GTAW Liquid Pool Convections and The Weld Shape Variations Under
GTAW Liquid Pool Convections and The Weld Shape Variations Under
GTAW Liquid Pool Convections and The Weld Shape Variations Under
net/publication/277823270
Microstructure and properties of welds in the lean duplex stainless steel LDX
2101
CITATIONS READS
28 488
1 author:
Elin Westin
Voestalpine
37 PUBLICATIONS 361 CITATIONS
SEE PROFILE
Some of the authors of this publication are also working on these related projects:
All content following this page was uploaded by Elin Westin on 03 May 2016.
Elin M. Westin
Doctoral Thesis
ISBN 978-91-7415-801-4
ISRN KTH/MSE--10/59--SE+METO/AVH
ISBN 978-91-7415-801-4
ISRN KTH/MSE--10/59--SE+METO/AVH
Copyright © 2010 Elin M. Westin. All rights reserved. No part of this thesis may be
reproduced by any means without permission from the author.
Printed at E-print
II
Abstract
Duplex stainless steels can be very attractive alternatives to austenitic grades due to
their almost double strength at equal pitting corrosion resistance. When welding, the
duplex alloys normally require addition of filler metal, while the commodity
austenitic grades can often be welded autogenously. Over-alloyed consumables are
used to counteract segregation of important alloying elements and to balance the two
phases, ferrite and austenite, in the duplex weld metal. This work focuses on the
weldability of the recently-developed lean duplex stainless steel LDX 2101® (EN 1.4162,
UNS S32101). The pitting corrosion resistance of this grade is better than that of
austenitic AISI 304 (EN 1.4307) and can reach the level of AISI 316L (EN 1.4404). The
austenite formation is rapid in LDX 2101 compared to older duplex grades. Pitting
resistance tests performed show that 1-2.5 mm thick laser and gas tungsten arc (GTA)
welded LDX 2101 can have good corrosion properties even when welding
autogenously. Additions of filler metal, nitrogen in the shielding gas, nitrogen-based
backing gas and use of laser hybrid welding methods, however, increase the austenite
formation. The pitting resistance may also be increased by suppressing formation of
chromium nitrides in the weld metal and heat affected zone (HAZ). After thorough
post-weld cleaning (pickling), pitting primarily occurred 1-3 mm from the fusion line,
in the parent metal rather than in the HAZ. Neither the chromium nitride precipitates
found in the HAZ, nor the element depletion along the fusion line that was revealed by
electron probe microanalysis (EPMA) were found to locally decrease the pitting
resistance. The preferential pitting location is suggested to be controlled by the
residual weld oxide composition that varies over the surface. The composition and
thickness of weld oxide formed on LDX 2101 and 2304 (EN 1.4362, UNS S32304) were
determined using X-ray photoelectron spectroscopy (XPS). The heat tint on these lean
duplex grades proved to contain significantly more manganese than what has been
reported for standard austenitic stainless steels in the AISI 300 series. A new approach
to heat tint formation is presented; whereby evaporation of material from the weld
metal and subsequent deposition on the already-formed weld oxide are suggested to
contribute to weld oxide formation. This is consistent with manganese loss from the
weld metal, and nitrogen additions to the GTA shielding gas enhance the evaporation.
The segregation of all elements apart from nitrogen is low in autogenously welded
LDX 2101. This means that filler wire additions may not be required as for other duplex
grades assuming that there is no large nitrogen loss that could cause excessive ferrite
contents. As the nitrogen appears to be controlling the austenite formation, it becomes
essential to avoid losing nitrogen during welding by choosing nitrogen-containing
shielding and backing gas.
III
Preface
Welding is an essential part in developing and commercialising a new stainless steel.
It is important to show that it has good weldability and to be aware of its limitations.
In this thesis, five papers collecting research work on welding of lean duplex LDX 2101
are presented, with a primary emphasis on the interrelation between microstructure
(phase balance, weld oxide formation, element distribution and precipitates) and
corrosion properties. The main focus has been on autogenous GTA and laser welding
of rather thin material (1-2.5 mm), since some of the grades often replaced by LDX 2101
can be welded without filler additions. The ability to improve the austenite formation
and pitting corrosion resistance by means of nitrogen additions to the shielding gas,
nitrogen-based backing gas, use of filler metal or laser hybrid welding methods was
also investigated. Although the weldability of the duplex stainless steels is far from
fully mastered, more knowledge on the weldability of these grades has been gained
and some new phenomena been identified and explained.
The main work in this thesis was carried out at Outokumpu Stainless at Avesta
Research Centre (ARC), Sweden and supervised by Prof. Staffan Hertzman. Courses and
thesis writing were primarily undertaken as an external PhD at the Division of Physical
Metallurgy, Department of Materials Science and Engineering, at Kungliga Tekniska
Högskolan (KTH), Stockholm, Sweden with Prof. John Ågren as supervisor. The first
section consists of an introduction to the duplex stainless steels and their weldability,
plus a summary of the main findings in this work. The second part consists of the
papers below, which will be referred to in the text by their respective letters.
D. Effect of laser and laser hybrid welding on the corrosion performance of a lean
duplex stainless steel
E.M. Westin, A. Fellman
In press: Journal of Laser Applications 13pp.
IV
Localized corrosion resistance of welded austenitic and lean duplex stainless
steels
M.M. Johansson, E.M. Westin, J. Oliver, R.F.A. Pettersson
Accepted for publication in: Welding in the World, IIW Doc.-No. II-1740-10 (2010) 14pp.
Short focal length scanner-fiber laser welding of stainless steel sheets and tubular
products
M.P. Vänskä, V. Kujanpää, E.M. Westin, T. Torvinen
Proc. ICALEO 2009, Orlando, FL, LIA, Paper 1803 (2009) 766-772.
Welds in the lean duplex stainless steel LDX 2101 – Effect of microstructure and
weld oxides on corrosion properties
E.M. Westin
Licentiate Thesis in Materials Science, KTH, Stockholm, Sweden, 2008.
Mechanical properties of welds in the new lean duplex stainless steel LDX 2101®
C. Ericsson, P. Johansson, M. Liljas, E.M. Westin
Proc. Stainless Steel World 2003, Maastricht, KCI Publishing, Paper P0356 (2003) 423-431.
V
Content
1 Stainless steels and their weldability ...................................................................... 1
1.1 Austenitic stainless steels ............................................................................... 2
1.2 Ferritic stainless steels ................................................................................... 4
1.3 Ferritic-austenitic (duplex) stainless steel ..................................................... 5
1.3.1 Lean duplex stainless steel ........................................................................ 6
1.3.2 Standard duplex stainless steel .................................................................. 7
1.3.3 Superduplex stainless steel ........................................................................ 7
1.3.4 Filler metal for welding duplex stainless steel............................................ 8
2 Alloying elements ................................................................................................... 9
3 Corrosion resistance ............................................................................................ 11
4 Welding methods.................................................................................................. 12
5 Characterisation techniques ................................................................................ 14
5.1 Composition and microstructure ................................................................ 14
5.1.1 HTHAZ simulation ................................................................................. 14
5.1.2 Microscopy ............................................................................................. 15
5.1.3 Chemical analysis ................................................................................... 15
5.2 Mechanical and corrosion properties .......................................................... 16
5.2.1 Mechanical testing .................................................................................. 16
5.2.2 Post-weld cleaning .................................................................................. 16
5.2.3 Corrosion testing ..................................................................................... 17
6 Aim of this work................................................................................................... 18
7 Microstructure of duplex welds............................................................................ 18
7.1 Solidification (Paper E) ................................................................................ 18
7.2 Weld metal austenite formation and morphology ...................................... 24
7.3 Ferritization, nucleation and growth of austenite in HTHAZ (Paper A)... 25
7.4 Theoretical modelling of austenite formation (Paper A) ............................ 27
7.5 Specification of phase balance ..................................................................... 29
7.6 Secondary phases ......................................................................................... 30
8 Corrosion resistance ............................................................................................. 33
8.1 Effect of nitrogen on corrosion resistance of duplex welds ........................ 34
8.1.1 Preventing nitrogen loss (Paper C) .......................................................... 34
8.1.2 Effect of nitrogen additions when laser welding (Paper D) ...................... 37
8.2 Effect of heat input on corrosion performance ........................................... 38
8.2.1 Low heat input ........................................................................................ 39
8.2.2 High heat input ........................................................................................ 40
8.3 Effect of element partitioning on corrosion resistance (Paper E) .............. 40
8.4 Element loss – evaporation and deposition (Paper B) ................................ 41
8.5 Weld oxides and their influence on corrosion properties (Paper B) .......... 43
VI
8.6 Discoloration of welds (Paper B) ................................................................. 48
8.7 Preferential location of pitting (Papers C and D) ....................................... 48
9 Laser welding of duplex stainless steel (Paper D) ................................................ 50
10 Mechanical properties........................................................................................ 52
10.1 Hardness ..................................................................................................... 53
10.2 Tensile properties ....................................................................................... 53
10.3 Weld metal impact toughness .................................................................... 53
11 Conclusions ....................................................................................................... 55
12 Summary of papers ............................................................................................ 56
Paper A. Weldability aspects of a newly developed duplex stainless
steel LDX 2101 ................................................................................................... 56
Paper B. Weld oxide formation on lean duplex stainless steel ......................... 57
Paper C. Pitting corrosion resistance of GTA welded lean duplex
stainless steel ...................................................................................................... 58
Paper D. Effect of laser and laser hybrid welding on the corrosion
performance of a lean duplex stainless steel ..................................................... 59
Paper E. Element distribution in lean duplex stainless steel welds .................. 60
13 Acknowledgements............................................................................................. 61
14 References .......................................................................................................... 62
15 Appended papers ................................................................................................... 66
VII
1 Stainless steels and their weldability
Stainless steels are alloyed with at least 12% chromium and become corrosion resistant
by formation of a passive film on the surface. By varying the composition of the steel
with chromium, nickel, molybdenum, nitrogen, etc., it is possible to achieve different
properties suitable for various applications. Stainless steels may be divided into
different groups on the basis of their microstructure. Of these austenitic, ferritic and
ferritic-austenitic (duplex) are the most commonly used. In daily life, most people
have austenitic stainless steel sinks, some ferritic cooking utensils and the water
heaters making the shower comfortable are today mostly made of a duplex grade.
Some stainless steels are presented in Table 1. There are several material standards
available. The most common names are given when first mentioned in the thesis, but
the main designations used throughout the thesis are found in the column “Material”
in Table 1.
Table 1. Examples of stainless steels.
LDX 2101® 1.4162 S32101 0.03 0.22 21.5 1.5 0.3 5Mn 26
1
This work focuses on fusion welding in which two pieces of base material are fused
together with an electric arc or a laser beam. This can be performed either with filler
metal additions or autogenously (without filler metal additions). Some examples of
filler metals that may be suitable are given in Table 2 with the EN ISO designations.
The various stainless steels available today show different weldability as discussed
more in detail in the Outokumpu Welding Handbook [1] and below. The final weld
metal corrosion and mechanical properties are determined by a complex mixture of
metallurgical, geometrical and surface effects. These effects may have varying
importance depending on the demands on the performance of the welded construction.
Table 2. Examples of suitable filler metals for welding different stainless steels.
Material EN ASTM/UNS Filler
2
carbon contents, intergranular corrosion (IGC) caused by chromium carbide
precipitates in the grain boundaries of the heat-affected zone (HAZ) is rarely an issue
nowadays, but titanium and/or niobium stabilized grades are, however, still specified
in some standards and by some users. The austenitic steels have about 50% higher
thermal expansion compared to carbon steel, ferritic and duplex stainless steels. This
means that larger deformation and higher shrinkage stresses may be a result from
welding. These grades have excellent formability and high toughness at low
temperatures, but the strength is somewhat lower than that of the other stainless steel
types. These grades may, in addition, be sensitive to stress corrosion cracking (SCC)
under certain conditions, i.e. a special corrosive environment in combination with
tensile stress in the material and often at elevated temperature.
The higher alloyed high performance austenitic stainless steels differ substantially
from more conventional grades with regard to resistance to corrosion and, in some
cases, also mechanical properties. This is mainly due to the high contents of
chromium, nickel, molybdenum and nitrogen, which results in very good resistance to
uniform corrosion and various types of SCC, high to excellent resistance to pitting and
crevice corrosion, good ductility, formability and weldability. Examples of high
performance austenitic stainless steels are listed, with increasing corrosion resistance;
AISI 904L (EN 1.4539), 254 SMO® (EN 1.4547, UNS S31254), EN 1.4565 (UNS S34565) and 654
SMO® (EN 1.4652, UNS S32654). These grades are, for instance, used in applications such
as process equipment in chemical process industries, flue gas cleaning, desalination,
seawater handling and heat exchangers. The high performance austenitic stainless
steels have a fully austenitic microstructure in the solution annealed condition. Most
standard austenitic stainless steels and their recommended fillers are designed to
solidify as δ-ferrite, distributing impurities such as sulphur and phosphorous more
efficiently, and are thus less sensitive to solidification cracking. For a fully austenitic
weld metal, impurities may be concentrated to the grain boundaries or the inter-
dendritic regions, resulting in low-melting phases and susceptibility to solidification
cracking. High-alloyed austenitic stainless steels may also show precipitation of
intermetallic phases in the weld metal and HAZ. Smaller amounts of precipitates do
not usually affect the corrosion resistance or mechanical properties of the weldment.
Welding should generally be performed using a moderate heat input (<1.5 kJ/mm),
with an interpass temperature not exceeding 100°C and the lowest possible dilution of
the parent metal. The need to minimize dilution from the parent steel often make
submerged arc welding (SAW) unsuitable. For superaustenitic grades, the weld metal
pitting corrosion resistance can be decreased due to microsegregation, primarily of
molybdenum, during solidification. This can be compensated by using over-alloyed
nickel base filler metal.
Contamination of the steel surface by metals with low melting points, such as copper
and zinc, can give rise to liquid metal penetration of the grain boundaries in the HAZ
heated to 750-800°C [2]. This can cause intergranular cracking and brittle fracture of the
normally ductile steel [3-5]. Such liquid metal embrittlement (LME) or contamination
cracking forms under the internal residual stresses always present after welding. LME
requires a susceptible microstructure, tensile stress and a liquid metal [6] and has only
been observed in face centred cubic (FCC) metals including the austenitic stainless
steel AISI 300 series [7,8]. The susceptibility increases with the alloy content of the
austenitic stainless steel.
3
1.2 Ferritic stainless steels
The standard ferritic stainless steels normally contain 11-18% chromium, but no or
only small amounts of nickel. The slightly higher proof strength than for austenitic
stainless steels, in combination with lower work hardening make ferritics an attractive
alternative where forming operations are necessary. Ferritic grades have good
resistance to SCC and provide an oxidation resistance sufficient for many applications
at temperatures up to 700°C to 950°C, depending on composition. Ferritic stainless
steels have, however, lower ductility and significantly decreased toughness at low
temperatures compared to austenitics. They have often lower corrosion resistance than
the standard austenitic grades and are therefore primarily used in indoor applications
and as alternatives to carbon steel, giving lower maintenance costs and longer service
life. AISI 409 (EN 1.4003) and AISI 430 (EN 1.4016) are low-alloyed ferritic grades which
can replace carbon steel in many applications. Typical applications for AISI 409 are
within the transportation sector, e.g. railroad carriages, buses, trucks and containers.
AISI 430 with higher chromium content is used in a variety of interior applications
including washing machines, dish-washers, sinks, refrigerators and tableware. The
higher alloyed grade AISI 444 (EN 1.4521) with high chromium and molybdenum
contents often offers corrosion resistance similar to standard austenitic grades and can
replace these in many applications. As for the duplex grades, ferritics should not be
used at temperatures between 300-550°C as they can become brittle. Another drawback
is that they generally have lower weldability than the austenitic and duplex grades. All
fully ferritic stainless steels are susceptible to grain growth in the HAZ, which, in turn,
can cause a coarse-grained weld metal. As this will decrease the ductility and
elongation, the heat input should be kept below 0.8 kJ/mm, which limits the maximum
material thickness. For high-alloyed ferritic grades and when welding with fully
ferritic fillers, fast cooling rates from high temperatures can result in martensite
formation in the weld metal and HAZ. Here, an optimized heat input is important to
avoid embrittlement after welding. Martensite formation can also be limited by
preheating the material to 50-250°C and the ductility of weldments restored by
annealing. Over-alloyed austenitic fillers produce a tougher weld metal and are
preferred if this is allowed by the application and service environment. High carbon
contents may cause precipitation of chromium carbides along the grain boundaries in
the HAZ with increased risk of IGC. With low levels of carbon and nitrogen and/or
addition of titanium and/or niobium stabilizers, most modern ferritic stainless steels
are ferritic at all temperatures and have improved weldability. These single phase,
non-hardenable grades normally do not need any preheating or heat treatment after
welding. Stabilized ferritic steels are also less prone to grain growth during welding.
Due to lower thermal expansion and higher thermal conductivity, distortion and
buckling may be lower during welding compared to austenitic stainless steels. Since
ferritic stainless steels are susceptible to hydrogen embrittlement, moist electrodes
and shielding gases that contain hydrogen should be avoided. If the gas protection is
insufficient during welding or if nitrogen is added to the shielding gas, formation of
chromium nitrides caused by an uptake of nitrogen from the atmosphere may occur.
Such precipitates can cause embrittlement and decrease the corrosion resistance. For
the same reason, contamination that may cause carbon pick-up, should be avoided.
4
1.3 Ferritic-austenitic (duplex) stainless steel
The ferritic-austenitic grades have a ferrite matrix intermixed with austenite and are
more commonly called ‘duplex‘ stainless steels from the Latin ’two-fold’. The duplex
microstructure combines properties of both phases that may even be enhanced in the
combination; the ferrite provides high strength and resistance to SCC, while the
austenite contributes good ductility and general corrosion resistance [9,10]. Excellent
resistance to localized corrosion in neutral and acidic chloride-containing solutions
can be obtained owing to increased chromium, molybdenum and nitrogen contents
[11-13]. The high mechanical strength also contributes high resistance to fatigue and
abrasive conditions. Duplex alloys can be cost-effective alternatives to austenitic
grades with equivalent corrosion resistance; especially in applications where the
doubled yield strength can be utilized in the design to decrease the wall thickness.
Duplex stainless steels are successfully used in pressure vessel and storage tank
applications where weight reduction by reduced wall thickness, decreases the cost for
material, welding and transportation.
There are numerous commercial duplex stainless steels available in the large family
ranging from the lower alloyed lean duplex grades, to the highly alloyed superduplex
grades. These normally contain 20-29% chromium, 1-8% nickel, 0-4.5% molybdenum,
0.1-0.3% nitrogen and 0.02-0.03% carbon. There are also some hyperduplex grades with
even higher alloying content. It is popular to differentiate the different grades in terms
of the main alloying components affecting the corrosion properties, and the pitting
resistance equivalent; PRE = %Cr + 3.3 × %Mo + 16 × %N is generally accepted as a
rough estimation of the localized corrosion resistance of duplex grades [14]. The
resistance to pitting corrosion in neutral chloride-containing solutions increases with
higher PRE numbers, but this should only be considered as an indication. Localized
laboratory corrosion tests may give another ranking of the grades than the PRE. Also
other elements such as manganese, tungsten, copper, sulphur and carbon may affect
the pitting performance [15]. One disadvantage of duplex grades may be their
moderate toughness at low temperatures, but the ductility is normally sufficient for
service temperatures down to –40°C. In addition, proneness to embrittlement after
thermal aging, limits the maximum service temperature of welded components to
250°C. Duplex steels are suitable for most forming operations used in stainless steel
fabrication. However, due to the higher mechanical strength and lower toughness,
operations such as deep drawing, stretch forming and spinning are more demanding to
perform than with austenitic alloys. The high strength of the duplex grades may also
cause a relatively high spring back.
Generally all fusion welding methods can be used for welding duplex stainless steels
on condition that suitable welding procedures and consumables are used. Weld metal
properties such as strength, toughness and corrosion resistance may be impaired by an
excessively large deviation of the phase balance compared to the parent metal [16,17].
Too high austenite fractions, which give a mixed ferrite-austenite solidification mode,
can result in increased segregation while too high ferrite fractions can cause
chromium nitride precipitation. Both of these phenomena can have a negative effect
on the pitting corrosion resistance. The chemical composition of the weld metal is
crucial and the solution normally is to add an over-alloyed filler wire specially
developed for the particular grade [18,19]. Nitrogen is also an important alloying
element in duplex grades, which increases the corrosion resistance and strength.
Nitrogen additions to the shielding and backing gas during autogenous gas tungsten
5
arc (GTA) welding have been reported to be beneficial for the pitting corrosion
resistance by preventing nitrogen loss [20-22]. The driving force for such escape of
nitrogen increases when welding nitrogen-alloyed grades, leading to a larger risk of
losing the desired properties. This degassing process of nitrogen can cause a more
ferritic weld metal surface with chromium nitride precipitates in the ferrite grains
exposed to the corrosive medium, hence impairing the resistance to pitting corrosion
and the toughness [16,23,24]. The weld microstructure is not only dependent on the
chemical composition, but also on the welding parameters, which affect the thermal
weld cycle [25]. The heat input should be sufficient to enable reasonable austenite
formation in the weld and HAZ. A minimum of 0.2-0.5 kJ/mm is usually required when
arc welding, depending on grade and material thickness. The heat input needs also to
be limited to maximum 1.0-3.5 kJ/mm and the maximum interpass temperature to 100-
150°C when multi-pass welding to avoid precipitation of detrimental phases in
previous passes. Post-weld heat treatment (PWHT) of welded duplex stainless steel is
normally not needed. By optimizing the welding procedure it is possible to ensure that
the necessary corrosion resistance and strength are achieved without heat treatment.
Typical duplex base metal and weld microstructures are shown in Figure 1.
Figure 1. (a) Base metal microstructure and (b) simulated high temperature heat affected
zone (HTHAZ) microstructure after reaching a peak temperature of 1360°C followed direct
by cooling at 20°C/s [A].
6
this type of duplex steel is generally good when using slightly over-alloyed filler metal
[27]. Fillers that may be suitable are ISO 23 7 N L or 2209 (ISO 22 9 3 N L). The more
recently-developed lean duplex grade LDX 2101® (EN 1.4162, UNS S32101) initiated the
boom in the lean duplex market and has become one of the largest duplex volumes sold
worldwide. LDX 2101 has 21% chromium and fairly low nickel content of 1.5% and the
composition is balanced with 5% manganese and 0.22% nitrogen to give rapid austenite
formation in both the weld metal and in the HAZ [28,29]. LDX 2101 has successfully
replaced the low-alloyed austenitic grades AISI 304L, AISI 316L and construction steel
in applications such as pressure vessels, bridges and storage tanks. The grade has
twice the yield strength of AISI 304L and the corrosion resistance in chloride-
containing environments is better. The pitting resistance of GTA and laser welded LDX
2101 is often in parity with that of AISI 316L [30,C,D]. If the high yield strength can be
utilized, large savings are possible on material, transport and filler metal costs, with at
least the same corrosion performance. LDX 2101 is also used within the transport and
automotive industry in such different applications as fuel tanks and tram bodies,
where crash tests have proven that the material has good energy absorption [31,32].
LDX 2101 and 2304, are due to high chromium content in combination with low
molybdenum content, good alternatives in pulp & paper applications such as in kraft
digesters and storage of alkaline pulping liquors [33]. Also in strongly oxidizing acids,
steels without molybdenum-alloying are often more resistant than the molybdenum-
alloyed steels. LDX 2101 and 2304 are also the dominating materials in domestic water
heaters.
7
1.3.4 Filler metal for welding duplex stainless steel
The equilibrium phase balance and corrosion resistance of the annealed base metal
cannot be attained when welding autogenously due to higher ferrite fractions, possible
element loss and segregation of important alloying elements. Use of over-alloyed
consumables is for this reason generally recommended for welding of all duplex
grades, in order to achieve corrosion resistance and impact toughness close to that of
the base metal. Consumables should have somewhat higher chromium and
molybdenum contents and may be alloyed with nitrogen for desirable optimum weld
metal corrosion resistance [16,34]. Use of consumables having minimum +10 higher
PRE has been suggested. A minimum filler metal nitrogen content of 0.14% for duplex
grades and 0.22% for superduplex steels has been recommended [35]. Nitrogen alloying
counteracts possible loss from the molten pool and inhibits nitrogen migration from
the high temperature heat affected zone (HTHAZ) [36]. Fillers generally contain 2-6%
more nickel than the base metal to control the phase balance, to maintain high corrosion
resistance and to improve mechanical properties. Nickel additions shift the austenite
formation to higher temperatures, resulting in higher weld metal austenite contents
[37]. Over-alloying can, however, be problematic with 25Cr grades because of the risk
of increased formation of σ phase or other intermetallic phases during the weld
thermal cycle [38]. Excessive amounts of nickel can also shift the solidification mode
from fully ferritic to a mixed ferritic-austenitic solidification, which increases
segregation of elements and may cause ductility loss [39]. Too high nickel contents in
the weld metal also dilute the nitrogen in a larger amount of austenite, and decrease
the resistance to pitting and crevice corrosion [40]. If austenitic fillers are used, the weld
metal may be fully austenitic and thereby show reduced strength and be more susceptible
to solidification cracking. However, in many cases, dilution by the parent steel gives
sufficient ferrite to ensure adequate properties.
Fillers such as ISO 23 7 N L and ISO 22 9 3 N L can be used for welding the lean duplex
alloys LDX 2101 and 2304. Duplex 2205 is, however, alloyed with molybdenum, so ISO
22 9 3 N L filler should be used to compensate molybdenum segregation in the weld
metal. When using the right filler metal, the duplex stainless steels can be welded to
construction steel and to other stainless grades. Table 3 shows fillers that may be
suitable when combining duplex grades with other stainless grades.
8
2 Alloying elements
The desired corrosion and mechanical properties of stainless steels are obtained by
optimizing the balance of the important alloying elements. From now on, the focus
will be on duplex grades.
Chromium
Chromium is the most important alloying element for stainless steel and a content of
at least 12% is needed to create and maintain the passive film giving the material its
corrosion resistance. Duplex grades normally contain relatively high levels of
chromium, typically 20-29% to stabilize the ferrite phase. Coordinated additions of
austenite-stabilizers, such as nickel or nitrogen, are required to maintain the phase
balance. Chromium is beneficial for the resistance to both uniform and localized
corrosion and decreases the pit propagation rate [42,43]. Chromium increases the
pitting potential, the critical pitting temperature (CPT) and the critical crevice
temperature (CCT), and improves the passive film stability in acidic environments.
There is a maximum limit to the chromium content of approximately 30-32%, where
intermetallic phase precipitation can markedly reduce the ductility, toughness and
corrosion resistance of these alloys.
Nickel
Nickel is a strong austenite stabilizer and a principal addition to austenitic stainless
steels. Nickel alloying may decrease the resistance to crevice corrosion resistance in
sodium chloride, and has been reported to be both beneficial and detrimental in pitting
corrosion tests [40,44]. In the duplex stainless steels, however, the main role of nickel
is to maintain the ferrite-austenite balance, rather than modifying the corrosion
resistance [43]. Optimum nickel contents balance the chromium and molybdenum
contents to give equal proportions of ferrite and austenite after solution annealing.
This appears to be most advantageous for the corrosion resistance, but also for the
mechanical properties [42]. Low nickel levels can result in formation of a high
proportion of ferrite and thereby decreased toughness. Nickel has also a positive
effect on the impact toughness at low temperatures.
Molybdenum
Molybdenum is a ferrite-stabilizing alloying element with a strong beneficial
influence on uniform and pitting corrosion resistance (included in the PRE) and on the
passivation properties [45]. A molybdenum content in excess of 3 or 3.2% has been
reported to be required to have high resistance to localized corrosion in acidic
environments and to crevice corrosion in warm seawater [42,46,47]. Molybdenum is
favourable in most environments, but in strongly oxidizing environments, such as
warm concentrated nitric acid and in hot alkaline solutions, grades containing
molybdenum are less resistant than alloys without molybdenum [33]. The addition of
molybdenum in duplex stainless steels should not exceed approximately 4% since it
makes the material more susceptible to intermetallic phase precipitation by widening
the σ phase field [48,49]. Molybdenum has also been suggested to promote
precipitation of α’, which is responsible for the 475°C embrittlement of ferritic
stainless steels and the ferrite phase of duplex grades.
9
Nitrogen
Nitrogen is an interstitial element that stabilizes the austenite and has strong influence
on several properties. Nitrogen significantly increases the strength of the duplex
grades, but may also improve the ductility and toughness of the alloy [49]. Nitrogen
has a strong beneficial influence on the passivity of stainless steels and is favourable
for increasing the resistance of the base metal to pitting corrosion (included in the
PRE), pit propagation, crevice corrosion, IGC and SCC [14,16,43,46,50-52]. Tsuge et al.
[14] estimated that the nitrogen content required for achieving the same pitting
resistance in both ferrite and austenite in 22Cr steels is approximately 0.18%. In base
metals with lower nitrogen content, the austenite would be less resistant to pitting.
The beneficial effects of nitrogen have been reported to be further enhanced in the
presence of molybdenum [42,51,53]. Nitrogen promotes the start of austenite formation
at higher temperatures during the weld cooling cycle and the duplex grades contain up
to 0.4% nitrogen to give improved austenite formation when welding [23]. Nitrogen has
been reported to reduce the elemental partitioning of chromium and molybdenum
between the ferrite and austenite and at the same time, hinder intermetallic phase
formation [48]. The effect of nitrogen on the driving force for σ phase formation may,
however, be smaller for duplex grades compared to that of the austenitic grades,
because nitrogen does not change the chromium activity as result of a simultaneous
change in phase fraction [54,55].
Manganese
Manganese stabilizes austenite and can partly replace nickel. Additions to stainless
steel have been used to increase the solubility of nitrogen, which have a strong bene-
ficial influence on the pitting resistance. It has been reported that manganese itself
may have a negative effect on the pitting resistance, but combined additions of nitro-
gen and manganese override this effect [48]. Replacing nickel with manganese and
nitrogen also makes the price of the material more stable since the nickel price has
fluctuated significantly in recent years. Examples include the low nickel lean duplex
stainless steel LDX 2101® [56] and the superaustenitic stainless steel 654 SMO® [57].
Other elements
Tungsten has become more commonly used as an alloying element in commercial
stainless steels where it is used as a supplement to molybdenum for improved
corrosion resistance [48,54]. When used in the PRE expression, the factor for tungsten
is approximately half of that for molybdenum because of higher atomic weight.
Tungsten has, however, also been reported to promote formation of intermetallic
phases and cause a more rapid embrittlement than molybdenum [15,58]. Copper is
added to highly corrosion resistant austenitics such as AISI 904L and 254 SMO®, and
duplex grades such as Ferralium 255 (EN 1.4507, UNS S32550 and Zeron 100 (EN 1.4501,
UNS S32760) to further improve the corrosion resistance in, for instance, reducing acids
such as dilute sulphuric acid [45,54]. In most modern duplex alloys, carbon is limited
to levels of 0.03 wt.% to minimize the risk of formation of chromium carbides and
thereby decrease the susceptibility of the duplex stainless steels to intergranular
corrosion [49].
10
3 Corrosion resistance
Stainless steels are corrosion resistant due to formation of an invisible, 2-4 nm thick,
passive film that is established in oxidizing environments when the steel contains at
least 12% chromium. This film has the ability to be rebuilt by oxidation of the
underlying metal when it has been damaged. There are, however, environments in
which permanent breakdown of the passive layer occur either uniformly or locally,
causing corrosion of the unprotected surface. Different media can cause different
types of corrosion attack, which may vary in nature and appearance. Uniform
corrosion or general corrosion occurs with an even corrosion rate over the whole
surface that is exposed to the corrosive medium (often for the steel an aggressive acid
e.g. hydrochloric acid or hydrofluoric acid). The corrosion rate is generally expressed
as the material loss in mm/year and can thus be used as an estimation of the lifetime.
Selective corrosion can also occur in two phase materials such as duplex stainless
steels. Different chemical compositions of the phases may lead to preferential attack
at the weaker phase. Pitting corrosion most often occurs where chloride ions cause a
local breakdown of the passive layer. The presence of halides, such as chlorides, in
neutral or acidic solutions increases the corrosivity of both organic and inorganic
acids. The solution becomes more aggressive at high chloride concentrations, low pH
and high temperatures, but also small amounts of chlorides, 250 ppm, may affect the
pitting corrosion resistance of stainless steels. One example is drinking water that can
cause corrosion of stainless steel in domestic water heaters [30]. The pits often appear
to be rather small at the surface, but may have larger cross-section areas deeper inside
the metal, Figure 2. Pitting corrosion is often more deleterious than uniform corrosion
due to the rapid propagation rate and it is not possible to circumvent the problem by
dimensioning with thicker gauges as for uniform corrosion. As the attack is small at
the surface and may be covered by corrosion products, pitting attack often remains
undiscovered until it causes perforation and leakage. Crevice corrosion occurs under
the same conditions as pitting, i.e. in neutral and acid chloride solutions. In the
stagnant solution inside a crevice, the supply of new oxidant is restricted and crevices,
such as those found at flanges or lap joints, are thus often the most critical sites for
corrosion. High chloride concentrations and low pH increase the probability of pitting
and crevice corrosion, as do high temperatures and stagnant solutions. Chloride-
induced stress corrosion cracking (SCC) is a brittle failure mode caused by the
combined effect of tensile stress, including residual stresses in welds, and a corrosive
environment. Most cases of SCC occur at temperatures above 50°C but failures at
ambient temperature have occurred on standard grade austenitic steels, such as AISI
304L and AISI 316L in swimming pool atmospheres [33]. Steels with a ferritic or duplex
structure and high performance austenitic alloys generally display a very high
resistance to SCC. lntergranular corrosion (IGC) occurs preferentially in chromium-
depleted grain boundaries as a consequence of precipitation of chromium carbides of
M23C6 type in the HTHAZ subject to 550-850°C. In the modern duplex and high alloy
austenitic stainless steels, sensitization caused by chromium carbide precipitation is
rarely a problem, because of the low carbon content of these grades [27]. When
chromium carbides appear, these are less harmful in duplex grades, since the ferrite
allows a rapid healing of depleted zones compared to austenitics [10]. Titanium and
niobium form carbides more easily than chromium and stabilized steels show good
resistance to IGC even though their carbon contents may be fairly high. Low carbon
grades and stabilized grades can be considered as equally resistant to IGC, unless
exposed for long periods at temperatures above 500°C, in which case stabilized grades
are to be preferred [33].
11
Figure 2. Principal cross-section of a corrosion pit [after 59].
When choosing a stainless steel for a certain application, it is important to consider all
factors that could affect the corrosion performance such as the corrosion environment,
concentrations, pH, impurity content and the service temperature. Other factors that
could have an effect on the performance of the product are weld defects, the presence
of oxide from welding or heat treatment, contamination of the steel surface by
particles of non-alloyed or low-alloyed steel, microbial activity, the presence of
crevices and chlorination of water. More information about the corrosion performance
of different stainless steels and the ability to withstand certain environment,
concentrations, pH, etc. can be found in the Outokumpu Corrosion Handbook [33].
4 Welding methods
There are many methods available for joining stainless steel, but fusion welding,
where the material is joined by melting and filler metal added when needed, predom-
inanates. The choice of welding method depends on what is available and practically
suitable for the specific application. The steel grade, required properties, material
thickness, welding position and surrounding environment are normally taken into
account when choosing the welding method. Here follows a brief description of the
welding methods used or that are referred to in this thesis work. More details of the
experimental work can be found in the appended papers. When fusion welding, the
melt pool is protected and the arc stability given by use of shielding gas or by
formation of a slag. When gas tungsten arc (GTA) or tungsten inert gas (TIG) welding,
the arc is formed between a non-consumed tungsten electrode and the workpiece in a
shielding gas atmosphere. The arc melts the base material and filler metal is added
from the side if needed. GTA welding can result in beautiful, smooth welds with high
surface and weld quality, with the highest impact toughness and best fatigue proper-
ties. The productivity, however, is low and the method consequently is used where
high demands are set. GTA welding is successfully used in many tube mills, within the
nuclear and process industries, otherwise primarily for thin materials and for produ-
cing high quality root beads in joints that are subsequently filled with a more produc-
tive method. In order to maintain satisfactory corrosion resistance, there are high
demands on the root protection when welding from one side. In plasma arc welding
(PAW), the arc is further constricted by a double-gas nozzle having a separate plasma
gas. PAW gives narrow penetration, relatively high welding speeds and is normally
used as an automatic process. When gas metal arc (GMA) or metal inert/active gas
(MIG/MAG) welding, the arc is formed between the workpiece and a continuously fed
solid wire electrode that melts in a shielding gas atmosphere. This is probably the
12
most common welding method due to its high productivity. The welding speed is con-
siderably higher than for GTA welding and the impact toughness is typically equally
high. The method is suitable for material thicker than 2 mm and primarily used in
fillet joints and when butt welding from both sides. Main disadvantages are that the
method causes some spatter formation and embedded surface slags, that can only be
removed by grinding. There is also an increased risk of forming defects such as lack
of fusion. The modern synergic pulse power sources have considerably improved the
conditions for GMA welding. GMA welding can also be performed as flux core arc
(FCA) welding with an electrode filled with a flux that forms slag and supplies alloy-
ing elements. Compared to welding with solid wire, higher welding speed and deeper
penetration can be obtained with smoother welds and improved resistance to fatigue.
There is lower risk of spatter formation and embedded slag, which makes post-weld
cleaning easier. Drawbacks are that the slag needs to be removed after welding and
shielding gas is still required. Shielded metal arc (SMA) or manual metal arc (MMA)
welding is performed manually with a covered electrode. The coating gives arc
stability and forms a slag that protects the filler and the melt during welding and
cooling. By choosing different covers, the weld properties and weldability can be
improved. The method is flexible, rather cheap and often used outdoors and for repair
welding. SMA is commonly used for the root weld when multipass welding, but the
method has fairly low productivity and cannot be automatized. Other drawbacks are
slag removal and that the covered electrodes easily absorb moist and thus need to be
stored in a controlled atmosphere. Submerged arc welding (SAW) gives very high
productivity and is primarily used when welding thick material. To protect the melt
and the arc from reacting with the surrounding atmosphere, the melt is covered with a
flux. The drawbacks are the handling of the flux and slag, and that the flux often
restricts the welding position to horizontal. The method also increases the risk of hot
crack formation in some stainless steels. In addition, all slag forming welding
methods give more oxides and slag particles in the weld metal, which decrease the
impact toughness compared to the gas shielded methods. Laser welding with a
coherent (single phase) light of a single wavelength (monochromatic) gives better
penetration than conventional welding methods and can significantly increase the
welding speed. A laser beam is highly focused with sufficiently high energy density
that the material melts and partly evaporates. Welding in such a keyhole, results in a
deep and narrow weld, but the small beam demands particularly careful edge prepara-
tion and high accuracy. Traditionally, the CO2 laser, where the laser beam is generated
in a gas mixture and transported via mirrors, is most common in the industry, follow-
ed by the Nd:YAG laser, where the laser beam is transported with fiber optics. The CO2
laser is available with higher power and gives high quality welds, while the Nd:YAG
laser has higher flexibility and is more suitable for robotic welding. In recent years,
the use of high-brightness solid-state fiber and disk lasers has increased rapidly. These
are available with higher powers than the CO2 and are more flexible than the Nd:YAG.
The ability to weld at higher speed with less heat input compared to the classic fusion
welding methods gives less distortion. General drawbacks with laser welding are that
the equipment generally involves a large investment and that some materials can form
undesired microstructure due to the rapid cooling. Laser welding is most common
within the automotive industry and in tubular mills. When laser hybrid welding, the
beam is combined with an arc welding method such as GMA or GTA. The benefits are
usually high welding speed, gap bridgeability and low distortion [60]. For duplex
grades, the most important improvement is the higher heat input compared to laser
welding, resulting in decreased cooling rates and hence improved austenite formation.
13
5 Characterisation techniques
This section gives an introduction to how the microstructure and material properties
have been studied. The characterisation techniques used in this thesis work are listed
in Table 4.
Table 4. Characterisation techniques and the papers where they have been used.
Operation Microstructure Corrosion Mechanical properties Chemical composition
Ferrite content A-E
Pickling C,D
ASTM G150 C,D
Wet paper test B,C
Ferroxyl test B,C
Weld simulation A
SEM/EDS A,C,E A-C
LOM A-E
TEM/EDS A,C A,C
XPS B,C
EPMA E E B,C,E
LECO C,E
Tensile test D
Impact energy A
14
5.1.2 Microscopy
The phase balance can affect both the corrosion performance and the ductility.
Cross-sections of the welds were prepared by grinding and polishing with SiO2 in the
last step. A modified Beraha etchant (60 ml H2O + 30 ml HCl + 1 g K2S2O5) was applied
to elucidate the weld shape and ferrite and austenite fractions. The ferrite content was
assessed in a light optical microscope (LOM) using image analysis (Optimas 6.1
software). With scanning electron microscopy (SEM) it is possible to generate images
of the surface. Different contrast modes can be used to distinguish between
topography and variations in composition. Specimens polished to mirror finish before
corrosion testing were studied in a LEO 440 SEM. In this case the examination was
carried out in back scatter mode to reveal the phases for determination of preferential
pitting location and to potentially find the fusion line. Crystallographic information
and phase identification were obtained from electrolytically polished samples
analyzed in a HKL Channel 5 electron back-scattered diffraction (EBSD) system using a
field emission gun scanning electron microscope, FEG-SEM Zeiss UltraTM 55. With
transmission electron microscopy (TEM) it is possible to study small particles and
identify these by their diffraction pattern. Carbon replicas were prepared on polished
cross-sections by etching in hydrochloric acid, coating with carbon then detaching the
carbon film with adherent particles in 8% bromine meth-anol. The examination of the
replicas was performed with a Philips CM 200 FEG-TEM.
15
The XPS spectrum is generated by plotting the number of photoelectrons (intensity) as
a function of binding energy in a small fixed energy interval [61]. The binding energy
of the peaks is characteristic of each element and the spectral peaks from a mixture
are approximately the sum of the individual constituents [59,62,63]. The quantification
of each state is taken as the area under the peak fit over the peak area sensitivity factor
[61]. Using tabulated binding energies data, the oxidation states present on the surface
can be determined. A reasonable estimate of background intensities is obtained by the
iterated Shirley method used in this work. A PHI Quantum 2000 Scanning ESCA
Microprobe was used for characterising weld oxide thickness and composition. The
effective lateral resolution in the small spot mode was set to about 100 µm to obtain an
average over several austenite and ferrite regions. Both line scan spectra and sputter
depth profiling were performed. The ability to distinguish between the different
chemical states will be diminished when sputtering due to changes in the chemical
states, but useful information on elemental distribution can still be obtained.
16
5.2.3 Corrosion testing
The most reliable test method to verify if a material is corrosion resistant or not is
naturally to test it in the specified environment in real conditions. This is rather time-
consuming and thus the material or welds often need to be tested in laboratory
conditions in more concentrated electrolytes and at elevated temperatures for faster
evaluation. Many corrosion types can occur, but only pitting corrosion has been taken
into consideration. In this thesis, the tests were carried out in 1 M NaCl in the flush-
port Avesta cell according to the ASTM G150 standard [64], Figure 3.
Figure 3. Schematic illustration of the Avesta cell and the location of the specimen.
In Papers B and C, a wet paper corrosion test is used, in which the weld cap is polished
manually until the visual heat tint has been removed. Then the welds are thoroughly
cleaned with washing-up detergent and ethanol. Thereafter, clean paper is moistened
using a tap water spray. The sheets are piled between wet paper and kept for
approximately 10 h; followed by visual examination for stains on weld surfaces and
papers.
17
6 Aim of this work
The objective of this thesis work was to contribute information on how to weld the
recently-developed lean duplex alloy LDX 2101. This grade is often used to substitute
austenitics in the AISI 300 series, which normally have better weldability than the
duplex grades. Austenitics can often be welded autogenously, while the duplex alloys
typically require over-alloyed consumables. The aim was to verify that LDX 2101 may
be an exception since it has lower alloying content than the traditional duplex grades,
combined with high austenite formation rate. This was addressed by pitting corrosion
testing GTA welds performed with and without filler metal, nitrogen additions to the
shielding gas and use of nitrogen-based backing gas. The main focus was the
interrelation between microstructure (ferrite-austenite phase balance, weld oxide
formation, element distribution and chromium nitride precipitates) and corrosion
properties. Laser welding and laser hybrid welding with different laser sources were
carried out to compare the laser weldability of LDX 2101 with standard duplex grades.
The base metal lean duplex grade LDX 2101 has a pitting corrosion resistance on a par
with that of austenitic AISI 316L. Austenitics in the AISI 300 series show a significant
decrease in corrosion resistance when weld oxides are present on the surface. Due to
the lean alloying, LDX 2101 is liable to behave in a similar way. The ambition was to
corrosion test welded LDX 2101 and compare with other grades in the as-welded
condition and after pickling, to show the benefits with post-weld cleaning. The loss in
corrosion resistance of welded material compared to that of the base metal would
thereby be possible to quantify. Variations in the weld oxide thickness and composi-
tion may affect the corrosion resistance and required pickling time. More weld oxides
are formed when adding nitrogen to the shielding gas when GTA welding. For this
reason, weld oxides present on LDX 2101 were examined in detail. The goal was to
explain how weld oxides form and how these differ in composition from those formed
on other grades. In the following chapters results from the papers are discussed and
placed into perspective by comparison to other published works. Some data is also
taken from papers by the current author, which are not included in the thesis.
When the solidification occurs with ferrite as the primary phase, the partitioning of
the metallic elements between the ferrite and austenite phases is not as prominent in
the weld metal, while nitrogen is partitioned and enriched in the austenite to a greater
extent than in the base metal [16,70]. However, it was first when Ogawa and Koseki
[23,71] illustrated the partitioning by mapping the weld metal that it was clearly
established that segregation of metallic elements could follow the dendritic
solidification structure. The element distribution in the dendrites is primarily affected
18
by the chemical composition of the material and to some extent by the cooling rate
[21,23]. The PRE implies that the pitting resistance is primarily governed by the amount
and distribution of the elements chromium, molybdenum and nitrogen. Segregation of
these important alloying elements in stainless steel welds may consequently locally
lower the corrosion performance.
LDX 2101 has improved austenite formation compared to most duplex grades. When
this modern nitrogen-alloyed grade is autogenously welded, there is limited grain
growth and ferritization of the HTHAZ. The austenite formation can be sufficient to
conceal the fusion line so it is more difficult to locate compared to other grades,
Figure 6. The fusion line and HTHAZ are clear in the 2304 weld in the left hand, but
cannot be seen in LDX 2101.
Local segregation and depletion along the fusion line of LDX 2101 welds were revealed
in Paper E by EPMA mapping, Figure 7. This is an observation that has not been
reported previously. The fusion line was depleted in silicon, molybdenum, nickel and
manganese while the same elements were enriched in the weld metal adjacent to the
fusion zone. The chromium content was rather uniform in the fusion zone and showed
no signs of depletion. This is suggested to be the effect of the epitaxial ferritic
solidification. The first solidified material contains primarily iron and chromium and
pushes all other analysed metallic elements in front of the solidification line. With
increasing constitutional undercooling, the planar growth continues as cellular growth
[76] and when the growth rate becomes critically high, the planar solid-liquid interface
becomes unstable. Enrichment of the same elements in the weld metal adjacent to the
depleted zone persists and from here the solidification continues as columnar
dendritic growth.
19
Figure 4. Distribution of alloying elements in the base metal of LDX 2101 [E].
20
Figure 5. Distribution of elements in weld metal of LDX 2101 welded with pure argon [E].
21
(a) (b)
Figure 6. Examples of weld microstructures over the fusion line. (a) 2304 (GTA welded bead-
®
on-plate with ISO 23 7 N L filler metal and pure argon as shielding gas and (c) LDX 2101
GTA welded autogenously bead-on-plate with pure argon as shielding gas. [E]
An experiment was carried out in Paper E to investigate if it was possible to locate the
actual fusion line within the depleted zone. An AISI 316L sheet of 0.12 mm was
clamped between two LDX 2101 plates and a weld was made bead-on-plate on the
22
surface starting on LDX 2101 material, passing over the AISI 316L sheet onto the next
LDX 2101 plate. The weld surface was ground and EPMA mapping of nickel and
manganese was performed from above. This was to determine where in the depleted
zone the AISI 316L material, with higher nickel and lower manganese than the LDX
2101 material, would melt. When melted close to the HTHAZ, this could indicate that
planar growth occurs. When present in the whole depleted zone, this would be a sign
of element diffusion from the HTHAZ into the melt at high temperature. The results
shown in Figure 8 indicate that the fusion line could be located anywhere between the
border of the depleted zone in the HTHAZ and the centre of the depleted zone.
Figure 8. Distribution of elements along the fusion line of LDX 2101 with an AISI 316L sheet
clamped between two LDX 2101 plates. The two images to the right are more detailed
analyses in the intersection where the AISI 316L sheet has been melted by the weld. [E]
The diffuse chromium pattern with no distinct variations over the HAZ and fusion line
could probably be explained by a horizontal tie-line in the ferrite-austenite two-phase
area, promoting austenite formation by rapid nitrogen diffusion [77,78]. There is only a
small difference in partitioning of chromium between ferrite and austenite in LDX 2101
due to the rather low nickel content. However, if the nickel fraction were to increase,
the phase distribution would change and the chromium would probably be more
concentrated to the ferrite phase, Figure 9. It means that mapping of chromium for
LDX 2101 shows a relatively uniform chromium distribution, while other duplex
23
grades with higher nickel content may show higher concentration of chromium in the
ferrite and nickel in the austenite.
The microstructure of the LDX 2101 weld metal is independent of the segregation
pattern, since nitrogen controls nucleation and growth of austenite by rapid diffusion.
When this nitrogen-alloyed duplex stainless steel is welded autogenously, the auste-
nite formation can be sufficiently good to conceal the fusion line and neither the den-
drites nor the depleted fusion zone, detected with EPMA, were visible in the polished
and etched condition [E]. This confirms that nitrogen plays the most important role for
the austenite formation in nitrogen-alloyed duplex stainless steel weld metals.
24
During cooling, initially allotriomorphic austenite is rapidly precipitated along the
ferrite grain boundaries in continuous networks and on further cooling, austenite
precipitates as Widmanstätten side-plates growing into the grains [88]. With sufficient
time, austenite particles with acicular morphology may appear inside the ferrite grains
[86,88]. The rate of transformation is governed by a large number of factors, which are
both process and material dependent. These include the composition of the alloy and
filler metal, and the dilution from the base metal [16,25]. The welding parameters, in
turn, influence the maximum temperature, time above the transformation temperature
range and the cooling rate, which further affect the ferrite grain size, number of
nucleation sites, nucleation rate, austenite growth and composition of the precipitated
phases [49,89]. Thicker material gauges result in higher cooling rates. The level of
inclusions may also influence austenite formation since inclusions are potential
nucleation sites for intragranular austenite in the same way as the inclusions, which
promote acicular ferrite in low-alloy steel weld metals [90]. Additional austenite
formation can take place by subsequent reheating at elevated temperatures either
when multipass welding or during PWHT [49]. Figure 10 illustrates the solidification
and subsequent austenite formation of duplex grades of LDX 2101 type.
Figure 10. Principle of dendritic solidification and austenite formation in LDX 2101 welds [E].
25
approximately 1000°C depending on the duplex grade. There are, naturally, transitions
between these zones and the complexity can increase when multipass welding is used.
Microstructural changes such as ferrite grain growth and chromium nitride
precipitation in the HTHAZ have a larger influence on the mechanical and corrosion
properties compared to effects in the LTHAZ. Consequently, most research is reported
for HTHAZ, but σ phase and chromium nitride precipitates have also been found in
three-pass simulated LTHAZ of UNS S32550, UNS S32750 and UNS S32760 [92]. This was
not seen in the lower alloyed grades UNS S31803 and UNS S32304, but the pitting
corrosion resistance decreased for all heat inputs and materials studied compared to
the base metal.
The HTHAZ width can normally easily be measured for grades such as 2304 and 2205,
but the width varies with the welding conditions and the chemical composition of the
plate [93]. The improved austenite reformation in the HTHAZ of the LDX 2101 and 2507
grades with higher nitrogen content can obscure the fusion line and make it difficult to
determine its location as previously shown in Figures 6 and 10 [E]. The width of the
HTHAZ is typically in the order of 1-2 grain diameters and it is a function of both
composition (and associated thermal width of the ferrite phase field) and the time
available for dissolution of the austenite [37]. The large microstructural gradients in
the HAZ, leading to very narrow regions with similar microstructure, make evaluation
of properties of an individual microstructure fairly complicated in the HAZ of real
weldments. This is particularly true when studying the effect on mechanical
properties. Thermo-mechanical simulation of separate test pieces is consequently
often required to create a sufficiently large area of uniform microstructure (fully
ferritized material) for subsequent metallographic examination and impact toughness.
Figure 11 shows typical examples of such Gleeble™ simulated HTHAZ specimens of
LDX 2101 cooled at various cooling rates.
Figure 11. Gleeble™ simulated HTHAZ microstructure held at 1360°C for 5 s followed by (a)
water quenching, (b) intermediate cooling in compressed argon and (c) cooling in air [94].
Duplex grades solidify in a ferritic mode and consequently, the HTHAZ close to the
fusion line will have a fully ferritic structure at temperatures above approximately
1350 ± 50°C depending on the alloy composition [81]. Nitrogen has a strong effect on
the ferritization of duplex steel, since the dissolution of austenite in the HTHAZ
primarily occurs via diffusion of nitrogen [75,95]. Nitrogen increases the ferrite-to-
austenite transformation temperature and thus delays ferritization and grain growth of
ferrite. This is because some residual austenite is retained at high temperatures and
prevents grain growth by grain boundary pinning [25]. With longer holding times
above the ferritization temperature, all the original duplex microstructure is dissolved,
and grain growth occurs as shown in Paper A. The ferrite fraction in the HAZ increases
at higher peak temperatures and with increasing cooling rates [71,96]. Grain growth
during ferritization can lead to high ferrite contents since nucleation of austenite
26
occurs primarily at grain boundaries and a coarse ferrite grain size may lead to less
austenite reformation on cooling [89,97]. This appears to be of less importance in
duplex grades with high nitrogen contents such as LDX 2101, where the effect of the
grain size on austenite reformation seems to be negligible as shown in Figure 12 from
Paper A. A higher nitrogen content results in more efficient austenite reformation and
makes the alloy less sensitive to rapid cooling rates [98]. The grain size, varied by alte-
ring the holding time at the ferritization temperature, had limited effect on the impact
toughness of HTHAZ simulated specimens of various duplex grades, while slower
cooling, giving improved austenite reformation, were beneficial [69]. This was also
seen in Paper A for LDX 2101, Figure 13. Higher cooling rates result in less austenite
reformation and decreased impact toughness, probably related to the larger mean free
crack path in ferrite and to presence of chromium nitrides. Similar results have pre-
viously also been reported by Komenda and Sandström [86] for 2205. A strong relation
between the width of the austenite located at ferrite grain boundaries and the impact
energy was found. As the width of austenite increased, so did the impact energy.
Figure 12. The effect of holding time at peak temperature on grain size and the subsequent
effect on the austenite content [A].
Figure 13. The effect of the austenite fraction, varied by altering the cooling rate, on the
impact toughness of simulated HTHAZ microstructures at different temperatures [A].
27
[99] of grain boundary nucleated growth and the Hillert-Engberg model on kinetics of
spherical and planar growth [100]. The paraequilibrium concept was adopted,
assuming that the phase transformation is controlled by the nitrogen redistribution
alone. The difference between overall steel nitrogen content and the ferrite nitrogen
content in paraequilibrium with austenite defines the driving force for austenite
growth. Substitutional diffusion would occur at high temperatures outside the
paraequilibrium range (here calculated with Thermo-Calc to be above 1288°C), where
chromium is assumed to control the growth rate. The kinetics of the austenite growth
were calculated and compared to experimental data with reasonable agreement, Figure
14. The model gives discontinuities in the curves where there is a shift from spherical
to planar growth. The calculated line in Figure 14c, representing the slowest cooled
specimen, demonstrates the effect of substitutionally controlled growth at tempera-
tures above 1288°C with 0.226 wt.% nitrogen. At higher temperatures there is no driving
force for austenite growth due to nitrogen according to the paraequilibrium. Instead
the kinetics are assumed to be controlled by chromium diffusion. The effect of
chromium diffusion decreases with increased cooling rate due to shorter time in the
actual temperature interval. At the highest cooling rate, Figure 14a, there will be no
time to allow Widmanstätten austenite to form. At moderate cooling rates,
representative of arc welding, Figure 14b and Figure 14c, the experimental data still
show a certain fraction of lamellar Widmanstätten austenite. The austenite reformation
in LDX 2101 was excellent and the Thermo-Calc modelling gave consistently lower
ferrite contents than what was experimentally obtained. The deviations between the
calculations and the experimental data could possibly be explained by the rapid
formation of Widmanstätten austenite during cooling and this should be included in
future model development.
Figure 14. Austenite fraction versus temperature compared with the experimental results.
Specimens were held at 1360°C for 0 s and cooled at different rates. [A]
The calculated influence of cooling rate on the austenite fraction is presented in Figure
15 for the grain sizes 130, 170 and 205 µm, respectively, and compared to experimental
data. Again the discrepancy is explained by the Widmanstätten austenite, which is not
considered in the calculations. The assessed effect of nitrogen content on austenite
reformation is shown in Figure 16. A nitrogen increase from 0.226 wt.% to 0.250 wt.%
would increase the austenite fraction by some 3% whereas a decrease to 0.200 wt.%
would lead to slightly larger decrease in reformed austenite. This seems to be valid
throughout the cooling rate range.
28
Figure 15. Austenite fraction at various cooling Figure 16. Effect of alloy nitrogen content
rates for different grain sizes (GS) compared (wt.%) and cooling rate on reformed auste-
with experimental results [A]. nite fraction in HTHAZ [A].
Figure 17. Comparison of the calculated austenite fractions for four different duplex stainless
steels. (a) Material cooled at 20°C/s resulting in a grain size of 205 µm and (b) material
cooled at 75°C/s resulting in a grain size of 170 µm at cooling rated from 1°C/s to 200°C/s. [A]
29
resistance to SCC. However, both experimental and practical experience has proven
that rather good properties are obtained over a relatively large range of ferrite and
austenite contents. Over the range 30-70% austenite, the phase balance has been shown
to be of minor importance [34]. There is also evidence that LDX 2101 welds with higher
ferrite contents than 65% may still show strength, hardness and corrosion performance
in parity with or close to that of the base metal [30,94,C,D]. If the measured phase
balance deviated from the specified one, it does not necessarily mean that the
properties are deteriorated, but rather that a more thorough control of the material
properties is needed [103]. A round robin test performed by the International Institute
of Welding (IIW) on identical duplex 2205 weld specimens also demonstrated large
scatter between different laboratories of as much as ± 20% of the measured ferrite
mean value [104,105]. This confirms that assessment of microstructure should be of
informative character and not a cause of rejection. It would thus be more relevant to
qualify a welding procedure by demonstrating with mechanical and corrosion testing
that the procedure, when applied to the base material at the proposed thickness, will
not deteriorate the toughness or corrosion resistance.
Figure 18. Calculated CCT diagrams showing formed austenite fraction for LDX 2101 at
cooling rated of 1°C/s to 200°C/s with a grain size of (a) 30 µm, (b) 50 µm and (c) 100 µm [A].
An intermetallic compound is a phase that is formed from two or more metals. The
most common intermetallic phase in stainless steel is σ, which may precipitate with an
adverse affect on ductility, toughness and corrosion resistance [107,112,113]. The σ
phase is an Fe-Cr-Mo compound enriched in iron, chromium, molybdenum, silicon and
tungsten, but with low nickel and manganese contents [114]. Depending on the
chemical composition of the base material, σ phase can form over a wide range of
temperatures from 600°C to 1000°C [108,109]. Ferrite-austenite grain boundaries are
common nucleation sites and carbide particles in the grain boundaries have been
reported to facilitate the nucleation [115]. Nickel as an alloying element promotes
austenite and decreases the ferrite content. This in turn concentrates chromium and
30
molybdenum in the ferrite phase and contributes to σ precipitation in the ferrite phase.
If nickel is substituted partly with nitrogen as an austenite former, this results
according to Komizo et al. [116] in a decreased nickel content in the ferrite phase and
the tendency to form σ phase decreases. The precipitation rate of intermetallic phases
is strongly related to the composition of the steel and weld metal. Embrittlement due
to formation of intermetallic phases is rarely a problem for the lean or standard duplex
grades, but of some concern for the superduplex steels [29,107,108]. R, π and χ are
formed at somewhat lower temperatures than σ, but have the same negative effect. σ
phase is in many cases used as a collective term for all intermetallic phases, since
proper phase identification is complicated and the various intermetallic phases often
are assumed to affect properties similarly [107]. χ and R phases may also be important
as precursors from which σ phase can form [117]. Mechanical and corrosion test
methods can be used to control the level of impairment, and impact toughness is a
very sensitive measure of σ phase even at the early stages of formation [107,109,113].
Intermetallic compounds can be dissolved and the corrosion and toughness properties
restored by a solution annealing heat treatment [91].
Although nitrogen has a high diffusion rate, the solubility in the ferrite is low and it
further decreases with decreasing temperature. Consequently, chromium-rich nitrides
can precipitate within the ferrite grains due to supersaturation during cooling
[23,24,89,96]. Precipitation of nitrides also occurs in the grain or phase boundaries as a
result of isothermal heat treatment in the temperature range 700-900°C [113,118]. The
most frequently reported chromium nitride is Cr2N [90,119]. Cr2N precipitates
particularly in HAZ and weld metal subject to rapid cooling or nitrogen loss resulting
in high ferrite contents. The precipitation of chromium nitrides can be reduced by
increasing the austenite level by higher heat input or by additions of austenite-
promoting elements such as nickel and nitrogen. At higher nitrogen contents, the
driving force for austenite formation increases and the start temperature for austenite
formation is higher; the diffusion distance required for nitrogen transport to grain
boundaries is thus decreased and austenite formation dominates [81]. Slow cooling
rates increase the austenite formation, allow more nitrogen to dissolve and hence
reduce the amount of Cr2N [49]. Figure 19a shows excessive ferrite content in a 22Cr
laser weld with high amounts of Cr2N precipitates. Adjacent to the intergranular
austenite phase a precipitate-free zone in the ferrite is observed, which corresponds to
the diffusion range of nitrogen during the weld thermal cycle. The nitrogen-depleted
regions are the result of the migration of nitrogen into the adjacent austenite during
the transformation [49]. The presence of Cr2N precipitates has repeatedly been
demonstrated to decrease the pitting resistance of welds [23,47,84,120,121] and is
attributed to adjacent depletion of particularly chromium and to some extent nitrogen.
This depletion leads to a local reduction of the PRE and the precipitates may become
preferential corrosion sites electrochemically [120]. The pitting propagates preferen-
tially within the nitride-rich centres of the ferrite grains and is often interrupted at
unaffected grain boundary austenite that has higher corrosion resistance [23,122,C],
Figure 19b. When present at the surface, Cr2N are known to decrease the corrosion
resistance [24,123], but the nitrides are not as harmful if these are not exposed to the
corrosive medium [124,C].
31
Figure 19. (a) A highly ferritic microstructure in 2205 with large amounts of chromium
precipitates in the ferrite and ferrite-ferrite grain boundaries. (b) Preferential pitting attack of
the ferrite phase in an LDX 2101 weld metal.
Figure 20 shows Cr2N precipitates in a HTHAZ simulated LDX 2101 specimen after air-
cooling [94]. The nitrides were more densely distributed after water-quenching giving
a higher cooling rate and consequently a higher ferrite content. The size of the Cr2N
precipitates was in parity with the size reported in the ferrite matrix of 2205 [90,119].
Under certain conditions non-equilibrium cubic chromium nitride (CrN) and hexagonal
Cr2N can be precipitated simultaneously [24,89,96,121]. The precipitation of CrN may be
explained by crystallographically favoured nucleation, in addition to greater driving
force for the precipitation of CrN compared to Cr2N at temperatures below
approximately 1000°C as suggested by Jargelius-Pettersson et al. [24]. Omura et al. [84]
confirmed that the fraction CrN / (CrN + Cr2N) increases in 2205 welds with increasing
cooling rate. With faster cooling, greater quantities of CrN were precipitated and it
was noted that CrN formed the greater part of the chromium nitrides when the cooling
rate was faster than 100°C/s. Taking into consideration the free energy of formation, it
may be assumed that chromium depletion around such a non-equilibrium phase is
small and the effect on pitting resistance minimal [24,84]. No CrN nitrides have been
found within the scope of this thesis, but their presence is not excluded.
32
[125,128]. Secondary austenite thus has slightly lower pitting resistance compared to
primary austenite, but normally shows better corrosion performance than the ferrite.
Formation of secondary austenite may consequently increase the corrosion resistance
of the weld, since it forms from ferrite via the dissolution of chromium nitrides
[107,118,129]. Figure 21 shows CO2 laser welds in LDX 2101 before and after PWHT,
where the austenite formation significantly increases after annealing.
Figure 21. CO2 laser weld metal in LDX 2101 before and after annealing [unpublished work].
As for all other ferritic and duplex grades, the upper temperature limits of LDX 2101
during service are set by the so-called 475°C embrittlement, occurring above
approximately 300°C and below about 500°C [107,108]. This is due to decomposition of
the ferrite phase into iron-rich ferrite and chromium-rich α’, which may cause
embrittlement [10,130]. Weld decay can also occur if the interpass temperature in
multipass welding is allowed to be much above the commonly specified 150°C, since
this will increase the time spent in the sensitising temperature range on cooling [111].
As the carbon content is kept low in the modern duplex alloys, carbide precipitates,
mainly M23C6 and M7C3, are rarely ever observed [108]. Small amounts of grain boun-
dary carbides have been found in simulated HTHAZ specimens in 2205 [119] and LDX
2101 [94], but these were concluded to have negligible effect on corrosion resistance.
8 Corrosion resistance
The pitting resistance of the weldment after adequate post-weld cleaning is generally
somewhat lower than for the parent material [12,34,46,C,D]. There are, however, a
number of metallurgical reactions that can occur and the corrosion resistance can be
further decreased by several factors and phenomena (as discussed above e.g. nitrides).
The effect of welding on the corrosion performance is controlled by a complex
combination of material properties, welding procedure and surface cleanliness, Figure
22. The material thickness and heat input affect the cooling rate, which together with
the material composition govern the phase balance in the HAZ. Use of over-alloyed
filler metal, nitrogen additions to the shielding gas and nitrogen-based backing gas
further control the weld metal phase balance and corrosion resistance by preventing
nitrogen loss and compensating element segregation. Weld oxides, which have a
negative effect on the corrosion performance, can be minimized by adequate backing gas
protection and be removed by post-weld cleaning (acid pickling being most efficient).
33
Figure 22. Factors affecting the corrosion performance when GTA welding.
34
Figure 23. The effect of weld metal Figure 24. The effect of weld metal austenite
nitrogen content and use of filler wire on content on corrosion resistance [C].
the weld metal austenite formation [C].
Figures 25 and 26 illustrate the effect of nitrogen additions on the net nitrogen content
and the resulting weld microstructure at the surface exposed to the corrosive medium.
Assuming that the LDX 2101 base material contains 0.22 wt.% nitrogen and pure argon
is used as shielding and backing gas, nitrogen loss will occur on both sides, because
the system strives to reach equilibrium, Figure 25a. The resulting microstructure
would then be essentially ferritic at the surface of the duplex weld metal as shown in
Figures 25b and 25c. If, on the other hand, 90% N2 + 10% H2 is used as backing gas,
there is no driving force for nitrogen loss on the rootside and when Ar + 2% N2 is used
as shielding gas, nitrogen is absorbed by the weld metal, giving in a more balanced
weld metal nitrogen content, Figure 26a. The nitrogen present at the surface improves
the austenite formation and makes the weld metal more resistant to pitting, Figures
26b and 26c.
Figure 25. (a) Nitrogen balance when welding with pure argon, (b) resulting LDX 2101 weld
metal microstructure with (c) high ferrite content at the surface indicating nitrogen loss [30].
Figure 26. (a) Nitrogen balance when welding with nitrogen additions to shielding and backing
gas, (b) resulting LDX 2101 weld metal microstructure with (c) high austenite content at the
surface [30].
35
Work by the present author not included in this thesis indicates that use of nitrogen
normally has larger effect on the austenite formation than filler when GTA welding,
Figure 27. LDX 2101 and 2507 showed higher austenite formation than 2304 and 2205. As
the thin parent materials were automatically welded without a gap, the amount of
filler wire was fairly small. The effect on the austenite formation would be larger
when welding thicker material with a gap, especially when welding manually. Figure
28 shows the CPT measured on the rootside of pickled 1 mm GTA welded specimens.
When LDX 2101 was welded with argon as shielding and backing gas, the CPT was at a
similar level to that of ferritic AISI 444 and lower than for AISI 316L. When adding
nitrogen to the shielding gas and using nitrogen-based backing gas, the CPT of welded
LDX 2101 was close to that of the base metal and at a similar level to that of AISI 316L.
Nitrogen also increased the CPT for 2304.
Figure 27. Effect of shielding and backing gas composition when GTA welding 1 mm LDX
2101, 2304 and 2205 with ISO 22 9 3 N L filler and 2507 with ISO 25 9 4 N L filler. Either with
pure argon as shielding and backing gas or with Ar + 2% N2 as shielding gas and 90% N2 +
10% H2 as backing gas. [30]
Figure 28. Critical pitting temperature (CPT) measured with ASTM G150 on the rootside of
pickled 1 mm GTA welds performed with argon as shielding and backing gas or Ar + 2% N2
as shielding gas and 90% N2 + 10% H2 as backing gas. AISI 444 and AISI 316L were
performed with ISO 19 12 3 L filler and LDX 2101 and 2304 with ISO 22 9 3 N L filler. [30]
36
There is often a practical maximum limit to how much nitrogen can be added to the
shielding gas. When GTA welding, additions of more than 3% N2 have been reported to
cause severe erosion of the tungsten electrode [133]. When GMA welding, nitrogen
should not be added to the shielding gas. Too high nitrogen levels can result in
problems with porosity in the weld metal, especially at high cooling rates, where there
may be insufficient time for the nitrogen to redistribute by diffusion. The welding
speed should neither be too high (rapid solidification) or too low (very large fusion)
when GMA welding high-nitrogen duplex grades.
Figure 29. (a) The effect of nitrogen additions to argon shielding gas on the austenite content
and (b) the effect of austenite content on the critical pitting temperature (CPT) measured with
ASTM G150 when autogenous Nd:YAG laser welding 1 mm LDX 2101 [D].
On the other hand, Nd:YAG laser-GTA hybrid welding allows some uptake of nitrogen
from the shielding gas [D]. The austenite formation can also be influenced by using
nitrogen-based backing gas [30]. As seen in Figure 30, autogenous CO2 laser welds
with nitrogen as backing gas have significantly higher austenite content than when
welding with argon.
37
Figure 30. CO2 laser welds performed on 1 mm LDX 2101, 2304, 2205 and 2507 using either
argon or nitrogen as backing gas [30].
The pitting corrosion resistance of the pickled CO2 laser welded samples was at the
same level as that of the base metal, Figure 31. The effect of the improved austenite
formation when using nitrogen as backing gas was therefore small, although the
pickling time decreased. The high pitting corrosion resistance can partly be explained
by the low heat input associated with laser welding, which results in low levels of
weld oxide, also by pickling having removed the surface nitrides. Pitting typically
occurred in the weld metal or 1-5 mm from the fusion line, in the parent material.
Figure 31. Critical pitting temperature (CPT) measured with ASTM G150 on the rootside of
pickled 1 mm CO2 laser welds [30].
38
balance between base metal and as-solidified weld metal can partly be avoided by
adding nitrogen to the shielding gas or by using a high nickel filler metal or both [131].
In the HAZ, the microstructure can essentially only be controlled by the cooling rate,
which is dictated by welding parameters and material geometry.
(a) (b)
Figure 32. CO2 laser welding resulting in (a) high ferrite content in 2205 (91 ± 3% ferrite) and
(b) better austenite formation in LDX 2101 (61 ± 3% ferrite) [30].
By using a laser hybrid welding process where the laser beam and the arc process act
in a common process zone, filler metal can be added to the melt pool at significantly
higher heat input, resulting in lower cooling rates. Laser hybrid welding with GMA has
been proven suitable for welding duplex stainless steels of up to 8 mm in one bead
[142]. Larger gauges can also be welded in one single bead, but the surrounding
material will cool down the material rapidly and the root may become essentially
ferritic resulting in lower corrosion resistance and toughness [143]. The heat input
when laser welding may also be increased by scanning the laser beam [144,145].
39
8.2.2 High heat input
High heat inputs usually result in lower cooling rates. This favours nucleation and
growth of austenite and can lead to better resistance to localized corrosion of both the
weld metal and HTHAZ [146,147]. Slow cooling allows diffusion of ferrite-stabilizing
elements such as chromium and molybdenum into the ferrite phase so these approach
the equilibrium values, and this has been reported to increase the corrosion resistance
[148,149]. Extremely high heat inputs should generally be avoided in order to prevent
excessive ferrite grain growth in the weld region, which can affect the ductility and
toughness. Too high heat inputs may cause precipitation of σ phase in the weldment.
This is rarely a problem in lean or standard duplex grades, but of some concern for the
superduplex steels, especially when multipass welding [103,107]. The maximum heat
input for 2507 is for this reason set to 1.0 kJ/mm when SAW. For lean duplex LDX 2101,
the heat input should be limited to 1.0-1.5 kJ/mm when SAW since too large fusion
could dilute the weld metal to lower nickel contents and thereby have a negative
effect on low temperature impact toughness [1].
Variations in the expected pitting corrosion resistance based on the calculated PRE
distribution of the mapped elements in Paper E, confirm that the ferrite phase would
have the lowest corrosion performance in both base and weld metal, which is
consistent with experimental corrosion test results on LDX 2101 welds [C]. It means
that the PRE value based on the element partitioning in ferrite is a more relevant
parameter than the overall chemical composition. Vannevik et al. [151] drew the same
conclusion when studying superduplex grades with 0.3-0.4 wt.% nitrogen, where the
ferrite was the most susceptible phase in both the base and weld metal. EPMA
mapping of the PRE distribution in the centre of the ferrite grains has, however, been
reported to be somewhat misleading, since these areas contain chromium nitride
precipitates [23]. Local chromium and nitrogen depletion around the nitrides may lead
to significantly lower corrosion resistance than for the surrounding ferrite matrix and
instead become preferential pitting sites.
40
Figure 33 shows the calculated PRE distribution in the fusion line from Paper E. The
average PRE was significantly higher in the austenite in both base and weld metal, but
no decrease in PRE was seen along the fusion line, since chromium and nitrogen are
evenly distributed and the molybdenum content low. It has also been found that
although the HTHAZ of LDX 2101 contains chromium nitride precipitates, pitting attack
rarely occurs in the fusion line of pickled duplex welds [C,D]. The exception may be
insufficiently pickled welds performed with pure argon.
Figure 33. Calculated PRE distribution along the fusion line of (a) Ar and (b) Ar + 2% N2 [E].
The lean duplex stainless steel LDX 2101 has improved austenite formation compared
to older duplex grades and the segregation of all elements apart from nitrogen is low.
This means that filler wire additions are not required as for other duplex grades
assuming that there is no large nitrogen loss that could cause excessive ferrite
contents. As the nitrogen appears to be controlling the austenite formation, it is
essential to avoid nitrogen loss during welding.
Khan et al. [152] have reported vaporization, primarily of manganese and iron from
laser weld metals of high manganese stainless steel in the AISI 200 series. These were
Nd:YAG laser welded at low laser powers. At a constant welding speed, the change in
41
the chemical composition was determined by the vaporization rate and the size of the
weld pool, with the latter being the dominant factor. Although the rate of vaporization
of alloying elements such as iron and manganese increased with the increase in laser
power, the composition change was more pronounced at low laser power due to the
small weld pool size. The vaporization rate increased and the weld pool size
decreased with increased welding speed. The fiber laser welds reported in Paper D
could be expected to behave similarly to these Nd:YAG laser welds since the high-
brightness lasers result in exceptionally narrow and deep welds. These welds also
showed the highest ferrite contents and lowest pitting corrosion resistance compared
to other laser types.
In Paper B, stationary (non-moving) GTA welding of LDX 2101 for 0-20 s was performed
with different shielding gases with up to 8% nitrogen. EPMA mapping on cross-
sections was used to produce quantitative images of the manganese, nitrogen and
chromium distribution for each weld and some of the data are plotted in Figure 34.
The manganese content showed a significant decrease with both increased stationary
welding time and with increased nitrogen fraction in the shielding gas. Nitrogen
additions to the shielding gas may enhance evaporation from the weld metal because
of the higher weld temperatures attained (increased voltage). The EPMA measurements
showed that the LDX 2101 weld metal absorbed nitrogen from the shielding gas. The
weld metal nitrogen content increased with increased amount of nitrogen in the
shielding gas and was rather constant with time. However, the nitrogen content
decreased with increased stationary arc welding time when pure argon was used. The
chromium content in the weld metal was slightly lower than in the parent metal, but
the scatter was large. The chromium losses appear to increase slowly with increasing
stationary welding time, apart from Ar + 2% N2 where there was little change. Bhatt et
al. [21] studied a 21Cr-7Ni-2.5Mo-1.7Mn-0.04N duplex steel using ISO 22 8 3 L filler and
different nitrogen additions to the argon shielding gas. When adding 5% nitrogen to
the shielding gas the chromium content decreased from 21.0 wt.% to 17.9 wt.%
compared to pure argon.
Figure 34. Weld metal composition as a function of shielding gas nitrogen content and
stationary arc welding time for (a) manganese, (b) nitrogen and (c) chromium [B].
The evaporation of weld metal species was also shown to affect the weld oxide
composition and thickness by subsequent deposition in Paper B. Diffusion, oxidation,
evaporation and redeposition are possible processes, which can affect the composition
and distribution of the weld oxide formed on the surface. Nitrogen additions to the
shielding gas appear to increase the evaporation and subsequent redeposition of metal
originating from the weld metal when GTA welding. Addition of 2% nitrogen to the
shielding gas gave a thicker oxide than that of pure argon on both LDX 2101 and 2304.
42
The explanation proposed is that with increased amount of nitrogen in the shielding
gas, the evaporation and the deposition increase; forming a thicker surface layer.
Several authors have studied weld oxides to explain their influence on corrosion
resistance. The traditional explanation that the reduction in corrosion resistance is due
to a thin chromium-depleted layer located in the underlying base metal and caused by
chromium diffusion from the bulk into the chromium-rich oxide has frequently been
debated [153,156-159]. The oxidation temperature, which varies with the distance from
the weld, has been suggested to influence the relative diffusion rates of iron and
chromium. AES and GD-OES sputter depth profiles have shown that heat tint formed at
relatively low temperatures consists primarily of iron [156-159]. It is suggested to be a
double-layered oxide, consisting of an iron-rich outer layer and an inner layer of more
chromium-rich oxide. Pitting attack is normally located 1-13 mm from the fusion line
depending on the material thickness and heat input. This coincides with the most iron-
rich oxide formed at around 600-700°C [156-158,160-162]. The chromium-rich oxide
formed at higher temperature is more resistant to corrosion attack. Azuma et al. [156]
have proposed that this acts as a passive film by forming CrOOH in chloride solutions.
The presence of heat tint on the weld and HAZ of any stainless steel will make the
surface more susceptible to pitting and crevice corrosion. Localized corrosion may
occur at significantly lower chloride concentrations and temperatures and it is
generally accepted that pickling is needed for optimum corrosion properties. The
corrosion resistance of welds with root surface oxides formed on duplex (LDX 2101,
2304, 2205 and 2507) and superaustenitic stainless steels (AISI 904L, 254 SMO and 654
SMO) have been compared to low-alloyed austenitic grades (e.g. AISI 304, AISI 316L
and AISI 316Ti) in different investigations [30,135-137,163-165,B,C]. Low-alloyed
stainless steels (e.g. AISI 304L, AISI 316L, AISI 444 and LDX 2101) appear to be more
sensitive to residual weld oxide than steels with higher corrosion resistance. When
blue coloured oxide cannot be avoided and no pickling is applied, a higher alloy grade
may be needed. Most failures have been found in AISI 304L and AISI 316L type of
steels, but residual weld oxide has also been identified to be the main cause of
43
corrosion attack in duplex grades. Figure 35 shows pitting attack in weld oxides
formed on LDX 2101.
Figure 35. Pitting attack in weld oxide formed on the (a) topside after GTA welding and no
pickling and (b) rootside that would require pickling or selection of a higher alloyed grade [30].
In Paper B, heat tints formed on the duplex steels LDX 2101 and 2304, welded with and
without nitrogen additions to the shielding gas, were studied by X-ray photoelectron
spectroscopy (XPS) to determine the effect of base metal and shielding gas
composition on the weld oxide. Compared to commodity austenitics (AISI 300 series)
where iron and chromium are dominant in forming weld oxides, lean duplex grades
show a relatively strong influence of manganese and nitrogen, Figure 36.
Figure 36. Results from surface XPS line scans on the top surface of LDX 2101 and 2304
GTA welds without taking the oxidation states into consideration [B].
Formation of heat tint is normally explained by oxidation of the parent metal and
diffusion from the weld metal. In Paper B, it is suggested that manganese is
evaporated from the weld metal and forms weld oxide by subsequent redeposition
from the gas phase, Figure 37. Nitrogen additions to the shielding gas enhance
evaporation from the weld metal because of the higher weld temperatures attained.
This in turn makes the weld oxide thicker, due to redeposition, changes the
composition and caused a double-layer structure to develop. For LDX 2101, the double-
44
layer was found to consist of manganese oxide and manganese oxynitrides, while on
2304 samples chromium oxynitrides were formed below the outer surface layer
consisting essentially of manganese oxide. When welding with pure argon,
manganese oxide dominated on both LDX 2101 and 2304. Nitrogen additions to the
shielding gas thus increase the weld metal manganese evaporation and encourage the
formation of oxynitrides.
Figure 37. Proposed transportation paths involved in weld oxide formation on the topside [B].
A schematic illustration of heat tint formation on LDX 2101 and 2304 when welding
with and without nitrogen additions to the shielding gas is presented in Figure 38. The
weld oxide formed on LDX 2101 was thicker and wider than the oxide formed on 2304;
and contained more manganese and nitrogen. This difference is considered to be
primarily due to the different steel compositions. No studies concerning the effect of
manganese on the heat tint formation have been found in the literature, but many
papers report manganese present in surface oxide on steel that has been oxidized for
longer times in isothermal exposures [166-168]. In LDX 2101 some nickel has been
replaced with manganese and nitrogen, whereas 2304 has both higher nickel and
chromium contents. The fraction of manganese increases and the oxide becomes both
thicker and somewhat wider when welding with nitrogen in the shielding gas. This is
again related to the evaporation-deposition process [B].
Figure 38. Proposed weld oxide composition on the top surface for LDX 2101 and 2304
welded with and without nitrogen additions to the shielding gas [B].
45
spraying the pickling agent or by applying a paste. The time required for pickling
depends on the material composition, surface roughness, pickling agent, pickling
temperature and weld quality. The pickling time needed is shorter if the surface is
clean and good shielding/backing gas protection is used. Brushing, grinding or shot
blasting before pickling may further improve the corrosion resistance by making the
pickling more efficient and decrease the required pickling time. Surface finish is an
important additional factor that influences the resistance to initiation of pitting and
possible crevice corrosion. The resistance increases with smoother surfaces.
When post-weld cleaning is not an option, the use of proper backing gas purging
becomes increasingly important. A shiny weld and a straw yellow HAZ are
empirically regarded as signs of sufficient root protection for adequate corrosion
resistance. The aim should be to limit the oxygen content in the backing gas to a
maximum of 25-50 ppm in order to avoid severe oxidation [135]. There may be cases
where stricter control is necessary. Backing gas should also be used when tack
welding, Figure 39.
Figure 39. GTA weld performed with high quality backing gas, giving minimum weld oxide.
The tack weld without purging requires longer pickling than the rest of the weld for adequate
pitting resistance. [30]
For conventional austenitic and ferritic stainless steels, pure argon is used as backing
gas. For nitrogen-alloyed stainless steels, purging with 90% N2 + 10% H2 can give cleaner
welds and higher pitting resistance than pure argon [12,135,136]. Hydrogen reacts with
residual oxygen to form water vapour instead of weld oxides on the rootside. This
could decrease the required purging time to reach 50 ppm residual oxygen and the
need for pickling. For various reasons, pure nitrogen may also be used as backing gas.
This is equally beneficial to the austenite formation, but is not as efficient in
decreasing oxidation as hydrogen-containing gases. Purging with 95% N2 + 5% H2 gives
a result being somewhere in between.
46
austenite formation. 2304 base metal has also higher corrosion resistance than the
other grades and the initial current peak does not exceed 100 µ A/cm2 although some
oxide dissolution occurs.
Table 6. Pitting corrosion resistance expressed as the critical pitting temperature (°C) of base
metal (BM) and the rootside of GTA welds in as-welded and pickled condition [30].
Welding Filler Gas composition Corrosion resistance
Grade
method metal Shielding Backing As-welded Pickled
444 BM --- --- --- 12 ± 3
444 GTAW 19 12 3 L Ar Ar N/A 7 ± 2*
316L BM --- --- --- 21 ± 1
316L GTAW 19 12 3 L Ar Ar N/A 19 ± 1
LDX 2101 BM --- --- --- 24 ± 1
LDX 2101 GTAW 22 9 3 N L Ar Ar N/A 5 ± 1*
LDX 2101 GTAW 22 9 3 N L Ar + 2% N2 90% N2 + 10% H2 N/A 23 ± 5
2304 BM --- --- --- 32 ± 1
2304 GTAW 22 9 3 N L Ar Ar N/A 18 ± 2
2304 GTAW 22 9 3 N L Ar + 2% N2 90% N2 + 10% H2 19 ± 3 27 ± 4
*Values below 10°C
Figure 40. Polarization curve of the topside of LDX 2101 welded with Ar + 2% N2 intentionally
stopped at three different potentials and the corresponding surface appearance. Pits are seen
at Position 3 but not at Position 1 or 2, where oxide dissolution was found alone. [165]
47
8.6 Discoloration of welds (Paper B)
In Paper B, four different commercial duplex stainless steel grades (LDX 2101, 2304,
2205 and 2507) were GTA welded bead-on-plate using pure argon and Ar + 2% N2 as
shielding gas. A simple corrosion test, in which polished duplex welds were
interleaved with damp paper for 10 hours, was used to demonstrate that the
composition of the heat tint formed during welding with nitrogen additions to the
shielding gas is different from the weld oxide when pure argon is used. The
specimens welded with pure argon were unaffected while all duplex materials welded
with Ar + 2% N2 displayed stains at different distances from the fusion line after the
test, Figure 41. The reason seems to be that manganese or chromium oxynitrides
formed in the latter case are responsible for the staining. The distribution of the
discoloration also corresponds to the iron-rich region where pitting normally occurs.
Iron deposits were also indicated by the ferroxyl test. The stains were, however, easily
removed and the corrosion resistance was restored by pickling as shown in Paper C.
Figure 41. Weld discoloration after the wet paper corrosion test [B].
48
of the whole weldment [30,146,C,D]. Nitrogen may even form a protective austenite
layer on the surface of the weld and HTHAZ, Figure 43. This increases the weld metal
corrosion resistance compared to that with pure argon as shielding and/or backing gas.
Figure 42. Weld metal surface and resistance of GTA welded LDX 2101 to pitting attack after
testing in 1 M NaCl in accordance with ASTM G150. Ar + 2% N2 as shielding gas resulted in
improved austenite formation at the top surface and made the weld metal more resistant to
pitting. [C]
(a) (b)
Figure 43. LDX 2101 GTA welded with (a) pure argon as backing gas showing nitrogen loss
and high ferrite content on the surface and (b) 90% N2 + 10% H2 giving a uniform phase
balance and a protective layer of austenite on the surface [30].
No pitting was found in the HTHAZ of LDX 2101 for pickled laser and lightly polished
and thoroughly pickled GTA welds [C,D]. Provided that the weld metal austenite
formation is sufficient and adequate post-weld cleaning has been used, pitting is often
located some millimetres from the fusion line [156,162]. This was also consistently
seen in this work [B-D]. The attack consequently occurs rather in the parent metal than
in the coarse grain zone with chromium nitrides and the location often corresponds to
the transition region where the weld oxide is no longer visible. The temperature in this
region is approximately 600-700°C and does not give rise to visually changed
microstructure. Several authors have concluded that this is where the oxide is most
iron-rich [156,158,160]. The absence of pitting in the HTHAZ indicates that chromium
nitrides are not always the limiting factor and the explanation lies probably in the
formation of weld oxide on the surface.
49
If the welds are ground flat prior to corrosion testing, then the heat tint effects are
eliminated and microstructural effects become dominant as illustrated in Paper C. In
this case, the pitting corrosion resistance decreased around 3°C due to exposure of
chromium nitrides in the weld metal and HTHAZ to the corrosive medium. On the
other hand, if the original top surface of the weld is retained and the weld oxide
instead removed by pickling, higher pitting resistance may be observed due to the
protective nature of the oxide film remaining after pickling [24,124,C]. In the root,
nitrogen-based backing gas has proven to be very efficient in increasing the pitting
resistance of LDX 2101 by forming an austenite layer on the outer surface [30,C].
LDX 2101 is a lean duplex stainless steel with improved laser weldability compared to
most duplex grades. This is related to the balanced alloying with manganese and
nitrogen to promote austenite formation. Laser welding of LDX 2101 has been
performed with and without filler wire, and laser hybrid welding with GTA and GMA
using Nd:YAG, CO2 and fiber lasers [30,94,178]. In Paper D, the aim was to show how
the ferrite content, the mechanical properties and corrosion performance of this
material are affected by laser welding and laser hybrid welding with different laser
50
sources. The work demonstrated that LDX 2101 can be laser welded without
deterioration in ductility and corrosion performance. It was, however, concluded that
filler addition when laser welding, or laser-GTA hybrid welding with and without
nitrogen additions to the shielding gas, and laser-GMA hybrid welding further improve
the austenite formation, ductility and the weld metal pitting resistance. Autogenous
fiber laser welding results in the narrowest and CO2 laser welding the widest welds,
Figure 44. Use of hybrid welding methods give wider welds and larger weld bead
areas. Nd:YAG laser-GTA hybrid welds had the smoothest surface owed to the GTA,
while fiber laser-GMA and CO2 laser-GMA may cause exaggerated weld bead
reinforcement that could have a negative impact on the fatigue properties [D]. All
welds fulfilled the yield strength and ultimate tensile strength requirements of base
metal LDX 2101. The elongation values were lower (typically 15-25% compared to min.
30% for the base metal) and particularly for the autogenous fiber laser welds with the
lowest austenite formation.
Figure 44. 1 mm thick LDX 2101 material welded with (a) autogenous Nd:YAG laser, (b)
Nd:YAG laser-GTA hybrid with ISO 23 7 N L filler and Ar + 3% N2 as shielding gas, (c)
autogenous CO2 laser, (d) CO2 laser-GMA hybrid with ISO 22 9 3 N L filler, (e) autogenous
fiber laser and (f) fiber laser-GMA hybrid with ISO 22 9 3 N L filler [D].
Figure 45 shows the effect of weld metal austenite formation on the pitting resistance
of laser welded LDX 2101 [D]. Autogenous CO2 laser welding typically results in better
austenite formation and pitting corrosion resistance than both the Nd:YAG and high-
51
brightness fiber lasers. Autogenous fiber laser welding resulted in the highest ferrite
contents and lowest pitting corrosion resistance compared to the other laser types. The
narrow welds might increase the alloying element loss as Khan et al. [152] reported for
Nd:YAG laser welding. Evaporation of austenite-stabilizing elements such as nitrogen,
nickel and manganese could reduce the austenite formation and loss of chromium and
nitrogen may decrease the pitting resistance. Apart from having the highest ferrite
content, another reason could be that pitting of fiber laser welds occurred in some
cases in association with small spatter on the rootside. Laser hybrid welding
significantly improved the austenite formation and made the weld metal more
resistant to pitting. Pitting was not found in the weld metal or HTHAZ, but instead in
the base metal 1-3 mm from the fusion line. The actual effect on the critical pitting
temperature was, however, not as significant. The largest improvement was seen
when adding nitrogen to the shielding gas when Nd:YAG laser-GTA hybrid welding
since this appears to counteract nitrogen loss. The pitting resistance of laser-GTA
welded LDX 2101 was, for instance, in parity with GTA welded LDX 2101 and AISI 316L
[30,C]. The increased austenite formation when hybrid welding was related more
strongly to the increased heat input than to the choice of filler metal.
Figure 45. The influence of weld metal austenite content on the CPT for LDX 2101 laser weld
roots after pickling compared to the parent material. The austenite fraction varied for different
laser methods, when adding filler metal and when using laser-hybrid welding methods. [D]
10 Mechanical properties
Holmberg [19] reported that the mechanical properties of duplex 2205 do not vary
significantly for normal heat inputs and typical ferrite levels obtained when using
suitable filler metals (23-53%). The tensile properties of welded joints are generally
acceptable, with strength levels on a par with that of the base metal or higher, but with
somewhat reduced ductility. The impact toughness is generally lower, but varies
significantly depending on welding procedures, filler compositions and the final
microstructure.
52
10.1 Hardness
The duplex grades show higher hardness with higher strength and are significantly
harder than for example AISI 316L weldments. The hardness of duplex welds and HAZ
is normally somewhat higher than that of the base metal. This is largely due to the
higher ferrite content, but a second contributory factor can also be residual stress. The
hardness of a simulated HAZ may increase with increasing peak temperature and
increasing cooling rate [94]. The weld metal hardness decreases with higher heat
inputs and slower cooling, which result in improved austenite formation [177]. Vickers
microhardness measurements displayed no large differences over FCA weld cross-
sections in LDX 2101 and 2304 [179]. LDX 2101 was, however, harder than 2304, and had
a higher strength, which was related to the finer grain size and higher nitrogen
content. In contrast to grades that can form martensite on welding, hardness
measurements rarely give much information about the weld metal properties of
duplex grades.
53
welds can further be decreased by higher ferrite contents and increasing specimen
thickness. The impact toughness is dependent upon several factors such as the weld
metal oxygen content, welding method, composition (primarily nickel content) and
microstructure [186]. Favourable results are normally obtained as long as the slag
levels are low and reasonable fractions of austenite have formed in the weld metal and
reformed in the HAZ [69]. Good low temperature toughness of duplex weld metals
have been obtained for GTAW, GMAW, SMAW and SAW, but the highest level is
normally obtained with GTAW; while flux protected welds have lower toughness due to
higher oxygen contents [16,19,35,141,187-189]. The toughness of duplex welds and HAZ
can be reduced by a high ferrite content and large fractions of Cr2N precipitates, which
increases with increased cooling rate and peak temperature [80,190]. Deleu and Dhooge
[191] simulated the HAZ of 2304 and concluded that any weld thermal cycle reduces the
impact toughness of all HAZ microstructures compared to the unwelded base metal.
This was also seen in Paper A, where HTHAZ simulated LDX 2101 showed decreased
impact toughness compared to the base metal and the toughness further decreased
when the specimens were cooled rapidly. HAZ microstructures with higher amounts of
undissolved austenite typically show higher impact values [69]. Use of proper welding
parameters, joint configuration and suitable filler metal, often over-alloyed with
nickel and also PWHT can increase the weld metal energy absorption considerably as
both the phase balance is restored and possible precipitates are dissolved [16,49].
Multipass weld deposits can also show higher toughness as a result of further austenite
formation in the reheated regions [69]. 27 and 40 J minimum Charpy-V impact energy
values are often specified depending on steel grade [192] and application and
documentation of thick plate confirms that duplex welds normally meet these
requirements for design temperatures down to about –40°C [103].
Sieurin et al. [179] showed that 2304 base metal had higher impact toughness than LDX
2101 base metal as a result of higher nickel content and finer microstructure, while
FCA weld metals showed rather the same values due to similar final composition.
When welding low-nickel duplex alloys such as LDX 2101, large dilution from the base
metal should be avoided as this may have a negative impact on the toughness. This
limits the maximum heat input to 1.5 kJ/mm for FCAW. For SAW the heat input may be
restricted to maximum 1.0 kJ/mm, which means this method is seldom the first option.
Sieurin and Sandström [183] correlated the impact toughness to the fracture toughness
by reference temperatures derived by Wallin [193]. Wallin’s master curve is the basis
for the American testing and analysis standard ASTM E1921-97 [194]. It determines the
fracture toughness in the brittle-to-ductile transition range, where the reference
temperature, T0, characterizes the onset of cleavage cracking. The statistical
correlation between fracture toughness and impact toughness T0 = T27J – 18 established
by Wallin [195], gives reasonable estimations of the fracture toughness of duplex
grades, when the impact transition temperature, T27J, is known from Charpy-V impact
testing. Fracture and impact toughness data have been generated for 30 mm thick
parent material and FCA welds of LDX 2101 and 2304, and submerged arc welded 2205
[179,183]. The reference temperatures were below –100°C for the parent materials and
around –100°C for the welds, showing sufficient fracture toughness for most low
temperature applications. The high nickel content in 2205 contributes higher fracture
toughness, which confirmed the high fracture toughness of both 2205 base and SAW
weld metal shown by Dhooge and Deleu [196].
54
11 Conclusions
The lean duplex stainless steel LDX 2101 has here been demonstrated to have good
weldability with rapid austenite formation. The pitting resistance of GTA welded LDX
2101 is after pickling generally significantly higher than that of AISI 304L and in parity
with that of AISI 316L. Due to low element segregation, LDX 2101 can be autogenously
GTA welded without deteriorated corrosion performance in terms of CPT, but then it
becomes increasingly important to avoid losing nitrogen during welding. Nitrogen
additions to the GTA shielding gas and filler additions increase the austenite formation
and make the weld metal itself more resistant to pitting. The highest measured
increase in pitting resistance was, however, seen on the rootside of GTA welds
performed with nitrogen-based backing gas.
The laser weldability of LDX 2101 is in many cases better than for other duplex grades.
Autogenous CO2 laser welding resulted in the highest austenite formation and pitting
corrosion resistance compared to both Nd:YAG and high-brightness fiber lasers. The
austenite formation increased with nitrogen-based backing gas compared to that with
pure argon, and also when laser hybrid welding, but had in this case small influence
on the already high CPT.
After corrosion testing on pickled LDX 2101 welds the pits were typically located in
the weld metal, randomly in the base metal or 1-3 mm from the fusion line; in the
parent metal rather than in the coarse grain zone with chromium nitride precipitates.
The absence of pitting in the HTHAZ indicates that chromium nitrides are not always
the limiting factor. Element segregation and depletion were found along the fusion
line of LDX 2101 welds using EPMA, but had small effect on the corrosion resistance of
the pickled welds examined in this work. When the weld metal and HAZ had sufficient
nitrogen content and hence adequate austenite formation, the weld oxide controlled
the location of pitting after pickling.
Weld oxides do not only form by diffusion. There is also a significant contribution
from deposition that affects both weld oxide composition and thickness. This new
mechanism can possibly explain why many works report no chromium-depleted zone
under the weld oxide on austenitic stainless steels in the AISI 300 series. Some element
loss occurs when GTA welding LDX 2101 and the evaporation of manganese from the
weld metal increases with increased nitrogen addition to the shielding gas. The heat
tint formed on LDX 2101 contains significant amounts of manganese, suggested to be
primarily evaporated from the weld metal followed by subsequent redeposition.
Nitrogen additions to the shielding gas increased this evaporation. Oxynitrides were
formed in the weld oxide on welds performed with nitrogen in the shielding gas and
these are suggested to cause discoloration when subjected to a wet paper corrosion
test. The oxide formed on LDX 2101, when welding with nitrogen-enriched shielding
gas, is thus different from that formed when pure argon is used, but all GTA welds
showed high pitting resistance after pickling.
The ASTM G150 test was unsuitable for measuring the CPT of unpickled LDX 2101
welds because the test terminated immediately at the start of the temperature ramp.
More research is needed to quantify the actual decrease in pitting resistance. Weld
oxides should be removed by pickling for optimal corrosion resistance.
55
12 Summary of papers
A summary of the appended papers follows, including motivation of the work and
main conclusions. The contributions of the present author are also stated.
The author wrote the paper together with S. Hertzman, carried out the welding and
thermal simulations and evaluated the microstructure and properties. B. Brolund and S.
Hertzman developed the theoretical model and B. Brolund performed the calculations.
56
Paper B. Weld oxide formation on lean duplex stainless steel
Four different commercial duplex stainless steel grades (LDX 2101, 2304, 2205 and 2507)
were GTA welded bead-on-plate using pure argon and Ar + 2% N2 as shielding gas. A
simple corrosion test, in which polished duplex welds were interleaved with damp
paper for 10 hours, was used to demonstrate that the composition of the heat tint
changes when nitrogen additions are made to the shielding gas. All duplex materials
welded with Ar + 2% N2 displayed stains at different distances from the fusion line
after the test. No such stains were seen on the argon welds. However, the stains were
easily removed and the corrosion resistance restored by pickling. An explanation for
the differences in weld oxide formation was proposed based on XPS surface analysis
and sputtering depth profiles of the heat tint formed on LDX 2101 and 2304. It was
revealed that manganese dominated in the weld oxide and the content increased when
nitrogen was added to the shielding gas. The weld oxide formed on LDX 2101 was
thicker and wider than on 2304 and contained more manganese and nitrogen. These
elements have been used to compensate for the low nickel content in LDX 2101.
Nitrogen additions to the shielding gas gave a double-layer weld oxide consisting of
manganese oxide, plus manganese oxynitride on LDX 2101 and chromium oxynitride
on 2304. A new mechanism based on evaporation from the weld metal and subsequent
redeposition was suggested to explain the observed phenomena and weld oxide layers.
Nitrogen additions to the shielding gas changed the composition of the heat tint by
suppressing iron and chromium oxidation, increasing weld metal manganese
evaporation and encouraging the formation of oxynitrides. The simple corrosion test
carried out by stacking welds between wet papers showed discoloration only for the
welds in nitrogen-containing atmospheres, not those with argon. The reason seems to
be the manganese or chromium oxynitrides, which are formed in the former case and
appear to be responsible for the staining.
The author wrote the paper, did the literature survey, invented the simple corrosion
test, evaluated the temperature measurements, assisted with welding, EPMA and XPS.
The XPS analysis and evaluation were mainly performed by C.-O.A. Olsson, who
together with S. Hertzman assisted in writing the paper.
57
Paper C. Pitting corrosion resistance of GTA welded lean duplex stainless steel
This paper discusses how the corrosion behaviour of duplex welds may be affected by
the microstructure and presence of weld oxides. LDX 2101 can be autogenously welded
without deterioration in the CPT, but additions of filler metal and nitrogen to the GTA
shielding gas and use of nitrogen-based backing gas can further improve the austenite
formation and make the weld metal more resistant to pitting. Nitrogen-based backing
gas showed the largest impact on the measured CPT. Autogenous welds performed
with pure argon have a higher ferrite content with more chromium nitride precipitates
at the surface. As pitting occurs preferentially in ferrite grains with large fractions of
chromium nitrides, the weld metal becomes most susceptible to pitting when welding
with pure argon. Provided that the weld metal austenite formation is sufficient and
adequate post-weld cleaning has been used, pitting is often located some millimetres
from the fusion line. The absence of pitting in the HTHAZ indicates that chromium
nitrides are not always the limiting factor and the explanation lies probably in the
formation of weld oxide on the surface. If the welds are ground flat prior to corrosion
testing, then the heat tint effects are eliminated and microstructural effects become
dominant. In this case, the pitting resistance can decrease somewhat due to the
presence of chromium nitrides in the weld metal and in the HTHAZ. On the other hand,
if the original top surface of the weld is retained and the weld oxide instead removed
by pickling, higher pitting resistance may be observed due to the protective nature of
the oxide film remaining after pickling. When welding with nitrogen-containing
shielding gas, a surface austenite layer may form, which can protect the chromium
nitrides in the HTHAZ from the corrosive medium.
This paper is a summary of the licentiate thesis work published in 2008 [197], which is
based on Paper B and earlier publications [94,178], intermixed with new results. The
author wrote the paper, did the literature survey, invented the simple corrosion test,
carried out the Gleeble™ simulations, performed the metallographic work, evaluated
the temperature measurements and pitting corrosion test results, assisted with
welding, EPMA and XPS. The XPS analysis and evaluation were mainly performed by
C.-O.A. Olsson, who together with S. Hertzman supervised the work. E. Keehan
performed the TEM work and K. Grönlund the EPMA measurements.
58
Paper D. Effect of laser and laser hybrid welding on the corrosion performance
of a lean duplex stainless steel
The balanced composition with high nitrogen and manganese contents in the lean
duplex LDX 2101 has given this material improved weldability compared to most other
duplex grades. The objective of this paper was to show how the ferrite content, the
mechanical properties and corrosion performance are affected by laser welding and
laser hybrid welding with different laser and arc sources. All welds fulfilled the yield
strength and ultimate tensile strength requirements of base metal LDX 2101; whereas
the elongation values were lower, typically in the range 15-25% compared to min. 30%
for the base metal. The CO2 laser welds showed highest ductility. In conventional GTA
welding, nitrogen additions to the shielding gas can improve the weld metal austenite
formation, but the effect when laser welding is low. Nd:YAG laser welding of LDX 2101
with shielding gas mixtures ranging from pure argon to pure nitrogen had negligible
effect on the ferrite content. The austenite formation in autogenously laser welded
LDX 2101 is not sufficient to completely avoid chromium nitride precipitation and the
weld metal pitting resistance is consequently affected. This was particularly seen in
fiber laser welds. Autogenous fiber and Nd:YAG laser welding resulted in high weld
metal ferrite contents and these were least resistant to pitting. Fiber laser-GMA and
Nd:YAG laser-GTA hybrid welding significantly improved the austenite formation and
made the weld metal more resistant to pitting. The actual effect on the average critical
pitting temperature was, however, not as significant due to scatter. The largest
improvement was seen when adding nitrogen to the GTA shielding gas when Nd:YAG
laser-GTA hybrid welding. The CO2 laser and laser-GTA hybrid welds, all showed high
austenite fractions and correspondingly high pitting resistance. Pure nitrogen as
backing gas had a measurable positive effect on the weld metal austenite formation,
when CO2 laser welding, but had small effect on the already high CPT. The increased
austenite formation when hybrid welding was related more to the increased heat input
than to the choice of filler metal. Autogenous fiber laser welding gave the narrowest
and CO2 laser welding the widest welds. Hybrid welding generally made the welds
wider and increased the weld metal reinforcement. Laser-GMA hybrid welding
resulted in excessive weld bead reinforcement that could have a negative effect on the
fatigue strength. In this sense, laser-GTA hybrid welding is more beneficial.
The author wrote the paper together with A. Fellman, did the literature survey,
performed most laser welding and experimental work, and evaluated the corrosion
measurements. A. Fellman led parts of the laser welding.
59
Paper E. Element distribution in lean duplex stainless steel welds
EPMA mapping was used to quantify and illustrate the element distribution in
autogenous GTA welds performed bead-on-plate on LDX 2101 with and without
nitrogen additions to the shielding gas. As for other duplex grades, the base metal
chromium, molybdenum and silicon were partitioned in the ferrite phase, while
nitrogen, nickel and manganese were concentrated in the austenite phase. In the weld
metal, there was a clear elemental distribution of nickel, manganese, silicon and
molybdenum in the original dendritic structure with the highest concentration in the
interdendritic regions. The chromium distribution was more uniform and slightly
enriched in the ferrite. Local segregation and depletion along the fusion line were
revealed by EPMA mapping. The fusion line was depleted in silicon, molybdenum,
nickel and manganese, while the same elements were enriched in the weld metal
adjacent to the fusion zone. The chromium content was rather uniform in the fusion
zone and showed no signs of depletion as a result of the epitaxial growth and dendritic
solidification behaviour. The microstructure is, however, independent of the
segregation pattern since it is instead controlled by the nitrogen distribution. Neither
the dendrites nor the depleted fusion zone were visible in polished and etched
condition, since nitrogen controls the austenite formation and obscures the fusion line.
Nitrogen consequently plays the most important role for the austenite formation in
duplex stainless steel weld metals. LDX 2101 has improved austenite formation when
welding compared to other duplex grades and the segregation of all elements is low
apart from nitrogen. This means that filler wire additions are not required, as for other
duplex grades, assuming that there is no large nitrogen loss that could cause excessive
ferrite contents. As the nitrogen appears to control the austenite formation, it means
that it is essential to avoid losing nitrogen during welding.
The author wrote the paper, did the literature survey and evaluated the EPMA
measurements. S. Hertzman performed most Thermo-Calc simulations and assisted in
writing the paper. K. Grönlund performed the EPMA work.
60
13 Acknowledgements
A large number of people have, directly or indirectly, contributed to this thesis work.
It has been valuable to have support from many skilled scientists, colleagues and
friends. Without their help none of this would have been possible.
My supervisor Prof. Staffan Hertzman at the Outokumpu Research Foundation and KTH
was a leading light with patient guidance and never-ending encouragement. Prof. John
Ågren at KTH for accepting an external doctoral candidate and for navigation through
the administrative complexities attached to submission of a thesis. Dr Claes-Olof
Anders Olsson at ARC (now at Sandvik Materials Technology) contributed knowledge
on particularly corrosion and surface analysis. Mats Liljas and Björn Holmberg shared
their knowledge of metallurgy and consumables during innumerable discussions. I am
indebted to my manager Dr Rachel Pettersson at ARC and Prof. Carl E. Cross at
Bundesanstalt für Materialforschung (BAM) for their invaluable contributions to the
scripts, contagious enthusiasm and extra boost, often in form of chocolate.
Thanks are expressed to the co-authors of the papers, and those who have contributed
with experimental work and technical discussions. Kaj Grönlund at Corr-Control in
Avesta is acknowledged for the EPMA work and Torvald Andersson at the Ångström
Laboratory in Uppsala for XPS work. Prof. Rolf Sandström and Dr Henrik Sieurin at
KTH (now at Vattenfall R&D) for work on fracture mechanics. Sten Wessman at
Swerea-KIMAB and Bengt Brolund at SSAB performed thermodynamic simulations. Dr
Enda Keehan (then working for ESAB) carried out TEM work at CTH. Support from and
stimulating discussions with friends and colleagues attending the IIW Annual Assem-
blies and ICALEO were also appreciated. Laser welding was carried out at Lappeen-
ranta University of Technology, Luleå University of Technology, BAM, IPG Laser and
Nordic Laser Production. Many thanks to Outokumpu Group Sales and Marketing, the
Outokumpu Business Units and particularly Daniel Serrander for all customer visits,
which motivated the research and to Terho Torvinen, Dr Anna Fellman, Prof. Antti
Salminen and Prof. Alexander Kaplan for guidance in the laser world. Fredrik Hägg
and all welders at Avesta Welding (Böhler Welding Group) are acknowledged for
fruitful collaboration. Jernkontoret and Stiftelsen Prytziska Fonden Nr 2, and ITM-
skolan and C.J. Yngströms fond gave financial support for finishing the thesis.
Outokumpu Stainless financed the research work. My managers are acknowledged for
encouraging postgraduate studies within the framework of research at ARC and for
never giving up hope. I want to thank all colleagues at ARC, especially Henrik Ahrman
for welding, Hasse Peth for corrosion testing, and Jan Y. Jonsson for express help with
microscopes, and the Physical Metallurgy, Corrosion, Instrumentation and Laboratory
departments, for advice and assistance in producing this thesis, but also for many non-
scientific discussions, coffee breaks and non-work related activities.
Finally I want to thank those that have been on my side with endless support
throughout these years - my family and friends. Special thanks to Louise, Anders, Siri,
Vonka, Hanna, Rosita, Anki, Peter, Andreas, Gunilla, Anna, Fiffi, Anna-Karin, Markus,
Leif, Roger, Gibba, Micke, Kerstin, Lelle, Alex, Malte, Lars-Erik, Erik, Ingrid, Lennart,
Åsa, Björn, Jacob, Hugo, Magnus and Tusse for being the most devoted supporters.
61
14 References
[1] Outokumpu Welding Handbook, First Edition, Sandvikens Tryckeri, 2010.
[2] C. Pohle, K. Wilken, J. Schuster, Welding & Cutting 9 (1996) 684-689 and E176-177.
®
[3] J.-E. Kull, Welding of galvanized carbon steel to HyTens with the new MIG/MAG CMT technique,
Diploma Work, MMK 2006:38 MME 778, KTH, Stockholm, Sweden (2006) 55pp.
[4] B. Joseph, M. Picat, F. Barbier, Eur. Phys. J. AP 5 (1999) 19-31.
[5] M.G. Nicholas, C.F. Old, J. Materi. Sci. 14 (1979) 1-18.
[6] E.F. Nippes, D.J. Ball, Weld. J. 61 (1982) 75s-81s.
[7] R.M. Bruscato, Weld. J. 71 (1992) 455s-459s.
[8] W.F. Savage, E.F. Nippes, M.C. Mushala, Weld. J. 57 (1978) 237s-245s.
[9] W. Gysel, G. Dybowski, H.J. Wojtas, R. Schenk, Proc. Duplex Stainless Steels ‘86, The Hague, NL, NIL
(1986) 98-108.
[10] H.D. Solomon, T.M. Devine, Proc. Duplex Stainless Steels ‘82, St Louis, MO, ASM (1984) 693-756.
[11] P. Combrade, J.P. Audouard, Proc. Duplex Stainless Steels ‘91, Beaune, France, 1 (1991) 257-281.
[12] B. Josefsson, Proc. Stainless Steels ‘91, Chiba, ISIJ (1991) 1069-1076.
[13] C.-O.A. Olsson, Corros. Sci. 37 (1995) 467-479.
[14] H. Tsuge, Y. Tarutani, T. Kudo, Corrosion 44 (1988) 5 305-314.
[15] S. Hertzman, J.-O. Nilsson, R. Jargelius-Pettersson, T. Huhtala, L. Karlsson, M. Nilsson, A. Wilson,
Mater. Sci. Tech. 13 (1997) 604-613.
[16] M. Liljas, R. Qvarfort, Proc. Duplex Stainless Steels ‘86, The Hague, NL, NIL (1986) 244-256/acom
(1986) 1-2 2-12.
[17] T. Kudo, H. Tsuge, T. Moroishi, Corrosion 45 (1989) 10 831-838.
[18] K. K. Baek, C.S. Lim, H.J. Sung, Stainless Steel World 10 (1998) 5 28-31.
[19] B. Holmberg, Stainless Steel World 9 (1997) 2 28-33 / ACOM 13 (1997) 3 1-7.
[20] S. Hertzman, R. Pettersson, K. Blom, E. Kivineva, J. Eriksson, ISIJ Int. 36 (1996) 7 968-976.
[21] R.B. Bhatt, H.S. Kamat, S.K. Ghosal, P.K. De, J. Mater. Eng. Perform. 8 (1999) 5 591-597.
[22] M. Vilpas, H. Hänninen, Materi. Sci. Forum 318-320 (1999) 603-608.
[23] T. Ogawa, T. Koseki, Weld. J. 68 (1989) 5 181s-191s.
[24] R.F.A. Jargelius-Pettersson, S. Hertzman, P. Szakalos, P.J. Ferreira, Proc. Duplex Stainless Steels ‘94,
Glasgow, Scotland, TWI, 2 (1995) 461-472.
[25] R. Mundt, H. Hoffmeister, Proc. Stainless Steels ‘84, Gothenburg, Sweden, CTH (1985) 315-322.
[26] S.M. Wessman, S. Hertzman, R. Pettersson, R. Langeborg, M. Liljas, Mater. Sci. Tech. 24 (2008) 3 348-
355.
[27] M. Liljas, Proc. Duplex Stainless Steels ‘94, Glasgow, Scotland, Paper KV, 2 (1995) 15pp.
[28] P. Johansson, M. Liljas, Proc. Stainless Steel Science & Market Congress, ATS, Paris, France (2002) 1-
26.
[29] M. Liljas, P. Johansson, H.-P. Liu, C.-O.A. Olsson, Steel Research Int. 79 (2008) 6 466-473.
[30] E.M. Westin, D. Serrander, in press for Welding in the World, IIW D oc. -N o. II-1748-10 (2010) 14pp.
[31] J. Gemmel, Crash properties of welded LDX 2101 space frames, Diploma Work, MMK 2006:37 MME
783, KTH, Stockholm, Sweden, (2006) 36pp.
[32] E. Ratte, S. Leonhardt, W. Bleck, M. Franzen, P. Urban, Steel Research Int. 77 (2006) 9-10 692-697.
[33] Outokumpu Corrosion Handbook, Tenth Edition, Sandvikens Tryckeri, 2009.
[34] R.A. Walker, T.G. Gooch, Brit. Corros. J. 26 (1991) 1 51-59.
[35] P. Rouault, C. Bonnet, Proc. Duplex Stainless Steels ‘97, Maastricht, NL, 1 (1997) 297-304.
[36] T.G. Gooch, Proc. Duplex Stainless Steels ‘91, Beaune, France, 1 (1991) 325-346.
[37] J.C. Lippold, I. Varol, W.A. Baeslack III, Proc. Duplex Stainless Steels ‘91, Beaune, France, 1 (1991)
383-391.
[38] T.G. Gooch, R.N. Gunn, Proc. Corrosion /94, Paper 385, Houston, TX, NACE (1994) 16pp.
[39] S. Pak, L. Karlsson, Scand. J. Metallurgy 19 (1990) 1 9-13.
[40] M. Miura, M. Koso, T. Kudo, H. Tsuge, Weld. Int. 7 (1990) 3 200-206.
[41] The Avesta Welding Manual - Practice and products for stainless steel welding, Avesta Welding
(Böhler Welding Group), 2004, 2005, 2007, Edita Vastra Aros, ISBN 91-631-5713-6.
[42] J. Sakai, I. Matsushima, Y. Kamemura, M. Tanimura, T. Osuka, Proc. Duplex Stainless Steels ‘82, St
Louis, MO, ASM (1984) 211-231.
[43] P. Guha, C.A. Clark, Proc. Duplex Stainless Steels ‘82, St Louis, MO, ASM (1984) 355-369.
[44] R.F.A. Pettersson, J. Flyg, Proc. Eurocorr 2008, Edinburgh, Scotland (2008) 12pp.
[45] C.-O.A. Olsson, D. Landolt, Electrochim. Acta 48 (2003) 9 1093-1104.
[46] H. Miyuki, T. Kudo, M. Koso, M. Miura, T. Moroishi, Proc. Duplex Stainless Steels ‘82, St Louis, MO,
ASM (1984) 95-112.
[47] N. Sridhar, J. Kolts, Corrosion 43 (1987) 11 646-651.
[48] C.V. R oscoe, K.J. Gradwell, Proc. Duplex Stainless Steels ‘86, The Hague, NL, NIL (1986) 126-135.
[49] I. Varol, W.A. Baeslack III, J.C. Lippold, Key Eng. Mater. 69-70 (1992) 217-251.
62
[50] R.F.A. Jargelius-Pettersson, J. Flyg, S. Wessman, Materi. Sci. Forum 318-320 (1999) 489-494.
[51] R.F.A. Jargelius-Pettersson, Corros. Sci. 41 (1999) 8 1639-1664.
[52] J.M. Lardon, J. Charles, F. Dupoiron, J.C. Bavay, Proc. HNS ‘88, Lille, France, (1989) 280-287.
[53] J.E. Truman, M.J. Coleman, K.R. Pirt, Brit. Corros. J. 12 (1977) 4 236-238.
[54] S. Hertzman, M. Nilsson, R. Jargelius-Pettersson, Proc. Duplex Stainless Steels ‘94, Glasgow,
Scotland, Paper 1, 2 (1995) 12pp.
[55] S. Hertzman, R. Pettersson, K. Frisk, T. Jerwin, Proc. Duplex 2000, Venice, Italy, (2000) 347-354.
[56] P. Johansson, M. Liljas, Stainless Steel World 14 (2002) 12 32-37.
[57] B. Wallén, M. Liljas, P. Stenvall, Mater. Design 13 (1992) 6 329-333.
[58] J. Charles, Proc. Duplex Stainless Steels ‘91, Beaune, France, 1 (1991) 151-168.
[59] L. Wegrelius, Passivation of austenitic stainless steel, Dissertation, CTH, Gothenburg, Sweden (1995).
[60] W.M. Steen, M. Eboo, Met. Constr. 11 (1979) 7 332-335.
[61] J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, Handbook of X-ray photoelectron spectroscopy,
Ed. J. Chastain, R.C. King jr., Physical electronics, Inc., Eden Prairie, MN (1992).
[62] G.C. Smith, Quantitative surface analysis for materials science, The Institute of Metals, London
(1991).
[63] D. Briggs, M.P. Seah, Practical surface analysis, Auger and X-ray photoelectron spectroscopy, 1
(1996), John Wiley & Sons, ISBN-10: 0471953407, 2nd Edition, 674pp.
[64] ASTM G150 - 99 (2004) Electrochemical critical pitting temperature testing of stainless steels, ASTM
Int., PA, USA, 13pp.
[65] R. Qvarfort, Corros. Sci. 28 (1988) 2 135-140.
[66] R. Qvarfort, Corros. Sci. 29 (1989) 8 987-993.
[67] ASTM G48 - 03 (2009) Standard test methods for pitting and crevice corrosion resistance of stainless
steels and related alloys by use of ferric chloride solution, ASTM Int., PA, USA, 11pp.
[68] S. Atamert, J.E. King, Acta Metall. Mater. 39 (1991) 3 273-285.
[69] H.-L. Cao, S. Hertzman, Proc. Duplex Stainless Steels ‘91, Beaune, France, 1 (1991) 363-372.
[70] N. Suutala, T. Takalo, T. Moisio, Metall. Trans. A. 10A (1979) 8 1183-1190.
[71] T. Ogawa, T. Koseki, Proc. Welding and Performance of Pipelines 1986, London, UK, 1 (1987) 115-124.
[72] S. Kunimitsu, O. Suzuki, S.I. Ozeki, Y. Sasaki, Y. Adachi, Y. Hosoi, ISIJ Int. 30 (1990) 7 511-515.
[73] I. Moreno, J.F. Almagro, X. Llovet, Mikrochim. Acta 139 (2002) 3-4 105-110.
[74] V.J. Gadgil, A.G.B.M. Sasse, J.J. Swens, B.H. Kolster, J. Mater. Eng. 13 (1991) 4 291-297.
[75] T.A. Palmer, J.W. Elmer, S.S. Babu, Mat. Sci. Eng. 374A (2004) 1/2 307-321.
[76] W.F. Savage, C.D. Lundin, A.H. Aronsson, Weld. J. 44 (1965) 5 175s-181s.
[77] S. Hertzman, M. Jarl, Metall. Trans. A. 18A (1987) 10 1745-1752.
[78] S. Hertzman, Metall. Trans. A. 18A (1987) 10 1753-1766.
[79] R.F.A. Pettersson, E. Johansson, Proc. Duplex World 2010, Beaune (2010) 12pp.
[80] T.G. Gooch, Proc. Duplex Stainless Steels ‘82, St Louis, MO, ASM (1984) 573-602.
[81] S. Hertzman, ISIJ Int. 41 (2001) 6 580-589.
[82] S. Hertzman, P.J. Ferreira, B. Brolund, Metall. Mater. Trans. 28A (1997) 2 277-285.
[83] V. Muthupandi, P. Bala Srinivasan, V. Shankar, S.K. Seshadri, S. Sundaresan, Mater. Lett. 59 (2005) 18
2305-2309.
[84] T. Omura, T. Kushida, Y. Komizo, Welding Int. 14 (2000) 4 257-260.
[85] H.-Y. Liou, R.-I. Hsieh, W.-T. Tsai, Corros. Sci. 44 (2002) 12 2841-2856.
[86] J. Komenda, R. Sandström, Acta Stereol. 14 (1995) 1 29-34.
[87] H. Hoffmeister, G. Lothongkum, Proc. Duplex Stainless Steels ‘94, Glasgow, Scotland, TWI, Paper 55,
2 (1994) 12pp.
[88] P.D. Southwick, W.K. Honeycombe, Met. Sci. 14 (1980) 7 253-261.
[89] S. Hertzman, W. Roberts, M. Lindenmo, Proc. Duplex Stainless Steels ‘86, The Hague, NL, NIL (1986)
257-263.
[90] T.H. Chen, J.R. Yang, Mat. Sci. Eng. 338A (2002) 1/2 166-181.
[91] C. Meadows, J.D. Fritz, Weld. J. 84 (2005) 7 26-30.
[92] S.D. Brandi, Mater. Sci. Forum 426-432 (2003) 5 4063-4068.
[93] B. Bonnefois, J. Charles, F. Dupoiron, P. Soulignac, Proc. Duplex Stainless Steels ‘91, Beaune,
France, YoU (1991) 347-361.
[94] E.M. Westin, E. Keehan, M. Ström, B. von Brömssen, Proc. ICALEO 2007, Orlando, FL, LIA, Paper 609
(2007) 335-344.
[95] H. Hemmer, O. Grong, S. Klokkehaug, Metall. Mater. Trans. 31A (2000) 3 1035-1048.
[96] J. Liao, ISIJ Int. 41 (2001) 5 460-467.
[97] P.J. Ferreira, S. Hertzman, Proc. Duplex Stainless Steels ‘91, Beaune, France, 2 (1991) 959-966.
[98] R. Dohnke, C. Gillessen, T. Ladwein, U. Reichel, Proc. Duplex Stainless Steels ‘91, Beaune, France, 2
(1991) 1375-1384.
[99] J. Cahn, Acta Metallurgica 4 (1956) 5 449-459.
[100] G. Engberg, M. Hillert, A. Odén, Scand. J. Metallurgy 4 (1975) 2 93-96.
63
[101] NORSOK Standard, Norwegian Technology Standards Institution.
[102] NACE Standard MR0175-99, “Standard Material Requirements, Sulfide Stress Cracking Resistant
Metallic Materials for Oilfield Equipment”, NACE Int., ISBN 1-57590-021-1 (1999).
[103] M. Liljas, G. Gemmel, Proc. Duplex America 2000, Houston, TX, Paper DA2-031 (2000) 199-209.
[104] J.C.M. Farrar, The measurement of ferrite number in real weldments - Final report, IIW Document
IX-H-590-04 (2004) 16pp.
[105] IIW D ocument IX-2072-03, Welding consumables - Predicted and measured FN in specifications - A
position statement of the experts of IIW Commission IX, ISO TR 22824-2003.
[106] G. Herbsleb, P. Schwaab, Proc. Duplex Stainless Steels ‘82, St Louis, MO, ASM (1984) 15-40.
[107] L. Karlsson, Welding in the World 43 (1999) 5 20-41.
[108] J.-O. Nilsson, Mater. Sci. Tech. 8 (1992) 8 685-700.
[109] L. Karlsson, L. R yen, S. Pak, Weld. J. 74 (1995) 1 28s-40s.
[110] J.-O. Nilsson, Proc. Duplex Stainless Steels ‘97, Maastricht, NL, 1 (1997) 73-82.
[111] R.A. Walker, D.N. Noble, Proc. Weldability of Materials, Detroit, MI, (1990) 117-125.
[112] Y.S. Sato, H. Kokawa, T. Kuwana, Sci. Technol. Weld. Joi. 4 (1999) 1 41-49.
[113] J.-O. Nilsson, P. Kangas, T. Karlsson, A. Wilson, Metall. Mater. Trans. 31A (2000) 1 35-45.
[114] Y. Maehara, Y. Ohmori, J. Murayama, N. Fujino, T. Kunitake, Met. Sci. 17 (1983) 11 541-547.
[115] C.H. Shek, G.J. Shen, J.K.L. Lai, B.J. Duggan, Mater. Sci. Tech. 10 (1994) 4 306-311.
[116] Y. Komizo, K. Ogawa, S. Azuma, Welding Int. 5 (1991) 4 277-282.
[117] A. Gregori, J.-O. Nilsson, Metall. Mater. Trans. 33A (2002) 4 1009-1018.
[118] J.-O. Nilsson, A. Wilson, Mater. Sci. Tech. 9 (1993) 7 545-554.
[119] R.-I. Hsieh, H.-Y. Liou, Y.-T. Pan, China Steel Technical Report 13 (1999) 13 14-26.
[120] H. Matsunaga, Y.S. Sato, H. Kokawa, T. Kuwana, Sci. Technol. Weld. Joi. 3 (1998) 5 225-232.
[121] K. Yasuda, K. Tamaki, S. Nakano, K. Kobayashi, N. Nishiyama, Proc. Duplex Stainless Steels ‘86, The
Hague, NL, NIL, Paper 24 (1986) 201-212.
[122] S. Hertzman, E. Symniotis, Proc. Stainless Steels ‘91, ISIJ, Chiba, Japan, 2 (1991) 1085-1092.
[123] T.G. Gooch, B.J. Ginn, Proc. Duplex Stainless Steels ‘97, Maastricht, NL, Zutphen, KCI Publishing BV
(1997) 311-319.
[124] C.-O. Pettersson, M. Holmquist, C. Mårtensson, Proc. Stainless Steels ‘96, Dusseldorf/Neuss, (1996)
184-191.
[125] J.-O. Nilsson, L. Karlsson, J.-O. Andersson, Mater. Sci. Tech. 11 (1995) 3 276-283.
[126] A.J. Ramirez, J.C. Lippold, S.D. Brandi, Metall. Mater. Trans. 34A (2003) 8 1575-1597.
[127] A.J. Ramirez, S.D. Brandi, J.C. Lippold, Sci. Technol. Weld. J. 9 (2004) 4 301-313.
[128] J.-O. Nilsson, P. Liu, Proc. Stainless Steels ‘91, Chiba, Japan, ISIJ, 2 (1991) 1109-1116.
[129] J.C. Lippold, A.M. Al -Rumaih, Proc. Duplex Stainless Steels ‘97, Maastricht, NL, 2 (1997) 1005-1010.
[130] M. Guttmann, Proc. Duplex Stainless Steels ‘91, Beaune, France, 1 (1991) 79-92.
[131] B. Bonnefois, P. Soulignac, J. Charles, Proc. Duplex Stainless Steels ‘91, Beaune, France 1 (1991) 469-
478.
[132] G. Rabensteiner, J. Tösch, Berg Huttenmann 140 (1995) 1 31-40.
[133] O. Jonsson, M. Liljas, P. Stenvall, Proc. Duplex Stainless Steels ‘91, Beaune, France, 1 (1991) 461-468.
[134] S.A. Urmston, G.K. Creffield, M.A. Cole, W. Huang, Proc. Duplex Stainless Steels ‘94, Glasgow,
Scotland, Paper 27, 2 (1995) 12pp.
[135] J. Vagn Hansen, T.S. Nielsen, P. Aastrup, Proc. Duplex Stainless Steels ‘94, Glasgow, Scotland, TWI, 2
(1995) 13pp.
[136] R. Saggau, H. Pries, M. Finke, Z. Metallkd. 92 (2001) 3 286-292.
[137] H. Wohlfart, R. Saggau, H. Pries, Proc. welding and Cutting 2001, Essen (2001) 138-142.
[138] Y.S. Sato, W. Dong, H. Kokawa, T. Kuwana, ISIJ Int. 40 (2000) S20-S24.
[139] W. Dong, H. Kokawa, Y.S. Sato, S. Tsukamoto, Metall. Mater. Trans. 34B (2003) 1 75-82.
[140] P. Roguin, Welding Int. 12 (1998) 6 461-467.
[141] B. Lundqvist, P. Norberg, K. Olsson, Proc. Duplex Stainless Steels ‘86, The Hague, NL, NIL, Paper 10
(1986) 16-29.
[142] A. Fellman, E.M. Westin, Proc. ICALEO 2008, Temecula, CA, LIA, Paper 1204 (2008) 545-553.
[143] E.M. Westin, K. Stelling, A. Gumenyuk, IIW Document IV-963-08, Welding in the World 55 (2011) 1/2
13pp.
[144] A. Salminen, E.M. Westin, Proc. ICALEO 2010, Anaheim, CA, LIA, Paper 1903 (2010) 668-675.
[145] M.P. Vänskä, V. Kujanpää, E.M. Westin, T. Torvinen, Proc. ICALEO 2009, Orlando, FL, LIA, Paper 1803
(2009) 766-772.
[146] N. Sridhar, L.H. Flasche, J. Kolts, Mater. Performance 23 (1984) 12 52-55.
[147] K. Ume, N. Seki, Y. Naganawa, T. Hyodo, K. Satoh, Y. Kuriki, Mater. Performance 26 (1987) 8 25-31.
[148] R.A. Walker, Mater. Sci. Tech. 4 (1988) 1 78-84.
[149] W.A. Baeslack III, J.C. Lippold, Met. Con. 20 (1988) 1 26r -31r.
[150] G. Rabensteiner, Welding in the World 27 (1989) 1/2 2-13.
[151] H. Vannevik, J.-O. Nilsson, J. Frodigh, P. Kangas, ISIJ Int. 36 (1996) 7 807-812.
64
[152] P.A. A. Khan, T. DebR oy, S. A. David, Weld. J. 67 (1988) 1 1s-7s.
[153] J.R. Kearns, Proc. Corrosion /85, Boston, MA, Paper 50, NACE (1985) 11pp.
[154] K. Asami, K. Hashimoto, Corros. Sci. 19 (1979) 12 1007-1017.
[155] J.R. Cahoon, R. Bandy, Corrosion 36 (1982) 6 299-305.
[156] S. Azuma, H. Miyuki, J. Murayama, T. Kudo, Corros. Eng. 39 (1990) 667-676.
[157] S. Turner, F.P.A. Robinson, Corrosion 45 (1989) 9 710-716.
[158] T. von Moltke, P.C. Pistorius, R.F. Sandenbergh, Proc. INFRACON 6, Cape Town, South Africa, SAIMM
Johannesburg, 2 (1992) 185-195.
[159] M.E. Somervuori, L.-S. Johansson, M.H. Heinonen, D.H.D. van Hoecke, N. Akdut, H.E. Hänninen,
Mater. Corros. 55 (2004) 421-436.
[160] P.K. Rastogi, B.K. Shah, A.K. Sinha, P.G. Kulkarni, Brit. Corros. J. 29 (1994) 1 78-80.
[161] R.F.A. Pettersson, J. Flyg, Eurocorr 2005, Lisbon, Portugal, Paper 644, Rolo & Filhos Lda (2005) 9pp.
[162] G. Herbsleb, E. Szederjei, Werkst. Korros. 40 (1989) 11 651-660.
[163] B. Holmberg, Svetsen 61 (2002) 3 11-13.
[164] L. Ödegård, S.-Å. Fager, Australas. Weld. J. 38 (1993) 24-26.
[165] M.M. Johansson, E.M. Westin, J. Oliver, R.F.A. Pettersson, in press for Welding in the World, IIW
Doc. -N o. II-1740-10 (2010) 14pp.
[166] A.L. Marasco, D.J. Young, Oxid. Met. 36 (1991) 1/2 157-174.
[167] F.H. Stott, F.I. Wei, C.A. Enahoro, Werkst. Korros. 40 (1989) 4 198-205.
[168] K. Yamanaka, Y. Matsuda, Corr. Eng. Sci. Tech. 39 (1990) 5 283-296.
[169] G.E. Coates, Mater. Performance 29 (1991) 8 61-65.
[170] A.H. Tuthill, R. Avery, Adv. Mater. Process. 142 (1992) 6 34-38.
[171] R. Ericsson, L. Schön, B. Wallén, Proc. Scand. Corr. Congress, NKM 8, Helsinki, (1978) 321-329.
[172] W. Racky, Stainless Steel Europe 6 (1994) 8 22-25.
[173] M.M. Johansson, Investigation and ranking of localised corrosion resistance of welded austenitic
and lean duplex stainless steel, ISRN KTH/MSE-09/34-SE+METO/EX, Diploma Work, Royal Institute of
Technology, 2009.
[174] N.A. McPherson, H. Samson, T.N. Baker, N. Suarez-Fernandez, J. Laser Appl. 15 (2003) 200-210.
[175] K. Baughn, N. Ahmed, L. Jarvis, D. Viano, Proc. Trends in Welding Research, Pine Mountain, GA,
ASM Int. (2002) 11-16.
[176] K. B orggreen, J.K. Kristensen, L.E. Hansen, M. Kocak, J.F. Dos Santos, Proc. Stainless Steel World ‘99,
The Hague, NL, NIL (1999) 267-274.
[177] A. El - Batahgy, B. Zaghloul, M. Kutsuna, Proc. Stainless Steel World ‘99, KCI Publishing BV, Paper 50
(1999) 739-749.
[178] E.M. Westin, Proc. Stainless Steel World America 2008, Houston, TX, Paper PS08025 (2008) 17pp.
[179] H. Sieurin, E.M. Westin, M. Liljas, R. Sandström, Welding in the World 53 (2009) r 24-r 33.
[180] J. Charles, M. Verneau, B. Bonnefois, Proc. Corrosion Control for Low C ost Reliability, Houston, TX,
Paper 539, 4 (1993) 2926-2943.
[181] C.A. Clark, P. Guha, Proc. Duplex Stainless Steels ‘82, St Louis, MO, ASM (1983) 631-648.
[182] D.J. Kotecki, Proc. Weldability of Materials, Detroit, MI (1990) 127-133.
[183] H. Sieurin, R. Sandström, Eng. Fract. Mech. 73 (2006) 4 377-390.
[184] B.E.S. Lindblom, B. Lundqvist, NE. Hannerz, Scand. J. Metallurgy 20 (1991) 5 305-315.
[185] S.K. Ahn, K.Y. Choi, S.C. Lee, Y.D. Lee, Proc. Duplex Stainless Steels ‘97, Maastricht, 1 (1997) 357-367.
[186] B. Bonnefois, F. Dupoiron, J. Charles, Proc. Duplex Stainless Steels ‘94, Glasgow, Scotland, Paper 87,
2 (1995) 8pp.
[187] A.W. Marshall, J.C.M. Farrar, Proc. Duplex Stainless Steels ‘86, The Hague, NL, NIL (1986) 40-47.
[188] U. Ekström, K. Olsson, Proc. Weld Pool Chemistry and Metallurgy, London, TWI, Paper 37 (1980) 323-
331.
[189] C. Ericsson, P. Johansson, M. Liljas, E.M. Westin, Proc. Stainless Steel World 2003, Maastricht,
Zutphen, KCI Publishing BV, Paper P0356 (2003) 423-431.
[190] T. Kuroda, K. Ikeuchi, Y. Kitagawa, Welding in the World 49 (2005) 5/6 29-33.
[191] E. Deleu, A. Dhooge, Proc. Stainless Steel World 2001, KCI Publishing BV, P0169 (2001) 184-198.
[192] EN 13445-2:2009 Unfired Pressure Vessels - Part 2: Materials, CEN, Brussels.
[193] K. Wallin, Int. J. Mater. Prod. Technol. 14 (1990) 342-354.
[194] ASTM E 1921-97, Standard test method for determination of reference temperature, T0, for ferritic
steels in the transition range, Annual book of ASTM standards 03.01, West Conshohocken, PA (1997).
[195] K. Wallin, Methodology for selecting Charpy toughness criteria for thin high strength steels,
Jernkontorets Forskning, Report from Working Group 4013/89, Stockholm (1990).
[196] A. Dhooge, E. Deleu, Proc. Duplex Stainless Steels ‘94, Glasgow, Scotland, TWI, Paper 77 (1995) 15pp.
[197] E.M. Westin, Welds in the lean duplex stainless steel LDX 2101 - Effect of microstructure and weld
oxides on corrosion properties, Licentiate Thesis in Materials Science, KTH, Stockholm, Sweden,
ISBN 978-91-7415-109-1, 2008.
65