Preferential Weld Corrosion: Effects of Weldment

Microstructure and Composition

C-M Lee, S Bond and P Woollin

Paper presented at NACE 2005 Houston, Texas, 3-7 April 2005

Abstract
Preferential weldment corrosion (PWC) of carbon and low alloy steels used for pipelines
and process piping systems in CO 2 -containing media has been observed increasingly
in recent years. In particular, this has been on weldments made by the manual metal
arc (MMA) process using electrodes containing Ni or Ni plus Cu. This paper presents
the results of a joint industry research programme which was conducted collaboratively
by three research organisations to investigate this corrosion mechanism and to seek
practical solutions.

The effect of composition and microstructure on PWC in CO 2 -containing media was

investigated on 12 weldments produced in X52 and X65 grade pipe materials using TIG
and MMA processes. Corrosion tests were conducted in a re-circulating vessel on
segmented weld electrodes in CO 2 -containing media, with two levels of chloride
content. The addition of increased amounts of nickel and silicon was detrimental, whilst
additions of molybdenum and chromium (of up to 0.7wt%) did not give improvements in
PWC behaviour. Autogenous weldments, made without filler additions, and weldments
made with matching composition consumables gave the best PWC resistance. It is also
shown that empirical relationships exist between PWC and hardness levels and
microstructure, with unrefined microstructures, having high hardness, being detrimental.
The implications of the data for design of welding procedures to minimise PWC are
considered.

Introduction
Preferential weldment corrosion (PWC) of carbon and low alloy steels used for pipelines
and process piping systems in CO 2 -containing media has been observed increasingly
in recent years. Attempts to control PWC have previously involved making minor
additions of noble metals (e.g. Ni, Cr, Mo, Cu) to the weld consumable in order to make
the weld metal cathodic with respect to the adjacent parent pipe and HAZ. This
approach has proved successful in preventing preferential weld attack in seawater
injection systems where additions of either Ni or Ni and Cu can be used to prevent
preferential corrosion providing care is taken to avoid over-alloying, which can induce
attack of the HAZ [1] .
The use of nickel-containing weld consumables has also been widely adopted in
production systems. However, while some companies have satisfactory experience of
using nickel-containing consumables, there have been examples of severe preferential
attack of the weld metal in sweet environments [2] .

Studies have shown that PWC in CO 2 -containing media is influenced by a complex

interaction of several parameters including the environment, flow conditions, scaling
effects, parent steel composition and welding procedure [3-5] . No general agreement
exists on the role of alloying elements and microstructure in preferential corrosion of
welds [3] .

A recently completed joint industry project investigated the PWC of ferritic steels in
CO 2 -containing environments. This paper reports the findings on the effects of weld
microstructure and composition on PWC from the research programme. Two other
papers, published in this conference, will focus on corrosion flow loop studies of PWC
and its inhibition in CO 2 environments [6] and PWC of 1%Ni welds as a function of
solution conductivity and inhibition [7] . Based on the findings of the project a set of
guidelines for the prediction, control and monitoring of PWC of ferritic steels has
recently been published [8] .

Experimental method
Welding

Three parent pipe materials were used on the project. These were:

 API 5L X52/ASTM A333 grade 6, 356mm diameter, 25mm wall thickness.

 API 5L X65, 508mm diameter, 10.3mm wall thickness.
 API 5L X60 (with 0.5%Cr addition), 273mm diameter, 12mm wall thickness.

The chemical analyses of these pipes are given in Table 1. Welding was carried out by
two processes, namely manual metal arc (MMA) and automated cold wire tungsten inert
gas (TIG) welding to produce 12 different weld compositions and microstructures. Four
elements, Ni, Cr, Mo and Si, were introduced into the weld metal in small amounts using
commercially available consumables. The two welding processes were used to achieve
low and high levels of dilution in welds containing Ni and Cr. Welds made with nominally
matching consumables and autogenous welds were also included for comparison.
Details of the welding consumables and significant alloying elements are given in Table
2.

Table 1 - Chemical analysis of the parent pipe materials

Element, wt%
Pipe Grade
C Si Mn P S Cr Mo Ni Al Cu Nb
 5L X52 0.15 0.28 1.21 0.013 <0.002 0.088 0.012 0.057 0.039 0.092 0.034
5L X60 0.09 0.27 0.89 0.012 0.004 0.59 0.027 0.010 0.027 0.004 0.029
5L X65 0.07 0.20 1.17 0.019 0.005 0.033 0.003 0.019 0.031 0.021 0.051

As <0.004, except X52 for which As=0.024; Co ≤ 0.011; Pb, Zr <0.005; Sn ≤ 0.010; Ti ≤
0.003, except X65, for which Ti = 0.042; W <0.01; Ce <0.02; Sb <0.002; B, Ca <0.0003.

Table 2 - weld details

AWS
Weld Significant % Allo
Weld Parent steel Welding consumable
type/(Target alloying elemen
number grade process designation
Dilution)* elements weld m
(closest)
W41 Matching filler X52/A333-6 MMA E7018 None -
W21 Matching filler X52/A333-6 TIG ER70S-6 None -
W39 Matching filler X65 TIG ER70S-6 None -
W25 High Si (20%) X52/A333-6 TIG ER70S-6 1.05%Si 0.55(Si
W20 High Ni (30%) X52/A333-6 MMA E8018-C3 1%Ni 0.58(N
W26 Low Ni (50%) X52/A333-6 TIG ER80S-Nil 1%Ni 0.41(N
W29 High Cr (20%) X60 MMA E8010-G 0.6%Cr 0.67(C
(0.5%Cr)
W31 Low Cr (50%) X52/A333-6 TIG ER80S-G 0.6-0.7%Cr 0.34(C
W43 High Cr (20%) X52/A333-6 MMA E8010-G 0.6%Cr 0.57(C
W33 Mo addition X52/A333-6 MMA E7015-A1 0.5%Mo 0.32(M
(20%)
W35 Autogenous X52/A333-6 TIG - - -
W37A Autogenous X65 TIG - - -
- Not applicable
* Matching filler implies matching composition

Corrosion Tests

Test Vessel. The design of the test vessel is shown in Figure 1; the cylindrical body of
the main vessel was made from titanium. A paddle was driven from a motor mounted
beneath the vessel to provide circulation. The test vessel was connected to a glass
reservoir to provide additional solution volume and pumps were used to circulate the
solution through the oxygen monitoring equipment.
 Fig.1. Schematic diagram of test vessel

Sample Preparation. A section of each weld was removed and machined to 90mm x
15mm x 7mm. The segments were electrically isolated by cutting the fusion boundary
and separating the HAZ from parent steel with a slitting wheel (<1mm thick) through the
thickness of the sample. Electrical connections were made to the five segments at the
back of the sample, which was mounted in resin together with an alloy 316 stainless
steel counter electrode. The complete sample had a small hole drilled at the centre for
inserting a salt bridge ( Figure 2).

Fig.2. Detail of corrosion test sample

Test Parameters. Details of test parameters are given in Table 3. Two chloride levels
were employed: 35 and 0.35g/l NaCl, both at 60°C and acidified with 1 bara CO 2 .
Table 3 - Corrosion test details

High Chloride Low Chloride

Temperature 60°C 60°C
Paddle rotation 44rpm 44rpm
(Peripheral speed) (0.5 m/s) (0.5 m/s)
Chloride (g/l NaCl) 35 0.35
CO 2 1 bara 1 bara
O 2 Level <10ppb <10ppb
pH 5-6 5-6
Duration 30 days 30 days
Test Procedure. The test samples were placed in the test vessel with the exposed
surfaces facing inwards. Prior to initiation of the tests the solution was pre-purged with
N2 for 24hrs followed by CO 2 gas purge for a further 2hrs. The pre-purged test solution
was pumped into the reservoir and also the test vessel, and the paddle was started. The
peripheral speed of the paddle was set to 0.5 m/s. The CO 2 gas purge at 1 bara
pressure and solution circulation between the test vessel and reservoir was maintained
and the test allowed to proceed for 30 days at a constant temperature of 60°C.

The oxygen level of the test solution was monitored using a dissolved oxygen meter and
maintained <10ppb. The pH and Fe 2+ ion concentration were also monitored on
samples taken periodically from the test solution. The Fe 2+ were measured using atomic
adsorption spectrometry. On completion of the test after 30 days, the specimens were
removed, and rinsed with distilled water and ethanol.

The electrochemical measurements were carried out using a computer controlled

potentiostat with a weld test facility on each of the five segments (i.e. weld metal, 2 x
HAZ, 2 x parent). Linear Polarisation Resistance (LPR)measurements was used for
calculating corrosion rates in the high conductivity solution and Electrochemical
Impedance Spectroscopy (EIS) was used in the low conductivity solution. Details of the
corrosion rate calculation methods are given in one of the associated papers [7] .

Results and discussion

Weld Characterisation
Compositionally, the 12 welds produced can be divided into 6 main categories; welds
containing Ni, Cr, Si and Mo alloying additions, welds made with nominally matching
filler and autogenous welds. Table 4 shows results of hardness and grain size
measurements of the 12 welds tested in the programme.

Table 4 - characterisation of weld metal microstructures

Weld Parent Measured grain Mean weld root Microst

Process Weld type
No. steel size (µm) hardness (HV5) R
W41 X52 MMA Matching 5.6 185 3
W21 X52 TIG Matching 11.7 229 1
W39 X65 TIG Matching 6.3 195 3
W20 X52 MMA High Ni 6.8 195 3
W26 X52 TIG Low Ni 4.6 218 3
W29 X60 MMA 0.5%Cr 3.5 230 0
W43 X52 MMA High Cr 5.7 235 3
W31 X52 TIG Low Cr 4.7 221 3
W25 X52 TIG Si 9.6 224 1
W33 X52 MMA Mo 5.5 220 2
W35 X52 TIG Autogenous 7.5 209 2
W37A X65 TIG Autogenous 7.9 186 3
R = Degree of refinement to an equiaxed ferrite and pearlite microstructure.
A = Amount of ferrite with aligned second phase.

Table 5 - comparison of weld metal corrosion rates

Calculated Average 5-10 days+

Calculated Peak Weld
Weld Metal Corrosion Rate
Corrosion Rate (mm/
Weld Parent Welding (mm/yr)
Weld type
No. steel process High Low
High Chloride Low Chloride
Chloride Chlor
Solution (**) Solution (*)
Solution (**) Solut
W41 X52 MMA Matching 5.4 6.2 7.2 7.9
W21 X52 TIG Matching 3.4 6.8 8.5 7.8
W39 X65 TIG Matching 2.5 2.4 6.8 4.8
W20 X52 MMA High Ni 3.5 14.0 7.9 18.2
W26 X52 TIG Low Ni 0.6 11.4 5.9 17.0
W29 X60 MMA 0.5%Cr 3.2 6.2 7.0 6.2
W43 X52 MMA High Cr 0.5 6.5 8.7 8.3
 W31 X52 TIG Low Cr 1.9 5.2 5.5 7.6
W25 X52 TIG Si 5.2 10.1 7.0 12.6
W33 X52 MMA Mo 3.8 6.0 6.9 9.1
W35 X52 TIG Autogenou 4.8 6.1 8.0 6.9
W37A X65 TIG s 4.8 2.7 6.6 5.1
Autogenou
s
+ 5-10 days was chosen, as it was the period of highest sustained corrosion rate prior to surface film formation
* Calculated from EIS data
** Calculated from LPR data
The deposition of welds with the two welding processes and a range of welding
consumables produced weld root beads with a range of microstructures. Most of the
welds had root microstructures that had been largely refined to equiaxedferrite and
pearlite. However two, W21 and W25, consisted predominately of ferrite with aligned 2
nd phase. The exception to the pattern was weld W29 which had a microstructure
consisting principally of grain boundary ferrite and acicular ferrite.

The microstructures were each assigned ratings in two categories; firstly the degree of
refinement of the microstructure towards one of equiaxed ferrite and pearlite, labelled R,
and secondly the extent of ferrite with alignedsecond phase, labelled A. A value of 0 to
3 was assigned in each category, to represent the visually assessed extent of
refinement and aligned second phase present. R=0 showed no refinement to equiaxed
ferrite and pearlite, R=3represented a fully refined structure of equiaxed ferrite and
pearlite. A=0 indicated little or no ferrite with aligned second phase, whilst A=3 indicated
the highest level of aligned second phase observed. Table 4 also shows the assigned
ratings of each of the 12 weldments.

Corrosion Tests

Current Measurements vs Time. The galvanic current measurements from selected

samples are shown in Figures 3 and 4. Note that the y-axis scales for the graphs are
not the same for low and high chloride tests due to a large difference in the magnitude
of the measured currents. In general, the magnitude of the current was the highest for
welds containing alloying elements. When reduced corrosion rates arose from film
formation, towards the end of the test, the galvanic currents followed a similar falling
trend.
 Fig.3. An example of current vs. time plot of weldment showing cathodic weld
metal behaviour: W20, X52, High Ni, MMA, tests conducted in low chloride
solution at 60°C, 1 bara CO 2

Fig.4. An example of current vs. time plot of a weldment showing anodic weld
metal behaviour: W33, X52, with Mo addition, MMA, tests conducted in low
chloride solution at 60°C, 1 bara CO 2

In Ni-containing weld samples (W20 and W26), the weld metal showed a consistent
cathodic behaviour with respect to the other segments, in low and high chloride tests,
Figure 3 . Two samples, X52 matching-composition MMA weld (W41) and X52 Mo-
containing MMA weld (W33), showed weld metal that exhibits consistently anodic
behaviour, as compared to the other segments, in low and high chloride tests, Figure 4.
In the Cr-containing welds, only the X60 0.5%Cr pipe MMA weld (W29) showed a
consistent cathodic behaviour. The other two welds with Cr additions showed both
anodic and cathodic behaviour in the different tests. TheX65 autogenous weld (W37A)
showed a consistent cathodic behaviour in all tests, but the X52 autogenous weld (W35)
showed both anodic and cathodic behaviour in different tests.

Corrosion Rates vs Time. Figures 5 and 6 show calculated corrosion rates from
selected samples from low chloride (Test 4) and high chloride (Test 3) tests. Typically,
the weld metal shows preferential corrosion in the early part of the test and then falls to
alevel nearer to that of the parent steel. After the initial peak, the falling corrosion rates
are attributed to changes in the metal surface condition. In the period from 5 to 10 days,
the metal surfaces are relatively free from asurface film, so they corrode relatively freely
in the solution. After this period, as Fe 2+ ions build up in the solution, some segments of
the weldment samples begin to form a protective scale on the surface and corrosion
rates begin to drop dramatically. This effect is typically seen first in theweld metal. This
is followed by the preferential corrosion of the HAZ which shows the next highest
corrosion rates and these segments subsequently form a protective scale and also
typically show reduced corrosion rate towards the endof the test. This result explains
the occurrence of preferential HAZ attack rather than preferential weld metal attack, as
observed in some field failures.

Fig.5. An example of calculated corrosion rate vs time results for tests conducted
in low chloride solution at 60°C, 1 bara CO 2 (W20, X52, High Ni, MMA)
Fig.6. An example of calculated corrosion rate vs time results for tests conducted
in high chloride solution at 60°C, 1 bara CO 2 (W21, X52, matching composition,
TIG)

Not all samples and segments showed a reduction in corrosion rate during the test. This
indicates that a build-up of protective scale did not occur in these segments. This is
confirmed by visual examination of samples after the test, where certain segments were
either partially covered with the protective film or the film formed was loosely adherent
to the surface and so unable to provide complete protection.

Effects of Chloride Concentration. Figure 7 shows the average calculated EIS

corrosion rates between 5-10 days from the low chloride test and Figure 8 shows the
peak LPR corrosion rates from the high chloride test. These values were chosen to be
representative of the freely corroding period before film formation and after the initial
transient.
 Fig.7. Average EIS calculated corrosion rate during the period 5-10 days; tests
conducted in low chloride solution at 60°C, 1 bara CO 2

Fig.8. Maximum calculated LPR corrosion rate; tests conducted in high chloride
solution at 60°C, 1 bara CO 2

With the exception of the Ni and Si-containing weld metal segments in the low chloride
test, the corrosion rates of all parts of the weldment are generally greater in the high
chloride test. However, the difference between the corrosion rates of the weld metal and
parent steel, i.e. the degree of preferential corrosion, is greater for the low chloride
solution test. For all weldments, it was noted that preferential weld metal/HAZ corrosion
was lower in the high chloride environment compared to the low chloride.
Effects of Composition. Figures 7 and 8 show that the weld metals made with
matching composition consumables or without consumable addition gave lower
corrosion rates and better resistance to preferential weld metal attack than those made
with alloyed consumables, with Ni being particularly detrimental. The data indicate that
silicon has a detrimental effect on preferential weld metal corrosion also but this effect
was less than that for nickel. It is noted that in another study on parent material, silicon
was shown to have a beneficial effect on CO 2 corrosion resistance at temperatures
greater than 93°C 9 . Molybdenum addition at the level examined had little or no effect
on preferential weld metal corrosion although other workers have found some beneficial
effects [2,10] . The data for chromium-containing weld metals were inconclusive. However
the data did not rule out the possibility that there might be some beneficial effect of
higher levels of Cr, as would be expected intuitively. Overall the best performance with
regard to reducing preferential weld metal corrosion was obtained with matching
composition or autogenous weld metals. However, preferential weld metal corrosion
was not avoided for any of the weld metals examined. Figure 9 shows an example of a
0.6wt%Ni-containing weld metal that was particularly prone to PWC, where
compositional effects dominate over microstructure.

Fig.9. Weld metal with 0.6wt%Ni, a fairly fine ferrite grain size and little aligned
second phase. Weld was deposited in X52 pipe by the MMA process, using
E8018-C3 coated electrodes, W20. The composition promotes PWC but the
microstructure does not

Nevertheless chromium is known to be beneficial, in the parent material, if present in

sufficient levels [10,11] and one potential solution to PWC would be to examine higher
chromium levels in the weld metal, with a view to reducing preferential weld metal
corrosion rates further. It should be recognised however that this might tend to increase
preferential HAZ attack if the corrosion resistance of the weld metal is increased
substantially.

Influence of Microstructure. The root weld metal microstructure classification is given

in Table 4. It was found that there was a reasonable correlation between microstructure
and preferential weld metal corrosion for weld metals with no significant deliberate
alloying (i.e. welds made with matching compositionconsumables and autogenous
welds). Weld metals having largely unrefined ferrite with aligned second phase root
microstructures (low R, high A), tended to give preferential weld metal corrosion.
Refined weld metals with less alignedsecond phase (high R, low A) tended to have
similar corrosion rates to the parent steel, except where a compositional effect, in
particular nickel addition, had an overriding detrimental influence, in particular in the low
chloridesolution.

Further correlations were developed, relating the peak corrosion rate of the weld metal
in each sample to the root weld metal hardness and grain size. Figures 10-13 show
plots of these correlations. The plots show a modest trend of increasing corrosion rate
with increasing hardness and increasing grain size for weld metal without significant
alloying additions, consistent with the visual microstructure assessments. Once again,
the addition of Ni, and to a lesser extent Si, tends to give higher corrosion rate for a
given hardness level or grain size in the low chloride tests. The effects of Cr and
Mowere small but not consistently beneficial or detrimental. Figure 14 shows an
example of a weld metal microstructure that promotes PWC where there is no over-
riding composition effect.

Fig.10. Variation of peak weld metal corrosion rate with mean Vickers hardness,
low chloride solution test
Fig.11. Variation of peak weld metal corrosion rate with mean Vickers hardness,
high chloride solution test

Fig.12. Variation of peak weld metal corrosion rate with grain size, low chloride
solution test
 Fig.13. Variation of peak weld metal corrosion rate with grain size, high chloride
solution test

Fig.14. Unalloyed weld metal with a fairly coarse prior austenite grain size and a
high level of aligned second phase. Weld was deposited in X52 pipe with the TIG
process and an ER70S-6 wire, W21. The microstructure promotes PWC but the
composition does not

In some cases preferential HAZ corrosion increased with increasing HAZ hardness,
consistent with the weld metal data. This suggests that pipe with low carbon equivalent
therefore might be preferred. However, the trend was not observed consistently. This
probably reflects interaction with the weld metal, i.e. preferential attack of weld metal
may tend to discourage preferential HAZ attack and vice versa.

Conclusions
A strong link between preferential weld metal corrosion and composition was found,
particularly in a low chloride solution, although preferential weld metal corrosion cannot
be prevented solely by the use of an alternative weld metal composition selected from
those studied. Greatest resistance to preferential weld metal corrosion was obtained for
autogenous root deposits or for welds deposited using consumables without significant
alloying addition. Addition of 1% nickel was detrimental, as was 1% silicon. Addition of
0.5% molybdenum or 0.6-0.7% chromium to the weld metal had no consistent beneficial
effect with respect to preferential weld metal corrosion.

Preferential weld metal corrosion increased with increasing hardness, increasing grain
size, an increasing level of aligned second phase and a decreasing level of
microstructure refinement of the root by the subsequent passes.

Preferential HAZ corrosion occurred during test when film formation occurred on weld
metal preferentially. Some evidence suggested that high HAZ hardness might
encourage preferential HAZ corrosion but this was not conclusive.

Welds made by TIG and MMA processes were compared but this was primarily to
achieve different weld metal compositions rather than to allow a direct comparison of
the welding processes. No distinct difference between the performance of welds made
by the two processes, with respect to preferential weld corrosion, was found.

Acknowledgement
This work was carried out in the Joint Industry Project 'Risk of Preferential Weldment
Corrosion of Ferritic Steels in CO 2 -Containing Environments', conducted 2000-2003 by
TWI, CAPCIS, and Institute for Energy Technology (IFE). The project was sponsored by
BP, ENI SpA, Health & Safety Executive (UK), Petrobras, Saudi Aramco, Shell UK Ltd,
and Total Fina Elf.

References
1. 'Preferential Corrosion of Carbon Steel Weldments in Oil and Gas Production
Systems', Joint Industry Project, CAPCIS/TWI, 1989.