Stainless Alloys ASTM A249 Supplemental Requirement 7 (S7 weld decay testing) is an accelerated corrosion test where welded austenitic stainless tube is subjected to boiling 20% hydrochloric acid. This test dissolves half the wall thickness in a matter of minutes to hours depending on the alloy. A wall thickness ratio is then generated, which compares the corrosion rate of the base metal to that of the weld or weld Heat Affected Zone (HAZ) on a worst-case basis. A ratio of 1.25 represents a weld that corrodes 25% faster than the base metal. In S7 a ratio of 1.25 or less is an acceptable result for this test. This corrosion test is applicable or has real-world application where tubes become coked or lined with organic matter, which can only be removed by a short-term hydrochloric acid cleaning operation. The austenitic stainless alloys are not suitable for long-term exposure to any signifcant level of hydrochloric acid (HCl). Nickel and high nickel alloys are some of the few metallic materials that exhibit useful long-term resistance to hydrochloric acid 1 . Short-term performance in boiling 20% hydrochloric acid can have little or no signifcance in other acids, environments, or caustics. Please see Figures 1 & 2. Typically weld decay environments or operations are found in sugar refning and in some paper pulp processing operations. The vast majority of stainless applications do not require S7 or weld decay corrosion resistance. Those environments that do are isolated and few, estimated at less than 0.8% of stainless tubular sales. FIGURE 1. (Left) Scanning Electron Microscope (SEM) secondary electron image of transverse RathGibson laser welded 304L tube section, which was weld decay tested using HCl acid per the ASTM A249 S7 supplement. Please note base metal thinning in excess of weld thinning. Also please note that this RathGibson weld lacks the Heat Affected Zone (HAZ) attack present in competitive laser welds. (Right) Optical image of 304L laser weld at higher magnifcation, showing complete weld recrystalization. Base Metal Weld Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein. 2 The weld decay test has been too frequently sold as a good general corrosion test with wide application. It is not. There are corrosion tests such as ASTM A262 practices A & E, which test for sensitization or susceptibility to intergranular attack and have good general applicability in a wide range of environments and alloys, in both oxidizing and reducing acids. The weld decay test was never designed as a test with wide application. Producers who push weld decay testing regardless of service environment do so simply because their manufacturing process makes doing so advantageous. The S7 weld decay test tends to preferentially attack weld retained delta ferrite in stainless alloys such as 304, 316, 317, 308, and 309. A small percentage of retained delta ferrite is evidence that the weld has generally undergone primary ferritic solidifcation 3 . The chemistry of these alloys and the resultant ferrite content in welds are controlled to achieve dramatically improved weld solidifcation cracking resistance due to the ferritic mode of solidifcation. This signifcantly improves solidifcation cracking resistance and makes the use of small deliberate sulfur additions possible. Sulfur is used for improved weld penetration, which is important particularly in tubular products where out-of-position feld welding is generally a given. In the base metal the ferrite is isolated and discontinuous; however, in conventional arc welds it will be skeletal, offering a near continuous path for preferential chemical attack by the hydrochloric acid. See Figure 4. Heat treatments to improve weld decay corrosion ratios, slightly reduce the ferrite content, but mostly they spheroidize the FIGURE 2. (Left) Scanning Electron Microscope (SEM) secondary electron image of transverse laser welded 304L tube section, which was weld decay tested using 85% Phosphoric Acid for 24 hours. Please note weld-metal thinning in excess of base-metal thinning. Please note these results are essentially reversed from the HCl test. (Right) Optical image of 304L laser weld at higher magnifcation, showing complete weld recrystallization. Alloy S7 Ratio Condition / Form Weight Loss (mpy) 304L 1.53.71 Mill Anneal GTAW 4,840 2.06 Mill Anneal Laser 691 1.6 Furnace Anneal GTAW 316L ~2.0 Mill Anneal GTAW 59.3* 2205 1.2 Mill Anneal Laser 1,087 825 Seamless 3650 625 Seamless >180+ Furnace Anneal GTAW 23.5 C-276 Seamless 5121* Furnace Anneal GTAW 13.3 Table 1. Boiling 85% Phosphoric Acid, 24-hour duration * Minor Cu variations are known to play large roll in corrosion rates 2 . Seamless data as reported by Huntington Alloys a Special Metals Company + 168 hour tests Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein. weld ferrite and break up its continuous skeletal nature 4 . This eliminates the preferential attack path in conventional welds and improves weld decay ratios. Laser Beam Welding (LBW) in the tube industry produces tubing at roughly 3 times the speed of conventional arc processes. It is LBWs high energy density, low total heat input and speed that cause suppression of the ferrite phase in the weld through very fast non-equilibrium solidifcation 5 . Conventionally, arc welded heats (304L, 316L) exhibiting weld retained ferrite will typically not display signifcant weld ferrite when laser welded at relatively high speed 5 . This suppression of ferrite results in acceptable weld decay corrosion ratios in laser welded tubing without the need for extended heat treatments. 3 FIGURE 3. Above is a competitive S7 Test exactly as shown in their published sales literature (laser welded alloy 304L) 6 . Please note the weld appears to be unrecrystallized and that there is signifcant attack at the fusion boundary. Compare this to Figure 1. FIGURE 4. Skeletal retained weld ferrite in as welded (GTAW) 304L. Photo on the top displays the weld and Heat Affected Zone (HAZ) at the ID or the root of the weld. Photo on the bottom is the same weld area only at higher magnifcation. Weld decay corrosion ratios will vary by the alloy because of each alloys chemistry and resultant weld retained ferrite. For example, in alloy 316/316L ferrite is nominally controlled to a weld ferrite number range of 25. However, for alloy 317/317L a slightly higher ferrite number of 48 is necessary to achieve appropriate weld cracking resistance 3 . In addition to the higher ferrite level, Alloy 317 has a higher nominal chromium and nickel content, the combination of which makes it diffcult to achieve good S7 ratios in 317. Manufacturers will frequently speak to their 304 S7 achievements (low ratios), mostly because they do not manufacture a full range of alloys, or understand what is required in some alloys for weld cracking resistance. Table 2 is a listing of RathGibsons average S7 ratios. Please note ratios are very much dependent on the alloy and predicted ferrite levels. Alloy 310, while being heavily alloyed by chromium and nickel has no ferrite and tests very well without any extended heat treatment! This is strictly related to the alloys lack of ferrite. Ferrites major beneft is in weld solidifcation cracking resistance. In most alloys S7 performance can be improved through chemistry control and elimination of ferrite. In effect, alloys such as 304, 316, and 317 could be produced without ferrite. As the alloy 310 example demonstrates, this would have a signifcant impact on S7 results. However, an elimination of ferrite would come with a signifcant weldability penalty. Alloy 310 cannot tolerate deliberate additions of sulfur because no ferrite is possible. This reduces ease of penetration, slows welding speed and makes the alloy far more susceptible to weld cracking. RathGibson does not take this approach. Instead S7 ratios are achieved through Laser Beam Welding (LBW) or extended heat treatment when necessary. While a ratio of 1.25 or less is required for an acceptable result in this test, too many producers have inferred that an infnitely lower ratio is better. As an example: a result of 0.95 is too often considered inferior to a lower result of say 0.65. This is shortsighted logic. A corrosion ratio of 1, effectively a seamless result, should be the ideal. This can in fact be experimentally demonstrated. As weld cold working and annealing are perfected, the weld in the resultant product will become increasingly hard to fnd metallographically and weld decay ratios will approach 1. Figure 5 represents a 304L laser beam welded tube where the cold work was not suffcient to assure complete recrystallization. This resulted in an S7 ratio of 0.66. Figure 6 represents a 304L laser beam welded tube where cold work was suffcient to assure complete recrystallization during annealing. This resulted in a S7 ratio 0.84, or closer to a 1 to 1 ratio. Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein. 4 Some users specify an S7 requirement as added assurance that quality welded tubing is supplied and this is true if the service environment involves hydrochloric acid clean-outs. However, for other environments and acids the applicability of this HCl test is questionable. Performance in a HCl test carries little implication in many other acid environments. It should be noted that there may be some additional cost and possible delays associated with this since S7 requires an extended anneal which in most applications is overkill. S7 weld decay / Hardness / A262/E RathGibson 0.84 / 86 Rb / Pass Competitive 0.66 / 86 Rb / Pass FIGURE 5. Transverse section of competitive laser welded 1" x 16 gauge (25.4 x 1.6 mm) 304L tubing. Left photo is at lower magnifcation with the tube ID surface visible at the bottom. Right photo is the same area at higher magnifcation. Please note no discernable recrystallization of cold work and the ID is unforged. These photos are similar to those used in the competitive Companys own literature, which appear to exhibit no obvious recrystallization. Alloy 310 results only Mill Annealed. All other alloys and tests represent extended off-line annealing. Ferrite number was calculated based on chemistry, not actual weld testing. Table 2. S7 Test Data Alloy 304/304L 316/316L 317/317L 321 347 309S 310 S7 Ratio 0.74 0.82 0.94 1.0 1.03 1.13 0.75 Ferrite Number 6.8 4 5 5.5 4 3.1 0 Cr (wt %) 18.3 16.5 18.2 17.2 18 22.39 24.6 Ni (wt %) 8.4 10.3 13.4 13.8 19.4 Cr + Ni 26.7 26.8 31.6 36.19 44 Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein. 5 FIGURE 6. Transverse section of RathGibson laser welded 1" x 13 gauge (25.4 x 2.4 mm) tubing. Left photo is at lower magnifcation with the tube ID surface visible at the bottom. Right photo is the same area at higher magnifcation. Please note complete weld recrystallization and the ID weld is well forged. Conclusions 1. The ASTM A249/S7 weld decay test is a special application corrosion test designed only for environments which use a short-term exposure of hydrochloric acid to clean out organic matter. The S7 test is a poor predictor of performance in other acids or environments. Intergranular corrosion or sensitization tests (ASTM A262 practices A or E) should be considered for other types of environments as these tests have good general applicability in a wide range of environments and alloy, in both oxidizing and reducing acids. 2. S7 weld performance is determined largely by weld ferrite morphology, or content, and the alloys nickel plus chromium content. S7 ratios slightly less than 1 should be preferred. Conventional Gas Tungsten Arc Welds (GTAW) are rendered S7 suitable by long-term heat treatments which break up the nearly continuous skeletal weld ferrite. Laser beam welds generally do not require extended heat treatments to achieve acceptable S7 ratios. This relates to the high solidifcation rate and the resultant suppression of weld ferrite (304L, 316L, and 317L). 1.2 1.1 1 0.9 0.8 0.7 20 25 30 35 40 45 Ni + Cr (wt %) S 7
R a t i o 304/304L 316/316L 317/317L 309S 310 Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein. References 1 Corrosion Engineering Bulletin (CEB-3) Resistance of Nickel and High Nickel Alloys to Corrosion by Hydrochloric Acid, Hydrogen Chloride and Chlorine. The International Nickel Company, Inc. 2 Trans. Am. Soc. Mech. Engrs., A Standard Laboratory Corrosion Test for Metals in Phosphoric Acid Service, 73 1951, page 975, by H. F. Ebling and M. A. Scheil 3 The Welding Journal, December 1988. Ferrite Number Prediction to 100 FN in Stainless Steel weld Metal by T. A. Siewert, C. N. McCowan, and D. L. Olson 4 The Welding Journal, July 1974. Ferrite in Austenitic Stainless Steel Weld Metal, by W. T. DeLong 5 The Welding Journal, June 1994. Solidifcation Behavior and cracking Susceptibility of Pulsed-Laser welds in Austenitic Stainless Steels, by J. C. Lippold 6 LTV CopperWeld. A Comparision of Laser-Welded and TIG-Welded Stainless Steel Tubing. Page 5 The following fgure is a comparison of the listed alloys S7 ration to their nickel plus chromium content. RNB071036182511 Lincolnshire, Illinois, USA (Corporate Headquarters) RathGibson North Branch, New Jersey, USA (Sales and Manufacturing) RathGibson Janesville, Wisconsin, USA (Sales and Manufacturing) RathGibson Clarksville, Arkansas, USA (Manufacturing) Greenville Tube Company www.greenvilletube.com Marrero, Louisiana, USA (Manufacturing) Mid-South Control Line www.controlline.com Buenos Aires, Argentina (Sales) RathGibson Melbourne, Australia (Sales) RathGibson Vienna, Austria (Sales) RathGibson Manama, Bahrain (Sales) RathGibson Shanghai, China (Sales) RathGibson Mumbai, India (Sales) RathGibson Singapore (Sales) RathGibson Seoul, Republic of Korea (Sales) RathGibson www.RathGibson.com sales@rathgibson.com Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein. The information herein was correct at the time of publication and is subject to change without notice. 2010 RathGibson, LLC.
Mechanisms of Deformation and Fracture: Proceedings of the Interdisciplinary Conference Held at the University of Luleå, Luleå, Sweden, September 20-22, 1978