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

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