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Materials Engineering & ManufacturingOverview of Research Activities and CapabilitiesDavid E. AlmanAssociate Director for Materials Engineering & Manufacturing, Research and Innovation Center, National Energy Technology Laboratory, 1450 Queen Ave. S.W., Albany OR 97321, USA, www.netl.doe.govOffice: (541) 967-5885, Mobile: (541) 979-7007, Email: david.alman@netl.doe.gov

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Materials Engineering & Manufacturing

Technology Deployment

Manufacturing

Lab Evaluations at Condition Field Trials

CharacterizationDesign & Synthesis

Science & Discovery

Atomistic Design and Discovery to Pilot Plant Demonstrations

BIAS SORBENT 2012 R&D 100 Award

Materials solutions to enable efficient and effective power cycles and resource recovery

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Materials Engineering & Manufacturing

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Integrated Alloy Development ApproachNETL: “From Concepts to Realization”

DFT and CALPHAD used to guide the optimization of alloy composition.

Outcome: NETL CPJ-7, New Fe-9Cr Alloy with an Increase Temperature

Capability of ∼ 50o F for this important class of power plant steel.

NETL’s computational toolsused to guide heat-treatingcycles to optimize the alloy’smicrostructure and properties.

Change in Enthalpy of Formation

Example Fe-9Cr Streel

J.A. Hawk, P.D. Jablonski & C. Cowen, Creep Resistant High Temperature Martensitic Steel, US Patent 9,181,597 B1 (11/10/2015).

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Materials in Extreme EnvironmentsDetermine & Predict Effect of Environment on Materials Performance

IN625: Mechanism Change

IN740: Modest Increase

Oxidation of Alloys in USC Steam Environments

Current focus materials for sCO2 power cycles

Fire Side Corrosion of Alloys in Oxyfuel Combustion Environments

TP347 700°C

Air Fired

Oxy, FGD 9% H2O

Oxy, FGD 20% H2O

Oxy No FGD

240 Hr

Oxidizing

480 Hr Oxidizing

720 Hr Oxidizing

960 Hr Oxidizing

1200 Hr Oxidizing

TP347H (Oxy FGD 20% H2O) 240hr at 700°C CO2+8%N2+20%H2O+2.5%O2+0.3%SO2

Environmental Resistance gaseous (oxidation) and hot corrosion Lab experiments that simulate real world conditions

Mechanical Performance (Creep, Fatigue and Fracture Resistance)

Microstructural analysis to determine strengthening mechanism

Simulations for service life predictionsPhase Field Simulation: γ/ Coarsening in H282

Model predicts lower γ / coarsening rate with increasing Ti/Al ratio. Experimentally validated through 20,000h

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Materials in Extreme Environments

1E-3 0.01 0.1 1

1E-6

1E-5

1E-4

∆K = 13.97ksi√in, R = 0.13

∆K = 20ksi√in, R = 0.13A = 2.3e-6

∆K = 28.7ksi√in, R = 0.13A = 4.88e-6

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∆K = 10ksi√in, R = 0.5A = 2.5e-6

da/dN - pH2S = 0.12psia da/dN - pH2S = 0.12psia da/dN - pH2S = 1.2psia da/dN - pH2S = 0.12psia - Coated

da/d

N (in

/cyc

le)

f (Hz)

∆K = 28.7ksi√in, R = 0.13A = 6.88e-6

pH = 7RT

2

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Effect of H2S on FCGR of Alloys for UDWwith DNV

0 25000 50000 75000 100000 125000 150000 175000 2000000

25000

50000

75000

100000

125000

150000

175000

200000

unaged peened, 200µm unaged peened, 500µm unaged peened, 1000µm

-Z"

Z'Effect of Surface Treatments

With WVUCorrosion of Casings in Cement

with PSU

S/N behavior of candidate riser alloys with SwRI

Sensor Developmentwith PSU

Performance Simulationwith PSU

Reliability & Mitigation: Alloys

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Materials in Extreme EnvironmentsReliability & Mitigation: Foamed Cements Characterization & Development

The Chief Counsel’s Report (2011) about the Macondo incident (stated: “The root technical cause of the blowout is now clear: The CEMENT that BP and Halliburton pumped to the bottom of the well failed to isolate hydrocarbons in the formation from the wellbore—that is, it did not accomplish zonal isolation.”

CT Scanning

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Modular Systems Materials & ManufacturingAdvanced Manufacturing

Materials Selection: Corrosive & Erosive Resistant, ASME Code Compliant

Easy to: apply environmental

barrier select ASME code

compliant material

Modular System

Barrier

BarrierMetal

Modular does not necessary mean small or complex geometry – but smaller than traditional approaches

Multiple materials over reactor typology

“Traditional”

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Electronic Ceramics for SOFCMaterials and structures to further enhance cost-competitiveness and durability of SOFC cells and stacks

400 µm

Development of robust electro-chemical materials for the efficient activation and transport

Computational & Characterization tools

Materials & Process Development

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Harsh Environment SensorsImprove efficiency, operational flexibility & system reliability

Composite Nanomaterials, Thin Films & Fiber Optics Development for Harsh Environment Sensing Devices & Platforms Monitor Environment (T,P) Monitor System Health (e,g., corrosion

sensors) Power Generation & Subsurface

Applications

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“Atomistic-scale” Engineering of Catalyst Performance“Nano-alloy” CO2 Conversion Catalyst by Design

Materials synthesis and synchrotron X-ray characterization

Computational modeling provides atomic-level details

and energetics

Performance testing quantifies CO2 conversion

vs. alloy composition

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Gas Separation: Oxygen Carriers for CLCProduction of syngas from methane with metal ferrites

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Gas Separation: Oxygen Carriers for CLCMixed Metal Oxides Development

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Gas Separation MaterialsPolymers, Composites, Metals & Ceramics: CO2 capture, O2 generation, H2 separation

0

100

200

300

0 5 10 15 20

Pressure, atm

CO

2 Ads

orbe

d, m

g/g

Small Pores

Large Pores

Flexible Pores

Rigid Pores

M[Ni(CN)4]n

Testing Computational Predictions

Designing NewCO2 Sorbents

0 10 20 30 40 500

1

2

3

4

Symbols: experimentsLines: simulations

298 K175 K

Exce

ss A

dsor

ptio

n (w

t%)

Pressure (bar)

87 K

NETL’s Pillared Cyanonickelate (PICNIC) MOF Sorbent Platform

Mixed Matrix Membrane Development

Performance EvaluationAt National Carbon Capture Center

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Alloy Fabrication Capabilities for Mission Critical Applications

Melt Processing Capabilities• Air Induction Melting: 300 lbs• Vacuum Induction Melting: 300 lbs• Vacuum Arc Remelt/Electro-Slag Remelt: 3 to

8 inch diameter cruciblesThermo-Mechanical Processing Capabilities• Heat-treatment furnaces:1500oC, inert

atmospheres and controlled cooling.• Press Forge: 500 Ton• Roll mills: 2 and 4 high configurations.

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NETL Severe Environment Corrosion Erosion Research Facility • Unique modular laboratory for evaluating the hot-corrosion and

erosion of materials in hostile atmospheres.• Safety Integrated System to allow for safe 24/7 unattended

operations.• Gas environment tailored by mixing with programmable mass flow

controllers. • Available gases: CO, CO2, CH4, H2, H2S, SO2, HCl, O2, N2, He, air,

H2O vapor.• Maximum temperature: furnaces: 1600oC; erosion rig: 750oC• Gas flow rates: 5-1600 ml/min (depending on gas).• Modules for conducting simultaneous experiments under different

conditionsMaterials Performance in Supercritical Fluids at Elevated Temperatures • Ultra-super-critical (USC) Steam Autoclave: Dual rated: 310 bar at 760oC

and 345 bar at 746oC. System to control steam chemistry (dissolved oxygen). Computer controlled for 24/7 unattended operations. Supercritical CO2 Autoclave: rated at 800oC and 275bar

• Corrosion & Oxidation Laboratories : Potentiostats, Galvanostats , Electrochemical Impedance Spectroscopy. Static and cyclical oxidation furnaces for 24/7 exposures to O2, H2O vapor, CO2

• High Pressure Immersion and Reactive Transport (HiPIRT) Laboratory: Autoclaves (5000psi-250oC), Flow Through Autoclaves (5000psi-500oC), Rocking Autoclave (7250psi-400oC). CO2 O2, SO2, H2S.

Fracture Mechanics and Creep Laboratory• Screw driven & servo-hydraulic frames for strength and fatigue (max.

load 1000 kn). Constant stress & strain load frames for creep testing.

Materials Performance in Extreme Environments

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Facilities for Fuel Cell ResearchSOFCEL

(Single cell testing)DOE FC stand

(Planar, A=16cm2)MCA

(Multi-cell array)The DOE Fuel Cell Test Facility, has been designed and constructed for the purpose of testing 3 to 30 kW fuel cell systems developed by the NETL sponsored developers, such as those in the Solid State Energy Conversion Alliance (SECA) program.

Active electrode area = 16 cm2

Sealing/separator: glass ceramics / mica Spinel coating on interconnect alloy

MCA (Multi-Cell Array) is a parallel-cell testing system installed at the NETL Morgantown, WV site, which has a capacity to test up to 12 button cells (dia. = 25–28 mm) in a parallel cell array connected to common fuel and air manifolds.

Single cell stand is utilized to test button-type fuel cells (active electrode area = 2 cm2). The system is designed to be readily engaged in various control systems and analyzing systems. Therefore, the system is adequate in analyzing fundamental properties of fuel cells.

Active electrode area = 2 cm2

Sealing/separator: mica Attachment: High steam generator,

GC etc.

FC setup configuration

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Sensor Materials Manufacturing & EvaluationCapabilities for Sensor Material and Device Development and Optimization for Harsh Environment Applications.

Custom Sensor Development Reactors

Optical Fiber Fabrication

Custom Sensor Development Reactors Simulate: Power Generation and Combustion Systems Subsurface / Geological Environments Pressurized Gas and Oil-Based Systems Processing of thin film and nano-composites.

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Material Synthesis Capabilities Colloidal Nanomaterials Synthesis:

Inorganic-organic Hybrid Materials Synthesis:

Inorganic Solid State Materials Synthesis:High-Temperature Solid-State Precipitation/Co-precipitation Sol-Gel Methods

(perovskites, delafossites) (layered hydroxides) (high surface area complex oxides)

Solvothermal & Flux Methods

(single crystal growth)

Single Metal ParticlesSmall Alloy ParticlesCore-Shell / Janus

Crooks Templating Methods

(metals, alloys, sub 2nm)

Seeded Growth Techniques

(shape controlled, heterostructures)

Hot Pyrolysis Injection

(metal-semiconductor, plasmonics, heterostructures)

Porous Materials Synthesis

(MOFs, COFs, porous coordination)

x x x x

xxx

y y y y

yyy

Surface Ligand Design & Exchange

(controlled hydrophobicity of particles)

Synthesis of Novel Organic MOF linkers

R

N

N

R

N

N

RCH3CF3FNH2C(O)HC(O)OCH3CH2NH2

(MOFs, COFs, porous coordination)

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Surface Science and Analysis Capabilities

LEEDIn SituEvaporator

ImagingXPS Ion Scattering

TPD

Custom Rxn Cell

Atomic Resolution STM

UPS

Atomic Resolution AFM

Surface StructureSurf

ace

Reac

tions

Surface Composition

• 4 dedicated surface chambers• Quantitative STM & single molecule studies• Well integrated w/NETL comp chem groups

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Computational Materials Science Capabilities

Ab Initio Molecular Orbital

Calculations

Classical MD & Equilibrium and Kinetic Monte Carlo

Simulations in Various Statistical Ensembles

Gaussian MolproTurbomoleQ-Chem, Dmol

Castep, VASP, Wien03, Dmol3, Siesta, PWSCF, CP2K, CPMD

MicrokineticsPhase-Field COMSOL CALPHAD

Length Scales

Met

hods MK, Microstructure

Phase Evolution Continuum Modeling

NAMD, GULP DL-POLY, LAMMPS, Compass, ReaxFF, in-house MD/MC

Å nm µm

Classical Mechanics Based Simulation

Capability

Meso-Scale Based Simulation Capability

Quantum Mechanics Based Simulation

Capability

Data

M

anag

emen

t

DFT Calculations for Systems with 1D/2D/3D PBC

Data Visualization, Analysis & Processing Data Archiving and Security

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Recent MEM Successes

Thick Wall Superalloy CastingsNETL’s CALPHAD Based Computational Tool to Specify Homogenization Heat-Treatments Enabling technology for Advanced Ultra-Super Critical Steam (A-USC) Turbines

Proven in industry casting for A-USC turbine components• Metaltek Step Block (300 lb): 1130°C/3 h + 1200°C/3

h + 1210°C/14 h• Flowserve Step Block (1000 lb): 1100°C/6 h +

1200°C/48 h• Special Metals ESR/VAR (10,000 lb): 1133°C/4 h +

1190°C/8 h + 1223°C/30 h• GE: ½ actual size valve body for an A-USC turbine

(18,500 lb casting)

Computational simulations specified heat-treating schedules.

Designed to match existing furnace capability at commercial heat-treating facility!

Multifunctional Contaminant Removal Sorbents to Improve Air

QualitySpecialized, patented sorbents developed by the

NETL in cooperation with enVerid Systems.

• Selectively remove carbon dioxide and volatile organic compounds from the indoor air.

• Avoid need for warm outside air, module can reduce energy consumption by >20 percent

• The system can be retrofitted onto a wide variety of existing HVAC systems

enVerid Systems HLR® module

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Materials Engineering & ManufacturingContacts

David E. AlmanAssociate Director Materials Engineering & Manufacturing(541) 967-5885david.alman@netl.doe.gov

Steven W. RichardsonSupervisor, Computational Materials Engineering Team(304) 285-4185steven.richardson@netl.doe.gov

James C. Fisher Supervisor, Functional Materials Team(304) 285-5293james.fisher@netl.doe.gov

Marisa D. Arnold (Stuart)Supervisor, Structural Materials Team(541) 967-5809marisa.arnold@netl.doe.gov

Donald V. MartelloSupervisor, Materials Characterization Team(412) 386-5948donald.martello@netl.doe.gov