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The mandate for the use of biofuels has resulted in increased risk of stress corrosion cracking-
related incidents caused by inadequate practices in the transport, handling and storage of
ethanol and methanol. A panel of industry experts and facility operators will discuss the causes
and effects of stress corrosion cracking. Sharing case studies and lessons learned, the panel
will reveal effective practices for addressing stress corrosion cracking from methanol and ethanol
at terminal facilities.
Moderator
Panelists
John Beaver, Ph.D., is a Corporate Vice President and Senior Principal Engineer in DNV GL’s
Pipeline Services Department, North American Oil and Gas. He is in the Incident Investigation
Section of DNV GL’s Materials and Corrosion Technology Center in Dublin, OH. His current job
responsibilities include providing technical support on failure analyses, root cause analyses,
litigation projects, consulting, and laboratory research programs. A major emphasis of Dr.
Beavers’ research has been the mechanistic and practical aspects of corrosion and stress
corrosion cracking (SCC). He earned a Bachelor of Science in Metallurgical Engineering with
Highest Honors from the University of Illinois and received his Ph.D. in Metallurgical Engineering
from the University of Illinois.
Chuck Corr is the Biofuels Technical Service Manager for ADM, Inc. He has over 30 years of
experience in the ethanol production industry and has spent his entire career with ADM.
John Farrell is the Segment Engineer Technical Authority for Storage Tanks and Pipeline for
BP Corporation. He received a Bachelor of Science degree in Civil Engineering from the
University of Illinois, Champaign-Urbana, and a Master of Science degree in Civil Engineering
from the University of Illinois – Chicago.
Russell Kane, Ph.D., is President of iCorrosion LLC. Dr. Kane has over 300 technical
publications and five books on corrosion and metallurgical topics. He received his Bachelor’s
degree, Master’s degree and Ph.D. in metallurgy and materials science from Case Western
Reserve University.
Chip Locke is Senior Project Manager at Kinder Morgan. In his current position, he has the
lead role in the maintenance, development and implementation of all engineering and
construction standards, maintenance procedures, preventative maintenance checklists and
technical memorandums. Locke is responsible for advising on technical matters relating to
terminal operations and serves as a facilitator for standards and procedures training. He is a
registered Professional Engineer in Indiana and Ohio. He earned a Bachelor of Science in civil
engineering from Purdue University and an MBA from Butler University.
Strategies for Mitigating Ethanol and
Methanol Stress Corrosion Cracking
Moderator
Dan Leslie, Marathon Petroleum Co.
Panelists
John Beavers, DNV-GL
Russ Kane, iCorrosion
Chuck Corr, Archer Daniels Midland
John Farrell, BP
Chip Locke, Kinder Morgan
Topics at a Glance
Part 1 - Research and Production
– Alcohol SCC Research
– API Bulletins
– Production & Experience
SCC
Susceptible
Material Tensile
Stress
Susceptible Material
• No Evidence that Typical Line Pipe or
Plate Steels are Resistant to e-SCC
• Weld Microstructures Have Similar e-SCC
Susceptibility to Base Metal
– Weld metal may be somewhat more resistant
SSR Tests if Different Steels
Base Metal
5.0E-06
E-95
4.0E-06 E-30
SCC CGR mm/s
3.0E-06
2.0E-06
1.0E-06
0.0E+00
W
W
l
W
ss
ee
SA
ER
R
R
le
St
FE
FE
am
LF
D
H
as
Se
2
6
2
C
X5
X5
X4
Effect of DSAW Welds
X46 DSAW
5.0E-06
E-95
4.0E-06 E-30
SCC CGR mm/s
3.0E-06
2.0E-06
1.0E-06
0.0E+00
Base Metal HAZ HAZ Weld Metal Weld Metal
Tensile Stress
• Primary Role of Welding in e-SCC is to
Introduce Residual Tensile Stresses
– Most failures occur near welds – Not in weld
microstructure
• Low pressure piping and tanks
• In High Pressure Transmission Pipelines
– Hoop stress from internal pressure may be
sufficient to cause e-SCC
Environment (Factorial Study)
• Oxygen and Steel Couple Are Most
Significant Factors
• Chloride, Methanol and Acetic Acid May
Be Important at Intermediate Oxygen
Concentrations
• Water and Blend Ratio
– Did Not Show up in Study
• Limited Range (Water)
• Not Investigated (Blend Ratio)
Environment (Factorial Study)
Effect of Blend Ratio and Oxygen
Effect of Blend Ratio and Oxygen
• Dissolved Oxygen is Most Important
Factor
• No SCC Below E-15
– E-15?? On the edge of a cliff
• E-85 Susceptible
• E-50 Appears to be the Worst!
Effect of Water
Hydrous Ethanol Will
Not Cause SCC
Mitigation of e-SCC
• Fundamental Research
John Farrell, BP
SCC IN TANKS
Ethanol SCC in Floating Roofs
• Steel Pan IFT: a small ethanol puddle was found
on the deck near a fillet lap weld during a routine
seal inspection. The tank was removed from
service and two cracks were discovered in deck
seams by wet fluorescent magnetic particle testing
(WFMT). The cracked sections were analyzed and
ethanol SCC was confirmed.
• Steel Pan IFT: a tank was removed from ethanol
service for scheduled modifications including fillet
welding the underside of the floating roof deck
seams in preparation for installation of an ethanol
resistant coating. Dye penetrant testing (PT) of the
recently completed fillet welds identified 32
cracks.
Ethanol SCC in Floating Roofs
• Steel pan IFT: pusher springs
that were part of a mechanical
shoe seal had
broken/snapped. This damage
was found in two tanks that
also experienced SCC in the
bottom weld lap seams.
Ethanol SCC in Bottoms
• Annular Ring: Annular butt weld seam
cracked. Additional WFMT revealed
additional cracks in or very near bottom
lap weld seams and in shell nozzle insert
plate welds.
• Bottom Plate Seams: Lap weld seams,
corner weld, and floating roof leg bearing
pad fillet weld seams were examined by
WFMT and cracks identified in 2 tanks
located at same terminal.
Ethanol SCC in Piping
• Terminal 1:
– Ethanol Piping at loading rack developed a
seep at/near pipe to elbow butt weld joint.
• Terminal 2:
– Minor seep/leak developed in carbon steel
piping in April. Seeps were located near pipe
support fillet weld. Piping was constructed &
placed in ethanol service in 1995.
– Upon detection of first leak, 3 more cracks
were found at similar support weld locations.
– Several months later, other leaks developed at
other support welds. Piping was replaced
utilizing different support design and PWHT of
completed piping installation.
Ethanol SCC in Shell
• Tank Shell Seams: During routine internal
examination of an ethanol tank, WFMT of the
uncoated shell vertical and horizontal weld
seams revealed cracks in all 1st course
vertical seams, most 2nd course vertical weld
seams, and about ½ of the 3rd course vertical
weld seams. Cracks were small (i.e. short,
tight) and were not visible without
magnification.
• Tank Nozzle Insert Plate Welds: During an
internal inspection, WFMT examination of
insert plate weld seams identified one small
(i.e. short, tight) crack in insert plate to shell
weld.
Ethanol Tank & Piping Practices
Tank :
– Tank bottoms, shell and undersides of floating roofs
are coated with epoxy coatings that are resistance to
ethanol.
– Store in Internal floating roof tank (No EFTs)
• Welded steel floating roofs are preferred
• Bolted or welded aluminum floating roofs are
acceptable.
• Mechanical shoe primary seal w/ stainless steel
shoes, hangers, & hardware.
Piping:
– All new piping components shall be subject to PWHT
– Welding of pipe supports to the parent pipe should
be avoided - the preference being to use clamp type
supports (e.g. U-bolts).
– Pipe stresses should be minimised e.g. do not use
maximum pipe support spacing, reduce spacing to
reduce stresses over supports
Tank Inspection Practice
Internal inspection of a tank that has been in ethanol
service, regardless of duration, includes Wet Fluorescent
Magnetic-Particle Testing (WFMT) of the following areas:
• Uncoated bottom lap welds.
• Internal corner weld (remove any existing coating,
regardless of condition, to perform this inspection).
• All uncoated internal shell welds beneath the first
horizontal shell weld, including vertical butt welds and
nozzle welds.
• Uncoated carbon steel floating roof welds exposed to
ethanol – if roof is not seal welded on the underside, the
top side lap welds shall be WFMT inspected, including
seams inside pontoons.
– Note: WFMT requires surfaces to be cleaned to a near-white
metal finish The area extending 6 inches into the base metal on
either side of the weld shall be prepared and WFMT inspected.
Daniel Leslie, Marathon Petroleum Company
Terminal #3
Construction Standards
• Applies to systems with ethanol concentration >= 15%
• Pipe Standards
– Piping must meet A106 Grade B
– All welds to be Post-weld heat treated (PWHT) during fabrication
– Valve assemblies to be uni-body
– Receipt Manifold and ethanol offload line must not be connected
• Tank Standards
– If shop fabricated (<14’ tall), entire tank to be PWHT
– Ethanol tank bottoms and walls to be coated to at least 3’ from the floor, and
must be coated at least 6” above nozzles and or manway (whichever is greater)
• Required coating: FastClad 105 ER or Carboline Phenoline 187 UHS
– Shell welds to be coated above 3’ line
– High-deck Floating Roofs in ethanol service to be replaced
Lewis “Chip” Locke, Kinder Morgan, LLC
A disastrous failure may occur unexpectedly, with minimal overall material loss.
Schematic of Stress Corrosion Cracking
(Corrosion Products) (Corrosion Products)
Corrosion Build Up
Tensile Force Tensile Force
Advancing Crack Tip
Common SCC Systems Table
Material Environment Concentration Temp Mode
Hydroxides high high I
Nitrates moderate moderate I
Carbonate/bicarbonate Low moderate I
Carbon steel
Liquid ammonia Low T
CO/CO2/H2O low T
Aerated water very high T
Low Alloy Steel (e.g. Cr‐Mo, Cr‐Mo‐V) Water ‐ moderate T
Water ( y>170 ksi) low M
Strong Steels Chloride ( y>120 ksi) low M
Sulfide ( y>90 ksi) low M
Chloride high high T
Austenitic Stainless Steel (including sensitized)
Hydroxide high very high M
Aerated water very high I
Sensitized Austenitic Stainless Steel
Thiosulphate or polythionate low low I
Chloride high very high T
Duplex Stainless Steels
Chloride + H2S high High moderate T
Martensitic Stainless Steels Chloride (usually + high H 2S) moderate low T
High Strength Steels Water vapor ‐ low T
Aluminium Alloys Chlorides low low I
Chlorides high Low T
Titanium Alloys Methanol ‐ Low T
N 2O 4 high high low T
Copper Alloys (excluding Cu‐Ni) Ammoniac and other nitrogenous low low I
Notes to SCC Table
1. This Table presents the systems for which SCC problems are well established and of practical
importance. The absence of a metal-environment combination from this Table does not mean that
SCC has not been observed.
2. There are rarely well-defined temperature or concentration limits for SCC, and the ratings given here
are indicative only. As an approximate guide the terms used equate to the following ranges of values:
Concentration Temperature
Low Up to 10‐2M Ambient
Moderate Up to 1 M Below 100 °C
High Around 1 M Around boiling
Very high Near saturation Above boiling
Note that significantly increased local concentrations may be obtained under the influence of local
boiling or evaporation, or by accumulation in pits and crevices, and cracking is often obtained for
nominal concentrations that are much lower than is indicated here.
3. The fracture mode is classified as intergranular (I) where cracks go along the grain boundaries,
trans granular (T) where cracks go across the grains, or mixed (M) where there is a combination of
the two modes, or where the mode can vary depending on the conditions. There are often
circumstances that can cause the fracture mode to change (e.g. chloride SCC of sensitized
austenitic stainless steel may give intergranular cracking).
4. Very high temperature (> 200 °C) water environments are very aggressive, and will cause SCC of
a wide range of materials. Expert advice is essential for materials selection for such conditions.
eSCC Industry Observations
• No eSCC was observed at tanks or piping at ethanol producers.
• eSCC does not appear to affect first tier transportation (barges, etc.)
• eSCC appears in the first storage point (terminals and blending facilities)
• There have been no reports of eSCC after blending even in E85.
• eSCC occurs primarily in piping/fittings and tank floors. The shell and critical
zone were less common but still had occurrences.
• eSCC also occurs in steel pan floating roofs and pontoons.
• eSCC has occurred in a little as 6 months to as long as 10 years.
• Both oxygen and chlorides seem to accelerate eSCC.
• Experimental SCC data is notorious for a wide range of scatter.
High Tensile Stress in Tanks
Tanks have several potential areas of stress at or near the bottom
– The critical zone with 1’ of the floor to shell weld
– Openings and nozzles such as manways Fillet Weld
API 650 and 653 shows details for openings, nozzles and patches that reduce
stresses in these areas. Rounded corners on repads, for example 1/8 inch
radius.
Construction Materials Affected by SCC
• In lieu of PWHT, abrasive blast the tank to peen the surface with clean, new
peen-shot-media. This relieves the surface tension on the steel.
• In addition or as an alternative, use new blast media (garnet or other mineral
grit) to create a profile of 2 to 2.5 mils SSPC-10 Near White Blast.
• Coat the tank with the appropriate coating for the product
¾ Many coatings resist ethanol - most epoxies, including coal tar epoxy.
¾ Methanol requires a high solids, epoxy novolac phenolic or a vinyl ester
• The lining material should be made with OAP pigment to facilitate blacklight
inspection
• The final step is to wet sponge holiday testing for coating milage of 20 mils
or less. High voltage is utilized on coating thicknesses above 20 mils
Company BMP
Fully lining chemical tanks is economically viable because the tanks are usually
small (10k to 30k bbls) and the chemical is valuable, with contaminated product
creating a substantial cost to KM in terms of money and customer relations.
Summary
• Stress Corrosion Cracking is a infrequent but significant issue
• Chloride Testing should be performed using approved methods.
• Number of tests are determined on square footages
• SCC occurs when material, tensile stress and environment overlap
• eSCC is most common but methanol and other chemicals can cause SCC
• SCC can be mitigated by PWHT, Shot-peening and internal tank coatings
• Internal coatings (liners) must be carefully selected to resist the product
• Liner Quality Control using OAP and holiday testing is a must
• Liners serve other functions than just carbon steel protection
Thank you