progress in superpower’s 2g hts wire development and ...doe+peer... · price $ 40/m = $ 400/ka-m...
TRANSCRIPT
superior performance.powerful technology.
SuperPower, Inc. is a subsidiary of Royal Philips Electronics N.V.
Progress in SuperPower’s 2G HTS Wire Development and ManufacturingV. Selvamanickam and J. DackowSuperPower : Y. Chen, Y. Qiao, S. Sambandam, A. Rar, X. Xiong, D. Hazelton, R. Schmidt, and Y. Xie
University of Houston : G.Majkic, I.Kesign, A.Guevara, S.Tuo, Y.Yao, Y.Zhang, N.Khatri, X.Tao, A.Sundaram, S.Lee, and E.Galstyan
2010 DOE Advanced Cables & Conductors Peer Review, Alexandria, VA, June 29 – July 1, 2010
Supported by CRADAs with Oak Ridge, Los Alamos, Argonne, Brookhaven National Laboratories and NREL & collaboration with Florida State Univ.
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Success of the DOE 2G Wire Development program• Successful integration of industry, national lab technologies with university support• Industrial scale HTS production techniques developed• Multiple world records for 2G wire performance in long lengths• World’s only demonstration of 1,000+ m long 2G wire• World’s first 2G HTS wire device inserted in the power grid• U.S. is the only source of ‘pre-commercial’ 2G wire
– Several hundred kilometers shipped– Price reduced three-fold in last three years even before onset of a commercial
market!
2
From FY09 reviewers’ recommendations:“SuperPower should be asked to be clear about wire costs, how to reduce them, and what costs might be expected in the future with improved or larger-scale processing. They were open about this previously, but were less clear on this topic this year.”
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Wire price-performance is the key factor for commercialization• Today’s 2G wire: 100 A performance at 77 K, zero applied magnetic field,
Price $ 40/m = $ 400/kA-m
• At this price, cost of wire for typical device project (other than cable) > $ 1 M (more expensive than the typical cost of the device itself !)Cost of wire for a 500 km cable project = $ 20 M (~ cost of cable project itself !)
3
Metric Today Customer requirementPrice $ 400/kA-m < $ 100/kA-m* For commercial market entry
(small market)< $ 50/kA-m* For medium commercial market< $ 25/kA-m* For large commercial market
*at operating field and temperature
Four to 15-fold improvement in wire price-performance needed !Four to 15-fold improvement in wire price-performance needed !
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Objectives of SuperPower program focused on meeting wire price-performance metrics• Higher self-field critical current in 2G wire by increasing film thickness
– HTS is still only 1 to 3% of 2G wire compared with 40% in 1G wire and is the only process that needs to be changed in 2G wire for high Ic
• Significantly modify in-field critical current performance of 2G wire– Maximize potential of rare-earth, dopant, nanostructure modifications to tailor in-field
critical current in device operating conditions• Reduce wire cost by high efficiency, simpler processes
– Silver electrodeposition instead of sputtering– Substrate planarization instead of electropolishing + buffer– Improved MOCVD precursor conversion efficiency (only 15% now)
• Reduce wire cost by increased yield– Develop new and enhanced on-line QA/QC tools
• Added value to customer with advanced wire architectures– Multifilamentary wire for low ac loss
4
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Program relevance to DOE-OE mission
• Strongly tied to the DOE-OE mission through the development of 2G HTS wires that meet all the necessary requirements (piece length, performance, cost, and manufacturing capacity) of systems that are being constructed to modernize the electric power grid and enhance the reliability and security of the energy infrastructure.
• The program has a direct impact on OE sub program goals namely, development of prototype wire achieving 1,000,000 A-m and production of HTS coil operating in applied magnetic fields up to 5 T at 65 K.
5
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010 6
SuperPower’s 2G wire is based on high throughput processes & superior substrate
YBCO
LaMnO3
MgO (IBAD + Epi layer)
Al2O3
100 nm
Y2O3
Hastelloy C-276
YBCO
LaMnO3
MgO (IBAD + Epi layer)
Al2O3
100 nm100 nm100 nm
Y2O3
Hastelloy C-276
2 μm Ag
20μm Cu
20μm Cu50μm Hastelloy substrate
1 μm YBCO - HTS (epitaxial)~ 30 nm LMO (epitaxial)
~ 30 nm Homo-epi MgO (epitaxial)~ 10 nm IBAD MgO
< 0.1 mm
• High throughput is critical for low-cost 2G wire and to minimize capital investment• SuperPower’s 2G wire is based on high throughput IBAD MgO and MOCVD
processes• Use of IBAD as buffer template provides the choice of any substrate• Advantages of IBAD are high strength, low ac loss (non-magnetic, high resistive
substrates) and high engineering current density (ultra-thin substrates)
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
• In FY09 SuperPower’s technology operations consolidated in Houston, enabling total focus on manufacturing in Schenectady.
SuperPower 2G wire program strategy
National LabsNational Labs
CustomersCustomers
CRADAs
SP staff @ Houston
UH subcontract in DOE-SP
program
SuperPowerManufacturing at Schenectady, NY
Manufacturing Operations in NY
Technology in Houston
Manufacturing objectives• High yield, high volume
operation• On-time delivery of high-
quality wire• Incorporate new technology
advancementsTechnology objectives• High performance wires • Highly efficient, lower cost
processes• Advanced wire architectures• Successful transition to
manufacturing
Best of both worlds: strong and concentrated emphasis on technology development & manufacturingBest of both worlds: strong and concentrated emphasis on technology development & manufacturing
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Full-fledged R&D operation in Houston• R&D equipment for entire 2G wire processing operation moved to Houston & set up. Five
SuperPower scientists managing operations at Houston full-time• Ten graduate students and two research faculty supporting R&D activities• Technology advances transitioned to manufacturing, has led to new product offering• $ 3.5 M Emerging Technology Fund award from state of Texas provides new pilot-scale
equipment for SuperPower-Houston & additional resources
8
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Improved pinning by Zr doping of MOCVD HTS wires
• Two-fold improvement in in-field performance achieved!• Process for improved in-field performance successfully transferred to manufacturing
• Systematic study of improved pinning by Zr addition in MOCVD films at UH• Process know-how transitioned to SuperPower
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‐30 0 30 60 90 120 150 180 210 240 270 300 330 360J c(M
A/cm
2 )
Crtiical cu
rren
t (A/12 mm)
Angle between field & tape normal (°)
0% 2.5% 5%7.50% 10% 12.50%
1.0 T, 77 K
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40
0 30 60 90 120 150 180 210 240
Critical current (A
/4 m
m)
Angle between field and c‐axis (°)
Standard Production wire
Enhanced Zr‐doped production wire
c‐axis
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Enhanced in-field performance of Zr-doped wires transitioned to long lengths
10
• Even with 16% lower self-field Ic, Zr-doped wire exhibits 80% higher Ic at B || c, and 71% higher Ic at min Ic angle compared with standard wire
• Very uniformity of in-field Ic over 130 m of Zr-doped wire (~ 3%)
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Benefit of Zr-doped wires realized in coil performance
Coil properties With Zr-doped wire With undoped wire
Coil ID 21 mm (clear) 12.7 mm (clear)
Winding ID 28.6 mm 19. 1 mm
# turns 2688 3696
2G wire used ~ 480 m ~ 600 m
Wire Ic 90 to 101 A 120 to 180 A
Field generated at 65 K 2.5 T 2.49 T
Same level of high-field coil performance can be achieved with Zr-doped wire with less zero-field 77 K Ic, less wire and larger bore
Same level of high-field coil performance can be achieved with Zr-doped wire with less zero-field 77 K Ic, less wire and larger bore
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
2010 effort on Zr-doped MOCVD wires
• In 2009, we fixed the HTS film composition at Y0.6Gd0.6-Ba-Cu-O (based work on undoped compositions) and found optimum Zr doping to be 7.5%
• Also, growth rate had to be reduced four-fold to 0.13 µm/min to achieve self-assembly of BZO and accompanying improved in-field performance
In 2010 we sought to determine
• If there is a rare-earth combination and content that works better with Zr-doped MOCVD wires (most BZO literature is on pure Y or pure Gd)
• How to regain the growth rate (affects wire throughput)
Fixing Zr dopant level at 7.5%, we investigated• influence of HTS film thickness• influence of Y : Gd ratio with a fixed (Y+Gd) value• influence of Y+Gd value at a fixed Y:Gd ratio• comparison of Gd-Y, Sm-Y, and Gd-Sm at a fixed rare earth 1 + rare earth 2 content• modified Ba-Cu composition and effect on growth rate
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Improvement with Zr in thicker films
Improvement in in-field critical current of Zr-doped wires increases with film thicknessImprovement in in-field critical current of Zr-doped wires increases with film thickness
All samples were of composition Y0.6Gd0.6BCO
20
70
120
170
60 90 120 150 180 210 240 270 300
Critical current (A
/12 mm)
Angle between field and c‐axis (°)
0% Zr, 1 pass 7.5% Zr, 1 pass
1.0 T, 77 K
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40
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180
60 90 120 150 180 210 240 270 300
Critical current (A
/12 mm)
Angle between field and c‐axis (°)
0% Zr, 2 passes 7.5% Zr, 2 passes
1.0 T, 77 K
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40
60
80
100
120
140
160
180
60 90 120 150 180 210 240 270 300
Critical current (A
/12 mm)
Angle between field and c‐axis (°)
0% Zr, 3 passes 7.5% Zr, 3 passes
1.0 T, 77 K
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Improvement in in-field critical current of Zr-doped wires increases with thickness
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Improved Ic retention at low fields, B || c (< 0.5 T) with decreasing Y:Gd ratioImproved Ic retention at low fields, B || c (< 0.5 T) with decreasing Y:Gd ratio
• All samples made in one run with 7.5% Zr.• Y+Gd maintained at 1.2 but ratio of Y:Gd
changed from 1.2:0 to 0:1.2 in steps of 0.2
00.20.40.60.811.2
012345
050
100150200250300350
0 0.2 0.4 0.6 0.8 1 1.2
Gd content
J c(M
A/cm
2 )
Critical current (A
/12 mm)
Y content
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1.0
1.2
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0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6J c(M
A/cm
2 )
Critical current (A
/12 mm)
Magnetic Field (T)
Y1.2Gd0.0Y0.8Gd0.4Y0.6Gd0.6Y0.2Gd1.0Y0.0Gd1.2
B || c, 77 K
0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
I c/ I c(B = 0)
Magnetic Field (T)
Y1.2Gd0.0Y0.6Gd0.6Y0.2Gd1.0Y0.0Gd1.2
B || c, 77 K
Influence of Y:Gd ratio
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Influence of Y:Gd ratio
• Increasing Ic in the vicinity of B || a-b with decreasing Y:Gd ratio while Ic in the vicinity of B || c is constant at 25 to 30% retention
• Higher minimum Ic with decreasing Y:Gd ratio
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90
100
60 90 120 150 180 210 240 270 300
Critical cu
rren
t (A/12 mm)
Angle between field and c‐axis (°)
Y1.2Gd0.0 Y1.0Gd0.2 Y0.8Gd0.4
Y0.6Gd0.6 Y0.4Gd0.8 Y0.2Gd1.0
Y0.0Gd1.2
1.0 T, 77 K
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60 90 120 150 180 210 240 270 300
I c/ I c(B = 0)
Angle between field and c‐axis (°)
Y1.2Gd0.0 Y1.0Gd0.2 Y0.8Gd0.4Y0.6Gd0.6 Y0.4Gd0.8 Y0.2Gd1.0Y0.0Gd1.2
1.0 T, 77 K
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
20 nm 20 nm
5 nm
BZO epitaxial particleBZO epitaxial particle
BZO (111) particlesBZO (111) particlesBZOrodBZOrod
BZO epitaxial particleBZO epitaxial particle
Y1.2Gd0 Y0Gd1.2
Additional defect structure in Gd1.2BCO wires for better B || wire pinning
BZO (111) particles along a-b plane in Gd1.2BCOTEM by C. Cantoni & A. Goyal, ORNL
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
4 105
6 105
8 105
1 106
1.2 106
1.4 106
-50 0 50 100
Gd1.2Y1.2Y0.6Gd0.6
Angle [deg]
65K, 5T
Influence of Y:Gd changes at lower temperatures
• Best in-field performance switches from Gd1.2 to Y1.2 composition with decreasing temperature
• Higher Tc of Gd1.2 composition could be a reason
88.5
89
89.5
90
90.5
91
91.5
92
92.5
0 0.2 0.4 0.6 0.8 1 1.2 1.4
y = 88.893 + 2.9645x R= 0.97963
Y1.2-x
Gdx
More details in ORNL-SuperPower CRADA Presentation, Wed, 1:00 p.m.
Measurements by , ORNL
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Influence of Y+Gd content• 7.5% Zr in all samples• Y content = Gd content• Y+Gd content varied
Critical current can be tuned in desired orientation of magnetic field in application by modifying total rare earth content even with a fixed Zr % !Critical current can be tuned in desired orientation of magnetic field in application by modifying total rare earth content even with a fixed Zr % !
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110
60 90 120 150 180 210 240 270 300
Critical cu
rren
t (A/12 mm)
Angle between magnetic field and c‐axis ( )
Y0.65Gd0.65 Y0.7Gd0.7 Y0.75Gd0.75 Y0.8Gd0.8
1.0 T, 77 K70
90
110
130
250
270
290
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330
350
1.2 1.3 1.4 1.5 1.6 Icat 1 T, || to tape (A/12 mm)
zero‐field I c(A/12 mm)
Y + Gd content
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Thicker (Gd,Y)2O3 precipitates along a-b plane in high (Gd,Y) wires
More details in ANL-SuperPower CRADA Presentation, Thu, 8:00 a.m.
TEM by Dean Miller, ANL
0.1
0.2
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0.4
70 75 80 85 90 95 100 105
I c/ I c(B=0)
Angle beteweend field and c‐axis (°)
(Y,Gd)1.2 (Y,Gd)1.3 (Y,Gd)1.4 (Y,Gd)1.5
1.0 T, 77 K
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
In-field performance of Zr-doped films is drastically modified by rare earth contentZr content maintained at 7.5% in all three samples
c‐axis
Fewer defects along a‐b plane in Y1.2 ; defects prominent along a‐b plane in (Y,Gd)1.5Fewer defects along a‐b plane in Y1.2 ; defects prominent along a‐b plane in (Y,Gd)1.5
Y1.2Y1.2
20 nm
(Y,Gd)1.5(Y,Gd)1.5
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40
60
80
100
120
140
60 90 120 150 180 210 240 270 300
Critical current (A
/12 mm)
Angle between field and c‐axis (°)
Y0.6Gd0.6 (Y,Gd)1.5 Y1.2
1.0 T, 77 K
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
With optimized (Y,Gd)-Ba-Cu-O, higher growth rates can be regained
• In 2009, (Y,Gd)-Ba-Cu-O composition optimized for undoped films was used
• With this composition, growth rate had to be reduced from 0.5 μm/min to 0.13 μm/min to achieve improved in-field performance with Zr doping
• In 2010, the Ba-Cu composition was optimized specifically for Zr-doped films
With new (Y,Gd)-Ba-Cu-O composition, growth rate tripled to 0.4 µm/min in 0.5 µm films major impact on throughputWith new (Y,Gd)-Ba-Cu-O composition, growth rate tripled to 0.4 µm/min in 0.5 µm films major impact on throughput
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1.16
1.36
1.56
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70 100 130 160 190 220 250 280
J c (M
A/cm
2 )
Critical cu
rren
t (A/12 mm)
Angle between field and c‐axis (°)
0.13 μm/min 0.4 μm/min
7.5% Zr1.0 T, 77 K
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Recipe for higher growth rate Zr-doped MOCVD transferred to manufacturing
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Critical current (A
/12 mm)
Angle between field and c‐axis ( )
0.5X growth rate : FY'09 recipe
1X growth rate : FY'10 recipe7.5% Zr1.0 T, 77 K
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Routine manufacturing of Zr-doped wires in long lengths
Long wires with Zr-doping with critical current of 250 to 300 A/cm are now a standard in our manufacturing operationLong wires with Zr-doping with critical current of 250 to 300 A/cm are now a standard in our manufacturing operation
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0 100 200 300 400 500 600 700
Crit
ical
cur
rent
(A/c
m)
Tape Length (m)
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Superior performance of 2010 Zr-doped MOCVD production wires
Production wires with new composition exhibit significantly improved performance over range of temperatures and magnetic fieldsProduction wires with new composition exhibit significantly improved performance over range of temperatures and magnetic fields
Measurements by B. Maiorov & L. Civale, LANL
More details in LANL-SuperPower CRADA Presentation, Wed, 3:30 p.m.
0.01 0.1 110
100
1000
I c [A/c
m]
μ0H [T]
best undoped FY'09 Zr-doped FY'10 Zr-doped
5K
40K
75K
H//c
2010 Zr-doped production wiresshow:
• large Ic increase at low temperatures at all fields up to 7 T
• Ic increase at high temperatures at high fields.
• absence of α at low T• very low α~0.27 at 75K
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Superior performance of 2010 Zr-doped MOCVD production wires
Zr-doped production wires with new composition exhibit significantly improved critical current at 4.2 K in high magnetic fields up to 30 T !Zr-doped production wires with new composition exhibit significantly improved critical current at 4.2 K in high magnetic fields up to 30 T !
Measurements by V. Braccini, J. Jaroszynski, A. Xu,& D. Larbalestier, NHMFL, FSU
T, K
0 20 40 60 80
Jc, M
A/cm
2
0
10
20
30
40
50
60
Production wire1.1 µm thick HTS filmIc (77 K, 0 T) = 310 A/cm
1 10
100
1000
T=4.2K
I c - 4m
m w
idth
(A)
B (T)
undoped, B perp. wire undoped, B || wire FY'09 Zr-doped, B perp. wire FY'09 Zr-doped, B || wire FY'10 Zr-doped, B perp. wire FY'10 Zr-doped, B || wire
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Develop high efficiency processes (higher throughput, lower cost)
• Goal: Substrate planarization to eliminate electropolishing & double buffer throughput
– Demonstrated planarized yttria and planarized alumina on unpolished substrates.
– Will be covered in CRADA presentations with LANL & ORNL• Goal: Improved MOCVD precursor conversion efficiency • Goal: Electrodeposition of silver on HTS film instead of sputtering
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Electrodeposition of silver• 2009: With NREL, demonstrated 3X reduction in silver thickness using benign Cu
electroplating solution chemistry.– Thicker silver is standard in 2G wire now mainly to protect HTS film from acidic electroplating
solutions used to apply Cu stabilizer– New chemistry is benign enough to apply even directly on YBCO
• 2010: Electrodeposition of silver in collaboration with NREL– Ag in 2G wire is a limiting factor in production
capacity and wire cost– Electrodeposition is a lower-cost alternative to
vacuum sputtering now used– Can be done in tandem with copper plating
further increases production capacity– Enabler for a low ac loss wire
100 μm
Cu Ag HTS
substrate
Cu
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Electrodeposition of silver• Silver nitrate in organic solvent• Process done in a reel-to-reel operation• Contact resistivity ~ 4 µΩcm2• Over current capability with ~ 2 µm electrodeposited
Ag = 20% more than Ic: comparable with sputtered Ag
More details in NREL-SuperPower CRADA Presentation, Thu, 9:00 a.m.
0
100
200
300
400
0 50 100 150 200 250
Volta
ge (µ
v)
Critical Current [A]
Burn out at 207 A, 360 µV
Ic = 171 A
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Scaled up electrodeposition of silver• Process scaled up to 100 m lengths
at 60 m/h* even in a small research-scale system
* 4mm wide equivalent
Critical current of HTS wire maintained over 100 m length after electrodeposition of silver & after oxygenation
Critical current of HTS wire maintained over 100 m length after electrodeposition of silver & after oxygenation
0 20 40 60 80 1000
100
200
300
After Ag Electrodeposition
Crit
ical
cur
rent
(A
/12
mm
)
Tape Position (m)
0 20 40 60 80 1000
100
200
300
400
Electrodeposition + oxygenation
Crit
ical
cur
rent
(A
/12
mm
)
Tape Position (m)
0 20 40 60 80 1000
100
200
300
As HTS deposited
Crit
ical
cur
rent
(A
/12
mm
)
Tape Position (m)
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Transport Ic measurement on 100 m long wire with electrodeposited silver
• Transport Ic of 200 to 250 A/cm measured over 100 m through electrodeposited silver– Silver-HTS interface is good for current transfer– Silver surface is good enough for press electrical contacts
• ED Ag is able to sustain 10 to 20% more current beyond take-off current
Silver electrodeposition is a scalable process for lower wire cost and is an enabler formultifilamentary 2G wire Silver electrodeposition is a scalable process for lower wire cost and is an enabler formultifilamentary 2G wire
0
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0 20 40 60 80 100
Critical cu
rren
t (A/12 mm)
Tape position (m)
‐20
0
20
40
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100
120
0 50 100 150 200 250 300
Volta
ge (µ
V)
Current (A)
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
2010 2G Wire Manufacturing Objectives
• 2009: Demonstration of kilometer-long 2G wires with minimum critical current of 282 A/cm
• 2009: Multiple world records (best: 300,000 A-m); still holding
• 2010: Focused on high-yield manufacturing
– Enhanced on-line QC tools– Routine manufacturing of
Zr-doped ‘Advanced Pinning’ wire: new product offering
– Reduce cost; improved price-performance metrics
32
040,00080,000
120,000160,000200,000240,000280,000320,000
Nov
-01
Jul-
02
Mar
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Nov
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Aug
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Apr
-05
Dec
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Aug
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Apr
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Jan-
08
Sep
-08
May
-09
Cri
tica
l Cur
rent
* Le
ngth
(A
-m)
62 m18 m1 m 97 m
206 m
90 A-m to 300,330 A-m
in seven years
158 m
322 m 427 m595 m
World Records790 m
1,065 m
935 m
1,030 m
0
100
200
300
400
500
0 100 200 300 400 500 600 700 800 9001000
Crit
ical
Cur
rent
(A/
cm)
Position (m)
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
On-line Vision system in pilot MOCVD
• Black and white images are taken every ~15 mm of the wire as it emerges from the MOCVD deposition chamber
• Vision inspection algorithms examine each image for certain qualities or changes • Each quality is assigned a value by its algorithm. A “map” of the wire is generated by
plotting the image’s quality value as a function of wire position• The ‘quality map’ is compared with Ic over wire length
850 900 950 1,000 1,050 1,100 1,150 1,200 1,250 1,300100
80
60
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20
0
0
100
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300
400
500
Def
ect C
ode
Valu
e (%
)
Absolute Position (m)
COVG Ic1T
Ic-1
T (A
mps
)
Training on Start of MOCVD TapePartial Training Used
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Drawbacks of Vision system with relative training
• The normal range was initially established by “training” the vision software on images of each wire at the beginning of their processing through MOCVD. Thus, the normal range was relative to that wire only.
• This approach had several drawbacks– The importance of process drift over time was ignored– As each wire sets its own normal range, only limited comparisons
between wire were possible– The values for the partial training images were noticeably different
from the values for the adjacent images, creating noise in the plot
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Vision system with reference training: a good predictor of critical current of long wires
• Training has been replaced by the use of a set of reference images from a previously inspected MOCVD tape with known good Ic
• Comparisons of ‘quality map’ with relative training against ‘quality map’ with reference training show a marked difference
– Reference training is found to be an even better predictor of Ic variation and tape quality
– Process drift is more easily discerned
850 900 950 1,000 1,050 1,100 1,150 1,200 1,250 1,300100
80
60
40
20
0
0
100
200
300
400
500
Training from Reference ImagesNo Partial Training
Def
ect C
ode
Valu
e (%
)
Absolute Position (m)
COVG Ic1T
Ic-1
T (A
mps
)
Real-time prediction of Ic during MOCVD process enabled by improved on-line vision systemReal-time prediction of Ic during MOCVD process enabled by improved on-line vision system
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
On-line Ellipsometry system in buffer deposition• Thickness of alumina barrier layer is critical to avoid diffusion of substrate species• Previously QC of alumina thickness was done off line at completion of run,
samples taken from both ends of 1,400 m long tape• New, in situ ellipsometry system installed in pilot buffer for real-time thickness of
alumina & other buffers
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
0
10
20
30
40
50
60
% o
f Pro
duct
ion
wire
s
Critical current (A/cm)
20092010
Significant improvement in quality of production wires in 2010
% wires > 2009 2010
250 A/cm 25% 60%
300 A/cm 8% 22%
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Significant improvements in volume of production wires in 2010
• Routine single-piece production length is 1,400 meters through every single step
• In 2010, we produced– Average of 4 wires/month exceeding 200,000 A-m sellable product– Average of 1 wire/month exceeding 300,000 A-m sellable product
(A-m calculated based on sum of individual piece lengths obtained from each long wire times critical current)
2009 2010 YTD Increase in CY’10
Monthly averageMeters (4 mm) 8,625 12,821 48%
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Advancing HTS adoption by enhancing value to the customer
• True measure of value to end customer best represented by: $/kA-m @ field and temperature of application
• Key drivers to improve this measure:– Reduction of Cost/Price ($/m)– Increase of global Ic at self field and 77K– Increase of Ic at application field and temperature utilizing advanced
pinning techniques
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
2009 to 2010 value enhancement• Price reduction
– ~10% Average Selling Price reduction year over year • Pricing is more market-driven than cost-driven• Major drivers of reduction of costs:
– Improved yield through MOCVD process– Improved productivity
– Buffer machine speeds– Post MOCVD processing speeds– Km/direct labor ratio
• Global Ic (self field @ 77K )– 15 - 25% average improvement (80A to ~100A)
• Integration of R&D efforts regarding MOCVD• Enhanced quality assurance – in situ measurements
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
2009 to 2010 value enhancement (cont’d.)
• Incorporation of Advanced Pinning (AP: Zr-doped MOCVD)Up to 100% increase of Ic at application field and temperature
• Transition from R& D to Manufacturing• 2 typical representative examples shown below
Operating Condition (Field ⊥ wire)
Ic-non AP*(A/4mm)
Ic-with AP*(A/4mm)
Improvement
60 K, 2 T 53.7 72.5 35%
30 K, 2T 124 254 105%
*Base-line Ic of 100 A/4mm at 77K,self field
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
2009 to 2010 value enhancement summary
Application Temperature (K) Field (T)
2009 $/kA-m
(@ temp and field)
2010 $/kA-m
(@ temp and field)
Improvement
Cable 77 0.01 513 368 36%*
Coils 60 2 838 494 70%
Rotating machinery etc. 30 2 302 105 188%
* Improvement derived from cost and self-field Ic gains only
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Rapidly decreasing price of 2G HTS wire through technology advancements
10 m demo
100 m demo
First year of pilot production
2 to 4x higher throughput
Creation of separateManufacturing andR&D facilities
500 m demo 1,000 m
demo
10
100
1,000
10,000
100,000
2004 2005 2006 2007 2008 2009 2010
Price ($/kA‐m
)
Year
77 K, self field
30 K, 2 T
AP wire (Zr‐doped) product introduction
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Goals for wire performance improvements
• Two-fold improvement in in-field performance achieved with Zr-doped wires• Further improvement in Ic at B || c: Goal is 50% retention of 77 K, zero field value at 77 K, 1 T• Improvement in minimum Ic controlling factor for most coil performance: Goal is first 30%
retention of 77 K, zero field value at 77 K, 1 T and then 50%• Together with a zero-field Ic of 400 A/4 mm at 77 K, self field 200 A at
77 K, 1 T in all field orientations.• Achieve improved performance levels at lower temperatures too (< 65 K)
10
100
0 30 60 90 120 150 180 210 240
Critical cu
rren
t (A/4 mm)
Angle between field and c‐axis (°)
Standard MOCVD‐based HTS tape
MOCVD HTS w/ self‐assembled nanostructures
Goal
c‐axis
200
10x 77 K, 1 T
0
200
400
600
800
1000
0 1 2 3
Crit
ical
cur
rent
(A/c
m-
wid
th)
Thickness (µm)
Goal
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Control of a-axis growth for higher self-field Ic in thick films
Current-blocking a-axis grains nucleate at CuO that forms at the initial stage of HTS film nucleation in MOCVD
45
1µm
SP M3-714
“a-axis” “misoriented”
More details in ANL-SuperPower CRADA Presentation, Thu, 8:00 a.m.
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
R
LaMnO3 grainsYBCO nuclei
CVD vapor10 20 30 40 50
103
104
105
106
20 mm
10 mm6 mm4 mm2 mm
LMO (004)LMO (002)
(005)(002)
2θ(deg)
(001)
0 mm
X‐18A beamline
New CRADA with BNL to study nucleation events in MOCVD
Data by S. Solovyov, BNL
Control of nucleation in MOCVD could lead to less a-axis growth in thick films (higher self-field Ic) and (improved in-field Ic) Control of nucleation in MOCVD could lead to less a-axis growth in thick films (higher self-field Ic) and (improved in-field Ic)
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Early detection of a-axis growth during MOCVD is valuable for high current wires
Critical current predicted based on (006) XRD peak intensity
Good correlation between measured Ic and (006) XRD peak intensityGood correlation between measured Ic and (006) XRD peak intensity
y = 1.0007x - 0.0235R² = 0.8411
0
100
200
300
400
0 100 200 300 400Pr
edic
ted
criti
cal c
urre
nt (A
)
Measured critical current (A)
Ic=4.95*counts (006)-125
0
50
100
150
200
250
300
0 0.5 1 1.5
YBCO (200)/(006) ratio
Crit
ical
Cur
rent
(A/c
m)
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
On-line XRD in new pilot-MOCVD system for real-time quality control
48
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Real-time XRD data during long-length MOCVD HTS wire manufacturing
(006)
(200)
Good correlation between real-time XRD data & critical current of long 2G HTS wiresGood correlation between real-time XRD data & critical current of long 2G HTS wires
0102030405060708090
100
100 2100 4100
Ic o
r R
eBC
O (0
06)p
eak/
100
position (for XRD estimated)
Non contact Ic
XRD peak/100
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010 50
A wide range of Technology Transfer, Collaborations, and Partnerships with numerous institutions
• Customers & partners – 2G wire engineering to meet applications requirements• National laboratories – Applied research for 2G wire performance improvements• Universities – Basic research to understand 2G wire properties• Texas Center for Superconductivity University of Houston
– Comprehensive research agreement on 2G wire development– License Agreement executed in 2010– Supports SuperPower technology development operations in Houston
• ORNL – CRADA in eighth year.– Optimization of Zr doping in MOCVD through microstructural & in-field Jc studies– Transfer of know-how from research MOCVD system at ORNL previously
loaned from SuperPower including new UV-assisted MOCVD !– Substrate planarization using alumina to replace electropolishing– More details in ORNL-SP CRADA presentation tomorrow
• LANL – CRADA in tenth year– System for reel-to-reel Ic measurements of long wires in a magnetic field– Planarization process & equipment know-how to replace electropolishing– More details in LANL-SP CRADA presentation tomorrow
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010 51
Technology Transfer, Collaborations, and Partnerships ranging from Universities to device manufacturers
• ANL – CRADA in sixth year– Understanding current limiting factors through coordinated characterization – Optimization of Zr incorporation in MOCVD wires– More details in ANL CRADA presentation on Thursday
• NREL: CRADA in third year– Silver electrodeposition for lower-cost wire– More details in NREL-SP CRADA presentation on Thursday
• BNL: Understanding of nucleation in MOCVD to improve Ic (S. Solovyov)• FSU: TEM, Flux pinning studies on MOCVD wires, High-field coil development
(D. Larbalestier, V. Braccini, J. Jaroszynski, A. Xu, D. Markewicz, H. Weijers )• NIST: Effect of strain on pinning, new cable approach (D. van der Laan)• NRL: Axial strain, transverse pull tests (R. Holtz)
• Baldor Electric: 2G wire testing and engineering for Naval Generator (Rich Schieferl)
• DOE SPI program: 2G conductor design & engineering for FCL DOE-SPI project (Juan Carlos Llambes, Drew Hazelton)
• Numerous customers: 2G conductor engineering for several applications FCL, magnets, cables, ROEBEL cables, current leads, high-field coils
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
FY10 Goals and PerformanceObjective: Improved pinning for enhanced high-field performance• Goal: Enhance critical current and recover high growth rates in Zr-doped wires
– FY09: 28% self-field retention in Ic at 77 K, 1 T, B ⊥ wire in R&D wires FY10: Achieved 39% retention in R&D wire
– FY10: 25 – 30% routine in production wires– Investigated role of rare-earth in Zr-doped
wires in detail• Continuously improving Ic at 77 K, 1 T with
increasing Gd content• Superior performance at 65 K in Y rich films• With increasing Y+Gd content, Ic continuously
increases when B || wire and continuouslydecreases when B ⊥ wire
– Enhancement with Zr-doped composition even better in thicker films in all orientations
• 130% vs. 91% at B ⊥ wire, 74% vs. 22% at minimum Ic orientation.
– Growth rate of Zr-doped MOCVD process tripled to 0.4 µm/min with optimized Ba-Cu composition
52
39% retention at 1 T !
39% retention at 1 T !
0%
20%
40%
60%
80%
100%
0
50
100
150
200
250
300
0.0 0.4 0.8 1.2 1.6
Zero‐field I cretention
Critical cu
rren
t (A/12 mm)
Magnetic Field (T)
B ⊥wire, 77 K
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
FY10 Goals and Performance
Objective 250 A/cm in routine production, Zr-doped wires as new productoffering, improve price performance & bring new MOCVD system into operation
– Substantial increase in Ic of production wires
– Monthly production average increased by~ 50% to ~ 13,000 meters
– Zr-doped MOCVD process fully transitionedto production: now a standard product offering (AP: ‘Advanced Pinning’ wire)
• 55 to 65% improvement in Ic over FY09 Zr-doped production wire at high fields
– Wire price-performance improved by 35% for cables and by ~ 200% to ~ $ 100/kA-mfor 30 K, 2 T applications
– New MOCVD system with 9-track helix (50% more output than current system) installed & operational
53
% wires > 2009 2010
250 A/cm 25% 60%
300 A/cm 8% 22%
Jc @ 4.2 K in field (A/4 mm)
FY’09 FY’10*
10 T, B ⊥ wire 201 310
20 T, B ⊥ wire 118 183
5 T, B || wire 1,219 1,893
10 T, B || wire 1,073 1,769
Production AP wires
* Jc = 50 MA/cm2 at 4.2 K, 0 T
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
FY10 Goals and PerformanceObjective: Develop high efficiency processes (higher throughput, lower cost)• Goal: Develop electrodeposition of silver and demonstrate long lengths
– Working with NREL, successfully developed electrodeposition process as an alternative to sputtering of silver overlayer
– Overcurrent capability comparable to sputtered silver (20% over Ic for 2 µm Ag)
– Scaled up process to 100 m lengths with good Ic, current transfer & stability
• Goal: Substrate planarization to eliminate electropolishing & double buffer throughput (also to use variety of substrates)
– Worked with LANL on planarization with yttriaand with ORNL on planarization using alumina
– 20 m lengths of planarized substrate with yttria and alumina demonstrated
• Goal: Develop improved MOCVD reactor for better precursor to HTS film conversion efficiency
– Based on modeling of present MOCVD reactor
– Developed enhanced reactor design
54
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
FY10 Goals and Performance
Objective: QC tools to qualify new wire requirements• Goal: Install on-line XRD in new Pilot MOCVD system
– On-line XRD installed and (006) peak intensity of long wires monitored in real-time and correlated with Ic over length
• Goal: Improve on-line vision system in pilot MOCVD, install on-line ellipsometerin pilot buffer system
– On-line vision system in pilot MOCVD ‘trained’ to more accurately predict Icnon uniformity of long tapes. Routinely used as QC tool for production
– On-line ellipsometer installed in proto buffer system for real-time thickness monitoring of buffer layers in production wires
• Goal: Use reel-to-reel in-field measurement system for long wires
– Reel-to-reel system constructed in FY’09 with LANL’s magnet stage used to qualify in-field critical current uniformity of Zr doped production wires
55
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
Reel-to-reel in-field measurement system set up based on technique developed at LANL
• LANL provided a magnet stage (0.52 Tesla over 7.5 cm) for in-field measurement on long tapes at all field orientations (360°) & associated testing know-how.
• SP constructed a reel-to-reel system with sensors, controllers and software using this magnet stage.
56
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
FY11 Plans
Manufacturing of long-length, high current wires at high throughput• Increase self-field performance of production 2G wires by 25%• Increase in-field performance of Zr-doped AP wires by additional 25%• Increase production capacity and throughput by 50 - 75%• Decrease cost by 20 - 30%
– Double volume of 500+ continuous meter wires• Improved pinning for enhanced high-field performance• Develop new techniques for consistent nanocolumnar structures to fabricate
thick HTS films MOCVD with high critical currents in high fields. – Achieve a 50% improvement in in-field critical current over the already
improved values, over a range of temperatures and magnetic fields.– Establish a new variable temperature-field-angular system capable of high
current measurements• Transition improvements made in R&D wires to production
57
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
FY11 Plans
Develop high efficiency processes (higher throughput, lower cost)• Construct new MOCVD reactor with improved reactor design and
plasma enhancement to increase conversion efficiency of precursor to HTS film by 25 to 50%
• Work with ORNL to develop UV-enhanced MOCVD to increase conversion efficiency of precursor to HTS film
• Implement repeatable electrodeposition of silver in 100+ m lengths with uniform thickness and demonstrate all electrodeposited stabilizer layers (silver + copper) over 100 m lengths
• Establish substrate planarization process to fabricate 100+m and optimize the buffer stack to achieve critical current performance similar to those obtained with electropolished substrates
58
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
FY11 Plans
QC tools to qualify wire requirements• Optimize use of on-line XRD in new Pilot MOCVD system to assure
high-yield operation• Use reel-to-reel in-field measurement system to qualify and improve in-
field performance of long wires• Use 2D Ic analysis as routine QC procedure to qualify and improve 2D Ic
uniformity of long tapesDevelop advanced 2G wire to meet customer requirements• Optimize newly constructed pilot system for multifilamentary 2G wires to
produce 100+m lengths of low ac loss conductor and use to fabricate and test prototype coils and cables
59
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
FY11 PlansEstablish Specialty Products Facility at Houston• Establish new SuperPower division at UH Energy Research Park• Enable rapid transfer of R&D from University of Houston collaboration to
pilot-scale manufacturing• Procure, install and bring into operation new pilot-scale MOCVD system
at the Specialty Products facility
• Install post-HTS processing and test equipment (silver deposition, oxygenation, 5 m transport Ic system, non contact Ic system)
• Staff new division with existing scientists as well as new engineers and technicians
60
Future location of SuperPowerSpecialty Products Facility
US DOE Peer Review – Advanced Cables and Conductors Program – June 29 – July 1, 2010
SuperPower is committed to HTS wire R&D to reach price-performance requirements of commercial market
Commercial market requirements could be reached five to 10 years sooner with R&DDOE support for HTS program is critical to maintain National Lab & University support Commercial market requirements could be reached five to 10 years sooner with R&DDOE support for HTS program is critical to maintain National Lab & University support
10
100
1,000
2009 2014 2019 2024
Price ($/kA‐m
)
77 K, 0 T, with R&D77 K, 0 T without R&D65 K, 3 T with R&D65 K, 3 T, without R&D50 K, 3 T with R&D50 K, 3 T, without R&D
commerical marketentry threshold
medium commercialmarket requirement
large commercialmarket requirement