DAMAGE MECHANISMS Forms of Corrosion

Corrosion Damage Mechanisms: AS/NZS 3788 Appendix M

Group I (1) General (uniform) corrosion (2) Localised corrosion (3) Galvanic corrosion Group II (4) Velocity effects (5) Intergranular attack (6) De-alloying attack Group III (7) Cracking phenomena (8) High temperature corrosion

Corrosion Matrix
Material * Time * Properties * Influence Environment - Concentration ie H2S - Oxidisers ie CO2 - pH - Inhibitors - Temperature Mechanical - Stress - Frequency - Form Physical - Flow Rate - Geometry = Corrosion Surface Corrosion - Passivation - Uniform - Galvanic - Crevice - Intergranular - Phase Selective - Erosion Corrosion Cracking - Initiation - Growth - Morphology Composition On-Line Off-Line Shut Down Matrix Structure Grain Boundaries Strength Toughness

Materials In Oil and Gas Plant

Typically dictated by component suppliers but often operator selected/specified: Carbon and Low Alloy steels Ferritic and Martensitic Stainless steels

Austenitic and Duplex Stainless Steels

Nickel-base Corrosion Resistant Alloys Titanium and Titanium Alloys

Ceramics, Cements, Concretes, Plastics, Rubbers and Woods

Coatings and Overlays

Material Properties

Composition

Metallurgy
Hardness Strength Fabrication Toughness (Impact Properties) Fatigue Strength Expansion

Time of Corrosion and Damage

On-Line
Off-Line

Start-Up and Shut-down

Standby

Upset (Operational Excursion)

Chemical Conditions
CO2 / H2S / NH3 / H2 / O2 / Cl Calculated Total H2S, CO2, NH3 and pH Passive Film Formation Aeration Microbiological Activity Scale Formers and Inhibitors

Physical Conditions
Pressure
Temperature Phases: Steam / Water / Condensate Flowrates and Geometric Effects Constraints and Supports

Thermal and Mechanical Stresses

Forms of Corrosion: AS/NZS 3788

Group I (1) General (uniform) corrosion (2) Localised corrosion (3) Galvanic corrosion Group II (4) Velocity effects (5) Intergranular attack (6) De-alloying attack Group III (7) Cracking phenomena (8) High temperature corrosion

Group I: Readily Observed by Visually Examination

(1) General Corrosion (2) Localised Corrosion (i) General (ii) Pitting (iii) Crevice (3) Galvanic

Group II: Additional Inspection Techniques May Be Required

(4) Velocity phenomena
(i) Erosion (ii) Cavitation (iii) Fretting

(5) Intergranular Corrosion

(i) Weld Decay (ii) Exfoliation (iii) De-alloying (Plug and Layer) (iv) Hydrogen blistering

Group III: Microscopic Examination Required

(6) Cracking Phenomena (i) Environmental Cracking (Sulfide, Chloride, Mixed and Hydrogen) (ii) Corrosion Fatigue (7) High Temperature Corrosion (i) Scaling (ii) Internal Attack and Fissuring

Corrodible Plant

Corrodible Plant

Corrodible Plant

Group I Appearance
Can often be identified upon visual examination

Group I Corrosion Examples

(1) General Corrosion

even, regular loss of metal planar surface

Steam, atmospheric rusting, dissolution of zinc by dilute acid

Boiler Water

Aerated Vent Steam

Group I Corrosion Examples

(2) Localized Corrosion

attack occurs at discrete areas or sites, large and shallow to small and narrow pitting and crevice

Cooling waters, Contaminated surfaces, unwashed areas

Corrosion Kinetics

Corrosion Products and Scales precipitated from corrosive solutions may be poorly formed (nonprotective) with LINEAR REACTION RATE or dense and adherent (protective layers) with PARABOLIC REACTION RATE, ie slowing with time)
non-protective layer
Extent of corrosion Extent of corrosion

protective layer

time

time

Linear Kinetics

Parabolic or Logarithmic

Carbon Steel in Geothermal Steam

Illustration of localised corrosion on shutdown/startup

Material Loss Rate Equations

Material Loss Constant * timen Linear Kinetics: ML = Constant * t and n = 1 ln ML = ln Constant + n ln t and Slope = 1 Parabolic Kinetics: ML = Constant * t0.5 and n = 0.5 ln ML = ln Constant + 0.5 ln t and Slope = 0.5
Logarithmic Kinetics: ML = Constant * Log (Constant*t + Constant)

ln ML = ln A + ln (ln(Bt+C)) and no single Slope If Constants A=B=C the Slope tends to 0.06

Linear Plotting
ML ML t10.5 + t20.5 Breakaway Kinetics ML t Linear Kinetics ML t0.5 Parabolic Kinetics ML ln (Bt + C) Parabolic Kinetics time

Logarithmic Plotting
n=1

Change of Slope = Change of Mechanism

n = 0.5

n = 0.06

time = 1, 3 and 12 Mo for Doubling of ML

CO2 Corrosion Rates

Localised & High
CO2 to H2S > 200 then CO2 corrosion predicted:

Alloy Type Effects

% CO2 Effects Temperature Effects Hydrogen Charging Rate is dependant on protective film formation

Group I Corrosion Examples

(3) Galvanic Corrosion

bimetallic corrosion, from electrical contact between dissimilar metals

Preferential attack on more anodic metal

Al Conductor Steel Reinforced

Galvanising Corrodes To Protect Al

Al Corrodes To Protect Steel

Group II Appearance
May require supplementary means of examination

Corrosion Rate at 55C

Corrosion Rate [mm/year]

Group II Examples
(4) Velocity effects Erosion-corrosion
- caused by relative movement between corrosive fluid and metal surface - accelerated by high velocity flow - mechanical effects - corrosion-related effects such as pH and oxygen content

7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0 3 4 5 6 7 pH 8 9 10 11 12 Dissolved O2=1 Dissolved O2=2 Dissolved O2=3 Dissolved O2=4 Dissolved O2=5 Dissolved O2=6 Dissolved O2=7 Dissolved O2=8

Group II Examples
(4) Velocity effects Cavitation
- caused by bubbles formed where the local pressure is below the vapour pressure

Fretting
- damage (often electromechanical) associated with motion between mating surfaces under load and vibration

Group II Examples
(5) Intergranular attack At grain boundaries Grains fall out (sugaring or grain dropping) Improperly heat-treated HAZ of welds

Group II Examples
(6) De-alloying corrosion Selective removal of one metallic constituent of an alloy De-zincification of yellow brass Graphitic corrosion of grey cast iron

Group III Appearance

May see surface breaking features or fracture but must be verified by microscopy, SEM
Cracking phenomena Stress Corrosion Cracking
Static stress

High-temperature attack Scaling

Scale

Corrosion fatigue
Dynamic stress

Internal attack

Fissures

Group III Examples

(7) Corrosion related cracking phenomena Corrosion-related environment cracking - Stress corrosion cracking (SCC) - Hydrogen-assisted cracking (HAC) - Liquid metal cracking (LMC)

Mechanical-electrochemical fatigue - corrosion fatigue

Transgranular/Intergranular SCC
Simple slip system
Formation of coarse slip steps Produce discontinuities

Initiating SCC

Transgranular/Intergranular SCC
Corrosive environment Pit initiation

Crack initiation Propagation SCC

SCC of Corrosion Resistant Alloys

SCC CONDITIONS + Aeration (oxygen) + Corrosive Species + Evapourative Concentration + Moisture or wetness + Tensile Stress (residual) + T > 60C + Material Susceptibility Alloy 2RK65 63 weeks at 100C Drip solution of : steam condensate with H2S 30 mg/kg chloride added

SCC Cracks May Propagate by Corrosion Fatigue

SCC and Corrosion Fatigue

Corrosion Fatigue

Alternating loading + corrosion process formation of extrusion & intrusions protective surface layer destroyed

local electrochemical attack

the lower the frequency of loading cycles, the more impact of corrosion because of time-dependency of corrosion processes

Hydrogen Embrittlement / SCC

Sour environment Corrosion and hydrogen charging

Tensile stress Propagation HE

Low Strength Steels Resist Sulfide SCC

Hydrogen readily diffuses into steels and high strength alloys suffer Sulfide Stress Corrosion Cracking or Hydrogen Induced Cracking

NACE MR0175 (1975 to 2001) Standard Material Requirement for

Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oilfield Equipment Sour Water and Sour Gas Systems Definitions

Low H2S Systems May be Classified as Sweet

Hardness and Cold Work Limits for Accepted Alloys Might Appear Conservative BUT Based on Experience

Use as low a Strength as can be tolerated by the Design

Heat Treatment Processes Specified Materials for Specific Facilities Identified

169

215 189

188 192 193 202 215 192 195 209 216

231 242

182

194

193

198

197

201 212 210 201 197 196 198

180 218 212 218 212

172

230

227

181

Example Vessel Meets hardness criteria of NACE Standard Thickness at limit for heat treatment (ASME) Welded with limited number of passes high heat input High Residual Stress HIC or SCC?

Constraints On the Standard

NACE MR0175/ISO 15156-1:2001(E), -2:2003(E) and -3:2003(E)

Guideline only

Basis for Agreement to Supply

Does not include synergistic effect of Chloride (NACE Test) Must do test pieces and cut up beforehand Hardness relationship to strength is material dependent

Limited to Sulfide SCC and HIC

Hardness of sub-surface areas can not be measured

Hardness conversions often debated

Metallurgical variations, new alloys or fabrication processes may not be classified

Testing can be expensive

Group III : (8) High Temperature Oxidation Corrosion

OXIDATION Oxygen absorbed on the surface of the metal and react to form oxides Solid corrosion layer formed Diffusion through the oxide layer controls rate of reaction Corrosion reaction will continue even if at low level Accelerated by spallation on temperature cycling thermal stresses Chlorination Sulphidation Nitridation Metal dusting / Carburization Molten Salts Corrosion

(8) High Temperature Corrosion Kinetics

High Temperature Oxide films may be porous (nonprotective layers) with LINEAR REACTION RATE or continuous and adherent (protective layers) with PARABOLIC REACTION RATE i.e. slowing with time.
non-protective layer
Extent of corrosion

protective layer
Extent of corrosion

time

time

Linear Kinetics

Parabolic or Logarithmic

Chlorination

Corrosion in flue gas derived from landfill gas engines. HCl Corrosion

Fe2O3 + HCl

FeOCl b-FeO(OH) ClFe2O3 + H2O Cl-

Fe3O4 + HCl

FeCl2.xH2O

Oxidation

High Temperature Oxidation of alloy 800H

Oxidation of turbine alloy through to catastrophic stages

Stability Diagram for Fe-SO2-O2 at 230oC

Metal Dusting

High temperatures (400 to 700oC) Localised corrosion often catastrophic failures In processes with high carbon activity in the gas phase Components disintegrate to fine dust of alloy components and carbon Inhibited by presence of sulphur compounds

Metal Dusting Industry Problem

Reformer plants

Syngas plants Methanol producers HBI plants Ammonia synthesis MTBE

Although sulphur helps inhibit the problem it also poisons the catalyst New technologies are being researched to overcome the problem

Corrosion Damage Mechanisms: AS/NZS 3788 Appendix M

Group I: Readily Observed by Visual Examination (1) General (uniform) corrosion (2) Localised corrosion (3) Galvanic corrosion Group II: May Require Supplementary Examination (4) Velocity effects (5) Intergranular attack (6) De-alloying attack Group III: May Require Microscopic Examination (7) Cracking phenomena (8) High temperature corrosion