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Werkstoffe und Korrosion 39, 135-142 (1988) Effect of delta ferrite content 135

References [4] F. P. Zjsseling: Br. Corr. J. 25 (1980) 51.


[5] D. W.Siituri, R. C. AZkire: J. Elchem. SOC.229 (1982) 481.
[l] B. F. Brown: Corrosion 26 (1970) 249. [6] K . Hebert, R. C. ANcire: J. Elchem. SOC.230 (1983) 1001.
[2] C. T. Fuji: “Localized Corrosion”, p. 144, NACE, Houston, [7] T. Hagyurd, J. R. Sunthiapillui: J. appl. Chem. 9 (1959) 323.
Texas (1974).
[3] 1. L. RosenfeZd, I. K. Murshukov: Corrosion 20 (1964) 11%. (Received: 27.07.1987) W 2533

Effect of delta ferrite content on the corrosion


resistance of type 316 clad metals
EinfluB des Deltaferritgehalts auf die Korrosionsbestandigkeitvon mit Stahl316
plattierten Metallen
K. Prasad Rao*, A. Uma Maheshwar Rao**
and G. J. Gururaja**

Austenitic claddings of type 316 were obtained by SMAW (Shielded Austenitische Plattierungen mit Stah1316 wurden durch Schutzgas-
Metal Arc Welding) and SAW (Submerged Arc Welding) processes, Metall-LichtbogenschweiRenund UnterpulverschweiRen mit Elektro-
using type 316L electrodes on low carbon boiler steel (SA 515 Gr60) den aus 316 L auf niedrig gekohltem Kesselblech (SA 515 Gr 60) her-
with type 309L as a barrier layer deposited by the SAW process. gestellt, wobei Stahl309 L als Sperrschicht mittels Unterpulverschwei-
Welding heat input was changed in order to obtain different ferrite Den aufgebracht wurde. Der Warmeeintrag beim SchweiRen wurde
contents in the cladding. The clad samples were post-weld heat treated variiert, um in der Plattierung unterschiedliche Ferritgehalte einzu-
at 650°C for 50 and 200 h. The top layer of the cladding was removed stellen. Die plattierten Proben wurden nach dem SchweiBen warme-
and the specimens were then subjected to intergranular corrosion tests behandelt (650°C, 50 und 200 h). Die oberste Plattierungsschicht
(ASTM A-262-75, practices A, B, C and E, viz. 10% oxalic acid wurde abgetragen und die Proben anschlieBend auf Anfiilligkeit fiir
electrolytic etch; ferric sulfate - 50% sulfuric acid; 65% nitric acid and interkristalline Korrosion untersucht (ASTM A-262-75, A, B, C und
copper-copper sulfate - 16% sulfuric acid tests) and controlled poten- E, d.h. 10% Oxalsaure, elektrolytisch, Eisensulfat + 5O%ige Schwe-
tial etching test. felsaure; 65%ige Salpetersaure; KupferKupfersulfat - 16%ige Schwe-
The study indicated that the ferrite content of the cladding felsaure); aul3erdem wurde auch ein Atzversuch bei kontrolliertem
decreases with increasing current. Ferrite transformed after PWHT Potential durchgefiihrt.
(post weld heat treatment) was relatively more in claddings obtained Die Untersuchung hat gezeigt, daB der Ferritgehalt der Plattierung
with low heat input and containing high ferrite content in the as-clad mit zunehmender Stromstarke abnimmt. Der Anteil des umgewandel-
condition. PWHT led to brittle fracture of high ferrite claddings ten Ferrits nach der Warmebehandlung nach dem SchweiRen war in
(above 10 FN). den Plattierungen mit niedrigem Warmeeintrag und hohem Ferritge-
The corrosion attack of ferrite was found to depend on environ- halt etwas erhoht. Die Warmebehandlungim AnschluR an das Schwei-
ment. 65% nitric acid attacked ferrite preferentially, whereas in acid- Ren fiihrte zum Sprodbruch von Plattierungen mit hohem Ferritgehalt
ferric sulfate, ferrite was intact and austenite was attacked. No sample (> als 10%).
exhibited susceptibility to intergranular corrosion in the as-clad or Der Korrosionsangriff des Ferrits ist abhangig vom jeweiligen
PWHT conditions in the copper-copper sulfate - 16% acid test. How- Medium: 65%ige Schwefelsaure treibt den Ferrit bevorzugt an, wah-
ever, PWHT specimens with low ferrite contents (3.55 FN) exhibited rend in Eisensulfat-Schwefelsaure der Ferrit intakt bleibt, der Auste-
grain boundary precipitation at the interface of two adjacent layers. In nit hingegen angegriffen wird. Keine der untersuchten Proben war im
general, ferrite was found to be beneficial in controlling corrosion unbehandelten Plattierungszustand oder nach Warmebehandlung
rates of clad metals after PWHT. Heat input, within the range studied, a n f a g fiir interkristalline Korrosion in KupferEupfersulfat - 16%
did not affect the corrosion rates significantly. 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
* Department of Metallurgical Engineering, Indian Institute of
Technology, Madras - 600036 India. Cladding low carbon steel with austenitic stainless steels by
** Bharat Heavy Plate and Vessels, Visakhapatnam - 530012, India. fusion welding is a most economical and widely used method.

0 VCH VerlagsgesellschaftmbH, D-6940 Weinheim, 1988 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. cracking resistance among the welded samples studied, fol-
However, in cases when strip is not available or when areas are lowed by type 309 L. Ferrite in type 316 L weld metal is prone
to be clad which are not accessible to strip cladding, cladding to sigma phase transformation upon PWHT. Not many studies
by rod electrodes or wire may be used. Invariably, the austeni- have been made on the role of sigma phase with respect to the
tic surfacing metals contain some amount of delta ferrite corrosion behaviour, but Sidarkina [9] found that sigma phase
(3 to 10%) in order to control hot cracking. Although clad- has no effect on intergranular corrosion.
ding has been practiced for many years, only scarce published In view of the lack of data on type 316 claddings, especially
information is available on the corrosion behaviour of such on their general and intergranular corrosion behaviour , an
claddings, especially on the role of delta ferrite. The limited experimental programme was undertaken to study the effect
available literature pertains mostly to type 304 and 347 clad of ferrite content and heat input using specimens in the as-clad
metals. and in the PWHT conditions.
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 2 Experimental
molybdenum. Preferential attack of delta ferrite is reported
for molybdenum-containing welds [I, 21. Volikova [3] found Low carbon boiler steel (SA515 Gr. 60, 200 x 150 x
molybdenum to cause corrosion in 65% nitric acid, while 20 mm) was the base metal.
Ogawa [4] found molybdenum to have no effect on pitting Electrodes of type 316L were used for depositing 5 mm
corrosion resistance, nitrogen to improve the same and man- thick claddings by Shielded Metal Arc Welding (SMAW) and
ganese to improve pitting resistance by way of increasing the Submerged Arc Welding (SAW) processes on a barrier layer
stability of nitrogen in the austenitic phase. Savage et al. [5] of type 309L (3 mm thick, deposited on carbon steel by the
found pits to initiate preferentially at delta ferrite-austenite SAW process). SAW cladding using type 316L was performed
interfaces. The deleterious effect of ferrite content on the cor- in order to obtain claddings with relatively high heat inputs.
rosion resistance of type 316 and 316L led to restriction of its The idea was to find out whether heat input affects the corro-
content for urea service to below 2FN [6]. Carruthers [l]sug- sion behaviour in boiling acid tests. Table 1 gives the chemical
gested post weld annealing as remedial method to overcome composition of base and filler metals used.
this shortcoming. In contrast, Vander Hust [7] found that fer- The welding current was varied in order to vary the ferrite
rite contents up to 10% do not influence the corrosion of contents. To obtain 5 mm thick claddings of type 316, several
austenitic stainless steels in urea synthesis. Viswanathan [8] passes were deposited and only the top layers were considered
found type 316 claddings to exhibit greater stress corrosion 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) also be noticed that carbon pickup increases with increasing
is given in Table 3. current in each process.
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 3.2 Ferrite content
against magnegage, and the results were reported in terms of
“Ferrite Numbers” (FN). Table 4 gives the ferrite content of Table 4 shows the ferrite contents of the deposited metals:
as-clad and PWHT samples. they are found to decrease with increasing current. Also, fer-
Bending samples (100 x 7 x 5 mm) were cut from each rite contents are decreased, in general, after PWHT. The per-
plate and bent. Microstructural studies were made after the centage amount of ferrite transformed after PWHT appears to
electrolytic etch in 10% oxalic acid to determine ferrite mor- be a function of both heat input and ferrite content in the as-
phology and grain boundary precipitation, if any. Modified clad condition. The trend was more clear after 50 h of PWHT.
Murakami etching (30 g potassium hydroxide and 30 g potas- The ferrite transformation after PWHT was higher in the met-
sium ferricyanide in 150 ml of distilled water at 90°C for 15 s) als deposited with low heat input and with high ferrite content.
was used for finding out the eventual formation of sigma After 200 hours’ PWHT, however, ferrite transformation was
phase. Corrosion tests included ASTM A-262-75 (10) test different and not very significant.
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 3.3 Microstructures
under a Scanning Electron Microscope (SEM). Controlled
potential etching was done on selected samples using Wenking Fig. la-b shows the as-clad samples (SMAW). The ferrite
Potentiostat Model 70TS1, in 20% sulfuric acid containing morphology changes from discontinuous vermicular to con-
0.1 g/1 ammonium thiocyanate. The polished samples were tinuous vermicular as the ferrite content increases; this is in
etched at preset potentials by transferring the samples to the conformity with earlier works [ l l , 121. A similar, but slightly
solution after applying the potential. The chosen potentials coarser ferrite morphology was found in SAW claddings.
were at, above and below the primary passivation potential Fig. 2 shows the microstructures of PWHT specimens; it can
(Epp)which corresponds to the “nose” of the anodic polariza- be seen that in these specimens the ferrite regions are attacked
tion curve. 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
3 Results
3.1 Chemical composition

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 SMAW claddings with high ferrite content (10.68 FW)after
cladding with high ferrite content (10.68 FN). In contrast, the PWHT were found to contain sigma phase when etched with
low ferrite claddings (3.55 FN) showed ferrite dissolution and modified Murakami reagent (Fig. 4), while in other claddings
precipitation of grain boundary carbide. 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


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
Fig. 2. Microstructure of a post weld heat treated sample (10% oxalic rates of metal claddings in both these boiling solutions are
acid etch), SMAW, 200 X; 10.68 FN, 200 h reported in Table 5. The corrosion rates are relatively low in
Abb. 2. Mikrogefiige einer Plattierung mit Warmebehandlung (10% the as-clad condition when compared with PWHT samples.
Oxalsaure), Schutzgas-Metallichtbogenschweiaen,200 x ; Ferritzahl: Among the as-clad samples, it is seen that an increase in ferrite
10,68, 200 h

Fig. 3. Microstructures of post weld heat treated samples (SMAW) at Fig. 4. Microstructure of a post weld heat treated sample (SMAW;
the interface between two adjacent layers (200 X); a) 10.68 FN, 200 h, modified Murakami etch) (1000 x). 10.68 FW, 200 h. Sigma phase was
b) 3.55 FN, 50 h observed as brownish red particles
Abb. 3. Mikrogefiige von nach dem Plattieren warmebehandelten Abb. 4. Mikrogefiige einer nach dem Schweiaen warmebehandelten
Proben (Schutzgas-MetallichtbogenschweiRen)an der Grenzflache Probe (Schutzgas-Metallichtbogenschweiaen), modifizierte Atzung
zwischen zwei benachbarten Schichten (200 x): a) Ferritzahl: 10,68, nach Murakarni, 100 X , Ferritzahl: 10,68, 200 h. Die a-Phase trat in
200 h, b) Ferritzahl: 3,55, 50 h Form von rotbraunen Teilchen auf
Werkstoffe und Korrosion 39, 135-142 (1988) Effect of delta ferrite content 139

Fig. 5. SAW samples (3.55 FN) after acid-femc sulfate test (5 x); Fig. 6. Microstructures of SAW samples (7 FN) after controlled
a) as-clad, b) PWHT, 200 h potential etching; a) below E,; b) at E,
Abb. 5. UnterpulvergeschweiOte Proben (Ferritzahl: 3,55) nach dem Abb. 6. Mikrogefiige von unterpulvergeschweilten Proben (Ferrit-
Saure-Eisensulfattest (5 +); a) unmittelbar nach dem Plattieren, b) zahl 7) nach k z e n bei kontrolliertem Potential: a) unter E, und b)
mit Warmebehandlung nach dern Plattieren (200 h) bei Epp

content does not increase the corrosion rate in either solution same specimen etched at E,, where ferrite is passivated. The
(in fact, there is a slight decrease in corrosion rate with austenitic matrix and the interface between austenite and fer-
increasing ferrite content). It can also be seen that corrosion rite are attacked. SAW claddings containing 7 FN (PWHT),
rates in acid-ferric sulfate are relatively higher than in 65% etched above E,,, showed that ferrite is passivated while
nitric acid. austenite is attacked severely with slight attack at the auste-
As for the corrosion rates of PWHT specimens the claddings nitelferrite boundary.
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 3.7 SEM-results
ferrite contents (SMAW clad - 3.57 FN, SAW - 3.55 FN)
exhibit corrosion rates which increase with the duration of Fig. 7 shows the as-clad metal (SMAW, 10.68 FN) after the
heat treatment. nitric acid test; attack of ferrite is visible. Austenite is found to
Fig. 5 shows the SAW claddings with low ferrite content be intact, except for some attack at points which are probably
(3.55 FN) after the acid-ferric sulfate test. In the case of the inclusion sites. Fig. 8 shows the as-clad metal (SMAW,
PWHT specimen attack at the interface between two adjacent 10.68 FN) after the acid ferric sulfate test. The ferrite network
layers can be seen. Similar attack is observed on SMAW clad- is intact whereas austenite is attacked, though not as signifi-
dings (PWHT). No significant interface attack is observed in cantly.
the as-clad condition. Fig. 9 shows the attack of SMWA specimens (3.55 FN) after
the acid-ferric sulfate test; only some ferrite zones are at-
tacked.
3.6 Potentiostatic etching Fig. 10 shows the PWHT sample (SAW, 3.55 FN) after the
acid-ferric sulfate test at the interface between two adjacent
Fig. 6a shows the microstructure of as-clad SAW metal con- passes. Intergranular corrosion is confined to ferrite-free
taining 7 FN, etched at a potential below E,,, where attack on areas. Similar intergranular attack at the interface is found in
ferrite is seen clearly. Fig. 6b shows the microstructure of the samples after the 65% nitric acid test, Fig. 11.
140 Prasad Rao, Maheshwar Rao and Gururaja Werkstoffe und Korrosion 39, 135-142 (1988)

Fig. 7. SMAW, as-clad, 10.68 FN after 65% nitric acid test Fig. 10. SAW clad, 3.55 FN, PWHT, 200 h, after acid-ferric sulfate
Abb. 7. Schutzgas-MetallichtbogenschweiBen (Zustand nach dem interface between two layers
Plattieren), Ferritzahl 10,68, nach Priifung in 65%iger Salpetersaure 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. 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. 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
Fig. 9. SMAW, 3.55 FN, PWHT, 50 h, after acid-ferric sulfate test wire cladding. The decrease in ferrite contents (Table 4) with
Abb. 9. Schutzgas-MetallichtbogenschweiSen, Ferritzahl 3,55, War- the change in current can be attributed to carbon Pickup and
mebehandlung nach dem SchweiBen, nach Priifung in Saure-Eisen- dilution effects. Carbon, being a potent austenite stabilizer,
sulfat decreases the ferrite content. The chromium equivalent will
Werkstoffe und Korrosion 39, 135-142 (1988) Effect of delta ferrite content 141

generally decrease with increasing dilution which, in turn, increased with the duration of PWHT in the case of low ferrite
decreases the ferrite content. This is in contrast to the samples.
behaviour of austenitic weld metals [141, where no significant The corrosion rates of PWHT samples, in general, are rela-
change was observed in ferrite content when welding parame- tively high compared with those observed for metal claddings
ters and heat input were varied. studied earlier [17]. This can be attributed to interface attack.
The decrease in ferrite content after PWHT can be attri- Wire cladding results in interface areas between two adjacent
buted to ferrite transformation yielding M2& and/or sigma layers larger than with strip cladding. Therefore, the corrosion
phase etc. As can be deduced from the results, there appears rates are also higher in the present case.
to be a relation between percentage transformation, heat input As far as the effect of ferrite on uniform corrosion (as-clad)
and ferrite content. The high percentage transformation in the is concerned, the corrosion rates indicate no harmful effects.
case of low heat input cladding after certain durations of In fact, it is beneficial, though not significantly. The corrosion
PWHT may be due to the fine ferrite morphology. Because rates either remain the same or decrease with increasing ferrite
the resulting as-clad ferrite is coarser with high heat input, it content. The SEM micrographs indicate that preferential
may take more time to get it transformed or dissolved. Of attack of ferrite depends on the environment. For example,
course, as the PWHT duration increases, these differences in ferrite is attacked only in 65% nitric acid, not, however, in
percentage ferrite transformation are reduced. These results acid-ferric sulfate where austenite is preferentially attacked.
are similar to those reported for Submerged Arc bead-on-plate Potentiostatic etching confirms the above finding (the poten-
weld metals [15]. tial fluctuations in the potentiostatic tests simulate different
The microstructures at the interface between adjacent clad- environmental conditions). Similar results were obtained on
ding layers are different from those of the core of the cladding. type 304 and 347 metal cladding [17,18]. Therefore, the attack
In the as-clad condition the ferrite morphology is finer in the of ferrite in austenitic cladding or weld metals is rather a func-
preceeding layer. It is interesting, however, that the low ferrite tion of environment and not of composition. This is in contrast
cladding after PWHT exhibits grain boundary precipitation; to the published information [l-31 according to which ferrite is
this structure is an indication of susceptibility to intergranular attacked in molybdenum-containing weldments.
corrosion. This is in agreement with the findings in the cor- The results also indicate that the heat-input within the range
roded samples (Fig. 5), where the interface is preferentially studied does not affect either general or intergranular corro-
attacked. This attack can be attributed to the high carbon sion rates in the boiling acid solutions. However, heat-input
levels of these clad metals (0.06-0.07%). The microstructures may have a significant effect on corrosion behaviour under
further show that these zones are ferrite-free or have rather certain environmental conditions [181. Incidentally, as already
low ferrite contents. In the as-clad condition, the low ferrite discussed, heat-input affects the percentage ferrite transforma-
contents (3.55 FN) may have been further reduced by the tion.
heat-effect during the deposition of the subsequent layer; as
the temperatures in the existing layers can reach 1100 to 5 Conclusions
1200"C, ferrite will go into solution [16].
These areas with relatively low ferrite contents after PWHT 1. Cladding with rod or wire electrodes results in relatively
exhibit considerable grain boundary precipitation. The etching high carbon contents compared to strip cladding with the
in modified Murakami solution indicates that delta ferrite to same number of passes.
sigma transformation is greatly influenced by the ferrite con- 2. Ferrite content in clad metals can be controlled by changing
tent. The absence of sigma phase in low ferrite cladding and its welding parameters. It decreases with increasing current.
presence in SMAW claddings (10.68 FN) supports the above 3. Ferrite transformed or dissolved after PWHT is a function
observation. of heat-input and ferrite content. It is higher for cladding
Bend test results also indicate that brittle failure will result deposited with low heat input and having high ferrite con-
when the cladding with high ferrite contents (above 10 FN) is tents in the as-clad condition.
post-weld-heat-treated. This embrittlement in SMAW clad 4. PWHT leads to sigma phase transformation in clad metals
(10.68FN) can be attributed to sigma phase which was with high ferrite content (10.68 FN) which results in brittle
detected metallographically. fracture in the bend test.
Corrosion tests to ascertain susceptibility to intergranular 5. Attack of ferrite depends on environment: In 65% nitric
corrosion did not produce macroscale cracking (10 x magnifi- acid, ferrite is preferentially attacked while in acid-ferric
cation). However, as reported earlier, grain boundary precipi- sulfate solution, ferrite is not attacked while austenite is.
tation confined to 4 or 5 grains were noticed in PWHT samples 6. Although no sample exhibited susceptibility to intergranu-
with low ferrite contents.This type of precipitation, which lar corrosion in the copper-copper sulfate-16% acid test,
caused preferential attack at the interface in the acid-ferric microstructural examination revealed grain boundary car-
sulfate test, did not give rise to cracking in the copper-copper bide precipitation at the interface for PWHT samples with
sulfate-acidtest. Interestingly, it was not possible to assess the low ferrite contents (3.55 FN). The acid-ferric sulfate test
susceptibility to intergranular corrosion of the P W T - produces preferential attack at the same site.
SMAW-cladding containing 10.68 FN: The sample broke into 7. Ferrite is beneficial in controlling corrosion rates of clad
two pieces at very small bending angles. However, microstruc- metals after PWHT.
tural observations did not reveal any grain boundary precipita- 8. Heat input, within the range studied, does not affect the
tion in these samples. corrosion rates significantly.
The corrosion rates (for PWHT samples) in both the acid-
ferric sulfate and the 65% nitric acid indicated the beneficial References
role of ferrite as for intergranular corrosion is concerned. The
corrosion rates decreased with increased duration of heat [l] M . E. Carruthers: "Weld corrosion in type 316 and 316 L stainless
treatment in the case of high ferrite claddings, whereas they steel and related problems"; Weld. J . 38 (1954)259-267.
142 Ergebnisse des Forschungs- und Entwicklungsprogramms Werkstoffe und Korrosion 39,142-145 (1988)

[2] H. C. Campbell: “Identifying corrosion and welding failures in [12] J. C. Lippold, W. F. Savage: “Solidificationof austenitic stainless
stainless-steels”; Mater. Prot. 44 (1963) 39-42. steel weldments, Part 2. The effect of alloy composition on fer-
[3] Volikova et al.: Svar. Prot. V (1970) 11-13. rite morphology”, Weld. J. 59 (1980) 48-58.
[4] T. Ogawa, K. Murata, S. Aoki, E. T. Suchetomi: “Effect of [13] K . Prasad Rao, P. K . Ramesh: “SAW strip cladding - A study on
molybdenum and nitrogen on chloride pitting corrosion in the effects of fluxes and process parameters”, to be published in
austenitic stainless steel weldments”, J. Jpn. Weld. SOC.48 Schweissen, Schneiden, Praktiker , DVS, Dusseldorf, W.-Ger-
(1980) 564-571 (in Japanese). many.
[5] W. F. Savage, Dequatte: “Localised corrosion and scc behaviour [14] K . Prasad Rao, K . N. Krishnan, V . Rama Rao, G . J . Gururaja:
of austenitic stainless steel weldments containing retained fer- “Effect of welding parameters on ferrite content”, Proceedings
rite”, Rennselaer Polytechnic Institute, U.S.A., 100-2462-6, of National Welding Seminar ’86, October 16-18, 1986, Indian
March 1980, 9 (E). Institute of Welding, Madras, India.
[6] M . Vyklickj, 0. Brenner, H . Hamour: “Comparison of the cor- [15] K. Prasad Rao, V . Sivakumar: “Effects of heat input and post
rosion resistance of austenitic stainless steels in urea”, Neue weld heat treatment on ferrite content and transformation, and
Hutte 24 (1979) 271-274. corrosion behaviour of type 316 L weld metal”, Annual Techni-
[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”, 1986, Bombay, India.
Metallography 3 (1970) 433-440. [16] N. C. Cole, G . M . Goodwin, C.M . Slaughter: “Effect of heat
[8] R. Viswanathan, J. I . Nuruinen, R. G . Aspden: “Stress corrosion treatment on the microstructure of stainless steel weld metal”,
behaviour of stainless steel welds in high temperature water con- Microstructural Science, Vol. 3, American Elsevier Publication
taining chlorides”, Weld. J. 58 (1979) 118-126. Comp. (1975) 789.
[9] Y. S. Sidarkina et al.: “An investigation of sigma-phaseon corro- I171 K. Prasad Rao, S. Prasannakumar: “Corrosion behaviour of
sion resistance of stainless steel alloys”, Zashch. Met. 16 (1980) austenitic weld and clad metals in accelerated boiling acid tests
589-594. simulating passive conditions”, Corrosion 42 (1986) 1-10,
[lo] ASTM Designation A262-75,1976 of ASTM Standards - Ameri- [181 K. Prasad Rao, S. Prasannakumar: “Electrochemicalstudies on
can Society for Testing Materials, Philadelphia, Pennsylvania, corrosion behaviour of austenitic stainless steel weld and clad
USA. metals” Corrosion 41 (1985) 234-242.
[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. (Revised version received: 26.8. 1987) W 2536

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 Die Korrosionsgefahrdungvon Ferngastransportleitungendurch die


0.g. Medien kann aufgrund bestehender Erkenntnisse in der Literatur
Untersuchungeniiber die Korrosionsgefahrdungvon wie folgt beschrieben werden:
Hochdruckleitungenfur wasserstoffhaltige Synthesegase - bei Feuchtgasen, die CO und C 0 2 enthalten, kann transkristalline
SpannungsriBkorrosion auftreten,
und ihre Inhibition durch Luftsauerstoff - vorzugsweise bei trockenen Gasen, die Wasserstoff enthalten, kann
ASt: A) BAYER AG, B) Mannesmann bei kritischer mechanischer Beanspruchung H-induzierte transkri-
5090 Leverkusen Forschungsinstitut, stalline SpannungsriBkorrosion oder Wasserstoffversprodung auf-
4100 Duisburg 25 treten.
FE-St: IN-ATU WT Mannesmann Mit Hilfe der nachstehend beschriebenen Untersuchungen sollten
Forschungsinstitut Grenzwerte fiir die Gefahrdung der Hochdruck-Stahlrohrleitungen
FL: Prof. Dr. H. Grafen Prof. Dr. W. Schwenk durch wasserstoffinduzierte SpannungsriBkorrosion bestimmt und
Laufzeit: 01. 07. 1983 bis 30. 06. 1987 Moglichkeiten des Korrosionsschutzes durch Inhibition aufgezeigt
werden.
Die Untersuchungen waren auch aus dem Grund relevant, weil die
1 Einleitung bestehende Erdgas-Import-Abhangigkeitdurch Synthesegaszustande
In mehreren westlichen Erdgas-Exportlandern werden Uberlegun- in einem gewissen Umfang vermindert werden kann. Daruber hinaus
gen angestellt, zur Streckung der Ressourcen Erdgas mit Synthese- sind die Untersuchungen auch geeignet, wichtige Grundlagen fur eine
gasen, z. B. aus der Kohlevergasung, zu verschneiden. spatere Wasserstoff-Technologie zu schaffen.