evaluation of corrosion products and methods of
TRANSCRIPT
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
2 Privileged and Confidential RJ Lee Group
• 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
3 Materials Challenges in Maintaining Aging Infrastructure - Concrete RJ Lee Group
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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