100 year history and evolution of stainless steels and welding – 1913 to 2013 damian j. kotecki...
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100 Year History and Evolutionof Stainless Steels and Welding
– 1913 to 2013Damian J. Kotecki
Damian Kotecki Welding Consultants
105 Barton Lane
Chapel Hill, NC 27516
440-368-4104
Mobile: 440-289-8673
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Before the First 100 Years• 1797 – Discovery of Chromium by
Klaproth and Vauquelin
• 1871 – Woods and Clark patent “weather resistant” alloys of iron with 5 to 30% chromium
• 1900 – Holtzer and Co. exhibit “rustless steels” at the Paris Exposition
• 1905 – Léon Guillet publishes a book entitled Stainless Steel in Paris
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1913• August 20 – Harry Brearly, at
Firth Brown in Sheffield, England, pours the first commercial heat of what we now know as stainless steel (essentially Type 410 martensitic steel)
• Eduard Maurer and Benno Straus produce first austenitic stainless steel at Friedrich A. Krupp Works in Essen, Germany
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1924• Irving Langmuir at General
Electric filed a patent application for Atomic Hydrogen Welding
• Predecessor of GTAW for welding stainless
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First Constitution Diagram - 1924
• For wrought steel, not weld metal
BennoStrauss
EduardMaurer
Chromium, per cent
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• Diagram of Strauss and Maurer, modified by Scherer et al in 1939
• For wrought steel, not weld metal
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Schaeffler Diagram – 1949Anton “Tony Schaeffler, Arcos
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DeLong Diagram – 1974and AWS A4.2 Standard
William DeLong, McKay Company
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WRC-1988 Diagram
ChrisMcCowan, Colorado School of Mines
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WRC-1988 vs. DeLong
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WRC-1992 Diagram(modified 2000)
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Stainless Refining for 6 Decades• If Cr was added to furnace charge, most
Cr was oxidized to the slag.• To achieve < 0.03% C, it was necessary
to add expensive low carbon ferrochrome after melting.
• Large cost differential between low carbon stainless and non-low carbon stainless.
• Non-low carbon stainless required annealing and quenching after welding.
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Sensitization - If Weld is not Annealed and Quenched
• M23C6 precipitates on grain boundaries in the HAZ.• Region adjacent to grain boundary is depleted in Cr.• Cr-depleted zones are preferentially corroded.
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Argon Oxygen Decarburization• Conceived in 1955 by blowing
argon-oxygen mixes over surface of molten steel – not successful on large scale.
• Joslyn Steel injected Ar-O2 at the bottom of the refining vessel (October 24, 1967).
• Joslyn achieved 0.008% C, 97% Cr recovery.
• Spread to other mills in 1970.
William Krivsky, Linde
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Unintended Consequence of AOD – Variable Penetration
• Automatic autogenous GTAW of tubing began to produce unpredictable penetration.
• Low penetration was specific to certain heats of steel.
• Many investigators thought the effect was due to trace elements, but which one(s)?
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Marangoni Effect• Heiple and Roper (1982) demonstrated
that variable penetration was caused by surface tension driven fluid flow in the weld pool.
• Very low S and/or addition of small amount of Al cause decreasing surface tension with increasing temperature.
• Increased S causes increasing surface tension with increasing temperature.
• AOD is very efficient at reducing S.
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Marangoni Effect• Decreasing surface tension with
increasing temperature causes outward fluid flow along pool surface.
• Increasing surface tension with increasing temperature causes inward fluid flow along pool surface.
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Marangoni Effect• S < 0.005% tends to cause outward
fluid flow along the weld pool surface.
• S > 0.010% tends to cause inward fluid flow along the weld pool surface.
• 0.005% < S <0.010% causes unpredictable fluid flow.
• Tinkler et al (1983) recommend S > 0.010% as a purchase specification for stainless steel tubing for automatic autogenous GTAW.
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Unintended Consequence of AOD – Addition of Nitrogen
• In AOD refining of stainless steel, nitrogen has been considered an inert gas, interchangeable with argon.
• This led to injection of some air in the AOD process, causing an increase in nitrogen in the stainless steel.
• Duplex stainless steels, invented in the 1930s, were considered unweldable through the 1960s, unless annealed after welding.
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Unintended Consequence of AOD – Addition of Nitrogen
• Use of AOD for refining duplex stainless steel introduced nitrogen into the steel.
• When nitrogen was specified as a necessary part of the composition, the as-welded properties improved.
• Ogawa and Koseki (1989 and 1990) demonstrated that nitrogen addition increases the rate of austenite formation in the weld metal and HAZ, causing the as-welded improvement.
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2205 Base Metal
22% Cr
6% Ni
3% Mo
0.12% N
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2205 Weld Metal
22% Cr
6% Ni
3% Mo
0.12% N
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2205 Weld Metal
22% Cr
6% Ni
3% Mo
0.18% N
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Definition of 2205 Duplex Stainless
• Originally composition was defined in ASTM by UNS S31803 (0.08 to 0.20% N).
• Work of Ogawa and Koseki caused ASTM to redefine 2205 as UNS S32205 (0.14 to 0.20% N) in year 2000.
• At higher N level, HAZ properties are much less sensitive to welding heat input.
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Unintended Consequences - FCAW
• 1980s saw a major shift in FCAW of stainless from large diameter self-shielded to small diameter gas shielded electrodes.
• Key feature of this shift was the patent of Godai et al describing addition of a “low melting oxide” to produce clean easy slag removal with a high SiO2 slag system.
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Unintended Consequences – FCAW (continued)
• Oxides of Pb, Bi and Sb were included.
• Bi was the principal oxide, many copies of these wires were produced.
• In the early 1990s, reports surfaced of in-service cracking at temperatures above 700°C. Investigations followed.
• Failed welds contained about 200 ppm Bi.
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• Nishimoto et al reported reheat cracking above 700°C in self-restrained cracking test in weld metal of 200 ppm Bi.
• Konosu et al reported reduced stress rupture properties at 200 ppm Bi.
Unintended Consequences – FCAW (continued)
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Bi Effect on Stress RuptureTest Temperature 650°CKonosu et al
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Late 1990s IIW Commission IX Round Robin of Bi Analysis
• Nominally Bi-free electrodes produced weld metal analyzed at 20 ppm Bi or less.
• Commercial Bi-containing electrodes produced weld metal analyzed at about 200 pp Bi.
• Requiring 0 Bi is not feasible, but requiring < 20 ppm Bi for FCAW weld metal for service above 550°C is feasible.
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State of the Art of Stainless FCAW
• Most manufacturers of 1.6 mm and smaller gas-shielded FCAW electrodes produce both nominally Bi-free electrodes and electrodes of about 200 ppm Bi.
• 200 ppm Bi has no adverse effect for service below 550°C – such electrodes dominate the market because they are more welder friendly.
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State of the Art of Stainless FCAW
• 20 ppm Bi maximum should be specified for high temperature exposure.
• AWS A5.22 now requires reporting Bi on material certificates.
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Conclusions
• The foregoing are my very personal views about landmark events in the history of welding stainless steels.
• The list is certainly not all-inclusive – others can offer their own views.