Inspection Degradation Mechanisms PDF

Inspection Main Degradation Mechanisms
An Overview for CDU, CCR, DHP, Isom.
Harmen J. Bouwman
Shell Global Solutions International

Degradation Types
1. Wall Thinning
2. Stress Corrosion Cracking
3. High Temperature Degradation
2
1. Wall Thinning
1. Contents
1.1 Introduction
1.2 Main Degradation Mechanisms
1.3 Morphologies
1.4 Inspection
1.5 Reporting
3
1.1 Introduction
4
Two Main Types of Corrosion
Electrochemical (wet-corrosion, low temperature)

In the presence of an electrolyte (water)
Below about 150 C
Chemical Attack (dry-corrosion, high temperature)

No liquid H2O present
Above about 230 C
Corrosion rates increase with:

Temperature
Flow
Low pH (wet corrosion)
5
Electro-Chemical Corrosion (Wet)
Oxygen
Medium
Fe2+
OH- O2 Reactions
Fe Fe2+ + 2e
e O2 + 2H2O + 4e 4OH-
Steel
Acid
HAc H+ + Ac-
Medium
H2
Fe2+
Hads Hads H+ Reactions

Fe Fe2+ + 2e
e 2 H+ + 2e H2 : Determines corrosion Rate: pH
Steel
6
Electro-Chemical Corrosion (Wet)
Stability protective layer
Corrosion
Rate
Corrosion product
FeS strongly adherent
oHigh protection
FeCO3 weakly adherent
Time
oLow protection
Mechanical impact
Turbulence (velocity)
For fresh material the CR is very high Impingement
Protective layer is formed by the corrosion (erosion-corrosion)
process CR decreases = Global CR Composition electrolyte, e.g.
Global CR is dictated by the stability of the Cl- and CN- on FeS
protective layer.
7
Chemical Corrosion (Dry)
Direct reaction between metal and corrosive species: O2, H2S, HCl
Corrosive species, e.g.: Porous layer
O2, H2S, HCl
Diffusion of species thru Layer
Layer
Corrosion at interface Layer/Metal
Metal Non-Porous layer

Diffusion of metal thru Layer
Corrosion at interface Layer/Atmosphere
Corrosion Rate
Difference between relative volume of Layer & Metal
Layer < Metal
Porous Layer No protection
Oxide > Metal
Non-porous/adherent layer possible Protection possible
Oxide >> Metal
Spalling of Layer Some protection possible
8
Chemical Corrosion (Dry)
Spalling
Layer
M e ta l
1 O ld L a y e r
N ew Layer
Layer M e ta l
4
M e ta l
2
S p a lle d
Layer Layer
N ew Layer
M e ta l
3 5
M e ta l
Oxidation rate
Linear
Weight Loss
Parabolic Linear : Porous or strong spalling layer

Parabolic : Non-porous layer
Logarithmic Logaritmic : Very thin non-porous layer
Time
1.2 Main Degradation Mechanisms
10
Wall Thinning
Sulphidic Corrosion & NAC T2
H2S/H2 Corrosion T1
CUI T3
HCl Corrosion T4
Sour Water Corrosion T7
Amine Corrosion T8
Dew Point Corrosion T9N-1
Acid Dew Point Corrosion T9N-2
NH3-Salts T10
Oxidation T11
Metal Dusting T12N
High Temperature HCl/Cl2 Corrosion T13N
Localized Corrosion by entrained water M1N 11
Structure of presentations Thinning
Specifics
Description
Mechanism
Materials
Morphology
Examples
12
Sulphidic Corrosion: T2
Specifics
Chemical Corrosion / Dry / High Temperature
Process related
Typical Units : CDU, HVU, TGU.
Description
Sulphidic corrosion consumes a metal by the reaction between the
metal surface and sulphur compounds (mainly H2S & mercaptans) in
liquid or gaseous hydrocarbon streams at temperatures above 230 C.
13
Mechanism
For CS the corrosion reaction
Outer
produces a layer of FeS on
layer
the surface of the metal. The
inner layer is fine grained, but
Inner the outer layer develops into a
layer porous amorphous structure.
Steel
The inner layer tends to be protective and slows down the corrosion rate.
Chromium steels and chromium-nickel steels produce tighter, finer-grained,
sulphide scales that can be very tenacious and therefore reduce the
corrosion rate much better.
Materials
Corrosion rate is approx. halved with each step up in %Cr:
CS 1Cr 2Cr 5Cr 9Cr 12Cr 18Cr8Ni
14
Morphology
General Thinning : In general
Localised Thinning : Turbulence
Pitting : Observed in furnace tubes
15
Examples
General Thinning in a partly insulated line
- Insulated
higher temp.
higher sulphidation rate
Non-insulated Insulated
16
Examples
Pitting in a furnace tube
17
Naphthenic Acid Corrosion: T2
Specifics
Process related
Typical Units : CDU, HVU, TGU.
Description
Naphthenic Acid corrosion consumes a metal by the reaction between
the metal surface and naphthenic acids (organic acids) in liquid or
gaseous hydrocarbon streams at temperatures above 230 C.
18
Mechanism
The corrosion reaction produces Fe-Naphthenates, which are soluble
in the oil phase and therefore a protective layer is not built up.
Materials
SS of the type 18Cr8Ni containing a sufficient level of Mo (> 2.5%)
provide sufficient resistance: 316 & 317
CS and Cr-steels provide limited resistance
19
Morphology
General Thinning
Localised Thinning : In general
Grooving (sharp edges)
Pitting (sharp edged)
20
Examples
General Thinning Pitting in

furnnace return bend
21
Examples
NAC in CS furnace tubes NAC in feed section of HVU

Sharp deep pits Grooving
22
Examples
NAC in bubble caps of 317

Fine pitting
23
Interaction Sulphidation - NAC: T2
Interaction between sulphur and naphthenic acid
Sulphidation of the steel and the enhancement of sulphur

corrosion under erosive conditions
Corrosion of the steel by Naphthenic Acids
Sulphidation of the steel and the enhancement of sulphur

corrosion by dissolution of the protective sulphide scale on the
steel surface by the naphthenic acids
Naphthenic acid and sulphur corrosion have both a

synergistic and mitigating effect on each other
24
H2S/H2 Corrosion: T1
Specifics
Process related
Typical Units : HTU, HDS, HCU
Description
H2S/H2-Corrosion consumes a metal by the reaction between the metal
surface and H2S in liquid or gaseous hydrocarbon streams containing
H2 at temperatures above 230C.
25
Mechanism
For CS the corrosion reaction

produces a layer of FeS on
the surface of the metal. The
Outer
inner layer is fine grained, but
layer
the outer layer develops into a
Inner course columnar form.
layer
Steel
The inner layer tends to be protective and slows down the corrosion rate.
Chromium steels and chromium-nickel steels produce tighter, finer-grained,
sulphide scales that can be very tenacious and therefore reduce the corrosion
rate much better.
Materials
Cr-Steels up to 5% does not offer a benefit over CS.
When CS is not sufficient than SS of the type 18-8 is applied.
26
Morphology
Uniform Thinning : In general
27
Corrosion Under Insulation: T3
Specifics
Electro-Chemical Corrosion / Wet / Low Temperature
Non-Process related
Typical Units : All Units
Presence of wet insulation for streams with operating temperatures
in the following range: - 5 < T C < 150
Notes:
- Wet condition due to ingress of water due to damaged insulation
- Wet condition lowers metal below operating temperature
- Metal temperature rules the corrosion
Description
Corrosion Under Insulation consumes a metal by the reaction between
the metal surface and an O2-containing water phase.
Note:
Corrosion will be aggravated by water leachable salts in insulation,
e.g.: chlorides, sulphates & acids 28
Mechanism
As for Electro-Chemical Corrosion, when O2 present.
Materials
Insulated CS & Cr-Steels
Morphology
Localized Thinning : In general
29
Example
Damaged Cladding Corrosion Under Insulation
30
HCl Corrosion: T4
Specifics
Process related
Typical Equipment : Overhead Atm. Dist. Column
Description
Hydrochloric Acid Corrosion consumes a metal by the reaction between
the metal surface and HCl in the water.
31
HCl Corrosion: T4
Mechanism
HCl H+ + Cl-
Medium
H2
Fe2+
Hads Hads H+ Fe Fe2+ + 2e

2 H+ + 2e H2: Determines Corrosion Rate (pH)
e
Steel
Forming of HClaq
Presence of a water phase
Condensation of water in vapor stream
Water wash of vapor stream
HCl dissolves in water, creating a (very) corrosive environment

Note: water wash has a diluting effect and will lower the corrosivity
32
HCl Corrosion: T4
Materials
Significant Corrosion rates for CS, when pH < 5
SS-type 18-8 is susceptible to pitting
CRAs: C-276, B2, 625, 825
Morphology
Localised Thinning : In case of Dew Point Corrosion
Pitting : SS-type 18-8
33
Sour Water Corrosion: T7
Specifics
Process related
Typical Units : CDU, HVU, TGU, HTU, HDS, HCU, FCC
(almost all units containing H2S)
Description
Sour Water Corrosion consumes a metal by the reaction between the
metal surface and H2S in the water.
Note:
NH4HS will be formed, when also NH3 is present, which
generally will be case in refinery streams.
34
Mechanism
H2S H+ + HS-
Medium
Fe2+
Hads H+ Fe Fe2+ + 2e
2 H+ + 2e H2
Habs e
Steel
Hinterstitial
For CS the corrosion reaction produces a layer of FeS on the surface of the
metal. This layer is very tenacious and slows down the corrosion rate.
Materials
CS < 2% NH4HS
12Cr/18Cr8Ni 2 < %NH4HS < 8
CRA (e.g. 825) >8% NH4HS
35
Forming of Sour Water
Presence of a water phase
Condensation of water in vapor stream
Water wash of vapor stream
H2S dissolves partly in water, creating a weak acidic environment

In general low corrosion rates
High corrosion rates, when pH < 4.5 due to acidic species
NH3, in general present in vapor stream, dissolves in water and increases

the amount of dissolved H2S and the pH (~ 8)
Increased corrosion rates
Note: Velocity/Turbulence increases corrosion rate markedly
36
Morphology
Localised Thinning : Turbulence
: Condensed water
: Under deposits
Pitting (wide) : Under deposits (pH > 8 Precipitation of FeS)
Examples
Localised thinning in a Localised thinning in a 37

bend due to turbulence head of an AC
Amine Corrosion: T8
Specifics
Process related
Typical Equipment : Amine-Absorbers/-Regenerators
& associated equipment/piping
Description
Amine Corrosion consumes a metal by the reaction between the metal
surface and both the dissolved acids (in refineries mainly H2S) and the
amine degradation products.
Pure Amines are non-corrosive.
38
Amine Corrosion: T8
Mechanism
As for Sour Water Corrosion
Increased corrosion rates under following conditions
Turbulence
Flashing
Impingement
39
Amine Corrosion: T8
Morphology
Uniform Thinning : Low stream velocities
Localised Thinning : High stream velocities
: Flashing
: Impingement
Grooving : See localized thinning
Pitting : See localized thinning
Example
Localized Corrosion on Tube ID

40
Dew Point Corrosion: T9N-1
Specifics
Process related
Typical Equipment : Overhead systems in CDU, HVU
: Effluent streams in HTs and HCU
: Process streams in SRU, TGU and Incinerators
: Sour Gas Lines
Description
Dew Point Corrosion consumes a metal by the reaction between the
metal surface and the dissolved acids (in refineries mainly H2S, CO2 and
HCl) in the condensed water.
Saturation temperature of the acid < water dew point
41
Mechanism
As for Sour Water Corrosion
HAc H+ + Ac-
Medium
H2
Fe2+

2 H+ + 2e H2
e
Steel
Forming of corrosive medium

Condensation of water vapor, when metal temperature falls below
the dew point
Corrosive species (H2S, HCl, CO2) dissolve in the condensed water
42
Morphology
Localised Thinning
Pitting
Expected locations
Locations, where metal temperature falls below dew point for
water vapor
Low points and dead ends, where condensed water might collect
Full system, when low points/dead ends can not be identified
Wet spots in insulated & heat traced lines
Condensation is prevented by insulation & heat tracing
43
Acid Dew Point Corrosion: T9N-2
Specifics
Both Process and Non-process related
Typical Equipment/Unit : Flue gasses in Boilers, Heaters & FCC-Regenerators
: Process streams in SRU & TGU
Description
Acid Dew Point Corrosion consumes a metal by the reaction between
the metal surface and the condensed acids (in refineries mainly SO2 &
SO3), which are diluted by condensed water.
Saturation temperature of the acid > water dew point.
The hygroscopic condensed acid will absorb water even below its dew
point.
44
Mechanism
As for HCl
HAc H+ + Ac-
Medium
H2
Fe2+

2 H+ + 2e H2
e
Steel
Forming of corrosive medium

Condensation of acid vapor, when metal temperature falls below the
temperature for condensation
Dilution of acid, when the metal temperature drops below the water
vapor dew point, resulting in free water
45
Morphology
Localised Thinning
Pitting
Expected locations
Locations, where metal temperature falls below temperature for
condensation
Wet spots in insulated & heat traced lines
Condensation is prevented by insulation & heat tracing
46
NH3-salt Corrosion: T10
Specifics
Process related
Typical Equipment/Unit : Effluent streams in HTs and HCU
Description
NH3-salt Corrosion consumes a metal by the reaction between the
metal surface and the desublimated NH3-salts (NH4Cl, NH4F & NH4HS),
when wetted.
The hygroscopic salts will absorb water even below its dew point.
47
NH3-salt Corrosion: T10
Mechanism
As for HCl and Sour Water Corrosion
Morphology
Localised Thinning
Wide Pitting with sharp edges
Example
NH4F-salt Corrosion in a
Lube Oil HT REAC-line
48
High Temperature Oxidation: T11
Specifics
Non-process related
Typical Equipment : Boilers & Heaters
Description
High Temperature Oxidation consumes a metal by the reaction between
the metal surface and oxygen.
O2-content has no noticeable influence on the corrosion rate, when >1 %
49
Mechanism
Direct reaction between metal and O2
Materials
Material Tolerable temperature C
CS 565
9Cr 705
304/321/347 925
310 1150
50
Morphology
General Thinning
Localized Thinning
Example
Oxidation of a carbon steel nut

on a stainless steel stud at 705 oC
51
Metal Dusting: T12N
Specifics
Process related
Typical Equipment : Heaters of CCR and HMU
Description
Metal Dusting consumes a metal (2Cr & 9Cr) by the reaction between
between the metal surface and carbon produced in a carburizing gas
phase.
52
Metal Dusting: T12N
Mechanism
Non-stable Fe3C Decomposes
Forming of free Carbon
Diffusion Fe3C 3Fe + C
2CO C + CO2
of C into Steel and Formation of Graphide
or
Formation of Fe3C and
C4H10 4C + 5H2
Removal of Metal
Fe Fe Fe
Carbon Layer Graphite
Fe3C
C C C Fe3C Fe3C
Steel Steel Steel Steel
53
Metal Dusting: T12N
Morphology
Pitting
Example
X-section Metal Whiskers

54
High Temperature Chlorination: T13N
Specifics
Process related
Typical Equipment : Regenerator of CCR
Description
High Temperature Chlorination consumes a metal by the reaction
between the metal surface and HCl/Cl2.
55
High Temperature Chlorination: T13N
Mechanism
Direct reaction between metal and HCl/Cl2.
Volatilisation of metallic chlorides
Materials
Tolerable temperature C
Material
Dry HCl Dry Cl2
CS 260 200
Alloy 400 230 430
Alloy B 450 540
Morphology
General Thinning
No scale smooth surface
56
Corrosion by Entrained Water: M1N
Specifics
Process related
Typical Equipment : All Units
Description
Corrosion by entrained water consumes a metal by the reaction
between the metal surface and the corrosives in the entrained water
(often HH4HS).
Note: The entrained water must wet the metal surface, which will occur locally.
Mechanism
Electro-chemical corrosion as for sour water
57
Formation of Entrained Water
Mixed Flow Vapor
Spray Flow
Separator
HCs Sour Water
Water-in-Oil Dispersed Oil-in-Water Dispersed

(Mist Flow) (Bubble Flow)
The mixed flow, resulting from condensation of vapor, is separated into:
Sour Water with entrained HC-droplets Oil-in-Water Dispersed (Bubble Flow)
HCliq with entrained water droplets Water-in-Oil Dispersed (Mist Flow)
Vapor (incondensables) with entrained water droplets Spray Flow
58
Alternative Mechanisms for Formation of Entrained Water
Dissociation of water by cooling
Water-in-Oil Dispersed
Generation of water droplets by

Presence of Condensed Water
Increasing Gas Velocity

High vapor velocities
resulting in spray flow
59
Morphology
Localized uneven thinning
Aqueous Corrosion, where water settles out
oLow points and dead ends (low flow velocities), e.g.
Bottom of equipment items
Drains in piping
oFittings in piping
Localized Erosion-Corrosion
oCombination of spray flow (vapor phase) and fittings (geometry)
60
Effect of Erosion-Corrosion on Corrosion Rate
Corrosion Corrosion
Rate Rate
Time Velocity
For fresh material the CR is very high Impingement might destroy the
protective layer
Protective layer is formed by the
Entrained water droplets
corrosion process CR decreases
High gas velocity
Global CR is dictated by the stability
of the protective layer. Geometries prone for impingement
Step-wise increase of CR
61
19-1-2009 8:29
Inspection
Equipment by UT-Scanning based on intrusive VT
Piping up to dia. 10/12 by Profile Radiography
Piping above dia. 10/12 by UT-Scanning
62
1.3 Morphologies
63
Morphologies for Thinning
General Corrosion
Even
Even General
Uneven Unenven
General
Localized Corrosion Even
Even Localized
Uneven Unenven
Localized
Pitting
Wide Wide
Pitting
Medium Medium
Pitting
Narrow Narrow
Pitting
64
Definition Morphologies for Thinning(1)
General Corrosion
Loss of wall thickness progressing over a large part the surface of the
metal component in question.
Localized Corrosion
Loss of wall thickness progressing over a relatively small part the
surface of the metal component in question.
Guidelines to assess General versus Localized Corrosion

Effected surface area of metal component
> 10 % General Corrosion
< 10 % Localized Corrosion
65
Even Corrosion
Loss of wall thickness progressing at approx. the same rate
Uneven Corrosion
Loss of wall thickness progressing at different rates
Guideline to assess Even versus Uneven Corrosion

Variation of wall thickness at effected surface area
< 0.6 mm Even Corrosion
> 0.6 mm Uneven Corrosion
Note:
Variation of wall thickness due for forming must be excluded, e.g. nuckle of head
66
Wide pitting
Ratio depth/diameter > 1/3
Medium pitting
1/3 < Ratio depth/diameter < 3
Narrow pitting
Ratio depth/diameter > 3
67
Registration Inspection Findings for Thinning
Morphology Code Severity Extent Density/Number per Area
General even Gen Depth N.A. N.A.
General uneven Ugen Depth N.A. N.A.
Localized even Loc Depth Dia. Attacked Location locations/m2
Localized uneven Uloc Depth Dia. Attacked Location locations/m2
Wide Pitting Wpit Depth N.A. pits/dm2
Medium Pitting Mpit Depth N.A. pits/dm2
Narrow Pitting Npit Depth N.A. pits/dm2
Class Depth Extent Density/

in mm in mm Number
1 < 0.2 < 10 1
2 0.2 0.5 10 50 25
3 0.5 1.0 50 - 100 6 10
4 12 100 - 200 11 20
5 23 200 500 21 50
6 35 > 500 > 50
7 57
8 7 10
68
9 > 10
Guidelines to define Components
Relatively small equipment items,

Full item
Reletively large equipment items
Split item up into components
Differentiate according to product stream
Different product streams in Shell Side and Tube Side of HEs
Differentiate according to product phase
Liquid phase versus vapor phase
69
Guidelines to define Component per Equipment Item
Heat Exchangers
Channel
Shell Side
Bundle
Air Coolers
Heads
Bundles
Vessel (Separator)
Lower Section, containing liquid
Upper Section, containing vapor
Medium Section subject to alternately liquid and vapor
(Boot)
Colmns, Reactors & large Vessels

Barrel
Head
Note: Nozzles & Manholes should be considered as separate components

70
1.4 Inspection
71
Assessment Thinning of Equipment
Visual
Digital Photos to register Morphology
Gauging
Profile gauge
Pitting gauge
UT from outside to assess Thinning Corrosion Rates
UT : Measurement points (MP), using digital equipment
UT-A : Measurement points, using A-screens
UT-B : Line Scans
UT-C : Area Scans
UT-G : Grid Scans
Note:
Type of scan to be based on both morphology and extent of attacked area
72
Assessment Thinning of Equipment
Grid scans
MPs on intersections Scanning of areas Combination

of grid lines between grid lines
Note:
73
Assessment Thinning of Equipment by UT
Reliability related to Morphology
Morphology UT UT-A UT-B UT-C UT-G
General Even
General Uneven
Localized Even
Localized Uneven
Wide Pitting
Medium Pitting
Narrow Pitting
Notes:
- UT is to be carried out from the outside. Therefore, areas with uneven
and/or localized corrosion observed during Internal Visual Inspection must be
marked at the outside.
- Both type and extend of UT should be related to both the extent and the
morphology of the attacked areas 74
Inspection Equipment on Thinning by UT during T/A
External inspection
UT on locations
defined on an equipment sketch
marked on the equipment item
Internal inspection
Discovery of areas with localized and/or uneven thinning
Digital Photos to register Morphology
Gauging to register inspection findings
Discovered areas
o To be defined on equipment sketch
o To be marked on outside of equipment item
UT-scanning for thinning of discovered areas from outside
75
Internal Inspection Equipment on Thinning during T/A
Start
Localized
and/or
Yes
uneven thinning
discovered
Uneven
General No
Thinning
Assess following parameters per

Yes
attacked area:
- Morphology
Define selected areas on
-Depth
equipment sketch - Extent
Mark the selected areas on -Number of locations/m2
equipment item or
Number of pits/dm2
Select UT-C or UT-G

for the selected areas Define selected areas on
No equipment sketch
Mark the selected areas on
equipment item
Apply selected
scanning method
from the outside
Select UT-B, UT-C or UT-G
for the selected areas
Apply selected
scanning method
from the outside
76
End End End

Inspection Tubes of Bundles on Thinning during T/A
Gauging for tube-end corrosion
ET on selected bundles (pilot by contractor)
77
1.5 Reporting
78
Reporting Findings
VI, supported by gauging
Format as defined in ITPs
Application of Registration Scheme
UT
Equipment sketch defining locations
Table recording the results per location
Gauging and ET of tubes of bundles
Sketch of bundle defining selected tubes
Table recording the results per examined tube
79
Reporting Findings
Format for VI, supported by gauging (example for vessels)
INSPECTION FINDINGS
Component Findings/Results
Shell Text one liners. According to Registration Inspection Findings for Thinning
Dished Ends Text one liners. According to Registration Inspection Findings for Thinning
Nozzles & joint faces Text one liners. According to Registration Inspection Findings for Thinning
Lining/Cladding Text one liners. According to Registration Inspection Findings for Thinning
Welds Text one liners. According to Registration Inspection Findings for Thinning
Vortex breaker Text one liners.
Coil Text one liners.
Baffles, demister, etc. Text one liners.
Level legs Text one liners.
Skirt saddles Text one liners.
Insulation Text one liners.
Insulation supports Text one liners.
Pressure Bolting Text one liners.
Holding down bolts Text one liners.
General All significant findings to be reported with reference to attached equipment sketch (key points) 80
Reporting Findings
N11
Format for UT
N37
46A 48A
46B 48B
N8
N17
N7
N35
45B
45A
N1
Tnom DCA MAT Feb. 2009 Next T/A
Body
mm mm mm Min. Max. Min. Max.
Btm dished end
Shell
Top dished end
Dia. Tnom DCA MAT Feb. 2009 Next T/A

Nozzles
mm mm mm mm Min. Max. Min. Max.
N1
N7
Etc.
81
Reporting Findings
Format for Tube-end Gauging
Sample: 8 (10%) Type: Random Min.Allowable-ID: 22.0 mm

Min. ID (mm)
Feb. 09 Next T/A Next T/A
Tube Nr Inlet Outlet Inlet Outlet Inlet Outlet
1.3
3.4
4.7
82
Reporting Findings
Format for ET
Technique: Sample type: random

Thinning (%)
Date Sample
<20 20-30 30-40 40-50 50-60 60-70 70-80 80-90 90-100
Feb. 09 8
83
Retreivability Inspection Findings
Locations must be reported in an unambiguous way

Testing/reporting direction must be defined on equipment sketch
The following guidance could be used:

Vertical equipments items
Direction from bottom to top head
Clock positions to be related to above direction, whereas manhole = 12 oclock
Horizontal equipment items

Direction from NE SW or from NW SE
Clock-positions to be related to above directions
84
Retreivability Inspection Findings
Examples
SW NE
Top
SE NW
Btm
85
2. Stress Corrosion Cracking (SCC)
2. Contents
2.1 Mechanism
2.2 Main types of SCC
2.3 Inspection
2.4 Reporting
86
2.1 Mechanism
87
Stress Corrosion Cracking (Wet)
Sequence of Events leading to SCC
Mechanisms
Brittle film rupture
Enobled layer
Passive film
Active path
Slip assisted dissolution
Hydrogen assisted cracking 88
Stress Corrosion Cracking
Models for Intergranular type of Cracking
Tarnish Rupture Model (Modified)

Brittle film rupture
Rupture of the protective surface film

Dissolution of the exposed metal until the protective film has been restored
Crack growth by repetition of the above process
89
2.2 Main types of Stress Corrosion Cracking
90
Stress Corrosion Cracking
Caustic Cracking S2
Polythionic Stress Corrosion Cracking S3
Chloride Stress Corrosion Cracking S4
Amine Stress Corrosion Cracking S5
Wet H2S Cracking S1
Carb.-/Bi-Carb. Stress Corrosion Cracking S1-1
91
Structure of presentations Stres Corrosion Cracking
Specifics
Description
Mechanism, when different from general types

Materials
Morphology
Microscopic
Macroscpic
Examples
Inspection, when different from general types

92
Caustic Cracking: S2
Specifics
Process related
Typical Units : CDU, Merox, Caustic Gas Treating
Description
Might occur when CS in the as-welded condition is exposed to a caustic
environment at (elevated) temperatures.
Notes:
1. Allowable temperature depends on caustic concentration
2. PWHT will extend the allowed operating temperature
From 70 to 110 C for 20% NaOH
3. Factors originating Caustic Cracking
Steam tracing
Steaming out
Temperature excursions 93
Materials
CS is commonly applied for caustic service
Ni-alloys are applied, when CS does not meet the
requirements anymore
94
Morphology
Microscopic : Intergranular cracking
Macroscopic : Cracking in weld region
Example
Network of fine cracks

Intergranular Cracking
95
Polythionic Stress Corrosion Cracking (PA-SCC): S3
Specifics
Process related
Typical Equipment : HTs, HCU
Description
Might occur when sensitized stainless steel, which has operated in an
H2/H2S environment (reducing sulphidizing), is exposed to the
atmosphere (O2 & humidity).
96
Materials
Sensitized stainless steel plate material is susceptible to PASCC
347 has highest resistance to sensitization
Sensitization
Operation at temperatures > 400 C for 321/347
Due to fabrication, e.g. welding & PWHT of base metal (1Cr, 2Cr)
97
Morphology
Microcopic : Intergranular cracking
Macroscopic
Mud type cracking
Elongated cracking
Example
98
Examples
Cracking in rolled bond cladding

Weld metal not sensitive to cracking
99
Chloride Stress Corrosion Cracking (Cl-SCC): S4
Specifics
Process related
Typical Equipment/Unit : CDU(Ovhd), HMU
(streams containing free water and chlorides)
Description
Might occur when stainless steel is exposed to an aqueous environment
above 50/60 C, containing Chlorides.
Presence of O2 enhances, whereas high pH reduces susceptibility
100
Materials
Susceptible materials are Stainless Steel of the type 18Cr8Ni
Up to 10 ppmw is tolerable in absence of O2
When O2 present than 1 ppmw might be sufficient
316 has highest resistance to Cl-SCC
At pH > 10 relatively high levels can be tolerated: up to 1000 ppmw
Relatively Resistant Materials
Super austenitic SS with Mo > 6%, e.g. 19hMo, 254SMO
Duplex Stainless Steels: DSS-2507 (difficult to weld)
Resistant Materials
Nickel Alloys with Ni% > 40,e.g. Monel 400, Incoloy 825, Inconel 625 and
Alloy C-276.
101
Morphology
Microscopic : Transgranular Branched Cracking
Macroscopic
Branched cracking
Crazy cracking
Example
102
Transgranular Branched cracking
Examples
Cl-SCC in head of HE External Cracking due to Chlorides

leached from insulation material
103
Amine Stress Corrosion Cracking (A-SCC): S5
Specifics
Process related
Typical Equipment/Unit : Amine Units, Absorbers in misc. Units
Description
Might occur when CS in the as-welded condition is exposed to an
aqueous lean amine solution.
Decreasing risk : MEA > DEA > MDEA > DIPA > SULFINOL
Notes:
1. Fresh amine solutions are not susceptible
2. Boundary between lean and fat (rich) solvent for gas loading
is 0.1 mol acid gas per mol amine
104
Material
Common material is CS
Susceptible to A-SCC in the as-welded condition
PWHT prevents A-SCC
105
Morphology
Microscopic : Intergranular Cracking
Macroscopic : In weld regions
Example
A-SCC in an elbow
106
Wet H2S-cracking: S1
Specifics
Process related
Typical Units : CDU, HVU, TGU, HTU, HDS, HCU, FCC
(almost all units containing H2S)
Description
Might occur when a susceptible steel is exposed to an aqueous
environment containing hydrogen sulphide, leading to hydrogen
charging
107
Mechanism
HAc H+ + Ac- H2S H+ + HS-
H2
Medium
Fe2+
Hads Hads H+ H+ Hads
e e Habs
Steel
Hinterstitial
Acid Corrosion Sour Water Corrosion

Recombination of H into H2 HS- recombination poison
at steel surface
Charging of steel with atomic H
Release of H2 via medium
108
Mechanism
Medium
H2S H+ + HS-
Fe2+
H+ Hads
e Habs
Steel
Hinterstitial
2H H2(gas) Hydrogen Embrittlement (HE)
Internal Cracks Cracking of Hard Zones

Blisters Hv > 248
Note:
- Wet H2S-cracking is strictly not a form of SCC
109
- It is Charging the material with H, resulting from Corrosion
Materials (SSC)
CS with Hv < 248
Materials (HB, HIC and SOHIC)

Standard CS
Plate materials are susceptible due to type 2 MnS-inclusions
Forgings not susceptible
Failures of seamless piping reported by exception
CS resistent to HIC special requirements
Limitations on chemical composition : S, C, Mn & P
Shape control non-metallic inclusions: Ca treatment round shapes
Limitation on Grade : Max. Grade 65 (UTS < 450 Mpa)
Testing on HIC-resistance : NACE TM 0177
110
Morphology
Sulphide Stress Cracking (SSC)
Hygrogen Blisters (HB)
Hydrogen Induced Cracking (HIC)
Stress Oriented HIC (SOHIC)
111
Examples
Sulphide Stress Cracking (SSC)
SSC in a hard Weld Region

112
Examples
Hygrogen Blisters (HB)
Blisters surface Blisters cracked open to surface
Blister at sub surface Blister at mid wall thickness
113
Examples
Hydrogen Induced Cracking (HIC)
(LINEAR) HIC SWC
114
Examples
Cracking in Weld
SOHIC in Weld Region
115
Examples
116
Inspection
SSC : As for SCC
HB : Visual
HIC & SOHIC : Combination of Special UT-techniques by Contractor
Normal wave, shear wave and ToFD
In general automated
117
Carbonate Stress Corrosion Cracking: S1-1
Specifics
Process related
Typical Units : FCC (units containing H2S and CO2)
Description
Might occur when CS/LAS is exposed to an environment of alkaline
sour water (pH>7.6), containing CO3=/HCO3-, when the material is in the
as-welded condition.
118
Materials
CS and LAS in the PWHT-condition is resistant to Carb. SCC
Morphology
Microscopic : Intergranular cracking
Macroscopic : Cracking in weld region
119
Example
Cracking at Stress Raiser
Penetration of Root Weld
Cracking in Base Metal

parallel to Weld
120
2.3 Inspection
121
Assessment Cracking in Equipment
Surface breaking
Near side
MT or PT
oRegistration by digital photos
Far side
UT-shearwave, when examined from other side
Embedded
Combination of specialized UT-techniques
Note: ToFD to be used for sizing
122
Registration Inspection Findings for Cracking
Density/Number per
Extent
Morphology Code Area
Cracking Cra Lenth Number of cracks / dm2

Blisters Bli Dia average blister Number of blisters / dm2
Class Depth Extent Density/

in mm in mm Number
1 < 0.2 < 10 1
2 0.2 0.5 10 50 25
3 0.5 1.0 50 - 100 6 10
4 12 100 - 200 11 20
5 23 200 500 21 50
6 35 > 500 > 50
7 57
8 7 10
9 > 10
123
2.4 Reporting
124
Reporting Findings
See format for VI as defined in ITP
INSPECTION FINDINGS
Text one liners. According to Registration Inspection Findings for Cracking
Shell
Reference to report, when applicable (HIC & SOHIC)
Dished Ends
Nozzles & joint faces
Lining/Cladding Text one liners. According to Registration Inspection Findings for Cracking
Welds Text one liners. According to Registration Inspection Findings for Cracking
Holding down bolts Text one liners. 125
General All significant findings to be reported with reference to attached equipment sketch (key points)
3. High Temperature Degradation Mechanisms
3. Contents
3.1 Types of HT Degradation
3.2 Reporting
126
3.1 Types of High Temperature Degradation
127
High Temperature Degradation
High Temperature Hydrogen Attack H1
Creep H2
Temper Embrittlement H3
Sigma-phase Embrittlerment H4
Sensitization H5N
Hydrogen Embrittlement H8N
128
Structure of presentations High Temperature Degradation
Specifics
Description
Mechanism
Materials
Morphology
Examples, when available
Inspection
129
High Temperature Hydrogen Attack (HTHA): H1
Specifics
Process related
Typical Units : CCR, HTs, HCU, Isomer, HMU
Description
Might occur when CS/LAS is exposed at high temperatures (> 240 ) to
an environment containing H2 (ppH2 > 7 bara)
130
Mechanism
Atomic hydrogen diffuses into steel & reacts with carbides in the steel:
Fe3C + 4H 3Fe + CH4
Schematic illustration showing process of

bubble growth and failure of grain boundary Original Microstructure: HTHA:
1: Ferrite 3: Decarburization
2: Pearlite 4: Fissure
131
Materials
Increasing resistance to HTHA : CS 1Cr/1Cr 2Cr
7 bara
ppH2
Temperature
HTHA Resistance Curves
Increased Resistance
No Hydrogen Attack !!
2.25%Cr-1Mo Steel
1%Cr-0.5Mo steel
1%Cr-0.5Mo + 1.25%Cr-Mo Steel

Carbon Steel
240 C
No Hydrogen Attack !!
Partial Pressure of H2
Note: Since some years the curve for Mo 132

is considered the same as for CS
Morphology
CS
Total Decarburization & Fissuring
Inspection
Advanced Ultrasonic Backscatter Techniques (AUBT)
to be carried out by a Contractor
133
Creep: H2
Specifics
Non-Process related
Typical Equipment : Heaters, HP-Steam Systems
Description
Time dependent deformation of materials under constant load at
elevated temperatures
Note:
Driving Force are the primary stresses: internal pressure and dead weight
134
Creep: H2
Mechanism
Development of failure
Original structure
Micro-cracking: < 2mm
Isolated cavities
Macro-cracking: > 2mm
Oriented cavaties
135
Creep: H2
Materials
Material Threshold temperature C
CS 410
1 Cr Mo 500
2 Cr 1 Mo 480
5 Cr Mo 470
9 Cr 1 Mo 515
304H 580
347H 595
136
Creep: H2
Morphology
Failure: End of third stage
137
Creep: H2
Inspection/Assessment
Dimensional measurements
Gouging deformation
Destructive techniques
Accelerated creep test on samples (cut-outs)
Non-Destructive techniques
Specialised UT (Conam)
Replica examination
Calculation of Usage Factor U
Based on actual operating conditions
Monitoring, when U > 0.6
138
Temper Embrittlement: H3
Specifics
Non-Process related
Typical Units : HTs & HCU (Rs & F/E-HEs)
Description(1)
Loss of ductility of low alloy CrMo-steels, when held within or cooled
slowly through a certain temperature range
Notes:
1. Temperature range : 370 575 oC
2. Most rapidly : 460 oC
3. Brittle at temperatures below 150 oC
139
Description(2)
Charpy Transition Curves for New and Embrittled Steel
Energy
TTNew TTEmbrittled
Hammer
Ductile
10 mm
2 mm Tshift
New
Tshift Embrittled
Charpy Impact Testing Brittle
Required energy
to break the specimen
Test Temperature
140
Mechanism
Segregation of impurity elements at the grain boundaries
Sb, P, Sn & As
Materials
Shift in transition temperature in tests

Highest susceptibility for 2 Cr1Mo- & 3Cr1Mo-steel
141
Morphology
Inspection
Not applicable
Mitigation
Limiting stresses at lower
Reactor failed after hydrotest temperatures
S/U S/D procedure
No hydrotest
142
Sigma-phase Embrittlement: H4
Specifics
Non-Process related
Typical Unit : FCC
Description
Loss of Ductility of Stainless Steels resulting from the precipitation of
Sigma-Phase (hard brittle phase containing about 50% Cr) at elevated
temperatures
Notes:
1. Temperature range : 540 924 oC
2. Most rapidly : 750 / 850 oC
143
Mechanism
Precipitation of sigma-phase at grain boundaries or within grains
Growth into ferrite grains : few hrs
Growth within austenite grains : few thousand of hrs
Materials
Growth into ferrite grains
Weld metals of Stainless Steels of the type 18Cr8Ni
Stainless Steels with %Cr > 17 (DSS)
Growth within austenite grains
Stainless Steels of the 300-series with high %Cr, e.g. 310 (&HK40)
Alloy 800 less susceptible than 300-series of SS
144
Morphology
Before Exposure After Exposure
Furnace fitting from 310

Exposure time > 2.5 yrs
145
Inspection
Not applicable
Mitigation
Growth into ferrite grains
Ferrite < 7 % for weld metal SS type 18Cr8Ni
Growth within austenite grains
S/U S/D procedure
No chock loads
146
Sensitization: H5N
Specifics
Non-Process related
Typical Units : HTs, HCU
Description
Sensitisation refers to the precipitation of carbides at grain boundaries
of Stainless Steels of notably the 300-series, resulting in depletion of Cr
in the areas adjacent to the grain boundaries.
Notes:
1. Range for sensitisation : 425 870 oC
- Within minutes : 650 oC
- Within hours : 500 & 800 oC
- Within years : 425 & 870 oC
2. When the precipitation is relatively continuous, the depletion
leaves the steel susceptible to intergranular corrosion (e.g. PA-SCC).
147
Sensitization: H5N
Mechanism
Precipitation of carbides at grain boundaries
Difference in diffusion velocity of C and Cr
Solution Annealed 18-8 Stainless Steel Sensitised 18-8 Stainless Steel
Grain Cr-Carbides
boundaries
Cr-Depleted Zones
NormalStructure
Grain Boundaries are Depleted from Cr

Grain Boundaries NOT Affected
%CR over X-Section of Depleted Zone
%Cr
Grain
Boundary
X-Section over 18
Depleted Zone
Cr-Depleted
Zone
Distance from Grain Boundary

148
Sensitization: H5N
Materials
Stainless Steels of the 300-series
Main Factors determining Sensitization
Chemical composition
Carbon-content
Alloying elements for chemical stabilisation: Nb & Ti
Heat treated condition
Solution Annealed : 1050 oC
Solution & Stabilised Annealed : 1050 / 950 oC
Annealing after welding : 950 oC
149
Sensitization: H5N
Morphology
Microstructure of sensitized AISI 304
150
Sensitization: H5N
Inspection
Not applicable
Testing
DOS-testing (Degree Of Sensitization)
Mitigation
Selection of grade of 18-8 SS
Low Carbon Grades
Chemical Stabilization
Heat treatment
Stabilizing
Homogenizing
151
Hydrogen Embrittlement: H8N
Specifics
Process related
Typical Units : CCR, HTs, HCU, Isomer, HMU
Description
Loss of ductility of CS and LAS when exposed at high temperatures to
an environment containing H2.
152
Mechanism
Dissociation of molecular H2 into atomic H
Diffusion of H into the steel
Restricting plastic flow
Enhanced susceptibility to brittle fracture initiating at:
o Existing defects,
o Locations of stress concentration,
when exposed to temperatures below 150 C
Materials
CS
LAS: Mo, 1Cr, 1Cr, 2Cr
153
Morphology
Inspection
Not applicable
Reactor failed after hydrotest
154
Inspection
Not applicable
Mitigation
Limitation of stresses (S/U-S/D Procedure)
o H-content > 3 ppm
Pressure < 1/3 Design value
Heating-/Cooling rate < 42 C/hr
o 1 < H-content ppm < 3

Heating-/Cooling rate < 42 C/hr
o H-content < 1 ppm
No limitations
155
3.2 Reporting
156
Reporting Findings
See format for VI as defined in ITP
INSPECTION FINDINGS
Shell Text one liners. Reference to report, when applicable (HTHA & Creep)
Dished Ends Text one liners. Reference to report, when applicable (HTHA & Creep)
Nozzles & joint faces Text one liners. Reference to report, when applicable (HTHA & Creep)
Lining/Cladding Text one liners.
Welds Text one liners. Reference to report, when applicable (HTHA & Creep)
Holding down bolts Text one liners.
General All significant findings to be reported with reference to attached equipment sketch (key points) 157
End
158

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Inspection Main Degradation Mechanisms

An Overview for CDU, CCR, DHP, Isom.

Shell Global Solutions International

Electrochemical (wet-corrosion, low temperature)

Chemical Attack (dry-corrosion, high temperature)

Corrosion rates increase with:

Hads Hads H+ Reactions

Metal Non-Porous layer

Parabolic  Linear : Porous or strong spalling layer

General Thinning Pitting in

NAC in CS furnace tubes NAC in feed section of HVU

NAC in bubble caps of 317

Interaction between sulphur and naphthenic acid

Sulphidation of the steel and the enhancement of sulphur

Corrosion of the steel by Naphthenic Acids

Sulphidation of the steel and the enhancement of sulphur

Naphthenic acid and sulphur corrosion have both a

For CS the corrosion reaction

Damaged Cladding Corrosion Under Insulation

Hads Hads H+ Fe Fe2+ + 2e

 HCl dissolves in water, creating a (very) corrosive environment

 H2S dissolves partly in water, creating a weak acidic environment

 NH3, in general present in vapor stream, dissolves in water and increases

Note: Velocity/Turbulence increases corrosion rate markedly

Localised thinning in a Localised thinning in a 37

Localized Corrosion on Tube ID

Hads Hads H+ Fe Fe2+ + 2e

Forming of corrosive medium

Hads Hads H+ Fe Fe2+ + 2e

Forming of corrosive medium

Oxidation of a carbon steel nut

Steel Steel Steel Steel

X-section Metal Whiskers

Mixed Flow Vapor

HCs Sour Water

Water-in-Oil Dispersed Oil-in-Water Dispersed

Generation of water droplets by

Increasing Gas Velocity

Guidelines to assess General versus Localized Corrosion

Guideline to assess Even versus Uneven Corrosion

Class Depth Extent Density/

Relatively small equipment items,

Colmns, Reactors & large Vessels

Note: Nozzles & Manholes should be considered as separate components

MPs on intersections Scanning of areas Combination

Assess following parameters per

Select UT-C or UT-G

End End End

Dia. Tnom DCA MAT Feb. 2009 Next T/A

Sample: 8 (10%) Type: Random Min.Allowable-ID: 22.0 mm

Technique: Sample type: random

Locations must be reported in an unambiguous way

The following guidance could be used:

Horizontal equipment items

Tarnish Rupture Model (Modified)

 Rupture of the protective surface film

Mechanism, when different from general types

Inspection, when different from general types

Network of fine cracks

Cracking in rolled bond cladding

Cl-SCC in head of HE External Cracking due to Chlorides

HAc H+ + Ac- H2S H+ + HS-

Hads Hads H+ H+ Hads

Parabolic Linear : Porous or strong spalling layer

HCl dissolves in water, creating a (very) corrosive environment

H2S dissolves partly in water, creating a weak acidic environment

NH3, in general present in vapor stream, dissolves in water and increases

Generation of water droplets by

Horizontal equipment items

Rupture of the protective surface film