The Effects of Phosphorus, Sulfur and Ferrite Content on W e l d Cracking of Type 309 Stainless Steel

The ferrite level that prevents cracking is found to be dependent on impurity level wherein, for low P + S, little or no ferrite is required to prevent cracking while, with ferrite contents greater than Ferrite Numbers 13 to 14, large amounts of P and S can be accommodated without cracking

By J. A. BROOKS A N D F. J. LAMBERT, JR.

ABSTRACT. The variation in weld cracking of different heats of Type 309 stainless steel is reviewed. Data are presented which show the combined effects of phosphorus plus sulfur level and ferrite content on weld cracking. The data demonstrate that chemistry specifications more restrictive than the current AISI specification are required to ensure crack-free autogeneous welds. Introduction As pointed out by Lundin et al.,1 the construction of nuclear power reactors using large amounts of austenitic stainless steels has renewed interest in the subject of ferrite and weld microfissuring. The potent effect of several percent ferrite in reducing cracking has been k n o w n for years2 and resulted in the development of a number of diagrams, such as that published by Schaeffler,3 and later revised by DeLong et al.,4 w h i c h predicts weld ferrite content from chemical composition. The relationship between ferrite content and weld cracking has led to the development of codes w h i c h require weld ferrite above a specified minimum level in an attempt to eliminate cracking. However, in some cases designers w o u l d like to minimize, or eliminate, ferrite for reasons such as preventing transformation of delta ferrite to sigma phase, or excluding magnetic phases, for example, in constructing hardware for super con-

ductivity. Therefore, conflicts often arise between the designer and w e l d ing engineer. Lundin and co-workers 1 determined the minimum ferrite content required to eliminate weld fissuring of several AISI 300 series alloy wire filler metals and thoroughly characterized the m i crofissures of "fissure b e n d " test samples. In their study they did not consider the effect of impurity elements which can alter the relationship between ferrite content and cracking. This relation was, however, clearly shown by one of the present authors for high nitrogen, high manganese stainless steels.5 In both weld wire filler metals and wrought material, phosphorus and sulfur levels in particular can vary considerably, and have a significant effect on weld cracking. Impurity levels in wrought material cannot be ignored, since cracking can

result in autogeneous welds or the root pass of multiple pass welds. The purpose of this paper is to demonstrate the importance of (P + S) content in the relationship between weld cracking and ferrite content of autogenously welded AISI 309 austenitic stainless steel, one of the alloys studied by Lundin. Material and Testing Studies were conducted on 42 different heats of Type 309 austenitic stainless steel which contained various phosphorus and sulfur levels. The heat chemistries are shown in Table 1. Alloys 1 to 16 were produced from 1 kg (2.2 lb) vacuum induction melted (VIM) heats, alloys 17 to 40 were from 1.8 kg (4 lb) V I M heats, and alloys 41 and 42 were from commercial heats. All material was homogenized and hot rolled to 0.25 mm (0.01 in.) thick strip. These strips were annealed at 1010 C (1850 F), air cooled, pickled, and finished w i t h a light cold-roll pass. All experimental heats were made from high purity starting material w i t h the main alloying elements balanced to provide a range in ferrite content when welded. However, it was intended that all heats should be w i t h i n the commercial AISI specification shown in Table 2. W h e n the allowable chemistry range of the Type 309 stainless steel is plotted on the DeLong Diagram 6 (Fig. 1), it is easily seen that autogeneous GTA welds in this alloy could exhibit ferrite levels from ferrite

Paper based on information included in presentation made under title of "Effects of Impurities on the Weldability of Electroformed Nickel" in a session sponsored by the Wrought Nickel Alloys Subcommittee of the Welding Research Council at the AWS 57th Annual Meeting held in St. Louis, Missouri, during May 10-14, 7976.

/. A. BROOKS is with the Materials Development Division, Sandia Laboratories, Livermore, California, and F. I. LAMBERT, JR., now retired, was with the Union Carbide Corp., Y-12 Plant, Oak Ridge, Tennessee.

W E L D I N G RESEARCH S U P P L E M E N T I 139-s

Table 1 - Chemistries of Type 309 Stainless Steel Heats Studied, Wt-% N heat N weld .026 .016 .140 .023 .031 .026 .025 .022 .022 .050 .026 .032 .020 .037 .029 .023 .012 .010 .006 Crack rating 1, 4 4 4 3 3 4 4 3 2, 4 1 4 3, 4 1 1, 1, 1, 2, 4, 4, 4, 4, 1, 1, 1, 1, 1, 3, 3, 3, 1, 1, 1, 1, 1, 1, 1, 1, 1, 4, 1

Heat 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42

Cr 21.7 21.6 21.7 21.7 21.7 22.4 22.3 22.7 22.7 23.2 22.0 21.9 22.4 21.7 22.0 22.7 22.2 22.0 21.9 21.9 22.1 22.1 21.9 21.9 24.0 23.7 23.6 23.8 23.9 23.5 23.6 23.6 25.1 24.9 25.0 24.9 25.1 24.8 24.6 24.7 22.6 22.6

Ni 15.0 14.9 15.0 14.8 14.9 14.2 13.9 14.3 13.9 14.3 13.7 13.3 13.6 13.3 13.5 13.7 14.0 14.3 14.3 14.3 14.2 14.3 14.6 14.2 14.0 14.2 14.3 14.2 14.1 14.3 14.4 14.3 14.1 14.2 14.2 14.2 14.0 14.3 14.5 14.3 13.7 14.36

Mn 1.44 1.48 1.76 1.54 1.44 1.43 1.47 1.58 1.41 1.44 1.50 1.77 1.45 1.68 1.45 1.55 1.75 1.74 1.74 1.74 1.58 1.58 1.61 1.60 1.55 1.56 1.52 1.54 1.53 1.60 1.60 1.59 1.58 1.62 1.63 1.60 1.56 1.60 1.67 1.60 1.56 1.50

Si .69 .75 .73 .73 .66 .71 .72 .68 .79 .67 .71 .54 .74 .53 .65 .56 .70 .70 .72 .71 .71 .73 .70 .70 .71 .72 .74 .73 .72 .71 .71 .71 .71 .70 .71 .71 .73 .73 .72 .71 .55 .44

C .075 .077 .078 .076 .082 .072 .048 .093 .046 .067 .062 .027 .100 .029 .100 .026 .043 .043 .041 .040 .051 .057 .059 .060 .054 .048 .051 .050 .054 .061 .074 .063 .049 .045 .067 .050 .049 .050 .068 .061 .06 .056

P .002 .043 .041 .039 .018 .058 .040 .042 .028 .018 .058 .043 .041 .031 .041 .018 .010 .015 .016 .021 .025 .020 .036 .004 .015 .015 .021 .028 .030 .034 .031 .037 .020 .021 .035 .030 .048 .044 .058 .051 .013 .025

S .003 .024 .033 .022 .013 .029 .027 .023 .027 .011 .031 .027 .023 .017 .013 .012 .005 .010 .010 .015 .024 .032 .033 .039 .009 .018 .018 .024 .043 .045 .052 .053 .015 .024 .024 .030 .044 .053 .054 .052 .007 .025

F.N.'* 1 2 0 1.9 1.0 6 9 5 12 7 6.5 9 6 7.5 4 12 8 6.5 6.5 6.5 7.0 6.5 4.5 5.5 15 14 13 14 14.5 12 10.5 11.5 ~20 18.5 17 18 -20 17.5 14.5 16.5 9 6.5

.007

.006

.014 .012

.016

.006 .007

.013

.017 .006

.006 .110 .056

1 1 2 2 4 3 4 4 1 1 1 1 1 2 3 2 1 1 1 1 1 1 1 2 1 4

"F.N.-Ferrite Number calculated from the DeLong Diagram using nitrogen of weld analysis, or 0.020 if not analyzed.

number* (F.N.) = 0 to F.N. > 18 depending upon heat chemistry. A weld test was established 7 to determine the cracking sensitivity of the 0.25 mm (0.01 in.) thick sheet. Strips, each 100 mm w i d e by 200 mm long, (315/6x7'/s in.) were welded endto-end to a standard Type 304L stainless steel strip of equal size. The test was performed by making a series of fusion passes side by side along the length of the combined standard and test specimen strips. The standard Type 304L stainless steel strip was used to help detect any sutble changes in weld parameters or weld technique which may effect weld bead geometry *Ferrite content is reported in ferrite number as preferred by the Welding Research Councilsee "Technical Note: Calibration Procedure for Instruments to Measure the Delta Ferrite Content of Austenitic Stainless Steel Weld Metal" by W. T. DeLong, Welding Journal, 52 (2), Feb. 1973, Research Suppl., pp. 69-s to 72-s.

ot test results. The samples, secured in a seam welding unit, were welded w i t h the following parameters: 30 A, 8 V, 610 m m / m i n travel speed w i t h argon shielding. Twelve to sixteen weld passes were usually made unless the test piece proved to be very crack sensitive, in which case the test was terminated early. This test was performed twice on each test panel. If the test specimen showed no visible

Table 2AISI Specification for Type 309S'"' Stainless Steel, Wt-%

Ni

Cr Mn Si P S
"S = low carbon grade.

0.080 (max) 12.00-15.00 22.00-24.00 1.0-2.0 1.00 (max) 0.04 (max) 0.03 (max)

cracks, the back side of the weld was painted w i t h dye penetrant and the top side w i t h a developer w h i c h could easily detect the through thickness cracks. A qualitative rating of 1-4 was established: (1) no cracks, (2) no more than t w o cracks, (3) more than t w o cracks, and (4) the dye check was not needed since it was possible to see through cracks. The ratings for each heat are shown in Table 1. A completed test specimen which proved to be very crack-sensitive is shown in Fig. 2. All cracks were centerline in nature and in some severe cases extended the total length of the test specimen. A section of test plate showing the weld geometry and spacing is shown in Fig. 3. The weld ferrite content was calculated from the DeLong Diagram since the specimens are much too thin for magne gage readings. W h e n available, the nitrogen analysis from the actual welds were used in these calculations since in some cases nitrogen was

140-s I M A Y 1978

CONSTITUTION DIAGRAM FOR STAINLESS STEEL WELD METAL

b r W i l l i a m T. D . t o n g

revised January, 1973

18

19 20 21 22 23 24 CHROMIUM EQUIVALENT = '/.Cr + %Mo + 1.5 X "/.Si + 0.5 X */.Cb

25

Fig. 7DeLong Diagram showing calculated ferrite levels of welds within the Type 309 stainless steel composition range of Table 2 and 0.05% maximum N

absorbed during welding. This can be seen in Table 1 by comparing the heat analysis w i t h the nitrogen analysis of the weld metal. The effect of nitrogen pick-up during welding has been discussed by Long and DeLong. 8 A nitrogen level of 0.02% was used for ferrite prediction when the weld metal analysis was not available. As a check between predicted and actual ferrite content, the ferrite content was

estimated for welds of five alloys using the line intercept technique. Scanning electron micrographs at X3000 were used to clearly distinguish the fine ferrite morphology. The measured and calculated values are shown in Table 3. As shown, fair agreement existed for all welds except heat 9, which had a measured ferrite content of 6% (F.N. 6), but a calculated value of 10.7% (F.N.12). As discussed

later, weld test behavior of this heat was more typical of 6 F.N. than 12 F.N. Results and Discussion In this study only phosphorus and sulfur content were considered in studying the cracking behavior even though other elements such as silicon and carbon can have an effect.

' 309 Ht. 42 304-309

Fig. 2Weld test sheet after dye penetrant inspection W E L D I N G RESEARCH S U P P L E M E N T I 141-s

Table 3Measured and Calculated Values of Weld Ferrite Content Ferrite

Heat number 4 5 9 11 14 Cal culated F.N. 1.9 1.0 12 8.8 10.5 Measured,

%
1.3 1.6 6 6.5 7.5

1.9 1.0 10.7 8.2 9.6

Fig. 3Top surface of weld test sheet showing sections of two test runs. Each test includes 12-14 GTA weld passes However, phosphorus and sulfur are known to be the most detrimental impurities c o m m o n to this type alloy, and silicon was intentionally held constant at a nominal range of -0.7%. Using "Relative Potency Factor" calculations proposed by Borland 9 and discussed by Cannonico, et al.,'" sulfur in iron is predicted to be much more detrimental than phosphorus in forming low melting eutectics responsible for cracking. However, from several studies discussed by Borland and Younger, 11 both elements seem to exhibit approximately the same potency in producing cracking. Thus, phosphorus and sulfur were considered to have equal effects on cracking and the sum of P + S was used for comparing the heats in this study. However, at low levels, the detrimental effects of sulfur are likely to be reduced by the formation of manganese sulfide. 5

The relationship found between (P + S) content and ferrite number on weld cracking is shown graphically in Fig. 4. The data can be separated into three regions: 1. A region where cracking is severe. 2. A region marginal in cracking resistance where a small amount of cracking resulted. 3. A region where no cracking occurred. Figure 4 demonstrates that for very low levels of P + S little or no ferrite was required to prevent cracking. However, as P + S level increased the ferrite content also had to be increased to resist weld cracking. At low ferrite levels, for each 0.01% increase in P + S content, an increase of about 4 F.N. was required to maintain the same cracking resistance. At

Weld Cracking ( rating 2 , 3 - 3 - 4 . ) Q Marginally Crack Sensitive) rating 1,2-2,2) O No Cracking! rating 1 )

/
.100 .090 .080
1*

' o
/ / /

/
Q

/ /
Cracking

:
8

J
/

/
N. /

I
o
o

/
O

.070
on +

/
/

.060 .050 .040 .030 .020 .010

i-

t 4* 7

/
/
**

#f /
0

o o o

'

NO CRACKING

o
8 10 12 Ferrite Number (F.N.)

14

16

18

20

Fig. 4Weld test results showing the relationship between (P + Sj content, F.N. and weld cracking. Ratings correspond to those shown in Table 1. Heat 9 measured 6 F.N.-see text

142-s I MAY 1978

ferrite number greater than about 13-14, high levels of P + S were accommodated w i t h o u t weld cracking. Heat 9 exhibited more weld cracking than expected using Fig. 4. The line intercept technique indicated an actual ferrite content of F.N. 6 w h i c h would be in much better agreement w i t h weld results than the calculated value of 12. A likely explanation is that in this heat more nitrogen was pickedup during welding than indicated by the chemical analysis which sampled 1-2 cm-. Nitrogen pick-up during welding of 0.09% rather than the assumed value of 0.02% w o u l d result in the observed discrepancy in measured and calculated ferrite levels. As shown in Table 1, large nitrogen increases actually did occur in several of the welds. The results from this study d e m o n strate that t w o choices are available to ensure crack-free welds: 1. Ensure that sufficient ferrite is produced in the weld deposit to prevent cracking at the maximum P + S level which can exist. 2. Or, reduce the allowable P + S level such that less ferrite is required to maintain the same cracking resistance. The latter case w o u l d be more attractive where large amounts of ferrite may be deterimental to other propertiesfor example, where ferrite may transform to sigma. In either case, a specification w i t h different chemistry limits than those allowed in many wrought alloy specifications is required to guarantee crack free welds. This is especially true for the more highly alloyed type of chemistry of the

AISI 300 series stainless steels. It w o u l d be expected that the relationship between weld cracking, P + S level, and ferrite content may be dependent upon welding conditions and constraint. However, the results from this study are in good agreement w i t h those of Lundin et a/.1 in that both studies show that ferrite number of about 4 is required to prevent cracking at a P + S = 0.02 level in the Type 309 stainless steel chemistry range. However, this study emphasizes the fact that the ferrite level that w i l l prevent cracking is very dependent upon impurity level. Summary The combined effects of phosphorus plus sulfur level and ferrite content on weld cracking of Type 309S stainless steel were studied. The ferrite level that prevented cracking was found to be very dependent upon impurity level. For very low levels of P + S, little or no ferrite was required to prevent cracking. At low levels of both ferrite and P + S an increase of 0.01% P + S required an increase of ~ 4 F.N. to maintain the same cracking resistance. However, for ferrite contents greater than F.N. 13-14 large amounts of phosphorus and sulfur could be accommodated w i t h o u t cracking. Acknowledgments We wish to acknowledge the experimental assistance of both D. Clark and A. Salmi of SLL, and Billy Cross from Oak Ridge, Y-12 plant. The review of the manuscript by D. Dawson and M. Mote is greatly appreciated.

References 1. Lundin, C. D., DeLong, W. T., and Spond, D. F., "Ferrite-Fissuring Relationship in Austenitic Stainless Steel Weld Metals," Welding Journal, 54 (8), Aug, 1975, Research Suppl., pp. 241-s to 246-s. 2. Borland, ). C, and Younger, R. N., "Some Aspects of Cracking in Welded CrNi Austenitic Steels," British Welding lournal, Vol. 7, 1960, pp. 22-59. 3. Schaeffler, A. L., "Constitution Diagrams for Stainless Steel Weld Metals," Metal Progress, 56, Nov. 1949, pp. 680 and 680-b. 4. DeLong, W. T., Ostrom, G. A., and Szumachowski, E. R., "Measurement and Calculation of Ferrite in Stainless-Steel Weld Metal," Welding Journal, 35 (11), Nov. 1956, Research Suppl., pp. 526-s to 533-s. 5. Brooks, |. A., "Weldability of High N, High Mn Austenitic Stainless Steel," We/ding lournal, 54 (6), lune 1975, Research Suppl., pp. 189-s to 195-s. 6. DeLong, W. T., "Ferrite in Austenitic Stainless Steel Weld Metal," We/d/ng yournal, 54 (7), July 1974, Research Suppl., pp. 273-s to 286-s. 7. Lambert, Jr., F. J., UnpublishedUnion Carbide, Oak Ridge Y-12 Plant, Oak Ridge, Tenn. 8. Long, G )., and DeLong, W. T., "The Ferrite Content of Austenitic Stainless Steel Weld Metal," Welding Journal, 52 (7), July 1973, Research Suppl., pp. 281-s to 297-s. 9. Borland, J. C, "Suggested Explanation of Hot Cracking in Mild and Low Alloy Steel Welds," Welding Research Abroad, Vol. VIM, No. 2 (Feb. 1962), pp. 73-87. 10. Canonico, D. A., Savage, W. F., Werner, W. )., and Goodwin, G. M., "Effects of Minor Elements on Weldability of Incoloy 800," Effects of Minor Elements on the Weldability of High-Nickel Alloys, Welding Research Council Symposium, 1969. pp. 6892. 11. Borland, |. C, and Younger, R. N., "Some Aspects of Cracking in Welded CrNi Austenitic Steels," British Welding Journal, Vol. 7, 1960, pp. 22-59.

PVRC/MPC Task Group on Fracture Toughness Properties for Nuclear ComponentsFinal Report
This publication, dated October 1977, was sponsored jointly by the Metal Properties Council, Inc. and the Welding Research Council. The four reports in this 292-page monograph summarize several years work on the analysis and application of fracture mechanics performed under the jurisdiction of the Task Group. The titles of the reports are: 1. PVRC-MPC Proposed Initial Program on Fracture Toughness Properties of Nuclear Components Material-Report to USAEC. 2. Crack Arrest Analysis and Testing for Nuclear Component Materials. 3. Elastic Plastic Analysis for Nuclear Component Materials. 4. Instrumented Precracked Charpy Testing for Medium Strength Nuclear Pressure Vessel Steels. Part ITest Procedure, Part IIRound Robin Test Program. The price of the monograph is $25 per copy. Discount prices: 5 to 20 copies, 20% discount; 20 to 50 copies, 33V3% discount; over 50 copies, 50% discount. Orders should be sent with payment to the Welding Research Council, United Engineering Center, 345 East 47th St., New York, NY 10017.

W E L D I N G RESEARCH S U P P L E M E N T 1143-s

IF YOU BUY FILLER WIFIALSf YOU'D BETTER BUY TMS FIRST.

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AWS A5.0-78 Filler Metal Comparison Charts 160 pages/S12.00 ea.

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