Werkstoffe und Korrosion 39, 135-142 (1988)
References
[l] B. F. Brown: Corrosion 26 (1970) 249.
[2] C. T. Fuji: “Localized Corrosion”, p. 144, NACE, Houston,
Texas (1974).
[3] 1. L. RosenfeZd, I. K. Murshukov: Corrosion 20 (1964) 11%.
Effect of delta ferrite content on the corrosion
resistance of type 316 clad metals
EinfluB des Deltaferritgehalts auf die Korrosionsbestandigkeitvon mit Stahl316
plattierten Metallen
Austenitic claddings of type 316 were obtained by SMAW (Shielded
Metal Arc Welding) and SAW (Submerged Arc Welding) processes,
using type 316L electrodes on low carbon boiler steel (SA 515 Gr60)
with type 309L as a barrier layer deposited by the SAW process.
Welding heat input was changed in order to obtain different ferrite
contents in the cladding. The clad samples were post-weld heat treated
at 650°C for 50 and 200 h. The top layer of the cladding was removed
and the specimens were then subjected to intergranular corrosion tests
(ASTM A-262-75, practices A, B, C and E, viz. 10% oxalic acid
electrolytic etch; ferric sulfate - 50% sulfuric acid; 65% nitric acid and
copper-copper sulfate - 16% sulfuric acid tests) and controlled poten-
tial etching test.
The study indicated that the ferrite content of the cladding
decreases with increasing current. Ferrite transformed after PWHT
(post weld heat treatment) was relatively more in claddings obtained
with low heat input and containing high ferrite content in the as-clad
condition. PWHT led to brittle fracture of high ferrite claddings
(above 10 FN).
The corrosion attack of ferrite was found to depend on environ-
ment. 65% nitric acid attacked ferrite preferentially, whereas in acid-
ferric sulfate, ferrite was intact and austenite was attacked. No sample
exhibited susceptibility to intergranular corrosion in the as-clad or
PWHT conditions in the copper-copper sulfate - 16% acid test. How-
ever, PWHT specimens with low ferrite contents (3.55 FN) exhibited
grain boundary precipitation at the interface of two adjacent layers. In
general, ferrite was found to be beneficial in controlling corrosion
rates of clad metals after PWHT. Heat input, within the range studied,
did not affect the corrosion rates significantly.
* Department of Metallurgical Engineering, Indian Institute of
Technology, Madras - 600036 India.
** Bharat Heavy Plate and Vessels, Visakhapatnam - 530012, India.
0 VCH VerlagsgesellschaftmbH, D-6940 Weinheim, 1988
Effect of delta ferrite content 135
[4] F. P. Zjsseling: Br. Corr. J. 25 (1980) 51.
[5] D. W.Siituri, R. C. AZkire: J. Elchem. SOC.229 (1982) 481.
[6] K . Hebert, R. C. ANcire: J. Elchem. SOC.230 (1983) 1001.
[7] T. Hagyurd, J. R. Sunthiapillui: J. appl. Chem. 9 (1959) 323.
(Received: 27.07.1987) W 2533
K. Prasad Rao*, A. Uma Maheshwar Rao**
and G. J. Gururaja**
Austenitische Plattierungen mit Stah1316 wurden durch Schutzgas-
Metall-LichtbogenschweiRenund UnterpulverschweiRen mit Elektro-
den aus 316 L auf niedrig gekohltem Kesselblech (SA 515 Gr 60) her-
gestellt, wobei Stahl309 L als Sperrschicht mittels Unterpulverschwei-
Den aufgebracht wurde. Der Warmeeintrag beim SchweiRen wurde
variiert, um in der Plattierung unterschiedliche Ferritgehalte einzu-
stellen. Die plattierten Proben wurden nach dem SchweiBen warme-
behandelt (650°C, 50 und 200 h). Die oberste Plattierungsschicht
wurde abgetragen und die Proben anschlieBend auf Anfiilligkeit fiir
interkristalline Korrosion untersucht (ASTM A-262-75, A, B, C und
E, d.h. 10% Oxalsaure, elektrolytisch, Eisensulfat + 5O%ige Schwe-
felsaure; 65%ige Salpetersaure; KupferKupfersulfat - 16%ige Schwe-
felsaure); aul3erdem wurde auch ein Atzversuch bei kontrolliertem
Potential durchgefiihrt.
Die Untersuchung hat gezeigt, daB der Ferritgehalt der Plattierung
mit zunehmender Stromstarke abnimmt. Der Anteil des umgewandel-
ten Ferrits nach der Warmebehandlung nach dem SchweiRen war in
den Plattierungen mit niedrigem Warmeeintrag und hohem Ferritge-
halt etwas erhoht. Die Warmebehandlungim AnschluR an das Schwei-
Ren fiihrte zum Sprodbruch von Plattierungen mit hohem Ferritgehalt
(> als 10%).
Der Korrosionsangriff des Ferrits ist abhangig vom jeweiligen
Medium: 65%ige Schwefelsaure treibt den Ferrit bevorzugt an, wah-
rend in Eisensulfat-Schwefelsaure der Ferrit intakt bleibt, der Auste-
nit hingegen angegriffen wird. Keine der untersuchten Proben war im
unbehandelten Plattierungszustand oder nach Warmebehandlung
a n f a g fiir interkristalline Korrosion in KupferEupfersulfat - 16%
Schwefelsaure. Proben mit niedrigem Ferritgehalt (3,55%), die nach
dem SchweiRen whnebehandelt wurden, wiesen an der Grenzflache
zwischen zwei benachbarten Schichten Korngrenzenausscheidungen
auf. Im allgemeinen hat sich der Ferrit als giinstig fiir das Korrosions-
verhalten von plattierten Metallen nach Warmebehandlung erwiesen.
Der Warmeeintrag im untersuchten Bereich fiihrte zu keiner wesentli-
chen Beeinflussung der Korrosionsgeschwindigkeit.
1 Introduction
Cladding low carbon steel with austenitic stainless steels by
fusion welding is a most economical and widely used method.
0043-2822/88/030?-0135$02.50/0
136 Prasad Rao, Maheshwar Rao and Gururaja Werkstoffe und Korrosion 39, 135-142 (1988)

Strip cladding is ideal insofar as it improves productivity.
However, in cases when strip is not available or when areas are
to be clad which are not accessible to strip cladding, cladding
by rod electrodes or wire may be used. Invariably, the austeni-
tic surfacing metals contain some amount of delta ferrite
(3 to 10%) in order to control hot cracking. Although clad-
ding has been practiced for many years, only scarce published
information is available on the corrosion behaviour of such
claddings, especially on the role of delta ferrite. The limited
available literature pertains mostly to type 304 and 347 clad
metals.
Published literature indicates that the effect of delta ferrite
on corrosion resistance depends on chemical composition.
Attack of ferrite appears to be associated with the presence of
molybdenum. Preferential attack of delta ferrite is reported
for molybdenum-containing welds [I, 21. Volikova [3] found
molybdenum to cause corrosion in 65% nitric acid, while
Ogawa [4] found molybdenum to have no effect on pitting
corrosion resistance, nitrogen to improve the same and man-
ganese to improve pitting resistance by way of increasing the
stability of nitrogen in the austenitic phase. Savage et al. [5]
found pits to initiate preferentially at delta ferrite-austenite
interfaces. The deleterious effect of ferrite content on the cor-
rosion resistance of type 316 and 316L led to restriction of its
content for urea service to below 2FN [6]. Carruthers [l]sug-
gested post weld annealing as remedial method to overcome
this shortcoming. In contrast, Vander Hust [7] found that fer-
rite contents up to 10% do not influence the corrosion of
austenitic stainless steels in urea synthesis. Viswanathan [8]
found type 316 claddings to exhibit greater stress corrosion
cracking resistance among the welded samples studied, fol-
lowed by type 309 L. Ferrite in type 316 L weld metal is prone
to sigma phase transformation upon PWHT. Not many studies
have been made on the role of sigma phase with respect to the
corrosion behaviour, but Sidarkina [9] found that sigma phase
has no effect on intergranular corrosion.
In view of the lack of data on type 316 claddings, especially
on their general and intergranular corrosion behaviour , an
experimental programme was undertaken to study the effect
of ferrite content and heat input using specimens in the as-clad
and in the PWHT conditions.
2 Experimental
Low carbon boiler steel (SA515 Gr. 60, 200 x 150 x
20 mm) was the base metal.
Electrodes of type 316L were used for depositing 5 mm
thick claddings by Shielded Metal Arc Welding (SMAW) and
Submerged Arc Welding (SAW) processes on a barrier layer
of type 309L (3 mm thick, deposited on carbon steel by the
SAW process). SAW cladding using type 316L was performed
in order to obtain claddings with relatively high heat inputs.
The idea was to find out whether heat input affects the corro-
sion behaviour in boiling acid tests. Table 1 gives the chemical
composition of base and filler metals used.
The welding current was varied in order to vary the ferrite
contents. To obtain 5 mm thick claddings of type 316, several
passes were deposited and only the top layers were considered
for experimental purposes. The welding data are given in

Table 1. Chemical composition of base metal (actual) and filler materials (specified)
TabeUe 1. Chemische Zusammensetzung des Grundwerkstoffs (effektive Werte) und der Zusatzwerkstoffe(Nominalwerte)

S.No. Sample Cr Ni Mo C Mn Si P S

1. base metal SA515 Gr 60 - - - 0.165 1.0 0.25 0.035 0.04

2. SMAW electrode 19.00 12.88 2.70 0.038 1.56 0.25 0.029 0.07
2.5 mm 0, E 316L
3. SMAW electrode 19.40 13.08 2.80 0.038 1.60 0.33 0.024 0.016
3.15 mm 0, E 316L
4. SAW wire electrode 24.0 12.5 - 0.038 1.00 0.65 0.03 0.03
3 mm 0, ER 309L
5. SAW wire electrode 18.86 12.71 2.62 0.035 0.82 0.80 0.030 0.010
3 mm 0 , ER 316L

Table 2. Welding parameters

Tabelle 2. SchweiSparameter

S.No. sample current, voltage welding speed flux heat input* no. of electrode used
Amps V cmlmin (KJ/mm) layers
per pass
1. SMAW 70-80 25 18 - 0.434 5 E 316L, 2.5 mm 0
2. SMAW 110-120 25 18 - 0.671 4 E 316L, 3-.15mm 0
3. SAW 350 30 40 Avesta 801 1.496 3 ER 316L, 3 mm 0
(agglomerated)
4. SAW 450 30 40 Avesta 801 1.924 3 ER 316L, 3 mm 0
(agglomerated)
* Process efficiencies for SMAW and SAW are considered as 0.7 and 0.95 (Ref.: Introduction to physical metallurgy of welding, by Kenneth
Easterling, Butterworths Publication - 1983).
Werkstoffe und Korrosion 39, 135-142 (1988) Effect of delta ferrite content 137

Table 3. Chemical composition of typical clad metals

TabeUe 3. Chemische Zusammensetzung typischer Plattierungswerkstoffe
~ ~~

S.No. sample Cr Ni Mo C Mn Si P S

1. SMAW-HF* 19.00 12.98 2.60 0.053 1.83 0.58 0.026 0.017

2. SMAW-LF* 18.56 12.43 2.40 0.063 1.48 0.57 0.027 0.019
3. SAW-HF 17.55 11.21 1.85 0.042 0.98 0.74 0.030 0.020
4. SAW-LF 17.06 11.30 2.31 0.073 0.98 0.74 0.030 0.020

* HF - high ferrite and LF - low ferrite contents - refer to Table 4 for ferrite contents.

Table 2. Chemical composition of typical claddings (top layer)
is given in Table 3.
The clad plates were postweld heat treated (PWHT) at
650°C k 5°C in a muffle furnace for 50 and 200 h. Ferrite
contents were measured with a “Ferrite Scope” calibrated
against magnegage, and the results were reported in terms of
“Ferrite Numbers” (FN). Table 4 gives the ferrite content of
as-clad and PWHT samples.
Bending samples (100 x 7 x 5 mm) were cut from each
plate and bent. Microstructural studies were made after the
electrolytic etch in 10% oxalic acid to determine ferrite mor-
phology and grain boundary precipitation, if any. Modified
Murakami etching (30 g potassium hydroxide and 30 g potas-
sium ferricyanide in 150 ml of distilled water at 90°C for 15 s)
was used for finding out the eventual formation of sigma
phase. Corrosion tests included ASTM A-262-75 (10) test
practices B, C and E, viz., ferric sulfate-50% sulfuric acid (for
finding out susceptibility to intergranular corrosion). The sam-
ples after test practices B and C of A 262-75 were viewed
under a Scanning Electron Microscope (SEM). Controlled
potential etching was done on selected samples using Wenking
Potentiostat Model 70TS1, in 20% sulfuric acid containing
0.1 g/1 ammonium thiocyanate. The polished samples were
etched at preset potentials by transferring the samples to the
solution after applying the potential. The chosen potentials
were at, above and below the primary passivation potential
(Epp)which corresponds to the “nose” of the anodic polariza-
tion curve.
3 Results
3.1 Chemical composition
also be noticed that carbon pickup increases with increasing
current in each process.
3.2 Ferrite content
Table 4 shows the ferrite contents of the deposited metals:
they are found to decrease with increasing current. Also, fer-
rite contents are decreased, in general, after PWHT. The per-
centage amount of ferrite transformed after PWHT appears to
be a function of both heat input and ferrite content in the as-
clad condition. The trend was more clear after 50 h of PWHT.
The ferrite transformation after PWHT was higher in the met-
als deposited with low heat input and with high ferrite content.
After 200 hours’ PWHT, however, ferrite transformation was
different and not very significant.
3.3 Microstructures
Fig. la-b shows the as-clad samples (SMAW). The ferrite
morphology changes from discontinuous vermicular to con-
tinuous vermicular as the ferrite content increases; this is in
conformity with earlier works [ l l , 121. A similar, but slightly
coarser ferrite morphology was found in SAW claddings.
Fig. 2 shows the microstructures of PWHT specimens; it can
be seen that in these specimens the ferrite regions are attacked
more severely than in the as-clad ones (for ex. Fig. lb).
Fig. 3a-b shows the microstructure of PWHT claddings at
the interface between two subsequent passes. It can be seen

Typical compositions of the clad metals are given in Table 3

for SMAW and SAW processes. Though 3 to 5 layers of metal
were deposited on the type 309 barrier layer, the carbon con-
tent of top layers remain in the range of 0.04 to 0.07%. It can

Table 4. Ferrite content of as-clad and PWHT samples

Tabelle 4. Ferritgehalt im Plattierungszustand und nach Wbnebe-
handlung

S.No. sample mean ferrite content (FN)

PWHT, hrs, at 650°C
as-clad 50 200

1. SMAW-HF 10.68 0.45 (96%)* 0.15 (98.5%)

2. SMAW-LF 3.57 0.25 (93%) 0.15 (96%) Fig. 1. Microstructures of as-clad metals (10% oxalic acid etch),
3. SAW-HF 7.00 1.35 (81%) 0.65 (91.5%) SMAW, 200 X ; a) 3.57 FN, b) 10.68 FN
4. SAW-LF 3.55 1.2 (66%) 0.3 (91%) Abb. 1. Mikrogefiige von Werkstoffen nach dem Plattieren (10%
Oxalsaure), Schutzgas-MetallichtbogenschweiSen,200 x : a) Ferrit-
* Values in brackets indicate % ferrite transformed or dissolved. zahl 337, b) Ferritzahl: 10,68
138 Prasad Rao, Maheshwar Rao and Gururaja Werkstoffe und Korrosion 39, 135-142 (1988)

Table 5. Corrosion rates (mm .y-') in acid-ferric sulfate and 65% nitric acid tests
Tabelle 5. Korrosionsgeschwindigkeit (mm . a-') bei Prufung in Saure-Eisensulfat sowie 65%iger Salpetersaure

S.No. sample acid-ferric sulfate 65% nitric acid

as-clad PWHT at 650 "C, hrs as-clad PWHT at 650"C, hrs
50 200 50 200
~ ~~~

1. SMAW-HF 2.50 28.4 26.3 0.149 47.1 1.85

2. SMAW-LF 2.99 37.2 54.9 1.290 17.8 1.78
3. SAW-HF 1.76 26.1 22.6 0.528 11.6 1.86
4. SAW-LF 4.72 34.5 38.1 2.840 1.2 40.60

that the morphology of ferrite is finer at the interface for the
cladding with high ferrite content (10.68 FN). In contrast, the
low ferrite claddings (3.55 FN) showed ferrite dissolution and
precipitation of grain boundary carbide.
SMAW claddings with high ferrite content (10.68 FW)after
PWHT were found to contain sigma phase when etched with
modified Murakami reagent (Fig. 4), while in other claddings
this phase was not detected; this etching turns the sigma phase
brownish red.

3.4 Bend test

All the clad metals gave a 180" bend in the as-clad condition.
After PWHT, the SMAW cladding with 10.68 FN failed in a
brittle fashion in the bend test, whereas the other samples gave
a satisfactory 180" bend.

3.5 Corrosion tests

Copper-copper sulfate - 16% acid test: Even with considerably

Fig. 2. Microstructure of a post weld heat treated sample (10% oxalic
acid etch), SMAW, 200 X; 10.68 FN, 200 h
Abb. 2. Mikrogefiige einer Plattierung mit Warmebehandlung (10%
Oxalsaure), Schutzgas-Metallichtbogenschweiaen,200 x ; Ferritzahl:
10,68, 200 h
high carbon levels no sample in the as-clad and PWHT condi-
tions showed fissures after the test when examined under
10 X magnification. However, PWHT samples of SMAW con-
taining 10.68 FN failed in a brittle fashion when bent.
Acid-ferric sulfate and 65% nitric acid tests: The corrosion
rates of metal claddings in both these boiling solutions are
reported in Table 5. The corrosion rates are relatively low in
the as-clad condition when compared with PWHT samples.
Among the as-clad samples, it is seen that an increase in ferrite

Fig. 3. Microstructures of post weld heat treated samples (SMAW) at
the interface between two adjacent layers (200 X); a) 10.68 FN, 200 h,
b) 3.55 FN, 50 h
Abb. 3. Mikrogefiige von nach dem Plattieren warmebehandelten
Proben (Schutzgas-MetallichtbogenschweiRen)an der Grenzflache
zwischen zwei benachbarten Schichten (200 x): a) Ferritzahl: 10,68,
200 h, b) Ferritzahl: 3,55, 50 h
Fig. 4. Microstructure of a post weld heat treated sample (SMAW;
modified Murakami etch) (1000 x). 10.68 FW, 200 h. Sigma phase was
observed as brownish red particles
Abb. 4. Mikrogefiige einer nach dem Schweiaen warmebehandelten
Probe (Schutzgas-Metallichtbogenschweiaen), modifizierte Atzung
nach Murakarni, 100 X , Ferritzahl: 10,68, 200 h. Die a-Phase trat in
Form von rotbraunen Teilchen auf
Werkstoffe und Korrosion 39, 135-142 (1988)
Fig. 5. SAW samples (3.55 FN) after acid-femc sulfate test (5 x);
a) as-clad, b) PWHT, 200 h
Abb. 5. UnterpulvergeschweiOte Proben (Ferritzahl: 3,55) nach dem
Saure-Eisensulfattest (5 +); a) unmittelbar nach dem Plattieren, b)
mit Warmebehandlung nach dern Plattieren (200 h)
content does not increase the corrosion rate in either solution
(in fact, there is a slight decrease in corrosion rate with
increasing ferrite content). It can also be seen that corrosion
rates in acid-ferric sulfate are relatively higher than in 65%
nitric acid.
As for the corrosion rates of PWHT specimens the claddings
with high ferrite contents (SMAW clad 10.68 FN, SAW clad
7 FN) show a decrease in corrosion rates with increased dura-
tion of heat treatment. In contrast, the claddings with low
ferrite contents (SMAW clad - 3.57 FN, SAW - 3.55 FN)
exhibit corrosion rates which increase with the duration of
heat treatment.
Fig. 5 shows the SAW claddings with low ferrite content
(3.55 FN) after the acid-ferric sulfate test. In the case of the
PWHT specimen attack at the interface between two adjacent
layers can be seen. Similar attack is observed on SMAW clad-
dings (PWHT). No significant interface attack is observed in
the as-clad condition.
3.6 Potentiostatic etching
Fig. 6a shows the microstructure of as-clad SAW metal con-
taining 7 FN, etched at a potential below E,,, where attack on
ferrite is seen clearly. Fig. 6b shows the microstructure of the
Effect of delta ferrite content 139
Fig. 6. Microstructures of SAW samples (7 FN) after controlled
potential etching; a) below E,; b) at E,
Abb. 6. Mikrogefiige von unterpulvergeschweilten Proben (Ferrit-
zahl 7) nach k z e n bei kontrolliertem Potential: a) unter E, und b)
bei Epp
same specimen etched at E,, where ferrite is passivated. The
austenitic matrix and the interface between austenite and fer-
rite are attacked. SAW claddings containing 7 FN (PWHT),
etched above E,,, showed that ferrite is passivated while
austenite is attacked severely with slight attack at the auste-
nitelferrite boundary.
3.7 SEM-results
Fig. 7 shows the as-clad metal (SMAW, 10.68 FN) after the
nitric acid test; attack of ferrite is visible. Austenite is found to
be intact, except for some attack at points which are probably
inclusion sites. Fig. 8 shows the as-clad metal (SMAW,
10.68 FN) after the acid ferric sulfate test. The ferrite network
is intact whereas austenite is attacked, though not as signifi-
cantly.
Fig. 9 shows the attack of SMWA specimens (3.55 FN) after
the acid-ferric sulfate test; only some ferrite zones are at-
tacked.
Fig. 10 shows the PWHT sample (SAW, 3.55 FN) after the
acid-ferric sulfate test at the interface between two adjacent
passes. Intergranular corrosion is confined to ferrite-free
areas. Similar intergranular attack at the interface is found in
samples after the 65% nitric acid test, Fig. 11.
140 Prasad Rao, Maheshwar Rao and Gururaja
Fig. 7. SMAW, as-clad, 10.68 FN after 65% nitric acid test
Abb. 7. Schutzgas-MetallichtbogenschweiBen (Zustand nach dem
Plattieren), Ferritzahl 10,68, nach Priifung in 65%iger Salpetersaure
Fig. 8. SMAW, as-clad, 10.68 FN after acid-ferric sulfate test
Abb. 8. Schutzgas-MetaIlichtbogenschweil3en (Zustand nach dem
Plattieren), Ferritzahl 10,68, nach Priifung in Saure-Eisensulfat
Fig. 9. SMAW, 3.55 FN, PWHT, 50 h, after acid-ferric sulfate test
Abb. 9. Schutzgas-MetallichtbogenschweiSen, Ferritzahl 3,55, War-
mebehandlung nach dem SchweiBen, nach Priifung in Saure-Eisen-
sulfat
Werkstoffe und Korrosion 39, 135-142 (1988)
Fig. 10. SAW clad, 3.55 FN, PWHT, 200 h, after acid-ferric sulfate
interface between two layers
Abb. 10- UnteV~ve@attieru% Ferritzahl 3,559 warmebehandelt
nach dem SchweiBen. 200 h. nach Priifung in Saure-Eisensulfat
(Grenzflache zwischen'zwei benachbarten Schichten)
Fig. 11. Same as Fig. 10, after 65% nitric acid test
Abb. 11. Wie Abb. 10, nach Priifung in 65%iger Salpetersaure
4 Discussion
Although 3 to 5 layers were deposited on a buffer layer of
type 309 steel, the relatively high carbon levels (0.04-0.07%)
in the claddings indicate that one has to be careful about the
dilution when surfacing with rod and wire electrodes, since the
percentage of dilution can be relatively high because of the
higher current densities. This is in contrast to strip cladding
studies [13] where the carbon pickup was 0.04 to 0.06% after
only one layer of type 309 cb strip had been deposited. Carbon
pickup further decreased after the subsequent passes. This can
be due to the relatively low current densities, despite the fact
that current levels used were much higher (500-700 Amps.)
than in the present study. The results indicate that for the
same number of passes, the carbon pickup will be higher with
wire cladding. The decrease in ferrite contents (Table 4) with
the change in current can be attributed to carbon Pickup and
dilution effects. Carbon, being a potent austenite stabilizer,
decreases the ferrite content. The chromium equivalent will
Werkstoffe und Korrosion 39, 135-142 (1988)
generally decrease with increasing dilution which, in turn,
decreases the ferrite content. This is in contrast to the
behaviour of austenitic weld metals [141, where no significant
change was observed in ferrite content when welding parame-
ters and heat input were varied.
The decrease in ferrite content after PWHT can be attri-
buted to ferrite transformation yielding M2& and/or sigma
phase etc. As can be deduced from the results, there appears
to be a relation between percentage transformation, heat input
and ferrite content. The high percentage transformation in the
case of low heat input cladding after certain durations of
PWHT may be due to the fine ferrite morphology. Because
the resulting as-clad ferrite is coarser with high heat input, it
may take more time to get it transformed or dissolved. Of
course, as the PWHT duration increases, these differences in
percentage ferrite transformation are reduced. These results
are similar to those reported for Submerged Arc bead-on-plate
weld metals [15].
The microstructures at the interface between adjacent clad-
ding layers are different from those of the core of the cladding.
In the as-clad condition the ferrite morphology is finer in the
preceeding layer. It is interesting, however, that the low ferrite
cladding after PWHT exhibits grain boundary precipitation;
this structure is an indication of susceptibility to intergranular
corrosion. This is in agreement with the findings in the cor-
roded samples (Fig. 5), where the interface is preferentially
attacked. This attack can be attributed to the high carbon
levels of these clad metals (0.06-0.07%). The microstructures
further show that these zones are ferrite-free or have rather
low ferrite contents. In the as-clad condition, the low ferrite
contents (3.55 FN) may have been further reduced by the
heat-effect during the deposition of the subsequent layer; as
the temperatures in the existing layers can reach 1100 to
1200"C, ferrite will go into solution [16].
These areas with relatively low ferrite contents after PWHT
exhibit considerable grain boundary precipitation. The etching
in modified Murakami solution indicates that delta ferrite to
sigma transformation is greatly influenced by the ferrite con-
tent. The absence of sigma phase in low ferrite cladding and its
presence in SMAW claddings (10.68 FN) supports the above
observation.
Bend test results also indicate that brittle failure will result
when the cladding with high ferrite contents (above 10 FN) is
post-weld-heat-treated. This embrittlement in SMAW clad
(10.68FN) can be attributed to sigma phase which was
detected metallographically.
Corrosion tests to ascertain susceptibility to intergranular
corrosion did not produce macroscale cracking (10 x magnifi-
cation). However, as reported earlier, grain boundary precipi-
tation confined to 4 or 5 grains were noticed in PWHT samples
with low ferrite contents.This type of precipitation, which
caused preferential attack at the interface in the acid-ferric
sulfate test, did not give rise to cracking in the copper-copper
sulfate-acidtest. Interestingly, it was not possible to assess the
susceptibility to intergranular corrosion of the P W T -
SMAW-cladding containing 10.68 FN: The sample broke into
two pieces at very small bending angles. However, microstruc-
tural observations did not reveal any grain boundary precipita-
tion in these samples.
The corrosion rates (for PWHT samples) in both the acid-
ferric sulfate and the 65% nitric acid indicated the beneficial
role of ferrite as for intergranular corrosion is concerned. The
corrosion rates decreased with increased duration of heat
treatment in the case of high ferrite claddings, whereas they
Effect of delta ferrite content 141
increased with the duration of PWHT in the case of low ferrite
samples.
The corrosion rates of PWHT samples, in general, are rela-
tively high compared with those observed for metal claddings
studied earlier [17]. This can be attributed to interface attack.
Wire cladding results in interface areas between two adjacent
layers larger than with strip cladding. Therefore, the corrosion
rates are also higher in the present case.
As far as the effect of ferrite on uniform corrosion (as-clad)
is concerned, the corrosion rates indicate no harmful effects.
In fact, it is beneficial, though not significantly. The corrosion
rates either remain the same or decrease with increasing ferrite
content. The SEM micrographs indicate that preferential
attack of ferrite depends on the environment. For example,
ferrite is attacked only in 65% nitric acid, not, however, in
acid-ferric sulfate where austenite is preferentially attacked.
Potentiostatic etching confirms the above finding (the poten-
tial fluctuations in the potentiostatic tests simulate different
environmental conditions). Similar results were obtained on
type 304 and 347 metal cladding [17,18]. Therefore, the attack
of ferrite in austenitic cladding or weld metals is rather a func-
tion of environment and not of composition. This is in contrast
to the published information [l-31 according to which ferrite is
attacked in molybdenum-containing weldments.
The results also indicate that the heat-input within the range
studied does not affect either general or intergranular corro-
sion rates in the boiling acid solutions. However, heat-input
may have a significant effect on corrosion behaviour under
certain environmental conditions [181. Incidentally, as already
discussed, heat-input affects the percentage ferrite transforma-
tion.
5 Conclusions
1. Cladding with rod or wire electrodes results in relatively
high carbon contents compared to strip cladding with the
same number of passes.
2. Ferrite content in clad metals can be controlled by changing
welding parameters. It decreases with increasing current.
3. Ferrite transformed or dissolved after PWHT is a function
of heat-input and ferrite content. It is higher for cladding
deposited with low heat input and having high ferrite con-
tents in the as-clad condition.
4. PWHT leads to sigma phase transformation in clad metals
with high ferrite content (10.68 FN) which results in brittle
fracture in the bend test.
5. Attack of ferrite depends on environment: In 65% nitric
acid, ferrite is preferentially attacked while in acid-ferric
sulfate solution, ferrite is not attacked while austenite is.
6. Although no sample exhibited susceptibility to intergranu-
lar corrosion in the copper-copper sulfate-16% acid test,
microstructural examination revealed grain boundary car-
bide precipitation at the interface for PWHT samples with
low ferrite contents (3.55 FN). The acid-ferric sulfate test
produces preferential attack at the same site.
7. Ferrite is beneficial in controlling corrosion rates of clad
metals after PWHT.
8. Heat input, within the range studied, does not affect the
corrosion rates significantly.
References
[l] M . E. Carruthers: "Weld corrosion in type 316 and 316 L stainless
steel and related problems"; Weld. J . 38 (1954)259-267.
142 Ergebnisse des Forschungs- und Entwicklungsprogramms
[2] H. C. Campbell: “Identifying corrosion and welding failures in
stainless-steels”; Mater. Prot. 44 (1963) 39-42.
[3] Volikova et al.: Svar. Prot. V (1970) 11-13.
[4] T. Ogawa, K. Murata, S. Aoki, E. T. Suchetomi: “Effect of
molybdenum and nitrogen on chloride pitting corrosion in
austenitic stainless steel weldments”, J. Jpn. Weld. SOC.48
(1980) 564-571 (in Japanese).
[5] W. F. Savage, Dequatte: “Localised corrosion and scc behaviour
of austenitic stainless steel weldments containing retained fer-
rite”, Rennselaer Polytechnic Institute, U.S.A., 100-2462-6,
March 1980, 9 (E).
[6] M . Vyklickj, 0. Brenner, H . Hamour: “Comparison of the cor-
rosion resistance of austenitic stainless steels in urea”, Neue
Hutte 24 (1979) 271-274.
[7] .I M.A . Vander Hast: “The influence of ferrite content on corro-
. cal Meeting - 40, Indian Institute of Metals, November 12-18,
sion resistance of austenitic stainless steel in urea synthesis”,
Metallography 3 (1970) 433-440.
[8] R. Viswanathan, J. I . Nuruinen, R. G . Aspden: “Stress corrosion
behaviour of stainless steel welds in high temperature water con-
taining chlorides”, Weld. J. 58 (1979) 118-126.
[9] Y. S. Sidarkina et al.: “An investigation of sigma-phaseon corro-
sion resistance of stainless steel alloys”, Zashch. Met. 16 (1980)
589-594.
[lo] ASTM Designation A262-75,1976 of ASTM Standards - Ameri-
can Society for Testing Materials, Philadelphia, Pennsylvania,
USA.
[Ill T. Takalo, N. Suntala, T. Moisio: “The relationship between
solidification and microstructure in austenitic and austenitic-fer-
ritic stainless steel welds”, Metall. Trans. A 1OA (1979) 512-514.
Ergebnisse des Forschungs- und Entwicklungs-
programms ,,Korrosion und Korrosionsschutz“
Die in den Kurzfassungen verwendeten Abkurzungen haben folgende Bedeutung:
ASt = Antragsteller
FE-St = Forschungsstelle
FL = Forschungsleiter
(siehe auch Vorbemerkung in Heft 511979)
Projekt Nr. A 1.1/2 A und B
Untersuchungeniiber die Korrosionsgefahrdungvon
Hochdruckleitungenfur wasserstoffhaltige Synthesegase
und ihre Inhibition durch Luftsauerstoff
ASt: A) BAYER AG, B) Mannesmann
5090 Leverkusen Forschungsinstitut,
4100 Duisburg 25
FE-St: IN-ATU WT Mannesmann
Forschungsinstitut
FL: Prof. Dr. H. Grafen Prof. Dr. W. Schwenk
Laufzeit: 01. 07. 1983 bis 30. 06. 1987
1 Einleitung
In mehreren westlichen Erdgas-Exportlandern werden Uberlegun-
gen angestellt, zur Streckung der Ressourcen Erdgas mit Synthese-
gasen, z. B. aus der Kohlevergasung, zu verschneiden.
Werkstoffe und Korrosion 39,142-145 (1988)
[12] J. C. Lippold, W. F. Savage: “Solidificationof austenitic stainless
steel weldments, Part 2. The effect of alloy composition on fer-
rite morphology”, Weld. J. 59 (1980) 48-58.
[13] K . Prasad Rao, P. K . Ramesh: “SAW strip cladding - A study on
the effects of fluxes and process parameters”, to be published in
Schweissen, Schneiden, Praktiker , DVS, Dusseldorf, W.-Ger-
many.
[14] K . Prasad Rao, K . N. Krishnan, V . Rama Rao, G . J . Gururaja:
“Effect of welding parameters on ferrite content”, Proceedings
of National Welding Seminar ’86, October 16-18, 1986, Indian
Institute of Welding, Madras, India.
[15] K. Prasad Rao, V . Sivakumar: “Effects of heat input and post
weld heat treatment on ferrite content and transformation, and
corrosion behaviour of type 316 L weld metal”, Annual Techni-
1986, Bombay, India.
[16] N. C. Cole, G . M . Goodwin, C.M . Slaughter: “Effect of heat
treatment on the microstructure of stainless steel weld metal”,
Microstructural Science, Vol. 3, American Elsevier Publication
Comp. (1975) 789.
I171 K. Prasad Rao, S. Prasannakumar: “Corrosion behaviour of
austenitic weld and clad metals in accelerated boiling acid tests
simulating passive conditions”, Corrosion 42 (1986) 1-10,
[181 K. Prasad Rao, S. Prasannakumar: “Electrochemicalstudies on
corrosion behaviour of austenitic stainless steel weld and clad
metals” Corrosion 41 (1985) 234-242.
(Revised version received: 26.8. 1987) W 2536
Die Korrosionsgefahrdungvon Ferngastransportleitungendurch die
0.g. Medien kann aufgrund bestehender Erkenntnisse in der Literatur
wie folgt beschrieben werden:
- bei Feuchtgasen, die CO und C 0 2 enthalten, kann transkristalline
SpannungsriBkorrosion auftreten,
- vorzugsweise bei trockenen Gasen, die Wasserstoff enthalten, kann
bei kritischer mechanischer Beanspruchung H-induzierte transkri-
stalline SpannungsriBkorrosion oder Wasserstoffversprodung auf-
treten.
Mit Hilfe der nachstehend beschriebenen Untersuchungen sollten
Grenzwerte fiir die Gefahrdung der Hochdruck-Stahlrohrleitungen
durch wasserstoffinduzierte SpannungsriBkorrosion bestimmt und
Moglichkeiten des Korrosionsschutzes durch Inhibition aufgezeigt
werden.
Die Untersuchungen waren auch aus dem Grund relevant, weil die
bestehende Erdgas-Import-Abhangigkeitdurch Synthesegaszustande
in einem gewissen Umfang vermindert werden kann. Daruber hinaus
sind die Untersuchungen auch geeignet, wichtige Grundlagen fur eine
spatere Wasserstoff-Technologie zu schaffen.