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Dr. Thad M. Adams
Materials Technology Section
Savannah River National Laboratory
DOE Hydrogen Pipeline R&D Project Review Meeting
January 5-6, 2005
Evaluation of Natural Gas Pipeline Materials for Hydrogen Service
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Hydrogen Technology at the SavannahHydrogen Technology at the Savannah
River SiteRiver Site
Tritium Production/Storage/Handling and HydrogenStorage/Handling since 1955
Designed, built and currently operate worlds largestmetal hydride based processing facility (RTF)
DOE lead site for tritiumextraction/handling/separation/storage operations
Applied R&D provided by Savannah River NationalLaboratory
Largest hydrogen R&D staff in country
Recent Focus on Related National Energy Needs
Current major effort on hydrogen energy technology(storage, production and infrastructure development)
Developing strategic university, industrial and otherpartnerships in hydrogen energy R&D anddemonstrations.
Advanced Hydride Laboratory
Fuel Cell Vehicle w/MH Storage
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Tritium Storage andTritium Storage and
Separation TechnologySeparation Technology
SRS Tritium Defense Programhas a > $200 M budget with> $25 M allocated to SRNL
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Hydrogen TechnologiesHydrogen Technologies
Metal & Complex Hydride
storage
compressors/pumps
purifiers/separators heat pumps/refrigeration
Battery / Fuel Cells
Ni metal hydride
Fuel Cells
Sensors
fiber optic
composite (ceramic)
Hydrogen Production
membranes
electrolysis
thermochemical water splitting biohydrogen
Materials Compatibility
H2 embrittlement
failure analyses
Safety
H2 safety analyses
codes and standards
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Hydrogen Isotope CompatibilityHydrogen Isotope CompatibilityUnderstanding & Mitigation of Effects on Metals & PolymersUnderstanding & Mitigation of Effects on Metals & Polymers
1E-10
1E-09
1E-08
1E-07
1E-06
1E-05
0 10 20 30 40 50 60 70 80 90
Stress Intensity MPa-m1/2
CrackGrowth
Rate,
m/s
300 appm Helium
600 appm helium
Decay Helium
Reduces
Threshold For
Cracking
Tritium Causes
Slow Crack Growth
Cracking Thresholds for Structural Alloys
0
500
1000
1500
2000
2500
3000
StorageModulu
s(MPa)
-100 -50 0 50 100 150Temperature (C)
A 1 HzA 1 HzA 1 HzA 1 HzA 1 Hz Unexposed 5 hours air 30 hours argon 30 hours air 60 hours air
UHMW PE 140C Exposure
Universal V2.6D TA Instruments
Dynamic Mechanical Analysis for Polymers
Tritium and Decay Helium Embrittlement of
Stainless Steel Weld Heat Affected Zone
Tritium (Beta Radiation) Degradation of UHMW-PE Valve Stem Tip
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Testing Tritium Exposed Samples
Hydrogen Isotope CompatibilityHydrogen Isotope Charging and Mechanical Testing
Tritium Charging Facility Schematic and Mock-up
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Hydrogen Isotope CompatibilityHydrogen Isotope CompatibilityHydrogen Isotope Effects on PolymersHydrogen Isotope Effects on Polymers
DMA - Present Study of Ultrahigh Molecular WeightPolyethylene (UHMW-PE), VespelTM, TeflonTM
FT-IR of Non-Exposed and T2-Exposed UHMW-PE
Colorimetry Used to Indicate Degree ofRadiation Damage and Remaining ServiceLife
Effects Charactized Using DMA, FT-IR, Color Measurements, Density, Offgas
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Hydrogen Isotope CompatibilityHydrogen Isotope CompatibilityHydrogen Isotope Effects on Containment AlloysHydrogen Isotope Effects on Containment Alloys
Fracture Toughness Samples Taken fromWelds and Base Metal
Samples Exposedto Tritium in
Charging Facility Aging and Testing
to CharacterizeEffects of Tritiumand Decay toHelium
Investigate Material Processing Effects(Forging, Welding, HAZ) on Embrittlementfrom Tritium and Decay to Helium
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MS
MS
Ion gagePressure gage+ adapter flange
Pressure controller
Valve
ValveValve
Valve
Valve
Blank Flange
ValveValve
Pressure Transducer+ Adapter flange
ValveIon Gage
Expansion Volume3 3/8 CFF 2 in tube
Blank Flange
Pressure gage +Adapter flange
Vac. Pressuregage
Vac. Pressure
gages +Adapter
Flanges
Mini CFF
Adapters
Dry VacuumSystem
1/4 VCR Male
Split tube furnace
Al-rich Permeation Barriers
Hydrogen Isotope CompatibilityPermeation Barrier Development and Testing
Schematic and Photograph of Permeation Test Rig
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New Hydrogen Research LaboratoryNew Hydrogen Research Laboratory
60,000 ft2 Center for Hydrogen Research in Progress
Located at Savannah River Research Park
30,000 ft2
reserved for academic & industrial partners Construction Started, Operation Scheduled for October 2005
Focus on Hydrogen Technology R&D
Advanced storage
Separation, production, sensors, safety and hydrogeneffects on materials
User Center/Demonstration Facility (e.g. Pipeline Project)
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Purpose:The project will provide a facility for the testing of safety codes andstandards with emphasis on the development of components, materials,and repair techniques for piping in high pressure hydrogen service.
Partners:ASME and SRNL will partner with industry and government to provide ademonstration project relevant to the needs for a new hydrogeneconomy.
Design
Leakage of mechanical joints
Fracture prevention and mitigation
Fatigue at high pressure
Repair technology
Compression technology
Fabrication Joint quality
Liner technology
Materials
Hydrogen embrittlement
New materials technology and testing
Heat to heat variation of ASTM specifications
Coating development
Inspection
Internal inspection Sensor development
Hydrogen Pipeline Demonstration ProjectHydrogen Pipeline Demonstration Project
Key Issue for the Demonstration Project
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ACTL
HRTL
FUEL
STATION
FUTURE
ELECTROLYZERREFORMER
FURTURE
RENEWABLE
H2 GENERATION
Test Section
Codes and Standards Test Loop
H
2Pipeline
StorageTank
ACTL Aiken County Technology Lab
HRTL Hydrogen Research Technology Lab
Test Section Test Section
Hydrogen Pipeline Demonstration ProjectHydrogen Pipeline Demonstration Project
SRNL i Add i th M j Ch llSRNL i Add i th M j Ch ll
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SRNL
is a recognized expert in hydrogen production, separation and hydrogenstorage R&D.
has ongoing R&D programs in several key areas of hydrogentechnology.
has a good track record in working with industrial, academic, and othergovernment agencies.
can provide complete solutions to customer problems (from research toprocess development to system demonstration).
SRNL is Addressing the Major ChallengesSRNL is Addressing the Major Challenges
to a Hydrogen Economyto a Hydrogen Economy
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DOE Goal for Hydrogen DeliveryDOE Goal for Hydrogen Delivery
Develop hydrogen fuel delivery technologies that
enable the introduction and long long-term viabilityof hydrogen as an energy carrier for transportation
and stationary power
-DOE Hydrogen Delivery Goal
DOE Hydrogen Delivery Focus
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HH22/NG Distribution Systems/NG Distribution Systems
Use Existing NG Pipeline System for H2 or H2+NG Transport
NG Transmission Pressure Range 500-1200 psigFew 100s Miles of Transmission Pipeline
NG Distribution Pressure Range
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HH22/NG Distribution Systems/NG Distribution Systems
Current Hydrogen Pipeline Infrastructure
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HH22/NG Distribution Systems/NG Distribution Systems
Current National Hydrogen Pipeline Infrastructure
Predominately Carbon Steel MaterialsX42, X52, X60, A106 Grade B, A357 Grade 5
Transmission Pressure Limited to 800psiPipe Sizes up to 12
K Ch ll f H D li
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Key Challenges for HKey Challenges for H22 DeliveryDelivery
Key Challenges
Pipelines Retro-fitting existing NG pipeline for hydrogen
Utilizing existing NG pipeline for Hythane New hydrogen pipeline: lower capital cost--Leakage/Seals-- Hydrogen Effects on Materials
Lower cost and more energy efficient compressionTechnology
Lower cost and more energy efficient liquefaction
Technology
Novel solid or liquid carriers
Operational Challenges: Retrofitting Compression/LeakageMaterials Challenges: Hydrogen Embrittlement
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HH22/NG Distribution Systems Operational Challenges/NG Distribution Systems Operational Challenges
Example - Compare H2 and Natural Gas
Compression & Pipeline Transmission:
Compress from Pinitial = 1 to Pfinal =1000 PSIG
4-stage, inter-cooled compression equipmentInitial temp = 70 F, Inter-stage temp = 90 FCompress the same volumetric quantity of each gas,i.e. XX million SCF/day:
Hydraulic characteristics of H2 and
Natural Gas are quite different:
100 miles of 20 I.D. PipelineGas temp = 70 F = constantInitial Pressure = 1000 PSIGFind volume rates of Natural Gas and H2 deliveredwith 200 PSI P:
Transporting Hydrogen across the existing Natural Gas
Infrastructure may result in a capacity de-rating (on a
delivered energy basis) of approximately 20-25%.
H2/NG Di t ib ti S t O ti l Ch llH2/NG Di t ib ti S t O ti l Ch ll
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H2/NG Distribution Systems Operational ChallengesH2/NG Distribution Systems Operational Challenges
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Leakage
Gaskets and Seals are more critical (compared to NaturalGas)
H2 (commercial purity) has no odor.Adding odorants as for Natural Gas, LPG etc. adds acontaminant that is poisonous to many fuel cell technologies
This will add cost to the H2 energy picture, either in pretreatmentto remove the contaminants, or in reduced servicelife of the affected systems.
Owing to the lower ignition energy and wider flammabilitylimits, H2 leaks are more likely to ignite than a Natural Gasleak.
Lower flame temperatures produce fires that are lessdamaging than Natural Gas fires.
H2/NG Distribution Systems Operational ChallengesH2/NG Distribution Systems Operational Challenges
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H2/NG Distribution Systems Operational ChallengesH2/NG Distribution Systems Operational Challenges
Adapted from Jasionowski et al,, Hydrogen for Energy Distribution, 1978
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H2/NG Distribution Systems Operational ChallengesH2/NG Distribution Systems Operational Challenges
Adapted from Jasionowski et al,, Hydrogen for Energy Distribution, 1978
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H2/NG Distribution Systems Operational ChallengesH2/NG Distribution Systems Operational Challenges
Adapted from Jasionowski et al,, Hydrogen for Energy Distribution, 1978
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H2/NG Distribution Systems Operational ChallengesH2/NG Distribution Systems Operational Challenges
Adapted from Jasionowski et al,, Hydrogen for Energy Distribution, 1978
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HH22/NG Distribution Systems Materials Challenges/NG Distribution Systems Materials Challenges
Materials of Construction
Hydrogen Embrittlement Presence of atomic hydrogen in carbon steel(permeability)
Toughness or ductility of the metal is decreased
Results in Cracking or Fissuring of the Metal
Potentially Catastrophic Failure of Pipelines!
Higher Strength Materials are moresusceptible to Hydrogen Embrittlement.
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Control of Hydrogen Embrittlement
The effect and level of hydrogen embrittlement on
materials is dependent on a large number of variablessuch as:
Environment temperature and pressure Hydrogen purity and concentration Hydrogen exposure time Stress state, secondary stresses, temperature range etc. Metal microstructure, physical, mechanical properties Metal surface finish and conditions
Type of material crack front
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Adapted from S. L. Robinson, Hydrogen for Energy Distribution, 1978
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
/ G S CH2/NG Di t ib ti S t M t i l Ch ll
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Adapted from S. L. Robinson, Hydrogen for Energy Distribution, 1978
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Di t ib ti S t M t i l Ch llH2/NG Di t ib ti S t M t i l Ch ll
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Adapted from S. L. Robinson, Hydrogen for Energy Distribution, 1978
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Di t ib ti S t M t i l Ch llH2/NG Di t ib ti S t M t i l Ch ll
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Adapted from S. L. Robinson, Hydrogen for Energy Distribution, 1978
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Distrib tion S stems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Adapted from S. L. Robinson, Hydrogen for Energy Distribution, 1978
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Adapted from Akhurst and Baker, Met Trans 12A, 1981
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Adapted from J. H. Holbrook et al, Battelle Labs, 1988
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Adapted from J. H. Holbrook et al, Battelle Labs, 1988
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Adapted from S. L. Robinson, Hydrogen for Energy Distribution, 1978
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
15% Loss of Hoop Stress in H2
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Adapted from S. L. Robinson, Hydrogen for Energy Distribution, 1978
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Adapted from J. H. Holbrook et al, Battelle Labs, 1988
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Avoid High Strength Steels
Avoid Pressure Cycles of the Pipeline
Limit Hardness of Pipe and Weld Materials
There is no consensus within the Technical
community on specific limits discussed
above. Additional research to establish
design, construction and operating limits willbe beneficial.
Rule of Thumb Control of Hydrogen Embrittlement
y gy g
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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The following should be considered when choosing pipingmaterial for hydrogen systems:
Hydrogen state (slush, liquid, or gas) Temperature, and/or temperature range PressureOther secondary loading conditionsCompatibility with operating environment (also include effectsdue to corrosion)
Ease of fabrication and assembly Potential to minimize damage due to hydrogen fires. Cost
Performance Criteria for Materials in Hydrogen Service
y gy g
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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To Mitigate the Effect of Hydrogen Embrittlement
Select materials for which sufficient performance data and industryconsensus for suitability in hydrogen service is available.
Evaluate welding procedures used in manufacturing and fieldjoints
for fitness for service in hydrogen environment
Avoid sources of stress concentration
Proper surface finish
Incorporate a thorough integrity management plan.Incorporate appropriate in service inspection method to discernhydrogen assisted cracking, and embrittlement
Explore the Use hydrogen attack inhibitors/permeation barriers
y gy g
H2/NG Distribution Systems Materials ChallengesH2/NG Distribution Systems Materials Challenges
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Materials Data Needs for Hydrogen Service Minimum Specified Yield Strength Minimum Specified Tensile Strength Yield Strength to tensile Strength Ratio Steel Chemistry
Weld-abilityMinimum Design Temperature Fracture Initiation Toughness Corrosion resistance, and corrosion prevention
Failure prevention program including periodicinspection
Resistance to environmentally causeddegradation
Coordinated research efforts is necessary to understand how line pipe steels are
affected when exposed to hydrogen (particularly at high pressures), how to
prevent or minimize the failure probability of a system, and finally to gather critical
data that is essential for the development of codes and standards and
government regulations
Mohitpour, Tempsys Pipeline Solution Inc, CANADA, 2004
SRNL H2 Pipeline ProgramSRNL H2 Pipeline Program
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Evaluation of Natural Gas Piping Materials for Hydrogen Service
SRNL Program Focused on Hydrogen Embrittlement Effects of Archival NG Piping MaterialsInitial Two-Year Program Beginning in FY05
FY05 Funding Level: $150K Fully BurdenedArchival NG Piping Provided by South Carolina Electric and Gas
SRNL Program Scope for FY05Baseline and H2 Exposed Mechanical Property Measurements
Hydrogen Threshold Stress Intensity MeasurementsBurst Prediction Modeling Development and Verification
SRNL Year-Two Program ScopeFracture Toughness Constraint Modified J-R Curve Testing
Fatigue TestingWeld Effects Testing
SRNL H2 Pipeline ProgramSRNL H2 Pipeline Program
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API 5L-X-42; 4.5 ODx 0.188 wall thicknessYield Strength:42ksi (min)-72ksi(max)Tensile strength:60ksi(min)-110ksi(max)Elongation in 2=1.944(A.2/U.9)
SRNL H2 Pipeline ProgramSRNL H2 Pipeline Program
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API 5L-Spec 2004X-42
C:0.22 maxMn: 1.30maxP:0.025maxS:0.015maxTi:0.04maxOther:
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X42 Archival NG PipeMicrostructurePolioshed and EtchedFerrite/Pearlite Microstructure
Single Weld Seam PipeEvidence of banding
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HH22/NG Mechanical Property Testing/NG Mechanical Property Testing
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SRNL High Pressure Hydrogen Facility
Mechanical Property Testing in HydrogenTemperature: Up to 350CPressure : Up to 30,000psiSub-miniture Specimens: 1 gage length
Fracture Toughness TestingC-Shaped Specimens
SRNL H2 Pipeline ProgramSRNL H2 Pipeline Program
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Adapted from J. H. Holbrook et al, Battelle Labs, 1988
SRNL H2 Pipeline ProgramSRNL H2 Pipeline Program
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Adapted from Gutierrez-Solana and Elices, ASM, 1982
HH22/NG Threshold Stress Intensity Testing/NG Threshold Stress Intensity Testing
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1/4-28 UNF
9/32 D typ 2
9/32 thru
Drill & tap1/4-28 UNF
Hydrogen Threshold Stress Intensity TestingBolt Loaded SampleMultiple Samples with Load Range from 0-500 lbs.Crack Dimensions: a/W0.5, Root Radius0.003in
C-shaped Samples will be Harvested from 4.5 and 2 Archival NG Pipe
Testing will be conducted at pressures of 500, 1000, and 1500psi
Testing will be conducted at Room Temperature 25C
Hydrogen Concentration will be Estimated Analytically Using DIFF
KTH will be Reported for Initial Conditions (i.e., crack growth initiation)
H2/NG Threshold Stress Intensity TestingH2/NG Threshold Stress Intensity Testing
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Determination of Burst PressureDetermination of Burst Pressure
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Finite Element Analysis
of Burst Pressure
For defected, repaired, or
welded pipelines withgeometry and materialdiscontinuities
For degraded pipelines
with local materialproperty variation due toprevious NG service orhydrogen exposure
For actual materialtensile property input (fullstress-strain curves up tofailure)
0
1
2
3
4
5
6
7
8
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Max. Pipe Radial Displacement (inch)
Pressure(ksi)
L= 1 x OD
L= 2 x OD
L= 4 x OD
L= 6 x OD
L= 10 x OD
X42 5L 4.5 x 0.188
Burst Pressure
L: Specimen Length
YearYear--Two Program FocusTwo Program Focus
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Component Fatigue and Hydrogen Environments
Adapted from J. H. Holbrook et al, Battelle Labs, 1988
YearYear--Two Program FocusTwo Program Focus
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Welds and Weld Metal Embrittlement Effects
Adapted from S. L. Robinson, Hydrogen for Energy Distribution, 1978
YearYear--Two Program FocusTwo Program Focus
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Advanced Fracture Modeling
Traditional fracture mechanics uses K (linear elastic materials)
or J (elastic-plastic materials) to characterize fracture processes
and failure events.
JIC and J-R Curves show certain amount of specimen geometry
dependence (data from 3PB, CT, CCP, SCP, SENB, SENT, DECP, etc.)
Develop a three-term asymptotic solution (J- A2) for a stationary crack.
Identify A2 as an additional fracture parameter. J-A2 controlled crack growth.
YearYear--Two Program FocusTwo Program Focus
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Advanced Fracture Modeling
Constraint Modified J-R Curves
Traditional ASTM J-R Curve:
J(a) = C1(a)C2
Constraint Modified J-R Curve:
J(a, A2) = Co(A2)+C1(A2)(a)C2(A2 )
The results can have full transferability from test specimen to large structure
SRNL Fracture Testing for A285SRNL Fracture Testing for A285Crack Resistance (JCrack Resistance (J--R) CurvesR) Curves
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0
200
400
600
800
1000
1200
1400
1600
0 2 4 6 8 10 12
a (mm)
J-integra
l(kJ/m2)
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45a (in.)
J-integral(in-lb/in
2)
SENB 1D (a/W = 0.32)
SENB 2C (a/W = 0.35)
SENB 2A (a/W = 0.59)
SENB 4C (a/W = 0.71)
CT (a/W = 0.47)
J-R Curve (A285)
SENB 2CCleavage Interruption
CT
SENB 1D
SENB 2A
SENB 4C
Increasing Constraint
Specimen size-dependent J-R curvesTypical fracture surface
REF:Lam, P.S., Chao, Y.J., Zhu, X.K., Kim, Y., Sindelar, R.L., Determination of Constraint-
Modified J-R Curves for Carbon Steel Tanks, J Press Vessel Tech, 12, pp.136-143, 2003
SRNL H2 Pipeline ProgramSRNL H2 Pipeline Program
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SRNL Program is Focused on Developing the Necessary Materials Data for
Demonstrating the Use of Existing NG Pipeline Network for Hydrogen Service
Mechanical Property Studies on Archival and New NG Pipe Fracture Mechanics Testing and Approaches for NG Pipeline Materials Component Fatigue Testing Burst Prediction and Modeling
The Initial Focus of this Program is Centered on Metallic Transmission NG Pipeline
Materials; However, the approach and methodology developed under this program
could be adapted to evaluating distribution piping materials which include both
metallic and polymeric materials
SRNL is working to leverage its experience at developing and operating hydrogen production,
storage, and delivery Technologies to develop the necessary technical data for
qualification of the existing NG pipeline network for hydrogen service
SRNL H2 Pipeline ProgramSRNL H2 Pipeline Program
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Acknowledgements
Researchers
Dr. Robert SindelarDr. Poh Sang lamDr. Elliot Clark
Mr. George Rawls
Lab Specialist/Technicians
Tina StefekThaddeus Reown