Evaluation of Corrosion Products and Methods of ...
Transcript of Evaluation of Corrosion Products and Methods of ...
Evaluation of Corrosion Products and Methods of Characterization
September 15, 2015
RJ Lee Group, Inc.
Keith Wagner
Who is RJ Lee Group
• 30+ years in business
• Multiple locations
– Monroeville, PA – Headquarters
– Pasco, WA
– Oakridge, TN
• 200+ professionals with backgrounds in various disciplines
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• Biology
• Chemical Engineering
• Chemistry
• Civil Engineering
• Computer Science
• Electrical Engineering
• Environmental Sciences
• Geology
• Industrial Hygiene
• Materials Science
• Mathematics
• Mechanical Engineering
• Metallurgy
• Mineral Processing
• Mineralogy
• Physics
• Materials Characterization
• Failure Analysis
• Forensic Engineering & Investigation
• Durability Modeling
• Environmental Assessment
• Risk Assessment
• Process Troubleshooting
• Field Sampling
• Site Inspections
• Quality Assurance / Quality Control
• Expert Testimony
• Data Management
RJ Lee Group - Areas of Experience
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• Microscopy
– Optical Microscopes
– Scanning electron microscopes
– Transmission electron microscopes
– High resolution electron microscopes
– Computer-controlled microscopy
• Surface Analysis: ESCA/XPS
• X-ray Diffraction
• X-ray Fluorescence
• Fourier Transform Infrared Spectroscopy
• Raman Imaging & Spectroscopy
• Analytical Chemistry
– ICP-ES and ICP-MS
– AA and IC
– GC-MS, GC-FID, GC-ECD
– DSC / TGA
Analytical Instrumentation 1st Mira delivered to EPA
Hitachi S-5500 SEM/STEM
Hitachi HD-2300 STEM
Thermo K-Alpha XPS
0.00E+00
1.00E+05
2.00E+05
3.00E+05
4.00E+05
5.00E+05
6.00E+05
7.00E+05
01002003004005006007008009001000110012001300
Co
un
ts /
s
Binding Energy (eV)
O1
s
Si2
pC1
s
N1
s
Na
1s
Mg1s Zn
2p
Ca
2p
B1
sC
l2p
K2
p
Al2
p
Fe
2p
0.00E+00
1.00E+05
2.00E+05
3.00E+05
4.00E+05
5.00E+05
6.00E+05
7.00E+05
01002003004005006007008009001000110012001300
Co
un
ts /
s
Binding Energy (eV)
O1
s
Si2
pC1
s
N1
s
Na
1s
Mg1s Zn
2p
Ca
2p
B1
sC
l2p
K2
p
Al2
p
Fe
2p
Internal Development and Instrumentation
RJ Lee Group Privileged and Confidential 5
Internal Development and Cutting Edge Technology
Innovative, Comprehensive Solutions for Clients
RJLG utilizes innovative technology for unprecedented
materials characterization abilities.
Example Area of Investigation
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Events of September 11, 2001
Kuwati Oil Fires
1994 Northridge Earthquake
Disaster Assessment
Corrosion Process Examples multiple causes and manifestations
1. General/Uniform corrosion
2. Galvanic and stray current corrosion
3. Intergranular and stress corrosion cracking
4. Crevice and Pitting corrosion
5. Microbiologically-Influenced Corrosion (MIC)
6. Environmentally assisted cracking
7. Corrosion fatigue
8. Fretting wear/oxidation
9. Particulate induced erosion corrosion or impingement attack
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Some Analytical Technique Capabilities
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• Microscopy
– Optical Microscope – morphology and optical properties (mineral/compound ID)
– SEM/EDS – morphology, elemental composition
– TEM/STEM – morphology, internal/crystal structure, elemental composition
– High resolution electron microscopes – nano-size features, structure and composition
– Computer-controlled microscopy – morphology, size distribution of features
• Surface Analysis
– ESCA/XPS – quantitative surface elemental chemistry, oxidation state determination (compound ID), depth profiles, some mapping capability
– Auger Spectroscopy – quantitative surface elemental chemistry, depth profiles, mapping capabilities
– Secondary ion mass Spec. (SIMS) – quantitative surface chemistry,, depth profile, mapping, detection limit in ppm range depending on matrix and element of interest
• Bulk Composition
– X-ray Diffraction – quantitative crystalline compound ID, phase ID
– X-ray Fluorescence – quantitative elemental ID, oxide conversion/equivalent
Some Analytical Technique Capabilities
• Organic Compound Analysis
– Fourier Transform Infrared Spectroscopy (FTIR) – bonding ID, organics, surfactants, silicones
– Raman Imaging & Spectroscopy – bonding ID, organics, surfactants, oxides, carbon, silicones
– GC-MS, GC-FID, GC-ECD – quantitative organic and compound ID
• Analytical Chemistry
– Inductively Coupled Plasma, ICP-ES and ICP-MS – quantitative elemental composition down to trace levels
– Atomic Absorption (AA) - quantitative elemental composition down to trace levels
– Ion Chromatography (IC) – quantitative anion and cation ID
• Thermal Analysis
– Differential Scanning Calorimetry (DSC) – thermal properties, phase changes, thermal durability/life expectancy
– Thermal Gravimetric Analysis (TGA) – mass change vs. temperature, thermal deterioration point, volatile compound quantitation
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Corrosion can be unpleasant or beautiful
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Regardless, corrosion is usually costly
Virtually all materials will corrode (or environmentally/chemically deteriorate)
under the right conditions
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Concrete Degradation Mechanisms Reinforcing Corrosion
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• Reinforcing steel in concrete vital to performance
– Maintains compressive stress fields
– Prevents easy opening of cracks that initiate
– Stress transfer by bond of cement and wire surface
• Loss of bond leads to failure
– Loss of compressive loads leads to tensile failure
– Volume expansion of wire on de-tensioning can cause cracks
• Loss of bond has multiple causes
– Corrosion • Expansive component
• Ongoing, difficult to arrest, impossible to reverse
– Poor steel condition • Improper manufacturer
• Improper coating
– Poor paste properties and deterioration
Environmental/Materials Selection Corrosion
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The selection and combination of
materials can lead to unforeseen
problems
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Environmental corrosion in Electronics
Anodic dissolution can occur in the presence of moisture and bias during
operation of the device.
Environmentally Assisted Cracking, Polymers
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Polymers also susceptible to
environmental “corrosion”
FTIR Spectrum showing indications of oxidation/corrosion of polymer compound
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Fire Suppression Pipe Leak
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Cross Section through ID Surface Pit
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Cross Section through ID Surface Pit
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Very little chloride detected in
surface corrosion product
Cross Section through ID Surface Pit
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Detection of chlorides near corrosion front
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Selected Drill Pipe Investigations
• Issues with extruded pipe surface quality
– Extrusion surface defects smears and laps
– hindered coating quality, adhesion and corrosion resistance
• Abrasion studies on coated aluminum pipe
– Wear studies addressing service life loss
– Surface scoring and tool mark evaluations
• Corrosion studies on steel drill pipe
– Corrosive wall cross-section loss
– Led to downgrading and limited service life
• Failure analysis of fractured steel drill pipe
– Pipe failed due to crack development
– Failure caused by tool plunge mark
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Drill Pipe Extrusions
Bad Surface Good Surface
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Good Extruded surface
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Bad Extruded Surface
Cross Section of Bad Extruded Surface
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Characterization of Thermally Applied Coating Materials
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Bad Extruded Surface Underneath Flake/Lap (Note bright spots are Sn-rich)
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Raman Spectrum collected from carbonaceous material under Flake/Lap
Raman shift (cm-¹)
500 1 000 1 500 2 000
10236617 black spots on Al_2
Oxide or sulfide Amorphous carbon
Abrasion Studies on Coated Pipe
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Slipper/Jaw Marks
Drag Marks
Slipper/Jaw Marks and Cross Sectional Depth Measurements
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Drag Marks on Surface and Cross Sectional Depth Measurements
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Drill Pipe Failed During Pressure Testing
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Fracture Origin at Tool Plunge Mark
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Fracture Surface of Crack Origin
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Depth of Surface crack
Depth of Tool Mark
Pipes Prematurely Retired Due to Cross Sectional Material Loss
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Issue thought to be corrosion/erosion on ID surface
Retired Pipe Corroded on OD ID was Polymer Coated
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Corrosion Products on OD Surface of Pipe
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BSE image of OD corrosion products
EDS spectrum indicates
chloride corrosion
Sample Corrosion Projects
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• Buried gas line Failure • Presumed to be caused by corrosion
• Failed Water Hose
• Failed Valve in closed loop cooling system
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• Protective coating missing at fracture location
• Incomplete fracture
• No indication of necking
• Fracture ductility only evident at top of pipe at ligament
NTSB Investigation Photo Pipeline Accident Brief
Number DCA-08-FP-006, March 5, 2008
NTSB Investigation Photo Pipeline Accident Brief
Number DCA-08-FP-006, March 5, 2008
Buried Gas Pipe Failure
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Buried Gas Pipe Failure
• Corrosion pit on bottom surface near origin in flattened dent area
• Pit depth only ~20% of wall thickness
• Pipe fracture surface exhibits brittle transgranular cleavage
• Pipe material is 70 HRB
• Nearest weld is approximately 2 feet away
NTSB Investigation Photo Pipeline Accident Brief
Number DCA-08-FP-006, March 5, 2008
NTSB Investigation Photo Pipeline Accident Brief
Number DCA-08-FP-006, March 5, 2008
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Was Corrosion the Root Cause of Failure?
• Small corrosion pit did not breach pipe wall
– No evidence that a leak could have come from this area
• Fracture mechanics determined that corrosion pit too small to affect fracture characteristics
– Pipe manufactured from API 5L Grade B steel – 70 HRB
– Material properties indicate fracture should have been ductile
– Current material properties indicate ductile character by the deformation of the ligament at the top of the pipe
• Brittle pipe failure mode did not match material condition – Pipe buried too deep for temperature to affect fracture characteristics
– Hydrogen embrittlement would exhibit intergranular fracture mode
– High strain rate only viable explanation of brittle character of fracture
Water Hose Fitting Failure
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Brass colored area
Copper colored area
Secondary crack
Water Hose Fitting Failure
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Shows intergranular fracture exhibiting
evidence of corrosive attack.
Water Hose Fitting Failure
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Shows brass colored area,
intergranular fracture in base metal
exhibiting little indication of de-
zincification.
Water Hose Fitting Failure
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Spectrum collected from copper
colored, area, indicates low zinc
content consistent with de-
zincification.
Valve Failure in Closed Loop Cooling System
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Valve Failure in Closed Loop Cooling System
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Pitting due to corrosive attack in
well maintained system, stray
current driven failure