The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels

The influence of stabilization with TITANIUM

on the HEAT-AFFECTED ZONE SENSITIZATION
of 11 to 12 % chromium ferritic stainless steels
under low heat input welding conditions
M. du Toit and J. Naudé

The occurrence of sensitization during continuous cooling after welding was investigated for two low chro-
ABSTRACT

mium ferritic stainless steels: a non-stabilized steel conforming in composition to EN 1.4003, and a corre-
sponding grade stabilized with titanium to increase its sensitization resistance. These steels transform partially
to austenite in the high temperature heat-affected zone (HTHAZ) adjacent to the fusion line during cooling,
with the austenite subsequently transforming to martensite below the Ms temperature. In the non-stabilized
condition these alloys are known to sensitize during continuous cooling after welding at low heat inputs levels
(below approximately 0.5 kJ/mm). The rapid cooling rates associated with low heat input welds suppress
austenite nucleation in the HTHAZ, resulting in almost fully ferritic microstructures. Chromium-rich carbides
precipitate at the continuous ferrite-ferrite grain boundaries, resulting in chromium depletion. Slower cooling
rates promote the formation of more austenite in the HTHAZ during cooling. The austenite absorbs excess
carbon, preventing supersaturation of the ferrite and inhibiting carbide precipitation. Titanium stabilization
does not prevent sensitization during low heat input welding, and may even be detrimental. The high tempera-
tures experienced by the HTHAZ promote the dissolution of titanium carbides, and the titanium is retained
in solid solution due to fast cooling. At lower temperatures chromium-rich M23C6 precipitates nucleate at the
ferrite-ferrite grain boundaries, resulting in sensitization. The titanium in solid solution acts as a strong ferrite-
38 former, increasing the ferrite content in the HTHAZ. The non-stabilized 1.4003 steel contained considerably
more grain boundary martensite in the HTHAZ after low heat input welding than the titanium-stabilized grade,
despite having very similar Kaltenhauser ferrite factors. The presence of grain boundary martensite in the
non-stabilized grade increased the resistance to sensitization under low heat input conditions.

IIW-Thesaurus keywords: Intergranular corrosion; Stainless steels.

1 Introduction
Low-carbon, 11 to 12 per cent chromium ferritic stain-
less steels are widely used as low cost, utility stainless
steels. These steels generally conform in composition to
grades S41003 (ASTM A240) and 1.4003 (EN 10088-2
and EN 10028-7), with the specified chemical composi-
tion limits for these grades shown in Table 1. A titanium-
stabilized version of these steels is commercially available
in South Africa under the trade name of 3CR12™, with
chemical composition limits shown in Table 1. The alloys
perform well in many wet sliding abrasion applications and
in aqueous environments, often replacing coated carbon
and galvanized steels in mildly corrosive surroundings [1-3].
Initial application of these steels was mostly confined to
materials handling equipment in corrosive/abrasive envi-
ronments, but the alloys are now used extensively in the

Table 1 — Specified chemical composition limits for grades S41003 (ASTM A240), 1.4003
(EN 10088-2 and EN 10028-7) and 3CR12™ [percentage by mass, balance Fe] [1]

Grade C Cr Mn Si Ni P S N Ti
0.030 10.5 – 1.50 1.00 1.50 0.040 0.030 0.030 Not
S41003
max. 12.5 max. max. max. max. max. max. specified
0.030 10.5 – 1.50 1.00 0.30 – 0.040 0.015 0.030 Not
1.4003
max. 12.5 max. max. 1.00 max. max. max. specified
0.030 10.5 – 2.00 1.00 1.50 0.040 0.030 Not 4(C+N)
3CR12
max. 12.5 max. max. max. max. max. specified to 0.6 max.

Doc. IIW-2059, recommended for publication by Commission IX “Behaviour of Metals Subjected to Welding.”
 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels
Although the 1.4003 steels normally contain more than 0.01 % carbon, this phase
diagram illustrates the general shape of the austenite and (austenite+ferrite) phase fields.
An increase in carbon content is expected to enlarge these phase fields
at the expense of ferrite [4].
Figure 1 – Vertical section of the ternary Fe-Cr-C phase
diagram at carbon contents below 0.01 %
coal mining industry, for cane and beet sugar processing
equipment, and for bulk transport of coal and ore.
The steels under consideration are designed to transform
partially to austenite on cooling, passing through the dual-
phase (austenite+ferrite) phase field on the Fe-Cr equi-
librium phase diagram (shown in Figure 1 for carbon con-
tents below 0.01 per cent). This partial solid-state phase
transformation of ferrite to austenite on cooling improves
the weldability and as-welded toughness by restricting
heat-affected zone (HAZ) grain growth [5, 6]. The 1.4003
steels are usually supplied in the fully annealed and
desensitized condition. Final annealing is performed at
temperatures below the A1 (normally between 700 °C and
750 °C) after air cooling or cold rolling [1, 2]). During the
annealing treatment, any austenite formed on slow cool-
ing through the dual-phase region transforms completely
to ferrite. Due to its low solubility in ferrite, the majority of
the carbon precipitates as chromium-rich carbides or car-
bonitrides during annealing, but any chromium-depleted
zones formed in the ferrite are healed through chromium
back-diffusion from the grain interiors.
The rapid cooling rates associated with welding, how-
ever, prevent the transformation of austenite to ferrite at
lower temperatures, and any austenite formed on cooling
through the dual-phase (δ+γ) region transforms to mar-
tensite below the Ms-temperature [5]. As a result of the
high carbon solubility in austenite, the austenite phase
that forms on cooling acts as a carbon sink, dissolving
significant amounts of carbon. When this austenite trans-
forms to martensite at lower temperatures, the amount of
carbon retained in solid solution in the martensite phase is
determined by the cooling rate. Martensite formed on fast
cooling retains higher levels of the carbon in supersatu-
rated solid solution. At slower cooling rates, the formation
of martensite is preceded by carbide precipitation in the
austenite, and less carbon is retained in solution in the
martensite phase [7].
The typical heat-affected zone microstructure of a 1.4003
weld is shown in Figure 2. The high temperature heat-
affected zone (HTHAZ) adjacent to the fusion line repre-
sents parent metal heated above the A3 temperature dur-
ing the weld thermal cycle, and is characterized by δ-ferrite
grains surrounded by grain boundary martensite. Despite
the partial solid-state phase transformation from ferrite to
austenite on cooling, the HTHAZ is normally character-
ized by a coarse grain size. This is in contrast to the much
finer grain size of the low temperature heat-affected zone
(LTHAZ) located farther from the fusion line. This region
has a structure consisting of ferrite and martensite, and
represents parent metal heated to temperatures between
the A1 and A3 temperatures during welding.
Austenitic consumables are preferred for welding the
1.4003 alloys. Although this leads to a property mismatch
between the weld and the surrounding base metal, the
tough austenitic weld metal improves the overall tough-
ness of the weld by absorbing some of the impact that
the joint may be exposed to during service. A matching
welding electrode is commercially available (classified as
E410NiMo, with modified chromium content), but it is not
recommended in applications where impact, shock, fatigue
or any other form of non-static loading is anticipated. This 39
electrode is only specified in applications where matching
corrosion resistance is essential.
2 Sensitization in the heat-affected
zone of 1.4003 welds
A number of field failures of 1.4003 welds due to inter-
granular stress corrosion cracking and pitting corrosion
in the heat-affected zone have been reported in the past
decade [7]. Although it is frequently claimed that nickel-
free stainless steels are immune to stress corrosion
cracking, such failures have been reported in both nickel-
free ferritic and martensitic stainless steels with corrosion
(Welded at a heat input of 0.9 kJ/mm and electrolytically etched
in a saturated oxalic acid solution) [8].
Figure 2 – The typical heat-affected zone microstructure
of a type 1.4003 steel
04 2011 Vol. 55 WELDING IN THE WORLD
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 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels
potentials within the passive range [9-11]. The stress
corrosion cracking of these stainless steels is generally
believed to be associated with some degree of sensitiza-
tion. Even though various sensitization models have been
proposed for stainless steels, chromium depletion is the
most widely accepted mechanism [12]. This theory states
that sensitization is caused by intergranular precipitation of
chromium-rich M23C6-type carbides, resulting in chromium
depletion of the matrix surrounding the precipitated par-
ticles. If chromium depletion reduces the chromium level
in the affected areas to below the concentration required
to maintain passivation, the steel becomes sensitized to
intergranular corrosion.
It was originally believed that the typical dual-phase heat-
affected zone microstructure that develops during weld-
ing (as shown in Figure 2) renders the 1.4003 type steels
largely immune to sensitization. The cooling rates during
welding are generally considered to be too fast to cause
sensitization of the austenite phase, whereas the ferrite
phase is rapidly desensitized by chromium back-diffusion
into depleted regions during cooling. This mechanism is
similar to that proposed for the enhanced sensitization
resistance observed in duplex austenitic-ferritic stainless
steels [13]. It has, however, since been confirmed that the
1.4003 steels are susceptible to sensitization under spe-
cific conditions.
40 The chromium depletion mechanism for sensitization
in the 1.4003 steels has been confirmed using trans-
mission electron microscopy with electron energy loss
(EELS) image filtering. Sensitized material demonstrates
chromium enrichment along the grain boundaries, as
well as distinctive chromium depleted zones adjacent to
these boundaries [14]. The intergranular precipitation of
chromium-rich carbides with associated grain boundary
Table 2 – Summary of the conditions leading to the four modes of heat-affected zone sensitization observed
in non-stabilized 1.4003 steels
Mode Imposed thermal cycle
Double thermal cycle, with heating above
the A1 temperature during final annealing,
1 followed by a second heating step to
temperatures between about 650 °C and
700 °C
Double thermal cycle, with heating above the
A1 temperature, followed by a second heating
2 precipitation on the prior
step to temperatures between about 550 °C
and 650 °C
Heating to a temperature close to the
3
liquidus, followed by rapid cooling
Heating to a temperature close to the
4 austenite grain boundaries
liquidus, followed by very slow cooling
chromium depletion in dual-phase ferritic-martensitic 12
and 13 % chromium steels has also been reported by
Tomari et al [15] and Frangini et al [16].
Investigation into the phenomenon of heat-affected
zone sensitization revealed that it only occurs under very
specific conditions in the non-stabilized 1.4003 steels.
Although these conditions are readily simulated in the
laboratory, actual instances of failure in service have been
rare. Laboratory simulations and in-service inspection
of welds revealed four potential categories or modes of
heat-affected zone sensitization in these materials. These
modes are described in more detail elsewhere [17], but a
brief summary is given in Table 2.
Modes 1 and 2, described in Table 2, require that the
material undergoes a double thermal cycle in order to
sensitize, and can successfully be prevented by stabilizing
the steels with titanium. Mode 4 sensitization is extremely
rare and also effectively prevented through stabilization.
Mode 3 sensitization, however, occurs during continuous
cooling after welding when low heat input levels result in
very fast cooling rates during the early stages of the weld
thermal cycle. These rapid cooling rates have been shown
to suppress austenite nucleation as the heat-affected
zone cools through the dual-phase (austenite+ferrite)
phase field, resulting in almost fully ferritic high tempera-
ture heat-affected zone microstructures. Due to the low
solubility of carbon in ferrite, the ferrite becomes super-
saturated in carbon in the absence of sufficient austenite,
and extensive carbide precipitation occurs at the ferrite-
ferrite grain boundaries during cooling. The fast cooling
rates also prevent the back-diffusion of chromium to the
depleted regions adjacent to the chromium-rich carbides,
resulting in a continuous network of sensitized ferrite-fer-
rite grain boundaries [18].
Relevant weld processing
Sensitized structure
conditions
LTHAZ of a weld deposited Martensite with Cr-rich carbide
on base metal containing precipitation on the prior
untempered martensite austenite grain boundaries
Multiple welds positioned in
Martensite with Cr-rich carbide
such a way that the HAZ of the
2nd pass overlaps the HAZ of
austenite grain boundaries
the 1st pass
HTHAZ generated by single- Coarse-grained δ-ferrite with
pass low heat input welds, arc precipitation of Cr-rich carbides
strikes or areas with excessive at continuous ferrite-ferrite
fillet weld overlap grain boundaries
HTHAZ generated by single-
Carbide precipitation at
pass welds performed at
excessively high heat input
during cooling
levels
 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels
A number of fillet weld failures associated with fast weld-
ing speeds and excessive fillet weld overlap have been
attributed to Mode 3 sensitization. A similar mode of
attack has been observed in areas associated with arc
strikes, shallow rapidly solidified weld toe cusp features
caused by welder hand movements in manual weld-
ing, and certain spatter features [19]. Mode 3 sensitiza-
tion only occurs in the high temperature heat-affected
zone and is unrelated to the parent metal microstructure.
Sensitization occurs in the vicinity of the weld toe where
the maximum joint stress concentration may be expected,
and as a result intergranular defects caused by Mode 3
sensitization have been observed to initiate and acceler-
ate fatigue cracking in highly stressed locations [19].
The degree of sensitization under low heat input condi-
tions is a function of the metallurgical phase balance in
the HTHAZ, and decreases significantly with an increased
volume fraction of austenite formed on cooling. If enough
austenite forms to absorb the excess carbon from the fer-
rite phase (carbon has higher solubility in austenite than
in ferrite), a continuous network of chromium-depleted
zones does not form and sensitization is prevented. The
HTHAZ phase balance is determined largely by the cool-
ing rate after welding and the steel composition. As the
heat input during welding increases, the cooling rate is
reduced and more austenite forms in the heat-affected
zone. This austenite transforms to martensite at lower
temperatures and remains as a grain boundary marten-
site network within the ferritic heat-affected zone down to
room temperature. Slower cooling after welding at higher
heat input levels also allows the ferrite to desensitize
through diffusion of chromium from the grain interiors into
any chromium depleted zones [18].
The chemical composition of the steel affects the HTHAZ
phase balance by influencing the temperature range over
which austenite is stable on cooling. The amount of fer-
rite retained in the HTHAZ can be estimated from the
empirical Kaltenhauser ferrite factor (KFF), shown in
Equation (1) [20]. In low KFF steels, the austenite stability
range extends to higher temperatures and over a wider
temperature range than in high KFF steels. This favours
the ferrite-to-austenite transformation, even under rapid
cooling conditions, resulting in higher martensite levels in
the HTHAZ after cooling.
KFF = [Cr + 6Si + 8Ti + 4Mo + 2Al + 4Nb] -
[2Mn + 4Ni + 40(C+N)]
Mode 3 sensitization can be prevented by ensuring
that heat input levels during welding do not fall below
approximately 0.5 kJ/mm, and by using steels with higher
amounts of austenite-forming elements (i.e. low KFF
Table 3 – The chemical compositions of the non-stabilized 1.4003 steel and Ti-stabilized 3CR12 examined
during the course of this investigation [percentage by mass, balance Fe]
Steel C Cr
Non-stabilized 1.4003 0.010 11.46
Stabilized 3CR12 0.005 10.83
steels) to promote the formation of austenite on cooling.
Titanium-stabilization has also been introduced to increase
the general sensitization resistance of these steels. It has,
however, been reported that titanium-stabilized steels with
high ferrite factors may be susceptible to Mode 3 sensi-
tization, since titanium carbide and carbonitride precipi-
tates are known to dissolve to varying degrees during the
weld thermal cycle [19], but no definitive study have been
published to confirm this hypothesis. Since the titanium-
stabilized 3CR12 grade is recommended for welding
applications due to its increased resistance to sensitiza-
tion, it is important to establish whether this higher sen-
sitization resistance extends to conditions conducive to
Mode 3 sensitization. This study therefore compares the
sensitization resistance of a non-stabilized 1.4003 type
steel to that of a titanium-stabilized 3CR12 material under
conditions known to cause Mode 3 sensitization during
welding.
3 Experimental procedure
3.1 Alloy compositions
During the course of this investigation, the susceptibility
of non-stabilized grade EN 1.4003 steel was compared
to that of titanium-stabilized 3CR12 under conditions
known to promote Mode 3 sensitization (i.e. welding at 41
very low heat input levels). The chemical compositions of
the steels examined during the course of this investiga-
tion are shown in Table 3. The stabilized grade was sta-
bilized with titanium at a level corresponding to approxi-
mately four times the combined interstitial (C+N) content.
The Kaltenhauser ferrite factor (KFF), calculated from
Equation (1), is included in Table 3 for both alloys. This fac-
tor quantifies the ratio of ferrite- to austenite-forming ele-
ments in the steel. As shown in Table 3, the non-stabilized
grade has a slightly higher ferrite factor, which predicts a
marginally lower austenite content in the high tempera-
ture heat-affected zone during welding. The steels were
supplied in the form of fully annealed and homogenized
plate of 6 mm thickness.
3.2 Welding procedure
In order to examine the influence of welding parameters,
(1) and in particular heat input, on the microstructure and sen-
sitization resistance of the HTHAZ adjacent to the fusion
line, the alloys shown in Table 3 were welded autogenously
(bead-on-plate welds without the addition of filler metal)
using heat inputs ranging from approximately 0.13 kJ/
mm to 0.66 kJ/mm. These heat inputs were selected on
the basis of previous work which showed that Mode 3
Mn Si Ni Ti KFF
0.54 0.73 0.35 0.02 12.81
0.80 0.74 0.58 0.19 12.44
04 2011 Vol. 55 WELDING IN THE WORLD
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 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels
sensitization in 1.4003 steels is likely at heat input levels
below approximately 0.5 kJ/mm [18].
Direct current gas tungsten arc welding (GTAW) with elec-
trode negative polarity was used and all welding was per-
formed using pure welding-grade argon shielding gas at
a flow rate of 15 l/min. The welding parameters selected
to produce the experimental welds at various heat input
levels are given in Tables I and II in the Appendix for the
non-stabilized and stabilized grades, respectively.
Equation (2) was applied to calculate the heat input, HI,
of each experimental weld (shown in Tables I and II in
the Appendix) from the welding parameters, where V is
the arc voltage, I is the welding current, and v is the weld
travel speed. The arc efficiency factor, η, was estimated
by comparing the actual heat input required to produce a
weld with a given weld pool diameter (measured experi-
mentally), with the heat input calculated from the weld-
ing parameters using Rosenthal’s conduction-driven heat
flow model [21].
KVI
HI
Q the HTHAZ a maximum of fifteen counts were performed
The average arc efficiency was calculated as 47.8 %. This
value approaches the upper limit of the range normally
quoted for gas tungsten arc welding (approximately 22 %
to 48 %) [22]. Electrode negative polarity was used for
welding, which focuses the majority of the heat gener-
42
ated by the power source into the workpiece and restricts
electrode heating, thereby limiting heat losses through the
non-consumable tungsten electrode.
3.3 Sensitization testing
Sensitization was evaluated using the 10 % oxalic acid
electrolytic etch described in Practice W of ASTM 763-93
[23]. In order to classify the resulting microstructures, pol-
ished and etched samples of each weld were examined
using an optical microscope. The oxalic acid etch reveals
the presence and location of any chromium-rich carbides
in the microstructure, but normally only serves as a screen-
ing test for sensitization as it cannot discern between sen-
sitized and healed (or desensitized) structures. Previous
Heat input = 0.66 kJ/mm
a) Unstabilized
Figure 3 – Optical photomicrographs of autogenous bead-on-plate welds performed at heat input levels of 0.6 kJ/mm
or higher, etched electrolytically in a 10 % oxalic acid solution
work, however, confirmed that the oxalic acid etch serves
as a reliable test for determining the susceptibility of the
1.4003 alloys to Mode 3 sensitization [17, 18]. This can be
attributed to the fast cooling rates experienced by welds
at the low heat input levels evaluated. These rapid cool-
ing rates suppress chromium back diffusion to the grain
boundaries and the presence of chromium carbides in the
high temperature heat-affected zone after welding there-
fore serves as a reliable indication of Mode 3 sensitization
in these materials.
3.4 Phase percentages and cooling rates
In order to determine the influence of welding parame-
ters on the microstructure of the high temperature heat-
affected zone adjacent to the fusion line, point count
methods were used to estimate the room temperature
martensite content of the HTHAZ of each weld. Point
counting was performed by randomly moving a grid with
25 arbitrarily spaced points within the HTHAZ of each
weld, counting all the points located within the martensite
phase (counted as one), or on a ferrite-martensite phase
(2) boundary (counted as half). Due to the narrow width of
for each weld. The thermal cycle during welding for a point
located within the high temperature heat-affected zone
was then calculated using Rosenthal’s conduction-driven
heat flow model for heat input levels of 0.66 kJ/mm and
0.22 kJ/mm [21].
4 Results and discussion
Optical photomicrographs of the heat-affected zones of
autogenous welds performed at the higher heat input
levels in the range evaluated (i.e. above 0.6 kJ/mm) are
shown in Figures 3 a) and b) for the non-stabilized and
titanium-stabilized grades, respectively. The high tempera-
ture heat-affected zones of both welds consist of coarse
ferrite grains, surrounded by grain boundary martensite.
Despite having a slightly higher Kaltenhauser ferrite fac-
tor (shown in Table 3), the non-stabilized grade shown in
Figure 3 a) contains a noticeably higher volume fraction
Heat input = 0.60 kJ/mm
b) Stabilized
 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels

martensite in the HTHAZ, with the majority of the grain
boundaries fully covered in martensite. Very little evidence
of sensitization is evident, with ditching (indicative of a
sensitized grain boundary) limited to isolated ferrite-ferrite
grain boundaries within the HTHAZ. The HTHAZ of the
stabilized grade, shown in Figure 3 b), is predominantly
ferritic, with isolated grains of martensite located at the fer-
rite grain boundaries. The stabilized grade contains some
sensitized ferrite-ferrite grain boundaries in the HTHAZ
adjacent to the fusion line, but all the ferrite-ferrite grain
boundaries in the HTHAZ are not sensitized.
The high-temperature heat-affected zone microstructures
of the non-stabilized and stabilized steels after welding at
heat input levels of approximately 0.3 kJ/mm and 0.2 kJ/
mm are shown in Figures 4 and 5. At these heat input
levels the non-stabilized grade [Figures 4 a) and 5 a)]
consists of ferrite grains and grain boundary martensite.
Less martensite is evident than in Figure 3 a), suggest-
ing that the faster cooling rates associated with the lower
heat inputs during welding suppressed the transforma-
tion of ferrite to austenite during cooling, resulting in less
room temperature martensite. Sensitization is restricted to
isolated ferrite-ferrite grain boundaries, while the ferrite-
martensite phase boundaries are unattacked and there-
fore not sensitized. This is in agreement with the findings
of Greeff and Du Toit [18], who reported that Mode 3
sensitization in 1.4003 steels is generally restricted to
the ferrite-ferrite grain boundaries. The high tempera-
ture heat-affected zone of the stabilized grade, shown in
Figures 4 b) and 5 b), is predominantly ferritic and the
continuous ferrite-ferrite grain boundaries are severely
ditched. This suggests that the high temperature heat-
affected zone is sensitized.
Figures 6 a) and b) show the heat-affected zone micro-
structures of the stabilized and non-stabilized grades
after welding at very low heat input levels in the region
of 0.1 kJ/mm. Both high temperature heat-affected
zones are predominantly ferritic, suggesting that the cool-
ing rates after welding were fast enough to completely
suppress the transformation of ferrite to austenite during
cooling. The continuous ferrite-ferrite grain boundaries of
both high-temperature heat-affected zones are ditched,
suggesting Mode 3 sensitization. The heat-affected
zone of the stabilized weld performed at a heat input of
0.15 kJ/mm appears to be more resistant to sensitiza-
tion than those of welds performed at heat inputs of 0.23
and 0.30 kJ/mm. A preliminary scanning electron micro-
scope (SEM) investigation suggests that the weld thermal
cycle at such low heat input values is too rapid to allow
complete dissolution of all TiC particles. Less carbon is
therefore available during cooling through the chromium
carbide precipitation range.

43

Heat input = 0.35 kJ/mm Heat input = 0.30 kJ/mm

a) Unstabilized b) Stabilized

Figure 4 – Optical photomicrographs of autogenous bead-on-plate welds performed at heat input levels
of approximately 0.3 kJ/mm, etched electrolytically in a 10 % oxalic acid solution

Heat input = 0.22 kJ/mm Heat input = 0.23 kJ/mm

a) Unstabilized b) Stabilized

Figure 5 – Optical photomicrographs of autogenous bead-on-plate welds performed at heat input levels
of approximately 0.2 kJ/mm, etched electrolytically in a 10 % oxalic acid solution

04 2011 Vol. 55 WELDING IN THE WORLD

N° 03 Peer-reviewed Section
 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels
Heat input = 0.13 kJ/mm
a) Unstabilized
Figure 6 – Optical photomicrographs of autogenous bead-on-plate welds performed at heat input levels
of approximately 0.1 kJ/mm, etched electrolytically in a 10 % oxalic acid solution
The results shown in Figures 3 to 6 suggest that the
difference in sensitization behaviour between the two
grades may be due to the variations in high temperature
heat-affected zone phase composition. Significantly more
grain boundary martensite is evident in the HTHAZ of the
non-stabilized 1.4003 grade at all heat input levels evalu-
ated, even though the Kaltenhauser ferrite factor predicts
a slightly lower austenite potential for this alloy. This is
demonstrated in Figure 7 for heat inputs of between
approximately 0.1 kJ/mm and 0.35 kJ/mm.
44 In order to clarify this inconsistency, the chemical compo-
sitions of the two grades of steel were presented on the
Balmforth diagram [24] shown in Figure 8. This diagram
is used to predict the microstructures of martensitic and
martensitic-ferritic stainless steel welds. According to the
Balmforth diagram, the non-stabilized grade is expected
to contain slightly more than 60 % ferrite in the HAZ,
whereas the titanium-stabilized grade is predicted to con-
tain approximately 85 % (a residual nitrogen content of
0.01 % was assumed for both steels). Although the dia-
gram was constructed to predict the HAZ microstructures
under higher heat input conditions, and therefore overes-
timates the ferrite content of the welds under investiga-
tion, the Balmforth diagram shown in Figure 8 attributes
Figure 7 – The martensite content of the high-temperature
heat-affected zone of the stabilized and non-stabilized
grades for heat input levels between approximately
0.1 kJ/mm and 0.35 kJ/mm (with 95 % confidence interval)
Heat input = 0.15 kJ/mm
b) Stabilized
a higher percentage of grain boundary martensite to the
HAZ of the non-stabilized grade, even though it has a
lower austenite potential. The Balmforth diagram proposes
a coefficient of 10 for titanium, which is slightly higher
than the coefficient for titanium in the Kaltenhauser fer-
rite factor equation. This suggests that the Kaltenhauser
ferrite factor may underestimate the coefficient for tita-
nium, a strong ferrite-forming element when in solid solu-
tion. Although titanium is also a strong carbide-former, the
cooling rates in the HTHAZ of the low heat input welds
examined in this investigation were most likely too fast to
allow extensive titanium carbide or carbonitride precipi-
tation. Preliminary SEM results suggest that most of the
titanium in the high temperature heat-affected zone of
3CR12 was retained in solid solution on cooling to room
temperature.
The higher percentage ferrite in the HTHAZ of the tita-
nium-stabilized grade can therefore most likely be attrib-
uted to titanium (a strong ferrite-former) going into solid
solution in the ferrite as the titanium carbide precipitates
dissolve during the weld thermal cycle.
Figure 9 displays heat-affected zone temperature pro-
files calculated from Rosenthal’s heat flow equations for
Figure 8 – Balmforth diagram [24] predicting
the microstructure of martensitic and martensitic-ferritic
stainless steel welds
 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels
Figure 9 – Calculated temperature cycles experienced
by the high temperature heat-affected zone at a point
located 100 μm from the fusion line for heat inputs
of 0.22 kJ/mm and 0.66 kJ/mm and a plate thickness
of 6 mm
a point located 100 μm from the fusion line in the high
temperature heat-affected zone for two heat input levels.
It is evident that the high temperature heat-affected zone
initially cools at a rapid rate from the peak temperature
experienced during the weld thermal cycle. This rapid
cooling rate through the higher temperature region of
the thermal cycle at low heat input levels effectively pre-
vents the reprecipitation of titanium carbides during cool-
ing, retaining the titanium in solution. The slower cooling
rate through the lower temperature region of the thermal
profile, however, promotes extensive precipitation of chro-
mium-rich M23C6 carbides. As shown in Figure 9, lower
heat input levels result in increasingly higher cooling rates.
These higher cooling rates suppress the diffusion-control-
led transformation of ferrite to austenite as the weld cools
through the dual-phase (austenite+ferrite) phase field,
resulting in carbon supersaturation of the ferrite. The fast
cooling rates associated with lower heat input levels also
prevent the back diffusion of chromium to the depleted
regions adjacent to the chromium-rich carbides, resulting
in a continuous network of sensitized ferrite-ferrite grain
boundaries.
As the heat input increases, the cooling rate is reduced
and more austenite forms in the heat-affected zone.
This austenite transforms to martensite at lower tem-
peratures and is retained down to room temperature as
a grain boundary martensite network within the ferritic
heat-affected zone. If enough austenite forms on cooling
to absorb excess carbon (austenite has a higher carbon
solubility than ferrite), a continuous network of chromium-
depleted zones does not form and sensitization is pre-
vented. Slower cooling after welding at higher heat input
levels also allows the ferrite to desensitize through diffu-
sion of chromium from the grain interiors into any chro-
mium depleted zones.
The results shown in Figures 3 to 6 confirm that stabili-
zation with titanium does not prevent Mode 3 sensitiza-
tion in 11 to 12 % Cr ferritic stainless steels during low
heat input welding. In this investigation, the non-stabilized
steel consistently outperformed the stabilized grade with
respect to sensitization resistance within the heat input
range evaluated. During the weld thermal cycle the tita-
nium is taken into solid solution in the high temperature
heat-affected zone as the titanium carbide precipitates
dissolve close to the fusion line. At low heat input levels
the cooling rate through the high temperature range is
too fast to allow the reprecipitation of titanium carbide,
and the titanium in solution suppresses the transforma-
tion of ferrite to austenite on cooling. The higher ferrite
content of the high temperature heat-affected zone then
effectively promotes sensitization. Excessively low heat
input levels (lower than approximately 0.2 kJ/mm in this
investigation) may effectively retard sensitization by pre-
venting the complete dissolution of TiC particles in the
heat-affected zone during welding.
5 Conclusions
This investigation examined the effect of titanium-stabili-
zation on the sensitization of two 11 to 12 % chromium
ferritic stainless steels during continuous cooling after
welding. Based on the results obtained, the following con-
clusions were drawn:
1. Sensitization of 11 to 12 % chromium ferritic stainless
steels during continuous cooling after welding is pos-
sible if low heat inputs are used. The rapid cooling rates 45
associated with welding at low heat input levels suppress
the partial transformation of ferrite to austenite as the
heat-affected zone cools through the (austenite+ferrite)
dual-phase region during welding. This results in largely
ferritic high temperature heat-affected zones adjacent to
the weld fusion line. Carbon supersaturation of the ferrite
phase occurs in the absence of sufficient austenite dur-
ing cooling, resulting in extensive carbide precipitation
on the ferrite-ferrite grain boundaries. Chromium back
diffusion is prevented by rapid cooling, and the ferrite-
ferrite grain boundaries are sensitized to intergranular
corrosive attack.
2. Titanium stabilization is ineffective in preventing sensi-
tization during continuous cooling after low heat input
welding, and depending on the chemical composition
and austenite potential of the steel, may even be det-
rimental. The rapid cooling rates experienced during
the initial cooling stages through the high temperature
range of the weld thermal cycle inhibit the precipitation
of titanium carbides or carbonitrides in the high temper-
ature heat-affected zone. As the cooling rate decreases
through the lower temperature region of the cooling
cycle, chromium-rich M23C6 precipitates form at the
ferrite-ferrite grain boundaries, resulting in sensitization.
3. The high temperatures experienced by the high tem-
perature heat-affected zone close to the fusion line
result in the dissolution of titanium carbides and car-
bonitrides, and the titanium is retained in solid solution
down to room temperature due to the fast cooling rates
associated with low heat input welding. The titanium in
solid solution acts as a strong ferrite-forming element,
resulting in significantly higher levels of ferrite in the
04 2011 Vol. 55 WELDING IN THE WORLD
N° 03 Peer-reviewed Section
 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels
high temperature heat-affected zone. The non-stabi-
lized 1.4003 steel evaluated during the course of this
investigation contained significantly more grain bound-
ary martensite in the high temperature heat-affected
zone after low heat input welding than the titanium-sta-
bilized grade, despite having very similar Kaltenhauser
ferrite factors (or austenite potentials). The presence of
grain boundary martensite in the non-stabilized grade
increased the resistance to sensitization under low
heat input conditions by preventing the supersatura-
tion of carbon in the ferrite phase.
4. Excessively low heat input levels (lower than approxi-
mately 0.2 kJ/mm in this investigation) may effectively
retard sensitization by preventing the complete disso-
lution of TiC particles in the heat-affected zone during
welding.
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 The influence of stabilization with TITANIUM on the HEAT-AFFECTED ZONE SENSITIZATION of 11 to 12 % chromium ferritic stainless steels

Appendix

Table I – Measured welding parameters and calculated heat input levels (considering an arc efficiency factor of 47.8 %)
of the autogenous welds performed to characterize the sensitization resistance of the non-stabilized 1.4003 steel
Welding current Arc voltage Welding speed Heat input
Weld number
[A] [V] [mm/s] [kJ/mm]
1 50 17 3.2 0.13
2 81 16 2.8 0.22
3 99 18 3.2 0.26
4 110 19 2.8 0.35
5 185 21 2.8 0.66

Table II – Measured welding parameters and calculated heat input levels (considering an arc efficiency factor of 47.8 %)
of the autogenous welds performed to characterize the sensitization resistance of the titanium-stabilized 3CR12 grade
Welding current Arc voltage Welding speed Heat input
Weld number
[A] [V] [mm/s] [kJ/mm]
1 50 20 3.2 0.15
2 81 17 2.8 0.23
3 99 17 3.2 0.25
4 111 16 2.8 0.30
5 185 19 2.8 0.60

47

About the authors

Prof. Madeleine DU TOIT (madeleine.dutoit@up.ac.za) and Mr. Johan NAUDE
(naude.johan@columbus.co.za) are both with Department of Materials Science
and Metallurgical Engineering, University of Pretoria, Pretoria, South Africa.

04 2011 Vol. 55 WELDING IN THE WORLD

N° 03 Peer-reviewed Section