Energy Materials Meeting Loughborough University, October 9-10, 2008 DOE Perspective on Advanced Energy Materials Robert Romanosky, Technology Manager.

Energy Materials Meeting Loughborough University, October 9-10, 2008

DOE Perspective on Advanced Energy MaterialsRobert Romanosky, Technology Manager

National Energy Technology Laboratory

January 6, 2009

2

NETL_WVU_MATERIALS_MEETING_1/6/2009

Materials Program Goals

• Development of a technology base in the synthesis, processing, life-cycle analysis, and performance characterization of advanced materials.

• Development of new materials that have the potential to improve the performance and/or reduce the cost of existing power and non-power technologies.

• Development of materials for new systems and capabilities.

3


Fossil Energy Key Material Research Areas

USC Boilers/Turbines

Fluid. Blwr.

Co

mb

usto

r

Ba

ck

pa

ss H

XR

Ash

MBHX

N2

Air

ID Fan

Gas Cooling

and Cleaning

Lime-stone

Coal

ASU

Oxygen

CO2 ToStorage

CO2RecycleO2

HTR

Fluid. Blwr.

Co

mb

usto

r

Ba

ck

pa

ss H

XR

Ash

MBHX

N2

Air

ID Fan

Gas Cooling

and Cleaning

Lime-stone

Coal

ASU

Oxygen

CO2 ToStorage

CO2RecycleO2

HTR

Oxy-Firing

AdvancedTurbines

Sensors

Fuel Cells

Gasifier

4


Ultra-Clean Energy PlantV E21 P

CO2 Sequestration

ISION NERGY LEXV E21 P

CO2 Sequestration

Oxygen Membrane

Electricity

ProcessHeat/Steam

POWER

FUELS

HydrogenSeparation


CO2 Sequestration

Oxygen Membrane

Electricity

ProcessHeat/Steam

POWER

FUELS

HydrogenSeparation

Gasification


CO2 Sequestration

Oxygen Membrane

Electricity

ProcessHeat/Steam

POWER

FUELS

HydrogenSeparation

Gasification


CO2 Sequestration

Oxygen Membrane

Electricity

ProcessHeat/Steam

POWER

FUELS

HydrogenSeparation

Gasification


CO2 Sequestration

Oxygen Membrane

Electricity

ProcessHeat/Steam

POWER

FUELS

HydrogenSeparation

Gasification

GasStream

Cleanup

Fuels/Chemicals


CO2 Sequestration

Oxygen Membrane

Electricity

ProcessHeat/Steam

POWER

FUELS

HydrogenSeparation

Gasification

GasStream

Cleanup

Fuels/Chemicals

Fue l Ce llF uel Cell

L iquids Convers ionLiquids Convers ion

High Effi ciency TurbineH igh Effi ciency Turbine


CO2 Sequestration

Oxygen Membrane

Electricity

ProcessHeat/Steam

POWER

FUELS

HydrogenSeparation

Gasification

GasStream

Cleanup

Fuels/Chemicals





CO2 Sequestration

Oxygen Membrane

Electricity

ProcessHeat/Steam

POWER

FUELS

HydrogenSeparation

Gasification

GasStream

Cleanup

Fuels/Chemicals





Coal

OtherFuels

Gasification &Combustion

Gasification &Combustion

Systems IntegrationSystem modelingVirtual Simulation

Advanced Materials

Instrumentation Sensors & Controls

UltraSuperCritical Materials

Gas Stream Cleanup Devices

Advanced Alloys

Seals & Electrodes for

Fuel Cells

ODS Coatings

Improved Refractories for Gasifiers

Thermal Barrier Coating for Turbines

5


Policy Goal

Technologies Gasification CombustionSeques-tration

Environ-mental Fuel Cells Turbines &

Engines

Coal

TechnologyPlatforms

HeatExchangers

Air/GasHeaters

Gas Separation

ParticulateControl

Vessel Liners

MaterialsTechnology

Coatings/Protection Materials

New Alloys Breakthrough Concepts

UltraSupercritical

Materials

FunctionalMaterials

Materials R&D

ElementsJoining Materials

Design Modeling MechanicalProperties

MaterialsCharac-

terization

Synthesis &Processing/Fabrication

Corrosion/Erosion Studies

Program Roadmap

ComponentTechnology

Turbine Blades/

Rotors/PipesCastings Membranes Hot-Gas

Filters

RefractoryCastables/

BricksAdsorbents

6


A Dash of Wolfram, A Pinch of NickelCreation of New Materials

7


Advanced Research Materials ProgramHIGH TEMPERATURE APPLICATIONS

• New Alloys - To increase the temperature capability of alloys for use in specific components required for advanced power plants by understanding the relationships among composition, microstructure, and properties.

• Functional Materials - To understand the special requirements of materials intended to function in specific conditions such as those encountered in hot gas filtration, gas separation, and fuel cell systems.

• Breakthrough Materials - To explore routes for the development of materials with temperature/strength capabilities beyond those currently available.

• Coatings & Protection of Materials - To develop the design, application, and performance criteria for coatings intended to protect materials from the high-temperature corrosive environments encountered in advanced fossil energy plants.

• Ultra Supercritical Materials – To evaluate and develop materials technologies that allow the use of advanced steam cycles in coal-based power plants to operate at steam conditions of up to 760°C (1400°F) and 5,000 psi

8

• Includes rig testing • Includes field testing

Evaluation

• Extended alloy lifetimes through improved coating performance and composition optimization

• Microstructure and properties of HVOF-sprayed Ni-50Cr coatings

• High-temperature corrosion resistance of candidate FeAlCr coatings in low-NOx environments

• Aluminide coatings for power generation applications

Development

Gasifier Refractory

Linings

Metallic Coatings for

Structural Alloys

Ceramic/ Composite Coatings

Coatings Clusters

Advanced Combustion/Gasification

Conditions

Development

• YSZ thermal barrier coatings by MOCVD• Modeling of CVD processing• Development of non-destructive evaluation

methods for ceramic coatings• Materials issues for syngas turbines

Evaluation

• Includes field testing

Gas Turbine Components

9

• Fireside and steamside corrosion of alloys for USC plants

• USC materials plant trials (B&W)• Improved metallic recuperator materials (Solar

Turbines CRADA)• USC steam tubing consortium

Evaluation

• Advanced pressure-boundary materials• High creep-strength alloys (Special Metals • Effects of off-normal metallurgical conditions on

performance of advanced ferritic steels

• Steam turbine materials and corrosion• Materials for USC steam turbines (consortium)

Development

Advanced Heat Exchangers/

Engines

High-temperature ‘Conventional’Wrought Alloys

ODS Alloys

New Alloy Clusters

Advanced Steam Conditions

Development

• Enabling the practical application of ODS-ferritic

steels• Optimization of ODS-Fe3Al and MA956 alloy

heat exchanger tubes• Control of defects and microstructure in ODS

alloys• Cross-rolling/flow-forming of ODS alloy HX tubes

Evaluation

• In-plant corrosion probe tests of• Corrosion and joining of ODS FeCrAl alloys for

very high -temperature heat exchangers• MA956 heat exchanger tubes

10

• Development of inorganic membranes for hydrogen separation

• Activated carbon composites for air separation

• Metal membranes for hydrogen separation

Development

Gasifier Refractory

Linings

Ceramic Membranes/Structures

Refractories

Functional Materials Clusters

Gas Filtration/Separation/

Clean-up

Development

• Low-chrome/chrome-free refractories for slagging gasifiers

• Protection systems: corrosion-resistant coatings

Evaluation

• field testing

Processing

• Gas sensors for fossil energy applications

• Brazing technology for gas separation membranes: advances in air brazing

11

Increased HT capability for

‘Conventional’Wrought Alloys

Increased HT capability for

‘Conventional’Wrought Alloys

Breakthrough Concepts

Breakthrough Concepts

Concept Development• ORNL-2D: Multiphase HT Alloys: Exploration of

Laves-strengthened steels• ORNL-4A: Novel structures through controlled

oxidation• ORNL-4C: Concepts for smart, protective high-

temperature coatings• AMES-2: Optimizing processing of Mo-Si-B

intermetallics through thermodynamic assessment of Mo-Si-B and related systems

• UT-2A: Effects of W on the microstructures of TiAl-based intermetallics

• WVU-2: Influence of impurities on ductility of Cr-based alloys and in-situ mechanical property measurement

• ORNL-2I: Development of ultra-high temperature molybdenum borosilicides-See below

Concept Development• Multiphase HT Alloys: Exploration of Laves-

strengthened steels• Novel structures through controlled oxidation• Concepts for smart, protective high-temperature

coatings• Optimizing processing of Mo-Si-B intermetallics

through thermodynamic assessment of Mo-Si-B and related systems

• Effects of W on the microstructures of TiAl-based intermetallics

• Influence of impurities on ductility of Cr-based alloys and in-situ mechanical property measurement

• Development of ultra-high temperature molybdenum borosilicides-See below

Enabling Technologies

• AMES-3: New Processing Developments in Metallic Powders for Fossil Energy Applications

• REMAXCO-5: Pilot facility for the production of


• New Processing Developments in Metallic Powders for Fossil Energy Applications

• Pilot facility for the production of silicon carbide fibrils

Concept Development

• ORNL-2I: Strengthening phases with increased

stability

Concept Development

• Strengthening phases with increased stability


Conditions


Conditions


• Interaction with ORNL-2C


• Interaction with ORNL

Strength/Env Resistance at T > Current

Alloys

Strength/Env Resistance at T > Current

Alloys

12


Materials Evaluation for Biomass and Black Liquor Gasifiers

• Gasification of black liquor and biomass involves high-pressure, high-temperature, and sometimes caustic conditions.

• Materials used in gasifier equipment must be robust andable to withstand the chemical and thermal conditions as well as the cycling aspects of gasifier operation

• Critical materials issues such as fatigue, corrosion, stability, and longevity of materials will be the primary focus of research

• Corrosion and corrosion fatigue studies will be conducted with the intent of identifying possible degradation mechanisms for metallic and refractory materials.

13


Hydrogen Membranes

• Hydrogen can be produced from coal, natural gas, biomass, and biomass derivatives through the use of gasification, pyrolysis, reforming and shift technologies.

• The use of membranes holds the promise of reducing cost by combining the separation and purification with the shift reaction in a reactive separation operation.

• Development is needed to improve hydrogen membrane separation and purification technology for use in the production of hydrogen

• The focus of the research should be on low cost, high flux rate, durable membranes systems that can be integrated with the shift reaction.

• Membranes of interest include ceramic ionic transport membranes, micro-porous membranes, and palladium based membranes.

14


UltraSupercritical Boilers and Turbines

• Current technology for USC Boilers– Typical subcritical = 540 °C– Typical supercritical = 593 °C– Most advanced supercritical = ~610 °C

• USC Plant efficiency is improved to 45 to 47% HHV

• Ultrasupercritical (USC) DOE goal for higher efficiency and much lower emissions, materials capable of:– 760 °C (1400 °F)– 5,000 psi– Oxygen firing

• Meeting these targets requires:– The use of new materials– Novel uses of existing materials 1600150014001300120011001000900

40

42

44

46

48

Temperature (°F)

Pla

nt

Th

erm

al E

ffic

ien

cy (

%)

3500 psi

5500 psi

Birks and Ruth

15


Technical Barriers• Long-term degradation of materials (100-300,000 hours) are not well

understood or characterized for this alloy class• Combination of creep strength, weldability (necessary component for

boiler fabrication), oxidation, and corrosion resistance• Effects of heat-treatment, fabrication variables, welding is critical• Need new welding processes, fabrication processes, etc.• Ability to produce material is also an issue

Microhardness map of Thick Section USC weld showing “soft” weld metal – long-term testing is needed to understand the implication of this type of weld on material performance

12

10

8

6

4

2

0

Dis

tan

ce (

mm

)

20151050Distance (mm)

450

400

350

300

250

200

Ha

rdn

ess, kg/mm

2

16


What and Why Oxy-fuel Combustion

• Energy production (in particular, electricity) is expected to increase due to population increase and per capita increase in energy consumption

• Oxy-fuel combustion is one option for providing increased capacity to satisfy the future energy consumption demand

• Can be used for retrofitting or new plants

• Global climate change - one of the sources for CO2 increase in the atmosphere is exhaust from fossil fuel combustion plants

• Oxy-fuel combustion readily supports the capture and sequestration of CO2 from power plants

17


Technological Barriers – Materials Needs

• Better understanding of material performance in oxyfuel environments

– Evaluate ash assisted hot-corrosion of boiler alloys– Develop computational models to predict fireside corrosion will aid

in the development of all advanced combustion systems– Evaluate other plant components e.g.,

coal pulverizers (wear-corrosion interactions)

• Future Capability: Combine Oxyfuel with USC.– Potential cleaner coal combustion technology

• Oxyfuel: ease of flue gas clean-up and CO2 sequestration• USC: maximize efficiency

– Need cost effective advanced alloys that can withstand the oxyfuel/USC environment

• higher temperatures and higher pressures than current systems

18


Advanced Sensor Materials

• Harsh Environmental Conditions

• Sensor Material Development

• Rugged Sensor Designs

Sensor

Signal Wire

1”

19


Driver for New Sensing Technology

• Advanced Power Generation:– Harsh sensing conditions throughout plant– Monitoring needed with advanced instrumentation and sensor technology.– Existing instrumentation and sensing technology are inadequate

• Coal Gasifiers and Combustions Turbines:– have the most extreme conditions

• Gasifier temperatures may extend to 1600 °C and pressures above 800 psi. Slagging coal gasifiers are highly reducing, highly erosive and corrosive.

• Combustion turbines have a highly oxidizing combustion atmosphere.

• Targeting development of critical on line measurements– Sensor materials and designs are aimed at up to 1600 °C for temperature

measurement and near 500 °C for micro gas sensors.– Goal is to enable the coordinated control of advanced power plants followed

by improvement of a system’s reliability and availability and on line optimization of plant performance.

20


Materials for Sensing in Harsh Environments(Optical and Micro Sensors)

•Sapphire

•Alumina

•Silicon Carbide

•Doped Silicon Carbide Nitride

•Yttria stabilized zirconia

•Fused/doped silica for certain conditions

•Interest in

– Active / doped coatings

– 3D porous or “mesh” nano-derived ceramics / metal oxides

21


Turbines

• Technical Barriers

• Environmental Conditions

• Research Underway

22


Gas Phase Conditions for Advanced Turbines

Parameter ST 2010 HT 2015

Combustor exhaust temp 2700 °F 2700 °F

Turbine inlet temp 2500 °F 2600 °F

Turbine exhaust temp 1100 °F 1100 °F

Turbine inlet pressure 250 psig 300 psig

Combustor exhaust compositionCO2 (9.27), H2O (8.5), N2

(72.8), Ar (0.8), O2(8.6)

CO2 (1.4), H2O (17.3), N2

(72.2), Ar (0.9), O2(8.2)

IGCC Based Syngas and H2 Fueled Turbines

IGCC Oxy-Fuel Turbine Cycle

Turbine Parameters OFT 2010 OFT 2015

Intermediate Pressure

Turbine inlet 1150 °F 3200 °F

Pressure 450 psig 625 psig

High Pressure

Turbine inlet - 1400 °F

Pressure - 1500 psig

Working Fluid Composition (%)

H2O (82), CO2 (17), O2 (0.1),

N2 (1.1), Ar (1)

H2O (75-90), CO2 (25-10),

balance (17) O2, N2, Ar

23


Turbine Materials Technical Barriers • Mechanical / chemical stability of bond coating interface

• Stresses developed as a result of CTE mismatch

• Change in thermal conductivity across the thickness of the ceramic as a result of service exposure

• Cleanup techniques with various levels of sulfur removal:

– MDEA: 20 – 30 (+) ppm

– Selexol: 2 – 11 ppm

– Rectisol: 0.01 – 6 ppm

– CO2 capture w/ deeper sulfur removal w/ less sulfur problems

• Research needed on:

– new materials & deposition procedures (techniques)

– new TBC structures with corrosion resistance

– environmental barrier coating (EBC)

– ceramic matrix composite (CMC)

These number will tend towards the lower numbers

24


What R&D is underway to address these issues?

• TBC compositions for corrosion resistance with no increase in thermal conductivity and good CTE match.

• TBC failure mechanisms with alternate fuels especially under high heat flux (HHF) conditions.

• Understanding deposition (condensation) kinetics for critical vapor species on high temperature surfaces – water vapor activated recession of TBC materials

• Effect of cooling strategy on TBC thermal gradient and degradation modes

• Deposition, erosion, or corrosion (D-E-C) due to contaminants (Si, Al, Ca, Mg, Na K, sulfate ions, As, P, Se etc.) when firing syngas– Simulated lab tests

25


Fuel Cells

• Technical Barriers

• Environmental Conditions

• Research Underway

26


Fuel Cell Materials

Material improvements process

• Faster kinetics for oxygen reduction to lower the irreversible losses for electrochemical charge transfer.

• Stable surface chemistries are sought with active sites for dissociative adsorption of oxygen

Technical barriers

• Cathode performance correlated with oxide surface chemistry in high partial pressures of oxygen– Cathode surface boundary is affected by cation dopant distributions – Local surface chemistry establishes adsorption sites with kinetic barriers

to charge and mass transport– Dopants and defect segregation modify surface chemistry – Modified atomic arrangements can provide stable and fast reaction sites

with improved electrochemical performance

27


Fuel Cell Materials

R&D Underway • Work to fully understand the surface chemistry of established cathode

oxides • Epitaxial growth through pulsed laser deposition to prepare thin film

model surfaces • Identify key correlations between surface structure, chemistry, and

performance parameters • Theoretical modeling to interpret the underlying chemistry and guide

modifications to the cathode surfaces.

Technology Future• Improve Cathode performance to extend functional operating

temperature from the current lower range of 750 °C down to 650 °C.

Technology Benefit• Reduce SOFC cost through more efficient operational performance.• Increase efficiency in advanced power generation systems

28


What Does the Future Look Like?

• The USA and the world will face great energy challenges with ever increasing environmental constraints

• Advanced fossil energy power systems will be needed

• The Advanced Research Materials Program is poised to have even greater impacts on future energy systems

– Novel materials for gas separation

– Fuel cell materials

– Next generation stainless steels with higher strength and better oxidation resistance

– Advanced coatings

– Prescriptive materials design and lifetime prediction for extreme environments

29


Fossil Energy Key Material Research Areas

USC Boilers/Turbines

Fluid. Blwr.

Co

mb

usto

r

Ba

ck

pa

ss H

XR

Ash

MBHX

N2

Air

ID Fan

Gas Cooling

and Cleaning

Lime-stone

Coal

ASU

Oxygen

CO2 ToStorage

CO2RecycleO2

HTR

Fluid. Blwr.

Co

mb

usto

r

Ba

ck

pa

ss H

XR

Ash

MBHX

N2

Air

ID Fan

Gas Cooling

and Cleaning

Lime-stone

Coal

ASU

Oxygen

CO2 ToStorage

CO2RecycleO2

HTR

Oxy-Firing

AdvancedTurbines

Sensors

Fuel Cells

Gasifier

30


Energy Materials Meeting Loughborough University, October 9-10, 2008 DOE Perspective on Advanced Energy Materials Robert Romanosky, Technology Manager.

Documents

development of materials

corrosion materials

materials technologies

breakthrough materials

development of new materials

advanced power plants

advanced fossil energy

ods fecral alloys