UNIVERSITY OF THESSALY

POLYTECHNIC SCHOOL
DEPARTMENT OF MECHANICAL ENGINEERING
LABORATORY OF MATERIALS

Diploma Thesis

Investigation of Stress-Oriented Hydrogen-Induced

Cracking (SOHIC) in an Amine Absorber Column of
an Oil Refinery
By
Papageorgiou Pantelis-Panagiotis

Supervisor:
Dr. Helen Kamoutsi

Submitted for the Partial Fulfillment

of the requirements for the degree of
Diploma in Mechanical Engineering

Volos
2019
© 2019 Pantelis-Panagiotis Papageorgiou
The approval of the Diploma Thesis by the Department of Mechanical Engineering of
the University of Thessaly does not imply acceptance of the author’s opinions. (Law
5343/32, article 202, paragraph 2).
 Certified by the members of the Thesis Committee:

First examiner Dr. Helen Kamoutsi

(Supervisor) Lab Teaching Staff, Department of Mechanical Engineering,
University of Thessaly

Second Examiner Dr. Nikolaos Aravas

Professor, Department of Mechanical Engineering,
University of Thessaly

Third Examiner Dr. Alexandros Kermanidis

Assistant Professor, Department of Mechanical Engineering,
University of Thessaly
Acknowledgments
This project is accomplished in the scope of partial fulfilment of the requirements for
the degree of Diploma in Mechanical Engineering at University of Thessaly.
For the completion of this Thesis, I would like to thank my thesis supervisor, Dr. Helen
Kamoutsi whose expertise, valuable suggestions, comments, guidance and patience
further considerably my knowledge, as well as for the support over this semester.
Furthermore, very special thanks go to Professor Nikolaos Aravas and Assistant
Professor Alexandros Kermanidis for accepting to be the referees of this work.
I would also like to express my great appreciation Professor Nikolaos Aravas, for his
important guidance at appendix A and Associate Professor Kyriaki Polychronopoulou
for conducting the SEM experiments.
I would also like to thank Professor Gregory Haidemenopoulos for giving me the
opportunity in the current Thesis to deal with such an interesting topic.
Last but not least, special recognition goes to my family and all my friends for their
continuous support and encouragement during this study.

Pantelis-Panagiotis Papageorgiou
Abstract
Stress oriented hydrogen induced cracking (SOHIC) of an amine absorber column
made of a HIC-resistant steel and operating under wet H2S service was investigated.
SOHIC was not related to welds in the column and evolved in two steps: initiation of
HIC cracks in the rolling plane and through-thickness linking of the HIC cracks. Both
the original HIC cracks as well as the linking cracks propagated with a cleavage
mechanism. The key factors identified were periods with high hydrogen charging
conditions, manifested by high H2S/amine ratio, and stress triaxiality, imposed by the
relatively large thickness of the plate. In addition, the mechanical properties of the
steel away from cracked regions were unaffected, indicating the localized nature of
SOHIC.
Table of contents
Acknowledgments.......................................................................................................... 4
Abstract .......................................................................................................................... 5
1 Introduction .......................................................................................................... 10
1.1 Description of the problem ........................................................................... 10
1.2 Thesis objectives ........................................................................................... 11
1.3 Thesis methodology ...................................................................................... 11
1.4 Thesis outline ................................................................................................ 12
2 Literature Review.................................................................................................. 13
2.1 Amine absorber column ................................................................................ 13
2.1.1 Operating conditions ............................................................................. 13
2.2 Corrosion ....................................................................................................... 15
2.2.1 Hydrogen service ................................................................................... 15
2.2.2 Corrosion by amine solution. ................................................................. 20
2.3 Material ......................................................................................................... 21
2.3.1 Vacuum induction melting (VIM). .......................................................... 21
2.3.2 Vacuum Arc Remelting (VAR)................................................................. 22
3 Material Studied ................................................................................................... 24
3.1 Amine absorber column ................................................................................ 24
3.1.1 Operating conditions ............................................................................. 24
3.1.2 Material .................................................................................................. 24
3.2 Experimental Procedures .............................................................................. 25
3.2.1 Sampling Position ................................................................................... 25
3.2.2 Ultrasonic Testing. ................................................................................. 26
3.2.3 Metallographic ....................................................................................... 27
3.3 Mechanical Testing........................................................................................ 28
3.3.1 Tensile Test ............................................................................................ 28
3.3.2 Charpy–V–Notch .................................................................................... 29
3.3.3 Vickers hardness test (HV), 0.3 kg.......................................................... 30
3.3.4 Fractography .......................................................................................... 30
4 Results and Discussion .......................................................................................... 32
4.1 Material characterization .............................................................................. 32
4.2 Stereoscope ................................................................................................... 33
 4.3 Metallographic Characterization of SOHIC and HIC ...................................... 35
4.4 Fractographic Analysis of Opened SOHIC crack ............................................ 46
4.5 Implications for H2S/ Amine Service ............................................................. 51
5 Conclusions ........................................................................................................... 53
6 Appendix A ............................................................................................................ 54
7 References ............................................................................................................ 55
List of Figures
Figure 1. Amine Absorber Column [1]. ........................................................................ 13
Figure 2. Steel with typical small imperfections. ......................................................... 16
Figure 3. Kind of cracking [20]. .................................................................................... 17
Figure 4. Mechanisms of SSC cracking ......................................................................... 19
Figure 5. Schematic of a top-opening, double-chamber vacuum induction melting
furnace [31]. ................................................................................................................. 22
Figure 6. Vacuum Arc Remelting [32]. ......................................................................... 23
Figure 7. Blistering in internal surface ......................................................................... 25
Figure 8. Shell section for analysis ............................................................................... 25
Figure 9. System of axes used for the positioning of specimens. ................................ 26
Figure 10.Positions of UT signals ................................................................................. 27
Figure 11. Diagram of Tensile Test ............................................................................... 28
Figure 12.Positions of tensile specimens as well as CVN-A and CVN-B specimens
relative to ID and OD.................................................................................................... 29
Figure 13.Positions of the CVN-C specimens relative to ID and OD. ........................... 29
Figure 14. HIC and SOHIC at location 604 .................................................................... 33
Figure 15. Opposing face at location 500. ................................................................... 34
Figure 16. HIC/Blisters at location 577 ........................................................................ 34
Figure 17. HIC/Blisters at location 577 ........................................................................ 35
Figure 18. Ferrite-pearlite microstructure of the investigated steel. .......................... 35
Figure 19. SOHIC at location 604 ................................................................................. 36
Figure 20. HIC at the location 604, at 1.06mm from ID. No.1 at the mapping ........... 37
Figure 21.HIC at location 604, at 12.4mm from ID. No.3 at mapping ......................... 37
Figure 22. HIC at location 604, at 9.3mm from ID. No.2 at mapping .......................... 38
Figure 23. HIC at location 604, at 30.5 from ID. .......................................................... 38
Figure 24. Mapping of section 604 .............................................................................. 39
Figure 25.HIC at location 577 ....................................................................................... 39
Figure 26.HIC at location 577 ....................................................................................... 40
Figure 27.HIC at location 577 ....................................................................................... 40
Figure 28. tip of HIC indicating propagation in ferrite between pearlite colonies. ..... 41
Figure 29. SOHIC at location 500 ................................................................................. 41
Figure 30. SOHIC at location 500 opposite surface. ....... Error! Bookmark not defined.
Figure 31. Magnification of Figure 30 in position 1. .................................................... 43
Figure 32. Magnification of Figure 30 in position 2. .................................................... 43
Figure 33. Magnification of Figure 30 in position 3. .................................................... 43
Figure 34. Magnification of Figure 30 in position 4. .................................................... 44
Figure 35. Magnification of Figure 30 in position 5. .................................................... 44
Figure 36. Magnification of Figure 30 in position 6. .................................................... 44
Figure 37. Magnification of Figure 30 in position 7. .................................................... 45
Figure 38. Magnification of Figure 30 in position 8. .................................................... 45
Figure 39. Magnification of Figure 30 in position 9. .................................................... 45
Figure 40. Magnification of Figure 30 in position 10. .................................................. 46
Figure 41. Assembly of SEM micrographs depicting the fracture surface of the opened
SOHIC crack at position 500. The location of HIC cracks and individual SEM
micrographs is indicated. ............................................................................................. 48
Figure 42. Boundary between SOHIC and “fresh” fracture. ........................................ 49
Figure 43.Dimple fracture in the “fresh” fracture region. ........................................... 49
Figure 44. Cleavage fracture at SOHIC region.............................................................. 49
Figure 45. Cleavage fracture in SOHIC region between HIC cracks. ............................ 50
Figure 46. A large HIC crack at the SOHIC fracture region........................................... 50
Figure 47. Cleavage fracture morphology of the internal blister/HIC crack wall. ....... 50

List of tables
Table 1.Chemical Composition .................................................................................... 24
Table 2.Mechanical Properties .................................................................................... 24
Table 3.Tensile test results at different locations throughout the thickness of the plate.
...................................................................................................................................... 32
Table 4. Results from CVN-A impact test configuration. ............................................. 32
Table 5. Results from CVN-B impact test configuration. ............................................. 32
Table 6. Results from CVN-C impact test configuration. ............................................. 33
Table 7. Results from Hardness Test Vickers. .............................................................. 33
1 Introduction
1.1 Description of the problem
Amine absorber columns in oil refineries are columns which are used to remove acid
gas from natural gas or natural gas liquid (NGL). The most common acid gas was
hydrogen sulfide (H2S) and carbon dioxide (CO2), where a down flowing amine solution
absorbs H2S from the up flowing sour gas stream. The H2S-rich amine solution, when
exiting the absorber, is routed to a regenerator to produce an H2S-lean amine that is
recycled for use in the absorber. This process is called sweetening process cause the
pH increasing of the stream [1].
Under specific operation conditions, where the ratio of H2S/amine is high, H2S
corrosion of the steel shell can take place, producing hydrogen, which can then enter
the steel and cause hydrogen blistering and hydrogen-induced cracking. According to
API 571 [2], it is atomic hydrogen that enters the material and diffuses through the
lattice. The hydrogen is then concentrated to various microstructural sites, such as
interfaces between the matrix and inclusions or interfaces between the matrix and
other phases. The local pressure increases and decohesion takes place, generating
internal blistering or so-called hydrogen-induced cracking (HIC). In most cases HIC
cracks are oriented parallel to the rolling plane. Under the action of applied or residual
stresses the HIC cracks arrange in a vertically (through thickness) stacked array.
Subsequently the array is joined by cracks between the individual HIC cracks, which
run perpendicular to the main applied stress. The interconnected HIC cracks, which
run through the thickness of the plate form a significant through-thickness crack. This
cracking is classified as stress-oriented hydrogen-induced cracking (SOHIC). As
mentioned above, hydrogen is produced by a corrosion reaction, such as when steel
is exposed to wet H2S service.
Hydrogen damage in wet H2S environments is classified as blistering, hydrogen
induced cracking, stepwise cracking [3], stress oriented hydrogen induced cracking
and sulfide stress cracking in API 571 recommended practice[2]while the assessment
of hydrogen damage is performed in accordance with API 579 [4] following the work
of Buchheim et al. [5] on the development of a fitness-for-service rules for the
assessment of HIC and SOHIC damage. While hydrogen blistering and HIC is a frequent
problem when steel operates in wet H2S service, SOHIC is a rather rare phenomenon
and when occurring is mostly associated with residual stresses at welds. SOHIC in
pipelines and pressure vessels has been thoroughly reviewed by Pargeter [6]. Most of
the case studies reported, associated with SOHIC, are related with SOHIC at welds and
concern mostly pipelines. There is only one case of SOHIC in an amine absorber
column, reported by McHenry et al. [7] regarding the Chicago refinery incident in
1984. Even in this case, SOHIC originated from the HAZ of a repair weld, which did not
receive a stress relieving post weld heat treatment. Following the Chicago refinery
incident, the Occupational Safety and Health Administration (OSHA) of the
Department of Labor issued, in 1986, a memorandum [7] stating, among others, that
in a survey of similar refinery vessels and associated equipment, conducted by the
National Association of Corrosion Engineers (NACE), approximately 60% of 24 amine
absorbers evaluated, exhibited cracking. In addition, 12 of 14 monoethanolamine
(MEA) units and three of five diethanolamine (DEA) units exhibited cracking. Sixteen
instances of cracking were reported in associated equipment (i.e., regeneration units
and piping) exposed to a chemically similar environment. Additionally, a similar survey
by the Japan Petroleum Institute indicated that cracking had occurred in 72% of the
amine gas treatment facilities, which had responded to the survey.
As mentioned above, most failure cases involving SOHIC refer to welded piping, such
as the work by Anezi et al. [8] in spiral welded pipes. The effects of loading and
microstructure have been discussed by Kobayashi et al. [9] as well as by Koh et al. [10],
while the effects of heat treatment on SOHIC of pressure vessel steels have been
discussed by Tsuchida et al. [11]. Most reported results refer to HIC, as the work of
Findley et al. [12] on the mechanism of HIC in pipeline steels and the work of Gan et
al. [13] on hydrogen trapping in H2S environments. In-situ observation of HIC
propagation is reported by Fujishiro et al. [14], while corrosion-induced microcracking
in H2S environments has been discussed by Okonkwo et al. [15]. A recent review of
HIC in pipelines and pressure vessel steels is presented by Ghosh et al. [16]. The
reported cases of SOHIC failures in pressure vessels are limited and mostly associated
with welds. The present case refers to SOHIC in the base plate of a pressure vessel,
away from welds. This is a rare case and it is, therefore, very important to investigate
the conditions and contributing factors of this type of damage.
A decommissioned amine absorber column, which exhibited hydrogen blistering in the
internal wall, was made available for study. The aim of the present work is to
investigate the underlying SOHIC damage and to identify the contributing factors that
led to cracking.
Parts of this thesis are contained in paper which was published in MDPI journal at 24
August 2018 and was presented at the ICEAF V 5th International Conference of
Engineering Against Failure 20 - 22 June 2018 Chios Island, Greece.

1.2 Thesis objectives

In view of the above considerations, the present thesis tries to further elucidate the
failure mechanisms that occurring in wet H2S service. Also, to explain the operation
condition that led to this failure.

1.3 Thesis methodology

Research was focused on steel SA-516 Gr 60 HIC resistant. The experimental
procedures involved the following actions:
1) Ultrasonic Test
2) Tensile Test
3) Charpy -V-Notch
4) Hardness Test Vickers
 5) Fractography

1.4 Thesis outline

The thesis outline is as follows:
1. Introduction
2. Literature review
3. Experimental procedures
4. Results and Discussion
5. Conclusions
2 Literature Review
2.1 Amine absorber column
2.1.1 Operating conditions
The removal of acid gas such as hydrogen sulfide (H2S) and carbon dioxide (CO2) from
natural gas or is usually necessary in gas plants and oil refineries. The absorption
process using aqueous solutions of alkanolamines is often used as a treatment
technology. Figure 1 illustrates the process flow diagram of a typical amine-
sweetening unit. The system consists of two major operations: absorption and
regeneration.

Figure 1. Amine Absorber Column [1].

A natural gas stream that contains acid gases (H2S and/or CO2) is introduced into an
absorber column where the stream is counter-currently contacted with an amine
solution. The acid gas contents are removed by chemical reactions with the amine.
After treatment, the natural gas is suitable for consumer use or further chemical
processing. This process is referred to as a gas sweetening process and treated gas is
called sweetened gas or liquid. After the absorption process, the amine solution,
(referred to as rich amine solution after selectively absorbing the acid gases) requires
regeneration before it can be used to sweeten sour gas again. The regeneration
column serves the function of stripping absorbed acid gases from the rich amine
solution. A flash tank is usually installed at the outlet of the absorber to permit the
recovery of the dissolved and entrained hydrocarbons and to reduce the hydrocarbon
contents of the acid gas product. The flash gas from the flash tank and the stripped
acid gas from the regenerator in amine units have the potential to emit hazardous air
pollutants and volatile organic compounds. In processes for complete acid-gas
removal, when the column contains enough trays or packed depth, treated gas quality
is determined by phase equilibrium, [1].
The amine solution temperature entering the absorber is usually 10 to 15oC higher
than the inlet feed gas temperature to prevent condensation of hydrocarbon in the
contactor, which can cause foaming. The inlet feed gas usually enters the absorber at
38 - 49 oC. Therefore, the typical range of lean amine solvent temperature is 46 - 57oC.
It is good practice for the lean amine solvent temperature not exceed 57 oC. High lean
solvent temperatures can lead to poor solvent performance due to H2S equilibrium
problems on the top tray of the absorber or increased solution losses due to excessive
vaporization losses. The temperature of rich amine leaving the absorber will be 54.4
to 71.1°C [17].
2.2 Corrosion
A common failure at the absorber is the corrosion by H2S service or by amine solution.
At this section are listed the categories of the failure.

2.2.1 Hydrogen service

Hydrogen damage failures are classified in two categories based on the corrosion
mechanism:

• Electrochemical processes arising from acid corrosion or cathodic protection

at low temperature, up to 100 oC.
• High temperature,200 oC until 900 oC, arising from the presence of hydrogen
gas at high pressure.
At the following subsection only the first category is analyzed, as in the case of the
absorber studied in this thesis, the operating temperature was 70 oC. As discussed in
the above, in the presence of aqueous solution of acids H2S, iron corrodes according
to two electrochemical reactions that occur simultaneously, a cathodic and an anodic
reaction. According to, the Groysman, Kane and Zheng [18-21] the anodic reaction is:

Fe(s) → Fe2+
(aq) + 2e
-

Which consists of the dissolution of iron in positive metallic ions (Fe2+) and electrons
remaining on the metal surface. These electrons concentrate on adjacent areas with
higher electric potential. The cathodic reaction is:
+
H2S + 2e- → 2Η(aq) + S2-
+
2 Η(aq) + 2e- → H2(g)

Hydrogen sulfide is collecting electrons from the anodic reaction releasing hydrogen
cations and sulfide anions. Also, electrons are collecting from the generated hydrogen
cations and are created hydrogens in gas form. Finally, the complete reaction is:
Fe(s) + H2S(aq) → FeS(s) + H2(g)
Depending on the chemical composition of the alloy, H2S concentration, temperature
and pH the net reaction can create different corrosion products (iron sulfides). Some
of them are:

• Iron (II) sulfide (FeS, amorphous)

• greigite (iron (II, III) sulfide, Fe3S4
• analog to magnetite Fe3O4)
• pyrrhotite (Fe1−xS, where x = 0–0.2, Fe7S8)
• troilite (FeS, crystallic)
• mackinawite (Fe1+xS, where x = 0–0.1or Fe9S8)
• marcasite (iron (II) disulfide FeS2, orthorhombic)
• pyrite (iron (II) disulfide FeS2, cubic)
If the iron sulfide concentration is low, a thin protective file is created at the surface
of the steel protecting it from corrosion. If the concentration is high, the iron sulfide
is more electrically potential than the iron surface and as a result corrosion reaction is
accelerated.
By the above net reaction atomic hydrogen forms, which is very active and diffuses
into the metallic lattice. When atomic hydrogen is concentrated, it recombines H2,
which due to its larger dimension is prohibited from entering, absorbing and diffusing
into the metallic lattice. On the metal surface this recombination occurs faster than
the gas phase. The ratio of rates of cathodic reduction of H+ and formation of H2 define
the intensity of hydrogen absorption by the steel. The ions S2- and HS- accelerated the
cathodic reaction of H+ and decrease the recombination, which results in the
increasing of absorption of hydrogen by metal.

Figure 2. Steel with typical small imperfections.

Some atoms of hydrogen polarize and form H- ions. Some other atoms and gaseous
molecular hydrogen are present in equilibrium inside the steel. The accumulation
positions are: micro-voids, blowholes, pores, non-metallic inclusions, cracks,
accumulation of dislocations, and grain boundaries.
The microstructure of steel has significant influence on the absorption of hydrogen.
Much greater hydrogen solubility occurs in austenite steel than in ferrite. The rate of
hydrogen permeability is greater in perlite structure than in martensite.

The mechanical properties of steel (plasticity, ductility, toughness and tensile

strength) are changed significantly when hydrogen is absorbed in the microstructure,
as a result creating cracks. These cracks are classified in two categories [20].
In the first category the cracks arise without any externally applied or residual stress:
 • Internal cracking.
• Stepwise cracking.
• Hydrogen induced cracking (HIC).
• Hydrogen pressure induced cracking (HPIC).
In the second category belong cracks which the failure occurs under applied or residual
stresses, static or cyclic, such as:

• Stress orient hydrogen induced cracking (SOHIC).

• Sulfide stress cracking (SSC).

Figure 3. Kind of cracking [20].

2.2.1.1 Cracks without stress

As discussing above, the accumulation of atomic hydrogen forms molecules of
hydrogen at trap sites inside the steel lattice. The rolled products, along elongated
inclusions or segregated bands of microstructure, contains trap sites [3].

Hydrogen blistering: Is called the blister that become visible, from the deformation of
adjacent steel, at the surface of the material. They are created by rise of pressure
inside the voids in which the concentrate of molecules hydrogen is increased [3, 22,
23].
Hydrogen Induced Cracking (HIC): According the ELBOUJDAINI’s paper [23], Hydrogen-
induced cracking occurs in three steps:

• Formation of hydrogen atoms at the steel surface and adsorption on the

surface.
• Diffusion of adsorbed hydrogen atoms into the steel substrate.
• Accumulation of hydrogen atoms at hydrogen traps, such as voids around
inclusions in the steel matrix, leading to increased internal pressure and crack
initiation and propagation.
They are a form of blistering in which laminating-type fissures (exfoliation) parallel to
the metal surface link in the through-surface direction.
Stepwise Cracking: This type of cracking is formed by adjacent links of the hydrogen
blisters and the hydrogen induced cracking. Because it grows without applied or
residual stress, it increased as corrosion continues. In Figure 3, is shown the
morphology of stepwise cracking [3, 22, 24].
2.2.1.2 Cracks arise from applied or residual stress.
Sulfide stress cracking (SSC): Like the others cracks, this type occurs when the
hydrogen is diffused inside the steel matrix. The mainly difference with others cracks
is that SSC remains in solid solution in the crystal lattice[3]. For the development of
the embrittlement must applied tensile stress at the material. In Figure 3, is shown a
hydrogen embrittlement by SSC.
The steels with high strength microstructure (martensite and bainite) maximize
resistance to SSC. There are a lot of processes for producing these steels. Some of
them is annealing normalizing, normalizing and tempering, quenching and tempering
(Q&T). According to the preferred process is Q&T [20, 25]. Because she has two major
benefits:

• The production of a martensitic structure in the material by balancing steel

composition and the critical cooling rate to produce complete martensitic
transformation.
• A fully martensitic, as quenched structure allows tempering to be conducted
at higher temperatures leading to production of a high SSC resistant spheroidized
carbide structure while retaining high strength.
 Figure 4. Mechanisms of SSC cracking

Stress oriented hydrogen induced cracking (SOHIC):

Finally, the last kind of cracks is the SOHIC. This cracking is related with SSC or Stepwise
cracking. The main difference of these cracks is that the SOHIC small cracks, like as
HIC, formed perpendicular at the applied or residual stress. As a result, the creation of
‘ladder-like’ crack. SOHIC is related to the increase triaxial stress of the molecule’s
hydrogen and the yield strength of the material [3, 22, 24].
2.2.2 Corrosion by amine solution.
In oil refineries aqueous amine solutions are used to avoid corrosion from acid
solutions, like H2S or CO2. Amines are not sorely responsible for the corrosion of steel.
Corrosion in oil refineries is mainly caused by acid solution and by amine degradation
products. The amines that are usually used, are listed below:

• Monoethanolamine (MEA): The methanol molecule loses an H bond and

attaches to the amine molecule, which also lose an H bond. The formula is
CH2OHNH2
• Diglycolamine (DGA) and Diethanolamine (DEA): These are secondary amines,
which are similar with MEA, but they have two alcohol molecules for one
amine molecule. The formula is NHR 2, where are represent the alcohol
radical.
• Methyldiethanolamine (MDEA) and Diisopropanolamine (DIPA): These are
tertiary amines with 3 alcohol radicals to the N atoms. The formula is NR3
In the amine solution oxidation of hydrocarbons, results in the production of
contaminants (for example acid solutions, chlorides, sulfate, thiosulfate), which react
with the amine producing salts (for example formate, acetate, chloride, sulfate,
thiosulfate). These products are called Heat Stable Amine Salts (HSAS) or simply Heat
Stable Salts (HSS). The characteristic of these products is that they cannot be
destroyed under normal regenerator conditions, they cannot be recovered by heating
and they must have specific concentration to avoid corrosion [20].

According to L. Beke, steel reacts with H2S to form a layer of FeS on the surface that
protects the steel from further attack. As long as the layer of FeS is intact, the overall
corrosion rate is quite low. The iron sulfide layer is soft and friable. It can be worn
away by high flow velocity or turbulence. High HSS content increases the viscosity and
density of the amine solution. At the same time if higher amine solution circulation
rates are required to circulate enough free amine to pick up the acid gas, solution
velocities go up. This combination can result in erosion of the protective iron sulfide
layer exposing bare steel to further sulfidic attack and higher rates of corrosion [26].
Liu, Dean and Bosen investigated the corrosion rate of carbon steel, inside
methyldiethanolamine solution, versus room temperature, pH, the HSAS
concentration and the H2S loading (mol H2S/mol amine). The corrosion rate of the
steel increased when the ratio of the H2S reduced. According to their report at 0 to
0.002 mole H2S/mole amine loading corrosion rates for both are from 381-406
μm/year, 0.01 mole H2S/mole amine loading corrosion rates are reduced to 127-152
μm/year and at 0.05 mole H2S/mole amine loading corrosion rates fall to 51-76
μm/year. This reduction of the corrosion rate implies that on carbon steel is formed a
protective film of iron sulfide. However, if the loading is bigger than the 0.35 the
corrosion rate increased [27].
2.3 Material
The steel, that used for an amine absorber column, is a C-Mn (Carbon-Manganese) or
ferritic steel, which according to ASTM standard A516 [28] is categorized in 4 Grades
(55, 60, 65, 70). As the grade grows, the higher it the tensile strength, in contrast to
the elongation which is decreasing. The material is normally used in applications
requiring moderate to low temperature service where excellent notch toughness is
important. A significant quantity of ASTM A516 Grade 60 boiler quality plate is used
by pressure vessel manufacturers and fabricators making process equipment for the
oil and gas industry. Some is also used for skid mounted pressure vessels and modules
on production platforms and much is used in refineries and downstream processes.
To avoid impurities and decrease unexpected failures the material suffered melting
practices. Such as vacuum induction melting (VIM) and vacuum arc melting (VAM).
Due to the corrosive environment used, the steel was tested by the NACE standard
TM-0284.
This standard test method, is to designed to evaluate, specifically to material’s
resistance to HIC and not the others failures expect the sour environments like as SSC,
SWC, blister cracking.
The unstressed specimens, i.e. pipe, they created as specified by the method and
exposing to one of the two standard test solutions. Solution A, a sodium chloride,
acetic acid (NaCl, CH3COOH) solution saturated with H2S at ambient temperature and
pressure, or Solution B, a synthetic seawater solution saturated with H 2S at ambient
temperature and pressure. After a specified time, the test specimens shall be removed
and evaluated the amount of the HIC which was created [29].

2.3.1 Vacuum induction melting (VIM).

According to ASM Handbook, the vacuum induction melting is used to removal of
undesired trace elements with high vapor pressures which must kept under very low
concentration in metal to avoid unexpected failure. The primary process of this
method, is the deoxidation. Deoxidation is calling the following reaction:
C + O → CO
With this reaction the oxygen remove form the melt. In addition to, this reaction
decreased the carbon and produce steels with low carbon. Also, the vacuum melting
is used to remove impurities by disassociation, flotation or volatilization, nitrogen and
hydrogen gasses, from the steels.
A VIM furnace, as it shown in Figure 5, melts the steel and at the same time is
connecting with a vacuum system to avoid blend impurities with the melting alloy. The
furnace contains induction coils and cooling coils. Induction coils are flowing by
electric and heat the charge material to being molten. These coils except that heating
the charge materials, creates magnetics fields that require current in the charge. The
cooling coils are used to cool the inductions coils by water flowing through the tubing.
The new furnaces operated under variable frequency and the melt can controlling to
obtain the most rapid heating/melting conditions [30].

Figure 5. Schematic of a top-opening, double-chamber vacuum induction melting furnace [31].

2.3.2 Vacuum Arc Remelting (VAR).

The vacuum arc remelting is used to improve the cleanliness and refine the structure
of standard air-melted or vacuum induction melted ingots. The fields of application
are the aerospace, power generation, chemical industry, medical and nuclear
industries.
Two major mechanical assemblies combine to form the vacuum vessel in which
melting occurs - the movable furnace head and the fixed melt station. The movable
furnace head is the upper section of the vessel. An integral ram assembly connected
to a highly sophisticated servo drive supports and controls the movement of the
electrode. The water-cooled ram extends through a vacuum seal in the head and the
electrode clamps to its lower extremity thus becoming the cathode of the arc melting
operation. The fixed melt station, which forms the lower half of the vacuum vessel,
consists of a removable copper crucible that is placed into a fixed stainless-steel water
jacket.
Once the electrode is clamped to the ram assembly the ram lifts the electrode while
furnace head is lowered to create a vacuum seal on top of the crucible. Once a vacuum
is established, the DC power supply is activated and the control system automatically
strikes a high current arc between the consumable electrode (cathode -) and the
crucible base (anode +) which quickly forms a molten pool of metal.
The gap between the melting electrode and metal pool (arc gap) is precisely
maintained and a controlled melt rate is established. The metal droplets falling
through the arc gap are exposed to the vacuum environment and the extreme
temperatures of the arc zone. This causes removal of dissolved gasses (such as
hydrogen, nitrogen and carbon monoxide), vaporization of undesired trace elements,
and improvement in oxide cleanliness, directional solidification of the ingot from
bottom to top and removal of inclusions by flotation during remelting. The remaining
inclusions are broken up and evenly distributed in the cross-section of the solidified
ingot.
Because of the water-cooled crucible, the molten pool of metal formed by the metal
droplets is solidified in a directional fashion. When the melt rate and arc gap are
correctly controlled this directional solidification prevents macro segregation and
reduces the amount of micro segregation thereby enhancing the material properties
of the solidified ingot [28, 30, 32].

Figure 6. Vacuum Arc Remelting [32].

3 Material Studied
3.1 Amine absorber column
3.1.1 Operating conditions
The column length, without the end cups, is 19 m. The internal diameter is 2.2 m and
the shell thickness 91mm. The service is characterized as wet H2S, H and amine service.
The amine was Methyldiethanolamine (MDEA). The operating pressure was 80 Kg/cm 2
and the operating temperature was 70 oC. The column had been field-hydrotested
before operation. In addition, all the welds had been 100% radiographically inspected
while a stress relieving PWHT was performed in all welds. The column operated for 11
years. Following the detection of blistering in the inside diameter (ID), shown in Figure
7, and based on a relevant API level-3 Fitness-For-Service analysis, a decision was
made to replace the vessel. In the 6-month period before replacement, hydrogen
permeation measurements were conducted at the outside diameter (OD), indicating
hydrogen flux values ranging from 10 to 120 pl/cm2s. It is to be noted that hydrogen
flux is related to corrosion activity, by H2S, at the ID. During the 11 years, the vessel
operated occasionally at high H2S/MDEA molar ratio, above the normal ratio of 0.3
reaching values up to 1. It is anticipated that this led to higher corrosion activity and
higher hydrogen generation and entry in the material.

3.1.2 Material
The chemical composition, of the studied material, is shown in the Table 1 and the
mechanical properties in the Table 2.
Table 1.Chemical Composition

Elements C Si Mn P S
Wt. % 0.16 0.2 1.13 <0.01 <0.01

Table 2.Mechanical Properties

Material SA 516 Grade

60
Tensile Strength 452
(Mpa)
Yield Strength 283
(Mpa)
Elongation (%) 39
3.2 Experimental Procedures
3.2.1 Sampling Position
A section of absorber column shell cut for investigation. The position of section was
5m from the bottom of the column (Figure 8). In the inside diameter, blistering was
evident. (Figure 7)

Figure 7. Blistering in internal surface

The shell section is shown in Figure 8. The section inspected by ultrasonic testing (UT).

Figure 8. Shell section for analysis

The system of axes used for reference is shown in Figure 9. A cylindrical coordinate
system is selected. The axis of the column is the z axis, while the θ axis is the
circumferential direction and the r axis is the thickness direction.
 Figure 9. System of axes used for the positioning of specimens.

3.2.2 Ultrasonic Testing.

This technique is used into materials to detect internal flows, characterize them, test
the thickness. These materials are steels, metals, alloys and into materials with less
resolution like as concrete, wood, composites. Also, it is used in many industries
including steel and aluminum construction, metallurgy, manufacturing, aerospace,
automotive and other transportation sectors.
In ultrasonic testing, an ultrasound transducer connected to a diagnostic machine is
passed over the object being inspected. The transducer is typically separated from the
test object by a couplant (such as oil) or by water, as in immersion testing. However,
when ultrasonic testing is conducted with an Electromagnetic Acoustic Transducer
(EMAT) the use of couplant is not required.
There are two methods of receiving the ultrasound waveform: reflection and
attenuation. In reflection (or pulse-echo) mode, the transducer performs both the
sending and the receiving of the pulsed waves as the "sound" is reflected back to the
device. Reflected ultrasound comes from an interface, such as the back wall of the
object or from an imperfection within the object. The diagnostic machine displays
these results in the form of a signal with an amplitude representing the intensity of
the reflection and the distance, representing the arrival time of the reflection. In
attenuation (or through-transmission) mode, a transmitter sends ultrasound through
one surface, and a separate receiver detects the amount that has reached it on
another surface after traveling through the medium. Imperfections or other
conditions in the space between the transmitter and receiver reduce the amount of
sound transmitted, thus revealing their presence. Using the couplant increases the
efficiency of the process by reducing the losses in the ultrasonic wave energy due to
separation between the surfaces.
Locations with UT signals are indicated by thick black horizontal lines (UT) in Figure 8.
The positions of the metallographic sections are indicated by perpendicular white
lines. Three positions were considered in this work: positions 500, 577, and 604, which
pass through the UT signals. The numbers indicate distances, in mm, from a reference
point on the vessel shell. It should be noted that the UT signal from position 577 was
scattered and not concentrated in a line, as the signals from positions 500 and 604. As
will be shown below, the UT signals from positions 500 and 604 correspond to SOHIC
cracking, while the signal from position 577 corresponds to HIC, i.e., isolated HIC
cracks without linking. An explanation is provided in Figure 10, correlating the UT
signal with the respective metallographic section.

Figure 10.Positions of UT signals

3.2.3 Metallographic
All specimens, from the above sampling position, were prepared using classical
metallographic techniques. The specimens were cut from the plate of the
corresponding material with the use of a cutting machine (Struers Discotom).
The specimens were initially grinded on SiC abrasive wheels. The sizes of grains were
120, 220, 320, 500, 800, 1000 grid. Polishing of the specimens followed on special disks
with diamond paste of 3μm and 1μm grain size respectively.
The surface was chemically etched with 4% Nital reagent. Nital is a solution of nitric
acid and alcohol. This reagent has a chemical composition of: 96ml C 2H5OH and 4 ml
HNO3[33]. The specimens were washed with distilled water and alcohol and dried in a
purge of warm air.
Finally, the specimens examined by optical metallographic microscope, Leitz
“Aristomet” (Leica Camera AG, Germany) at magnification 50x─500x.

3.3 Mechanical Testing

3.3.1 Tensile Test
A tensile test is used to identification the material properties. These are Young’s
Modulus, Elastic Modulus, Tensile Modulus, Yield Strength (or Yield Point) and Offset
Yield Point or Proof Stress. This test forms a diagram of Stress (or applied force)
function to Strain (or change in length) (Figure 11) though the machine’s program. The
information for the diagram is carried out from the force which apply the machine’s
grabs onto the specimen and also, from an elongation meter which is placed above
the specimen [34].

Figure 11. Diagram of Tensile Test

The standard that used is ASTM EN10002-1:2001 and the test are occurred in
destructive testing lab at university of Thessaly. This standard covers the tensile
testing of metallic materials. Method of this test as elevated temperatures. The
specimens for this and rest tests extracted form a region with no UT signals, i.e., a
region free from cracking (HIC or SOHIC). The exact locations of the tensile specimens
relative to the inside diameter (ID) and outside diameter (OD) are shown in Figure 12
of the paper.
 Figure 12.Positions of tensile specimens as well as CVN-A and CVN-B specimens relative to ID and OD.

Figure 13.Positions of the CVN-C specimens relative to ID and OD.

3.3.2 Charpy–V–Notch
The most common Charpy’s impact test method is the V–Notch Charpy and method
Izod. In this project the method that used is V–Notch Charpy. The impact test is a
destructive testing, like the tensile test, which is used to identification the relationship
of ductile to brittle transition in absorbed energy at a series of temperatures. High
impact energy corresponds to ductile fracture and low impact energy corresponds to
brittle fracture.
The test is performed using several machined bar specimens 1cm x 1cm x 5.5cm with
a 2mm deep notch at the middle of a specified flat surface – usually a “V” notch. The
specimens are tested at a series of specified temperatures (e.g. -20oC, -10oC, 0oC,
+10oC, +20oC). Once a specimen reaches the precise temperature, it is quickly placed
into a special holder with the notch oriented vertically and toward the origin of impact.
The specimen is struck by a “tup” attached to a swinging pendulum of specific design
and weight. The specimen breaks at its notched cross-section upon impact, and the
upward swing of the pendulum is used to determine the amount of energy absorbed
(notch toughness) in the process [34].
Tests are occurred in destructive testing lab at Ebetam S.A and the standard that used
in this project was ASTM E23. For the CVN testing, three specimen orientations were
used, depicted in Figure 12Figure 13. In the CVN-A configuration, the specimen length
is along the transverse direction (q) and the notch is in the thickness (r) direction. In
the CVN-B configuration, the specimen length is along the longitudinal axis (z) of the
vessel shell and the notch in the transverse (q) direction. In the CVN-C configuration,
the specimen length is along the thickness direction of the shell (r) and the notch in
the transverse direction (q). Two impact test specimens were tested for each location.

3.3.3 Vickers hardness test (HV), 0.3 kg

Hardness is a measure of the resistance to localized plastic deformation induced by
either mechanical indentation or abrasion. The square-base pyramidal diamond
indenter is forced under a predetermined load ranging from 1 to 120 kg into the
material to be tested. After the forces have reached a static or equilibrium condition
and further penetration ceases, the force remains applied for a specific time (10 to 15
s for normal test times) and is then removed. The resulting unrecovered indentation
diagonals are measured and averaged to give a value in millimeters. These length
measurements are used to calculated the Vickers hardness number (HV). The Vickers
hardness number (formerly known as DPH for diamond pyramid hardness) is a number
related to the applied force and the surface area of the measured unrecovered
indentation produced by a square-base pyramidal diamond indenter. The Vickers
indenter has included face angles of 136° and the Vickers hardness number (HV) is
computer from the following equation:

2𝑃 136𝑜
HV= 2 sin
𝑑 2
where P is the indentation load in kg, and d is the mean diagonal of indentation, in
mm [34].

3.3.4 Fractography
Fractography is used to determine the cause of failure in engineering structures. With
this method it is impossible to develop and evaluate theoretical models about the
grown of the failure.
The crack growth is shows up in different type. For example, fatigue, stress corrosion
cracking, hydrogen induced cracking or stress orient hydrogen induced cracking have
got different growth behavior.
Common features that may cause crack initiation are inclusions, voids or empty holes
in the material, contamination, and stress concentrations. "Hachures", are the lines
on fracture surfaces which show crack direction. The broken crankshaft shown at right
failed from a surface defect near the bulb at lower center, the single brittle crack
growing up into the bulk material by small steps, a problem known as fatigue. The
crankshaft also shows hachures which point back to the origin of the fracture. Some
modes of crack growth can leave characteristic marks on the surface that identify the
mode of crack growth and origin on a macro scale e.g. beach marks or striations on
fatigue cracks. The areas of the product can also be very revealing, especially if there
are traces of sub-critical cracks, or cracks which have not grown to completion. They
can indicate that the material was faulty when loaded, or alternatively, that the
sample was overloaded at the time of failure [35].
The crack at location 604 was opened for fractographic analysis by Dr. Kyriaki
Polychronopoulou in the laboratory of the department of mechanical in the Khalifa
university of Science and Technology. In order to open the crack, a section containing
the crack was cut and cooled to -30 OC for 24 h. Then, the section containing the crack
was put in an anvil. The crack was opened by impact on one side of the section with a
hammer. A small section of “fresh” fracture area was generated. Investigation of the
fracture surface was performed in a JEOL JSM-7610F SEM (JEOL, Tokyo, Japan)
equipped with a field emission gun. The operating voltage was 20 kV.
4 Results and Discussion
4.1 Material characterization
The tensile properties are shown in Table 3. In addition to yield strength, ultimate
tensile strength, and elongation, the elastic modulus was determined to be 210 GPa.
In general, the measured properties agree with the manufacturer’s data. Although
there is a slight decrease in the ultimate tensile strength relative to the manufacturer’s
data, the elongation of the material is high and indicates a ductile material. This
argument is also in agreement with the impact test results, which are shown in Table
4Table 5Table 6 for CVN-A, CVN-B, and CVN-C configurations respectively. All notch
configurations exhibited high impact values that do not indicate any deterioration of
the notch ductility of the material in the regions away from cracking. In other words,
the observed cracking was highly localized. Finally, the Table 7 contain the result of
Hardness Test Vickers.
Table 3.Tensile test results at different locations throughout the thickness of the plate.

Location Yield Strength UTS Elongation

(mm from ID) (MPa) (MPa) (%)
15 290 432 46.4/45.06
30 287 430 42.26/37.2
50 291 439 38.0/39.4
70 286 438 40.4/38.5
Manufacture Data 283-285 445-452 38-39

Table 4. Results from CVN-A impact test configuration.

Notch Position Specimen ID CVN Energy CVN Average

(mm from ID) (Joule) (Joule)
15 A1/A5 186/194 190
30 A2/A6 184/180 182
50 A3/A7 170/186 178
70 A4/A8 168/168 168

Table 5. Results from CVN-B impact test configuration.

Notch Position Specimen ID CVN Energy CVN Average

(mm from ID) (Joule) (Joule)
15 B1/B5 186/178 182
30 B2/B6 216/188 202
50 B3/B7 190/192 191
70 B4/B8 184/182 181
 Table 6. Results from CVN-C impact test configuration.

Notch Position Specimen ID CVN Energy CVN Average

(mm from ID) (Joule) (Joule)
27.5 C3/C6 170/186 178
36 C2/C5 154/160 156
63.5 C1/C4 186/190 188

Table 7. Results from Hardness Test Vickers.

Spec. 1 2 3 4 5 6 7 8 9 10 11
Hv) 147.8 145.7 155.9 143.3 147.7 147.4 136.9 143.7 148.7 137.3 147.7

4.2 Stereoscope
All the specimens are observed by stereoscope. At location 604 are founded HIC and
blisters and some of them are connected, Figure 14.

Figure 14. HIC and SOHIC at location 604

The opposing face from the section 500 is observed by stereoscope and in the Figure
15 is shown clearly the hic and a black line which probably is look like sohic.
 Figure 15. Opposing face at location 500.

At location 577 are observed HIC/blisters near the ID.

Figure 16. HIC/Blisters at location 577

 Figure 17. HIC/Blisters at location 577

4.3 Metallographic Characterization of SOHIC and HIC

The microstructure of the steel is depicted in the micrograph of Figure 18, indicating
that the microstructure consists of ferrite and pearlite. The white section of the Figure
18 is the ferrite and the black section is the pearlite.

Figure 18. Ferrite-pearlite microstructure of the investigated steel.

The metallographic section at location 604 is shown in Figure 19, which is an assembly
of micrographs starting from the inside diameter (ID) of the sell. This is a typical form
of stress-oriented hydrogen-induced cracking (SOHIC). Although, microscopically, the
crack direction changes several times during propagation, macroscopically, it is a
through-thickness crack with a direction perpendicular to the applied stress. The crack
appears to interconnect blisters/HIC cracks, which have formed at various levels
across the thickness of the plate. The HIC cracks lie on the rolling plane and are stacked
normal to the rolling plane. The HIC cracks are linked with cracks which run in a
direction normal to the rolling plane and perpendicular to the applied hoop stress. The
initiation is at 5 mm from the ID, while the overall crack length is 23 mm.
Figure 19. SOHIC at location 604.
There are also some HIC cracks that most of them are founded above and under from
SOHIC which probably they are connected with SOHIC, and one of them is founded
right from SOHIC.

Figure 20. HIC at the location 604, at 1.06mm from ID.

Figure 21.HIC at location 604, at 12.4mm from ID.

Figure 22. HIC at location 604, at 9.3mm from ID.

Figure 23. HIC at location 604, at 30.5 from ID.

In Figure 24 is depicted mapping of this section.

Figure 24. Mapping of section 604

The metallographic section at location 577 is depicted in Figure 25Figure 26,Figure 27.
So many blisters/HIC cracks have formed, but they are not interconnected, at least at
the plane of observation. This can explain the scattered mode of the UT signal at
position 577. The propagation of HIC cracks is through the ferrite phase, between the
pearlite colonies at ferrite/pearlite interfaces, as depicted in Figure 28. A similar crack
propagation mechanism has been also observed by Gingel and Garat in an API 5L grade
X60 pipeline steel [36].

Figure 25.HIC at location 577

Figure 26.HIC at location 577

Figure 27.HIC at location 577

 Figure 28. tip of HIC indicating propagation in ferrite between pearlite colonies.

The metallographic section at location 500 is depicted in Figure 29. The crack has
initiated at 5 mm from the ID and has an overall length of 30 mm. This type of cracking
is also classified as SOHIC.

Figure 29. SOHIC at location 500.

In Figure 30 the metallography of the second corresponding surface, that is revealed

after cutting at location 500 is depicted.
Figure 30. SOHIC at location 500 opposite surface.
Figure 31. Magnification of Error! Reference source not found. in position 1.

Figure 32. Magnification of Error! Reference source not found. in position 2.

Figure 33. Magnification of Error! Reference source not found. in position 3.

Figure 34. Magnification of Error! Reference source not found. in position 4.

Figure 35. Magnification of Error! Reference source not found. in position 5.

Figure 36. Magnification of Error! Reference source not found. in position 6.

Figure 37. Magnification of Error! Reference source not found. in position 7.

Figure 38. Magnification of Error! Reference source not found. in position 8.

Figure 39. Magnification of Error! Reference source not found. in position 9.

 Figure 40. Magnification of Error! Reference source not found. in position 10.

Both cracks at locations 500 and 604 (Figure 19, Figure 29) are, therefore, classified as
SOHIC. They interconnect blisters/HIC cracks and they propagate from the ID towards
the OD under the action of the applied stress. According to API RP 571 [37], SOHIC
consists of arrays of small HIC cracks, initiated at internal blisters in the rolling plane.
These HIC cracks are stacked in a direction normal to the applied hoop stress and are
linked by cracks normal to the stress. SOHIC should not be confused with stepwise
hydrogen-induced cracking (SWC), which exhibits a not-aligned stepped morphology
in the absence of stress. The limited cases of SOHIC failures that are reported in
Pargeter’s review [6] indicate that SOHIC requires a combination of severe hydrogen
cracking conditions and stress. In the present case, the amine absorber column was
operated under high H2S/MDEA ratios for certain time periods, promoting high
hydrogen charging conditions. In addition, it has been suggested [6] that triaxial
loading can encourage the formation of small HIC cracks by increasing the hydrogen
solubility in the steel. Stress triaxiality can be induced by the large plate thickness (91
mm). It is expressed by the ratio σh/σ, where σh is the hydrostatic stress and σ is the
von Mises equivalent stress. The triaxiality ratio was calculated (see Appendix A) for
the operating conditions and was found as 0.5, which is a number indicating that the
material was subjected to a moderate triaxial stress state. In addition, it is interesting
to note that the HIC cracks form even though the radial stress is compressive.
However, these cracks do not propagate in the rolling plane, but instead they are
linked in the radial direction under the action of the hoop stress.

4.4 Fractographic Analysis of Opened SOHIC crack

As discussed above, the SOHIC crack at location 500 was opened for fractographic
analysis. A low magnification assembly of SEM micrographs is shown in Figure 41. The
region of “fresh” fracture, resulting by the opening procedure and the region of SOHIC
fracture are indicated. The boundary between the fresh fracture and SOHIC is depicted
in Figure 42. It is clear that there are two fracture modes. The fresh fracture area is
characterized by dimple fracture, also indicated in Figure 43, while the SOHIC area is
characterized by cleavage, indicated in Figure 44. In addition, several blisters/HIC
cracks can be seen on the fracture surface. The entire SOHIC region, including the
areas between blisters is characterized by cleavage as indicated in Figure 45. No black
deposit, related to FeS, was found on the fracture surface. In addition, EDX analysis
performed on the cleavage areas did not detect the presence of sulfur. The absence
of black deposits and sulfur indicate clearly that cracking is not related to sulfide stress
cracking (SSC). A large blister/HIC crack is depicted in Figure 46. It was possible to
approach the interior of this blister in order to investigate the morphology of the
blister wall as it results by the HIC crack opening due to the build-up of hydrogen
pressure. The internal wall is depicted in Figure 47, indicating a cleavage fracture
surface. Thus, blistering and HIC cracking proceeded with cleavage of the material.
Figure 41. Assembly of SEM micrographs depicting the fracture surface of the opened SOHIC crack at position 500.
The location of HIC cracks and individual SEM micrographs is indicated.
Figure 42. Boundary between SOHIC and “fresh” fracture.

Figure 43.Dimple fracture in the “fresh” fracture region.

Figure 44. Cleavage fracture at SOHIC region.

 Figure 45. Cleavage fracture in SOHIC region between HIC cracks.

Figure 46. A large HIC crack at the SOHIC fracture region.

Figure 47. Cleavage fracture morphology of the internal blister/HIC crack wall.
It is important to note that location 577 exhibited only stacked HIC cracks with no
evidence of crack linking. This indicates that the SOHIC sequence involves the
formation of HIC cracks first, followed by through thickness linking of the HIC cracks,
in agreement with observations by Crolet and Adam [38] and Ohki et al. [39]. Both HIC
formation and linking involve transgranular cleavage fracture mechanisms as
indicated by the fractographic analysis of the opened crack at location 500. The
transgranular propagation mode is in agreement with the findings of Bruckhoff et al.
[40], however the cleavage mode of linking is not in agreement with the suggestion of
Pargeter [6] that linking is through a slip mechanism or of Azevedo [41] who observed
ductile fracture mode in linking hydrogen blisters in an API 5L X46 steel. Slip may be
involved in the transport of hydrogen, as shown by several studies [42, 43] but the
propagation of the linking cracks is clearly through a cleavage mechanism. The
cleavage mode of the linking cracks confirms the important influence of stress
triaxiality in SOHIC since triaxiality introduces plastic constraint and promotes
cleavage fracture. Triaxiality effects have been discussed by other investigators, such
as the effect on hydrogen concentration by Toribio et al. [44], the effect on ductility
by Mirza et al. [45] and the effect on fracture behavior by Borvik et al. [46].

4.5 Implications for H2S/ Amine Service

The results presented above indicated that the failure mechanism of the absorber
column, which operated under wet H2S conditions, was SOHIC. The main characteristic
of SOHIC is the presence of HIC cracks lying on the rolling plane, stacked one on top of
the other and linked with cracks running perpendicular to the hoop stress. The SOHIC
sequence involves the formation of HIC cracks first, followed by through thickness
linking of the HIC cracks. The major contributing factors have been: (a) high hydrogen
charging conditions, since for some time periods the vessel operated under high
H2S/MDEA ratios, (b) stress triaxiality, imposed by the relatively large thickness of the
plate. The role of these two factors have been discussed thoroughly above. An
additional factor that may have to be considered is the type of steel used for the
construction of the vessel. As discussed in the review by Ossai et al. [47] there is a
need for high quality steel, free from inclusions and other microstructural defects that
could act as sites for hydrogen related crack initiation. For wet H2S service it is typical
to use a HIC-resistant steel. However, as indicated by the resulting cracking, a HIC-
resistant steel might not be SOHIC-resistant in particular when subjected to high
hydrogen charging conditions. This argument has also been raised by Pargeter [6]. As
mentioned above, inclusions could act as potential sites for HIC. It appears that clean
steels, such as the HIC-resistant steels, contain fewer stringer-type inclusions than
conventional steels. In these cases, HIC is rather initiated on other interfaces, such as
ferrite-pearlite interfaces. The metallographic analysis at the 577-position revealed
that HIC cracks propagate in the ferrite matrix between pearlite colonies, as also
observed in [48]. It is apparent that the use of a HIC-resistant steel should not be the
only measure for mitigating SOHIC. Current practice in the fabrication of pressure
vessels, operating in similar environment, calls for the use of austenitic stainless-steel
lining, in order to reduce hydrogen diffusion and hydrogen entry to the steel plate. In
addition, operating conditions should be carefully monitored to minimize service
under high H2S /amine ratios.
Finally, it is important to note that the results of mechanical testing indicated that the
ductility of the steel, in regions away from the observed cracking has not deteriorated.
Tensile elongation and notch ductility were maintained at high levels. However, even
in a highly localized form, SOHIC did take place, indicating the type of hydrogen
damage that can take place in an otherwise ductile material.
5 Conclusions
Taking into account the results presented above, the following conclusions can be
drawn:
(1) The cracking in the amine absorber column shell is classified as stress-oriented
hydrogen induced cracking (SOHIC).
(2) SOHIC proceeds in two steps: (a) initiation of small HIC cracks lying in the rolling
plane and stacked in a direction normal to the applied stress, (b) through thickness
linking of HIC cracks.
(3) The propagation of the HIC cracks as well as the through-thickness link cracks is
associated to cleavage fracture mechanisms.
(4) The key factors identified in this failure were: (a) short periods of high hydrogen
charging conditions as manifested by high H2S/MDEA ratios and (b) stress triaxiality
imposed by the relatively large thickness of the plate.
(5) The results indicate that a HIC-resistant steel might not be immune from SOHIC.
Under high hydrogen charging conditions HIC cracks can initiate at interfaces other
than stringer-type inclusions, such as ferrite/pearlite interfaces in the microstructure
of the steel.
6 Appendix A
The stresses in the shell of a thick-wall cylindrical vessel subjected to an internal
pressure are

 z = ( pi ri2 − poro2 ) / (ro2 − ri2 )

  = [( pi ri2 − poro2 ) / (ro2 − ri2 )] − [ri2ro2 ( po − pi ) / (r 2 (ro2 − ri2 ))]

s r = [(pi ri 2 - poro2 ) / (ro2 - ri 2 )]+[ri 2ro2 (po - pi ) / (r 2 (ro2 - ri 2 ))]

where σz, σθ and σr are the axial, circumferential (hoop) and radial stresses
respectively, pi and po are the internal and external pressures, ri and ro are the internal
and external radii of the cylinder. Inserting pi=8 MPa, po=0.1MPa, ri=1100mm and
ro=1191mm, then at position r=1110mm, i.e., 10mm from the internal surface, the
stresses are σz=45.8 MPa, σθ=98.5 MPa and σr=-7 MPa. Stress triaxiality is defined by
the ratio s h / s , where s h is the hydrostatic stress and s is the Von-Mises equivalent
stress given by:
1
 h = ( z +   +  r )
3

1
= [( z −   )2 + (  −  r )2 + ( r −  z )2 ]
2

Inserting the above values for stresses, the triaxiality ratio is derived as s h / s = 0.5 .
7 References
1. Kh., M., et al., AMINE ABSORPTION COLUMN DESIGN USING MASS TRANSFER
RATE SIMULATION. 2005.
2. Damage mechanisms affecting fixed equipment in the refining and
petrochemical industries, in API RP 571. 2011, American Petroleum Institute:
Washington, D.C.
3. Guidelines on Materials Requirements for Carbon and Low Alloy Steels for H2S
Containing Environments in Oil and Gas Production.
4. Fittness-for-service. 2007, American Petroleum Institute: Washington, D.C.
5. Buchheim, G.M., D.A. Osage, and J.C. Staats, Development of Fitness-for-Service
Rules for the Assessment of HIC and SOHIC Damage in API 579-1/ASME FFS-1.
2008: p. 761-775.
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