKA/cmx KA/cm2
Birr (T); 77 K ---- 8–10 6 - 8 6 - 7 5 - 6
Better suppgperconducting performance
2 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Potential of LREBCO (LRE=Nd,Sm..) bulks
• Advantages compared to YBCO: 1600
※ Exhibit better superconductivity 1500
High TTHigh 1400
cc erature (K) Nd pp T P = 1359K (3. 2 at. % Nd) Sm T P = 1333K (1.8 at.% Sm) High JJHigh cc at a high applied magnetic field Tem 1300 Y T P = 1278K ( 0.6 at.% Y) at. % Y at. % Sm ※ High growth rate at. % Nd 1200 0 2 4 6 8 due to high RE solubility in solvent at. % Nd, Y and Sm
• Problems to be solved :
9 ※ Formation of solid solution (LRE1+xBa2-xCu3Oy) due to
LRE/Ba substitution, leading to low Tc ※ Lack of suitable seed due to high peritectic temperature T p
3 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
1. Oxygen1. Oxygen--controlledcontrolled growth
4 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
NdNd BaBa CuCu OO 1+x1+x 22--xx 33 77--yy NdNd--BaBa--CuCu--OO syyystem
x p(O22), T= constantT= constant 2. CompositionComposition--controlledcontrolled growth
5 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. 95 K SmBCOSmBCOgrowngrown in 1 atmoxygen pressure by TSSG Supercond. Sci. Technol. 17 (2004) L47
SmB CO123CO1,2,3 crystals grown from d ifferent liquid with Ba/Cu =0.50,0.52,0.54 3. TemperatureTemperature--controlledcontrolled growth
6 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
RE in La Nd Sm Eu Gd Dy Ho Y Er Yb
(RE)Ba2Cu3O7 Melting point 1068 1085 1060 1046 1040 1010 1005 1005 990 960 (± 5oC)
---- 95 93.5 93 92.5 92 92 92 92 92
Tc (K) PO2 PO2 PO2 PO2 air air air air air
Jc @77K; 1T ---- 40-50 40-50 50-60 20-30 xKA/cmx KA/cm2
Birr (T); 77 K ---- 8–10 6 - 8 6 - 7 5 - 6
Cation stoichiometry of Sm123 is more controllable: Wide growth window in liquid composition and oxygen pressure
7 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
EffectsAddition of adding of BSm242 BaBa--richrich Sm secondary22BaBa44CuCu22OO9 phasephasephase on aironairair--processedprocessedprocessed SmBCOSmBCOSmBCO superconductor bulks Supercond. Sci. & Technol. 2009 Optimized addition of Ba -rich phase
pre-calcinated BaO (with Ba-rich addition Ba-Cu-O Sm210 2 Sm211) Sm242 ( our lab) compound
Ba mol% Addition amount 40 mol% 2-4 wt% 5 mol% 10 mol% 15 mol% 30 mol% =0.3302
Ba/Cu ratio in 0.755 0.8 0.72-0.75 0.71 0.75 0.79 0.89 precursor
Tc(K) 90 89 93 94 94 93 <88
△Tc(K) 21.5151 3>10
the appropriate ratio of Ba:Cu ranges from 0.72 to 0.8
8 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
Effects of adding BaBa--richrich Nd22BaBa44CuCu22OO9 phasephase on aironairair--processed NdBCO superconductor bulks
Supercond. Sci. & Technol. 2014
Tc and Jc were effectively enhanced with increasing the Ba/Cu ratio (BCR) . Optimal properties were achieved when BCR reaches 0.80.
9 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Trapping mode controlled continuous growth of SmBCO bulk Either self-nucleation or discontinuous BN Peng Cryst. Growth & Des. (2013) growth occurs in air-processed SmBCO Reduction of t.c.s value caused discontinuous growth t.c.s : tempera ture coe ffic ien t o f so lu bility
211 caused discontinuous growth
Δc ⎛ ∂c ⎞ ΔT ⎛ ∂c ⎞ J = = ⎜ ⎟ ⋅ = ⎜ ⎟ ⋅ R Δt ⎝ ∂ ⎠T ΔtT ⎝ ∂T ⎠T R=constant in a normal cooling process ⎛ ∂c ⎞ ⎜ ⎟ didereasing shlharply in SmBCO system ⎝ ∂T ⎠T i.e. noticeable reduction of t.c.s with decreasing temperature !!! 211 coarsening/ Reduction in effective Growth slows down Reduction in 211 segregation supersaturation and terminates J (solute flux)
10 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Δc ⎛ ∂c ⎞ ΔT ⎛ ∂c ⎞ J == ⎜ ⎟ =⋅ ⎜ ⎟ ⋅ R Accelerated cooling rate at a proper time Δt ⎝ ∂T ⎠T Δt ⎝ ∂T ⎠T ⎛ ∂c ⎞ ⎜ ⎟ dereasing sharply SmBCOin system ⎝ ∂T ⎠T BN Peng Cryst. Growth & Des. (2013)
211 Coarsening and Growth segggregation are continues partially suppressed
Optimized profile for continuous growth of SmBCO bulks
11 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Potential of LREBCO (LRE=(LRE=Nd,SmNd,Sm..) bulks..) bulks
• Advantages compared to YBCO: ※ Exhibit better superconductivity
High TTHigh cc
High JJHigh cc at a high applied magnetic field ※ Higher growth rate due to high RE solubility in solvent
• Problems to be solved :
※ Formation of solid solution (LRE1+xBa2-xCu3Oy) due to
LRE/Ba substitution, leading to low Tc 9※ LkfLack of suitabl e seed ditbl GtiblkdGenetic bulk seed ; REBCO film seed
12 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
Our review paper on Prog.Prog. in Mater. Sci. 68 (2015) 97--159159159 (IF= 27 . 42）
13 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Amazing superheating phenomenon
Low Peritectic Temperature (1010ºC) YBCO Thin-film Seeding at High Processing Temperature (~1057ºC) Growing NdBCO Thick-films
14 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
• 20x20 mm2 ihin the a-blb plane.
• ~ 010.1mm in the c-axis.
• Growth rate ~ 10μm/min.
•• YBCO thin film seed.
•• Growth temperature=1057 ºC
15 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. InIn--situsitu observation of the YBCO melting
1010ºC Room temperature 3min
J. Phys.: Condens. Matter (2003)
1050ºC 3min 1060ºC 3min
1) YBCO thin film can superheat about 50K;
2)orientation relationship:<001>(100)Y211∥<110>(001)MgO
16 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Universal superheating of thin films & Wide feasibility in seeding the growth of REBCO
1.Using YBCO film-seed, LPE growth was succeeddided in various REBCO ox ides 2.REBCO film-seeds were extended in various growth processes including TSMG 3.Various REBCO films universally possess high thermal stability in TSMG 4.YBCO films on various substrates
17 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Usinggg YBCO fffilmilm--seedseed, LPE gggrowth was succeeded in various REBCO oxides
RE123 systems Mixed RE123 systems NiNi--NdBCONdBCO (~1057ºC) 1057ºC)(1057ºC) NdBCONdBCO (~1057ºC)(~1057ºC) SrSr--NdBCONdBCO (~1057ºC)(~1057ºC) NdNd--YBCOYBCO (1000~ 1030ºC) SmBCOSmBCO YbYb--YBCOYBCO (970~980ºC) (1020~ 1055ºC) CaCa--YBCOYBCO (957~980ºC) ZnZn--YBCOYBCO (966~984ºC)
18 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. REREBCOBCO filmfilm--seedsseeds were extended in variiious growththth processes
•• TopTop--SeededSeeded Solution-Solution-GrowthGrowth (TSSGTSSG))
--SinSingle crystal.
•• TopTop--SeededSeeded Melt--GrowthGrowth (TSMG)
--sinsingle domain bulkc 211 + melt •• Liquid phase epitaxy growth (LPELPE)) --thick fil filhik mt m
19 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. VariousVarious REBCO films universally possess high thermal stability in Top--seeded MeltseededMeltMelt--growthgrowth a
c 211 + melt
HH Xu Supercond. Sci. Technol. (2012)
NdBCO bulk (16 mm in dia.) Tmax= 1117 ºC for15h1.5 h
Tolerable Tmax of films in MG 20 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. YBCO films on variousvarious substratessubstrates Only for Y123/ MgO? a universal superheating phenomenon 960°C 1080°C 1110°C
Y123/LAO
970°C 1040°C 1060°C J. phys. Chem. B (2012) Y123/STO Indicating a substantial superheating phenomenon 982°C 1020°C 1040°C
Y123/MgO
Peritectic melting: α (Y123)Îβ(Y211)+ Liq. on substrate
Thermal stability: Y123/LAO>Y123/STO>Y123/MgO Extremely high level of superheating of Y123/LAO, over 100K
21 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
Suppgerheating mechanism of YBCO thin film
YBCO oxide: Anisotropic surface energy in crysta lline plane
a-b plane: low surface energy, with high thermal stability
Thin film: quasi-two-dimensional structure, difficult to melt
22 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
Tmax(~1045 ººC) < Tp(SmBCO)
J. Phys. D: Appl. Phys. (2009)
(100) or (010) surface of SSmBCOmBCO ccrystalrystal after MG experiment
23 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Advantages of REBCO thin film (((or buffered f ffffilm))) as seed materials in MG • Capable to endure high Tmax, and good for: –– Seedinggggg highh--ppperformance & higggh Tpp REBCO bulks such as Nd BCO an d SmB CO –– Growing largelarge--sizesize REBCO, since the growth window could be widened by using a higher Tmax –– RecyclingRecycling failed REBCO bulks, since the remnant of solid REBCO can completely decompose by using a hig her Tmax • Easy to get sliced, with highly controlled orientation i.e., awella well-defined a-b plane and precisely known a-direction, which especially benefits the control of grain boundaries in the multimulti--seedseed process • CillilbltilCommercially available to gain large-sidfilized film-seeds with high quality - seeding full --growth of large --sizedsized REBCO bulk with large c-growth sector and high performance - processing in batch growth
24 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. 1. seed1. seed：：YBCO buffered NdBCO film 1. Jc (0 field)：68,000A/cm2 2. precursor:123+211+242+2411 Jc (H field)：38,000A/cm2 3. growth atmosphere: airair 222. TcTc：：94. 3K943K3K94 3K 4. mini-pellet：yes 3. trapped field：？ 5. Ag addition: no 4. fully-grown in a-b plan: 32 mm in dia.
Growth Properties conditions
Phys ica C(C (2014)
SBCOblk(SmBCO bulk (32mm idi)bin dia) by cold-seeding melt-growth
25 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Recycling failed YYBCOBCO superconductor bulk using HH Xu J. of NdBCO/YBCO/MgO filmfilm--seededseeded TSMG method Appl. Phy. (()2012)
T Tmax max 1105 ºC 1115 ºC
A simple & effective recycling process in this work! Recycling failed (GdBCO/Ag) bulk Recycling failed YBCO bulk Grinding failed bulk into powder & Capping a liquid-rich pellet on failed recycling Physica C 469 (2009) 1153 bu lk, Y123: Y211=10 :1 i n wei ght
2 reported work
Supercond. Sci. Technol. 23 (2010) 065012 Tmax=1040 ºC in cold-seeding (a) The recycled sample Tmax=1100 ºC (b) The reference sample in hot-seeding
26 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. MultiMulti--seededseeded melt growth of bulk YBCO using thinthin--filmfilm seeds TY Li J. of Appl. Ph y. (2010 )
Φ= 0° Φ= 90°
(100)/(100) grain boundary (110)/(110) grain boundary Ba-deficient residual melt
d1 d2
Contact angle of grains (Φ) 16.4 10.4 7.2 5.7 d (μm) Φ (°) 0376090 Table: Width of grain boundary for different grain contact angle.
•The amount of residual melt at grain boundaries decreases with the increment in the value of “Ф” . • Cleaner grain boundaries result directly in higher trapped fields.
27 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
multi-seed arrangement for MSMG seeds with different arrangement
symmetri cal (100)/(100) and (110)/(110) impinging region with residual melt
1)as-grown domain with different size 2)non-equilibrium shape
Growth rate: (110) > (100)/(010) Multi-seeds arranged asymmetrically with (110)/(110) orientation leading to: asymmetrica l (110)/(110) arrangement 1)Enlargement of the domain size Clean grain boundary! 2)Enhancement of superconducting property.
28 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. SeedSeed--sizesize effect on growth & supercondsupercond.. HC Li Cryst. Growth & Des. (2015) Performance of YBCO bulks Two merits** 1. commercial availability of the large size
2. superior thermal stability (Tmax up to 1120ºC)
YBCO bulks induced by NdBCO film-seeds with different sizes of 2*2, 4*4, 7*7 and 9*9 mm2, respectively the triangle region (representing c-GS) in side views becomes increasingly larger with increasing the seed size, verifying that the grown YBCO bulk with LSS possesses a larger volume fraction of c-GS
29 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
REBCO thin film, as a quasi-two- dimensional structure, with low surface energy , potentially possesses higgph superheatin gpyg capacity.
However, its therma l s ta bility extrinsically depends on the chemical process.
30 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. First reports on superheating Liq. Phase Epitaxy GrowthÎHigh Temp. of REBCO thinthin--filmsfilms Optical MicroscopyÎMelt Growth (001) Surface : low surface energy
J of Cry Growth 234 (2002)
for ~5 seconds:
J Phys: Condens Matter (2003
Supercon d Sc i & Tec hno l (2005
31 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Modified toptop--seededseeded meltmelt--growthgrowth for large sized
YBCO and Y11--xxCaCaxxBaBa22CuCu33OOyy cryyystals Cryy(st Growth & Des (2014)
CrystEngComm (2014)
Melt Starting Cooling Y211 trapped Growth materials rate K/H in grown crystal Y123+ Conventional 0.5-1 ~30 vol % 30 mol % Y211 Modified Y123 <0.2 ~3 vol %
Large single crystals of YBCO is a matter of significant importance in study on superconductivity by Neutron Scattering Experiments !!!
32 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Film thermal stability correlation with liquid property in ggyrowth of YBCO crystal Conventional Modified Modified Y123+30 mol % Y211
Y123Y123Y123
Tmax =1120ºC Tmax =1080ºC Tmax =1070ºC
Film thermal stability decreases in Modified MG
33 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Summary (I ) SmBCO HTS bulk
• 1. High superconducting properties Tc & Jc: Chemical composition control of (LRE)BCO; Introduction of Nano-particle • 2. Large size: High growth rate ; • 3. Reliable and repeatable process: Wide growth
widindow (Tg, composition and P(O 2)); • 4. Cost effective: air-pp;rocess; continuous growth; time- saving; batch process
34 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015. Summary (II )REBCO film-film-seedseed 1. Exploiting advantages of REBCO film-seed in MG
• Capable to endure high Tmax, • Easy to get sliced, • CillCommercially availabl e t o gai n l arge-sidized film-seeds with high quality ththfhe growth of REBCO b ulk supercond uct ors i s f urth er extended for practical applications and fundamental study.
2. NdBCO thin film, as a quasi-two-dimensional structure, with low surface energy, potentially possesses high superh ea ting capac ity. HitHowever, its therma l stabilit y extrinsically depends on the chemical process in TSMG.
35 IEEE/CSC & ESAS SUPERCONDUCTIVITY NEWS FORUM (global edition), April 2016. Invited presentation PC-1-INV given at ISS 2015 in Funabori, Tokyo, Japan, November 16 to 18th, 2015.
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