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Degradation of High Temperature Materials in Traditional and Modern Energy Systems
ICAER Conf, IITB, 10-12 December 2013
Ge Le1, Andrew Czerwinski2,4, BV Mahesh1,2, Manoj K. Mahapatra1, Prabhakar Singh1,
RK Singh Raman2,3
1 Center for Clean Energy Engineering, University of Connecticut, USA2 Department of Mechanical and Aerospace Engineering, Monash
University, Melbourne, Australia3 Department of Chemical Engineering, Monash University, Melbourne,
Australia4 Engineering and Materials Division, HRL Technology Pty Ltd,
Mulgrave, Victoria, Australia
Degradation of High Temperature Materials in Traditional and Modern Energy Systems
MOTIVATION
•Improving Efficiency and Environmental Impact of Traditional Systems, and
•Developing New Systems
Mitigation of Materials Degradation in New and Traditional Energy Systems
Degradation, Failure and Fracture. .
Major Issues in both New and Traditional Energy Systems
Oxidation-assisted Microstructural Degradation of Fe-Cr Alloys for Nuclear and Coal-fired Plant Steam Generators 2.25Cr-1Mo Steel Weldment (Cross-sections): Steam / 600 oC
Base Metal Heat Affected
Zone (HAZ)
•HAZ: extensive cavity formation at grain boundaries
•Creep resistance of HAZ is generally much inferior
Singh Raman, Metall Mater Trans A (several publications): 1995-2003
Improving Efficiency and Environmental Impact of Traditional Systems
• Higher Temp of Operation: Supercritical / Ultra-supercritical Plants (Steam Generators / Boilers)
• Novel / Smarter Approaches to Monitor Materials Degradation of High Temp Equipment
Challenges for Higher Temperature Materials:Advanced Fossil Fuel Power Plants
Unique Oxidation Test Facility: Loy Yang B Power Station, Australia
A joint facility of:
- Five Power plants in Vic state,- Vic State Govt,- Monash Univ,- HRL Technology,- Oak Ridge National Lab, USA
Testing Using Real Power Plant Steam
PhD project: 12,000 h data
Lab Test Facility for Oxidation Kinetics Data:Fossil Fuel Plant Steam Generators
Lab and Power Plant Oxidation Kinetics Data:Steam Generator 9Cr-1Mo Steel (T9)
Good agreement in plant and laboratory data
Lab and Power Plant Oxidation Kinetics Data:Steam Generator 9Cr-1Mo Steel (T92)
No good agreement in plant and laboratory data
Extrapolation of Plant Oxidation Kinetics Data:Steam Generator 9Cr-1Mo Steels
(T92: V+Nb+W, T91: V+Nb, T9: plain)
Mitigation of Materials Degradation inAn Alternative Energy System (e.g., SOFC)
- 70% cost of SOFC: Interconnection / BOP materials- Chromia evaporation: cell contamination
Suppression of Chromium Evaporation
Least Cr Evaporation from Aluchrom Alloy
Ge, Verma, Goettler, Lovett, Singh Raman, Singh, Oxide Scale Morphology and Cr Evaporation Characteristics of Alloys for Balance of Plant Applications in Solid Oxide Fuel Cells, Metallurgical & Materials Trans A, 44a (2013) 193 – 206.
Suppression of Chromium Evaporation: FIB
Ge, Verma, Goettler, Lovett, Singh Raman, Singh, Metall & Mater Trans A, 44a (2013) 193 – 206.
(Cr,Mn)3O4
Cr2O3
AISI 310S
Al2O3
Aluchrom:850 oC / 3% humidity
Aluchrom:950 oC / 12% humidity
Al2O3
Nicrofer 6025HT Ni, Fe, Cr mixed oxide
Cr2O3
Grain Boundary Corrosion is Expected to be Extremely Enhanced in the Case of
Nanocrystalline Alloys
Singh Raman et.al., J. Mater Sci Letters, 9 (1990) 353
Mitigation of Materials Degradation:Grain Size Effect
Oxidised 2.25Cr-1Mo steel (550oC)
Extensive Grain Boundary oxidation /
Notching / Grain detachment
Remarkable Oxidation Resistance due to Nanocrystalline (nc) Structure of Fe-Cr Alloys
0
0.2
0.4
0.6
0.8
1
1.2
0 500 1000 1500 2000 2500 3000 3500
Wei
ght g
ain
per
unit
are
a, m
g/cm
2
time, min
microcrystalline (mc)nanocrystalline (nc)
mc, 30 min mc, 2 hr mc, 52 hr
nc, 30 min nc, 2 hr nc ,52 hr
Singh Raman, Gupta, Koch, Philosophical Magazine, 90 (2010) 3233
Oxidation (300 oC / Air) of nc and mc Fe-10Cr Alloys
Oxidised nc and mc Fe-10Cr Alloys
mc ncOxidised: 350oC / Air / 52h
nc and mc Fe-10Cr and Fe-20Cr Alloys Oxidized (300oC/120min): Cr Depth Profiles
0.0E+00
2.0E+06
4.0E+06
6.0E+06
8.0E+06
1.0E+07
0 100 200 300 400 500 600
Cou
nts
/sec
Time, sec
nc Fe20Cr
mc Fe20Cr
nc Fe10Cr
mc Fe10Cr
Cr - Profile
Singh Raman, Gupta, Corrosion Science, 51 (2009) 316
Our Nanocrystalline Fe-Cr Alloys Find Potential Application in Clean Energy Systems
Solid Oxide Fuel Cells (highest efficiency fuel cells)* High Cr alloys for Interconnect, Heat exchanger, Piping * Materials Issues: - 70% cost: Interconnection / BOP materials- Chromia evaporation: cell contamination
Rolls Royce Solid Oxide Fuel Cell
Effect of temperature on grain growth
• Rapid grain growth above 600 °C• Addition of Zr stabilizes the grain size even at 1000 °C !!
Mahesh, Singh Raman, Koch , J. Mater. Sci. 47 (2012), 7735-7743
MONASH Universit
y
MONASH Universit
y
Effect of Tamperature and Zr Addition on Grain Growth
- ARC Discovery and - North Carolina State University
Graphene: ‘Thinnest Known Corrosion Resistant Coating’
Graphene: Flat monolayer of sp2 hybridized carbon atoms arranged in a 2D honeycomb lattice
Single layer of graphite
Remarkable Mechanical Properties of Graphene
Young’s modulus: 1 TPa (steel ~0.2 TPa)
Stiffness: 1060 GPa
Graphene film vs Steel (similar thickness):
Graphene is 100 times stronger than the strongest steel
1 m2 graphene can bear 4 kg mass
Remarkable Mechanical Properties of Graphene Impermeable to most standard gases, including He
Impermeable to most fluids including small molecules
Inert even to most aggressive chemicals (e.g. HF)
Hydrophobic due to the non-polar covalent double bonds
Can Graphene act as a corrosion barrier?
Corrosion / Oxidation Resistance due to Graphene Coating
Chen S, Brown L, Levendorf M, Cai W, Ju S-Y, Edgeworth J, et al. Oxidation Resistance of Graphene-Coated Cu and Cu/Ni Alloy, ACS Nano. 2011 2012/01/26;5(2):1321-7
Graphene coated upper half of the
penny (Cu Alloy) does not corrode
Comparison of Corrosion Data from Different Groups
-0.3
-0.25
-0.2
-0.15
-0.1
-0.05
0
0.05
0.1
Po
ten
tial (V
) vs S
CE
graphene coated Cu
uncoated Cu
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
Po
ten
tial
(V)
vs S
CE
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
-9 -8 -7 -6 -5 -4 -3 -2 -1
log i (A/cm2)
Po
ten
tia
l (V
) v
s S
CE
Prasai et al
Kirkland et al
Singh Raman et al
Anodic current density is an order of magnitude lower (in Na2SO4)
Ecorr has shifted towards more noble direction
Anodic current density is similar (in 3.5% NaCl)
Ecorr is more negative
Anodic current density is two orders of magnitude lower
(in 3.5% NaCl)
Ecorr is 40 mV more positive
Best corrosion resistance due to graphene coating
till date!
EIS of Graphene-coated and Uncoated Cu
1
100
10000
1000000
0.01 1 100 10000 1000000
Frequency (Hz)
|Z|
(Ω c
m2)
Graphene coated CuUncoated Cu
Confirmation of two orders of magnitude higher corrosion resistance due to graphene coating
Singh Raman, Banerjee.....Ajayan, Majumder et al, Protecting copper from electrochemical degradation by graphene coating, Carbon, 50 (2012) 4040.
External Collaborators: Raman Singh • Centre for Clean Energy Engineering (C2E2), University of
Connecticut,
• US Office of Naval Research (ONR), Naval Research Lab (NRL)
• North Carolina State University (Prof K Koch)
• Consortium of Five Power Generators in Vic state, and HRL Technology
• Rice University (Prof PM Ajayan)
• ETH, Zurich (Prof P Uggowitzer)
• Technion (Prof Dan Schechtman)
• Alcoa, BHP-Billiton
• Australian Vinyls
• DSTO, CSIRO, IITB-Monash Research Academy