Corrosion Damage (Forms of Corrosion)

Engineering Encyclopedia
Saudi Aramco DeskTop Standards
CORROSION DAMAGE (FORMS OF CORROSION)
Note: The source of the technical material in this volume is the Professional Engineering Development Program (PEDP) of Engineering Services. Warning: The material contained in this document was developed for Saudi Aramco and is intended for the exclusive use of Saudi Aramcos employees. Any material contained in this document which is not already in the public domain may not be copied, reproduced, sold, given, or disclosed to third parties, or otherwise used in whole, or in part, without the written permission of the Vice President, Engineering Services, Saudi Aramco.
Chapter : Corrosion File Reference: COE-101.02
For additional information on this subject, contact PEDD Coordinator on 874-6556
Corrosion Basics Corrosion Damage (Forms of Corrosion)
SECTION
PAGE
CORROSION DAMAGE (The Various Forms of Corrosion) .......................................... 6 Engineering Failures ................................................................................. 6 Corrosion Risks ........................................................................................ 7 GENERAL CORROSION (UNIFORM METAL WASTAGE) ......................................... 10 LOCALIZED CORROSION .......................................................................................... 16 Galvanic Corrosion ............................................................................................ 16 Intergranular Attack ........................................................................................... 23 Sensitization and Weld Decay ........................................................................... 25 Exfoliation .......................................................................................................... 27 Pitting Corrosion ................................................................................................ 29 CRAs/Passive Metals ............................................................................. 30 Pitting in Sour Service............................................................................. 35 Crevice Corrosion, Under Deposit & Under Insulation Corrosion ...................... 37 Fretting .............................................................................................................. 42 VELOCITY RELATED ATTACK ................................................................................... 44 Flow Assisted Corrosion.................................................................................... 46 Erosion- Corrosion............................................................................................. 48 Impingement Attack........................................................................................... 53 Cavitation Damage ............................................................................................ 54 ENVIRONMENTALLY ASSISTED CRACKING ........................................................... 59 Stress Corrosion Cracking (SCC)...................................................................... 61 SCC Mechanisms ................................................................................... 65 Hydrogen Embrittlement (HE)............................................................................ 69 Hydrogen Damage Of Oil Field Equipment In Sour Service .............................. 72
Saudi Aramco DeskTop Standards i
Sulfide Stress Cracking (SSC)........................................................................... 76 Stress Orientated Hydrogen Induced Cracking (SOHIC)................................... 78 Corrosion Fatigue .............................................................................................. 81 HIGH-TEMPERATURE DEGRADATION AND CORROSION ..................................... 85 High Temperature Micro-structural Changes and Embrittlement....................... 86 High Temperature Oxidation.............................................................................. 89 Sulfidic Corrosion .............................................................................................. 90 Hydrogen Attack (Decarburization).................................................................... 95 Carburization and Metal Dusting ....................................................................... 98 Hot (Molten Salt) Corrosion ............................................................................. 101 GLOSSARY ............................................................................................................... 103
LIST OF FIGURES Figure 1 Bath tub Curve of Failure Rate / Hazard Function versus Age ..................... 7 Figure 2 General or Uniform Corrosion Mechanisms .................................................. 10 Figure 3 Corrosion Allowance Concept ....................................................................... 11 Figure 4 Predicted CO2 Corrosion Rates [] .................................................................. 12 Figure 5 General Corrosion Field Observations ....................................................... 13 Figure 6 Representation of Galvanic Corrosion .......................................................... 16 Figure 7 Stainless Steel Fastener in a Galvanized Sheet Lack of Insulation Washer caused Accelerated Corrosion of Zinc Coating and Steel Substrate ............................................ 17 Figure 8 Dissimilar Metal Couple Mechanism ............................................................. 18 Figure 9 Weldment Corrosion in a Condensate Line (CO2 system) ............................ 18 Figure 10 Area Principle for Galvanic Corrosion ......................................................... 21 Figure 11 Example of Design Detailing Required to Control Galvanic Corrosion........ 22
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Figure 12 Intergranular Corrosion of Pump Impeller ................................................... 24 Figure 13 End Grain Attack (Intergranular Corrosion initiated in Crevice) of Washer fabricated from 420 SS after 3 years Wash Water Duty ............ 24 Figure 14 Representation of a Sensitized Grain Boundary in 304 Stainless Steel ...... 25 Figure 15 Schematic Illustration of Weld Decay .......................................................... 26 Figure 16 Exfoliation of Rolled Aluminum Alloy Sheet................................................. 27 Figure 17 Pitting Corrosion.......................................................................................... 29 Figure 18 Pitting of 410 SS Bubble Caps & Tray (NGL stripper column), Typical of Pit Morphology on Stainless Steels and CRAs Exposed to Cl- & H2S,........ 30 Figure 19 Polarization Curve of 304 SS in a Chloride Containing Solution showing Passivation, Film Breakdown Transients and the Pitting Potential ............. 31 Figure 20 Electrochemical Noise Transients from Pitting Events ................................ 33 Figure 21 Resistance to Pitting & Crevice Corrosion with Alloying Additions .............. 34 Figure 22 Corrosion Pit in C-Steel in a Sour System................................................... 35 Figure 23 Crevice Corrosion under a Gasket between Water Box and End Plate ...... 37 Figure 24 Initial Stage in the Development of Crevice Corrosion between Two Bolted Plates........................................... 39 Figure 25 Later Stages of Crevice Corrosion Concentration Cell............................. 40 Figure 26. Perforation of Web of Pipe Bridge Support due to Corrosion under Fire Protection Insulation (a form of crevice corrosion)..................... 41 Figure 27 Fretting Between Two Surfaces .................................................................. 43 Figure 28 Effect of Fluid Flow on Rates of General Corrosion .................................... 47 Figure 29 Representation of Erosion-Corrosion .......................................................... 48 Figure 30 Erosion-Corrosion of a Copper Alloy Tube, Seawater Cooling.................... 49 Figure 31 CO2 Mesa Corrosion - a form of Erosion-Corrosion.................................. 49 Figure 32 Increased Metal loss due to Erosion Corrosion........................................... 51 Figure 33 Erosion-Corrosion of CRAs in a Choke valve Well Test.............................. 52 Figure 34 Impingement Attack .................................................................................... 53
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Figure 35 Steps in Cavitation Damage........................................................................ 55 Figure 36 Cavitation Damage at T in an LPG line, caused by Mixing of Two Streams that Contained Traces of Water, (Better to allow Mixing in a Tank)................................................................ 56 Figure 37 Cavitation Damage of Pump Impeller.......................................................... 57 Figure 38..Factors that Combine to cause Environmental Cracking ............................ 59 Figure 39 Example of a Stress Raiser......................................................................... 60 Figure 40 Stress Corrosion Cracking .......................................................................... 61 Figure 41 Chloride Induced Cracking of Austenitic Stainless Steel ............................. 63 Figure 42 Stress Corrosion Crack in Brass ................................................................. 63 Figure 43 Caustic Cracking of C-Steel and Inter-granular Micrograph of Fracture...... 64 Figure 44 Carbonate/bicarbonate Cracking Under Tape Wrap on a Pipeline.............. 65 Figure 45 SCC in Duplex SS Test Specimen .............................................................. 66 Figure 46 Typical SCC Data for Selection of Materials ............................................... 67 Figure 47 Illustration of Data from Crack Growth Tests............................................... 68 Figure 48 Hydrogen Embrittlement of Cadmium Plated Bolt (10 years Service) ......... 69 Figure 49 Canopy Collapse due to Hydrogen Embrittlement ...................................... 70 Figure 50 Molecular Hydrogen Gas Bubbles Formed in Most Acids but Diffusion of Atomic Hydrogen into Steel in Sour Systems..................... 72 Figure 51 Hydrogen Damage Processes .................................................................... 73 Figure 52 Diffusion of Hydrogen Atoms Through the Wall of a Tank or Pipe That Results in the Formation of a Blister....................................... 74 Figure 53 Hydrogen Blister.......................................................................................... 74 Figure 54 Hydrogen Induced Cracking (HIC) & Stepwise Cracking (SWC)................. 75 Figure 55 Sulfide Stress Cracking ............................................................................... 77 Figure 56 Pipe Rupture of Wet Sour Gas Line After 6 Weeks Service........................ 78 Figure 57 Alternating Tensile and Compressive Stresses in a Rotating Shaft ............ 81
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Figure 58 Curves of Stress Amplitude (S) versus Number of Stress Cycles (N) ......... 82 Figure 59 Appearance of Corrosion Fatigue Failure ................................................... 83 Figure 60 Steam Leak Failure in a Boiler due to Creep Rupture................................. 86 Figure 61 Liquid Metal Attack of Alloy 800 .................................................................. 88 Figure 62 Oxidation of 316 Stainless Fitting................................................................ 90 Figure 63 Effect of Sulfur Content on Corrosion Rates Predicted by Modified McConomy Curves in 290- 400 C (550-750F) Temperature Range...... 91 Figure 64 Modified McConomy Curves Show the Effect of High Temperatures on the Sulfidic Corrosion Rate of Carbon Steel and Various Chromium Steels .................................. 92 Figure 65 Mechanism for High-Temperature Sulfidic Corrosion.................................. 93 Figure 66..Sulfidation of Alloy 600................................................................................ 95 Figure 67 Effect of Hydrogen on Sulfidic Scales ......................................................... 96 Figure 68 Nelson Curves for High Temperature Hydrogen Attack ............................ 97 Figure 69 Diffusion of Carbon into Steel or Nickel Alloy and Resulting Cracks ........... 98 Figure 70..Carburization and Subsequent Brittle Failure of Reformer Tube from Ethelyne Plant after 20 days due to poor control of Decoking, 1100C ...... 99 Figure 71 Metal Dusting Pits ..................................................................................... 100 Figure 72 Hot Salt (Na2S4) Corrosion of 35Ni-19Cr-Cb Austenitic Steel at cyclic Temperatures between 150 - 927 C (300 - 1700 F) ................. 102 LIST OF TABLES Table 1 Failure Modes, Corrosion Damage and Loads ................................................. 9 Table 2 Saudi Aramco Corrosion Rate Guidelines ...................................................... 13 Table 3 Corrosion Potentials (Galvanic Series) in Flowing Seawater ......................... 20 Table 4 SCC Environments for Various Metals ........................................................... 62
CORROSION DAMAGE (THE VARIOUS FORMS OF CORROSION)

Most structures and oil/gas equipment are fabricated from C-Mn steels, an economic choice that carries potential risks from internal and external corrosion damage. The level of protection for any particular item/application must consider the material and the corrosive environment plus the desired service life, consequences of failure and financial requirements (life cycle costs and the rate of return on the investment). Some of the costs for corrosion control of C-Mn steel (use of inhibition, maintenance coatings, and replacement of galvanic anodes for CP), including increased inspection and repairs are delayed to the operational phase of the project. The alternative approach and employed for highly corrosive environments, is to use corrosion resistant alloys (CRAs) and materials but this requires increased investment during construction / fabrication. Understanding the causes of corrosion damage enables engineers to locate areas at risk and also identifies means of controlling future problems. There is seldom only one correct solution to a corrosion problem since each particular option depends on the risks, future benefits, time constraints and prior history/experience. Typical corrosion failures are presented below but further examples and case studies can be found in Forms of Corrosion edited by Aramco employees [1, 2]. Engineering Failures In engineering terms failures occur when equipment, items or components do not perform to either the design specification or to the operational criteria. All facilities have increased rates of failure when newly commissioned, or after a maintenance period, compared to normal operation. Failure rates also increase with age due to deterioration processes including corrosion.
Forms of Corrosion, Recognition and Prevention, Vol. 1, Edited by C. P. Dillon, Published by NACE International, Houston, TX. Forms of Corrosion, Recognition and Prevention, Vol. 2, Edited by D. R. McIntrye, Published by NACE International, Houston, TX.
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Much of the corrosion damage observed in practice is age related typical of the wear out phase of equipment and is often a combined result of fouling build-up (scales and biofilms), corrosion and fracture (metal wastage, pitting, grooving and cracking). Older equipment therefore requires increased inspection and monitoring to identify potential failures.
EARLY LIFE FAILURES AGE RELATED FAILURES
FAILURE RATE OR HAZARD FUNCTION
RANDOM FAILURES
START UP DATE
OPERATIONAL LIFE
Figure 1 Bath tub Curve of Failure Rate / Hazard Function versus Age Failure rate statistics, or probability of failures, are typically expressed in terms of probability density functions or hazard functions. Early life failures follow a hyper-exponential distribution or decay, random failures have a negative exponential or constant rate, whilst age related failures have a normal distribution. The "bath tub curve, Figure 1, combines these three failure types. Corrosion Risks A fundamental management process is the identification of hazards and use of risk assessments. A hazard has the potential to cause harm or damage. Produced hydrocarbons are flammable and some fluids also contain toxic hydrogen sulfide so that there is always a risk of death and injury from equipment failures in oil and gas production and downstream processing.
Saudi Aramco DeskTop Standards 7
Industrial risk evaluations as employed in risk based inspection (RBI SAEP-343 Risk-Based Assessment for In-Plant Static Equipment) and loss prevention, involves evaluation of potential hazards that may affect the business. These include safety risks, integrity of assets, environmental risks, financial risks from various decisions and risks from poor corrosion control. Risk is the combination of: 1. the severity of the effect (the consequences), and 2. the likelihood of it happening (failure mode and probable frequency). Risk (Criticality) = Effect (Consequences) x Likelihood (Mode) Failure criticality potential failure risks are examined to predict the severity of each failure in terms of safety, decreased performance, total loss of function and environmental hazards. Failure effect - potential failures are assessed to determine probable effects on performance and the consequences of component failures on each other. Failure mode - anticipated operational conditions are used to identify most probable failure modes, their likely frequency, damage mechanisms and locations. In the case of corrosion related failures the failure mode is the result of interaction of corrosion damage on operational and accidental loads. Corrosion is not a cause of failure but provides a major contribution to the mode of failure. Failures are usually the result of poor decisions in materials selection, chemical treating, inadequate inspection/monitoring, operation & maintenance. Corrosion damage is typically found as: uniform corrosion - metal loss due to general corrosion, for example, atmospheric corrosion / rusting galvanic corrosion - accelerated corrosion due to the effect of mixed metals or compositional/metallurgical factors as in the corrosion of weldments
localized attack - pitting, crevice corrosion, often the result of a small anode area in a large cathode flow induced corrosion erosion corrosion, cavitation, impingement attack, the result of high fluid velocities, changes in pressure and second phases such as sand environmentally assisted cracking cracks that initiate with specific metal environment combinations (stress corrosion cracking), corrosion fatigue
The relationships between the failure modes, corrosion damage and loads are illustrated in Table 1. Table 1 Failure Modes, Corrosion Damage and Loads Failure mode:
local leakage longitudinal / transverse rupture collapse or buckling
Corrosion damage (corrosion morphology):
uniform corrosion and erosion isolated pitting flow induced localised corrosion (mesacorrosion) & erosion longitudinal & transverse cracking longitudinal & transverse grooving (for example, weld corrosion)
Loads:
pressure (internal and external) forces (tensional / hoop stresses, compressive, bending / torsional) impacts (collisions, dropped objects)
Catastrophic failures / structural collapse / rupture of high pressure vessels and gas lines have obvious safety and environmental implications. These events are rare because codes of practice, safety standards / operational procedures aim to prevent extreme cases of failure. The industry is also making increased use of criticality and risk based methods that aim to identify potential failure modes and areas at increased risk (RBI), see Module 8 for further details.
GENERAL CORROSION (UNIFORM METAL WASTAGE)

General corrosion is attack over the entire exposed surface, or a large area, of a metal. The corrosion mechanism involves microscopic corrosion cells that comprise anodic areas of high metal content (for example, ferrite) and small associated cathodic areas (for example, iron carbide/cementite), Figure 2.
Electrolyte H+
Fe2+
Fe2+ Fe2+ e-
H+
Fe2+ eeCathode e-
Anode
Cathode Electrolyte Current Flow
Metal
Cathode Area Anode Metal
Figure 2 General or Uniform Corrosion Mechanisms
The metal loss is distributed uniformly across the exposed surface. The rate often decreases with time of exposure as semi-protective corrosion product films grow across the surface, for example, iron carbonate in CO2 systems or iron sulfide in H2S systems. In some acidic solutions, such as hydrochloric acid, a protective film is not formed and the corrosion rate increases with time as the cathodic cementite is exposed.
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Examples of general corrosion include active dissolution in acidic solutions, CO2 and H2S corrosion in produced waters, atmospheric corrosion, corrosion in boilers and natural environments. The assumption that uniform attack will occur is the basis of many designs that employ C-steel fabrications, the designer uses the concept of a corrosion allowance. Corrosion Allowance - the additional thickness above that required to retain the operational pressure. The aim is to provide time for metal wastage (general corrosion) during the life of the project. It assumes a gradual and controlled metal loss.
Corrosion Allowance Thickness for strength
Extra thickness that is lost during service life
Figure 3 Corrosion Allowance Concept
For example, linepipe specification API 5L lists wall thickness in 1.6 mm increments for 16 dia lines. If a thickness of 11.1 mm is required to contain the pressure then the wall thickness would have to be increased to 15.9 mm to provide a minimum corrosion allowance of 4 mm. In principle, general corrosion should be the easiest to deal with in terms of risk to an operation. Handbooks/data sheets are available, including the Aramco materials standards. Corrosion models that use spread sheets for assessment of rates in CO2 and H2S systems, both with and without inhibition, can also be used. An example of the prediction of general corrosion rates in CO2 systems is shown in Figure 4. Such models are used during the design process to assess the likely operational life and determine the required corrosion allowance.
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Figure 4 Predicted CO2 Corrosion Rates [3]
CO2 Corrosion Rate Calculation Model M-506, Norwegian Technology Standards Institution, http://www.nts.no/norsok
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In practice, the observed surface may look roughened and look like very shallow pitting, Figure 5, due to slight differences in local stress levels in the metal or minor variations in diffusion due to thermal convection/low flow rates.
Figure 5 General Corrosion Field Observations
Table 2 Saudi Aramco Corrosion Rate Guidelines General Corrosion Rate Rating Low Moderate Severe Very severe (py) <25 25 - 125 126 - 254 >254 (mpy) <1.0 1.0 4.9 5.0 10.0 >10.0 (py) <305 305 610 635 2438 >2438 Pitting Rate (mpy) <12 12 24 25 96 >96
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Note the corrosion units, either micron is 10-6 meter) or
py microns per year (a
mpy mils (thousandths of inch per year, 10-3 / yr).
Saudi Aramcos goal in oil/gas production systems constructed of C-steel is to keep average corrosion rates below 125py (5mpy). Higher pit penetration rates may be tolerated compared to the general corrosion rate. The concept is that pitting has to penetrate the full wall thickness to cause leakage, whereas general corrosion/metal loss over a relative large area could under high internal pressures result in local plastic deformation of the ductile steel and possible fracture/rupture. The failure mode with general corrosion is often rupture of pipelines, vessels or pipework due to thinning of the metal plus the operating pressure but sometimes the area of damage is limited and local leakage occurs. Inspection and monitoring for general corrosion includes:
Corrosion Inspection Methods
n tio er e ap
Corrosion Monitoring Methods
n se io ce oi n at N o a e i l t t a m is a lip r c ic nt er es riz m Ca Sc hy P pe ra a R c e l t i s t p e l o s al en In ch ra ne en on ho rP on al ro ric ig og -s og n Pe t l a t p r i u l a c c e w u d d e s tr e e te n Vi Hy Do Ra Ul Dy In Co El El Li
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Corrosion control will depend on the material of construction, the corrosive environment and the particular application. In most production systems C-steels are the materials of first choice because of cost implications. C-steels often require the use of corrosion control to mitigate the effects of corrosion.
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Methods used to Control General Corrosion Corrosion Control Use corrosion resistant materials Apply coatings Use corrosion inhibitors Apply cathodic protection Remove oxygen from environment Add corrosion allowance during design Internal Environments External Environments
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LOCALIZED CORROSION Galvanic Corrosion

Galvanic corrosion is the increase in corrosion that occurs when two dissimilar metals are electrically connected and exposed to a conductive corrosive environment. The two metals are called a galvanic couple. In a galvanic couple, the more active metal (lower potential) becomes the anode and corrodes faster. The metal with the higher corrosion potential becomes the cathode (the more noble metal) and is protected. Galvanic corrosion is represented by the illustration in Figure 6.
Anodic metal
Original surface
Cathodic metal
Surface after corrosion
Figure 6 Representation of Galvanic Corrosion Examples of galvanic corrosion include: Mixed metal combinations, iron / copper, galvanized steel / stainless steel, cathodic protection by sacrificial/galvanic anodes, Figure 6. Corrosion involving metallic coatings, cathodic coatings (galvanized or zinc rich paints) protect steel substrates by sacrificial action. Perforation of anodic coatings (nickel plate, tin plate in cans) causes accelerated substrate corrosion, Figure 7.
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Corrosion at repairs, replaced metals have a different metallurgical and surface condition, than the original corroded / filmed metal. For example, with new / repaired fittings welded to vessels / pipework the new / clean metal often becomes an anode and corrodes faster when put into service unless protected by inhibition or CP, Figure 8. Replacement rebar is cathodic in repaired chloride contaminated concrete. Corrosion of weldments, usual practice is to use a cathodic weld metal to prevent a small active anode area in a large cathodic area of parent plate. However, nickel containing weldments (used for strength in oil industry fabrications) that are cathodic can still exhibit high corrosion rates in CO2 environments of low conductivity (dilute brines and condensate lines), Figure 9.
Figure 7 Stainless Steel Fastener in a Galvanized Sheet Lack of Insulation Washer caused Accelerated Corrosion of Zinc Coating and Steel Substrate
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Current Flow Old Pipe New Pipe Old Pipe
Figure 8 Dissimilar Metal Couple Mechanism
Figure 9 Weldment Corrosion in a Condensate Line (CO2 system)
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Mechanism of Galvanic Corrosion Galvanic corrosion is caused by the potential difference between two dissimilar metals or between a weld metal and the parent plate. The metal with the more negative potential is anodic. It corrodes faster when it is part of a galvanic couple. The metal with the more positive potential is cathodic. It corrodes slower when it is part of a galvanic couple. Some combinations are engineered to allow the anode to corrode, for example, thin copper tubes and a thick steel tube plate. The corrosion potential of a particular metal varies in different environments and depends on temperature and electrolyte composition, the hydrogen ion concentration or the presence of oxygen. It cannot be assumed that a particular metal will remain anodic to another metal in all environments. Lists of metals arranged according to their corrosion potentials in a specific electrolyte are called galvanic series. A galvanic series for metals freely corroding in sea water is shown in Table 3. Potential values will vary depending on conditions (type of soil, sea water, soil, process fluid) and the reference electrode used. The magnitude of the coupling current (and the corrosion rate of the anode) depends on: 1. the relative corrosion potentials of the metals/alloys in a galvanic series for the particular corrosive environment, Table 3 the conductivity of the liquid electrolyte (low conductivity can intensify the local attack, see Figure 9) the ratio of the areas of the anode and cathode, Figure 10 (small anodes have higher metal loss/penetration rates) cell is driven by large current generated at cathode by corrodant.
2. 3.
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Table 3 Corrosion Potentials (Galvanic Series) in Flowing Seawater (Volts vs Saturated Calomel Reference Electrode, SCE)
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Note CRAs that rely on a passive film for protection can corrode by active corrosion (lower potentials as shown by the black boxes in the series). This can occur when a galvanic cell is set up between a crevice (anode no oxygen) and the outer metal surface (cathode dissolved oxygen environment). Area Principle - The area principle controls the rate of corrosion (current density) of each metal and the amount of current flow (galvanic coupling current) between the anode and cathode in a galvanic couple. The anode corrosion rate is the combination of its natural corrosion current plus the coupling current. The anode current density is the current divided by the surface area of the anode. The cathode current density is the current divided by the surface area of the cathode. For a given amount of current, the metal with the smallest area has the largest current density. For example, the current density of a small anode is very large. The current density of a relatively large cathode is very small. If a small anode is used with a large cathode, the anode will corrode very rapidly. The area principle, shown graphically in Figure 10, states that the anode corrosion rate increases with the ratio of the cathodic to anodic areas.
Anode Corrosion Rate 1
Ratio (Cathode Area / Anode Area) Cathode Area Anode Area
Figure 10 Area Principle for Galvanic Corrosion

Failure mode with galvanic corrosion includes local leakage, due to local metal thinning and perforation, and transverse rupture of pipes and pipework, due to grooving, the loss of weld metal in low conductivity CO2 systems and high velocity fluids.
Figure 11 Example of Design Detailing Required to Control Galvanic Corrosion
Corrosion inspection and monitoring for galvanic corrosion includes:

Corrosion Inspection Methods Corrosion Monitoring Methods
ce an
M e n is PR o t io L a N n e s e e d l t n a tio le ip ap is rm ic nt al po cr y ec es up a m u C S Pe h p r o R c e o t s i t p e l n C h l e a n C c o n en on ca al lI ge gr al -s ci nh Pe tro tri lig ro io ci ua l a e c c w r d d e e s e t e e t Sp Vi Hy El Do Ra Ul Dy In Sp El
Yes
No
Yes
Yes
Yes
No
Yes
No
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Methods used to Control Galvanic Corrosion Corrosion Control Use metals close together in galvanic series Do not use small anode areas with large cathodes Insulate dissimilar metals completely Apply and maintain coatings Use corrosion inhibitors Apply cathodic protection Add corrosion allowance to anodic sections or design for easy replacement Internal Environments External Environments
Intergranular Attack
Intergranular attack (IGA) is preferential corrosion at, or adjacent to, the grain boundaries of some alloys and metals (stainless steels, nickel alloys, chromium-nickel alloys and aluminum alloys). The driving force is the difference in corrosion potential (galvanic effect) between the matrix grains and the grain boundary. This is caused by differences in chemical composition, migration of impurities and formation of second phases during alloy manufacture and fabrication (examples include, Mg5Al8, CuAl2 in aluminum alloys, Fe3C, Cr23C6 in iron based alloys and stainless steel, and Mo6C in Ni-Cr-Mo alloys). Intergranular attack initiates at the surface but then develops as small pits and local cracks that follow the grain boundary. The crack width is sometimes widened by further corrosion and whole grains may fall out.
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Figure 12 Intergranular Corrosion of Pump Impeller Residual stress from fabrication can enhance the attack and local areas of stress assisted intergranular corrosion may be found. With rolled aluminum alloys the aluminum oxide corrosion product is trapped between the grains and exfoliation occurs (a form of swelling or laminar / layered corrosion discussed below). Extruded rods of ferrous and non-ferrous alloys are also prone to end-grain attack, another example of intergranular corrosion.
Figure 13 End Grain Attack (Intergranular Corrosion initiated in Crevice) of Washer fabricated from 420 SS after 3 years Wash Water Duty
The metallurgy and chemistry of the alloy is important for the control of IGA; heat treatments and cold work affect both grain size / shape and composition/location of constituents. Solution heat treatments (to just below the melting point) tend to dissolve alloying elements but rapid quenching holds elements in the super saturated solid solution and constituents tend to precipitate out. This precipitation of second phases is increased by heating during the rolling, drawing or welding process.
Sensitization and Weld Decay

Sensitization, the formation of chromium carbide precipitates (Cr23C6), occurs when some stainless steels (e.g., Type 300) are heated to 400 to 900 C (800 to 1600 F) in the rolling mill / fabrication shop or during site welding. In this temperature range, carbon rapidly diffuses to grain boundaries where it reacts with chromium to form chromium carbide (Cr23C6). This process is dependant on both the temperature and time that the metal is held at the temperature. The high temperature solid state reaction uses up, or depletes, chromium on both sides of the grain boundaries, Figure 14 and Figure 15. Chromium-depleted areas have lower corrosion resistance than the grains (these contain > 12% chromium). Stainless steels with > 0.02% carbon are susceptible to sensitization and IGA. For example, commonly used austenitic stainless steels (e.g., Type 316 and particularly 304) can contain up to 0.08% carbon. It is therefore often preferable too specify lo carbon L-grade stainless steels, <0.02% C.
Grain boundary Grain Grain
Chromium Carbide
Grain
Chromium carbide precipitate
Chromiumdepleted area
Grain
Grain
Figure 14 Representation of a Sensitized Grain Boundary in 304 Stainless Steel
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Figure 14 (a) is a plan of a sensitized grain boundary and Figure 14 (b) the cross-sectional view of the grain boundary. Chromium carbide forms at the grain boundary. The areas next to the grain boundaries contain less chromium. Corrosion occurs in the chromium-depleted areas. Sensitization associated with welding is often referred to as weld decay. The thermal cycles during welding results in carbide precipitation in the weld metal, fusion zone and parent plate parallel to the weld. Welding of stainless steels must follow special procedures to minimize problems.
Figure 15 Schematic Illustration of Weld Decay L grade austenitic stainless steels (304L, 316L) have a carbon content of <0.02% and are therefore less susceptible to sensitization. Other stainless steels contain stabilizers, alloying additions of titanium and niobium (Type 321 and 347) that form titanium or niobium carbides easier than chromium carbide.
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Exfoliation
Exfoliation is the unique form of intergranular attack that can occur on rolled aluminum alloys. Corrosion starts at the cut edges of rolled sheet and follows the parallel elongated grain boundaries. The corrosion damage has a leaf like appearance due to the growth of aluminum oxide corrosion product that forms between the grains.
Wing Skin (Aramco Aircraft) Figure 16 Exfoliation of Rolled Aluminum Alloy Sheet Age hardened aluminum alloys (e.g., the copper containing 2000 series) obtain their strength by controlled precipitation of fine, highly dispersed CuAl2 but this also produces a denuded zone adjacent to the grain boundaries. Corrosion resistance is improved by cladding the alloy with a layer of pure aluminum. Aluminum fabrications, such as ductwork, extractor fan blades aircraft skin and components are susceptible. Care must be taken to provide adequate protection (by use of anodized aluminum oxide coating produced by special electrolysis processes) but particularly at cut or drilled edges (use a sealant or organic coating). Failure mode with intergranular corrosion includes cracking, leakage and rupture. The initial corrosion damage causes loss of material and locally a decrease in strength. In some cases the intergranular cracks can become a site for the initiation of corrosion fatigue and stress corrosion cracks.
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Corrosion inspection and monitoring for intergranular corrosion includes:
Corrosion Inspection Methods

n tio c nt y pe ra t ic s ph e s n a n I r n o on al -s og Pe p i u a u r d e s t Vi Co Ra Ul Dy
Corrosion Monitoring Methods
n se e oi tio n nc a N o a e ti al st rm ic si iza e e r P R em la al en ch Po c g i o r o tr tr a dr ec ec ne y l l i H E L E
Yes
Yes
Yes
Yes
Yes
No
No
No
No
Methods used to Control Intergranular (Galvanic) Corrosion Corrosion Control Avoid temperatures that sensitization (400 900C). cause Stainless Steels & Nickel Alloys Aluminum Alloys
a a
Add alloying elements that form carbides easier than chromium (e.g., titanium or niobium). Lower the carbon content below 0.02%. Follow special welding procedures. Apply coatings
a a a
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Pitting Corrosion
Pitting is a term used to describe a range of phenomena. These often also include micro-biologically induced pitting corrosion and erosion-corrosion pits. The present discussion focuses on the attack of CRAs, aluminum alloys and rebar in concrete by chloride ions and pitting in sour systems. Pitting is a highly localized and intense attack that initiates at a break in the passive film / protective corrosion product layer. The break may occur at specific areas, for example, inclusions / discontinuities in the surface that cause a weakness as the film is formed, e.g. manganese sulfide inclusions in stainless steel. The growing pit is a small anode that is driven by the relatively large surrounding cathode area of protective film, Figure 17. Some pits grow a cap of corrosion product that partially covers the pit mouth whilst other pits retain the original passive film as a partial cover. The environment within the pit becomes acidic due to production of metal ions whilst the cathodic reaction outside the pit can cause a local increase in pH. Pits may continue to grow and cause perforation of the metal wall.
Original surface
Pit
Pit
Figure 17 Pitting Corrosion
29
CRAs/Passive Metals Pitting is a major concern for the specification of CRAs and alloys such as aluminum whose use depends on the maintenance of the passive layer rather than an assumed corrosion allowance. The corrosion morphology observed in the field can range from a large number of small shallow pits, Figure 18, to deep cavities and large hemispherical pits.
Figure 18 Pitting of 410 SS Bubble Caps & Tray (NGL stripper column), Typical of Pit Morphology on Stainless Steels and CRAs Exposed to Cl- & H2S, Pitting in sour environments starts at an area of film damage but then the amount of sulfide that diffuses into the growing pit is unable to re-grow the protective iron sulfide film. Higher pit penetration rates may be tolerated in C-steel fabrications compared to the general corrosion rate, see Table 2 Saudi Aramco Corrosion Rate Guidelines, page 8. Mechanisms of Pitting of CRAs The classic pitting example is stainless steel in chloride containing environments, for example, marine atmospheres and seawater, but the same corrosion process also occurs on rebar in chloride contaminated concrete and other metals.
30
Corrosion attack is initiated by the adsorption of chloride ions onto the passive protective oxide film. This causes local film dissolution (metal chlorides are more soluble than oxides) and/or cracking/rupture of the film (a process often called unstable pitting). Film rupture is increased at higher temperatures, in higher chloride ion concentrations and by an increase in the corrosion potential (often due to high oxygenated environments or the presence of oxidizing species such as ferric ions). Once the corrosion potential exceeds the pitting potential, Figure 19 (shown by the rapid increase in current at the upper limit of the passive region) for the particular material / environment combination then the pit is able to grow or propagate (a process called stable pitting). Chloride salts are more soluble than oxides and hence not only does the film dissolution process increase in the presence of chlorides but the film repair process in the growing pit is also limited.
500
E (mV SCE)
200
-100
-400 0 0.1 1 10 100 1000 10000
Log i (m A/cm 2 )
Figure 19 Polarization Curve of 304 SS in a Chloride Containing Solution showing Passivation, Film Breakdown Transients and the Pitting Potential
31
Laboratory tests/polarization curves are typically used to determine pitting potentials. The procedure is to progressively raise the potential of a test specimen by means of a potentiostat and record the potential current relationship. In Figure 19 the pitting potential is ~ +400 mV and the re-passivation potential (which indicates susceptibility to crevice corrosion) where the negative going curve cuts the passive region is about -100 mV. Pitting potentials (and crevice potentials) are strongly influenced by the temperature, Figure 21. Film breakdown current transients events in the passive region are sometimes seen before the large current increase showing the on-set of active metal dissolution at the pitting potential. Pitting processes can also be seen by monitoring the potential and current transients (electrochemical noise) produced on freely corroding probes. Film breakdown events (unstable pitting) are observed as an increase in current when the metal substrate is exposed but the current transient stops when the film is repaired locally by fresh corrosion product. Stable pitting is seen as a current flow and low potential transient that extends up to tens of minutes, Figure 20.
32
Figure 20 Electrochemical Noise Transients from Pitting Events The current flow that occurs following a film rupture event causes a rapid potential decrease (depolarization) as electrons flow in the metal from the freshly exposed anodic area to cathodic areas. The excess electrons are initially stored in the capacitor provided by the passive oxide film. Once the film repairs its self, by growth of fresh film locally, then further cathodic current removes the excess charge and the potential transient shows a recovery or re-polarization. Pitting is a stop-start process, it is more extensive and progressive in stagnant fluids, flowing liquids appear to wash out the growing pit (the turbulent flow probably removes any remaining passive film that covers the incipient pit mouth).
33
Pipe work and pumps fabricated from stainless steels that are kept in continuous service are often free from pits but can fail under stagnant (shut down) conditions. Some seawater pumps fabricated from alloys that contain lower nickel, chromium and molybdenum contents have to be washed down with clean water and kept dry when taken out of service. Pitting resistance equivalent number (PREN) These empirical relationships can indicate the resistance to pitting by quantification of the beneficial effect of alloying additions: PREN = %Cr + 3.3%Mo + 30%N
Figure 21 Resistance to Pitting & Crevice Corrosion with Alloying Additions A PREN can be used to indicate service temperature limitations as a function of the critical pitting temperature (CPT). Pitting of stainless steels and nickel alloys is a major corrosion concern in chloride containing environments (sea water systems, cooling waters, refinery process equipment and some downhole completions).
34
The higher the chloride concentration and temperature the greater the amount of Cr and Mo required in the alloy to control the pitting. Pitting potentials decrease with increase of temperature and hence all alloys have a critical pitting temperature (CPT) above which they are susceptible to pitting. For example, alloys that perform well in cold North Sea water may not be suitable for Arabian seawater duty. Protection of C-steel rebar in concrete relies on the maintenance of the passive iron oxide film. This film is not as protective as the chrome rich film on CRAs but provides long life in the strong alkaline environment in concrete. Localized pitting initiates from chloride induced film breakdown in marine and subka environments. Growth of these pits leads to larger macrocorrosion cell development followed by cracking and spalling of the concrete as the non-protective corrosion product film/rust grows on the rebar. Pitting in Sour Service
Figure 22 Corrosion Pit in C-Steel in a Sour System
35
Systems that contain significant amounts of H2S, even in the presence of CO2, have low rates of general corrosion. Sulfide ions essentially act as a corrosion inhibitor to provide protection against general corrosion by formation of iron sulfide films. A break in the sulfide film (a possible site for a pit) can give rise to a low sulfide concentration in the pit and no film repair. Although iron sulfide films make good cathodes and can drive the growing pit there are often no obvious indications of electrochemical noise (unstable pitting or stable pitting). Neither are pitting potentials from polarization data reported as with CRAs in chloride containing environments. The failure mode resulting from pitting corrosion damage is usually local leakage.
Corrosion inspection and monitoring for pitting corrosion includes:

Corrosion Inspection
ct io n ra et t li Ca pe
Corrosion M onitoring
an st i s ce oi lN se n tio a e
ti a ap rm ic iza cr e r m S Pe a R c e l t i e l o s a I en ch ra ol n en on rP on ric al ro ig -s og og nh Pe l t t a p i r l u a c c e u w r e d d s t e e te n Vi El Dy In Co El Do Ul Ra Hy Li pe ns y ph
Yes
No
Yes
Yes
Yes
Yes
Yes
No
No
Yes
No
Pitting is usually reported as depth of penetration or pit depth. Note that other forms of a pitting type of attack such as microbiologically induced corrosion and erosion-corrosion can not be discriminated by most inspection methods.
36
Methods Used to Control Pitting Corrosion Corrosion Control Use corrosion inhibitors & oxygen scavengers Coat vessels and pipes Use cathodic protection Keep equipment clean Select the proper alloy C-steels CRAs
Crevice Corrosion, Under Deposit & Under Insulation Corrosion

Crevice corrosion and under deposit corrosion is a localized attack that occurs in confined areas because of the restricted geometry. These include gaskets / flanges, Figure 23, fasteners, spaces behind rivets / lap joints, under any build up of debris / adherent deposits, under bio-films and scratches in coatings. Trapped stagnant liquids develop a different chemistry that is more corrosive than the original / outer environment.
Figure 23 Crevice Corrosion under a Gasket between Water Box and End Plate
Corrosion Mechanism Figure 24 shows the initial development of crevice corrosion between two metal plates bolted together in aerated sea water. At first, corrosion reactions occur over the entire surfaces of the metal plates. In the crevice the concentration of metal ions and hydrogen ions becomes higher and, in the case of natural environments/sea water, oxygen concentration becomes lower. However, the metal in the crevice continues to corrode. As more positively charged metal ions are formed in the crevice area they attract negatively charged chloride ions from the sea water. The metal ions (M+) and the chloride ions (Cl-) combine to form metal chlorides (MCl). Metal chlorides, particularly chromium chlorides, react with water to form acidic conditions that cause more metal ions to dissolve. MCl Metal + H2O Water MOH + Metal H+ClAcid
38
Aerated Seawater
O2
Na +
OH OH -
O2 M+
e e e M+ M+ e
CIOH -
O2
CI-
Na +
O2
OH -
M+ e
O2
OH -
O2
OH -
M+ M+ e O2
Na +
Figure 24 Initial Stage in the Development of Crevice Corrosion between Two Bolted Plates Each metal ion that goes into solution produces an electron. The electrons flow through the metal to cathodic areas outside the crevice. The electrons react with available oxygen to form hydroxide ions. The cathodic reactions protect the metal surface outside the crevice. However, the area inside the crevice continues to corrode. The major driving force for the increased corrosion current flow is the differential concentration cell between the outer environment and the crevice environment. The main controlling factor becomes the diffusion of ions in the restricted geometry. Crevice corrosion often starts slowly, but it progresses at an increasing rate.
O2 O2
Na
+
OH -
OH OH -
e e e
O2 O2 CI Na
+
CI CI CI H+
M+ O2
OH -
M+ CI M+ M+
M+ CI CI H+ M+
O2
O2
OH -
H+ CI -
OH -
M+
Figure 25 Later Stages of Crevice Corrosion Concentration Cell Materials that rely on passive films for protection are more susceptible to crevice corrosion in chloride containing environments than C-steel. CRAs are particularly susceptible because of the generation of nickel and chromium ions in the crevice, the diffusion of chlorides and generation of acidic conditions ion the crevice. It should also be noted that crevice corrosion occurs more readily than pitting on CRAs as shown by the differences in the critical pitting temperature (CPT) and critical crevice temperature (CCT) for the alloy, see Figure 21. This approach indicates the service temperature limitations. Corrosion resistance is improved by use of alloying additions, e.g. 3% Mo (type 316 stainless steel) and >5% Mo in nickel alloys. Typical problem areas for crevice type corrosion are: Crevices at flanges and gaskets on pipe work Crevices at support clips on instrument lines fabricated from lower grade stainless steels Under insulation (crevices produced between wet thermal insulation / fire insulation and metal surfaces of pipe work / vessels) Under deposits/sludges at the bottom of tanks and lines.
40
Failure mode is usually local leakage at the flange or region of deposit / wet insulation.
Figure 26. Perforation of Web of Pipe Bridge Support due to Corrosion under Fire Protection Insulation (a form of crevice corrosion)
Corrosion inspection and monitoring for crevice corrosion:

CorrosionInspection CorrosionM onitoring
n se e oi tio nc a N a e t l p ti n tio ip ra rm sis ica al iza nt po c e y ec e r a u m C S h P p la e o tr ic t s p e lR en ch ra ol ne Po lC en on ca l In i o e g h a s r g i r r a i og o n P a l t t i r c l u a e c c w d d e e s tr e e n te Vi Do Ra Hy Ul Li Dy In Sp El El
Yes
No
Yes
Yes
No
Yes
No
No
No
No
41
Methods Used to Control Crevice Type Corrosion Corrosion Control Design out crevices in new constructions Fill crevices by continuous welds, solders, sealants Apply cathodic protection immediately on immersion in sea water Keep equipment clean and thermal insulation dry Select the proper alloy C-steels CRAs
Fretting
Fretting is corrosion in areas of contact between two materials. The contact areas must be under a load and the surfaces must rub against each other to continuously remove the film of corrosion product. The rubbing action is only over a small distance, for example, when vibrations are transmitted to stationary bearings which means that the lubricating fluid is lost and fretting occurs on the bearing surface due to the small reciprocating motion. Fretting can occur under dry atmospheric conditions. The metal surface appears as pits and grooves surrounded by corrosion products. Fretting occurs in engine components, bolted parts, and other machinery. It has also been observed on pipe runs supported on PTFE pads. Mechanism Fretting is produced by very small movement (as little as 10-8 cm) between two materials which causes a combination of oxidation and wear. Most metal surfaces are protected by thin oxide layers (Figure 27) but when materials rub together under a load, the oxide layers break off and fall as debris. The surfaces fuse together at the contact areas and re-oxidize but when the two surfaces start to move against each other, the contact areas break into small pieces. Small pieces oxidize to form a residue.
42
Stationary
Exposed metal Oxide layers Cold Weld
Moving
Oxide particles
Figure 27 Fretting Between Two Surfaces
Visual inspection/microscopic examination are used to identify the problem. Control methods include removal of the cause of mechanical movement , use of rubber mountings, increased movement can improve lubricant flow between surfaces.
43
VELOCITY RELATED ATTACK
Background Fluid flow can cause corrosion (erosion-corrosion, impingement attack and cavitation damage) in pumps, process vessels, tubulars, pipe work and pipelines by various mechanisms. The corrosion damage is often seen as smooth grooves or waves in the metal surface (erosion-corrosion, Figure 30) but sometimes as roughened / sharp surfaces (impingement, Figure 34 and cavitation, Figure 37 and Figure 37). The processes involved are complex and involve an understanding of hydrodynamics, mass transfer processes and electrochemical corrosion principles. A basic overview is presented below to enable participants to appreciate the background to the modeling approach used in corrosion predictions and industry standards used to limit the effects of velocity related corrosion damage. Hydrodynamic Processes Fluid velocity is important but is only one parameter of many that determines corrosion in flowing liquids. Most equipment operates under turbulent flow. Turbulent flow in a pipe is defined by a Reynolds Number of >3,000. This dimensionless group is given by Re = vd/ where = viscosity, v = velocity, d = pipe diameter and = fluid density. The use of dimensionless groups or numbers is a standard engineering procedure that allows different hydrodynamic conditions (e.g. various pipe diameters) to be compared on the same basis. Turbulent flow means virtually all the fluid is highly mixed by eddy motion. Transfer processes between the bulk fluid and the wall take place across a thin boundary layer of stagnant fluid attached to the wall. With turbulent flow the boundary layer is continuously penetrated by eddies or vortices, that significantly increase the transfer processes (heat, mass and energy transfer).
44
Heat transfer at the wall causes heating or cooling/condensation of the fluid that can locally increase corrosion rates. Energy transfer to the wall (determined by the fluid to wall shear stress, Pa) is responsible for pressure drops / head losses in pipes. For example, the pressure drop P = 4 L/d over a length L is normally expressed by the dimensionless group ( / v2) and a dimensionless correlation can be used to relate momentum transfer to the velocity:
vd = 0.0395 2 v
0.25
The continuous impact of eddies can also cause fatigue cracking of corrosion product scales and this can lead to erosion-corrosion in some systems (high velocity lines and tubulars). Corrosion and Mass Transfer Processes Eddy penetration across the boundary layer increases the rate of diffusion at the wall of both corrodant (dissolved oxygen or acidic gas species) and reaction products (removal of ferrous ions), that in turn increases the rate of corrosion product film dissolution. The corrosion rate (icorr) at a film free surface is related to the mass transfer coefficient (k, m s-1) by the equation i = nFk(Cb - Cs) where F is the Faraday, n is the number of electrons in the reaction and Cb and Cs are the bulk and surface concentrations respectively. Momentum () and mass transfer (k) processes are similar (they are controlled by eddy transport across the boundary layer) hence both k and can be correlated to fluid velocity, v, using dimensionless equations of the form:
k v
2/3
= constant Re a v 2
45
The equation shows that corrosion rates are a complex function of velocity. This approach is the basis of corrosion predictions in CO2 systems (NORSOK model) but these are also modified by the effect of corrosion product films. Films decrease corrosion rates by controlling mass transport through the film, 1/Koverall = 1/kfluid + 1/kfilm (de Waard-Miliams and ECE models). The effect is seen in Figure 28. Film coefficients depend on film thickness and film porosity. The above transfer processes that cause increases in corrosion rates can occur with single phase fluid flow. Corrosion damage is often increased by the presence of a second phase, for example, particles (sand in produced fluids), liquid droplets in gas streams (gas wells and steam return lines) and gas bubbles in liquid streams (oil/gas wells). These can also give rise to erosion-corrosion and impingement attack as outlined below.
Flow Assisted Corrosion

Effect of fluid flow General corrosion rates increase as corrosive liquids pass through pipework or over metal surfaces. Corrosion rates are controlled by the concentrations of reactive species at the metal surface and the boundary between the film and the bulk fluid. Increased fluid flow increases the rate of transport of corrodent to the metal surface and also increases the rate of diffusion of metal ions away from the surface of the film. The effect of fluid flow on general corrosion is illustrated by the predicted corrosion rates of steel in a CO2 system, Figure 28.
46
Figure 28 Effect of Fluid Flow on Rates of General Corrosion The corrosion rate data in Figure 28, which uses shear stress as the fluid flow parameter, shows that corrosion increases significantly as the fluid flow increases from stagnation through laminar flow up to about 10 Pa. The rate of metal loss then increases more slowly under turbulent flow conditions at shear stresses greater than 20 Pa. The film has an increased influence on the corrosion process at high flow rates. Increased wall thinning is often seen at local areas such as bends and down stream of protrusions / flow disturbances. This is because of the higher turbulence intensity and regions of back flow with developing boundary layers or flow separation with unstable boundary layers. These conditions cause high mass transfer and high corrosion rates. These areas are also subject to erosion-corrosion, where the films are removed locally.
47
Measures to control flow assisted corrosion include the use of corrosion inhibitors, selection of resistant materials, decreasing the flow velocity, minimizing turbulence promoters (i.e. smoothing the hydrodynamics), installation of wear plates and baffles in vessels and tanks and design for replacement sections such as elbows.
Erosion- Corrosion
Erosion corrosion is the corrosion increase that results from loss of films under high velocity / highly turbulent fluid flow. A simple concept is that the fluid (a liquid, or a wet gas) washes away the protective corrosion film on a metal. In practice, the mechanism is more complex, high turbulence intensity increases the energy transfer from fluid to the wall / fluid to surface shear stress leading to the rupture of protective films, such as iron carbonate, by a fatigue mechanism. Increased turbulence also increases the dissolution rate of the protective film and sometimes even prevents the re-adsorption of the film forming species. Erosion-corrosion often causes a metal surface to have smooth grooves or waves with a directional pattern as shown in Figure 29. It is often observed as a pattern of undercut pits, Figure 30.
Original surface
Surface after corrosion
Flow
Figure 29 Representation of Erosion-Corrosion
48
Figure 30 Erosion-Corrosion of a Copper Alloy Tube, Seawater Cooling
Figure 31 CO2 Mesa Corrosion - a form of Erosion-Corrosion
49
Erosion-corrosion is characterized by a rapid increase in corrosion above a critical flow condition or velocity, Figure 32. The industry standard, API RP 14E, is also used in SAES-1-033 to asses the erosional velocity as given by:
Ve =
where:
C dm
Ve = fluid erosional velocity, feet/second
dm = density of the gas & liquid mixture at operating pressure and temperature, lbs/cu-ft C = an empirical constant where for C-steel C = 100 for continuous service, C = 125 for non-continuous service. (For solid-free fluids where corrosion is not anticipated or when corrosion is controlled by inhibition or by employing corrosion resistant alloys, values of "C" up to 150 to 200 may be used for continuous service. When "C" values higher than 100 for continuous service are used, periodic surveys to assess pipe wall thickness should be considered). Figure 32 illustrates the increase in corrosion rate in a brine / CO2 test at a C-value of ~100 equivalent to a shear stress of between 50 to 100 Pa.
50
Figure 32 Increased Metal loss due to Erosion Corrosion Erosion-corrosion cells may also be formed due to local turbulence or flow separation down stream of protrusions / bends or within valves or pumps or in the entry section of heat exchanger tubes. The effect is increased by multiphase flow, entrained bubbles and slugging. With C-steel fabrications the use of suitable corrosion inhibitor packages can control most of the observed metal loss rate, for example, in high production multiphase wells or pipelines with slug flow. However, as the flow rate increases even higher then the inhibitor effectiveness will decrease and may even fail.
51
Measures to control erosion-corrosion include the selection of resistant materials, decreasing the flow velocity, minimizing turbulence promoters (i.e. smooth hydrodynamics, use of slow bends), installation of wear plates and baffles, selection of appropriate inhibitors and design for replacement sections. CRAs require increasing amounts of Cr, Ni and W to provide protection against erosion corrosion in, for example, high velocity gas systems.
Figure 33 Erosion-Corrosion of CRAs in a Choke valve Well Test
52
Impingement Attack
The presence of second phase in a fluid, for example, bubbles and sand particle or liquid droplets in gas / steam lines, can impact on the metal surface. This can cause damage to the metal substrate and loss of protective films. Hard particles, scale / sand, may cause sufficient abrasion to produce sharp profiles or grooves in the substrate.
Solids in solution
Figure 34 Impingement Attack It is sometimes difficult to distinguish between erosion-corrosion and impingement attack. Erosion corrosion usually has a smooth surface profile whilst impingement attack often results in roughened surface (the surface of tubulars and lines that have suffered sand impingement usually have very sharp protrusions).
53
Measures to control impingement attack include the selection of resistant materials, filtering out unwanted solids, installing water traps in steam lines, installation of wear plates and baffles in tanks and vessels, and design for replacement sections.
Cavitation Damage
Cavitation in fluids results from the formation of fluid vapor bubbles followed by the bubble collapse. The vapor bubbles form in a low pressure zone and subsequently collapse (implode) in a higher pressure region. This causes a local hammering action and mechanical damage of surfaces. Repeated implosions of vapor bubbles on a surface can damage the protective film and locally deform metals. Mechanism At a given temperature, a fluid can exist as liquid and vapor at a pressure called its vapor pressure. Cavitation occurs when the absolute pressure at a point in the liquid decreases to or below the vapor pressure of the fluid. The process is seen when a fluid (water) is in a cylinder fitted with a piston (Figure 35).
54
1
Prote
Nucle
Corrosion occurs
Figure 35 Steps in Cavitation Damage The sequence of events that causes cavitation is: (1) The pressure on the water is reduced when the piston is pulled away from the water. If the pressure is reduced to or below the vapor pressure of the water, then voids or bubbles will form at nucleation sites. (2) When the piston is pushed against the water, the pressure increases and the bubbles collapse. (3) The collapse of a bubble produces very strong shock waves. Cavitation damage occurs when shock waves create holes (4) in the surface film and metal surface. (5) A new vapor bubble forms at the same place. (6) The bubble collapses and destroys the film. (7) The exposed area corrodes and the film reforms. Local pressure drops in pumps and at restrictions / expansions can cause cavitation (the formation of vapor bubbles from the flowing liquid). The local and intense concentration of collapsing vapor bubbles then damages films and metallic substrates.
55
These effects must be considered in the selection of pumps (need a net positive suction head) and the design and operation of plant and lines Figure 36. A poorly designed / maintained pumping system such as a control valve or a partially blocked filter upstream of the pump can cause damage as shown in Figure 37.
Figure 36 Cavitation Damage at T in an LPG line, caused by Mixing of Two Streams that Contained Traces of Water, (Better to allow Mixing in a Tank)
56
Figure 37 Cavitation Damage of Pump Impeller Control measures for cavitation damage include:
careful material selection: (1) use of hard metals, alloys containing high levels of nickel, chrome, cobalt and tungsten (work hardenable surfaces are more resistant) or (2) for some pump impellers use a soft rubber coating / plastic that adsorbs the cavitation energy operation at pressures below the vapor pressure of the liquid (good design is the key factor preventing cavitation but clogging of upstream filters can cause operational problems). good design to avoid areas of large hydrodynamic pressure differentials, includes smooth surface finishes
Pumps should be selected with appropriate suction heads, or be of a super cavitating pump design where the cavitation zone is formed beyond the pump impeller (as with outboard motors and hydrofoils). The use of resilient coatings which absorb cavitation energy (rubber lined pumps). The temporary injection of air or gas bubbles upstream of the pump can absorb cavitation forces in the fluid, this lowers the pump efficiency but protects the pump until an improved pump or design is employed.
57
Failure mode with flow assisted corrosion is leakage or rupture depending on the location and extent of the corrosion damage. Valves can experience thinning of internal components and linings whilst with pumps there will be excessive vibration due to loss of metal on the impeller. Corrosion inspection and monitoring for flow assisted corrosion includes:
C orrosionInspection
c pe s In tio
C orrosionM onitoring
is No e
s Vi
l ua
e i e ta l p to is at m t li p ca ra r ni z s i n a i c e y o e r a m C S h P a r M l e t ic t p e lR en ra ch ol ne Po en on ns on ca g i e o i g h s g r o t r r i o o n P t a t a ll w up di e dr tra ec br ec te ne Do El Ra Dy In Co Li El Vi Ul Hy
Y es
N o
Y es
Y es
Y es
Y es
Y es
Y es
Y es
Y es
N o
Y es
Methods Used to Control Flow related Corrosion Damage (erosion-corrosion, impingement & cavitation) Corrosion Control Design within erosional velocity limitations Improve flow design, use slow bends, minimize local high turbulence intensity areas Use specially selected corrosion inhibitors Increase corrosion allowance on elbows, etc Apply coatings Apply cathodic protection Select materials with better protective films Remove / filter out solids, reduce water droplets in steam Design to minimize hydraulic pressure difference, use pumps with appropriate suction head C-steels CRAs
58
ENVIRONMENTALLY ASSISTED CRACKING
Environmentally assisted cracking, sometimes called environmental fracture, are general terms that encompasses various phenomena such as stress corrosion cracking (SCC), sulfide stress cracking (SSC), hydrogen cracking or hydrogen embrittlement, and corrosion fatigue. The material cracking process is the combined action of a corrosive environment, temperature and mechanical stresses. Many fatigue induced failures are probably corrosion fatigue cracks due ingress of water or corrosive liquids, often the result of poor detail design or poor maintenance practice.
SUSCEPTIBLE MATERIAL
CORROSIVE ENVIRONMENT
SCC
STRESS RESIDUAL & APPLIED
Figure 38..Factors that Combine to cause Environmental Cracking
59
The stresses may be static (residual stresses from welding during fabrication or repair), applied (the working load) or fluctuating (the normal operating condition with rotating equipment and piping systems carrying pumped fluids). Surface defects, sharp corners and corrosion pits can act as stress raisers, Figure 39. Stress raisers concentrate tensile forces at local areas. Some environments are not only able to initiate local attack that form pits but can then produce local corrosive conditions in the pits that accelerate the corrosion damage by a cracking process.
Figure 39 Example of a Stress Raiser
A major concern with environmentally assisted cracking is premature failure of components because of rapid propagation of cracks. It is therefore important when selecting materials for service in corrosive environments that appropriate Aramco standards are used. In some applications it is vital that a corrosion expert is consulted and a literature check is carried out to eliminate materials susceptible to stress cracking.
60
Stress Corrosion Cracking (SCC)

Sress Corrosion Cracking is caused by the combined action of a mechanical load / tensile stress plus a specific corrosive environment and temperature on a susceptible alloy. Stress corrosion cracking (SCC) may be considered as a brittle type of failure in what is a normally ductile material.
C o r r o s io n p ro d u c t film M 2+
M 2+ T e n s ile F o rc e s A d v a n c in g c ra c k
T e n s ile F o rc e s
M e ta l
Figure 40 Stress Corrosion Cracking
Residual stress alone may promote this form of attack, for example from welding during fabrication, hence it can occur without applying an external load. SCC is a severe form of localized corrosion that gives rise to transgranular cracks (hydrogen embrittlement or active metal path dissolution), intergranular cracks (differences in composition due to segregation), or both, see for example Figure 41 to Figure 43.
61
Most alloys will undergo stress corrosion cracking in specific corrosive environments, Table 4 SCC Environments for Various Metals. Some combinations are of particular concern in oil/gas production, for example, hydrogen cracking and sulfide stress cracking. Some environments are formed during shut down, for example, polythionic acid produced from reaction of sulfide deposits with atmospheric oxygen in hydrocrackers and catalytic reformers. In practice SCC can appear to be unpredictable in that minor changes of composition or heat treatment can affect the susceptibility. Advice from a corrosion specialist should be obtained for specification of materials to control SCC.
Table 4 SCC Environments for Various Metals Alloy Carbon steel High-strength steels Austenitic stainless steels High-nickel alloys Copper alloys Aluminum alloys Titanium alloys Environment Hot nitrate, hydroxide, carbonate solutions Aqueous solutions that contain H2S Hot chloride solutions, acid chloride solutions (e.g., MgCl2, BaCl2), contaminated steam High purity steam Ammoniacal solutions, ammonia vapor, amines Aqueous Cl-, Br-, and I- solutions Aqueous Cl-, Br-, and I- solutions, organic liquids, N2O4 Aqueous Cl- solutions
Magnesium alloys
62
Common problems include trans-granular / inter-granular SCC of austenitic stainless steels in chloride containing environments (seawater and oil field brines) at above 60C, Figure 41.
Figure 41 Chloride Induced Cracking of Austenitic Stainless Steel Copper alloys in contact with fluids that contain ammonia or amines are often at risk from SCC. Early examples were see in the mid 1800s by the British Army in India where brass cartridge cases in contact with ammonia vapors cracked in humid monsoon conditions (season cracking of brass).
Figure 42 Stress Corrosion Crack in Brass

Caustic cracking of carbon steels occurs in the presence of sodium hydroxide at elevated temperature, >46 C (115 F) depending on the caustic concentration but at > 5% NaOH is highly likely at > 82 C (180 F). The key factor is usually the local metal temperature.
Figure 43 Caustic Cracking of C-Steel and Inter-granular Micrograph of Fracture
Cracking can occur in C-steel distillation columns where caustic is used for pH control, off-line were equipment corrodes during steam cleaning or where steam tracing lines are left heated, in boiler feedwater equipment , including piping bolts where water leaks occur past gaskets. Post-fabrication stress relieving (Post Weld Heat Treatment, PWHT) is a major control method. Many early catastrophic failures of caustic cracking were in the 1800s with riveted steam raising boilers. Heated crevices tended to concentrate sodium ions from the water and cause a build up of hydroxyl ions. Remedial action was the introduction of appropriate water treatments.
64
A major cause of failure of older Aramco pipelines (>20 y) is external SCC referred to as carbonate / bicarbonate cracking, Figure 44. This is due to the slow pH change that occurs next to steel exposed to soils due to coating damage or tape wrap disbondment. The pH change is the result of oxygen reduction and occurs both with and without CP. Many old lines are now being recoated to mitigate the risk of failures.
Figure 44 Carbonate/bicarbonate Cracking Under Tape Wrap on a Pipeline
SCC Mechanisms The three basic mechanisms include: (1) Active path corrosion where the protective film is fractured by the stress allowing active metal dissolution at the crack tip Hydrogen embrittlement where the hydrogen produced by a corrosion reaction diffuses into the metal and embrittles the zone in front of the crack tip Film induced cleavage where the film undergoes brittle failure and the propagating crack penetrates the metal.
(2)
(3)
65
The morphology - transgranular cracks or intergranular cracking, is a characteristic of the specific metal-environment combination. Segregation at grain boundaries means different local corrosion behavior and possibly inter-granular active path dissolution or hydrogen embrittlement. Trans-granular cracks look like cleavage along crystallographic planes, this suggests a film induced cleavage or hydrogen embrittlement process. Research is continuing to provide understanding of SCC mechanisms. Laboratory testing can provide guidance on the use of materials and information on cracking phenomena. A typical test specimen used in testing is shown in Figure 45, the specimen is pre-loaded to a known applied stress value and immersed in the test solution.
Figure 45 SCC in Duplex SS Test Specimen
66
Figure 46 Typical SCC Data for Selection of Materials
Mechanical and corrosion processes are illustrated from predictions of crack propagation rates determined from plots of stress intensity factor, K, versus log (crack velocity), Figure 47. Crack growth does not occur below a threshold stress intensity factor, KIscc. Increasing the load causes the crack velocity to increase until it is limited by the corrosion reaction rates. As K approaches Kc, (the critical stress intensity factor for fracture in an inert environment) mechanical fracture processes increase the crack velocity and crack velocity increases again.
67
Figure 47 Illustration of Data from Crack Growth Tests
Dissolution processes can limit the rate of metal dissolution in a crack, so aluminum (a reactive metal) has a maximum crack growth rate of ~10-6 m/s. For hydrogen embrittlement (hydrogen induced SCC) the limiting factor is hydrogen diffusion at the crack tip and crack velocities can be up to 1 m/s.
68
Hydrogen Embrittlement (HE)

Hydrogen embrittlement occurs when hydrogen atoms diffuse into a metal and cause a loss of ductility and tensile strength. This conversion of a ductile steel into a brittle type material can result in sudden failure, for example, cracking / fracture, Figure 48 and Figure 49. Metallurgical factors can influence susceptibility. High strength body centered cubic materials are more susceptible with face centered cubic materials (austenitic steels) being less susceptible. Quenched and tempered C-steel (hard material) is susceptible to hydrogen embrittlement. Cracking takes place above the critical tensile stress. Even atmospheric corrosion can generate sufficient atomic hydrogen to embrittle high tensile fasteners and cause failures, Figure 48.
Figure 48 Hydrogen Embrittlement of Cadmium Plated Bolt (10 years Service)
A major catastrophic failure was the collapse of a large canopy over the entrance of the Berlin Congress Hall, Figure 49, the result of water penetration onto high strength steel tendons.
69
Many post-/ pre-tensioned concrete structures such as pretensioned and post-tensioned bridge beams, bund walls and concrete pipes (where high strength steel wire is spirally wound and covered with mortar) have failed catastrophically when the steel has become exposed to rain water due to loss of concrete / mortar cover.
Figure 49 Canopy Collapse due to Hydrogen Embrittlement
High strength wires, used in civil engineering constructions for ground anchors and for pre-tensioned concrete beams, are usually produced by a patenting process (a drawn pearlitic structure) that is more resistant to damage by hydrogen. Ground anchors used in wet saline conditions are usually designed with double protection against water ingress. High strength steel fabrications are particularly at risk from hydrogen embrittlement. Examples include nodes on offshore platforms from hydrogen generated from impressed current cathodic protection systems that are providing over protection.
70
Post-weld Cracking due to HE Cracking can also occur post fabrication due to the introduction of hydrogen produced during welding of moist surfaces. Steels with higher carbon content are more susceptible to cracking caused by hydrogen entry during welding. Hydrogen generated in arc welding from the welding flux dissolves more readily in the liquid weld metal as atomic hydrogen than in solid metal but after the weld metal solidifies, the atomic hydrogen will diffuse from the weld metal into the heat affected zone where higher stresses may lead to failure from hydrogen embrittlement.
Measures to control stress corrosion cracking include: (1) Careful material selection, usually the most cost effective method. For example, duplex and ferritic stainless steels are more resistant to chloride induced stress corrosion cracking than austenitic stainless steels. Reduction of the stress, can be effective if caused by residual stresses, for example post weld heat treatments Modification of the environment, not always possible Lower the potential to below the SCC range cathodic protection and even inhibition can control some processes.
(2) (3) (4)
71
Hydrogen Damage Of Oil Field Equipment In Sour Service

Hydrogen damage is not a specific form of corrosion. It is a general description of the corrosion related damage found in sour systems - hydrogen embrittlement, hydrogen-induced cracking (HIC), blistering of steel, sulfide stress cracking (SSC), stress orientated hydrogen induced cracking (SOHIC). In most acids hydrogen generated by the corrosion reaction is produced as gas bubbles in the process fluid but in sour systems the sulfide film assists the atomic hydrogen to diffuse into the steel, Figure 50. Only the hydrogen atom (H) is small enough to diffuse through metal. Cyanides and arsenic compounds in the electrolyte also inhibit the formation of molecular hydrogen and help hydrogen to enter into steel. Once a hydrogen atom enters the metal several damage processes may occur in a susceptible steel, for example, blistering, Figure 53, and HIC, Figure 54.
Acid Solution
H+
H2 H+
Fe 2+ H Anode Fe2+ H+ H+ H Cathode
e Metal
H H H
Figure 50 Molecular Hydrogen Gas Bubbles Formed in Most Acids but Diffusion of Atomic Hydrogen into Steel in Sour Systems
72
In a susceptible steel the atomic hydrogen can form molecular hydrogen gas at a void or other defect. The build up of pressure from molecules of hydrogen gas trapped at the defect in the steel can cause a blister as found in older low-strength steels, Figure 52. Hydrogen blisters seldom lead to rupture of metal walls and they rarely cause brittle failure.
Hydrogen Induced Cracking
HIC Stepwise Cracking Hydrogen Blistering
Sulfide Stress Cracking
SSC A form of stress corrosion cracking often associated with high hardness and high stress, for example welds
Stress Orientated Hydrogen Induced Cracking
SOHIC Combination of HIC and SSC
Figure 51 Hydrogen Damage Processes
73
Air
Void H2 H H2 H2 H H2 H2 H H2 H H2
Metal
H2 H H2 H
Blister
H2 H2 H2
H2 H Hydrogen atom
Figure 52 Diffusion of Hydrogen Atoms Through the Wall of a Tank or Pipe That Results in the Formation of a Blister
Figure 53 Hydrogen Blister
74
The hydrogen gas molecules trapped at the defect can also give rise to hydrogen induced cracking (HIC) and stepwise cracking (SWC) in susceptible steel, Figure 54. The process is again due to the high internal hydrogen pressure and increased local stresses that cause adjacent small blisters to link up.
Figure 54 Hydrogen Induced Cracking (HIC) & Stepwise Cracking (SWC)
HIC tends to link up long adjacent cracks by a ductile tearing to form stepwise cracking. With older steels, that have a banded type of microstructure, HIC (along the centre line) and blisters (close to the surface) invariably form along the rolling direction with cracks aligned parallel to the surface. Modern manufacturing specifications can now produce C-Mn steels that meet demands for increased strength, low temperature toughness, weldability and increased resistance to hydrogen sulfide. Use of clean steels, control of inclusions and alloying additions, modification of casting processes and multistage rolling to optimize grain refinement (thermo-mechanical treatments plus accelerated cooling) produces a microstructure that has high strength and small grain size that is less susceptible to HIC in sour service.
75
Sulfide Stress Cracking (SSC)

Sulfide stress cracking is the term used by the oil and gas industry for the stress corrosion cracking that occurs in sour environments. SSC is a special case of hydrogen stress cracking a form of hydrogen embrittlement. Hydrogen enters the steel when the metal corrodes in sour oil field waters. Hydrogen entry may be increased by cathodic protection in sour environments. Temperature affects sulfide stress cracking, hydrogen embrittlement and hydrogen-induced cracking of steels in H2S service. SSC and hydrogen embrittlement are most likely to occur at temperatures up to 65C (150F). Sulfide stress cracking (SSC) affects high-strength carbon steels with a hardness above 22 Rockwell C. Other alloys have different hardness limits in sour environments. Sulfide stress cracks may begin at surface notches or pits on the metal surface (Figure 55). Cracks can also begin within the metal at discontinuities or defects such as inclusions, carbides, or grain boundaries. Both tensile stresses and hydrogen entry into the steel are required for SSC to occur.
76
H y d ro g e n a to m s
H H H
H H H H
H H
H H
A d v a n c in g c ra c k
M e ta l
Figure 55 Sulfide Stress Cracking
SSC does not occur below a certain threshold stress intensity for a particular metal structure. Increasing the hydrogen pressure within the metal increases the chances for SSC. SSC is also most likely to occur at temperatures of about 20C (70F). Failures due to SSC do not always occur rapidly.
77
Stress Orientated Hydrogen Induced Cracking (SOHIC)

SOHIC is where a stacked array of small blisters are joined by hydrogen induced cracks aligned in the through-thickness direction of the steel. The main feature is that the cracks propagate along the heat affected zone of the seam welds in spirally wound pipe. The process can be considered as a combination of hydrogen induced cracking and stepwise cracking, and in some cases, the hydrogen embrittlement form of stress corrosion cracking. It usually occurs in the base metal adjacent to the HAZ where residual stresses (from welding) and from the applied stresses (operating pressure) are highest. High residual stress combined with stress raisers caused by the geometry of the weld crown can accelerate the initiation processes.
Figure 56 Pipe Rupture of Wet Sour Gas Line After 6 Weeks Service
78
The line shown in Figure 56 had a further 20 failures during hydrotesting following repair. The line was de-rated to limit the hoop stress to <25% of specified minimum yield stress and corrosion inhibitor was injected at 4X normal dose rate to minimize the generation of hydrogen. Resistance to H2S and HIC The concern in sour service is hydrogen damage, HIC and SSC. The industry standard NACE MR0175 defines hydrocarbon sour service as a H2S partial pressure greater than 0.05 psia or more than 2 ppm in the water phase. Seamless pipe is inherently more resistant to HIC (not made from rolled plate material). Welding Changes in the microstructure or chemical composition of the weld area can lead to failures unless precautions are taken. For example, martensite may crack under certain conditions and improper welding procedures can result in cracking failures in wet, sour environments due to sulfide stress cracking and stress-oriented hydrogen induced cracking. Failure in the weld or heat-affected zone may be minimized by properly post-weld heat treating the welds. Hydrogen Damage Processes include: (1) Hydrogen is generated through corrosion, overprotection by CP, during electroplating and by microbial activity of SRB Diffusion of atomic hydrogen into susceptible steels can lead to embrittlement In sour systems atomic hydrogen can also lead to blistering and cracking, caused by the inward diffusion of atomic hydrogen into the metal, that then forms molecular hydrogen at voids Sulfide stress cracking (SCC) occurs in high strength materials above a critical tensile stress
(2) (3)
(4)
79
Failure mode with cracking and hydrogen damage can be sudden and catastrophic involving collapse of civil structures, rupture of vessels and lines, although in some cases a leak may be detected when the crack tip penetrates the wall. Corrosion inspection and monitoring for hydrogen damage includes:
Corrosion Inspection
n io ct e p s er lip er ap
Corrosion Monitoring
c an n t io oi lN se io at
s e a st a on r rm ic si iz nt a p c e y e r a m u C P la e tr o tS ic ph e lR ns en ch ra ne ol Po en lC on ca lI g o e g i h a g r s r a i r i o o P n t a t ll w dr e di ec su tra ec ec te ne Vi In Li El Hy Dy Sp Ul Ra El Do
Yes
Yes
Yes
Yes
Yes
Yes
No
No
Methods Used to Control Environmental Assisted Cracking Corrosion Control Select materials / welding procedures that are resistant to SCC, HIC & SSC Use corrosion inhibitors Remove corrosive agents Apply coatings Apply cathodic protection, provided that mechanism is anodic dissolution Change design or decrease the load / stress C-steels CRAs
80
Corrosion Fatigue
Corrosion fatigue occurs when corrosion reduces a metals ability to support alternating stresses. The applied stresses may alternate between equal or unequal values of tension and compression. A rotating shaft that supports a load is an example of alternating tension and compression (Figure 57). Oil field drill strings used to drill wells often fail because of corrosion fatigue.
Load
Compression
Tension Bearing Support Bearing Support
Figure 57 Alternating Tensile and Compressive Stresses in a Rotating Shaft Corrosion accelerates the fatigue process as illustrated by S-N curves, Stress Amplitude (S) versus Number of Stress Cycles (N), for materials in air compared with a corrosive environment, Figure 58. For example, fatigue is more common in environments that cause pitting. Mechanism Metals that support alternating loads are susceptible to fatigue even when corrosion is not present. Alternating loads cause very small cracks to form. At first, a crack grows very slowly. Later, the crack grows to the point where stresses cause it to grow rapidly. If the material is brittle, the crack can cause rapid fracture.
81
Figure 58 Curves of Stress Amplitude (S) versus Number of Stress Cycles (N)
Pits often start cracks in the metal, the pit acts as a stress raiser. The cracks begin to grow as the structure undergoes cycles of tension and compression. Sometimes, cracks grow across grains and grain boundaries. Cracks reduce the cross sectional area of the metal. The metal fails when it cannot support the tensile load.
82
Initiation site ( corrosion pit or mechanical damage ) Smooth surface ( with bench marks )
Rough fracture surface
Figure 59 Appearance of Corrosion Fatigue Failure
83
Fatigue cracking involves movement at slip planes and possible fracture of brittle inclusions that then act as crack nuclei. The fatigue crack growth may be predictable using linear elastic fracture mechanics. When corrosion is present the crack growth rate increases and the mechanisms proposed are similar to those in stress corrosion cracking: for example, hydrogen embrittlement, anodic dissolution and film induced cleavage. Corrosion fatigue failures have a characteristic appearance often referred to as beach marks due to the ripple effect. Under the microscope or electron microscope the fracture surface may have ductile striations, as expected if the surface was fractured in air, and also brittle striations, due to intermittent cleavage with arrest marks corresponding to each cycle. Sometimes intergranular fracture associated with hydrogen embrittlement or active path dissolution may also occur. Failure mode with corrosion fatigue may be sudden and catastrophic, but often the cracks may take years to propagate, shafts will fracture, structures can collapse and lines rupture.
84
HIGH-TEMPERATURE DEGRADATION AND CORROSION

High-temperature corrosion of carbon steels can be a problem at temperatures above 260C (500F) but is a particular concern at temperatures above 500C (900F). High-temperature corrosion is rarely found in upstream petroleum production operations because temperatures seldom reach 260C (500F). High-temperature corrosion occurs on the flame side of boiler plant or in refinery operations that process hydrocarbon gases, especially where gas streams contain reactive chemicals or pollutant mixtures of oxygen, sulfur compounds, halogen gases (chlorine) and carbon. Some compounds can deposit on metal surfaces as molten salts and cause hot corrosion. Molten salt problems are the result of naphthenic acids and vanadium salts in oils or from sodium sulfate produced from sulfur compounds. Typical high temperature damage processes are:
Microstructural changes and embrittlement grain growth, hardening, sensitization, sigma phase formation, liquid metal embrittlement Oxidation reaction with a hot environment, usually containing oxygen and/or pollutants Sulfidation - sulfidic corrosion caused by sulfur compounds Carburization diffusion of carbon into the metal, particularly in the presence of hydrogen Hot corrosion corrosion under molten salts, sodium sulfate and vanadium oxides
The high temperature corrosion processes are typically controlled by the type/ chemical stability of corrosion product scales and solid state diffusion of species through the scales.
85
High Temperature Micro-structural Changes and Embrittlement

Creep is a continuous deformation over a period of time at a critical stress and is accelerated at elevated temperatures. For example, steel alloys become susceptible to creep above 370 C (700 F). Increasing the molybdenum content increases creep resistance up to 530 C (1000 F). At higher temperatures low alloy steels oxidize rapidly and highly alloyed steels and alloys are required for resistance to both corrosion and creep. The design of vessels and piping systems for use at elevated temperatures are covered in design codes. However, creep and rupture of tubes, Figure 60, can still occur due to poor burner settings, flame impingement, fouling by coke deposits inside pipes, inadequate control of air and steam during thermal decoking and insufficient spacing that causes tubes to sag.
Figure 60 Steam Leak Failure in a Boiler due to Creep Rupture
86
Grain growth at higher temperatures will decrease the tensile strength but increase both creep and rupture strength. This effect becomes significant with c-steels above 730 C (13350 F) and above 900 C (1650 F) for austenitic stainless and high nickel-chromium alloys. Grain growth is used in metallurgical examinations to identify previous local over heating. Hardening of steels with >0.25% C is due to martensite formation that occurs when steel is heated to above the upper critical temperature followed by rapid cooling, a problem during welding and severe overheating as in a fire. Sigma phase embrittlement is due to formation of the ironchromium brittle phase (FeCr) from ferrite in high chromium alloys and austenitic stainless steels (>17% Cr) during heating to 430 540 - 815 C (1000 - 1500 F) for short periods or 370 C (800 F) for extended periods. This increases the tensile strength and hardness but also decreases the ductility to the point of brittleness. Sigma phase embrittlement causes cracking on cooling from operational temperatures in cast supports and tubes in process heaters, pyrolysis furnaces, catalytic regenerators or after welding of Type 316 and 347 stainless weldments. Limiting the ferrite content of stainless to <10% will help prevent the problem and ASTM A447-50 provides further guidance for control of sigma phase formation. Liquid metal attack and embrittlement are forms of accelerated metal loss and embrittlement that can result in catastrophic failure of a normally ductile metal. This occurs with alloys in contact with specific liquid metals, for example, copper alloys exposed to mercury (found in some crudes) and austenitic stainless steels exposed to molten zinc or aluminum (during welding or a fire).
87
Figure 61 Liquid Metal Attack of Alloy 800
The chrome nickel alloy in Figure 61 was from an ethylene reformer pipework operating at 925 C (1700 F). The thermal insulation was improperly fitted so that hot air heated the outer aluminum weather cover. The aluminum melted and ran on to the hot pipework.
88
High Temperature Oxidation

High-temperature corrosion reactions occur when a metal is exposed to hot gaseous environments. The reactions are different from aqueous electrochemical corrosion reactions as water is not present to from an electrolyte. The initial reaction is direct metal oxidation with reduction of the corrosive component of the gas. The rate increases as the temperature increases but is also controlled by the thickness and the type of corrosion product scale produced. Oxidation is a general term to describe a reaction between alloys and hot gaseous environment that contains oxygen, sulfur, chlorine, etc. In the present context the term is restricted to gas environments that contain mainly oxygen. Oxidation resistance of alloys depends on the presence of alloying additions of chromium, aluminum and silicon that form protective scales on the metal surface. Increased levels of pollutant gases, such as sulfur compounds, produce mixed corrosion products rather than protective oxides and these can result in corrosion damage. Alloys for high temperature service include: High alloy steels (austenitics) - 304,321, 347, 310,alloy 20 Nickel base alloys Ni-20%Cr, Inconel, Incoloy, Nimonics Cobalt base alloys Co-30%Cr, Stellites In oxygen atmospheres the scale formation starts with an initial / transient stage (linear rate versus time, t) followed by a decrease in rate with time and the establishment of a steadystate scale (a parabolic rate law x2 = kt where the rate of reaction inversely proportional to scale thickness, x). Low alloy steels in oxygen environments, as in boiler plant and some high temperature refinery processes below 260C (500F) rely on protection by Fe3O4 scales, but above 570C (300F) FeO becomes stable and the oxidation rate increases rapidly. Many alloys rely on Cr2O3 or Al2O3 for protection at higher temperatures. Ni-Cr alloys with 20 to 40% Cr develop Cr2O3 below the initial transient NiO-rich scale.
89
Above 900C Cr2O3 oxidizes to the volatile CrO3. Ni base alloys need >15% Cr and <3%Al to become Cr2O3 formers and >5% Al and ~ 5% Cr to become Al2O3 formers. Al2O3 scales are susceptible to cracking and spalling in service at high temperatures unless reactive elements such as yttrium or cerium are added to the alloys.
Figure 62 Oxidation of 316 Stainless Fitting The furnace outlet manifold fitting, Figure 62, was thermally insulated which caused a temperature increase to 850 C (1500 F). Mo in 316 can oxidize at 775 800 C (1420 1470 F).
Sulfidic Corrosion
High-temperature corrosion caused by oxidation from sulfur compounds is called sulfidic corrosion. Most high-temperature corrosion in refineries is caused by sulfur containing gases produced by sulfur compounds in crude oil. Sulfur compounds are usually reported as total weight percent sulfur. There are many types of sulfur compounds in crude oils. Most of these compounds are converted to H2S under refinery conditions.
90
The formation of liquid sulfides can destroy protective scales locally and may penetrate the alloy in an intergranular manner. Even if the sulfide does not form a melt on the surface of the metal in the diffusion of metal ions in the scale can be rapid giving high rates of scale growth and metal loss. The corrosion rate of steels increases with the weight percent of sulfur. Figure 63 shows the effect of higher sulfur content on the corrosion rate of the steels for temperatures between 290 and 400C. According to Figure 63, increasing the sulfur content of a crude oil from 0.5 weight percent to 1.0 weight percent will increase the corrosion rate about 20 percent.
10 5 Sulfur Content, wt % 2 1 0.5 0.2 0.1
0.05 0.02 0.01 0.4
0.8 1.2 1.6 Corrosion rate multiplier
2.0
Figure 63 Effect of Sulfur Content on Corrosion Rates Predicted by Modified McConomy Curves in 290- 400 C (550-750F) Temperature Range
91
Figure 64 shows the effect of temperature on the sulfidic corrosion rate of carbon steel and several chromium steels. All of the steels in Figure 64 were exposed to crude oil with a sulfur content of 0.6 weight percent. Notice that the corrosion rate is lower for steels with higher amounts of chromium.
Temperature, C
100 50 20 250 300 350 400 10. Sulfur content : 0.6 wt %
5 2 1 0.5 0.2 0.1
0.1
0.01
0.05 0.02 0.01 450 500 550 600 650 700 750 800
10-3
Temperature, F
Figure 64 Modified McConomy Curves Show the Effect of High Temperatures on the Sulfidic Corrosion Rate of Carbon Steel and Various Chromium Steels
Corrosion rate, mm/yr
Corrosion rate, mpy
10
92
Diffusion processes can be used to describe high-temperature corrosion mechanisms. Figure 65 is a diagram that shows sulfidic corrosion of a steel surface. Hydrogen sulfide is first absorbed at favorable sites on the metal. Then the hydrogen sulfide reacts with iron to form iron sulfide according to the following chemical reaction.
2+ Fe + Ferrous Ion
H2S Hydrogen Sulfide
FeS + Iron Sulfide
H2 Hydrogen Gas
A scale of iron sulfide corrosion deposits forms on the metal surface. The scale then grows until it covers the metal surface. The iron sulfide scale also becomes thicker. Ferrous ions diffuse away from the metal surface through the scale. Sulfide ions diffuse from the hydrocarbon stream through the scale toward the metal. The iron and sulfide ions react to form iron sulfide. Electrons also diffuse through the sulfide scale to the hydrocarbon interface where they reduce hydrogen ions to hydrogen atoms.
S-2
Metal ions and electrons
Fe2+ e
H2S
H2S
e Fe2+ S-2 S-2
H2S
Sulfide ions
H2S
e Fe2+ S-2
H2S
Figure 65 Mechanism for High-Temperature Sulfidic Corrosion
93
The composition of the iron sulfide scale depends upon the amount of hydrogen sulfide in the hydrocarbon stream and other process conditions. The scale next to a steel surface will contain a higher concentration of iron than sulfur. The corrosion product scale near the hydrocarbon stream will usually contain a higher concentration of sulfur than iron. The corrosion resistance of an alloy is determined by the rate of diffusion of ions and electrons through the iron sulfide scale. In many environments protection against sulfidic corrosion is provided by the oxides formed from the alloy additions that form chromium oxide (Cr2O3), alumina (Al2O3) or silica (SiO2). If the sulfur activity (partial pressure, concentration) of the environment is high then sulfide phases will form. Sulfidic attack will occur at breaks in the protective oxide scale. Sulfur in the alloy then reacts with the alloying elements to form sulfides, which redistributes the protective elements and interferes with the reformation of the oxides. The sulfur tends to penetrate down grain boundaries. At higher temperatures, the melting point and vapor pressure of the scale become important factors. A scale with a low melting point or a high vapor pressure will not be retained and will not provide protection against corrosion. Note that many high temperature alloys are designed to form protective oxides not protective sulfides. Sulfides of alloying elements that form low melting eutectics include: Alloying Element Ni Fe Co Cr Al Phase Ni3S2 FeS Co2S4 CrS AlS Melting point (C) 645 986 880 ~1350 ~1070
94
Figure 66..Sulfidation of Alloy 600
Time to failure of the 18 inch diameter, inch thick tube was 1 month for the nickel based alloy operating at 1040 C (1900 F). The scanning electron microscope micrograph showed excessive chromium and nickel rich sulfides. The proposal was to replace the NiCrFe alloy 600 with FeCrCoNi alloy 556.
Hydrogen Attack (Decarburization)

High temperature hydrogen attack occurs in c-steels and low alloy steels exposed to high partial pressures of hydrogen above 200 C (390 F). This is not a low temperature embrittlement process but is the result of a hydrogen reaction with carbon from the carbide matrix of the alloy. H2 2H (dissociation of hydrogen) Fe3C 3Fe + C (dissociation in solid solution) 4H + C CH4 (decarburization reaction)
95
The presence of hydrogen modifies the sulfide reaction at iron sulfide scales, Figure 67.
Figure 67 Effect of Hydrogen on Sulfidic Scales The corrosion damage is in two forms: (1) internal decarburization, with attack along grain boundaries in the alloy followed by fissuring due to a build up of methane reaction product (2) surface decarburization, again from reaction of the carbides with atomic hydrogen but with diffusion and escape of the methane from the surface. Internal fissuring tends to occur with c-steels, CMo and Cr-Mo steels at higher partial pressures of hydrogen, whilst surface decarburization is more common in Cr-Mn steels at higher temperatures and lower partial pressures. Improved resistance is achieved by increasing the chromium and molybdenum alloying additions, Mo has four times the resistance than Cr to high temperature hydrogen attack.
96
Industry practice is to rely on corrosion resistance predictions presented as a series of curves (Nelson curves) for c-steel and low alloy steels at different hydrogen partial pressures and temperatures, Figure 68. (API RP 941 Steels for Hydrogen Service at Elevated Temperatures and Pressures in Petroleum Refineries and Petrochemical Plant.)
Figure 68 Nelson Curves for High Temperature Hydrogen Attack
97
Carburization and Metal Dusting

Carburization and metal dusting are forms of high temperature attack that occur in reducing environments containing high concentrations of carbon, for example, methane (CH4), carbon monoxide (CO), carbon dioxide (CO2) and light hydrocarbons. Carburization is the process of high temperature diffusion of carbon into an alloy and its reaction with alloying elements to form carbides. It occurs at very low oxygen partial pressures when the carbon content of the environment at the metal surface is high. Examples include carbon monoxide in reformer tubes or under coke deposits on furnace tubes. Diffusion of carbon through nonporous scales of chromium oxide (Cr2O3) or alumina (Al2O3) is slow (chromium and aluminum are alloying additions). However, in practice the oxides are layered in areas where the scale has cracked and re-formed (self repair).
Figure 69 Diffusion of Carbon into Steel or Nickel Alloy and Resulting Cracks
98
Gaseous species concentrate in the outer more porous regions and this assists the diffusion gradient that allows carbon to enter the alloy and react to form carbides. This leads to changes in mechanical properties and also to loss of oxidation resistance. Austenitic steels tend to be less resistant than ferritic (high solubility of carbon in austenite), whilst >20% Cr can adsorb considerable amounts of carbon to form (CrFe)23C6 and ferrite.
Figure 70..Carburization and Subsequent Brittle Failure of Reformer Tube from Ethelyne Plant after 20 days due to poor control of Decoking, 1100C
Metal dusting is a rapid, often catastrophic, localized carburization of steels in the temperature range 430 815 C (800 - 1500 F) exposed to environments rich in mixtures of hydrogen and carbon, for example, methane (CH4), carbon monoxide (CO), carbon dioxide (CO2) and light hydrocarbons. Failures are found in dehydration units, fired heaters, ethylene cracking units and gas turbines. The environment is reducing which means that retention of protective oxides is difficult to achieve with many alloys.
99
The corrosion attack produces small pits filled with carbon or a dust mixture of graphite, carbides, oxides and metal powder. The mechanism involves local saturation of the surface layers with carbon, leading to carbide (Fe3C) precipitation and growth followed by decomposition to iron and graphite. Figure 71 shows the pitting type attack observed with metal dusting. This metal dusting example is from an ethylene pyrolysis furnace tube in an environment containing 31% H2, 10% CO, 19% CO2, 5.5 % CH4. The recommendation was to replace the nickel-chromium alloy, Alloy 800, with a lower nickel alloy
Figure 71 Metal Dusting Pits
100
Hot (Molten Salt) Corrosion

Hot corrosion is a general tem used to describe the attack by molten salts, for example, liquid pollutants produced in combustion gases that contain small amounts of impurities, particularly sodium, sulfur and vanadium. The impurity pollutant can be in the fuel or the air. For example, turbine engines that burn sulfur containing oil or gas and also operate in a salt containing atmospheres such as marine or subkha regions can form a sodium sulfide melt on the blades. Fuel ash corrosion can be a serious problem with fired boilers or hydrocarbon furnaces. Oils used as fuels can deposit on super heaters and convection tubes to form melts that cause a severe form of corrosion damage due to the liquid type electrolylitic flux. Alkali-metal sulfates are solid below 450 C ( F) and the rate of attack is slow. Above their dew point, 980 C (390 F) for sodium sulfate, the attack is again low. Between these temperatures the rate of hot corrosion increases with catastrophic attack at around the melting point of the salt. The breakdown of the scale involves either mechanical fracture or an electrochemical corrosion in the molten salt electrolyte (either an acidic or basic salt fluxing mechanism).
101
Figure 72 Hot Salt (Na2S4) Corrosion of 35Ni-19Cr-Cb Austenitic Steel at cyclic Temperatures between 150 - 927 C (300 - 1700 F) Vanadic slags such as sodium vanadate (Na2O6V2O5) are formed with some oils by the reaction of vanadium pentoxide vapor (V2O5) with sodium sulfate (Na2SO4). The vanadium slag dissolves the protective oxide scale from the metal (as a flux). Corrosion increases with temperature and vanadium content of the oil. For example, with between 20 150 ppm vanadium the tube temperature should be restricted to between 650 C (1200 F) and 850 C (1550 F) depending on sulfur content and the sodium / vanadium ratio. Above 150 ppm vanadium the temperature should be limited to 650 C (1200 F). Alloys with high nickel content and particularly with a high chromium content are more resistant. Firing a boiler with a low excess air (<1%) minimizes the formation of sulfur trioxide in the firebox and this produces a high melting mixed slag of vanadium trioxide and pentoxide rather than just vanadium pentoxide. Additives such as magnesium oxide and organic magnesium compounds raise the melting point of the deposits giving rise to porous / fluffy deposit layers that are easily removed rather than sticky / highly corrosive slag.
102
GLOSSARY
area principle corrosion allowance Failure failure mode The corrosion rate of an anode increases with the ratio of the cathodic area to the anodic area. Thickness added to the wall of a pipe or vessel to provide the required life against corrosion attack. Termination of the ability of a system, structure or component to perform its required function The manner of failure. For Risk-Based Assessment, the concern is loss of containment of pressurized equipment items. Some examples of failure modes are pinhole, crack, and rupture. Two dissimilar metals that are electrically connected in an electrolyte. Also, two similar metals in dissimilar electrolytes. A list of metals and alloys arranged according to their electrical potentials in a specific environment. Localized deformation on a metal surface caused by the pressure of hydrogen trapped in the metal at voids or other metallic defects. A failure process caused by a decrease in the toughness and ductility of a metal due to the presence of atomic hydrogen. A brittle metal cracking failure due to the presence of atomic hydrogen in the metal. Undesirable elements or compounds in a material. Particles of insoluble matter in a metallic matrix. The particles are usually oxides, sulfides, or silicates. Cracking that occurs between the grains in a metal.
galvanic couple
galvanic series hydrogen blistering
hydrogen embrittlement hydrogen stress cracking Impurities Inclusions intergranular cracking
103
Qualitative Risk Assessment (Analysis)
Methods that use engineering judgement and experience as the basis for analysis of probabilities and consequences of failure. Qualitative risk analysis techniques become quantitative risk analysis methods when consequence and failure probability values are estimated together with their respective descriptive input. The explicit use of risk-based assessment to plan, justify and aid the assessment of results from inspection, testing and monitoring regimes. Note that RBI can result in inspection efforts increasing, decreasing or being redirected to higher risk areas.
Risk-Based Inspection (RBI)
104

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