Investigation and ranking of Localized Corrosion Resistance

of Welded austenitic and lean duplex stainless steel

ABSTRACT

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SAMMANFATTNING

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Content
Content......................................................................................................................................iv
1 Introduction............................................................................................................................1
2 Theory......................................................................................................................................2
2.1 Stainless steel...................................................................................................................2
2.1.1 Ferritic stainless steels...............................................................................................2
2.1.2 Austenitic stainless steels...........................................................................................4
2.1.3 Ferritic-austenitic duplex stainless steels..................................................................5
2.1.4 Martensitic stainless steels.........................................................................................7
2.1.5 Alloying elements......................................................................................................8
2.2Corrosion..........................................................................................................................9
2.2.1 Uniform corrosion....................................................................................................10
2.2.2Galvanic corrosion....................................................................................................11
2.2.3Localised corrosion...................................................................................................12
2.3 Corrosion testing...........................................................................................................16
2.3.1 Polarization curves...................................................................................................17
2.3.2 The Avesta Cell........................................................................................................20
2.3.3 The Multicell............................................................................................................21
2.4 TIG Welding..................................................................................................................22
2.5 Weld oxide formation ...................................................................................................23
2.6 Post-weld cleaning.........................................................................................................25
2.6GDOES............................................................................................................................26
3 Experimental.........................................................................................................................28
3.1Material...........................................................................................................................28
3.2 Welding...........................................................................................................................28
3.3 Post weld cleaning.........................................................................................................29
3.4Corrosion testing............................................................................................................30
3.4.1 Avesta Cell...............................................................................................................30
3.4.2 Multicell...................................................................................................................30
3.5 GDOES...........................................................................................................................31
4Results....................................................................................................................................32
4.1 Base metal......................................................................................................................32
4.2 Topside............................................................................................................................33
4.2.1 Avesta Cell...............................................................................................................33
4.2.2 Multicell...................................................................................................................36
4.2.3 GDOES....................................................................................................................38
4.3 Root side.........................................................................................................................39
4.4 LDX 2101 weld metal microstructure ........................................................................40
5Discussion..............................................................................................................................41

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 5.1Base metal.......................................................................................................................41
5.2 Topside............................................................................................................................42
5.2.1 Avesta Cell...............................................................................................................43
5.2.2 Multicell...................................................................................................................46
5.2.3 GDOES....................................................................................................................46
5.3 Root side.........................................................................................................................47
5.3.1 Multicell...................................................................................................................47
5.3.2 GDOES....................................................................................................................48
5.4 Ferrite content...............................................................................................................48
6 Conclusions...........................................................................................................................49
7 Suggestion to further work...................................................................................................50
8 Acknowledgements................................................................................................................50
9 References.............................................................................................................................51
Appendix A...............................................................................................................................53
Appendix B...............................................................................................................................54

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1 Introduction
The passive film naturally formed in oxidizing environments protects the stainless steel and
makes it corrosion resistant. When welding these materials, the high temperature will cause
thermal growth of the passive film forming weld oxide, often referred to as heat tint. The
resulting reduction in corrosion resistance is often explained by a chromium-depleted layer
under the chromium-rich weld oxide, but the pitting attacks normally occur where the oxide is
most iron-rich [1, 2, 3]. As the low-alloyed grades appear to be most sensitive, most work has
been performed on austenitic steels of 304 and 316 type. However, recent work has shown
that the lean duplex stainless steel LDX 2101® is more sensitive to residual weld oxide in the
standardized pitting resistance test ASTM G150 than 316. An initial current peak in the test
prevents actual measurement and this needs to be confirmed by other means [SSW 2008]. An
important difference between the weld oxides formed on the lean duplex grades LDX 2101
and 2304 is that these are considerably more manganese-rich than the heat tint on 304 and 316
that is more chromium-rich [4]. It is not known to which extent this manganese fraction
affects the corrosion resistance. Normally it is assumed that all weld oxide will be removed
with a suitable post-weld cleaning procedure before being used in a real application. The most
efficient way is to remove it by chemical pickling. Environmental aspects can sometimes limit
the cleaning to mechanical treatments; often known to cause reduced corrosion resistance
compared to pickling. For instance polishing of the heat tint can visually give it a shiny
surface concealing residual oxide. The effect of insufficient post-weld cleaning of lean duplex
grades of LDX 2101 type on the pitting resistance is unknown and the manganese-rich oxide
could play an important role for the corrosion performance. Recent work has also shown that
most manganese in the heat tint is deposited from the weld metal, which is further enhanced
by nitrogen additions to the shielding gas [4].

For this purpose, GTA welding is performed on the lean duplex grade LDX 2101 with and
without nitrogen additions to the shielding gas. The austenitic grades 304 and 316L are
welded with the same procedure using only argon as comparison. The welds are cleaned by
either laboratory pickling, polishing or left in as-welded condition. Each combination is
corrosion tested in the Avesta Multicell based on the ASTM G61 standard (pitting potential),
with six specimens for improved statistics. GDOES is used for measuring oxide composition
and thickness, and to explain phenomena revealed during corrosion testing. The weld
microstructure is shown and a literature review of the previous work on weld oxides is
presented.

The aim of this diploma work was to investigate the pitting resistance of welded LDX 2101.
Previous examinations have shown that residual weld oxides formed on this material prevents
reliable measurements using the standard ASTM G150 pitting test. An initial current peak
exceeding the threshold value according to the ASTM G150 standard was suspected to give
large underestimations of the pitting resistance. This current peak was investigated by
recording polarization curves based on the ASTM G61 standard. Pitting potentials was
measured in as-welded condition for LDX 2101 using 304 and 316L as reference materials.
The second aim was to rank the three grades (304, LDX 2101, 316L) based on the pitting
potential of the base metal, in as-welded condition and after post-weld cleaning by either
polishing or pickling.

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2 Theory
This first section gives an orientation of the materials and the experimental work that has
been carried out. A general description of the most common types stainless steel and their
properties is given together with a presentation of the different corrosion types that commonly
occur in stainless steels. Theory behind corrosion testing is given and the used welding
method is presented. Finally different types of post-weld cleaning methods are described.

2.1 Stainless steel

Stainless steel contains a minimum of 10.5% chromium. The outer surface of such an alloy
will react spontaneously with atmospheric oxygen or in aerated aqueous solutions and form a
2-3 nm thin protective chromium oxide layer [5, 6, 7]. This oxide makes the alloy passive,
hence the name “passive film”, and improves the general corrosion resistance of the alloy. The
oxidation and formation of the thin passive layer on the steel surface are dependent on how
clean the surface is. Anything that blocks the steel surface from contact with oxygen such as
dirt, oil, grease, coatings and paint could prevent the formation of the passive layer and result
in decreased corrosion resistance. The passive film will be destroyed locally if the metal is
scratched, but if sufficient amounts of oxidants are available, the metal will react
spontaneously with oxygen and repassivate the scratch.

Stainless steels are generally weldable, but special procedures might be needed. Welding
normally results in a local change of the microstructure in the heat-affected zone (HAZ) and
the weld metal, compared with that of the base metal. This can shift the phase fractions in the
material and alter the desired phase balance, which can result in segregation, grain growth and
formation of intermetallic phases that could change the corrosion performance and
mechanical properties of the steel [8].

Stainless steels can be divided into different application areas such as stainless steel, acid-
proof steel and high-temperature steel. Another way to arrange the steels is by their alloying
elements; chromium steel, chromium-nickel steel and chromium-nickel-molybdenum steel.
However, the most common arrangement is dividing them according to their microstructure
into the different phases:

• Ferritic steels
• Austenitic steels
• Ferritic-austenitic (duplex) steels
• Martensitic steels

2.1.1 Ferritic stainless steels

Ferritic stainless steels are in principle ferritic at all temperatures. These grades are alloyed
with 13 – 18% chromium, and in some cases up to 30% [9]. Fully ferritic steels (1.4016)
normally contain 17% chromium. Titanium or niobium is often added since these elements
bind carbon easier than chromium and thus prevent formation of chromium carbides. Figure 1
shows the microstructure of a ferritic stainless steel. Low alloyed (12 – 13% Cr) ferritic
stainless steels are primarily used in the automotive industry for applications such as exhaust
systems. Ferritic stainless steels with less than 20% chromium are often used in applications

2
such as household utensils and vehicle components. The high alloyed grades containing, 20 –
30% chromium are most common in high temperature applications such as flues and furnaces
[9].

Figure 1. Microstructure of a ferritic stainless steel.

Ferritic stainless steels have higher yield strength but a lower tensile strength than the
common types of austenitic stainless steels. Another difference is that their elongation at
fracture is only half of that of austenitic stainless steels [10]. Small increases in strength can
be achieved by performing solution hardening with carbon and nitrogen.

The corrosion resistance of ferritic stainless steels can vary depending on application area.
The risk of stress corrosion cracking (SCC) is decreased when a ferritic microstructure is
present in the steel. Low alloyed (12 – 13% Cr) ferritic stainless steels are becoming more and
more common, where the modern types e.g. type 430 have low carbon content and good
resistance to atmospheric corrosion and SCC [10].

Some of the disadvantages with ferritic stainless steels are embrittlement due to the
precipitation of the brittle intermetallic sigma phase in the 500 – 800°C interval during long-
time exposure. Another is the 475°C embrittlement. Higher chromium contents increase the
risk of sigma phase precipitation and 475°C embrittlement [11].

The weldability of ferritic stainless steels is highly dependent on the chemical composition of
the steel. For older types of stainless steels the problem with precipitation of chromium
carbides, due to higher carbon content, sometimes resulted in intergranular corrosion. This is
not a large problem with modern ferritic stainless steels. The weldability has been improved
by lower carbon and nitrogen contents, which results in a fully ferritic structure at all
temperatures. Ferritic stainless steels with higher carbon content can, however, be rather
sensitive to intergranular corrosion. All ferritic stainless steel are sensitive to grain growth in
the heat-affected zone (HAZ) [10]. This grain growth can reduce the ductility of the steel,
requiring that the heat input during welding should be kept as low as possible. The HAZ can
be brittle, mainly caused by partial toughening of the area adjacent to the weld and by grain
coarsening. The embrittlement caused by the formation of martensite can be reduced by post
weld heat treatment at 750°C, but embrittlement caused by grain coarsening will remain [9].
The stabilized ferritic grades have improved weldability by preventing grain growth.

Hydrogen embrittlement can also be a problem when welding ferritic stainless steels, but it
can be avoided if all sources containing hydrogen such as in electrodes and shielding gases is

3
limited to a low level. When welding ferritic stainless steels, austenitic filler materials are
recommended for optimal ductility, while ferritic fillers are used when the application requires
a fully ferritic microstructure [10].

2.1.2 Austenitic stainless steels

The most common type of stainless steel is the austenitic grade 1.4301, 304 containing 18%-
Cr and 8%-Ni. This steel has good corrosion properties in many environments, and comes in
different types with varying carbon and nitrogen contents. Some of them are stabilized with
titanium or niobium. Figure 2 shows the microstructure of a fully austenitic stainless steel.
Austenitic stainless steels can be used in a wide range of applications such as processing and
high corrosive environments, e.g. offshore installations, high temperature equipment, paper
and chemical industries.

Figure 2. Typical microstructure of an austenitic stainless steel.

Austenitic stainless steels are a group of steels with varying properties; the most important
being corrosion resistance. The various grades have different corrosion performance and can
be used in a wide range of applications. Austenitic stainless steels can be divided according to
their properties into the following groups:

• Austenitic without molybdenum (e.g. 304 and 304L)

• Austenitic with molybdenum (e.g. 316, 316L, 317L and 904L)
• Stabilized austenitic (e.g. 321, 321H and 316Ti)
• Fully austenitic with high molybdenum (e.g. 254 SMO®)
• Heat and creep-resistant (e.g. 321H, 253 MA and 310S)

Austenitic stainless steels with or without molybdenum have a microstructure consisting of

austenite and in some cases a small fraction of delta ferrite. The compositions for these types
of alloys are typically 17 – 20% chromium and 8 – 13% nickel. The most common stainless
steel type is 1.43XX, 304 with 18% chromium and 8 – 9% nickel. This is used in mild
corrosive environments, for instance within pulp and paper. When alloyed with molybdenum
these austenitic grades commonly contain 2 – 3% molybdenum, which increases the pitting
resistance of the alloy [10]. 1.44XX, 316 is an example and this material can be used in
environments with somewhat higher chloride contents.

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Stabilized austenitic stainless steels have an addition of titanium or niobium to prevent
precipitation of chromium carbides. These grades are preferably used in high temperature
applications.

Fully austenitic stainless steels are high alloyed with 20 – 25% chromium, 18 – 35% nickel
and up to 0.4% nitrogen. These are used in highly demanding corrosive environments such as
in offshore and chemical industries.

The most characteristic mechanical property for austenitic stainless steels is their excellent
ductility at both high and low temperatures. Fully austenitic stainless steels have good impact
toughness and a generally high yield and tensile strength. Austenitic stainless steels have
excellent corrosion resistance. The carbon content is normally low (<0.03%), which increases
the resistance to intergranular corrosion. There are many different grades of austenitic
stainless steels available to meet the different types of corrosive environments. Chromium and
nickel alloys have good general corrosion, but to acquire good resistance to pitting and
crevice corrosion, molybdenum contents up to approximately 5% might be necessary. For
improved hot cracking resistance and better weldability austenitic stainless steel grades such
as type 316 are often manufactured to result in some ferrite fraction. Resistance to SCC
increases with increased nickel and molybdenum content, but the same elements also promote
formation of intermetallic phases [10].

The weldability of standard austenitic stainless steels is generally very good, while the fully
austenitic grades might need some more attention due to increased risk of hot cracking,
segregation and precipitation of intermetallic phases. If ferrite is present in the microstructure
during solidification, impurities such as sulphur and phosphorus will dissolve into the ferrite.
When a fully austenitic structure is present the impurities tend to segregate in the austenitic
grain boundaries, which increase the risk of hot cracking. To avoid hot cracking and
precipitations of intermetallic phases, specially developed filler metals are used to obtain the
desirable microstructure and phase fractions. The heat input during welding of fully austenitic
stainless steels might be restricted and need to be controlled. In most cases no preheating or
post-weld heat treatment is necessary.

2.1.3 Ferritic-austenitic duplex stainless steels

Duplex means twofold, which in this case designate phases i.e. duplex stainless steels contain
a two-phase microstructure of ferrite and austenite. The purpose of duplex stainless steels is to
combine the benefits from each phase for overall improved properties. Figure 3 shows the
microstructure of a duplex stainless steel.

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 Figure 3. Typical microstructure of a duplex stainless steel.

The duplex grades have an optimised composition typically containing 18 – 26% chromium, 4
– 8% nickel, 0 – 4.5% molybdenum, 0.1 – 0.50% nitrogen and 0.02 – 0.03% carbon [12].
These are heat treated during manufacturing to result in equal propositions of ferrite and
austenite. Duplex stainless steels are often divided into three different groups with increasing
alloy content:

• Lean alloyed duplex stainless steels (LDX 2101® and 2304)

• High alloyed duplex stainless steels (2205)
• Superduplex stainless steels (2507)

The most common duplex stainless steel is 1.4462 (2205), but the use of lean duplex grades
has grown the last years.

Duplex stainless steels have very high mechanical strength, which can sometimes be up to
two times higher than that of the austenitic grades. The ductility is good, especially at room
temperature, but not as good as for austenitic stainless steels [9].

In duplex stainless steels the high chromium content, and often additions of molybdenum and
nitrogen, give the steel a high resistance to pitting and crevice corrosion. The duplex grade
2205 has e.g. a higher pitting resistance than the austenitic type 316. Furthermore, the duplex
microstructure has superior resistance to SCC, and the low carbon content makes them
resistant to intergranular corrosion [10].

The weldability of duplex stainless steel is generally good. However, the fluidity of the melt is
somewhat lower compared with austenitic stainless steels. The welding parameters should
therefore be adapted for welding in duplex stainless steel and may not be the same as for
austenitic stainless steel. Duplex stainless steel solidifies with a fully ferritic structure, with
subsequent austenite precipitation and growth during cooling. If the cooling rate is very high,
e.g. if the heat input is too low, then there is increased risk of excessive ferrite contents due to
the fact that there is insufficient time for nitrogen diffusion and associated austenite
transformation. Ferrite contents exceeding 65% – 75% or more can result in reduced
corrosion resistance and ductility. A high content of nitrogen is added in modern duplex
stainless steels in order to stabilize austenite at higher temperatures when welding. When
welding superduplex grades, slow cooling in the temperature range of 700 – 980°C should if
possible be avoided to minimize the risk of formation of intermetallic phases, which can have
a negative effect on corrosion resistance and toughness. Heat input should be controlled and is

6
typically 0.5 to 3.0 kJ/mm. The filler metals used when welding duplex stainless steels should
be matched with the parent metal and are in most cases over-alloyed. The nickel content in the
filler metal is higher than in the parent metal in order to stabilize the precipitation of austenite
during the rapid cooling after welding [10].

Duplex stainless steels are mainly used in applications where it is possible to make use of
their high mechanical strength combined with a good corrosion resistance. Typical
applications are; heat exchangers, pressure vessels, pulp digesters, chemical industry
equipment, rotors, fans and huge tanks used for transporting or storing chemicals.

2.1.4 Martensitic stainless steels

Martensitic stainless steels have a chromium content of typically 12 – 17%, a carbon content
exceeding 0.1% and if added, a nickel content of a few percent [9]. The formation and
maintenance of a martensitic microstructure is possible because of the high carbon content,
compared with e.g. austenitic and duplex stainless steels. A martensitic microstructure can be
seen in Figure 4. Martensitic stainless steels are used for knifes and razor blades where a
sharp edge is important. The strength in martensitic stainless steels can be enhanced by
precipitation hardening and formation of intermetallic phases when adding certain alloying
elements. The heat treatment procedure of these types of stainless steels should be carefully
controlled. The corrosion resistance of martensitic stainless steels are modest, but can be
improved by addition of molybdenum. Molybdenum alloyed martensitic stainless steels have
high strength, good erosion resistance and are used in applications such as process vessels,
within the petroleum industry and for propellers.

Figure 4. Typical microstructure of a martensitic stainless steel.

The mechanical properties for martensitic stainless steels are characterised by very high yield
strength, tensile strength and a high hardness. The elongation and impact toughness of
martensitic stainless steels are normally poor [10].

Fully martensitic stainless steels have poor weldability due to the high hardness and low
ductility. This makes these types of stainless steels very sensitive to hydrogen cracking, unless
a careful preparation is carried out before welding. To minimize the risk of hydrogen cracking
preheating and post weld annealing should be performed. To obtain optimal mechanical
properties matching filler material should be used, otherwise austenitic and duplex fillers are
most common, giving highest weld metal ductility.

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2.1.5 Alloying elements

Chromium – Cr
Chromium is the most important element in stainless steels. It stabilizes ferrite and minimum
10.5% is needed to create and maintain the passive film. Chromium is known to increase the
pitting potential, the critical pitting temperature (CPT) and the critical crevice temperature
(CCT). An increased chromium content helps to increases the passive film stability in acidic
environments and decreases the pitting propagation. Coordinated increases of nickel, or
nitrogen are required to maintain the phase balance and addition of chromium is presently
limited to about 27% due to risk of precipitation of intermetallic phases [13]. For austenitic
steels the chromium content is typically 17 – 18%, while the duplex stainless steels have 20 –
29%.

Nickel – Ni
Nickel is a strong austenite stabilizer. To be able to attain a fully austenitic microstructure in
steels with 18% chromium, additions of approximately 8 – 9% nickel is required to balance
the ferrite stabilizing element chromium. Nickel is an important element for improving the
pitting and crevice corrosion resistance of welded duplex components and consumables are
consequently somewhat over-alloyed in nickel [14]. Low nickel levels can result in the
formation of a high proportion of ferrite in the duplex microstructure with subsequent loss in
toughness. It should be noted that the principle role of nickel in duplex stainless steels is not
to modify corrosion resistance, but rather to control ferrite/austenite balance in the
microstructure [12].

Molybdenum – Mo
Molybdenum is a ferrite stabilizer that increases the corrosion resistance to localised and
uniform corrosion. In steels where molybdenum is added, additions of austenite stabilizing
elements such as nickel or manganese are needed to maintain the austenitic microstructure. A
molybdenum content in excess of 3 or 3.2% is required to have a good resistance to localized
corrosion in hot sea water and to ferric chloride tests [15]. For lower molybdenum contents,
complete resistance to pitting cannot be achieved in acidic environments even by increasing
the chromium content of the alloy [16,13].

Nitrogen – N
Nitrogen is an austenite stabilizing element and is increasingly used for improving the
corrosion resistance of duplex steels. Apart from increased localised corrosion resistance such
as pitting and crevice corrosion, nitrogen increases the strength of the alloy when it is in
solution. The duplex grades normally contain 0.1 – 0.3% nitrogen to have an improved
austenite formation when welding. The addition of nitrogen in duplex stainless steel is
associated with an increase in the A4 temperature, leading not only to an increase in austenite
content at peak temperatures, but the transformation also starts at higher temperatures during
the weld cooling cycle. Sakai et al. [17] demonstrated the beneficial effects of nitrogen and
molybdenum on pitting corrosion resistance and Truman et al. [18] showed that the beneficial
effects of nitrogen seem to have been further enhanced in the presence of molybdenum.
Nitrogen also improves the ductility and toughness of duplex stainless steels due to its
austenite stabilizing effect. Ogawa and Koseki [19] indicated that an increase in the nitrogen
content of duplex stainless steels improves the pitting corrosion resistance of the weld. [12].

8
Manganese – Mn
Manganese stabilises austenite and is used in the lean duplex stainless steels together with
nitrogen to compensate the lower nickel content. This makes the price of the material more
stable since the nickel price has fluctuated significantly over the last years.

Carbon - C
Carbon is a strong austenite stabilizing element. Carbon atoms are dissolved interstitially in
the steel, which results in build up of internal stresses that results in increased strength. The
new and modern process metallurgy techniques used today allow production of steels with
very low carbon content. Carbon in duplex stainless steels is limited to levels of 0.03% to
minimize the formation of carbides and/or carbonitrides that could make the material
susceptible to intergranular corrosion. The negative effect is that by decreasing the carbon
content, which is a strong austenite stabilizer, another austenite stabilizing element must be
added to maintain an austenitic microstructure. Thus, the composition of the older standard
austenitic stainless steels has changed from 18% chromium and 8% nickel to 18% chromium
and 9 – 10% nickel [12].

Silicon – Si
Silicon is a ferrite stabilizing element. Silicon is common in high-temperature and special
grade steels, improving the hardenability and tensile strength.

Titanium – Ti and Niobium – Nb

Titanium and niobium are stabilizing ferrite and are used when it is difficult to maintain the
carbon content at low levels. These two alloying elements have higher affinity to bind carbon
than chromium, hence prevent the formation of chromium carbides that could cause
intergranular corrosion. As stainless steels normally have low carbon content, titanium and
niobium additions are primarily used in high-temperature steels with higher carbon contents.

2.2 Corrosion
Corrosion is defined as dissolution of a metal or metal alloy due to the reaction with the
surrounding environment. Most metals are in a thermodynamically unstable form, and
corrosion means that the same amount of energy needed to extract these metals from their
minerals in nature are emitted during chemical reactions. When the material has corroded it
has transformed to the more thermodynamically stable form, and corrosion is thus the result
of the driving force when nature struggles towards thermodynamic equilibrium [20]. During
the corrosion process two different types of reactions will take place at the same time; the
anodic and the cathodic [20].

The anodic reaction (1) occurs when the metal oxidise and electrons are going into the
electrolyte (conductive medium):

M → M n + + ne − (1)

A cathodic reaction can either occur as oxygen reduction in acidic solutions (2) or hydrogen
evolution (3):

O2 + 4 H + + 4e − → 2 H 2 O (2)

9
 2 H 2 O + 2e − → H 2 + 2OH − (3)

For neutral or basic solutions oxygen reduction in form of Reaction (4) is the most common:

O2 + 2 H 2 O + 4e − → 4OH − (4)

Corrosion of stainless steels can occur in many different forms depending on the environment,
the metallurgical properties of the steel and the local stress. This result in different types of
corrosion attacks, the most common forms being:

• Uniform corrosion
• Galvanic corrosion
• Localised corrosion
• Pitting corrosion
• Crevice corrosion
• Stress corrosion cracking
• Corrosion fatigue
• Intergranular corrosion

To avoid corrosion attack of the steel, designers and engineers have to be aware of the service
environment to be able to choose the right type of stainless steel for use in corrosive
conditions. The pitting resistance equivalent number (PRE) [21, 22] in Equation (5) is
generally accepted as a rough estimation of the corrosion resistance of duplex grades.

PRE = Cr + 3.3 × Mo + 16 × N (%) (5)

For austenitic stainless steels, the effect of nitrogen is even attributed to 30 × N [23].

2.2.1 Uniform corrosion

Uniform corrosion is characterised by an even corrosion of a surface that is exposed to a
corrosive environment, Figure 5. Therefore the corrosion rate is often measured in terms of
reduction of thickness per unit time, often expressed in millimetres per year (mm/y). Uniform
corrosion of stainless steels mainly occurs in acid or hot alkaline solutions. The corrosion
resistance for stainless steels in oxidising acids such as nitric acid is generally good. However,
in non-oxidising acids the maintenance of the passive film is not always possible.
Hydrochloric and hydrofluoric acids are very aggressive environments for most types of
stainless steels, thereby limiting the service environments to low temperatures and
concentrations [24].

10
 Figure 5. Uniform corrosion on the outside of a steam tube that has
been exposed to sulphuric acid [24].

The resistance to uniform corrosion can be improved by addition of chromium, nickel and
molybdenum. One difference is that molybdenum containing stainless steels show less
resistance to uniform corrosion in strongly oxidising environments such as warm concentrated
nitric acid, compared with steels without molybdenum.

Uniform corrosion results in decomposition of the steel at an even rate compared to other
types of corrosion, which is why uniform corrosion is relatively easy to control. Failure
caused by uniform corrosion is often due to improper selection of the type of steel grade for
the service environment [24].

2.2.2 Galvanic corrosion

Galvanic corrosion takes place when two dissimilar materials are connected electrically to
each other e.g. in a conductive liquid, electrolyte, Figure 6. This is often called a galvanic cell.
In a galvanic corrosion process, the more noble metal, the cathode, will be protected against
corrosion while the less noble, the anode, is attacked. To classify different types of conducting
materials a series called the galvanic series can be utilised. The galvanic series are valid for a
special environment, often seawater at certain temperatures. Some factors that will affect the
galvanic corrosion are e.g. the difference in nobility between the two metals, the surface area
ratio of the two metals and the conductivity of the electrolyte [24].

Figure 6. Galvanic corrosion on carbon steel (right) that has been 11

welded to stainless steel (left) and exposed to seawater [24].
2.2.3 Localised corrosion
In contrast to uniform corrosion, where all or large sections of the passive layer breaks down,
localised corrosion involves a local breakdown of the passive layer. Many different forms of
localised corrosion can take place in stainless steels. The most common forms are pitting
corrosion, crevice corrosion, stress corrosion cracking, corrosion fatigue and intergranular
corrosion.

Pitting corrosion
Pitting corrosion often appears in acidic or neutral chloride solutions. A local pitting attack is
initiated when chloride ions penetrates the protecting passive film. When the passive film is
locally destroyed, the base metal under it will no longer be protected. This can be considered
a galvanic cell, where the small area of base metal can be considered as an anode and the
large area of the remaining passive film acts as a cathode. At the anode an oxidation reaction
takes place, while a reduction reaction occurs at the cathode. The effect of having a small
anode area compared to a much bigger cathode area is rapid corrosion of the base metal,
hence creating a pit [24]. Pits often appear to be small at the surface, but it is common that
they have a rather large cross-section area deep inside the metal, Figure 7.

Figure 7. Pitting corrosion in a tube for cooling water [25].

The reactions that take place between the dissolved metal ions at the anode and the electrolyte
results in decreased pH in the pit, Figure 8. In order to still have an electroneutral balance, the
negative charged chloride ions migrate into the pit to balance the positive charge of the metal
ions. This will further increase the already aggressive environment, and this process is
accelerating with increasing size of the pit. The passivation of the metal is thus obstructed and
the result is often small and deep pits growing at a high rate. The high propagation rate makes
this form of corrosion dangerous, and the risk of pitting corrosion increases with increased
chloride concentration, increased temperature and decreased pH [24].

12
 Figure 8. Reaction mechanisms for pitting corrosion [26].

Crevice corrosion
Crevice corrosion is as pitting corrosion a form of localised corrosion that occurs under same
conditions, in acidic or neutral chloride solutions. The main difference is that this form of
corrosion occurs in crevices e.g. in flange joints, instead of an open surface. An example of
crevice corrosion is shown in Figure 9.

Figure 9. Crevice corrosion under a valve flange in a pipe that

carried heated seawater [24].

The reactions inside and outside the crevice are initially similar, but the transportation of
oxygen into the crevice is limited, Figure 10. The reduction of oxygen will thus cease after
some time while the oxidation of the metal continues both outside and inside the crevice. An
excess of metal ions with positive charge in the crevice attracts the negative charged chloride
ions outside the crevice, and in order to maintain electroneutral balance the chloride ions will
migrate into the crevice. As for pitting corrosion this process increases the chloride
concentration and decreases the pH in the crevice, which gives an even more aggressive
environment and the passive film breaks down. Initiation of crevice corrosion is easier than
pitting corrosion due to the more rapid process of changing the environment in the crevice
[24].

13
 Cl-

O2 OH- O2 OH-
Me2+

Cl-
Cl- Me2+ H+
O2 OH-
Me2+ Cl-
H+

Figure 10. Reaction mechanisms for crevice corrosion [25].

Stress corrosion cracking

The combination of tensile stress and a corrosive environment can result in stress corrosion
cracking (SCC) causing brittle failure of the material. SCC mainly occurs in chloride
containing solutions at temperatures exceeding 50°C. The attacks have a crack like
appearance propagating as branches through the material, Figure 11. In contrast to pitting and
crevice corrosion, SCC often requires lower concentrations of chlorides and oxidising
substances. If the chloride solution contains hydrogen sulphide (H2S), which exists in e.g. oil
and gas wells, the risk of cracking increases. Another type of environment that is known to
cause SCC is strong alkaline solutions at high temperatures, pH over 14 and a temperature
above 120°C [24].

Figure 11. Micrograph showing typical stress corrosion cracking [24].

Corrosion fatigue
Corrosion fatigue causes brittle failure of the material, Figure 12. It occurs when exposed to a
cyclic load in a corrosive environment. Cyclic loads can cause fatigue below the ultimate
tensile strength, but when a corrosive environment is present failure may occur at even lower

14
loads. This form of corrosion mainly takes place at ambient temperature and in solutions that
can be considered relatively harmless compared to other forms of corrosion. Residual stresses
from production can have a negative affect on the resistance to corrosion fatigue, but can be
reduced by heat treatment. To decrease the risk of corrosion fatigue for susceptible
applications, a material with high mechanical strength should be used such as duplex instead
of austenitic stainless steels [24].

Figure 12. Corrosion fatigue cracks in a paper machine suction roll shell,
made of austenitic 1.4432 (ASTM 316L) [24].

Intergranular corrosion
Intergranular corrosion might occur as a result of chromium carbide (Cr 23C6) or intermetallic
phase precipitation in stainless steels. Due to the high chromium content, chromium carbide
precipitation makes the areas adjacent to the grain boundary depleted in chromium. The
chromium-depleted areas along the grain boundaries can cause corrosion if the material is
exposed to a corrosive environment, Figure 13. Intergranular corrosion occurs mainly in non-
reducing acids and strong oxidising conditions are often needed to initiate an intergranular
attack. The resistance to intergranular corrosion can be reduced by for example solution
annealing, low carbon content and alloying (stabilising) with titanium or niobium. Modern
stainless steels have low carbon contents making intergranular corrosion comparably rare
[24].

15
 Figure 13. Intergranular corrosion caused by carburisation
inside of a tube that carried dilute sulphuric acid [24].

2.3 Corrosion testing

Corrosion testing can be used to predict a typical service lifetime for a steel grade, which
depends on many factors such as environment and temperature. Laboratory experiments do
not perfectly correspond to the corrosion performance in real-life, but provide good prediction
of the corrosion behaviour for many applications. Corrosion testing estimates the reduction of
corrosion resistance when the material properties have been changed compared with the base
material. This can often be the case when the material is joined together with welding
techniques.

In this work, the purpose of the corrosion tests is to rank the three materials in certain
specified conditions. Ranking using CPT is often used, but in this case the ASTM G61– 86
method was needed. 304 returns invalid (too low) results [unpublished work, E. M. Westin]
when using the ASTM G150 method, so the ranking was instead based on the pitting potential
to be able to compare 304 with LDX 2101 and 316L. This also makes it possible to study the
materials in as-welded condition. All tests were carried out at 35°C to ensure that the
measurements were above the CPT for all grades and especially 316L, to facilitate
comparison of 316L with LDX 2101 and 304. Both pitting potentials and repassivation
potentials are obtained from the ASTM G61 – 86 measurement (Figure 14). All corrosion
measurements in this work are based on the ASTM G61 – 86 standard, but the scanning
direction is not reversed as in Figure 14. The measurement is instead stopped when reaching a
current of approximately 5 mA. This type of procedure saves time, and only the pitting
potentials are of interest in this work. Another reason is that Turner et al. [27] performed
corrosion tests on 316L and 304L and showed that when performing cathodic polarization
experiments the weld oxide was removed by reduction, thus resulting in lower reproducibility.
Therefore, the polarization experiments were limited to anodic polarization to obtain better
reproducibility of the experiments. For that reason the measurements in this work is also
limited to anodic polarization. The main purpose was to use the Multicell for all corrosion
tests, which have shown to provide reliable and rapid results for estimating the pitting
potentials from flat surfaces without forming crevice corrosion [28]. The Multicell
measurements are also based on ASTM G61 – 86.

When the ASTM G61 – 86 standard is followed the result of a measurement will be a
polarization curve with a different appearance than in Figure 15. This can clearly be seen in

16
Figure 14, measurements carried out by R. Qvarfort [29], where the ASTM G61 – 86 has been
followed. After reaching the pitting potential, EP, the current will increase to around 1 to 50
mA and then the scanning direction will be reversed, resulting in a loop that gives the
repassivation potential (ERP). The polarization curve will have different appearance depending
on the temperature where the measurement has been carried out, above or under the critical
pitting temperature (CPT), Figure 14 (a) and (b), respectively. The observed appearance in
curve (b) is due to transpassive corrosion [29]. CPT is defined as the lowest test temperature
at which pitting corrosion occurs in a specific environment [24].

EP
ERP

Figure 14. Polarization curves of a passive metal obtained in 1 M NaCl, at

temperature (a) above the CPT (b) below the CPT [29].

2.3.1 Polarization curves

When connecting a metal surface to an external power source it will be polarized and there
are many different types of correlations between current and potential. When measuring a
polarized metal it is possible to plot a current-potential curve, more known as a polarization
curve [30]. When performing a polarization measurement the tested metal is used as working
electrode, which is further connected to a counter electrode and a reference electrode that are
in connection with an electrolyte. A potentiostat is used to maintain a constant potential
between the work and the reference electrode, resulting in a measurable current flow. These
measurements are often carried out in an electrochemical cell, in this case the Avesta Cell,
which will be described later. There are many different types of measuring techniques
available, but in this work, only potentiodynamic and potentiostatic methods were used.

Potentiodynamic polarization curves are characterized by measurements with a linear change

of potential with time. A value of 10 mV/s is often used according to ASTM G61 – 86 and the
scanning direction is reversed when a current of 5 mA is reached [31]. In potentiodynamic
measurements, parameters such as scan rate and potential step can be set. The drawback is
that this type of testing is rather time-consuming. Potentiostatic polarization curves on the
other hand are obtained by maintaining the applied potential at specified discrete steps until
the current has become constant, or reaches the defined maximum time value. When a
constant current or the maximum time is reached, the potential will change to a higher

17
potential defined by the user from the start. For the potentiostatic measurement both, potential
step and the maximum time at each potential can be set, but also the sensitivity that is
defining the change in current to reveal whether the current is constant or not.

A schematic polarization curve for a passive metal is illustrated in Figure 15, showing an
active passive behaviour in an acidic environment. The corrosion potential, E Corr is the
potential that a metal generates between itself and the counter electrode in the cell, which is
caused by the difference in nobility between the two metals. For example platinum can be
considered noble and less susceptible to corrosion compared to zinc. The corrosion potential
is also known as open circuit potential (OCP), often used in software for polarization
measurement e.g. general purpose electrochemical system (GPES). Platinum has a potential
of approximately 0.2 mVSCE and zinc –1.0 mVSCE in seawater [20]. Where SCE stands for
saturated calomel electrode. The current at ECorr is the same for both the anode and the
cathode, but with different signs. With increasing potential, the active area is reached where
the anodic process will dominate and the metal will be actively dissolved, Reaction (1). The
passivation process takes place at the passivation potential EPP. At this point the corrosion rate
of the metal is reduced 103 to 106 times below the rate in the active area [20]. This passivity is
caused by the formation of a thin protective corrosion product surface film consisting mainly
of hydrated oxide. This film acts as a barrier to the anodic dissolution, Reaction (1). At the
transpassive potential, ETR, the current will increase caused by either oxygen evolution
(Reaction (2) or (4), depending on the pH) and/or oxidation of the metal to higher valence
states, without passive film formation. When the electrolyte is acidic, often in H 2SO4 of
different molarities, the measured curve will follow the schematic in Figure 15 from the
cathodic to the transpassive area. However, if the electrolyte is containing aggressive halides
such as chloride and bromide ions, the current can rapidly increase before the transpassive
area, still in the passive area, resulting in pitting attack. This potential is called the pitting
potential EP.

18
 Figure 15. Schematic polarization curve of a passive metal [32].

Figure 16 shows a potentiostatic polarization curve for as-received 316L, which has a typical
appearance for a passive metal in sodium chloride.

316L
316L As received
As-received 1 M1NaCl
M NaCl 35°C
at 35°C
Potentiostatic
Potentiostatic
0
1.000x10
1.000x10-1
Current density [A/cm2]

1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.050 0 0.050 0.100 0.150 0.200 0.250 0.300 0.350
Potential, VSCE

Figure 16. Passive metal in 1 M NaCl at 35°C.

IR drop has not been taken into consideration when performing measurements in the Avesta
Cell, as the resistance of the used electrolyte was approximately 20 ohm and at 100 µA/cm2
the resulting IR drop will be approximately 2 mV [32]. IR drop was not compensated in the
Avesta Multicell for the same reason.

19
2.3.2 The Avesta Cell
The Avesta Cell provides the possibility to study pitting corrosion without forming crevice
corrosion. This is achieved by pumping distilled water, usually 2 – 6 ml/h, to replace the
chloride solution in the microcrevice between the sample and specimen holder, Figure 17
[33].

Figure 17. Schematic picture of the Avesta Cell design [32].

The cell used in this work is relatively small, containing approximately one decilitre of
electrolyte solution. A larger version is available containing approximately one litre of
electrolyte used for larger samples. The temperature of the electrolyte is maintained at the set
temperature, in this case 35°C, by using the Haake Phoenix II thermostat that circulates
thermostated liquid in the cell wall. As can bee seen in Figure 17, the gas inlet, the counter
electrode, the thermometer and the luggin capillary are inserted from the top of the cell. No
extra mixing bar is needed when using a small Avesta Cell at a fix temperature. The
thermometer is of type PT 100 and the reference electrode is a saturated calomel electrode
(SCE). The reference electrode is in connection with the sample via a salt bridge. During the
measurement N2 gas is flushed into the electrolyte to provide stirring and to maintain a low
oxygen level in the electrolyte. The sample is mounted to the bottom of the cell using an o-
ring and two filter papers to obtain tight connection between the sample and the cell to
prevent that electrolyte can percolate. The filter paper is used to distribute the distilled water
evenly on the sample and thus prevent crevice corrosion.

All samples that were corrosion tested in the Avesta Cell or the Multicell were of the size
30×30 mm (Figure 18) to have a test area of 1 cm2, according to the ASTM G61 – 86
standard.

20
 Figure 18. Schematic illustration of sample dimensions used in the Avesta Cell
and the Multicell.

2.3.3 The Multicell

The Avesta Multicell used in this work was developed by C.-O.A. Olsson [34]. The cell
design is similar to the Avesta Cell, but instead of one sample, six samples can be measured
simultaneously. In the Multicell approximately one litre of electrolyte is used for one
measurement. In similarity with the Avesta Cell, a pump is used to provide the samples with
distilled water flow of approximately 6 ml/h per channel, in this case a six-channel Alitea
403U/C6 pump. A schematic representation of the electrical connections of the Multicell is
illustrated in Figure 19. The connections are similar to the ones in the Avesta Cell, but with
the difference that all samples in the Multicell are connected to a box before the computer and
the potentiostat.

Figure 19. Schematic illustration of electrical connections of the Multicell [32].

21
The box contains a shunt resistor and a switch, where the shunt resistor is a low resistance
precision resistor used to measure electrical currents caused by voltage drops. For all channels
a maximum current is set and when that value is reached the switch disconnects the
connection to the sample. The value of the shunt resistor is adapted to provide a correct
estimation of the current just below 100 µA, which is in the region where the pitting potential
is evaluated in the Multicell. When performing a measurement with the Multicell the resulting
data is not representing a polarization curve as for the Avesta Cell. Currents measured under
the range of the shunt resistor are only detected as noise [32]. As for the Avesta Cell nitrogen
gas is flushed into the electrolyte and the samples are connected to the cell using o-rings and
filter paper. The same type of thermostat as for the Avesta Cell is used, Haake Phoenix II,
maintaining a temperature of 35°C in the electrolyte (1 M NaCl) using a PT 100 thermometer.
The reference electrode used in this cell was a saturated Ag/AgCl type.

2.4 TIG Welding

All welding methods used for construction steel can also be used for stainless steel. Tungsten
inert gas (TIG) or gas tungsten arc welding (GTAW) is characterised by high quality weld
metal deposits, great precision, superior surface homogeneity and high strength. In TIG
welding an electric arc is created between the tungsten electrode and the workpiece, where the
arc is melting the parent metal. Filler material can be added from the side if needed, Figure
20. TIG welding can be performed either manually or automatically with or without filler
material, Figure 21.

Figure 20. The principle of TIG welding [10]. Figure 21. Schematic overview of the TIG
welding process [35].

The tungsten electrode can vary between 1.0 to 4.8 mm in diameter and be made of pure
tungsten or a tungsten alloy (1 – 2% thorium, zirconium or cerium oxides), where the
tungsten-thorium alloy is the most common type of electrode. The angle of the electrode is an
important parameter, which has a major effect on the penetration of the material. As can be
seen from Figure 22, small angles (15 – 30°) result in a wide arc with low penetration and
wider angles (60 – 75°) result in a narrower arc, thus giving deeper penetration. The effect of

22
different polarities can be seen in Figure 23. In this work, the direct-current electrode negative
(DC-) type is used [10].

Figure 22 The electrode angle and its effect on Figure 23. Effect of different polarities on weld penetration
penetration [10]. [35].

The productivity of the TIG welding method is relatively low both if the amount of melted
weld metal is determined per unit time or in terms of welding speed. Preheating of the TIG
wire (hot wire TIG) can increase the productivity. TIG welding is favourable in tube joints
and for root beads and is often used when a high requirement on the surface appearance is
needed. TIG welding is common in the nuclear and process industry where good weld quality
is required, but also for thin material in general and one-side welding of tubes. Another
possibility with this method is the ability to re-melt eventual geometrical deviations in the
junction between weld and base metal and therefore improve the fatigue properties of the
weldment. It is very important for optimum corrosion resistance and mechanical properties to
use a suitable filler material when welding high alloy stainless steels such as 2205 and 254
SMO®. It is also vital to use shielding and purging gas to achieve optimal corrosion properties
after welding.

2.5 Weld oxide formation

The oxide formation that occurs during welding is a complex process to predict and hard to
describe in detail. The basic concept of oxide formation is that alloying elements with the
highest affinity to oxygen (most negative Gibbs free energy of formation) preferentially reacts
and forms an oxide containing the alloy element and oxygen. According to Pettersson and
Flyg [1] weld oxides forms extremely fast and will not reach equilibrium conditions, which
means that kinetics will dominate the process. A chromium depletion is frequently reported to
be present at the surface of weld oxides and if the diffusion rate of chromium to the outer
surface is too low then iron or other elements with affinity to oxygen will tend to oxidise,
often resulting in lower corrosion resistance. Gibbs free energy of formation for the most
common reactions can be obtained using the Ellingham diagram [36], but the reactions are
based on equilibrium reactions, which do not correspond to the reactions formed in weld
oxides. It can be determined what element has the highest affinity to oxygen from the
Ellingham diagram, but this is for the most common reactions only. The weld oxide can have
different stoichiometric formulas depending on what is the most thermodynamic stable oxide
composition. Pettersson and Flyg [1] found iron oxide on the topside of TIG welded 316L

23
stainless steel at approximately 3 mm from the FL. When studying TIG welded 316L stainless
steel an obvious difference in oxide thickness between the top and root side could be seen,
200 nm compared to 30 nm for the root side. This was explained by the controlled level of
oxygen at the root surface, which will slow down the oxidation kinetics and thus result in a
thinner oxide. Furthermore, no iron oxide layer could be identified on the root side, meaning
that the diffusion of chromium was sufficiently high for maintaining and causing growth of
the chromium oxide.

Von Moltke et al. [2] reported that a chromium-rich oxide layer is present under the iron-rich
layer and means that the oxidation temperature influences the diffusion rate of iron and
chromium. Chromium reduction in the weld oxide at the highest temperatures was related to
evaporation of chromium oxide, CrO3 [2]. Furthermore, von Moltke et al. [2] concluded that
the iron-rich oxides are most harmful and that chromium-rich oxides are more resistant to
corrosion. Von Moltke et al. [2] also suggest that the iron-rich oxide acts as an ion-selective
membrane that absorbs chlorides, but also prevents them from leaving by diffusion. This
results in increased chloride concentration followed by pit initiation.

A schematic description of mechanisms occurring during welding has been suggested [4] for
heat tint formation on LDX 2101 and is illustrated in Figure 24. Weld oxide formation is often
described by oxidation of the base metal and diffusion from the weld metal [4]. Westin et al.
[4] showed that manganese is evaporated from the weld metal and then forms weld oxide by
subsequent redeposition from the gas phase. Furthermore, nitrogen addition to the shielding
gas showed enhanced evaporation from the weld metal caused by the higher temperatures that
were attained, which resulted in a thicker weld oxide that also contained oxynitrides. Another
suggestion from Westin et al. [4] was that the weld oxide might also absorb nitrogen from the
shielding gas. They also found an oxide at 14 mm from the fusion line where the maximum
temperature was 200°C. This oxide was suggested to have formed by redeposition and not due
to oxidation, because of the relatively low temperature.

Figure 24. Schematic description of mechanism occurring during welding of LDX 2101 [4].

Figure 25 shows an illustration of oxides that forms when welding LDX 2101 depending on
which shielding gas that has been used, suggested by Westin et al. [4]. LDX 2101 welded with
pure argon has a chromium and nitrogen-rich manganese oxide. A double layer oxide is

24
formed on LDX 2101 when nitrogen is added to the shielding gas, which most probably
contains manganese oxynitrides. The manganese fraction and the thickness of the weld oxide
became thicker when Ar + 2% N2 shielding gas was used, which was suggested to be related
to the absorption-evaporation-deposition process.

Figure 25. Schematic illustration of oxides formed on LDX 2101 with and without nitrogen
addition to the shielding gas [4].

2.6 Post-weld cleaning

Post-weld cleaning is important to attain the desired aesthetic appearance, hygienic and
corrosion requirements of stainless steel after the welding process. A clean, smooth and
faultless surface is normally required to achieve high corrosion resistance. Many different
types of cleaning methods, both mechanical and/or chemical, can be utilized depending on the
requirements of the corrosion resistance for the application in the specific environment. The
most common cleaning processes are grinding, blasting, brushing, electropolishing, pickling
and combinations of mechanical and chemical methods. Before using any of these methods a
careful cleaning with a suitable degreasing agent should be used to remove any organic
contaminants from the steel surface.

Grinding is suitable for removing weld defects and deep scratches on the surface by using a
grinding disc. For minor surface defects a flapper wheel is often sufficient. If coarse grinding
is needed (40 – 60 mesh), then a subsequent finer grinding (180 mesh) should be performed
[10]. Polishing can be performed (220 mesh or higher) after the grinding process when even
higher demands are set on the material. The chromium-depleted zone beneath the weld oxide
can be removed if proper grinding is performed [10].

Polishing can sometimes be sufficient for cleaning thin oxides e.g. TIG weld oxides. The
chromium-depleted zone is not removed when this method is used, but oxides and dirt that
cause localized corrosion are removed. Scotchbrite or some type of polishing cloth is often
used.

Sand and grit blasting, is mostly used for cleaning of large surfaces. The blasting material
must be clean to obtain good results when using this method. Common blasting materials are
olivine sand and smooth glass beads. Also blasting should be carried out with caution to
minimize the coarseness of the surface. Performing sand blasting without a followed cleaning
procedure with other methods, results in the lowest corrosion resistance compared with most
other post-weld cleaning methods.

Brushing can often be sufficient for removing weld oxide and maintaining a relatively good
corrosion resistance. Stainless steel or nylon brushes are often used. This method does not
result in excessively coarse surfaces, but with no guarantee for complete removal of the

25
chromium-depleted zone. However, the risk of contamination is relatively high and therefore
use of clean tools is important.

Pickling is the best method to remove oxides and iron-contamination, and thus to restore the
corrosion resistance to a level close to that of the base metal. When pickling, a mixture of
approximately 8 – 20% nitric acid and 0.5 – 5% hydrofluoric acid is often used. Rinsing with
clean water is important after the pickling process. Chloride containing agents such as
hydrochloric acid should be avoided, since these can increase the risk of pitting corrosion.
Different pickling methods can be utilized depending on the requirements and size/geometry
of the material. Some of the most common types are; pickling in a bath (20 – 65°C), pickling
with pickling paste (10 – 40°C), pickling with pickling solution (gels) and electropolishing.
Pickling in bath is used when such equipment is available and when the material match the
size of the bath. Pickling paste is used when pickling a material that cannot be moved, when
no pickling bath or when no other equipment is available. When pickling solution is utilized a
gel like solution is sprayed on the material, as for blasting this method is favourable when
pickling large surfaces. Electropolishing can give optimal corrosion resistance due to
controlled corrosion of the material surface and may also improve the surface finish [10]. Shot
blasting before using pickling paste or pickling solutions sprayed on the material can be
beneficial since it reduces the needed pickling time.

2.6 GDOES
The glow discharge optical emission spectroscopy (GDOES) instrument can be used to for
bulk, surface and depth profiling of both conducting and non-conducting materials e.g. weld
oxides [37]. The instrument is based on argon glow discharge, which is a low-pressure plasma
that is electrically neutral, containing negatively charged electrons and positively charged
argon ions, Figure 26. Low pressure of argon is filled in the cavity between the anode and
cathode to initiate the plasma. At room temperature and with no applied potential between the
anode and cathode, the gas acts as an isolating medium. If applying a sufficiently high
potential between the anode and cathode, a current can flow creating a low-pressure plasma.
Electrons flow from the electrode with a negative potential, in this case the cathode, to the
electrode with a positive potential. The electrons are colliding with argon atoms to form
positive argon ions that are attracted to the negative electrode (sample). Positive argon ions
with sufficiently high energy will knock off atoms, but also secondary electrons, when they
hit the sample surface. The secondary electrons are attracted to the positive electrode (anode)
and some of them will collide with argon atoms on their way to the anode, thus maintaining
the discharge. However, the sputtered cathode atoms will collide with high-energy electrons
or metastable argon ions to form exited atoms. Those excited atoms are in a metastable state
so they will de-excite. When the atoms de-excite they will emit photons with a characteristic
wavelength that can be detected with the optical spectrometer to measure the composition of
the sample. All elements are analysed simultaneously during the measurement. Radio
frequency (RF) is used, which alternates the potential at the anode and cathode, in order to
avoid charge accumulation in the cavity and thus allowing analysis of both conductive and
non-conductive materials [38]. In this work, GDOES results can give information on oxide
composition, thus provide better understanding of the corrosion test results.

26
 Window
Photons
Ar
Cathode atoms in
fundamental state
λ Positive ionised
argon atoms
Cathode atoms in
excited state

Electrons
Vacuum
Copper anode

R Cathode (sample)
F
Cooling

Figure 26. Schematic illustration of the glow discharge process.

It is important that the sample surface is flat to be able to obtain a vacuum before the
measurement starts. If measurements are carried out on a non-flat surface, a special sample
holder can be used to obtain valid results, Figure 27.

Figure 27. Picture of the special sample holder

for non-flat surfaces.

27
 3 Experimental
All polished, ground and/or pickled samples were left in laboratory atmosphere for at least 24
hours before measurements.

3.1 Material
Three different stainless steel grades were used in this work; two austenitic (304 and 316L)
and one lean duplex (LDX 2101®). Their chemical compositions and properties are
summarised in Table 1 and 2, respectively. The 304 and 316L grade were chosen as
comparison to LDX 2101.

Table 1. Chemical composition and PRE number for 304, 316L and LDX 2101.
Name EN C Si Mn P S Cr Ni Mo Cu N PRE*
LDX 2101 1.4162 0.03 0.62 5.0 0.02 0.001 21.5 1.58 0.2 0.25 0.20 25.4
304 1.4301 0.05 0.45 1.5 0.03 0.005 18.2 8.02 0.2 0.46 0.05 19.7
316L 1.4404 0.02 0.36 1.8 0.03 0.002 17.5 10.06 2.1 0.41 0.05 25.2
*PRE=pitting resistance equivalent, calculated with Equation 5.

Table 2. Mechanical properties of grades 304, 316L and LDX 2101.

Rp0.2 Rm A5 Mill finish Thickness
Name EN
[Mpa] [Mpa] [%] [mm]
LDX 2101 1.4162 591 787 40 2E (brushed) 2.2
304 1.4301 309 640 56 2B* 3.0
316L 1.4404 376 636 53 2B* 3.0
*2B=Cold rolled, heat-treated, pickled, skin passed.

All material was delivered by Nyby. All samples that were corrosion tested in the Avesta Cell
and/or the Multicell were cut in 30×30 mm. The material used for characterisation of the heat
tint in GDOES were initially ground and polished to 3 µm mirror finish on the side that will
be analysed.

All samples were carefully cleaned with acetone and methanol before welding, corrosion
testing and GDOES measurement.

3.2 Welding
All stainless steel grades were mechanically TIG welded bed-on-plate (BOP) with a modified
EWM TIG 450 DC-P using a tungsten-thorium electrode with an angle of 60° and a diameter
of Ø1.6 mm. The arc and electrode stick-out lengths were 3.0 and 7.0 mm, respectively, and
the gas cup inner diameter was Ø12 mm. In this work no filler material was used during the
welding process. Three different types of shielding gases were used with a gas flow of 15
l/min; Ar or 90% N2 + 10% H2 was used as purging gas and Ar or Ar + 2% N2 as shielding gas,
Table 3.

Table 3. Welding parameters, HI=heat input=U×I/v.

28
 Analyzed Shielding U V HI Thickness
Name Purging gas I [A]
side gas [V] [mm/s] [kJ/mm] [mm]
304 Cap Ar Ar 14.3 163 6.7 0.3 3.0
304 Root Ar Ar 14.3 163 6.7 0.3 3.0
304 Root Ar none 14.3 163 6.7 0.3 3.0
304* Cap Ar Ar 16.1 163 10.0 0.3 3.0
304* Root Ar Ar 15.5 163 10.0 0.3 3.0
304* Root Ar none 15.7 163 10.1 0.3 3.0
316L Cap Ar Ar 14.6 163 7.0 0.3 3.0
316L Root Ar Ar 14.6 163 7.0 0.3 3.0
316L Root Ar none 14.6 163 7.0 0.3 3.0
316L* Cap Ar Ar 15.7 163 10.0 0.3 3.0
316L* Root Ar Ar 15.6 163 10.1 0.3 3.0
316L* Root Ar none 15.5 163 10.1 0.2 3.0
LDX 2101 Cap Ar Ar 14.8 163 9.2 0.3 2.2
LDX 2101 Root Ar Ar 14.8 163 9.2 0.3 2.2
LDX 2101 Root Ar none 14.8 163 9.2 0.3 2.2
LDX 2101 Cap Ar+2% N2 90% N2+10% H2 14.9 163 10.3 0.2 2.2
LDX 2101 Root Ar+2% N2 90% N2+10% H2 14.9 163 10.3 0.2 2.2
LDX 2101* Cap Ar Ar 15.3 163 10.1 0.2 2.2
LDX 2101* Root Ar Ar 15.8 163 10.1 0.3 2.2
LDX 2101* Root Ar none 15.4 163 10.1 0.2 2.2
LDX 2101* Cap Ar+2% N2 Ar 15.6 163 10.1 0.3 2.2
LDX 2101* Root Ar 90% N2+10% H2 15.4 163 10.1 0.2 2.2
LDX 2101* Root Ar+2% N2 none 15.9 163 10.1 0.3 2.2
* GDOES specimens polished to 3 µm mirror finish before welding.

Cross-sections of the LDX 2101 welds were ground and polished with SiO2 as a final step.
The welds were then etched and the ferrite content was measured with light optical image
analysis.

3.3 Post weld cleaning

Both welded samples and the base metal were pickled. Different pickling times were chosen,
depending on the cleanness of the welds. The samples were pickled until they looked visually
clean. LDX 2101 required the longest pickling time, Table 4.

Table 4. Pickling time for grades 304, 316L and LDX 2101 in 3.4M HNO3 + 3M HF at 60°C.
Pickling time, base Pickling time, welded material
Name EN
metal [minutes] [minutes]
LDX 2101 1.4162 0.5 19.0 – 21.0
304 1.4301 0.5 2.0
316L 1.4404 0.5 2.5

Polishing on the welded samples and the base metal was performed using a Flex LP 1503 VR
electrical machine with a rotation speed of 2700 rpm and an Schleif-Vlies polishing wheel
with K80 coarseness, Table 5. The welded samples were polished until they looked visually
clean.

Table 5. Polishing with K80 coarseness on 304, 316L and LDX 2101 with a rotation speed of 2700
rpm.
Name Analyzed Shielding gas Purging gas Times* Thickness

29
 side [mm]
304 --- --- --- 40 3.0
304 Cap Ar Ar 50 3.0
304 Root Ar Ar 30 3.0
304 Root Ar none 30 3.0
316L --- --- --- 40 3.0
316L Cap Ar Ar 60 3.0
316L Root Ar Ar 30 3.0
316L Root Ar none 30 3.0
LDX 2101 --- --- --- 40 2.2
LDX 2101 Cap Ar Ar 100 2.2
LDX 2101 Root Ar Ar 30 2.2
LDX 2101 Root Ar none 40 2.2
LDX 2101 Cap Ar+2% N2 90% N2+10% H2 80 2.2
LDX 2101 Root Ar+2% N2 90% N2+10% H2 30 2.2
* Back and forth, without applied external force (until no coloured heat tint could be seen).

3.4 Corrosion testing

In this work base metal and welded samples were corrosion tested in five different conditions;
as-welded, as-received, polished, wet ground to 320 mesh and pickled. All corrosion tests
were performed in 1 M NaCl at 35°C. The corrosion tests were mainly performed using the
Multicell, but complementary measurements was also carried out using the Avesta Cell.

3.4.1 Avesta Cell

The cell is connected to the Autolab PGSTAT30 potentiostat and a computer using the GPES
interface. Standard values of parameters used for potentiodynamic measurements in the GPES
are; step potential to 2.44 mV, scan rate to 0.1667 mV/s, start scan at OCP, wait 10 minutes
for OCP and current boundaries disabled (no change in scan direction after pitting corrosion
occurs, Figure 15). The temperature was set to 35°C and the measurement is not started until
that temperature is reached in the electrolyte. On the other hand, when performing
potentiostatic measurements the following parameters were used in the software; step
potential of 25 mV, maximum time interval of 4 minutes, minimum abs(di/i) per second to
zero, minimum abs(di) (A) to 1e-7. Pitting potentials are evaluated where the current density
exceeds 100 µA/cm2 for at least 60 seconds.

3.4.2 Multicell
Solatron 1287A potentiostat was used for the Multicell experiments together with the
Labview software interface. Standard set values of parameters used for Multicell
measurements in the Labview software were; scan rate to 0.1667 mV/s, Measure interval to
1000 ms, Current limit to 1 mA, wait 15 minutes for OCP. In this case the OCP value is the
mean value for all six samples. The temperature was set to 35°C and the measurement was not
started until that temperature was reached. Pitting potentials were evaluated where the current
density exceeded 100 µA/cm2 for at least 60 seconds.

30
 3.5 GDOES
The weld oxide composition was characterised at different depths using an RF GDOES, the
GD-Profiler HR, from Horiba Jobin Yvon.

Measurements were carried out using a 2 mm copper anode. The sample is attached using
vacuum, and then an RF applicator together with a cooling block is positioned on the backside
of the sample. Finally a mechanical arm is placed on the back of the cooling block to fasten
the sample, Figure 28. The topside of the welded samples was mounted directly in the
instrument, due to the relatively flat surface on the topside. The root side was too uneven to be
tested with the available sample holders.

Mechanical arm Sample Applied Radio Frequency

Cooling block
Figure 28. Mounting of sample, before (left) and after (right) the mechanical arm is in right position.

The flush time was 60 s, the background measurement lasted 5s, the sputter time was 70 s at
an applied pressure of 650 Pa. Figure 29 illustrates how the GDOES measurements were
performed on the topside of the welded samples.

BM
WM

HT

LT

31
 Figure 29. Schematic illustration of how the measurements were
performed on the topside where BM = base metal, LT = low temperature
oxide, HT = high temperature oxide and WM = weld metal.

4 Results
The visual impression when comparing the cleanness of the polished and pickled samples to
the as-welded condition was that the pickled appeared to be cleanest. The polished surface
was shinier than the pickled one, but some darker areas could be identified 1-2 mm from the
fusion line (FL), especially for LDX 2101 welded with nitrogen addition to the shielding gas.

4.1 Base metal

The base metal condition was primarily corrosion tested with the Multicell and only a few
measurements were performed using the Avesta Cell for comparison. In as-received condition,
LDX 2101 had the lowest pitting potential, Figure 30. The pitting potential for both LDX
2101 and 304 increased when polished with K80 coarseness, compared with the as-received
condition. After polishing to 320 mesh, LDX 2101 was in parity with that of 304 but not
316L. 316L even showed somewhat lower values after polishing than in the as-received
condition. An increase in pitting potential could be seen when as-delivered LDX 2101
samples were pickled. However, this was not the case for 304 and 316L where 304 returned
the lowest value. 316L returned a somewhat higher value in the pickled condition compared
with 320 mesh. As can be seen from Figure 26, all cleaning methods increased the pitting
potential for LDX 2101, and the best was wet grinding with 320 mesh. 304 in polished
condition only resulted in small increase in the pitting potential compared to the as-received
condition. For 304, the pickled condition resulted in the lowest pitting potentials, and the
highest was obtained in the polished condition. Detailed information on the of pitting
potential results from Figure 30 can be found in appendix A, Table 1.

Base metal 1M NaCl at 35°C

500
As-received
450
Polished (K80)
Pitting Potential [mVSCE]

400 320 mesh

350 Pickled
300
250
200
150
100
50
0
304 LDX 2101 316L
Grade

Figure 30. Pitting potential of base metal in 1 M NaCl at 35°C.

32
4.2 Topside
Pitting potential measurements using the Multicell for as-welded condition resulted in low
pitting potential values and no pitting attack occurred on LDX 2101 and 304 samples. The
Avesta Cell was for that reason used on LDX 2101, 304 and 316L in as-welded condition.

4.2.1 Avesta Cell

Figure 31 shows the potentiodynamic and potentiostatic curves of the as-welded samples of
LDX 2101 using Ar + 2% N2 as shielding gas. These were rather similar to each other with an
active passive behaviour. For the potentiodynamic curve (a) an initial top was present around
–450 mVSCE, a smaller at approximately –90 mVSCE and finally a relatively sharp increase at
the end of the curve. The potentiostatic curve (b) is smoother with an initial top around –480
mVSCE, a smaller at approximately –100 mVSCE and finally a sharp increase at the end. After
the corrosion measurement, pitting attacks could be identified 1 – 2 mm from the FL where a
dark oxide was present. Only a few attacks could be identified in the weld metal.

LDX 2101 As welded

Ar Ar + 2N2
TopTop
1 M1 NaCl
M NaCl 35°C
(a) LDX 2101 As-welded + 2N 2
at 35°C
Potentiodynamic
Potentiodynamic
0
1.000x10
1.000x10-1
Current density [A/cm2]

1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.600 -0.500 -0.400 -0.300 -0.200 -0.100 0 0.100

Potential, VSCE

(b) LDX2101
LDX 2101As-welded
As weldedAr
Ar++2N
2N2Top
2
Top11MMNaCl
NaClat35°C
35°C
Potentiostatic
Potentiostatic
1.000x10 0
Current density [A/cm2]

1.000x10-1
1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.600 -0.500 -0.400 -0.300 -0.200 -0.100 0 0.100
Potential, VSCE

Figure 31. (a) Potentiodynamic polarization curve and (b) Potentiostatic polarization curve of topside of as-
welded LDX 2101 using Ar + 2% N2 as shielding gas.

33
LDX 2101 welded with pure argon as shielding gas showed a somewhat similar
potentiodynamic curve as LDX 2101 welded with Ar + 2% N2, Figure 32a. An initial peak is
present at approximately –385 mVSCE a smaller at 63 mVSCE and a slightly sharper increase
after 48 mVSCE. However, the potentiostatic curve had a different appearance, showing a
decreased current density in the middle of the curve at approximately –324 mVSCE. The
decrease is followed by a sharp increase at –300 mVSCE, and then further decreasing to –124
mVSCE where the cureve finally increases to the end (Figure 32b). The current density was
lower for samples welded with pure argon most of the time compared with samples welded
with nitrogen additions. Pitting attacks mainly occurred 1 – 2 mm from the FL and almost no
attacks were found in the weld metal. This was not the case for LDX 2101 welded with
nitrogen additions to the shielding gas where attacks occurred both 1 – 2 mm from the FL and
in the weld metal.

(a) LDX
LDX 2101
2101 As weldedArArTop
As-welded Top1 1MMNaCl
NaClat35°C
35°C
Potentiodynamic
Potentiodynamic
0
1.000x10
1.000x10-1
Current density [A/cm2]

1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.450 -0.400 -0.350 -0.300 -0.250 -0.200 -0.150 -0.100 -0.050 0

Potential, VSCE

LDX
LDX 2101
2101 As weldedArArTop
As-welded Top1 1MMNaCl
NaClat35°C
35°C
(b)
Potentiostatic
Potentiostatic
1.000x10 0
1.000x10-1
Current density [A/cm2]

1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.450 -0.350 -0.250 -0.150 -0.050 0.050

Potential, VSCE
Figure 32. (a) Potentiodynamic polarization curve and (b) Potentiostatic polarization curve of topside as-
welded LDX 2101 performed using pure argon as shielding gas.

The results for as-welded 304 did not show the same appearance as for LDX 2101 (Figure
33). It can be noticed that no initial peak is present, but only a smooth top at approximately –

34
20 mVSCE for the potentiodynamic curve. The potentiostatic curve also showed a smooth top,
but at approximately –15 mVSCE, and no initial peak could be identified in the beginning of
the curve. Pitting primarily occurred 1 – 5 mm from the FL and in the weld metal.

(a) As welded Ar Top 1 M NaCl

304 As-welded NaCl 35°C
at 35°C
Potentiodynamic
Potentiodynamic
1.000x10 0
1.000x10-1
Current density [A/cm2]

1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.250 -0.200 -0.150 -0.100 -0.050 0 0.050

Potential, VSCE

(b) 304As-welded
304 As weldedAr
ArTop
Top11M
M NaCl
NaCl at
35°C
35°C
Potentiostatic
Potentiostatic
1.000x10 0
1.000x10-1
Current density [A/cm2]

1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.175 -0.150 -0.125 -0.100 -0.075 -0.050 -0.025 0 0.025 0.050

Potential, VSCE
Figure 33. (a) Potentiodynamic polarization curve and (b) Potentiostatic polarization curve of the topside of
as-welded 304.

The results for the as-welded 316L samples showed a similar polarization curve as for LDX
2101, but at much lower current densities, Figure 34a. A smooth initial top is present in the
beginning at approximately –99 mVSCE. The current density is then decreased until a sharp
peak at 100 mVSCE and then another sharp peak at 120 mVSCE decreasing to 127 mVSCE where
the current density finally increases at the end of the curve. The potentiostatic curve is similar
to the curve of 304 with no initial top at the beginning but a sharp increase at the end at
approximately 41 mVSCE. For 316L the pitting attacks occurred in the weld metal.

35
 (a) 316L
316L As welded Ar
As-welded ArTop
Top11MMNaCl
NaCl35°C
at 35°C
Potentiodynamic
Potentiodynamic
0
1.000x10
1.000x10-1
Current density [A/cm2]

1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.200 -0.150 -0.100 -0.050 0 0.050 0.100 0.150 0.200

Potential, VSCE

316L AsAs-welded
welded Ar Ar
Top 1 M1 NaCl 35°C
(b) 316L Top M NaCl at 35°C
Potentiostatic
Potentiostatic
0
1.000x10
1.000x10-1
Current density [A/cm2]

1.000x10-2
1.000x10-3
1.000x10-4
1.000x10-5
1.000x10-6
1.000x10-7
1.000x10-8
1.000x10-9
-0.200 -0.150 -0.100 -0.050 0 0.050 0.100 0.150

Potential, VSCE
Figure 34. (a) Potentiodynamic polarization curve and (b) Potentiostatic polarization curve of the topside of
as-welded 316L.

4.2.2 Multicell
Figure 35 shows the pitting potential for the various surface conditions examined in the
Multicell. Detailed information on the pitting potential values can be found in appendix B,
Table 2. 316L reached pitting potential values over 300 mVsce, LDX 2101 between 200-300
mVSCE and 304 reach values around 200 mVSCE. LDX 2101 welded with Ar + 2% N2 shielding
gas reached a somewhat higher value than samples welded with pure argon. Polishing
improved the pitting potential for 316L to a level close to the pickled condition, where it was
insufficient for 304 and LDX 2101. Polishing was particularly inefficient for the LDX 2101
welds performed with Ar + 2% N2 as shielding gas. Pitting potential values in as-welded
condition could only be obtained for 316L.

36
 Topside 1M NaCl at 35°C

500
450 As-welded
LDX 2101 316L
Pitting Potential [mVSCE]

Polished (K80)
400
Pickled
350
300 304
250
200
150
100
50
0
Ar Ar Ar + 2%
Ar+2% N2 N2 Ar
Shielding gas

Figure 35. Pitting potentials of topside welds in 1M NaCl at 35°C.

As can be seen from Figure 36, no pitting attacks occurred in the weld metal for the two
austenitic grades in pickled condition. The opposite was observed for pickled LDX 2101
welded with pure argon as shielding gas, Figure 36c. However, when nitrogen was added to
the shielding gas pitting also occurred 1 – 2 mm from the FL, 36d.

Figure 36. Pitting attacks on topside pickled samples of (a) 304, (b) 316L, (c)
LDX 2101 pure argon as shielding gas and (d) LDX 2101 using Ar + 2N2 as
shielding gas.

37
4.2.3 GDOES
The result from the GDOES measurements on the topside in the as-welded condition can be
seen in Figure 37. A high fraction of manganese is present at the surface in weld metal, high
temperature and low temperature oxide on LDX 2101 welded with pure argon and with
nitrogen additions. This was not the case for 304 and 316L. The thickest oxide formed on the
weld metal can be observed for LDX 2101 welded with Ar + 2% N2 shielding gas and the
thinnest was formed on 316L.

The results from the high temperature oxide showed that a high fraction of manganese was
present in the outer oxide layer of LDX 2101. This is especially true for LDX 2101 welded
with nitrogen additions. The oxygen curve follows the manganese curve for all grades but
with different fractions, where LDX 2101 welded with nitrogen additions is the most distinct
example. Nickel depletion can be observed for almost in almost all cases, except in the low
temperature oxide of 304 and 316L. The silicon content in the high temperature oxide at the
surface of LDX 2101 welded with pure argon is almost ten times higher compared with LDX
2101 base metal, approximately 6% compared to 0.62% for the base metal. A somewhat
higher chromium and nitrogen content can be observed for LDX 2101 welded with pure argon
than welded with nitrogen addition to the shielding gas in the weld metal and the high
temperature oxide. Chromium enrichment can be observed in the high temperature oxide for
LDX 2101 and a small fraction for 316L, but not for 304. Iron depletion occurs at the surface
for 316L and LDX 2101, almost none in 304. The manganese content in the high temperature
oxide is extremely high for LDX 2101 welded with nitrogen additions to the shielding gas,
where approximately 55% manganese can be identified at the surface. The nitrogen content is
also highest for LDX 2101 welded with nitrogen additions, but 304 have almost three times
higher nitrogen content at the surface. The silicon content is not very high except for LDX
2101 welded with pure argon, where a content of over 6% can be observed at the surface. The
oxygen curve follows the manganese curve relatively well for LDX 2101.

An interesting observation is that a chromium depletion was present in the weld metal for 304
and 316L, but not for LDX 2101. It can also be seen that the silicon content in the weld metal
is almost four times higher at the surface of 304 than in 316L.

Almost no chromium depletion occurs for the austenitic grades in the low temperature oxide.
LDX 2101 welded with nitrogen additions showed the highest depletion at the surface.
Manganese enrichments are observed for LDX 2101 at the low temperature oxide surface.

38
Figure 37. GDOES results in as-welded condition on the topside of the weld metal, the high temperature (HT)
oxide and the low temperature (LT) oxide of 304, 316L and LDX 2101.

4.3 Root side

Regarding the root side the majority of the measured samples, both as-welded, polished and
the pickled welds returned valid results. Only a few measurements on the root side were
performed in the Avesta Cell. No GDOES measurements were performed due to problems
with high oxygen and nitrogen signals.

The results of the Multicell root side measurements in as-welded condition clearly show the
difference when welding with or without purging gas. 316L appeared to be least sensitive to
residual oxide. The highest pitting potential for LDX 2101 in as-welded condition could be
observed when the 90% N2 + 10% H2 purging gas was used, Figure 38. A more detailed
information on the pitting potential results can be found in appendix B, Table 3.

39
 As-welded root side 1M NaCl 35°C

300

250
Pitting Potential [mVSCE]

304 LDX 2101 316L

200

150

100

50

0
none Ar none Ar 90%
90%NN2
2 ++ none Ar
10%HH2
10% 2

Purging gas

Figure 38. Pitting potentials for the root side of as-welded samples.

Figure 39 shows that the pitting potentials became much higher when the welds were polished
or pickled compared to the as-welded samples. One interesting observation is that LDX 2101
welded with pure argon reached higher pitting potential than 316L in the pickled condition.
Furthermore, samples welded with 90% N2 + 10% H2 as purging gas reached the lowest values
of all pickled root side samples. Detailed information on pitting potential results can be found
in appendix B, Table 3.

Root side 1M NaCl at 35°C

600
As-welded LDX 2101 316L
Pitting Potential [mV SCE]

500 Polished (K80)

Pickled
400 304

300

200

100

0
none Ar none Ar 90% N2
90% N2 + none Ar
10%
10% H2
H2

Purging gas

Figure 39. Pitting potential of the root side welds in 1 M NaCl at 35°C.

4.4 LDX 2101 weld metal microstructure

40
Figure 40 shows the weld metal microstructure at the cap surface for LDX 2101 welded with
pure argon and 2% nitrogen addition to the shielding gas. LDX 2101 welded with pure argon
showed somewhat less Widmanstätten austenite and more chromium nitride precipitates, seen
as dark areas at the surface. These are of Cr2N type [39]. The ferrite content in weld metal was
74 ± 3% when using pure argon as shielding gas. An average ferrite content of 71 ± 3% was
obtained when Ar + 2% N2 shielding gas was used, and less chromium nitrides precipitated at
the surface.

(a) Welded with pure argon as shielding gas (b) Welded with Ar + 2%N2 as shielding gas
Figure 40. Cross-section of LDX 2101 weld metal microstructure using different types of shielding gas.

5 Discussion
The used corrosion testing method in this work did not classify the materials fairly in all
conditions. LDX 2101 returns lower pitting potential result than expected when using the
ASTM G61 – 86 test method compared to the ranking obtained using the CPT method for the
same material. This is probably due to the higher surface sensitivity in the pitting potential
corrosion test ASTM G61 – 86 compared with the CPT test ASTM G150. The main reason
why the ASTM G61 – 86 method was used was to be able to perform corrosion measurements
in the as-welded condition and also to compare the results with 304. The CPT method works
well with pickled welds, as can be seen in Figure 42.

5.1 Base metal

Figure 41 shows typical CPT measurements for various materials. The ranking of the base
metal in this work in as-received condition according to ASTM G61 (Figure 30), did not
follow the ranking obtained using the more established ASTM G150 method [24]. For the
ASTM G61 method 304 showed higher pitting potentials than LDX 2101, but in the ASTM
G150 LDX 2101 reaches much higher values being rather more in parity with 316 than 304.
The calculated PRE numbers in Table 1 correspond relatively well with the CPT values in
Figure 41 regarding the ranking of the base metal. One explanation for the lower pitting
potential of LDX 2101 in ASTM G61 method can probably be the coarser surface of LDX
2101 (2E) compared to the smoother on 304 and 316L (2B).

41
 Figure 41. Typical values of critical pitting
temperatures (CPT) for base metal in 1 M NaCl
according to ASTM G150 using the Avesta Cell [24].

5.2 Topside
The results from the as-welded samples were difficult to interpret and that is why LDX 2101
welded with Ar + 2% N2 as shielding gas, was studied in more detail using the Avesta Cell.
This was carried out to see whether the initial top (Figure 31b) was caused by low corrosion
resistance or by oxide dissolution. However, the curve for 304 is harder to interpret compared
with LDX 2101 and that is why 304 were not further investigated. For the pickled welds, only
small difference of the curves could be identified, and that is why the Multicell was used, to
get improved statistics and faster measurements.

Figure 42 shows some critical pitting potential values for 316L, LDX 2101 and 2304 [SSW
2008, unpublished + en till, prata med west]. All samples were at least polished and some also
pickled. It can be noticed that LDX 2101 base metal have similar results as 316L, but even
better when welded both with and without filler metal and nitrogen additions to the shielding
gas. What is interesting in Figure 42 is that no measurable results were obtained for polished
but not pickled LDX 2101 welds. This was concluded to have been caused by oxide
dissolution. 304 were also included in Figure 42, but no measurable values could be obtained
since 304 have too low pitting resistance. This ranking could not be observed in this work
when ASTM G61 – 86 standard was used, Figure 30 and 35, respectively.

42
 30 2304
LDX 2101
25
316L
20 Base metal
CPT [ºC]

Ar
15
Ar + 2.5% N2
10 Polished

0
BM None 316L- BM None LDX 2205 BM None LDX
Si 2101 2101
Filler metal type

Figure 42. Critical pitting temperatures for pickled topside on 316L, LDX 2101 and 2304 [ref Elin,
unpublished work].

5.2.1 Avesta Cell

The corrosion test in the Avesta Cell was performed on the as-welded samples that strongly
deviated from a typical pitting potential curve of a passive metal (Figure 16) by having an
initial peak at the beginning before reaching a lower stable current, Figure 31b. This was
especially the case for LDX 2101 when using Ar + 2% N2 as shielding gas. 316L followed the
standard curve (Figure 16) relatively well and only a smooth top could be observed. When
following the standard potentiodynamic pitting potential corrosion test ASTM G61 – 86 a
scan rate of 10 mV/min is used. However, this rate was probably too high for measuring as-
welded samples because of weld oxide dissolution. The scan rate needs to be tested and
adapted for the as-welded samples. In order to study the as-welded samples a potentiostatic
measurement was utilized, providing faster measurements compared to using a
potentiodynamic method with very low scan rate. The potentiostatic polarisation curve of
LDX 2101 with Ar + 2% N2 shielding gas appeared similar to a curve for a passive metal in
an acidic solution (Figure 15), by showing one top at the beginning of the curve (Figure 31)
followed by a sharp increase at the end. The potentiostatic curve of as-welded 304 (Figure
33b) and 316L (Figure 34b) had a similar appearance. The major difference was that 304 had
higher current densities, probably due to oxide dissolution as for LDX 2101. Two peaks could
be observed for potentiodynamic measurement of 316L in Figure 34a, which can be
pittinitiations that repassivates.

A difference on where the pitting attacks occurred could be seen for the three grades in as-
welded and pickled condition. The difference for LDX 2101 between as-welded and pickled
was; there was no attacks 1 – 2 mm from the FL when pickling LDX 2101 welded with pure
argon, but no difference could be seen when nitrogen additions was used. This was probably
due to residual weld oxides caused by a too short pickling time. However, for 304 the attacks
did not appear in the weld metal after pickling, which was also the case for 316L. The as-
welded 316L samples had pitting attacks in the weld metal, but after pickling all attacks
occurred 1 – 2 mm from the FL, Figure 36.

The most interesting welds, LDX 2101 welded with Ar + 2% N2, were further investigated. A
number of different measurements on LDX 2101 with Ar + 2% N 2 were carried out and some
of the measurements were terminated between the first peak and the sharp increase at the end,

43
numbered 1, 2 and 3 in Figure 43. This was performed to verify that no pitting occurred
before the sharp increase at the end of the curve, thus identify an approximately potential
were the pitting actually occurs in as-welded condition on LDX 2101. As the potentiostatic
measurement does not follow the ASTM G61 – 86 standard, the results are not fully verified,
but should rather be interpreted as a rough estimation of the pitting potential it confirms that
LDX 2101 does not show pitting attacks before number 2 in Figure 43. However, IR drop
compensation has not been taken into consideration, which can affect the result somewhat.
According to the obtained results the initial top is most probably due to dissolution of oxides.
This is supported by the fact that no pitting attack could be observed on the samples
terminated at number 1 (Figure 43). Pitting attacks mainly occurred in the weld metal or 1 – 2
mm from the FL. These probably initiate under the dark oxide located 1 – 2 mm from the FL
followed by pit initiation in the weld metal.

LDX
LDX2101
2101As Welded Ar+2N2
As-welded Ar + 2N/ 2Formier
Top 1 M10NaCl
1M NaCl
35°C35C
080407
Potentiostatic
0
1.000x10
i / A [A/cm ]

3
2

1.000x10-1

1.000x10-2 1 2
Current density

1.000x10-3

1.000x10-4

1.000x10-5
-0.600 -0.500 -0.400 -0.300 -0.200 -0.100 0 0.100
Volt,EV/ SCE
V

44
 Start

Nr 1

Nr 2

Nr 3

Figure 43. Polarization curve of the topside of LDX 2101 welded with Ar + 2% N2 with three different stop
potentials marked with corresponding pictures.

One interesting observation is that LDX 2101 samples welded with Ar + 2% N 2 showed a dark
oxide adjacent to the FL (Figure 44b) after corrosion measurements. As can be seen in Figure
44a, this was not the case for LDX 2101 welded with pure argon as shielding gas. This dark
oxide that forms or is revealed during the corrosion measurement is probably one important
factor that affects the pitting potential for LDX 2101 in as-welded condition, but also the
difference in polarization curves of samples welded with pure argon and those with Ar + 2%
N2. The samples in Figure 44 have, however, not been corroded to the same current level,
which can probably be the reason for the higher amount of pits in Figure 44b. The oxide
formed when using Ar + 2% N2 is thicker and contains more manganese. It is possible that
this reduces the pitting resistance, but this is difficult to measure due to the oxide dissolution.
One reason for this was most likely due to formation of an oxide that contains higher fraction
of manganese when nitrogen addition is used in the shielding gas, but also due to redeposition
of manganese from the gas phase and formation of oxynitrides, see weld metal and high
temperature oxide in Figure 37 [4].

45
The dark oxide 1 – 2 mm from the FL on LDX 2101 with nitrogen addition to the shielding
gas represents the “high temperature” (HT) oxide measured with GDOES, Figure 37. If
comparing GDOES results of LDX 2101 welded with pure argon and welded with nitrogen
addition it can clearly be seen that the latter contains a much higher fraction of manganese.
The chromium fraction is also lower for LDX 2101 welded with nitrogen addition according
to the results in Figure 37. This can maybe explain the somewhat lower pitting potential for
samples welded with nitrogen addition in as-welded condition. No such reduction of the
pitting resistance when using Ar + 2% N2 was seen for the pickled condition in the ASTM
G150 tests in Figure 42, but it has been stated that welds performed on LDX 2101 with
nitrogen additions requires pickling for avoiding discoloration and to have measurable
corrosion resistance [SSW 2008, Weldox paper].

(a) Welded with pure argon as shielding gas (b) Welded with Ar + 2%N2 as shielding gas
Figure 44. Difference between Ar and Ar + 2%N2 as shielding gas on the oxide adjacent to the fusion line.

5.2.2 Multicell
304 reached the lowest pitting potential, 316L the highest and LDX 2101 values between 304
and 316L. One interesting observation is that pickled LDX 2101 welded with nitrogen
addition to the shielding gas reached a somewhat higher pitting potential value than samples
welded with pure argon. This is in accordance with CPT results showing that improved
austenite formation improves the pitting resistance [SSW 2008]. The reason for that is most
probably the reduction of the amount of chromium nitride precipitates or due to the removal
of the manganese-rich weld oxide formed when nitrogen addition was used in the shielding
gas [4]. Pickling was the only cleaning method that removed the oxides present on the LDX
2101 samples and restored the corrosion resistance to an acceptable level, Figure 35. Also the
austenitic grade 304 restored the corrosion resistance to an acceptable level when pickling
was performed. Polishing was not sufficiently effective for restoring the corrosion resistance
for either LDX 2101 or 304. As no valid result could be obtained on the as-welded samples,
most likely caused by weld oxide dissolution, they were instead measured in the Avesta Cell.

5.2.3 GDOES
High chromium-enrichment can be observed under the surface for 316L and LDX 2101 in the
weld metal. Furthermore an iron-enrichment can be seen close to the surface for the two

46
austenitic grades, but not for LDX 2101. Another interesting observation is that all grades
have higher silicon content than 316L at the surface, especially 304. LDX also shows high
manganese content at the surface of the weld metal compared with the two austenitic grades.

The GDOES measurements from the topside (Figure 37) clearly show significantly higher
manganese content on the LDX 2101 specimens. High manganese fractions were seen in the
weld metal, and in both the high temperature and low temperature oxide formed on LDX
2101. This was further enhanced by using nitrogen additions to the shielding gas. This can
probably be explained by the suggested absorption-evaporisation-deposition process [4]. It
states that the majority of the manganese in the weld oxide originates from deposited weld
metal species and only to some extent from base metal diffusion.

5.3 Root side

The majority of the measurements carried out on the root side followed the standard curve
(Figure 16) for a passive metal relatively good. The reason why the Multicell measurements
turned out well can probably be explained by the fact only oxidation could occur at the root
side since the root was not molten. Previous work have shown that on the topside both
oxidation and deposition from the weld metal can occur, which is probably why the results of
the weld oxide on the topside is different from the root side [4].

5.3.1 Multicell
The Multicell results for the root side in as-welded condition were in agreement with earlier
work regarding the ranking between the grades LDX 2101, 304 and 316L. One interesting
observation is that LDX 2101 increased the pitting potential from approximately 100 mVSCE
in as-welded condition to almost 300 mVSCE in the pickled condition. The low value for the
as-welded condition can probably be explained by manganese oxides formed on LDX 2101,
due to the higher manganese content in the alloy compared to 304 and 316L [4]. One reason
for the high pitting potential values obtained in pickled condition compared to the pickled
base metal can maybe be explained by different pickling times, see Figure 34 and 26. Pickling
time for the welded samples was most likely more adapted than for the base metal. Only one
pickling time was tested for the base metal and that time was probably not the most optimal.
Another observation is that pickled LDX 2101 welded with no purging gas resulted in higher
pitting potential than for samples welded with 90% N2 +10 H2, which is known to be a
superior purging gas. This can also be a result of the pickling time. As all LDX 2101 was
pickled for equally long time, this time might be relatively optimal for some of the oxides, but
not for all of them. However, the same pickling time can be to long for the oxide formed when
90% N2 +10 H2 purging gas was used, but perfect for the oxide formed when pure argon was
used. Detta är föreslag från Elin istället för markerad text ovan: “What has previously been
known is that 90% N2 + 10% H2 gives better corrosion resistance than pure argon in as-
welded condition. In pickled condition the results deviates significantly from what is
previously known from ASTM G150 measurements and ?…? experience.” Vad hände med
pickling time?

Ericsson et al. [40] showed how the pitting resistance of 316 stainless steel changed with
different post-weld cleaning methods, Figure 45. The pitting potential increased with
increased degree of surface finish, which means that the susceptibility to pitting is decreased.
In this work, this pattern could only be seen for the topside, Figure 30 and 39. The root side
results from measurements of 316L with pure argon as purging gas, LDX 2101 with 90% N 2

47
+10 H2 purging gas and 304 without any purging gas did not follow the pattern. One important
factor is that only two measurements were carried out on the polished welds, which makes is
hard to interpret the results when they have similar pitting potential values. The initial ranking
between the materials also deviated from expected values.

Figure 45. Pitting resistance for different cleaning methods after annealing at
1050°C for five minutes in 0.1 M NaCl at 25°C [40].

5.3.2 GDOES
To perform measurements on the root side a special sample holder was used, but the results
were not fully validated. The high oxygen and nitrogen signals obtained during test
measurements with the special sample holder were most probably caused by air leakage into
the cavity where the glow discharge process occurs. Measurements on the root side can be
performed when the special sample holder is fully tested and verified. This will give valuable
information that could help the interpretation of the corrosion results.

5.4 Ferrite content

The effect of nitrogen additions to the shielding gas on the average weld metal austenite
content was small 74 ± 3% to 71 ± 3% when Ar + 2% N2 was used. The austenite formation at
the cap side that is normally exposed to the corrosive media was, however, significantly
improved, and the amount of chromium in the nitrides at the surface was reduced. This can be
explain why the majority of the pitting attacks occurred in the weld metal for LDX 2101
welded with pre argon, while nitrogen additions improved the corrosion performance. Earlier
work [39] has shown that nitrogen addition to the shielding gas increases the austenite
formation.

48
6 Conclusions
Three different types of stainless steels (304, LDX 2101®, 316L) were TIG welded bed on
plate without filler material. Two post-weld cleaning methods were performed on the welded
samples, polishing with K80 coarseness and pickling in pickling bath. Two types of ASTM
G61 – 86 based measurements were performed, one was recording polarization curves in the
Avesta Cell and the other was measuring pitting potentials in the Multicell. Recording of
polarization curves in the Avesta Cell was further investigated on the topside of LDX 2101
welded with nitrogen additions to the shielding gas. Surface analysis with GDOES was
performed on the welded samples to provide better understanding for the corrosion results.

• Residual weld oxides reduced the corrosion resistance according to ASTM G61 – 86,
especially for 304 and LDX 2101. Polishing to K80 coarseness somewhat improved
the corrosion resistance on both top and root side. Pickling restored the corrosion
resistance to the highest level in most cases, especially on the topside for 304 and
LDX 2101. 316L generally showed the highest pitting potential values both on top and
root side.

• The ranking of the three investigated grades were not the same if comparing the
ASTM G61 – 86 used in this work with the more common ASTM G150 corrosion test
method. It seems like the ASTM G61 – 86 method was more dependent on the surface
roughness of the sample than ASTM G150.

• LDX 2101 welded with Ar + 2% N2 developed an oxide that was hard to remove with
polishing and pickling, only pickling was sufficiently good for improving the
corrosion resistance. However, when the oxide was removed a somewhat higher
pitting potential was obtained compared with samples welded with pure argon. This is
probably due to the improved austenite formation in the weld metal when using
nitrogen additions in the shielding gas, which decreases the chromium nitride
precipitates.

• The high temperature oxide formed on the cap side of LDX 2101 welded with
nitrogen addition to the shielding gas has higher manganese content in the outer oxide
layer compared with LDX 2101 welded with pure argon, which will probably have a
negative effect on corrosion resistance if not removed.

• The initial current peak that occurs for LDX 2101 in the beginning of the ASTM G150
measurement can also be identified when using ASTM G61 – 86 method in the
Multicell, which in both cases exceeds the set threshold value of 1 mA. The ASTM
G61 – 86 Avesta Cell measurements of LDX 2101 in as-welded condition showed that
a sharp increase in current density occurs at the beginning of the measurement,
exceeding the threshold value 1 mA. This increase in current density is most probably
due to oxide dissolution and results showed that no visible pitting attacks could be
identified after the first current peak, which indicates that the corrosion resistance is
higher than what the standard measuring techniques show.

49
 • The relatively high pitting potential values on the root side compared with the topside
of LDX 2101 in pickled condition can probably be explained by the redeposition of
manganese from the weld metal, which most probably occurs on the topside.

• The weld oxide formed on LDX 2101 when adding nitrogen to the shielding gas
becomes thicker and the composition deviates somewhat from that of the weld oxide
formed when using pure argon. LDX 2101 with nitrogen addition showed slightly
lower pitting potential values in as-welded condition, but somewhat better than pure
argon in pickled condition. The former is addressed to oxynitrides formed from
deposition from the weld metal and the latter due to improved weld metal pitting
resistance.

7 Suggestion to further work

It would be beneficial to validate and adjust the special sample holder, for non-flat specimens,
to obtain valid GDOES measurements on the root side of the welded samples, which in turn
could give some explanation to the pitting potential results on the root side.

As different materials and different shielding gas types needed different pickling times to
become visually clean, the effect of different pickling times should be investigated.

GDOES measurements on samples that have been corrosion tested to see how the surface
composition, and especially on LDX 2101, is changed after aborted measurements showing
oxide dissolution, but no pitting attack

The GDOES instrument should be calibrated for using the 1 mm anode instead of the 2 mm
used in this work. This would give better precision when analysing the different oxide zones
on the welded specimen.

Performing ASTM G150 tests with increased threshold values to determine the CPT more
accurately.

CPT measurements of all conditions should be performed for better comparison with earlier
work. Investigations of other post-weld cleaning methods such as pickling paste, shot
blasting, polishing, wet grinding with different coarseness and combining mechanical and
chemical methods would show the necessity of post-weld cleaning.

Performing polarization curves on welded samples of LDX 2101, 304 and 316L using ASTM
G61 – 86 standard with lower scan rate.

8 Acknowledgements

50
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52
Appendix A

MULTICELL MEASUREMENTS
TABLE 1. Pitting potentials of base metal. BASE METAL

Material Epit (Average) [mVAg/AgCl] Epit (Average) [mVSCE] STDAV* Number of samples

As-received
304 284 239 30 2
LDX 2101 160 115 4 2
316L 437 392 11 2

320 mesh
304 294 249 16 9
LDX 2101 303 258 45 6
316L 397 352 25 6

Pickled base metal

304 176 131 none 1
LDX 2101 224 179 14 2
316L 400 355 10 2

Polished base metal (K80)

304 302 257 6 2
LDX 2101 278 233 1 2
316L 416 371 none 1

∑(x −x )
2

* STDAV =
N −1

53
Appendix B

MULTICELL MEASUREMENTS
TABLE 2. Pitting potentials of welded topside. WELDED TOPSIDE

Material Shielding gas Epit (Average) [mVAg/AgCl] Epit (Average) [mVSCE] STDAV* Number of samples

As-Welded
304 Ar --- --- none 0
LDX 2101 Ar --- --- none 5
LDX 2101 Ar+2% N2 --- --- none 0
316L Ar 138 93 4 6

Polished (K80)
304 Ar 87 42 9 2
LDX 2101 Ar 73 28 13 2
LDX 2101 Ar+2% N2 --- --- none 6
316L Ar 333 288 8 2

Pickled
304 Ar 247 202 28 6
LDX 2101 Ar 287 242 62 4
LDX 2101 Ar+2% N2 294 249 68 3
316L Ar 378 333 13 6

TABLE 3. Pitting potentials of welded root side. WELDED ROOT SIDE

Material Purging gas Epit (Average) [mVAg/AgCl] Epit (Average) [mVSCE] STDAV* Number of samples

As-Welded
304 none 93 48 5 5
304 Ar 131 86 17 6
LDX 2101 none 52 7 1 3
LDX 2101 Ar 167 122 17 6
LDX 2101 90% N2 + 10% H2 187 142 50 4
316L none 159 114 2 4
316L Ar 203 158 6 3

Polished (K80)
304 none 257 212 3 2
304 Ar 249 204 11 2
LDX 2101 none 253 208 20 2
LDX 2101 Ar 280 235 25 2
LDX 2101 90% N2 + 10% H2 263 218 55 6
316L none 321 276 78 2
316L Ar 434 389 1

Pickled
304 none 253 208 56 6
304 Ar 300 255 20 6
LDX 2101 none 299 254 72 8
LDX 2101 Ar 426 381 102 10
LDX 2101 90% N2 + 10% H2 227 182 64 10
316L none 375 330 17 6
316L Ar 389 344 11 6

∑(x −x )
2

* STDAV =
N −1

54