HEAT RESISTANT ALLOYS

James Kelly Director of Technology

TABLE OF CONTENTS INTRODUCTION...............................................................................................1 DEFINITIONS What Are Heat Resistant Alloys? .........................................................2 Rolled Alloys Products Nominal Compositions ..................................3 Heat Resistant Alloy Specifications .....................................................4 EFECT OF ALLOYING ELEMENTS ............................................................5 RESISTANCE TO THE ENVIRONMENT .....................................................12 Oxidation ..................................................................................................13 Laboratory Oxidation Testing ..............................................................17 Carburization............................................................................................22 Metal Dusting/Catastrophic Carburization/Carbon Rot.....................26 Nitriding .....................................................................................................29 Sulphidation .............................................................................................30 Halogen Gas Hot Corrosion ...............................................................34 Molten Salts .............................................................................................38 Molten Metals ..........................................................................................40 Magnetism ................................................................................................45 STRENGTH AT TEMPERATURE ..................................................................48 Tensile Strength ......................................................................................48 Elastic Modulus.....................................................................................48 Yield Strength..........................................................................................49 Ductility.....................................................................................................49 Creep and Rupture .................................................................................50 Creep-Rupture Testing ..........................................................................52 10,000 hour Rupture Strength Data ....................................................54 0.0001% per hour Minimum Creep Rate Data ...................................55 THERMAL FATIGUE ........................................................................................56 WEAR .................................................................................................................58 Erosion .....................................................................................................58 Galling ......................................................................................................58 PHYSICAL METALLURGY .............................................................................60 Sigma .......................................................................................................60 Grain Growth ..........................................................................................63 HEAT RESIS TANT ALLOY GRADES ...........................................................65 Iron-Chromium Alloys ............................................................................65 Fe-Cr-Ni alloys, Ni under 20%.............................................................67 Fe-Ni-Cr alloys, Ni 30 to 40% ..............................................................69 Ni-Cr-Fe alloys, Ni 45 to 60% ..............................................................71 Ni-Cr-Fe alloys, Ni over 60%, 15 to 25%Cr.......................................72 Cast heat resistant grades.....................................................................74 DESIGN ..............................................................................................................78 Thermal Strain.........................................................................................79 Weldments ...............................................................................................81 Thermal Expansion ................................................................................82 Thermal Expansion Coefficients ..........................................................84 Section Size .............................................................................................85 i

SELECTING THE ALLOY ...................................................................................86 Temperature..............................................................................................86 Atmosphere ...............................................................................................87 CUTTING AND FORMING..................................................................................88 Shearing ....................................................................................................90 Bending and Forming................................................................................90 Spinning and Deep Drawing .....................................................................93 Machining ..................................................................................................94 Forging ......................................................................................................95 WELDING ............................................................................................................96 Carbon Steel vs Stainless.........................................................................97 Shielding Gases ........................................................................................98 Cold Cracking versus Hot Cracking..........................................................99 Distortion ...................................................................................................100 Penetration ................................................................................................101 Fabrication Time........................................................................................101 Welding Austenitic Alloys ..........................................................................102 Alloys under 20% Nickel ...........................................................................103 Alloys over 20% Nickel..............................................................................104 Gas Metal Arc Welding .............................................................................105 Flux Cored Welding...................................................................................106 Shielded Metal Arc Welding......................................................................107 Gas Tungsten Arc Welding .......................................................................108 Plasma Arc Welding..................................................................................109 Submerged Arc Welding ...........................................................................111 Resistance Welding ..................................................................................111 Weld Filler Selection .................................................................................113 Dissimilar Metal Joints ..............................................................................114 Heat Resistant Alloy Weld Filler Metals ....................................................115 BRAZING AND SOLDERING..............................................................................116 APPLICATIONS Bolts...........................................................................................................119 Cast Link Belts ..........................................................................................120 Muffles .......................................................................................................123 Radiant tubes ............................................................................................125 Rotary Retorts & Calciners .......................................................................126 Salt Pots ....................................................................................................126 Springs ......................................................................................................133 FIELD FAILURES ................................................................................................134 The Melted Radiant Tube .........................................................................134 The Hole in the Box...................................................................................135 The Culprit Copper ....................................................................................136 THUMBNAIL BIOGRAPHIES OF RA ALLOYS ..................................................139 CHEMICAL SYMBOLS........................................................................................140 BIBLIOGRAPHY ..................................................................................................141 HISTORY.............................................................................................................143 TRADEMARKS....................................................................................................144 GERMAN STANDARDS COMPARED WITH AMERICAN TEMPERATURE CONVERSION CHART

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along with several alloys designed for corrosion applications. Contact Rolled Alloys Technology & Marketing Services. RA 353 MA ®. Several of these are proprietary to Rolled Alloys. Our technical expertise. and copper produced. a newer edition may be available. +1-734-847-0561. specialty welding fillers and weld overlay wires.INTRODUCTION We cannot but marvel at the fact that fire is necessary for almost every operation. We have modified the chemistry and mill processing of RA330 on three separate occasions to maximize its effectiveness in heat treat applications. RA333®. We have an experienced sales force. 200 Rolled Alloys has specialized in supplying wrought heat and corrosion resistant alloys for a half century now. Pliny the Elder. We. By fire minerals are disintegrated. Beginning in the 1970’s. 2005 ©Rolled Alloys 2005 Note: This document continues to be developed and expanded. and we ha ve significant market share in others. Our current laboratory data. by fire gold is purified. in fire is iron born and by fire it is subdued. generated the data to obtain ASME Code coverage of RA330 to 1650°F (900°C). If your copy is more than two years old. RA 253 MA ®. includes documented field experience and laboratory studies back to 1952. our internal purchasing specifications are designed for more rigorous quality control levels than required by these industry-wide specifications. UNS or AMS chemistries. Rolled Alloys initiated and drafted eleven separate ASTM specifications for our proprietary and semi-proprietary alloys. James Kelly -1- . to create the present market for RA330®. Although RA330 and RA333 are both sold to published ASTM. Bulletin 401 minor corrections May 13. FAX +1-734-847-3915. and RA 602 CA TM alloys. laboratory personnel and a more detailed inventory of heat and specialty corrosion resistant alloys than any other supplier. and with those fabricators who also specialize in heat resistant alloy fabrication. has been generated under the direction of Timothy J. Rolled Alloys worked with the industrial furnace builders. Book XXXVI. to which this paper is an introduction. We currently stock over a dozen different grades of heat resisting alloys. Natural History. both oxidation testing and metallography. ten more aerospace grades used in gas turbine engines. Carney During these years. together with our suppliers.

the alloy becomes austenitic. and may be difficult to weld. the martensitic and the precipitation hardening. In spite of poor strength. There is a class of very low carbon martensitic stainlesses which obtain their high strength by an age-hardening.What are heat resistant alloys? Heat Resistant alloys. These materials cannot be strengthened by heat treatment. which is near the melting point of these materials. With the addition of 20% nickel to a 25%Cr-iron base. the alloy becomes austenitic. with roughly ten times the strength of RA446. or precipitation hardening. These include types 410. neither of these are of any use above 1200°F (~650°C). An addition of carbon permits the straight chromium grades to be hardened by heat treatment. They are magnetic. the so-called “885°F” (475°C) embrittlement. carbides or nitrides are effective. They have a body-centered cubic crystal structure. are simply iron with anywhere from 11% to about 26% chromium added. but they are not resistant to aqueous corrosion by sulphuric acid. molybednum or titanium is responsible for the precipitation hardening mechanism. When enough nickel is added to the iron—chromium mix. At room temperature the austenitics are more ductile and generally easier to fabricate. and above the temperatures where hardening mechanisms other than solid solution. and to attack by low melting point metals. Ferritic grades are very weak and often brittle. the same as does iron. to sulphur bearing atmospheres. Nearly all heat resistant alloys of interest to us are austenitic. An addition of copper (such as in 174PH®). at red heat. silicon. It is these austenitic alloyswhich are of primary interest to us. B and C. One example is RA310. They are non-magnetic as supplied. There are two fundamental types of heat resistant alloys. -2- . with 25% chromium. although after certain high temperature service conditions some may become magnetic. These ferritic grades also have a little manganese. The straight chromium grades also divide into two more classes of stainless steel. Note—the ferritic grades have some resistance to hot SO2 or H2S gas. Martensitic stainlesses can be heat treated to maintain high strength through about 900°F (482°C). all straight chromium grades embrittle severely after being held in the 700 to 1000°F (370 to 540°C) temperature range. and constitute the martensitic stainlesses. Austenitic alloys of interest to us cover the range from about 8% to 80% nickel. process. are those solid solution strengthened alloys (intended) for use at temperatures over 1400°F (760°C) and limited in the extreme to 2400°F (1316°C). The ferritic alloys. from our perspective. such as RA446. Like the ferritic stainlesses. ferritic heat resistant alloys may be used for their good resistance. The austenitic alloys all have much greater creep-rupture strength than the ferritics. as they are used over very broad temperature ranges. just like RA446. mostly included for their benefits in hot working the alloy at the steel mill. the “ferritic” and the “austenitic”. including molten copper. However. carbon and nitrogen. with a maximum use temperature of 1200°F (649°C). and the 440’s A. and much greater ductility.

02C 40Fe 0.45 2.16N 0.15N 73Fe RA410 RA410S RA17-4 RA321 RA347 ® Stainless 12 -12 -15.Rolled Alloys Products.2 0.3 17 9.2 3 --- 19 20 19.08C 0.7 50 0.3Cu 0.6 Cb 0.40C 43Fe 0.5 0.05Ce 36Fe 0.3 0.17N 0.05C 52Fe 0.10C 2Fe 0.06C 2Fe 0.14C 0.7 35 63 31 13 20 76 61.5 24 0.9 2.2 -- 0.3 9.6 13 37.4 --- -0.2 0.0 19 35 1.7 ------ ------ ------ ------ ---0.6 -----14 15 -0.3 0.5 3 ------------ 3 ------------ 3 ------------ -----2.1 52 51 52.25 21 11 1.2 3.5 22.3 0.5 -1.3Cb 75Fe 70Fe 0.5 61 0.3 TM WASPALOY 19 RA188 22 L-605 20 0.4 1.5 10.02Zr 0.5 4.2 3.4 0.4 0.05C 0. Nominal Composition Cr RA333® RA330® RA330HC RA 253 MA ® Ni Si Mo Co W Al Ti Other Heat Resistant 25 45 1.06C 3.07C 45Fe 0.5 1.5 0.3 21.01C 0.4 6.3 20 22.05C 18Fe 0.6 0.5Cb 70Fe 87Fe 87Fe 0.05C 43Fe 0.5 0.2 -0.6 --0.08C 8Fe 0.10C 2Fe -3- .2 -0.07 ---- 9 9 3 5.3Cu 0.25 19 35 1.001B 0.05C 0.04C AL-6XN RA20 Corrosion Resistant 20.7 57 22.05C 5Fe 5Cb 19Fe 0.5Cb 0.02C 48Fe 3.05C 14Fe 0.4 4 --- 1.8 9.05C 62Fe 0.04Ce 65Fe 0.08 19Fe 3.5 25 0.08Zr 9.22N 0.7 17.4 -- ------0.4 0.16N 67Fe RA X RA625 RA718 C-263 René 41® Aerospace 22 47 0.5Fe 0.08 RA 353 MA ® 25 RA 602 CA® RA800H/AT RA309 RA310 RA600 RA601 RA446 25 21 23 25 15.5 0.08C 3Fe 0.1 33 5.1 -0.4 --0.1Y 0.8 0.2 1.2 0.1 ---- ---- ---- ---- RA2205 0.7 --20 10.7 0.4 0.

sheet. sheet.Nr. strip (1. strip (2. Bars and shapes 1.(1.4833 SA-479 A 479 1.4633) Rod. strip (N08810) Rod and bar Smlss pipe &tube RA309 S30908 Plate.4763) RA600 N06600 Plate.4816 5665 5870 2. strip (2. strip (1. strip (2.4835 SA-312 A 312 SA-249 A 249 ASME Code Case 2033-1 -A 240 .4816) Rod.4833 SA-312 A 312 SA-240 A 240 5521 1. sheet.1. sheet.4845) Bars and shapes Pipe RA446 S44600 Plate.1.4833.4854) Bars and shapes Pipe RA 602 CA N06025 Plate.1.4845 SA-479 A 479 5651 1. sheet.4876) SB-407 B 407 SA-240 A 240 . wire Bar.4608 -B 719 5717 -B 722 -B 723 -B 726 SB-536 B 536 5592 1. strip (1. strip (1.4893 SA-479 A 479 1. bar.4851 5715 -4- .rings Smlss pipe & tube ASME ASTM AMS W. bar. sheet.1. strip (1. sheet.) RA333 N06333 Plate. forgings.4886) Bars & shapes Billets & bars Smless pipe.Nr.4851) Rod.4608) Bar Smless pipe.4763 SB-168 SB-166 SB-167 SB-168 SB-166 -SB-167 B 168 B 166 B 167 B 168 B 166 -B 167 -2. bar. strip (2. wire Smlss pipe & tube RA601 N06601 Plate.4933) Pipe RA310 S31008 Plate. sheet. strip (1.sheet.-SB-408 B 408 .4854 ---A 312 -B 168 2. tube Welded pipe Welded tube RA330 N08330 Plate.Heat Resistant Alloy Specifications Alloy UNS Product Form (W. tube Welded pipe Welded tube Fusion weld pipe RA 253 MA S30815 Plate.4886 SB-511 B 511 5716 -B 512 SB-535 B 535 SB-710 B 710 -B 739 -B 546 SA-240 A 240 . sheet. wire RA800H/AT N08811 Plate.4845 SA-312 A 312 -A 176 .4633 -B 166 SB-409 B 409 .4893) Bars and shapes Pipe Welded tube RA 353 MA S35315 Plate./EN -B 718 5593 2. sheet.

anywhere from 8% up to 80%. but heat resistant alloys are primarily alloys of iron. that is. Nickel counteracts. While RA446 with 25%Cr 75%Fe (iron) is a ferritic alloy. rather weak. IRON (symbol Fe) Heat resistant alloys may contain anywhere from 8 to 75% iron. is a ferritic alloy. with a face centered cubic (FCC) crystal structure. 75% iron. Both the tendency to form ferrite. When added to a mix of iron and chromium. Chromium adds to high temperature strength. -5- . High chromium also contributes to sigma formation. 55% iron alloy called RA310. that is. NICKEL (symbol Ni) Nickel is present. high temperature strength. Iron base alloys require a certain amount of nickel to be added before they become austenitic. RA310 is much stronger and more ductile than RA446. Again speaking metallurgically. In some proportions iron is a strengthening element. are counteracted by nickel. Silicon is one of the most effective elements in contributing carburization resistance. and to form sigma. RA446. Other elements are added to improve these properties. or body centered cubic (BCC) crystal structure. and a few are mainly nickel and chromium. chromium and nickel.EFFECT OF ALLOYING ELEMENTS Starting with a base of iron. Metallurgically speaking. and resistance to both carburization and nitriding. chromium tends to make the atomic structure “ferritic”. the tendency for an alloy to form sigma. but doesn’t necessarily stop. CHROMIUM (symbol Cr) Chromium is the one element present in all heat resisting alloys. if one substitutes 20% nickel for some of that iron one gets a 25% chromium. the most important alloying elements in heat resisting alloys are: chromium (Cr) for oxidation resistance and nickel (Ni) for strength and ductility. Iron itself has a ferritic. High nickel is bad for sulphidation resistance. Nickel decreases the solubility of both carbon and nitrogen in austenite. with a body centered cubic (BCC) crystal structure. nickel tends to make the atomic structure “austenitic”. Oxidation resistance comes mostly from the chromium content (the same is true of aqueous corrosion resistance). which is essentially 25% chromium. nickel increases ductility. iron is a ferritizing element. in all of the “austenitic” heat resistant alloys. Metallurgically speaking. 20% nickel. and to carburization resistance. but it is easily oxidized and carburized unless protected by other elements.

10% carbon. A silica (silicon oxide) layer. Nitrogen may be controlled like carbon as a strengthening element in both the heat and the corrosion resistant grades. the cast alloys are not very ductile.03%. as well as resistance to absorbing nitrogen at high temperature.. with RA 602 CA near 0.4841) and 1. continued THE NEXT GROUP of alloying elements present in all heat resisting alloys is silicon. have less than 0.S. CARBON (symbol C) Carbon. is a strengthening element.Silicon can decrease weldability in some. carbon. All the cast heat resistant alloys have silicon. They may either be tolerated at some level as undesirable impurities. In Europe silicon is used to improve a number of heat resistant alloys. Silicon. In corrosion resistant grades carbon is considered an undesirable element. Sulphur is generally undesirable. by contrast. Carbon is controlled within certain limits in heat resisting alloys as a strengthening element. and is kept as low as practical. While strong.EFFECT OF ALLOYING ELEMENTS. When not used deliberately. for example. is what helps the alloy resist carburization. silicon improves resistance to alkali metal hot corrosion. At high enough levels. -6- .04%. SILICON (symbol Si) Silicon improves both carburization and oxidation resistance.2%Si. but some sulphur is used to improve machinability.2%. nitrogen. there may be about 0.4828. alloys. such as the AvestaPolarit inventions.40% C. Silicon decreases the solubility of carbon in the metal (technically it increases the chemical “activity” of carbon in the alloy).05% or so N in austenitic stainless and nickel alloys. sulphur and phosphorus. The metallurgical effects of silicon are that it tends to make the alloy ferritic.75% carbon. in part because it increases fluidity of the molten metal.35% up to 0. Corrosion resistant grades. Phosphorus is quite harmful to weldability in nickel alloys. and sometimes much less. but it also becomes less ductile. even a few hundredths of a percent. and RA330HC at 0. or controlled for their effects on metal properties. The cast heat resisting alloys usually have from 0. affects the fluidity of the molten metal.03% carbon. just under the chromium oxide scale on the alloy. Most wrought heat resisting alloys contain around 0.05 to 0. As the carbon level increases. the 35% nickel content is more than enough to prevent any embrittling sigma to form from the Si. RA333® about 1% silicon. not all. RA330® has 1. Rolled Alloys has long been the only company to produce wrought heat resistant alloys containing silicon. RA 253 MA ® and RA 353 MA ®. In the U. which is an important variable in the steelmaking process. normally above 0. or to form sigma. All may be considered impurities arising from the steel making process. under 0. and the German alloys 314 (1. In RA330. the alloy becomes stronger.

001% being not uncommon. molybdenum. tungsten. This is fairly easy to do with current melting processes such as the AOD (argon-oxygen decarburization) or ESR (electro-slag remelt) furnaces. -7- . Nitrogen is used to strengthen Outokumpu’s heat resistant grades 153 MA ®. Because phosphorus is so harmful to nickel alloy weldability. Carbon may actually be dissolved in the alloy. the steel mill normally refines the metal to a very low sulphur content. NITROGEN (symbol N) A small amount of nitrogen serves to strengthen austenitic heat resisting alloys. and is commonly below 0. A small amount of nitrogen is specified in RA446. continued Carbon is an “austenitizing element”. titanium. This causes a little austenite to form (in with the ferrite) while it is being hot worked. Too much nitrogen can embrittle them.3%. Phosphorus cannot be removed during the refining process.02%. These are chemical compounds of carbon with chromium. To improve hot workability. the harmful effects of S on hot working and welding may be reduced to a degree by the addition of some manganese. Nitrogen at 0. and increases its resistance to chloride pitting corrosion. Sulphur is also detrimental to weldability. and tends to retard or prevent formation of ferrite and sigma. it is present as small. 253 MA ® and 353 MA ®.010% in most nickel alloys. and even lower P would be preferred. Nitrogen is also an “austenitizing” element. so for 304 and 316 bar it is kept up around 0. It has the benefit of improving machinability. may have much higher sulphur. 0.23% is used in the corrosion resistant alloy AL-6XN® to prevent sigma formation. This in turn helps keep the grain size from getting too large. or. likewise Haynes® HR-120®. AL-6XN is refined to extremely low sulphur. hard particles called carbides. one must start with low phosphorus raw materials. SULPHUR (symbol S) Sulphur is normally regarded as an impurity.CARBON (symbol C). more commonly. such as 303. ziconium or columbium (niobium). PHOSPHORUS (symbol P) Phosphorus is harmful to weldability. 0. Free machining stainless steels. To produce alloys with low phosphorus. It tends to retard or prevent ferrite and sigma formation. Along with simply removing the sulphur in the refining process. the nickel weld fillers themselves are normally specified to have no more than 0.015% phosphorus. and therefor maximize yields. It also raises the tensile and yield strengths of AL-6XN.

but oxidation resistant only to 1800 or 2000°F (1000 or 1100°C). and is added to many austenitic weld fillers. COBALT (symbol Co) Cobalt at the 3% level in RA333 improves strength slightly and enhances oxidation resistance at extreme temperatures. tungsten. aluminum. like nickel. Tungsten metal. 5% in the cast alloy Supertherm and 14% in Haynes alloy 230®. others like aluminum and the rare earth elements are largely for oxidation resistance. RA330-04 achieves its hot cracking resistance from about 5% manganese added to the 35%Ni 19%Cr base. lanthanum and yttrium. such as the 15%Co in cast Supertherm® or 12. Tungsten is a carbide forming element. Tungsten oxidizes in air readily above 950°F (510°C). 3% in RA333. with thoria or rare earth oxide additions. columbium (also called niobium). It increases solubility for nitrogen and has for decades been used in the Nitronic® series of stainless steels from AK Steel (formerly Armco). TUNGSTEN (symbol W) Tungsten is a large. which is required for this application. Cobalt base alloys L605 and 188 are very strong. molybdenum. It is mildly detrimental to oxidation resistance. to 0. High cost and variations in availability tend to limit the use of cobalt alloys to gas turbine engine applications. Copper and vanadium are used in some corrosion resistant alloys but not in the heat resistant grades. Some of these elements are added for strength. -8- . so is limited to 2% maximum in most heat resistant alloys. 6170°F (3410°C). Larger amounts are required for a significant strengthening. in RA 253 MA. and boron. Cobalt is an austenitizing element. but is prevented from doing so by the argon or helium weld shielding gas. Tungsten also promotes formation of sigma. zirconium.5% in the LBGT combustor alloy 617. manganese. continued OTHER METALLIC ALLOYING ELEMENTS include cobalt. Manganese improves weldability. and restricted further. that is. the rare earth elements such as cerium.EFFECT OF ALLOYING ELEMENTS. MANGANESE (symbol Mn) Manganese is used in steelmaking to improve hot workability. titanium. Manganese is usually considered an austenitizing element. is used for the electrode in gas tungsten arc welding. which may incorporate other carbide forming elements such as chromium. it reacts with the carbon in the alloy to form a hard particle. both as a partial substitute for nickel and to permit a substantial nitrogen addition. heavy atom used as a strengthening addition.80% max. It is tungsten’s very high melting point. and of ferrite.

X750. Around 0. TITANIUM (symbol Ti) Titanium is added in small amounts.-0. but it is normally used in such small amounts as to be inconsequential in this respect. -9- . and Haynes 214 4.3. Age hardening alloys used in aerospace. RA 602 CATM has 2. Aluminum is a ferritizing element.4% Al.1—0. Renè 41®.. 3% Mo is used in RA333. heavy atom used to increase high temperature creep-rupture strength. WASPALOYTM and 718. Commercially pure molybdenum metal is used for vacuum furnace fixturing. In aqueous corrosion alloys titanium is referred to as a “stabilizing” element.5% aluminum.MOLYBDENUM (symbol Mo) Molybdenum is another large.2% Al. cobalt. Molybdenum is also a carbide forming element. depend upon some larger amount of titanium. as part of steel mill melting practice.2%Ti is used. Molybdenum promotes sigma formation. Titanium also promotes sigma and ferrite.4%. Titanium metal itself. unless counterbalanced by austenitizing elements such as nickel. etc. alloy 601 contains 1. and is a ferritizer. although it has a very high melting point (3040°F/1671°C). At around 0. in the last stages of AOD refining. about 0. because of its very high melting point. and promotes sigma formation. in deoxidation of nickel alloys. Ti is a strong carbide former. to 3% or so. ALUMINUM (symbol Al) Aluminum is added at the 1 to 5% level for oxidation resistance. and high temperature strength. 4730°F (2610°C).1 to 0. C-263. such as A-286. It is used in the age hardening (precipitation hardening) alloys. both stainless and nickel base. and it is the titanium carbides that strengthen RA800AT. 625 and 617 all contain 9% molybdenum. However. for their age hardening properties. the various Nimonic® alloys. Alloys X. for strength in austenitic alloys. This is about as much Mo as can be tolerated in a heat resistant alloy without serious oxidation problems in heat treat furnace applications.7%. aluminum is added to most nickel alloys as a deoxidizing agent. which is very good for strength but not so good for oxidation at extreme temperatures (2100°F/1150°C). is not really a heat resistant metal. Titanium alloys are used up to about 600°F (316°C) in aerospace applications. Molybdenum helps weldability in austenitic alloys. molybdenum metal has no oxidation resistance above 800°F (427°C) and would literally disappear in a cloud of white smoke if exposed to air at red heat.

since about 1940 in Germany. It is added in very small amounts. Columbium is very harmful to oxidation resistance.6% Cb in 625 is good for both strength and weldability.02 to 0. and to prevent corrosion after welding in 347 stainless and nickel corrosion resistant alloys 20Cb3®.1%. A larger amount.1% level for oxidation resistance in 214 and RA 602 CA. The technology has been known. ZIRCONIUM (symbol Zr) Zirconium is a strong carbide former.05% range to for oxidation resistance in Haynes alloys 230.COLUMBIUM (symbol Cb) . 556 and 188. called mischmetal. At the 5% level. 0. The cerium is added as an alloy of several rare earths.5%. In RA 253 MA and RA 353 MA the Ce helps chromium form a thinner. As yttria. YTTRIUM (symbol Y) Used at the 0. and in the newer ferritic heat resistant alloys. CERIUM (symbol Ce) Cerium is the major rare earth element responsible for the excellent oxidation resistance of RA 253 MA. G-3 and G-30.7%Cb is used in various high nickel weld fillers (82. of yttria (Y2O3) is used as an oxide dispersion strengthening element in the ODS ferritic alloys such as Inconel® MA956. lanthanum and yttrium are used singly or in combination to increase oxidation resistance in austenitic alloys both wrought and cast. For this reason we limit the amount of residual Cb that may be present in RA330. LANTHANUM (symbol La) Used at the 0. it also increases oxidation resistance. a ferritizing element and promotes sigma formation. it is the age hardening element in alloy 718. less than 0. 182). Residual cerium oxides in the metal may contribute to creep-rupture strength.4 to 0. the mill analyzes only for Ce. For chemistry control purposes. .005 to 0. while the 3. to increase strength in RA 602 CATM. also called NIOBIUM (symbol Nb) Columbium is added at the 0. About 2 to 2. Columbium is a strong carbide former. tighter and more protective oxide scale. and in RA333. . and in alloy 214. S. It oxidizes (burns) very readily.8% level for strength in several heat resisting alloys. while higher amounts are beneficial.10 - . THE RARE EARTH ELEMENTS cerium. . but little used. Mischmetal is encountered in everyday life as the “flint” in a cigarette lighter. This low amount of Cb is harmful to weldability. practically speaking around 1800°F/980°C and higher.

It is used in high temperature braze alloys.002% is typical. This is specifically true of alloys such as RA333. and is used at rather low concentrations. specifically the Nickel-Silicon-Boron braze alloys developed by Dr.BORON (symbol B) Boron increases creep-rupture strength. X and 230. Boron is somewhat harmful to weldability of nickel alloys. Boron is an interstitial element and tends to concentrate at the grain boundaries.11 - . even though the matching base metal alloy has a boron addition. Robert Peaslee. so nickel alloy weld filler is often made without boron. . 0.

or denickelification2 of the 67Ni-31Cu alloy Monel® 400. Corrosion Problems with Copper-Nickel Components in Sea Water Systems.RESISTANCE TO THE ENVIRONMENT “Corrosion resistance” at high temperatures is a general term for resistance to a variety of hot gaseous or liquid environments that can eat holes through the metal.. It is difficult to run high temperature corrosion tests in the laboratory and obtain results that can be used to predict metal behavior in service. liquid metal environments and other types of high temperature corrosion. NACE Corrosion 98. with a critical eye. at that test temperature. turn it completely into a pile of scale or seriously embrittle a formerly ductile alloy. good performance of a new alloy in this test only indicates that the alloy MAY perfo rm well in service. Heavily carburized metal actually increases in volume. Still. carbon. 1948 2. Read these data. The types of high temperature corrosion most commonly encountered are oxidation.12 - . chlorination and attack by low melting metals. sulfidation. The Corrosion Handbook. but the laboratory test itself must be validated by documented service experience for it to be a useful engineering tool. Based on extensive experience and lab work. if not encountered. but is less often considered. carburization. Nevertheless in high temperature corrosion selective removal of one or more alloying elements through the life of the equipment is the norm. chlorine. In many high temperature environments one significant effect of corrosion is to continuously change the actual chemistry of the alloy throughout its life.D. as well as those of other suppliers. Even two laboratories running the same type of test may not come up with numerical results that agree with one another. Lenard and R. sulfur.R. John Wiley & Sons. the data are not directly useful for predicting metal wastage/corrosion rates of high temperature equipment in service. NACE Houston. edited by Herbert H. In the following pages we will present the results of both laboratory testing. we have confidence that our oxidation data may be used to compare relative performance of one alloy with another. D. Welland. As oxidation rates vary with thermal cycling. It includes (but is not limited to) the effects of oxygen. hot salt corrosion. phosphorus. Texas . With the exception of selective leaching (parting corrosion). although the alloy rankings should be similar. page 69. controlled service experience and experience reported by others. the metal may increase in carbon and nitrogen content. with consequent major change in mechanical properties. We must emphasize that laboratory data are a necessary first step. New York. Or. Paper Number 599. It is even more difficult to obtain data useful as an engineering tool to predict life of equipment in sulphidation. Nitriding may be important. various molten salts and low melting metals. Uhlig.R. this is rather uncommon in aqueous corrosion of nickel base alloys or stainless steels. nitrogen. the examples being dezincification of copper-zinc alloys 1. and no loss in cross section. References 1. Ph. among other variables. carburization.

It also cracks from both thermal and mechanical strains. Because of its high melting point. which is more protective against oxidation because it cracks and spalls off less than would a thicker scale.04% cerium in RA 253 MA that is responsible for the excellent oxidation resistance of this rather lean 21Cr. There are two basic ways in which a metal may be resistant to oxidation.OXIDATION For our purposes. which protects it from further oxidation. Silicon oxidizes to SiO2. coupled with oxidation resistance. the scale must be able to “heal” these defects. but once formed it protects the metal against further oxidation. The second way a metal may resist oxidation. otherwise known as chromia. There is no actual flame. or scale. it may be inert and simply not react chemically with oxygen in the air. silicon also contributes to oxidation resistance. the precious metals gold (Au) and platinum (Pt). the silica forms a sub-scale underneath the chromium oxide scale. Although chromium itself oxidizes even more readily than iron. this means the high temperature chemical reaction of a metal with the oxygen in the air. Cerium promotes a thinner scale. It forms the oxide Cr2O3. and the one of interest to us.5%. One of the most effective is silicon. The effectiveness of the chromium oxide scale may be improved by very small additions of rare earth elements. 3217°F (1769°C). like magnesium (once used in flash bulbs) and titanium do burn in the conventional sense and cause serious industrial fires. In RA85H. At the 1. but a red hot “coal” develops and enough sparks fly to endanger clothing. by more chromium diffusing to the surface to form a new protective film. For a high temperature alloy to have useful oxidation resistance. Of course. Two examples come to mind. Simply put. Other elements are added to the alloy to improve the protective nature of this oxide film or scale. This silica subscale is how silicon provides resistance to carburization. to a degree. At this high level silicon appeared to offer resistance to molten alkali salt corrosion. 11Ni alloy. and small pieces spall off each time the metal is cooled down. the oxide it forms is very thin. which is no longer produced. such as cerium. is that the metal or alloy may form an adherent oxide film. platinum is actually used for some laboratory ware and other items which must withstand extreme temperature. It is the 0. lighting a match to a nail does absolutely nothing. The scale contains defects through which oxygen and other elements may pass. is chromium. But if one takes very fine iron wire—specifically.13 - . and adheres tightly to the metal. the silicon was much higher. Even iron burns. The chromia scale also protects the alloy against carburization and sulfidation. most metals can burn when they get hot enough. to continue to react with the alloy. in alloys such as RA330. First. Some. 3. 0000 steel wool—it may indeed be ignited by a match. If enough silicon is present. or silica. The protection is by no means perfect. This oxide layer forms very quickly at high temperature.2% Si level in RA330. . The element most often used to form such a protective oxide layer.

continued Aluminum is also used to improve oxidation resistance. RA 602 CA does not oxidize internally. is inclined to be tightly adhering.5% aluminum in Haynes alloy 214 is enough to form an alumina scale.7% Al typical in alloy 601 is not enough to form an alumina scale. The 4. thereby offering little or no protection. 601 oxidizes internally. silicon and other oxides are more tightly adhering than others at different temperatures. Certain combinations of chromium. In order to actually develop an Al2O3 . because the base metal and the oxide expand and contract at different rates. depending upon its thickness and which of the numerous chromium oxide compounds is formed. scale a rather high amount of aluminum is required. and effectively seals out the air or oxygen from the metal underneath. it is actually the most easily oxidized. So long as the oxide layer is intact. nickel. With some alloys it is possible to reach a temperature where the scale or oxide is no longer tightly adhering and will be loose. blue or yellow. or the cutlery on our dinner tables. as the result of heating and cooling. This is not a problem in plate gauges. The 1. the oxide coating becomes green.14 - . and 214 is extremely oxidation resistant (above 1800°F/982°C). This may sound like double talk. iron. it is oxidized and a layer of chromium oxide (and oxides of other elements as well) is formed. Some examples are 321. the metal is protected and further oxidation proceeds very slowly. The Protective Film While chromium is given credit for promoting oxidation resistance and is without question the most effective element in this respect. will “pop” the oxide layer. and 309. This in turn depends upon the temperature and availability of oxygen to combine with chromium. which is acceptable at 1600°F (870°C) but scales unacceptably at 1800°F (980°C). This contributes to the oxidation resistance of RA 602 CA. but it really isn’t. even at room temperature. has a microscopically thin and transparent film of chromium oxide present. or alumina. The oxide layer is dense. At 2. Several things may tend to destroy our protective layer: Expansion and contraction. though perhaps it may be a consideration in thin sheet. Even the chromium plate on automobiles. When pure chromium or a chromium-bearing alloy is exposed to oxygen. When formed at high temperatures. Because of aluminum at this somewhat lower level. the more hazard there is of the protective coating flaking off. . an excessive temperature for the specific alloy can destroy the protection normally offered by the oxide layer.2% aluminum. The more rapid the rate of expanding and contracting. or the more quickly the metal is heated and cooled. Thus.OXIDATION. which isn’t very useful above 1900°F (1040°C). RA 602 CA alloy will form an alumina subscale. but it is enough to enhance oxidation resistance of 601. black.

We have observed this on 309 (above) and 310. Laboratory data which do not duplicate cyclic conditions or stresses imposed in actual service can be misleading as a measurement of an alloy’s oxidation resistance. such as the stretch of a bar under load. Mechanical deformation and creep. Upon investigation we found that the alloy had been heated in service to the incipient melting temperature.2metre) on the firing end. U sed at a nominal furnace operating temperature 1750°F ( 955°C) for annealing malleable iron castings. a given item may appear to have insufficient oxidation resistance. the oxide coating is fragile and brittle and will spall off. A jam-up in the furnace broke the tube.The Protective Film. RA330 and 600 alloy. . continued Composite radiant tube. The grains were sliding apart so as to leave voids at the triple points. a condition sometimes called “warts”.15 - . RA333 for 4 feet (1. resulting in apparent porosity of the 11gage (3mm) muffle wall. On one occasion we saw warts on an RA333 brazing muffle. When an alloy is used at a temperature exceeding its capabilities the scale may breakdown locally. on the RA309. It is to be expected that the tube metal temperature would be perhaps 100—150°F (55—85°C) higher. Note the crater-like appearance of local oxidation. In service. may also destroy the protection. middle portion RA330 and exhaust end fabricated of RA309. or warts. whereas that particular property would have been more than adequate had the strength been sufficient to avoid excessive creep. While the metal is ductile and yields in creep. occasionally on RA 253 MA.

Fluoride-bearing fluxes from coated welding electrodes must be carefully and thoroughly removed. is not reduced. Cast Heat-Resistant Alloys for High-Temperature Weldments: “Where in fact the addition of molybdenum has conferred . green rot. oxidation resistance and thermal shock resistance requirements were not suitable. since there are now voids in the coating where some of the oxides previously existed. This actually has little strength and no ductility. It has the characteristic greenish-black color of chromium oxide and. which disappears as a powder. columbium (niobium) and vanadium. so that the alloys normally selected for the strength. Upon exposure of the alloy to an oxidizing environment once more. being more stable. has the appearance of rotten wood. the oxygen is free to penetrate to the metal and form another layer of oxide. Otherwise they continue to function as a flux. Another form of chemical destruction that may be encountered is corrosion from welding fluxes. The salts attacked the protective oxide coating. a mass is eventually formed consisting only of porous chromium oxide. as we previously discussed. Avery’s classic work on heat resistant alloys. they act as fluxes and destroy the protective film1. we know of one case where minute amounts of potassium nitrate/nitrite austempering salts were present on fixturing used in a carburizing atmosphere. a protective oxide coating is formed. Green rot is the result of the alloy being alternately exposed to oxidizing and reducing conditions. damaging not only oxidation resistance. The presence of this chloride salt resulted in a chemical attack upon the protective oxide coating. With continuous exposure to the two conditions.16 - . Catastrophic oxidation is. If these oxides are formed and retained in the scale. but the chromium oxide.The Protective Film. green rot tends to be more prevalent in alloys containing about 65% or more nickel. continued Of great concern are environments that promote the destruction of the protective layer by some chemical reaction. When the alloy is exposed to highly reducing conditions. upon fracture. but also carburization resistance. the nickel and other less stable oxides may be reduced to pure metal. In years past. oxidation which proceeds so rapidly that complete failure of the material occurs in an extremely short time. we knew of a few cases where parts being heat-treated were first coated with sal ammoniac (ammonium chloride). 2. with or without other oxides that may have been sufficiently stable to resist reducing. so that a normally carburization resistant alloy carburized very quickly and uniformly. form oxides that are volatile at relatively low temperatures. as its name implies. For example. To the best of our knowledge. The effect of molybdenum is important enough that we would like to quote directly from the late Howard S. Green rot might be considered one form of destruction of the protective oxide coating. such as molybdenum. Certain elements. Hence the name. When the alloy is exposed to the oxidizing environment.

For example. However they are of value when one compares the data from new alloys. or solid deposits under which the atmosphere is of course stagnant. alloy X may not well tolerate stagnant conditions or temperature extremes. As a simple coupon test for 3000 hours or so does not simulate all the things that can happen in service. or underneath solid deposits. and the tests are cyclic. which may occur in certain areas of electrically heated equipment. 4 . 22% chromium and 9% molybdenum. This is most serious under those conditions that cause catastrophic oxidation which stems from the volatile nature of molybdenum oxide (MoO3). At lower temperatures in free-flowing atmospheres alloy X is highly oxidation resistant. If an alloy performs well on test. a stagnant atmosphere. That is. Likewise. It has. Specimens are usually of plate gages. and extreme temperatures. containing 47% nickel. we have a great deal of experience with the good performance of RA333 and RA330. Results are reported as weight gain. Alloys with high molybdenum contents are subject to catastrophic oxidation under these conditions. that is. with those of existing grades. generally around 1900°F (1040°C) or above.4665). W. after all.The Protective Film. the chief problem may be surface stability. lids are quickly placed on the crucibles to contain spalling oxide. 4 to 6 in a tray. Alloy X (N06002. especially in the 1800— 2300°F (980—1260°C) range. that means it MAY perform well in service. Samples are heated in porcelain crucibles.17 - . is then weighed every cycle. it is possible for an alloy to look very good in the laboratory and not at all so good in production equipment. The tray is then removed from the furnace. . 309 is about the only one of our heat resistant alloys that occasionally gives disappointing performance. This oxide is likely to form in stagnant atmospheres. Which means they are not useful for predicting metal wastage of components in actual service. One thing the coupon test does not simulate is the effect of creep strain spalling off the scale.” Catastrophic oxidation may be a serious problem under certain operating conditions. may completely disappear from catastrophic oxidation when heated for some months at 2200°F (1200°F). The crucible. Another is the effect of stagnant atmospheres. We measure weight gain. in milligram/centimeter2 . at temperatures up to 2200°F (1204°C)3. The numerical results are valid only for the specific conditions of the test. with a threshold for trouble around 1400—1500°F (760—816°C). served for decades as the primary alloy used in gas turbine flight engine combustors. Laboratory Oxidation Testing In order to evaluate new and competitive alloys we perform considerable laboratory oxidation testing at Rolled Alloys. However. continued better hot strength.Nr. 2. the total amount of oxygen (and nitrogen) that has reacted with the test specimens. and the assembly allowed to air cool to room temperature. containing specimen and scale. for about 160 hours (one week) at temperature.

it would be hard to make a case that a 4 month test adequately represents service conditions. alloy 600 plate is a useful material for retorts and muffles operating in the 2100-2200°F (1150—1200°C) temperature range. As this is weight gain data. Note 600 alloy which shows a 153 mg/cm2 weight gain at 2100°F (1149°C). small numbers a relatively light degree of oxidation. in order to compare all alloys for about the same exposure time. All but the RA309 tests were run for 3000 hours. simply from having less total chromium. continued And. may show greater oxidation rates than thick specimens. In our considered view. However. RA 602 CA is clearly the best by far in our test series. Thin samples. unlike what is assumed about aqueous corrosion rates. in plate form.S. The alloys were cycled to room temperature once a week. If one expects the equipment to last 1. Nevertheless. Another point to remember is that alloys high in molybdenum and columbium may be sensitive to catastrophic oxidation. we know that 304 1/4” plate will simply disappear in 2-3 months when used in air around 1700-1800°F (930—980°C). 310 is somewhat superior to RA330. as a guide to an alloy’s usefulness. high numbers mean heavy oxidation. should not lose structural integrity due to metal loss. RA330 better retains its protective oxide. which does not take into account many of the ways by which the protective oxide scale may be damaged. which gains 64 mg/cm2 at 1600°F (871°C). has generated pressure to extrapolate such data. By experience. or other high temperature corrosion data. The specimen continually changes chemistry throughout the test (it loses chromium. significant extrapolations of oxidation. One would expect to use these numbers. Nevertheless the declining availability of experienced engineers in the U. but that is still only about 4 months. along with service experience. somewhat differently.18 - . Bear in mind that these data still represent simple laboratory oxidation testing. and in the neighborhood of 300 mg/cm2 at 1800°F (982°C). One might want a little actual service background when considering alloys with weight gains in the 100-300 mg/cm2 range. for example. More rapid thermal cycling would not only increase oxidation rates but might also change the relative performance of some alloys. finally. for more elevated temperatures. valid or not.OXIDATION. particularly under stagnant atmospheres. When thermal cycling is added. Likewise RA 353 MA is used quite successfully at such temperatures. Numbers under 20 may give assurance that the alloy. the laboratory test does not properly simulate time. We would look at the higher alloys.A. that one being extrapolated from a 1600 hour run. . 3000 hours seems a reasonable length of time to run a test in our laboratory. silicon and aluminum by scaling). The good resistance to scaling of RA 602 CA in test has also been borne out by service experience in rotary calciners and CVD retorts. One example is 304 stainess. 2 or 10 years. are not valid. Data shown on the following bar graphs is all for 3000 hour (~18 weeks) exposure. In static 1000 hour oxidation testing. oxidation data ought in our opinion be viewed qualitatively.

Vol 41. Transactions ASTM. Avery. Pennsylvania 2. 980 1095 and 1150C. J.19 - . Nos. Leslie and Fontana. Conference Proceedings of the 2 nd International Conference on Heat-Resistant Materials 11-14 September. 1949. HeatResistant Materials II. Oxidation Rates of Some Heat Resistant Alloys.C. Wilson. Oxidation Resistance of Eight Heat-Resistant Alloys at 870. pages 1213-1247. Tennessee . Gene Rundell and James McConnell. New York 3. 3/4. Oxidation of Metals. ASTM Philadelphia. Kelly and J. August 1969. New York. H.D. WRC Bulletin 143. Welding Research Council. 1995 Gatlinburg. Vol. 36.S. Cast Heat-Resistant Alloys for High-Temperature Weldments.References 1. 1991 4.

20 - RA 253 MA RA330 .Exposed for 3000 Hours Cycled Every 160 Hours 250 200 200 Weight Gain (mg/cm2) 154* 150 113 1600F 1800F 2000F 2100F 100 64 53 54 32 19 1 5 20 11* 1 4 50 0 RA304 RA309 RA310 Alloys .

Exposed For 3000 Hours Cycled Every 160 Hours 350 333 324 295 300 Weight Gain (mg/cm) 250 232 1800F 2000F 2100F 2200F 2250F 156 138 2 200 150 143 145 153 100 83 58 61 50 36 21 4 11 4 18 34 21 12 11 18 49 50 32 0 RA800H RA625 RA600 RA X RA 353 MA RA333 RA601 RA 602 CA Alloys .21 - .

low carbon steel parts are heated in a prepared furnace atmosphere that provides the carbon which diffuses into the surface layers of the steel.CARBURIZATION The femper of Iron for Files It must be made of the best Steel. many heat treat cycles. it is still oxidizing to the chromium and silicon which provide most of the alloy’s resistance to carburization. and beat them together. that they may be covered all over: then put on the cover. The end result is that low carbon steel parts acquire a high carbon steel surface. But I shall teach you to temper them excellently G. radiant tubes and other fixturing in the furnace also pick up carbon through many. and then lay a heap of burning coals all over it. charcoal and all.22 - . and put them into it. and crossways. for the Salt will melt with any moisture of the place or Air. and so they will become extream hard. The powder being prepared. that it may polish. Typical composition1 of an endothermic gas (Class 302) is 39. For perhaps three thousand years it was performed by packing the low carbon iron parts in charcoal.7% hydrogen and 0. 1589. and excellently tempered. like the steel work pieces. then make an Iron chest to lay up your files in. The fixtures are made of carburization resistant alloys. Even though the atmosphere is reducing to iron. Sources for the History of the Science of Steel 1532—1786. once the heat resistant alloy has picked up sufficient carbon. Temperatures are usually around 1750°F (950°C).7% carbon monoxide. Cyril Stanley Smith Carburizing is one of the most commonly performed steel heat treatments. controlled addition of a hydrocarbon gas. and lute well the chinks with clay and straw. and plunge the files into very cold water. then raising the temperature of the pack to red heat for several hours. Even a carburization resistant alloy eventually carburizes. may also be used as a carrier gas. Nevertheless. or an easily vaporized liquid. This is the usual temper for files. This carrier gas is subsequently enriched by a small. with a dew point –5°F (–20°C). which is the source of carbon. . The entire pack. from bulk tanks. made by partially burning natural gas. strewing on the powders by course. with a sharp edged tool: having made the Iron tender and soft. while the interior or “core” of the part retained the toughness of low carbon steel. make your iron like to a file: then cut it checquerwise. for we fear not if the files should be wrested by cold waters. Now. B. beaten Glas. that it may be red-hot about an hour: when you think the powder to be burnt and consumed. was then dumped into water to quench it.8% nitrogen. The surface became very hard. as I said. and Chimney-soot. and put them into an Oven to dry.8% methane. and lay them up for your use in a wooden Vessel hanging in the Smoak. that they may be powdered fine: mingle well one part of this with as much common Salt. This atmosphere has traditionally been “endothermic”. 100% nitrogen. such as propane. 20. Pack hardening is uncommon today. that the smoak of the powder may not breath out. its room temperature ductility will be greatly reduced. and fit other iron as it should be: Take Ox hoofs. The alloy bar frame baskets2. with propylene or other hydrocarbon injected to provide the necessary carbon. 38. Ed. Austenitic alloys do not harden when quenched. take the chest out from the coals with Iron pinchers. Della Porta. When the steel is quenched it combines the hardness and wear resistance of this high carbon steel “case” with the toughness of the low carbon steel interior (core).

The oxide scale is primarily chromia. The degree of embrittlement depends upon the amount of carbon absorbed3. so that a very high nickel grade simply will not carburize to the same level as will a lower nickel material. Even RA309 has somewhat better carburization resistance than RA 253 MA. which is of practical consequence in steel coil annealing covers. RA601 and RA 602 CA are all more carburization resistant but also more expensive. RA330 usually does the best job for the money. This. once an alloy has absorbed about 1% carbon it will no longer have measurable room temperature ductility. 800H does not well tolerate the effects of carburization.Carburization embrittles high temperature alloys. We once examined a sample of 310 sheet which contained 4% carbon. and the common stainlesses do not possess adequate resistance to carburization for use as fixturing in commercial carburizing heat treat furnaces. with silicon being a very potent assist5. or impacted at room temperature. so that they can not be straightened or weld repaired. Carburization resistance in an alloy is conferred almost entirely by the protective oxide scale 4. Generally speaking. Enough ductility may remain while at red heat for the metal to perform its task. and could readily be broken by hand. absorbed during service. RA 353 MA. but RA 253 MA is not resistant to carburization. RA600. Ferritic grades such as 446 are quite poor in carburization resistance. so long as it is not excessively strained at high temperature. 2. grain growth is from the operating temperature. RA 253 MA has worked as furnace fixturing because it is strong. These lower alloys such as RA309 and RA310. and more importantly. along with the nickel content. because it is invariably coarse grained. . Carbon enters the atmosphere from the organic compounds used when the green powder compact is pressed. Nickel lowers the solubility of carbon in the alloy. and upon the microstructure. Alloy 601 used in a powdered iron sinteri ng muffle.23 - . RA333. in part because it lacks silicon but also. Brittle fracture at room temperature comes from the large amount of carbon.34%. The nitrogen-hydrogen atmosphere is not supposed to be carburizing.

Not due to carburization.Carburization. As the alloy will not develop much of a protective scale. On high fire this soot burns out. test time is important. as nitrogen from the atmosphere can react with alloying elements such as chromium. Carburization testing Laboratory carburization testing must be carried out in some approximation of the industrial atmosphere of interest. the silica subscale.24 - . . Finally. This is one reason why full penetration welds of the return bend to straight leg are essential for maximum life in radiant tubes. The growth of this soot deposit acts like tree roots growing in rock. We have noted that carburization resistance depends upon the chromia scale. locally overheating and weakening the metal. There have been laboratory carburization tests run in an atmosphere of hydrogen—2% methane. One may also wish to consider the nitrogen level. Whether ethylene tubes or heat treat fixtures. we emphasize the need to have designs and weldments that do not provide crevices in which carbon deposition may occur. On low fire soot may deposited in the root crevice (as well as in surface defects of cast return bends). then. in order to form a similar protective scale 7 . As it is the oxide scale which is primarily responsible for carburization resistance. such an atmosphere is an excellent way to achieve the objective of actually carburizing the alloy. with no control of oxygen partial pressure. such as cracks in weld joints or surface defects on castings. and may affect carburization. In the case of wrought alloys. which are free of surface defects. becomes a handy tool to judge whether or not alloy fixturing has enough ductility remaining to be weld repaired or straightened. In addition it would be a good idea to include thermal cycles about like the expected service conditions 6. it is unlikely that such a test should rank alloys as they perform in actual service. in some grades. continued When nickel heat resisting alloys become carburized. The test temperature should be similar to that anticipated in service. and. it happens that many also become magnetic. Soot may deposit from the atmosphere and “coke” in any crevices. It literally pries open lack of fusion in the weld or turns small pin holes into large cavities. but a purely mechanical problem that may occur in a carburizing atmosphere is of some concern. A pocket magnet. some partial pressure of oxygen is almost always present. For this reason the test atmosphere must contain an oxygen partial pressure comparable to the expected service atmosphere.

92 .045” (1. and the 1750°F (954°C) results are from plate samples exposed to the actual furnace operating temperature.443 1. Various depth of cuts were machined in the samples and the carbon contents analyzed. There is some period of time during which significant carbon absorption does not take place.25 – . carburization testing may require long exposure.20” (0. 1900°F (1038°C) are from a composite electric heating element made of the five alloys shown. before the results correlated with service experience. The higher temperature results. Experience related to us from one furnace company indicated that the test had to be run for at least 1000 hours.14mm) depth on the element and 0.56 -- 1750°F (954°C) 4300 hour exposure %carbon 0. Alumina and titania will not be dissociated by this atmosphere.344 0. for example.03 2. This is necessary to dissociate the oxides of most alloying elements.0-1.86 2. to inhibit brazing. 70% of the hours in nitrogen. Even alloy 800H contains enough titanium to turn light gray in a common vacuum heat treat furnace.53 3. The following results. N06025 and N0811 would form aluminum and titanium oxide films in a nominal hydrogen— methane atmosphere. When the atmosphere simulates that of industrial interest. In order to braze even stainless steel (with no Al or Ti) in hydrogen it is normally considered that the dew point should be –60°F (–51°C) or lower8 .508mm) depth on the plate sample. Very small amounts of oxygen can form enough alumina or titania scale. 1900°F (1038°C) 2260 hour exposure alloy RA333 RA330 617 601 600 310 %carbon 1. In both cases the total exposure hours were distributed as follows: 20% of the time in endothermic gas enriched with natural gas to carbon potential 1. Such films may affect carburization.6 1. Results here are reported at 0.2%C relative to iron.Carburization testing. One might expect that grades such as N06601. from that same company.98 1. continued In the absence of dew point (oxygen partial pressure) control the results may not even be repeatable. and 10% of the time reflected air burnout cycles at 100°F (56°C) reduced temperature. are from tests conducted in an electrically heated industrial carburizing furnace.096 -3.

METAL DUSTING A somewhat aggravating problem in carburizing atmospheres is “metal dusting”, a.k.a. “catastrophic carburization”, or “carbon rot”. This occurs at lower temperatures, typically 800—1200°F (430—650°C) in heat treating furnaces. Such temperatures exist in a carburizing furnace (nominal 1750°F/950°C) where alloy tube hangers, atmosphere sampling tubes or electrical leads pass through furnace walls, and in some areas of Ipsen furnace chains. The exact mechanism may be disputed, but the effect is that the metal disappears. A bar may look just like a beaver had chewed away on it. In other cases, the metal literally appears worm-eaten on the surface. In the petrochemical industry, a small amount of sulphur (40—50 ppm H2S) is sometimes added to the process gas stream to “poison” the high temperature chemical reaction that is metal dusting. Alloys vary greatly in susceptibility to metal dusting. RA333, by experience and several years testing in the heat treat industry, is the best known choice. RA85H was also good, though not quite so resistant as is RA333. RA330 is so-so, 800H perhaps worse, and 600 alloy is the least resistant. Neither 310 nor 601 will solve metal dusting problems. One direct alloy comparison, below, shows two RA333 GMAW beads with only minor surface smoothing, while the 3/16” (4.8mm) RA310 plate between them suffered nearly complete loss of section9.

This example is from a rotary retort used to carburize small parts at an operating temperature of about 1750°F (940°C). Spiral flights of RA310 welded to the inside served to transport work pieces through the retort. As the retort was externally fired, the 3/8” (7.9mm) 600 alloy shell was above the temperature range for metal dusting. Metal dusting was a serious problem with flights at the entry end of the retort. Here the cold work pieces chilled the RA310 flights down into the metal dusting temperature range.

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METAL DUSTING, continued

Furnace chain severely attacked by metal dusting. This is an application where RA333 has given the best service life in original equipment.

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METAL DUSTING, continued

RA330 carburizing furnace anchor bolt, 3/4” (19 mm) diameter. Failure by metal dusting. RA330 gave better life than 600 alloy in this application. Three possible solutions here, depending upon the cost of furnace down-time, are to: 1.) Simply keep replacing the part in RA330 2.) Alonize® the replacement RA330, or 3.) Replace the part in RA333. The following test results are from a direct comparison of alloys for 25,594 hours (3 years) at temperature, in the metal dusting zone of a Surface Combustion carburizing furnace. 1” (25.4mm) Sch 40 oxygen probes of various alloys with different surface treatments were inserted through the furnace roof. The atmosphere is endothermic enriched with 0.7—0.8% methane to a 1.20% carbon potential, operating temperature 1700°F (927°C). Metal dusting occurs in the region where temperatures are roughly 1100°F (600°C), as the pipe passes through the refractory. Alloy RA333® RA85H® RA330® 214TM HR-120TM HR-160TM Condition As received Preoxidized As received Preoxidized As received As received Preoxidized As received As received Results Dark, no pits at 27,594 hours Some pits at 16,183 hours Black, no pits at 8122 hours Black, no pits at 7549 hours Pitted, test stopped at 19,472 hours Many pits, test stopped at 19,472 hours Many pits, test stopped at 19,472 hours Pitted—removed from test at 11,264 hours Pitting started at 24,422 hours

Preoxidizing treatments provided no benefits or were counter productive. Although aluminum diffusion coatings are usually considered to provide resistance to metal dusting, the 4.5% nominal aluminum content of alloy 214 was ineffective.

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RA446 plate exposed 3000 hours in air at 2100F (1150C). Jessop Steel Co. and contents as high as 0. Carbo-nitriding is a process carried out in an atmosphere containing both carbon and nitrogen. though not usually sufficient to cause of failure.462% were measured. . Commercial nitriding. shows some internal oxidation. Mill certification. An increase in nitrogen content may occur during high temperature service in air. Temperatures are usually higher than for nitriding but lower than carburizing. Initial nitrogen content 0. by removing chromium from the matrix.18C 0. the Floe process.03Mo 0. because the cycles are much shorter.089%. but the nitrogen content is rarely analyzed. roughly 1300—1650°F (705—900°C). A great deal of attention is given to carbon-pickup in alloys at high temperature. Carburization decreases nitrogen solubility in Ni-Cr-Fe alloys. Heat 26445 0. usually is done with RA600 alloy fixturing. A lamellar phase near the grain boundaries was apparently a nitride phase.84Cr 0.26Ni 24. Because of the reduced solubility. This locally concentrated the nitrogen.29 - .089N Nitrogen has been associated with blistering and severe reduction of creep-rupture strength in carburized HL (30Cr 20Ni) steam-methane reformer tubes10. Thermal fatigue cracking gradually develops and grows with each cycle. Chromium nitrides in this photomicrograph are the needles at 60 angles.NITRIDING Nitrogen reduces alloy ductility in a manner similar to carbon. The life of alloy fixturing in a carbo-nitriding application cannot be expected to equal that in a straight carburizing environment. Absence of nitrides probably due to chromium depletion from oxidation. Surface. First.g. probably for two reasons. nitrogen then diffused ahead of the advancing carburized front. and its life will be shortened accordingly. Second. The hours or years of exposure are not the important things affecting an alloy’s (quenching fixture) life. but rather the number of cycles it receives. A part in a carbo-nitriding environment will receive many more cycles in a given length of time than if it were in a carburizing application. which the authors associated with microvoids and cracks.15%. e.47Si 0. and times are shorter. It was postulated that this could result in high nitrogen gas pressure.03Cu 0. at top. because the embrittling effect of carbon and nitrogen combined is more drastic.70Mn 0. after exposure nitrogen reached 1.

. K. W. ASM. Netherlands 1999 10. J. September. in spite of other disadva ntages it has. Stainless Steel World 99 Comference. Factors affecting carburization behavior of cast austenitic steels. Ohio 1993 9. Bennett.NITRIDING. environments. Texas 1986 3. When the environment is oxidizing the alloy is more likely to form a protective chromium oxide scale. Corrosion/83 Paper Number 266. A. Houston. Brazing and Soldering. Brazing of Heat-Resistant Alloys. Houston. Low-Alloy Steels. Carburization of Cast Heat-Resisting Alloys in Synthetic Petrochemical Environments. Metals Park. Houston. Under the most severe conditions an alloy completely free of nickel. Metals Park. Houston. Wenschof and J. Destructive Accumulation of Nitrogen in 30 Cr 20Ni Cast Furnace Tubes in Hydrocarbon Cracking Service at 1100C. such as RA446 may be required. B. 7. RA309. Under reducing environments the alloy forms chromium sulphide. rather than a chromium sulphide. January 1985. Texas 1980 8. Texas 1976 6. with 25% chromium and 20% nickel. Furnace Atmospheres. which is non-protective. The problem is more severe under reducing. J. Welding. Corrosion 86 Paper Number 377. D. Hall. National Association of Corrosion Engineers. Corrosion/80 Paper Number 168. J. National Association of Corrosion Engineers. and J. E. The higher the nickel the more sensitive the alloy is to sulphidation attack. or low oxygen. Metals Handbook ® Ninth Edition. Harris. H. R. RA310. Houston. Carburization of Cast Heat-Resistant Alloys. 9. National Association of Corrosion Engineers.30 - . The Influence of Carburization on the Mechanical Properties of Wrought Nickel Alloys. Materials Performance. at 13% nickel. G. The Hague. H. Rundell. Jones. Texas SULPHIDATION Environments containing sulphur may rapidly attack high nickel alloys. M. James Kelly. ASM Handbook ® Volume 6. National Association of Corrosion Engineers. R. R. D. is useful in many sulphur bearing environments. If sulphur is a problem. Corrosion. Corrosion/76 Paper No. Texas 1983 5. Volume 4 Heat Treating. Roach. Evaluation of Heat Resistant Alloys in Composite Fixtures. Schley and F. and Tool Steels. 1967 National Association of Corrosion Engineers. may be preferred for some applications. continued References 1. Houston. Houston Texas 7. Effects of Silicon Content and Oxidation Potential on the Carburization of Centrifugally Cast HK-40. Metal Dusting in the Heat Treating Industry. Corrosion/77 Paper No. we do not suggest using any alloy with more than 20% nickel. Texas 1977 4. National Association of Corrosion Engineers. Kane. Ohio 1981 2. ASM International. D. Hossain. R. Kane.

SULPHIDATION. Sometimes the distinction isn’t obvious. We have heard it stated that oxygen partial pressures are about 10-8 underneath calcium sulphate deposits on some fluidized bed components. and rather little CO2 or H2O. carbon monoxide (CO). This is 1/4” (6. or even carbon dioxide (CO2) and/or water vapor (H2O). methane (CH4) or other sources of carbon. Atmosphere air plus the SO2 and SO3 driven off in the process. in contact with the metal the actual amount of oxygen available to form a scale may be very. then the metal may be heavily attacked under the deposit. operating temperature 1840°F (1004°C). An example of under deposit attack is shown below. and there is some excess oxygen (O2). some rather long. Previously used RA310 had failed by more uniform thinning. If the deposit contains sulphur. and lasted 2 to 2 1/2 years. After about a year the RA 253 MA kiln shell had developed holes roughly 3/4” (20mm) across. From Rolled Alloys Report Number 94-72 .31 - . very small.35mm) thick RA 253 MA from a kiln processing ferrous sulphate monohydrate to red iron oxide pigment. Underneath those deposits. continued An oxidizing environment is one in which sulphur is present as sulphur dioxide (SO2). there may be solid deposits on metal in an oxidizing environment. For example. there may be hydrogen (H2 ). regardless of how much oxygen is in the atmosphere above it. In reducing environments sulphur is in the form of hydrogen sulphide (H2S).

where a source of carbon. such as methane (CH4) is present along with the hydrogen sulphide Even 1/2% of H2S can be quite destructive. 875. No. . RA333.or lamp black.101356 MPa. continued Types of Scale Developed on Type 310 Stainless Steel as a Function of Oxygen and Sulfur Partial Pressures in the Gas Environment at Temperatures of 750. One example is in carbon black manufacture. and 1000C. RA330. Conversion factor: 1 atm = 0. ANL Neg. 617 and even some of the high cobalt alloys may fail by sulphidation. High nickel alloys are quite unsuited for high temperature service in the sulphidizing environments of carbon black plants. 601. Low-grade oil is heated. 306-79-6251 Most sulphidation failures occur under highly reducing conditions.SULPHIDATION. 600. to break it down into soot—which is carbon. That is.32 - . with very little oxygen. The oil used as feed stock normally contains up to 3 percent sulphur. 800H. alloys X. Specifically.

ANL-80-5. Massalski. are often molten at operating temperature. Final Report (1 October 1972-31 December 1985) as subcontractor to The Materials Properties Council. Natesan. 65th Edition. Argonne. Melting points of some metal-metal sulphide eutectics are3 : 1175°F (635°C) for Ni-Ni3S2. where corrosion rates accelerate dramatically.. Ohio 4. Handbook of Chemistry and Physics. continued Nickel reacts chemically with sulphur very readily. Gas Corrosion of Metals. which at least are solid. References 1. Inc. 1611°F (877°C) for Co-Co4S3 and 1810°F (988°C) for Fe-FeS. If sufficient molten metal sulphide forms underneath the chromium oxide scale. 1980 2. Florida 1984—1985 . Teodor Werber. Metals Park. Unlike metal oxides.SULPHIDATION. Eventually. 1986.33 - . High-Temperature Corrosion in Coal Gasification Systems. for a variety of reasons. Warsaw. American Society for Metals. Poland 1978 5. Howes. it may literally wash that scale away. translation published by the Foreign Scientific Publications Department of the National Center forScientific. Technical and Economic Information. Binary Alloy Phase Diagrams. Maurice A. The Fe0-FeS eutectic melts at 940C4 . New York. It is the time to break-away corrosion. or metal-metal sulphide eutectics. Thaddeus B. K. Illinois U. New York. metal sulphides. corrosion enters a “break-away” mode2 . In general.S.A. the corrosion rate in sulphidation may be more or less parabolic for some period of time. Boca Raton. H. Editor. CRC Press Inc. Valid laboratory corrosion testing for sulphidation resistance requires very long time exposure. that is significant. CORROSION AND MECHANICAL BEHAVIOR OF MATERIALS FOR COAL GASIFICATION APPLICATIONS. Stanislaw Mrowec. CrS-Cr2S3 doesn’t melt until 2462°F (1350°C)5. rather than the linear or parabolic corrosion rate. 3.. Argonne National Laboratory.

and for HCl follow.HALOGEN GAS HOT CORROSION Unlike oxides. is exceeded in short time tests in dry Cl2 Corrosion in Dry Chlorine. Good discussions of this subject are given in the old INCO® Corrosion Engineering Bulletins CEB-3 for HCl and Cl2 . For FeCl3 the limit is much lower. and lower yet for MoCl5. just slightly lower for CoCl2. For CrCl3 and NiCl2 that would be about 600°C. In order to form a protective scale it is generally considered that the metal chloride vapor pressure must be below 10-4 atmosphere. about 75°C.34 - . about 160°C. As a practical matter. 50°C. Corrosion in dry Chlorine Gas Metal Approximate temp. the high nickel alloys 600 (UNS N06600) and 400 (N04400) are most commonly chosen for hot halogen gas resistance. °F. When halogens are present in high temperature environments any oxide scale present becomes porous and non-protective. and CEB-5 for HF and F 2. and AlCl3. Data for 100% Cl2. metal halides are volatile. °F 60 1000 1000 850 650 600 950 450 350 300 150 120 1100 1050 900 750 650 1000 500 400 350 250 600 1200 1200 1000 850 750 1050 500 450 400 450 1200 1250 1250 1000 900 850 1050 550 450 400 500 1000 1000 800 650 600 500 400 400 --- 950 950 750 600 550 900 350 250 250 100 copper metal ignites in hot Cl2 at about 600°F carbon steel ignites in hot Cl2 at about 450-500°F . mils/year. 100% 30 Nickel alloy 600 alloy 400 316 304 Platinum CopperA SteelB Gold Silver A B Suggested upper temp limit for continuous service. at which given corrosion rate.

M. “Corrosion by Chlorine and by Hydrogen Chloride at High Temperatures”. The data were obtained from short-time laboratory tests and offer only a rough guide to maximum practical temperature limit of materials. No. & Eng. 7 pp 839-844 At lower halogen concentrations alloys forming a chromia layer can tolerate higher temperatures. 75µm (ASTM 4. Paper 00239 Corrosion 2000. The original data from which INCO developed their table was published in 1947.35 - . show that alloy 600 can form a protective oxide at 800°C in 0. 125µm (ASTM 3). Grain size has an effect. Chemistry. the alloy does not develop a protective scale.5). mils/year is exceeded in short time tests in dry HCl limit for Corrosion rate. DeLong and J. Fine grain size increases diffusion rate of chromium to the surface. being superior to 600 with coarser grain size. . mil/year. At 2%Cl2.Corrosion in Dry Hydrogen Chloride. 100% Metal Approximate temperature.1%Cl2. W. Vol 39.R. Data in Bender and Schütze. same temperature. Brown.B. 100 hour test. °F. Ind.H. °F Both of these tables were abstracted from INCO Bulletin CEB-3. 600 with finer grains. at which given corrosion rate. in dry HCl 30 Nickel alloy 600 alloy 400 316 304 Platinum Copper Steel Gold Silver 850 800 450 700 650 2300 200 500 1800 450 60 950 900 500 700 750 -300 600 -550 120 1050 1000 650 900 850 -400 750 -650 600 1250 1250 900 1100 1100 -600 1050 -850 1200 1300 1350 1050 1200 1200 -700 1150 --950 900 450 800 750 2200 200 500 1600 450 Suggested upper temp continuous service. Auld.

7 0.18 662 350 9 0. 100% Chlorine Gas. CEB-5.4 1.38 1112 600 24 0.5 13.4 1565 6018 -4248 78.5 -0.84 797 425 115 2.1 44. The following industrial data were obtained from 30 day test exposures.0 0.36 - .0 0.9 100% Chlorine Gas. 30 day test Temp mils/yr mm/yr F C 977 525 8 0.8 11.7 1. 30 day test Temp mils/yr mm/yr F C 572 300 6 0.0 538 80 400 700 1000 200 nickel 304 304L 347 600 29.7 0.6 1. .23 707 375 15. Corrosion by dry fluorine gas °F Temperature Material 400 °C Exposure time.2 24.5 16.1 6.1 7. hours 5 24 24* 120 5 24 24* 120 5 24 120 5 5 27 204 370 Corrosion Rate.2 0.15 617 325 7 0.39 752 400 33 0.4 0.3 7. mils per year 2.1 0.5 0.5 0. type 304/321 stainless.7 2.3 0.3 0.5 0. except * which were conducted in bombs at initial pressure of 250 psi.61 1157 625 47 1.9 -0 1.1 3.5 25.2 1.2 Corrosion of nickel alloys by hot 100% F2 gas is given in Table 14.2 1022 550 12 0. Most of that data is reproduced below.3 1067 575 15 0.5 0.3 21.5 0. alloy 600.9 1.Longer time tests show lower corrosion rates.6 0 2.2 1.7 1.4 4.8 ----3451 All tests were made in flowing fluorine gas.

“Corrosion of Metals and Alloys by Fluorine. .B. or some molybdenum effect.36 0.05 0.33 0. Alloy 59 (N06059) has performed satisfactorily in an oxidizing atmosphere with HF. Inc.41 Comments iridescent tarnish film “ black film “ “ adherent dark film “ “ Hastelloy is a registered trademark of Haynes International Inconel and Monel are registered trademarks of Special Metals. Allied Chemical Company. Test duration 36 hours.3 0. INCO CEB-5 Material Hastelloy® alloy C Inconel® alloy 600 Hastelloy alloy B Nickel 200 Nickel 201 Monel® alloy 400 Monel alloy K-500 70-30 Copper-Nickel Corrosion Rate mils/year mm/yr 0. Jackson.41 0.37 - . August 2002. General Chemical Division.7 2 9 14 13 16 16 0.02 0. From Table 17. In atmospheres containing a significant partial pressure of oxygen these laboratory data in pure halogens or halide gases have limited utility as the basis for alloy selection.” Contract AF 04 (611)-3389 Corrosion Tests in Hydrogen Fluoride Gas Temperature: 930 to 1110F (500 to 600C).008 0. we would suggest including a heat resistant alloy such as the 3%Mo alloy RA333® (N06333). RA333 has shown good resistance to hot corrosion by the fluoride flux used in aluminum salt bath brazing environments. it is not clear to us whether it is the better oxidation resistance of the higher chromium alloys. where alloy 617 weld filler was inferior to alloy 600. that is responsible. If the customer intends to perform tests in his environment.The original source of this fluorine data was: R.2 0. Examination of the 600 alloy part. removed from service after many years life. showed some corrosion from sulphur and phosphorous as well. At this writing. The heat resistant alloy X (UNS N06002) has outperformed alloy 600 in oxidizing gases containing HCl.

Fluoride salts are more aggressive than are chloride salts.MOLTEN SALT CORROSION Hot chloride salts.0044 0. Molten fluorides are used to flux metals and alloys for brazing operations. Along with fluxing the oxide film on the workpiece. 1100-2200°F (600-1200°C) Depth of Intergranular Attack Grade Nickel. Preheat and high heat salts were mixtures of potassium.2 0.0138 Plate samples were exposed in a commercial heat treat salt line.5 1. which is non-protective and water soluble. RA446. Eventually most of the chromium may be removed from the alloy.0069 0.32 0. quench in 600°C (1100°F) nitrate/nitrite salt. although we have seen tolerable results from the 1. Corrosion in Molten Chloride Heat Treat Salts. RA 253 MA.7 0.0075 0.18 0. and particularly salt fumes mixed with air. high heat salt 1200°C (2200°F). A service trial of various alloy fixtures used in aluminum salt bath brazing at 1125°F (607°C) gave the following results: Alloy RA333 600 Nickel 200 C-276 601 Total Life. sodium and barium chlorides. weight % 3.35 inch 0. They saw 210 to 252 cycles in preheat salts 700°C (1290°F) and 815°C (1500°F). .0125 0. to be unsuitable for aluminum salt bath brazing operations.7% silicon grade.8 1. In general the higher nickel alloys. days 197 (end of test—no failure) 112 51 40 14 Other work has shown the 25% chromium ferritic grade. air cool. such as 600. leaving primarily iron and nickel. are very corrosive to heat resistant alloys.38 - .19 0. are preferred. fluorides also attack the chromium oxide film on heat resistant alloy fixturing.2 mm 0.11 0. more chromium diffusing to the surface reforms the scale. A more detailed account of hot salt corrosion mechanisms is given on pages 126-132 under Salt Pots. As fast as the scale is removed. weight % RA85H 15 RA 253 MA 11 RA600 76 RA309 13 RA330 35 Silicon. The alkali metals in the salt turn the protective chromium oxide scale into an alkali chromate.

while only 0. 500 parts per million) of vanadium is “high” enough to be destructive. deposits on hot and vanadium. Mostly based on rumor.S. 6 or “Bunker C” may contain both sulphur When this oil is burned. It will eat away most heat resistant alloys in less than a year. RA330. we might suggest RA333 or RA 253 MA as worth trying. while HE (28Cr 9. 50Cr-50Ni cast IN -657 (UNS R20501) is the best. Heavy oils such as No. along with sodium sulfate. V2O5. IN-657 is expensive and readily embrittled.A. . The alloys with good resistance to fuel ash corrosion are usually cast compositions that are both weak and brittle. makes a molten compound which corrosive. This vanadium is aggressively A high level of sulphur in the oil might be 2 or 3%. RA333. we have no good comparative field data for these wrought alloys.05% (or. Available wrought alloys are not at all as resistant to fuel ash corrosion but are used for their much better ductility. RA 253 MA and RA310 have all been used or are on trial. pentoxide. and HE is particularly weak and brittle. Frankly. the vanadium forms vanadium pentoxide. Venezuelan oil is particularly high in vanadium and is often used in the Northeastern U.Vanadium Pentoxide Equipment fired with residual fuel oil suffers corrosion wherever the fuel ash metal.39 - . but they definitely will not be as good as 50%Cr-50%Ni cast.5Ni) is said to be reasonable. RA625.

7% columbium (niobium) weld filler 82. that molten metal may dissolve. Dissimilar Metals—must not be used in contact with molten metals.40 - . ERNiCr-3. right above the metal. balance Fe) has been used for stoppers in bottom pour aluminum ladles. Aluminum—molten aluminum dissolves any Fe. One example known to us was a lead pot fabricated of heavy RA330 alloy plate. or even the ferritic stainlesses. a molybdenum addition appears to benefit austenitic stainless or nickel alloys. where contact with low melting metals is concerned the lower nickel alloys. and how much molten metal is present. RA330 (35%Ni 19%Cr 1. 15% Mo.3% Mo. or may crack. Depending upon which metals are involved. One example is 316L. which at 2% Mo seems to work better than does 304. That it has been successful at all is due entirely to the tenacious oxide film on the titanium. depending upon how long it takes the aluminum to reduce and/or wash away the hot rolling scale from the bar. 6. As a ROUGH rule of thumb. are preferred. the temperature and the state of stress. High nickel alloys. Alloy C-276. A phenomenum known as mass transfer1 may dissolve the higher nickel alloy preferentially. such as RA600 (76%Ni) tend to be attacked more severely. has performed better than 316L at 1000°F (538°C) in 26% aluminum. 7% lead. Analysis of the weld bead showed that it was now a lead alloy. Nevertheless. in contact with molten zinc for galvanizing or die casting operations. has been used in continuous zinc galvanizing at about 850°F (454°C). Embrittlement—liquid metal embrittlement may occur just below the melting point of the low melting metal. Fe-Cr. The same molten metal may either dissolve or crack2 the heat resisting alloy. General Nickel—with respect to nickel-chromium -iron or nickel-chromium alloys. AL-6XN® alloy.2%Si balance Fe) 11 gage/3mm wall cooling tubes have been used in an aluminum melting furnace. Titanium tubing has been used to siphon molten aluminum. the higher the nickel content. . bar of alloys such as RA446 (25% Cr. with about 5% columbium (niobium) and traces of chromium and nickel.MOLTEN METALS From time to time one or another heat resistant alloy is used in contact with a low melting point metal in its molten state. the more rapidly the solid metal dissolves in the molten. It failed when the weld bead separated from the base metal. likewise for the cobalt alloys. depending upon the stress level. Life is erratic. Ni-Cr-Fe or Ni-Cr alloy. It had been welded with the 72% nickel 19% chromium 2. 67% zinc. Molybdenum—in resisting corrosion by molten zinc alloys. Wherever molten aluminum splashes on the RA330 it goes right through it like hot water throug h snow. the heat resistant alloy.

The metallic calcium vapors haven’t been much problem but down toward the retort base it is cooler. Metals Handbook (ASM). The lead. one American file manufacturer switched from molten lead to bismuth in its 1450°F (788°C) austenitizing baths. austenitized by immersion in molten copper. When maintained at 1450°F (788°C) no problems have been reported to us. 430 stainless (16. RA446. Calcium carbonate has been used as part of the mix. the loops are attacked. continued Antimony—we have no definite experience. now bismuth. The hydrogen reduces it to calcium metal. The fracture surface is very similar in appearance to Figure 12. page 60. are corrosive to Ni-Cr-Fe alloys. Haynes® International have made this alloy under their own trade name HS 150. The old Belgian alloy UMCo-50. at high temperatures under a hydrogen atmosphere. Copper—molten copper and copper base alloys penetrate the grain boundaries of any austenitic iron. We have no experience to confirm this. can have the austenite grain boundaries neatly outlined by copper metal.41 - . All of the austenitic alloys will fail rapidly in contact with molten copper or copper alloys. Bismuth—To satisfy OSHA. was said to function well in contact with molten copper. from using scrap lead. There are indications that lead baths which have been contaminated by antimony.25%C) weld filler. Volume 10. 8th Edition. balance Fe) and. 50%Co 28%Cr 22%Fe. Calcium—molten calcium can crack RA330. more likely. Cadmium—we have no experience. These pots have two loops of 2” Sch 40 RA330 pipe welded to the bottom. balance Fe). for the electronics industry. This figure illustrates 2024-T4 aluminum cracked by mercury.5%Cr. Skimmers for removing slag from ladles of molten brass or copper are mild steel. balance Fe) works slightly better. and molten calcium condenses on the retort wall. RA330 retorts are commonly used to process ferrites. Even carbon steel. and presumably higher nickel alloys as we ll. RA330 retorts crack at this location. E-Brite ® (26%Cr 1%Mo. when available. . When too much heat is applied.MOLTEN METALS. Siphons for handling molten copper have been 446 seamless tubing. Launders for handling molten copper are successfully made of the high chromium ferritic alloy RA446 (25%Cr. nickel-chromium-iron or nickel-chromium alloy. pots are fabricated of RA330 plate welded with RA330-04 (35%Ni 19%Cr %Si 5%Mn 0. An induction coil fits through the loops and heats the bismuth.

A dry hydrogen or hydrogen-nitrogen brazing atmosphere does not permit the muffle to develop any protective oxide film. Alloy X behaves in a similar manner. Eventually some copper braze spills onto the bottom of the muffle. RA 253 MA and RA330. Note that these are laboratory test results. However E-Brite was found significantly more resistant to molten lithium than either nickel or cobalt base alloys. Even small amounts of spilled copper will completely penetrate the nickel alloy floor along the grain boundaries. this high nickel allo y is dissolved by molten lead. One practical solution is a sheet of 430 stainless or fibrous refractory on the muffle floor. more likely sulphur bearing coke of some sort. continued Molten copper attack can be a problem in muffles used for copper brazing steel. not necessarily confirmed in service. With an exothermic brazing atmosphere the Ni-Cr-Fe alloy (usually RA330) muffle develops a scale which may be protective enough to prevent small amounts of copper from actually wetting the muffle floor. The most direct approach to this local corrosion is to make the metal wall twice as thick at the lead-air interface. Had we been asked. with the appearance of cast bars. are fabricated of mild steel. Alloy 600 is another story.MOLTEN METALS. With enough copper the scale may be penetrated and the muffle attacked. brought in when scrap lead is used. when operated 1650°F (900°C) with molten lithium. bearing in mind that all austenitic alloys will eventually fail from molten copper attack. One might consider the 11% nickel alloy RA 253 MA for muffle bottoms. With other alloys it is the lead oxide on the surface that attacks the metal sides severely at the lead-air interface. Based on laboratory tests. RA310. Sulphidation and carburization also occur at the lead-air interface. copper. . The molten lead is usually covered with so-called charcoal. One shop reported longer life when the 15% Ni grade RA85H was used for muffle bottoms. and sometimes melting.42 - . rather than RA330 or RA601. we would have suggested first annealing the head to remove forming stresses. to reduce lead fumes and oxidation. Pure lead should be used. increases attack from the molten metal itself. or lead pans. RA309. Hydrogen then escapes through the hole and burns like a to rch. Antimony. although the lower nickel grades may be preferable. removed from the corrugated bottom of an 11 gage/3mm wall RA333 muffle. The lead still oxidizes. Ferritic stainlesses are said to be subject to chromium leaching. Lead—molten lead heat treating baths. to keep molten copper from contacting the austenitic alloy muffle. the surrounding area. The lead itself isn’t terribly corrosive to these alloys. TZM molybdenum and pure iron (to 1000°C) are said to have good resistance to molten lithium corrosion. Lithium—a vessel fabricated in the 1970’s of RA333 for the US Navy liquid metal embrittled & cracked from residual stress in the formed head. Corrosion of RA333 occurs primarily by selective leaching of the nickel. locally overheating. caused by this protective covering. We have seen some 15 pounds of copper.

10% praseodymium and 1% neodymium.8mm) plate and RA 253 MA sheet have been used for side shields in the tin float process of plate glass manufacture. Because carbon steel scales on the outside (fireside) of the melting pot. In hydrogen atmosphere braze retorts. Tin—both RA446 3/16” (4. then re-deposited. 304 stainless steel. Rare Earths—the same manufacturer of ferrites who had problems with molten calcium cracking RA330 has also had both cast and fabricated Ni-Cr-Fe alloy grids crack. melts well below the annealing or even stress relieving temperature of the austenitic alloy to be brazed. Solder (lead-tin)—no molten metal attack reported. nevertheless we urge anyone planning to use RA330 for such an application to run their own test program. Selenium—In the 1970’s. magnesium tends to leach the nickel out of Ni-Cr-Fe alloys. molten silver braze alloy dripping on the bottom of an RA330 retort will penetrate this austenitic alloy at the grain boundaries and cause hydrogen leaks. 309. again more to withstand the ammonium chloride flux than the Pb-Sn alloy. Temperatures are low. Apparently rare earth compounds used in the manufacture of ferrites were reduced to metallic form by the hydrogen atmosphere. RA330 is no good at all in molten zinc. and to have pock-marked carbon steel in the same bath. in contrast to copper braze metal. respectively. . RA333 alloy has been used in tin can soldering applications. continued Magnesium—used in reduction of TiCl4 is normally contained in mild steel pots. Deposits on the cast grid analyzed 34% samarium.43 - . The nickel-chromium-iron alloy outside provides high temperature strength and oxidation resistance while the carbon steel inside is more compatible with the molten magnesium. One reason is that silver braze. or steel pots lined with 430 stainless. Melting at 1202°F (650°C). RA330 was used as 1” (25mm) diameter fabricated tubular heating elements in five 9’s purity selenium and arsenic selenide at 500 and 600°F (260 and 316°C). and it seems reasonable to assume that the other nickel-chromium-iron alloys such as 800H or 600 are as bad or worse. RA85H. Tin at 600°C (1112°F) under hydrogen atmosphere is reported to have dissolved. Cold worked 300 series stainless steels can not be silver brazed without danger of cracking. Silver—silver braze alloys have long been known to crack or dissolve austenitic alloys. These have been either RA 253 MA or RA330 explosively clad to mild steel. and the chloride fluxes used are more of a corrosive problem than is the solder itself.MOLTEN METALS. Our observations have been that commercially pure iron. in the process of decontaminating soil. 316L stainless. A lower nickel alloy would probably have been more satisfactory for these grids. Zinc—molten zinc and zinc-aluminum alloys are used for galvanizing and die casting. a few experimental clad pots have been tried. No degradation of product purity was reported. They dripped on the cooler grid at the bottom end of the retort. AL-6XN and alloy C-276 have all been used in molten zinc/zinc alloy with some degree of success.

zinc. Sleeve bearings. The chute through which the steel sheet passes into the zinc had a tip of C-276 where it entered the molten zinc bath. The iron sink roll was weld overlaid with 316 stainless.9 .12) metal loss. The high thermal stress coupled with zinc wetting the 309 metal inside cracked the tube. When 1” (25mm) round bars of both RA330 and 316 stainless were both used in the same zinc die cast alloy scrap recovery project the 35% nickel alloy was severely eaten away and chromium was selectively leached out. i. low manganese. low silicon nearly pure iron. The 316 bars merely developed a galvanized coating with no appreciable metal loss. The 309 weld bead is attacked to a greater degree than the base metal.2008 (5.79) 0.1328 (3.118 (3.142) 0. They tried 316 for the trunnion sleeve.9 3. then Rolled Alloys convinced them to try RA85H.1188 (3. Recently we have found definite success with AL-6XN alloy for small sink rolls and bearings for galvanizing wire. Temperature was about 1000°F (540°C) We observed that one steel company involved in continuous hot-dip galvanizing of sheet made the 850°F (454°C) zinc pot and sink arms of low carbon. This was confirmed in service.0 4. were fabricated of C-276 (UNS No.0 4. but this coating is subject to damage by mechanical abuse.0104 (0.44 - .00 0.574) 0. it looked like RA330 cracked by molten calcium or 2024-T4 aluminum cracked by mercury. as well as for the sink roll itself. N10276) sheet. to ride on these 316 overlaid journals.0226 (0. and the 316 did not last long. ratio to AL-6XN® 1.0056 (0.0034 (0.05) 0. which had leaked full of zinc die casting alloy. Now AL6XN is used for both the trunnion and the sleeve bearing.1164 (2.120 (3. which was an improvement. 850°F (454°C) alloy AL-6XN 556TM 1008 RA309 RA85H® RA446 316 original thickness average metal loss inch (mm) inch (mm) 0.2 7. was heated rapidly with an oxy-acetylene torch to melt out the zinc.0234 (0.6 1.e. and for the past 3 or 4 years they have been using AL-6XN.432) 0.MOLTEN METALS.110 (2.96) 0. At the zinc-atmosphere interface the pot was sheathed with 316 stainless steel.264) 0. Rolled Alloys laboratory immersion testing in molten zinc ranked these alloys similar to how they behaved in service: 250 hour test in molten zinc. Initially the company used 316.10) 0.0) 0.086) 0. continued Zinc die casting pots have been heated by gas fired immersion tubes fabricated of RA309..37) 0. as were the journals. over AL-6XN trunnions. The tubes are usually plasma sprayed with zirconia to enhance life. The fracture surface was typical of liquid metal embrittlement.044 (1.017 (0. On test. AL-6XN looked even better.594) 0. One failed 309 tube.02) 0.

Consider going the other way. Older Canadian coins are a high nickelcopper alloy. the new 85. There are three metallic elements which. but depending upon the exact chemistry. Nuclear Metallurgy. Hydrocarbon Processing. The 66% nickel 31% copper alloy 400 is usually non-magnetic. If 10.MOLTEN METALS. of course. is non-magnetic. 1956.A. Pure nickel is also magnetic. even though they may be austenitic. because of its 15. Although the chromium is still present in the alloy. And. of course. with a hexagonal close packed structure at temperatures below 783°F (417°C). an austenitic alloy can also be magnetic. It is easy to confuse ferritic and austenitic with magnetic and non-magnetic. are magnetic. Bryant. A Symposium on Behavior of Materials in Reactor Environment. it is effectively . But. and austenitic stainless and nickel alloys are usually non-magnetic. and a face centered cubic structure at higher temperatures.45 - .5% chromium. the small amount of ferrite in an austenitic stainless weld bead (E308. Ferritic stainlesses are magnetic. May. commercially pure nickel is an austenitic metal. J. It is the addition of chromium that makes alloys based on iron and nickel (or cobalt) become non-magnetic. 1973 MAGNETISM Austenitic heat resistant alloys are non-magnetic as produced. 2. are magnetic. continued References 1. U. Piping by liquid metal attack. Likewise iron-nickel alloys. the magnetic properties sharply increasing at about 30% nickel and being highest in the range 50 to 80% nickel1. Gurinsky. in all combinations. Service conditions that cause this magnetism are often carburization. with 76% nickel and 8% iron. Even RA600. to save on nickel). austenitic alloy. David H. New York. Usually this indicates that for one reason or other the metal is no longer fit for service. Cobalt is the third magnetic element.S.) is also magnetic. Cantwell and R. American Institute of Mining and Metallurgical Engineers. even though it has an austenitic (face centered cubic) structure.3%Ni 8%Fe 5%Cr alloy would become a magnetic. etc. at least on a cold day. Iron. E309. 2. Alloys of iron and nickel are magnetic. and are magnetic (the newer are not.E. New York. a particular heat may be magnetic. pages 114-117. nor is it capable of being weld repaired. February 20. The Behavior of Materials in Aggressive Liquid Metals.E. in their pure state. and it is also a magnetic metal. internal attack by molten salts or selective attack by some molten metal. and many European coins are magnetic. Carburization makes nickel heat resisting alloys become magnetic because the chromium reacts chemically with carbon to form chromium carbides. Flare tips by severe cracking. Institute of Metals Division. is magnetic and has a ferritic (body centered cubic) structure. and removing chromium.5% of that chromium were removed and replaced by nickel (and the %ages recalculated). After high temperature service they sometimes become rather strongly magnetic. How to Avoid Alloy Failures in: 1. pages 5-20.

Monitoring the Carburization of Furnace Tubes in Ethylene Plants. Also. iron and chromium. and we have observed metal which used to be RA330 but which had become a 1%Cr-Fe-Ni alloy. Houston. just enough to feel with a magnet. July 1949 JISI .46 - . Smit. largely chromium oxide. 10. Reference 1. B. Hoving and K. There are a couple other times when austenitic stainless steels may be magnetic. Krikke. J. RA310 is normally non-magnetic.J. continued removed from the solid solution matrix of nickel. W. scale.D. when a leaner stainless such as 304 is cold worked it becomes magnetic because a small amount of the austenite actually transforms to martensite (a hard. and has been used for structural elements around the superconducting magnets in MRI equipment for hospitals. Paper No. rather than carburization. RA330 depleted to 12-15% Cr is common. H. This is evident on sheared edges. Burns. and A. Constitution of Iron-Nickel-Chromium Alloys at 650° to 800°C.P. Their will also be a slight chromium-depleted zone underneath the. Cook. so it is possible that a slight degree of magnetism felt on a used fixture is simply the scale. and especially so in deep drawn sheet components. Chromium is physically removed from the alloy by the normal corrosion mode in neutral salt pots. Corrosion 76. This is approximately illustrated by the following Fe-Ni-Cr ternary diagram of magnetism vs alloy content2. because austenitic heat resistant alloys are supposed to be non-magnetic. right down to liquid nitrogen temperatures. The iron oxide component of scale is also magnetic. Rees. R. magnetic phase). The specified chemistry range of 309S stainless (UNS S30908) is broad enough that a small amount of ferrite may be present in the hot rolled annealed metal. Cold working has little or no effect on the magnetism of higher alloys such as RA330 or RA333. This can be very upsetting to customers who think they have the wrong material. National Association of Corrosion Engineers. Texas 1976 2.MAGNETISM. Lower nickel grades such as RA310 or RA 253 MA do not so readily become magnetic when carburized.

47 - ..

in the elastic range (room temperature. This is the “elastic” portion of the tensile test. stress divided by strain. is usually reported only by its tensile strength in psi (N/mm2. At room temperature the modulus of RA333 is 29. in pounds (Newtons). is the Elastic Modulus. or how “springy” it is. The modulus decreases at higher temperatures. claw hammers. This means that. The slope of that line. One may say that steel is three times stiffer than aluminum. etc. is the stress required to pull a specimen until it breaks apart in two pieces. Tensile Strength Tensile strength. At cherry red heat.000 psi (201 GPa). The tensile test is carried out by mounting a specimen in a machine which pulls on it with a slowly increasing load until it breaks. to give pounds/inch2 (Newtons/millimeter2). or MPa).000. Above about 1000-1200°F (540-650°C). where a plot of stress versus strain would be a straight line. with the symbol E. though. by the specimen cross sectional area.200. For room temperature applications—steel guitar strings.000 psi (207 GPa). both steel and nickel alloy.48 - .STRENGTH AT TEMPERATURE The strength of a metal at high temperature is measured differently than at room temperature. also called Young’s Modulus. . The strength of wire. the only important mechanical property is creep or rupture strength. tensile or yield strength can NOT be used as a basis for design. stress less than the yield strength) for a given stress aluminum will stretch or bend three times as much as will steel. The load in pounds (Newtons) is measured and recorded throughout the test. for example. the modulus of steel is about 30. yield strength or hardness. Elastic Modulus In the early stages of the tensile test the specimen is stretching elastically.000 psi (69 GPa). while that of 6061-T6 aluminum is only about 10. By about 1000°F (538°C) the material is no longer elastic. It is calculated by dividing the breaking load. This is important.—the designer needs to know the tensile strength. automobile frames. or ultimate strength.000. At ordinary temperatures. when the load was removed the specimen would go back to its original length. Were the test to be stopped. in square inches (mm2). This is the measure of the stiffness of the metal. like a rubber band.

. The Tensile Strength could be 107. and not by its tensile properties.2% Y. For example. the 0. (mm/mm) = Change in length/Initial length Ductility Before the specimen breaks it has stretched out a great deal. But the machine would also be useless if its parts bent. in. . and has necked down in the area where it breaks.02% Y. For austenitic alloys it is usually recorded on the mill test report as either the 0. Stess = (Load/Area) 0./in.S. 0 Strain. Both are measures of ductility. or N/mm2 ) and the 0. Tensile Strength 0. or yielded.S. yield and tensile strength may be used for design up to about 1000°F (5380°C). more commonly in the U. obviously the design stress has to be below the tensile strength of the metal. This is called the “Yield Strength” (or Proof Strength).000 psi (324 MPa) When designing a machine part. so the designer must keep the stress somewhere below the yield strength of the metal. Drop in stress due to thinning of specimen cross section. usually well before the specimen breaks.2% Offset Yield Strength 47. The amount it had stretched when it broke is the “% Elongation”.2% Offset Yield Strength. or the thing would break in two. or. Above this temperature.1% Offset Yield Strength.000 psi (738 MPa.S. and the amount it necked down is the “% Reduction of Area”. at room temperature an RA333 tensile specimen might have 48% Elongation and 62% Reduction of Area. it takes a permanent stretch. the life of the part will be limited by the metal’s creep-rupture properties.Yield Strength At some point during the tensile test. For heat resistant alloys.49 - .

to some degree.50 - . but very. weeks.000 hours. It is the stress required to completely break a specimen within a given amount of time. People tend to have rather strong feelings about one or the other creep measurement. Rupture “Rupture Stress”. 1500°F (816°C). or “Creep-Rupture Strength”. is called its “creep rate”. The other measure of creep. He would then pick his design strength based on the speed of deformation. 1%. at high temperature one must assume that the metal is going to creep. That is. All this. Now let us say that this metal bar is loaded. In the furnace industry another common criterion for setting design stresses is to use some fraction of the stress that would result in rupture at 10. ASME uses whichever is lower. say. when it wasn’t even loaded up to the yield strength (as measured by a short-time tensile test). or 0. For some period of time the creep rate is more or less constant. Creep The rate. Design stress may be set at some fraction of this number. in % per hour. is reported as both a stress. or deform.00001%/hr. unless it corrodes away or stress-corrosion cracks. or 0. This is the “minimum creep rate”. Minimum creep rate data and total creep rate data are not interchangeable. at which the metal is stretching. This is true even for light loads. and a number of hours. or “secondary creep rate”. A very small amount of deformation will occur at first (first stage creep). It will keep on stretching for hours.000 hour rupture stress. The minimum creep rate (mcr) is used as one basis for design at high temperature. 67% of the extrapolated 100. is “total creep”. That is. maybe years. that load can be left there practically forever. so whenever possible we provide both minimum creep and total creep data. and the one used in Europe. In practice. Nothing will happen.Creep-Rupture Why creep and rupture strength? Metals behave much differently at high temperatures than they do near room temperature. or speed. Then that metal bar will begin to stretch. Theoretically. the designer might settle on an acceptable amount of creep deformation over the projected life of the equipment. again keeping the stress below the yield strength—while it is glowing cherry red.000 hour mcr. or 100% of the extrapolated 1% in 100. creep rate. The ASME uses for one of its criteria 100% of the extrapolated stress for 1% in 100. that is.000 hours. . very slowly. the stress required for the specimen to actually stretch a total of. in the furnace industry one design criterion is the stress required for a minimum creep rate of 1% in 10.0001% per hour.000 hour minimum creep rate. Creep rate is expressed as per cent deformation per hour. acceptable in his application. until it finally breaks in two. If a metal bar is loaded to just below its yield strength at room temperature.

Rupture Third-Stage Creep

Second-Stage Creep

Elongation

First-Stage Creep

Time

The picture below shows a broken creep-rupture specimen of RA330, tested at 2000°F (1093°C).

About full scale Creep strength is more important than rupture strength. For example, at 1800°F (982°C) the alloys RA330, RA309 and RA310 all have comparable 10,000 hour rupture strength, about 560--660 psi (3.9--4.6 N/mm2). However in service an RA330 muffle or retort can retain its shape for years, whereas one of RA309 or RA310 would collapse. The reason is, these stainless heat resisting grades have only 40—55% of the creep strength of RA330 at 1800°F (982°C). Normally we expect the strongest alloy to do the best job. This does depend on how that strength is achieved. For example, RA333, RA85H, RA 253 MA and RA 353 MA are strengthened by various alloy additions, with a medium-fine grain size. As a result, they all have good to excellent thermal fatigue resistance in quench applications. The least expensive way to obtain high creep-rupture strength is by giving the alloy a high temperature solution anneal. An aim of ASTM 5 or coarser grain size gives much better creep and rupture strength than does a finer grain size. However, coarse grained materials lose thermal fatigue resistance as they gain creep strength. In our experience, material with grain size coarser than ASTM 4 will be unsatisfactory in liquid quench applications. A quenching fixture, for example, made of 800H would resist creep deformation but quickly break up in pieces from thermal fatigue. The supposedly “weaker” RA330, with its finer grain, can give very good life in quenching service.

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Creep-Rupture Testing Above 1800°F (982°C) oxidation affects the results of a creep-rupture test. As the creep voids oxidize the material undergoes an apparent strengthening. This can be seen by comparing the 2000°F (1093°C) results obtained using 0.252” (6.4mm) diameter test specimens with those from 0.505” (12.83mm) diameter specimens. For an alloy such as RA330 the results from the thinner specimen are so influenced by oxidation as to be unrealistically high. RA333 is considerably less affected at this temperature. By 2200°F (1204°C) even the largest available (0.505”/12.83mm dia.) test specimens in RA333 are probably affected. This makes it difficult to compare very high temperature creep rupture data from different sources, as the test specimen diameters are rarely recorded. For both RA330 and RA333 all currently published creep-rupture data was obtained using the la rger diameter specimens, at Joliet Metallurgical Laboratories, Joliet, Illinois, U.S.A..

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Cantilever Beam Creep Test

RA85H RA601

RA330

RA310

RA309

For design purposes, creep and rupture data are usually plotted on log-log charts. A visual illustration of relative creep strengths is obtained by simply clamping alloy strips at one end and measuring how much they sag or droop from their own weight. These five alloys were held at 1600°F (871°C) for 500 hours. The maximum stress in each beam, caused by its own weight, was calculated to be 1890 psi (13 N/mm2). RA309 sagged 6 inches (152 mm) in the first six hours, and continued to bend in the opposite direction once the free end touched the furnace floor. RA310 sagged 6 inches (152mm) in about 48 hours. RA85H and RA601 sagged very little in 500 hours, with RA330 showing slightly more deformation.

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750 2.280 3.500 22.000 ----42.600 3.050 2.000 -- 1200 2.500 23.000 -~13.200 23.000 ---29.500 1.200 42.200 9.800 12.300 7.000 1400 -1.800 14.300 5.500 7.700 5.000 7.600 22.600 5.700 2.100 2350 1850 3200 --~5000 1700 --------1.900 15.500 30.500 4.400 7.400 11.900 3.500 15.000 17.500 22.000 ~45.000 36.800 2.800 4.000 --98.650 1.54 - .400 -----2.300 1.100 5.500 -~32.700 9.050 1.000 --17.200 12.300 5.200 3. ( ) Extrapolated data .200 6200 7.500 1.300 3.700 3.000 21.500 -22.500 13.400 9.500 8.500 70.500 12.000 --128.000 17.000 31.000 14.000 8.000 --48.000 7.500 2.000 5.700 13.400 2.800 27.000 11.000 ------------® 1000 12.000 -- 1100 -3.000 Hour Rupture Strength.700 5.200 11.200 1.600 1. 304H 316L 321 321H 347.000 940 1.200 4.500 24.300 25.150 560 660 630 1.200 16.250 3.000 -19. psi TEMPERATURE °F ALLOY COR-TEN B RA446 304L 304.200 15.700 3700 3600 ---~8500 1600 -450 1.000 1300 --6.000 8.900 1.050 1150 820 1490 --~2000 1900 --------860 --400 -930 630 --990 --~1300 2000 --------680 --(280) -680 360 -(330) 670 --~700 2100 -------------(450) --(200) 440 ---- 2200 -------------(320) 140 --290 ---- RA800AT RA 353 MA RA333® RA600 RA601 RA 602 CA RA625 RA718 617 ® ® --------- * COR-TEN B is a Registered Trademark of US Steel Corporation + One Heat Tested 617 data picked off log-log curves published by Special Metals Corp.000 + 2.300 12.000 1500 --2.347H RA 253 MA RA309 RA310 RA330 ® ® ® 900 22.200 9.100 4.600 5.800 1650 1200 2180 --~3000 1800 -230 ------1.600 14.Average 10.500 -25.860 1.000 39.100 3.000 9000 13.500 8.

000 --41.800 8.500 1.000 -- 3.000 ------------- 6.000 7.100 3.500 23.900 7.000 14.900 1.500 600 570 1.000 3.000 9.150 3. 304H 316L 321 321H 347.000+ 260 2.100 -- 130 1.700 8.000 680 3.600 17.500 2.600 2.300 1.000 20.950 10.900 5.500 4.55 - .100 2.300 27.300 9.750 750 2.200 43. psi.050 880 760 -- -------490 -------- -------(250) -----430 -- ---------------- ---------------- --- * COR-TEN® B A Registered trademark of US Steel Corporation + One Heat Tested ( ) Extrapolated .000 -25.900 3.000 ---21.000 27.500 18. 347H RA 253 MA® RA309 RA310 RA330® RA800AT RA333® RA601 RA718 900 20. for 0.500 14.800 12.050 4.300 3.400 3.200 7.000 100.400 2.400 1.100 5.000 -- -------1.700 -- -------2.700 -4.100 1100 -- 1200 1.100 7.700 + 1300 -- 1400 -- 1500 -- 1600 -- 1700 -- 1800 -- 1900 -- 2000 -- 2100 -- 2200 -- 16.200 4.000 14.000 6.950 1.100 2.650 --- -------890 220 280 500 1.800 18.850 7.800 1000 11.100 7.500 -22.000 74.350 2.800 7.700 7.500 --53.300 8.700 16.400 4.800 11.800 5.Average Stress.200 2.600 16.700 2.600 6.000 4.000 1.000 1.600 2.0001% Per Hour Minimum Creep Rate TEMPERATURE °F ALLOY COR-TEN ® B RA446 304L 304.700 4.000 --10.000 20.300 2.

Experimental work and theoretical analysis indicate the cause to be plastic flow induced by expansion and contraction during heating and cooling. or cools. This is common in vacuum heat treating of tool steels and some stainless grades. cracks start at the surface and grow deeply. In carburizing service. Since metal expands when heated. In a rigidly welded angle frame design the long bottom side pieces may crack while the shorter ends and the top frame remain sound. and by favorable operating conditions. and in salt bath heat treating. In fixtures or bar baskets.) Light sections. a Thinner metal heats and cools more uniformly than thick. Heat resistant alloys also have low thermal conductivity. Heat resistant alloys all have high coefficients of thermal expansion. After some number of these strain cycles the metal cracks. Avery. S. Material for thermal cycling service should have a grain size ASTM 4 or finer.56 - . perhaps one fourth that of carbon steels. The Mechanism of Thermal Fatigue. The effect can be minimized by proper design. and give no external sign that anything is wrong until it suddenly breaks. and then contracts the same amount when cooled again. Uneven heating and cooling.) Grain size & alloy choice. serpentine rather than straight flat bars and loose. In neutral hardening operations the bar may begin to crack internally. Even a nitrogen gas quench is effectively a rapid cool if carried out from 2000°F (1100°C). Rapid cooling is usually thought of as oil or water quenching. pinned joints r ther than rigidly welded. before the center does. this alternately strains the center and the outside surface. No alloy will compensate for inadequate design where cracking from thermal cycling is concerned. but from surface to center of the metal itself. The most important items to consider regarding equipment which will be thermally cycled are: 1. Most will expand at a rate of about 2/10 inch per foot (17mm per meter) when heated from room temperature to 1800°F (982°C). Individual round bars crack because the surface of the metal heats. 2. is the rule for heat resistant alloy service.) Design—basically flexible or loose. This may include corrugations.THERMAL FATIGUE Metal parts exposed to fluctuating temperatures for long periods eventually deteriorate. The bottom members of deep bar frame baskets cool and contract before the middle and top do. . not only with respect to different parts of the same fixture. if possible. 3. Metal Progress August 1959 Thermal fatigue is the cracking which happens after a metal is repeatedly heated and cooled rapidly. one area individually quenches faster than another. selection of alloys that combine high hot strength with low thermal expansion coefficients. H.

9mm) dia. RA330 in his bar frame basket. because it is both strong and ductile. That is.57 - . Ductility alone is not enough. so the thermal strains are lower. And for that matter. But the thermal strains from quenching the larger bar are significantly greater. of course. . RA600 is ductile. which he was where load carrying ability was concerned. but RA333 survives repeated quenching better because of its strength. up to 5/8” (15. continued Some alloys are better than others. It is thermal stresses that cause more distortion and cracking in heat resistant alloy equipment than do the mechanical loads imposed on the part. RA333 has been our best alloy in resisting thermal fatigue. can permit additional life improvement. The strength. in turn.7mm) dia. the tensile ductility of RA333 at 1600°F (871°C) has been measured at 75% elongation. We had one customer who cut his life in half simply by going from 1/2” (12. Thinner sections heat and cool more unifo rmly. Both strength and ductility are important. bars. The use of the lightest possible metal sections cannot be overemphasized.THERMAL FATIGUE. if the designer makes use of RA333’s strength to use thinner plate and smaller diameter bars. He thought he was making the basket stronger.

used to power military aircraft. practical approach to minimizing galling problems. AvestaPolarit provide the following information for their “MA” grades: Coupons of three different MA grades were exposed in the cyclone of the Nässjö plant in Sweden. A combination of a cobalt base against nickel or iron base alloy is a good. X-40 (25. . Grade RA 153 MA ® RA 253 MA RA 353 MA Maximum Thickness Reduction inch mm 0.071 0. The situation does not improve at elevated temperatures. All of these are relatively soft. in particularly erosive areas. e. 556. During 1999. Galling Austenitic stainless and nickel alloys are known to be susceptible to galling at room temperature. 188. tube shields of RA 353 MA were installed in-bed in a number of coal fired fluidized bed boilers. But even at room temperature. Final results are still pending.WEAR Wear resistance is often related to hardness at room temperature. solid solution or carbide strengthened grades--NOT the hardfacing Stellite® alloys.6 0.008 1.5Cr 54Co 10. or even known.5W 0. By far the best antigalling resistance at high temperature is possessed by the cobalt alloys.50C). Normal temperatures 1580-1635ºF (860-890ºC). their anti-galling properties are rarely used. 4200 hours fired with wood waste and 1800 hrs with Polish coal.8 0. outside of the gas turbine industry. In the 1960’s General Electric’s J79 engine. and for galling resistance. the 21Cr 11Ni alloy RA 253 MA had been considered one of the most erosion resistant materials for fluidized bed cyclone construction.. The cobalt alloys in question form a relatively soft. The X-40 parts were regarded as “self lubricating”.2 Until the development of the 25Cr 35Ni grade RA 353 MA.58 - . These austenitic heat resistant alloys do not possess wear resistance in the conventional sense. with peak bed temperatures of 1920ºF (1050ºC). L605.5Ni 7. used cast X-40 linkage in the afterburner system. Due to the cost of cobalt alloys. lubricious oxide which prevents galling. There is some limited information available for erosion.g.024 0. Erosion Erosion resistance appears somewhat related to oxidation resistance. heat resistant alloys are rarely harder than Rockwell B100 (Brinell 240).

. L605 (Haynes 25) on one of the nickel or stainless parts would function to prevent galling against the other side of the couple.WEAR.59 - . Galling. for example. Boron nitride spray is used for high temperature lubrication. continued In other industries it may be that a weld overlay of.

The Sigma Phase. heavy wall 310S muffle. Some high alloy ferrous metals are subject to embrittlement at certain elevated temperatures as a result of the formation of a constituent called the “sigma phase.00% silicon. Alloy Casting Institute. the 310 roof cracked badly. One example of a failure due to sigma involved a long. Ideally. which tended to collapse it. 0. Some materials change after a few hundred or thousand hours in service. called sigma. to reduce sigma in RA310. columbium. the possibility of the occurrence of phases other than the well-known alpha and gamma may sometimes be overlooked in the consideration of alloys suitable for high temperature applications. Sigma forms in the 1100-1600°F (600-870°C) temperature range. This usually happens with high chromium. carbon and nitrogen retard its formation.A. After a few years the user inserted jacks and tried to jack up the roof which had fallen in. The most common problem is that the alloy forms a hard. brittle nonmagnetic phase. July 1945. brittle sigma phase can be formed an alloy steel may lose ductility to such an extent that its usefulness may be seriously impaired. The ASTM specifications for 310S (N31008) permit 1.PHYSICAL METALLURGY An important property of alloys utilized for heat resistant service is the ability of the metal to retain its desirable characteristics throughout the range of probable operating temperatures.” If appreciable amounts of the extremely hard. It operated about 1200°F (650°C) with a vacuum inside. and become brittle instead of tough and ductile 1. silicon. Chromium. Sigma Phase All of our nickel-bearing stainless and nickel base alloys have an austenitic structure. a heat resistant alloy should retain these qualities throughout its service life. The overall chemical composition of the alloy remains the same. But enough sigma can completely embrittle the alloy when it reaches room temperature. New York. It happens more quickly. Although the existence of this phase has been observed for a number of years. Sigma may not seriously harm the alloy while it is operating at high temperature. U.S. and are ductile and non-magnetic when they are placed in service. Francis B. Alloy Casting Bulletin Number 5. But.60 - .75% maximum. and AMS 5521 1. All RA310 plate. and embrittles more severely. aluminum and titanium promote sigma. low nickel grades such as 309 and 310. instead of straightening. Nickel.5% silicon maximum. sheet and bar is made to restricted silicon. New York. . when the alloy has been cold worked. molybdenum. Foley. And these cracks grew further when they tried to weld repair them.

We mentioned that silicon promotes sigma. Although RA330 might normally be regarded as overkill for a 1200°F (650°C) application. but that RA330 does not embrittle from sigma. This will re-dissolve the sigma and restore ductility so that the metal can be straightened and weld repaired. after it goes back into service. either in service or laboratory test. RA330 does not form sigma or embrittle at any temperature range. Even 304H. will not embrittle as badly as 310S. Of course. along with moderate chromium. can take a long time to occur and is less harmful at elevated temperature than at room temperature.61 - . below about 1400°F (760°C) these two grades have limited usefulness. continued The solution would be not to use 310S or 309S at this low temperature. that even silicon as high as 2% would be unlikely to result in sigma. The following is taken from work done for the ASME on superheater tube materials 2. sigma will again begin to form. where RA330 has embrittled from sigma. Test Temp Condition 304 100 (136) 100 (136) 50 (68) 85 (115) 75 (102) -100 (136) 70 (95) ---100 (136) 100 (136) 100 (136) -100 (136) 100 (136) Charpy V-notch energy. Indeed. foot-pounds (J) Alloy 321 347 316 100 (136) 100 (136) 75 (102) 100 (136) 95 (129) -100 (136) 100 (136) 100 (136) --100 (136) 100 (136) 100 (136) 100 (136) 100 (136) 100 (136) 100(136) 50 (68) 35 (47) 90 (122) 45 (61) 65 (88) -----100 (136) 85 (115) 85 (115) 100 (136) 100 (136) 100 (136) -65 (88) 40 (54) 70 (95) 30 (41) -65 (88) 35 (47) -25 (34) -100 (136) 100 (136) 100 (136) 100 (136) 95 (129) 85 (115) 310 100 (136) 25 (34) 10 (14) 10 5 (14) (7) 800 100 (136) 50 (68) 55 (75) 60 30 (81) (41) 68°F unexposed (20°C) 18 mo 1200°F 36 mo 1200°F 68°F 18 mo 1350°F (20°C) 36 mo 1350°F 68°F 4 mo 1500°F (20°C) 6 mo 1500°F 18 mo 1500°F 30 mo 1500°F 34 mo 1500°F 36 mo 1500°F 1200°F unexposed (649°C) 18 mo 1200°F 36 mo 1200°F 1350°F unexposed (732°C) 18 mo 1350°F 36 mo 1350°F 20 (27) -----100 (136) 85 (115) 60 (81) -35 (47) 40 (54) -100 (136) ----100 (136) 75 (102) 80 (108) -85 (115) 70 (95) . There are no recorded instances. brittle 310S muffle the only thing to do is to anneal it by heating 1900°F (1038°C) or higher.Sigma phase. which will form a certain amount of sigma. Faced with an existing. This is because RA330 has sufficient nickel. The embrittlement due to sigma varies from alloy to alloy.

2% Offset Tensile.100 (136) -.8 54.6 -Charpy energy ft-lb 88.69 34. from Jessop Steel Co. inches 0.93 ---0.05 bal A B current production 304 averages 9% nickel 321 currently melted to typical 9.6 RA % 63.600 52.-- Chemical Compositon of Tube Materials Tested Above alloy UNS Cr Ni Mo Cb Ti C Fe 304A S30400 18.96 --0.200 32.8 48.62 - .45 0. However the exposure time.--. Yield.400 10.7 47.20 1. continued 1500°F unexposed 100 (816°C) 4 mo 1500°F 6 mo 1500°F 12 mo 1500°F 18 mo 1500°F 30 mo 1500°F 34 mo 1500°F 100 (136) -100 100 100 --100 (136) -100 (136) 100 (136) 100 (136) 100 (136) -100 (136) 100 (136) -----100 (136) -100 (136) 100 (136) 100 (136) -40 (54) 100 (136) 30 (41)--. psi psi 92. Washington.5 44.100 87.600 14.300 26. Pennsylvania AR –as received.42 ---0.9 35.600 38.500 86.019 0.3% nickel C average nickel content of current production 316L is about 10. The following are some test results: Test Temp ºF 80 80 80 80 1200 1500 1800 Condition Ultimate 0.500 27.2 ---- AR PE 1200 PE 1500 PE 1800 PE 1200 PE 1500 PE 1800 Lateral Expansion.4 64. 1 inch thick plate.6 34. specification is 0. 1000 hours.77 13.Sigma Phase.060 --- 310 Heat No.15--0.48 10.--.07 bal B 321 S32100 17.06 bal 316C S31600 16.1 Elong % 46.9 40. ºF All data is average of three tests Some reduction of Charpy V-notch energy is shown after exposure at 1500F.600 84.3 76.7 87.800 7.200 33.79 12..07 bal 800D N08800 20.2 60.4 39.0 57. mill annealed PE – pre-exposed 1000 hours at temperature.070 0. .--.23 --0.100 23.66 ---0.93 10.05 bal 347 S34700 17.000 72.8 24.56 21.06 bal 310 S31008 24.60% each The Metal Properties Council3 performed studies on 310 and other materials after various elevated temperature exposures.90 -0.2% D titanium and aluminum not reported.56 -0.065 0. 24659. was too short for much sigma formation to occur.

annealed PE = pre-exposed at 1400°F Grain Growth Most Rolled Alloys heat resisting alloys are produced to a medium-fine grain size.600 18. These aside.000 -0. . these grades being annealed 2150°F (1177°C) minimum to deliberately coarsen grain size.800 -47. continued Both RA 353 MA ® and RA 253 MA show a reduction in toughness after intermediate exposure.Sigma Phase.2% Offset Elong Yield.000 88.7 16 7. foot-pounds 240 (test machine limit) 96 167 130 AR PE 1400 AR PE 1400 AR=as received.9 6. meant for furnace belt pins.4 3. usually somewhere in the range ASTM 1-8 (250-11µm) for the smaller bar.6 3. In this case chromium nitride precipitation is in part responsible 4.63 - .500 35.5 65 -RA % 70 60.900 32.9 7. psi % 34. The 3/4” (19mm) diameter bar RA333SA. and all forms of 800H/AT are definite exceptions.7 34 4.5 40.4 25 72 204 ----- ----- RA330® shows retains high tensile ductility and Charpy V-notch energy after 1000 hour exposure to 1400ºF 5: Test Temp ºF 75 75 1400 1400 Condition Ultimate Tensile. foot-pounds RA 353 MA RA 253 MA 310S 8. sheet and light plate sizes.5 59 -Charpy V -notch impact energy. Exposed 5000 hours at ºF 1292 1472 1652 200 hours at ºF 1742 1832 1922 2012 Charpy V-notch Impact.4 5. 85. the grain size of a metal sample may be an aid to estimating what temperature the metal may been subject to in service.

Rundell.190 4. Gene R.5) 4 (90) 4 (90) 3 (127) 3 (127) 2 (180) (90) 4 (90) 4 (90) 3 (127) 2 (180) 2 (180) (90) 3 (127) 3 (127) 3 (127) 2 (180) 1 (254) (90) 3 (127) 2 (180) 2 (180) 2 (180) 1 (254) (127) 3 (127) 3 (127) 2 (180) 1 (254) 1 (254) (127) 3 (127) 2 (180) 1 (254) 1 (254) 00 (508) 5 5 5 4 4 4 3 3 Light plate coupons were exposed6 in a vortex finder at an Eastern U. U. Although the initial grain size was not recorded. Behavior of Superheater Alloys in High Temperature. Rolled Alloys Investigation 27-84.S. U. Rundell.A.15 0. U. minutes 10 15 30 60 120 (63.A. Crucible Inc. continued Grain size of RA330 versus time and temperature. 6. . box annealed. New York.192 4.17 0.Grain Growth. RA310 and RA330 all experienced significant grain growth. Pennsylvania. June. August. The following is old data. ASTM.83 0. hot rolled hand mill sheet. U.88 Final Grain Size ASTM µm 5 62 4 88 00 508 4-00 88-508 00 and 508 and coarser coarser References 1. and may be influenced by prior mill processing: Temperature F C 1900 1038 1950 1066 2000 1093 2050 1121 2100 1149 2150 1177 2200 1204 ASTM Grain Size Number (µm) Time at temperature. 4.242 6. 1972. as compared with the maximum 2 hours of the above table. these particular materials most likely were produced with ASTM 4-7 (88-31µm) initial grain size. George E. New York. RA309. August.A.259 6. Philadelphia. Rolled Alloys Investigation 27-84.A.04% carbon alloy. while RA 253 MA and RA333 showed no measurable effect.243 6. Rolled Alloys Bulletin 1353. 1968 3. chemical company for 1862 hours at 1850°F (1010°C).S. 110. Occurrence and Effects of Sigma Phase. Michigan. Response to grain growth may vary from heat to heat. High Pressure Steam. Materials Research Center.. arc furnace melted (no AOD remelt). Private communications of January 10 and June 22. Lien. 1950 2.S. Because of the long time exposure. Symposium on the Nature. Special Technical Publication No.S. 1984 Temperance. RA 353 MA® alloy 5.S. Gene R.58 0. editior.5) 4 (90) 4 (90) 3 (127) 3 (127) 2 (180) (63. Michigan. The American Society of Mechanical Engineers. Alloy RA333 RA 253 MA RA330 RA310 RA309 Sample thickness inch mm 0.A. laboratory annealing of 0. 1984 Temperance.64 - .

430 sheet has been used to line the bottom half of RA330 brazing muffles. formerly called MF-1 by Allegheny Ludlum. It also hardens when welded.65 - . 409 is formable and weldable. This embrittlement is well known in the petrochemical field. 410S is a lower carbon. 409 has usable oxidation resistance up to about 1200°F (650°C). 409. as is a columbium (niobium) stabilized solid wire. 409 is processed in the mill to be a minimum cost grade. 409 plate is sometimes welded with alloy 82 wire for better weld bead toughness. through enhanced oxidation resistant grades from AK Steel (formerly Armco) & Allegheny Ludlum to advanced oxide dispersion strengthened (ODS) alloys from Kanthal® and Special Metals ®. comparable to or slightly lower than that of carbon steel. about 0. Iron-Chromium Alloys These range from simple ferritic or martensitic grades such as 409. 410 is a martensitic grade. Very cheap. might even be called brittle. All ferritic or martensitic alloys with 12% or more chromium embrittle very severely when held in the 800-1000F (430-540°C) temperature range.14% C. such as RA446. These alloys have low ductility. Commercial kitchens and bake ovens use quantities of 430. . as are stainless exhaust systems. The metal can lose ductility to the point that it will crack in several pieces just from clamping it in a vise. that being the temperature of most severe embrittlement. The iron-chromium alloys have low coefficients of thermal expansion. 430 is the most broadly available ferritic stainless.000 hours service. that it can be hardened by heat treatment. is the lowest chromium alloy that qualifies as stainless. although it is reported to embrittle after some 50. magnetic. Automotive catalytic converter shells are made of 409. Because of their low strength at temperature (excepting the ODS versions). to protect the austenitic alloy muffle bottom from braze attack. A matching composition flux cored wire is available. and some of the environmental and mechanical requirements to be met in service. more weldable version of 410. and those with higher chromium contents. it is time to take a look at some of the available alloys on the market today.HEAT RESISTANT ALLOY GRADES Now that we have reviewed the influence of the various alloying elements. and requires both pre-heat and immediate post weld anneal to keep the weldment from cracking. “silverware” is 430. having enough carbon. It is called “885°F” (475°C) embrittlement. It has the advantage of being low enough in Cr to avoid 885°F/475°C embrittlement for some time. used for both corrosion resistance and as a heat resistant grade. Being very low carbon and titanium stabilized. RA446 and RA410. their use is limited to non-stressed parts.

66 - . gives RA446 the best resistance to sulphidation—usually—of the heat resistant alloys. It is not broadly available from distributors. having at best less than 10% the creep strength of an austenitic nickel alloy. The disadvantages of the ODS materials at this time include cost in the neighborhood of $50/lb ($110/kg). leaving the weldment with only the (very low) strength of a conventional ferritic stainless. by about 5% aluminum with rare earths. The ODS ferritic grades available in the US are Inconel® MA956 and Kanthal® APM. at 25% chromium. RA446 is very weak at red heat. Melting from arc welding destroys the oxide dispersion. along with no nickel at all.8mm). limited availability and fabrication. This means that at room temperature RA446 plate may crack whe n hit in a mechanical press break. At Rolled Alloys we have used Kanthal APM to 2100°F (1150°C) in our oxidation test tray (currently it is RA 602 CA). Currently. that is. This permits it to be used around molten copper or brass. This grade is made only in very light gage strip for automotive catalyst support systems. 18SR sheet is available in full coil lots only. and titanium stabilized. at least 250°F (120°C). Y2 O3. into the Fe-Cr-Al matrix. . Allegheny Ludlum’s ALFA-IVTM uses aluminum and rare earths to achieve extremely good oxidation resistance with 20%Cr. This high chromium. No longer available in sheet gages (under 3/16 inch/4. RA446. The largest single use may be as electrodes for heating neutral salt baths. has the oxidation resistance needed for 2000°F (1100°C) service. As a result. quite unlike conventionally produced ferritic grades.HEAT RESISTANT GRADES. Oxide dispersion strengthened (ODS) grades achieve extreme temperature oxidation resistance in the same manner as ALFA-IV. These alloys are produced by mechanically incorporating the rare earth oxide.35mm) MA956 plate. RA446 is used for applications where nothing else will handle the corrosive environment. the ODS alloys have very high creep rupture strength. There has been some degree of success with laser seam welding 1/4” (6. Sandvik has in recent years begun extruding Kanthal APM into finished radiant tubes for industrial furnace use. RA446 has a very high ductile-to-brittle impact transition temperature. AK Steel’s (formerly Armco) 18 SRTM uses both silicon and a critical ratio of titanium to aluminum to achieve oxidation resistance well in excess of what would be expected from its chromium level. In spite of its mechanical properties. continued 439 is about a percent higher in chromium.

05 0. This is also the group from which alloys with useful sulphidation resistance are chosen.02 0.5 0.5 Al ----1.25 --0. But for constant temperature or slow heating and cooling.3 20 22 19.5 -Ti 0.05 0.5 0.015 0. Although the “L” grade is principally used for appearance or for aqueous corrosion resistance.67 - .14 0. Oxidation resistance and strength include some of the best available (RA 253 MA). With 0. Nevertheless the 316L is chosen to better resist aqueous corrosion for fans which must operate part of the time at high temperature.4 0. 304 can be considered and is used quite extensively.015 0. likewise dual certified.4006 -------Cr 11 12 16. at temperatures not above 1500°F/815°C. and also near room temperature.HEAT RESISTANT GRADES.4 25 Si 0. dual certified with 304.5 0. 304 is limited to this temperature by oxidation resistance.8 4.7 5 5.5 Y2 O3 -- Iron-Chromium-Nickel Alloys. All of these grades can embrittle from sigma formation to some degree.4841) have sufficient carburization resistance for heat treat service. RA310.03% carbon maximum the design stresses at 1500°F (816°C) might be about 40% lower than for 304H. or 304H. It has a fairly high coefficient of expansion. .08 0. We would prefer some other material fo r an item that was to be heated and cooled rapidly.4 0. Nickel 20% and under These range from the high volume 304 and 321 up to a true heat resistant alloy. only RA85H and 314 (W.015 0.4 -C 0. 1. Flat rolled products are usually either 304L. the “H” version of this steel may be used to about 1500°F (815°C). Ferritic and Martensitic Alloys alloy 409 410 430 439 18 SR ALFA IV Kanthal APM MA956 RA446 UNS S40900 S41000 S43000 S43035 ---S67956 S44600 EN -1.2 17. with 304L and 304H bar also available. is rarely used because it is not broadly available. it retains strength at temperature.02 0. continued Nominal Chemistry.5 17. 316L Not really a heat resistant alloy but used as such anyway.3 0.Nr.4 --0. 304 The basic “18-8” stainless is AISI type 304.05 Other -----0.03 Ce+La rare earths 0. even though it would be stronger at high temperatures. Because 304 is austenitic. particularly for fans. Bar may actually be just plain 304.3 0.6 0. 316H.

Low cost. In oxidizing atmospheres RA253 MA has very good resistance to SO2 (sulphur dioxide). The ferritic RA446 and the lower nickel RA309 might be preferred for very strongly reducing environments with sulphur present. 321 resists oxidation in high temperature service to about a 100°F (56°C) higher temperature than does 304. better than RA330 at constant temperature but not so good as RA330 when the temperature cycles. which is too high for the grade to develop titanium carbides. The maximum suggested continuous use temperature for RA 253 MA is 2000°F (1100°C). hence resistance to polythionic acid stress corrosion cracking. 0. also known as 310HCbN. tolerating some 12% SO2 for extended periods at 1800F (982C).08% max carbon) is one of the most widely used heat resistant alloys. previously restricted to electrical resistance alloys (and the cobalt alloy 188). RA 253 MA is not particularly carburization resistant (RA309 is slightly better) nor has it performed well in REDUCING sulphidizing conditions (H2S). RA309 (really 309S. The columbium (niobium) addition helps hot corrosion resistance at moderate temperature but is harmful to oxidation resistance around 1800°F (982°C) and upwards. a heavy calcium deoxidation. RA310 is one of the three alloys which should be considered where sulphidation is concerned. nitrogen and silicon.68 - . i. ASTM specifications require 321 to be annealed 1900°F (1038°C) minimum. continued 321 This is a modification of the basic 18-8 grade with the addition of titanium to stabilize it against carbide precipitation in high temperature service or from the heat of welding. is a nitrogen-columbium strengthened version of 310 with improved hot corrosion resistance up to perhaps 1600°F (870°C). it is suggested that welded fabrications of 321 be heat treated for 4 hours at 1600°F (871°C).. For maximum resistance to carbide precipitation in service. RA310 has very good oxidation resistance. RA309 tolerates carburization well enough to be the grade of choice in carbon saggers. Intermediate temperature embrittlement can be a problem. RA310 maintains useable oxidation resistance beyond 2100°F (1150°C). In a more complex mix of chemicals RA310 is generally superior to RA309 in hot corrosion and is considered one of the standard materials of construction for coal gasifier and coal fired fluid bed combustor internals. be properly stabilized. Nickel 20% and under. useful cyclic oxidation resistance to around 1850-1900°F (1010-1040°C) and fairly good sulphidation resistance characterize this grade.Fe-Cr-Ni alloys. the other two being RA446 and RA309. . RA 253 MA® achieves excellent strength and oxidation resistance through rare earths. and is used up to 1600°F (871°C). It was the first commercial NiCrFe alloy to use this technology. Thousands of feet of steam boiler tubing are on test at TVA. HR3C. RA 253 MA is strong. with two to three times the creep strength of RA309. and 309 weld fillers are often used for dissimilar metal welds. Fabrication is simple.e.

For the money. 314 is widely used in Europe. a. The cracking problem may be avoided by heat treating the welded fabrication 1625°F (885°C) for 1 1/2 hours.A. Nr.) Combined aluminum + titanium 0. Rolled Alloys supplanted 314 with RA330 a generation ago in the U. Nominal Chemistry. for thicknesses up to 1inch (25mm). and the newest.05 0.4841) is essentially 310 with 2% silicon. coupled with mediocre oxidation resistance.20%. For the most part.04Ce 65Fe 62Fe 1Al 61Fe 52Fe 0.S.5 20 20 20 Si 0.k.10 N --0.69 - .5 25 25 25 Ni 9 9. is a very strong alloy broadly used in the petrochemical and refining industries.4Cb 52Fe 51Fe Iron-Nickel-Chromium alloys.a. Silicon increases the already good oxidation resistance of 310 and adds both carburization and nitriding resistance. it is the German mills that make this grade. RA 353 MA ® RA800AT TM . This has been suggested as the cause of cracking problems. .851. 800HT®. coupled with the high chromium. and amount.20 0. 2.) High temperature grain coarsening anneal.3 21 23 18. Nickel 20% and under alloy 304 321 RA 253 MA RA309 RA85H RA310 HR3C 314 UNS S30400 S32100 S30815 S30908 S30615 S31008 -S31400 EN 1.) Carbon 0. commonly resulting in grain size ASTM 1-3.3 11 13 14. The alloy does have some drawbacks.01 0. 800AT gets its strength by a combination of: 1. such as RA330 and 800H.08 0.5 2.5 0.8 3.25 -Other 70Fe 0. and may be why the 800AT chemistry has been less well accepted in Europe.3 17.06-0.10% 3. This. Nickel 30-40% This nickel range covers some of the most successful heat resistant grades.7 1. Add one hour per inch (25mm) of thickness greater than 1” (25mm)1 . the very coarse grains which are necessary for high creep-rupture strength are quite bad for thermal fatigue/ thermal shock resistance.17 ---0.4301 1.4835 --1. First. Fe-Cr-Ni Alloys.314 (W.4541 1.5 0.2Ti 70Fe 0.. largely keeps 800AT out of heat treat service. Here 800AT is used as their basic structural material.0 C 0.7 0.05 0. The second disadvantage is that the high combined aluminum + titanium content causes 800AT to form a very small amount of the age hardening constituent gamma prime at around 1100°F (600°C) or so.5 0. 2100°F (1149°C) minimum.4845 --Cr 18.06 0. much as RA330 is the basic heat treat alloy. N08811. it is hard to beat the strength of 800AT. 314 may has lower creep strength than 310. 1. However. and is often casually referred to as “310” there. of sigma formation.05 0. silicon also increases the rate.

And perhaps influenced by the success of 35%Ni 15%Cr Misco Metal. and was available in two grades. RA330 has much better resistance to deformation (creep strength) than RA309 or RA310. Because of its oxidation resistance. weldability by GMAW.10%.10% max (no minimum) carbon. usually with cast HT links. kilns. Grade 2 became Incoloy 800H in the early 1970’s. and the Al + Ti controlled. outlasting muffles of alloys 600 and 601. was announced in July. Our highest temperature well documented experience with RA330 was a palladium brazing muffle. utility coal burners and boiler tube shields. with some AISI 330 and a smaller amount of RA333®.RA330HC uses 0. annealed around 1800°F (980°C). compared to 601. and Grade 2 was solution annealed for greater creep-rupture strength. courtesy the Korean War nickel shortage. RA 353 MA® may be regarded as an improved RA330 for use at 1830°F (1000°C) and higher. It is not uncommon for RA330 retorts to operate as high as 2250°F (1230°C) metal temperature. RA 353 MA is finding extensive use in retorts. Nickel 30-40%. . By applying a minimum carbon of 0. At intermediate temperatures RA330 never embrittles from sigma like RA309 or RA310. Eventually Incoloy became Incoloy 800.05%.4% carbon to provide high shear strength for use as pins in cast link belts.06-0. or matching RA 353 MA GTAW and GMAW bare wire. Incoloy 800 Grade 1 was fine grained.25% silicon addition enhances both carburization and oxidation resistance. continued There are three versions of “800” alloy. Prior to this time the only heat resistant alloy Inco promoted was the 76%Ni alloy 600. 0. 2450°F (1343°C) and good oxidation resistance permits RA330 to be used at more extreme temperatures than any other currently available grade. 1951.70 - . where it has twice the strength. In response the carbon was increased slightly to 0. . and raised from 0. 35% nickel has been found to be the optimum level for carburization resistance and strength in the Fe-Ni-Cr alloy system. RA330® is truly the workhorse alloy of the heat treating industry.7% typical to about 1% typical. Oxidizing hot corrosion resistance is good.Iron-Nickel-Chromium alloys. Welding is by either RA 353 MA DC lime type covered electrodes. and 100°F (56°C) higher melting point. radiant tubes. The 1. The majority of all wrought alloy fixturing in use today is RA330. and alloys 600 and 601. The original “Incoloy®”. 11 gage (3mm) operating 2300 to 2370°F (1260 to 1300°C). A combination of fairly high melting point. During the 1980’s the ASME design stresses for 800H were challenged. as are its hot erosion capabilities in cyclone applications. brazing muffles.

Rotary retorts of 3/16” (4. as well as advanced grades for thermal processing. RA333 kilns 35 foot (1070 mm) long have been used to calcine zeolites for a decade now. . Nickel 45-60% These alloys include RA333 and other superalloys developed for gas turbine use.06 0.05 Other 0.2 1. RA333 pins tend to outlast the usual cast HT links. RA X.4854 Cr 21 19 19 25 Ni 31 35 35 35 Si 0. 600 (ductile. where RA333 has outperformed RA330. but weak) and alloy X.6Ti 45Fe 43Fe 43Fe 0.16N 0. without danger of burning a hole through the tube. It is now slowly being replaced by alloys 188 and 230 in flight engines. causing the whole muffle to fail.4886 -1. RA333 is particularly good in resisting erosion from flame impingement. used to harden steel shot. RA333 permits a thinner tube.05Ce 36Fe Nickel-Chromium-Iron alloys.4 1. RA333 3/4” bar is used for cast link belt pins.Nominal Chemistry. and usage te nds to be in niche markets. RA333 has excellent resistance to thermal shock. Rather few people use X in heat treat service.05 0.8 mm) RA333 plate. It has excellent oxidation resistance in freeflowing atmospheres to rather high temperature. tungsten and molybdenum.2 1. and by 230 and 617 in land based gas turbines.2 C 0. Costs are higher. while alloy X plate at that temperature may completely disappear. and has a 1% silicon addition to enhance carburization resistance. A higher alloy link.71 - . 2100°F (1150°C). This includes water quenching applications. RA333 is strengthened with 3% each of cobalt. Because of both strength and ductility. such as Supertherm®. For example. may be suggested to maximize overall belt life when using RA333 pins. Nickel 30-40% alloy RA800H/AT RA330 RA330HC RA 353 MA UNS N08811 N08330 -S35315 EN -1. Nevertheless. RA333® is one of the best performing wrought alloys for industrial heating applications. developed in the early 1950’s by Haynes® as Hastelloy® alloy X. through 2200°F (1200°C).40 0.4Al 0. have been giving 10 year life since the 1960’s. Fe-Ni-Cr alloys. thus better heat transfer and energy efficiency. Direct service comparison with 601 in the same furnace has confirmed the superiority of RA333. RA333 maintains oxidation resistance to 2200°F (1200°C). This was a problem for us when some RA333 Mo reduction muffles were welded with alloy X covered electrodes. has been for years the standard alloy for gas turbine engine combustors. at more extreme temperatures or under stagnant atmospheres the 9% molybdenum content may render this alloy susceptible to catastrophic oxidation. In service the weld beads disappeared. as in radiant tubes.

as the old 82 (columbium/niobium bearing) weld disappears. extremely oxidation resistant. and has been used for land based gas turbine combustors. 15 to 25% Chromium This group includes RA601. which is not. Nominal Chemistry.5Mo 0. and in nitric acid catalyst support grids.7Co 0.Nickel-Chromium-Iron alloys.05 0. RA600 has moderate hot strength.08 0. it is commonly welded with alloy 82 (ERNiCr-3). continued RA333 is highly resistant to metal dusting. with good retention of ductility and excellent oxidation resistance. CVD retorts and vacuum furnace fixtures.03 0. and RA600. Nickel 45-60% alloy RA333 RA X 617 230 UNS N06333 N06002 N06617 N06230 W/Nr 2. It is used for retorts and muffles.4608 2.3 0.02La Nickel over 60%. often simply called by Inco’s tradename “Inconel®” RA601 is a strong. 230 is a strong alloy.4663 -Cr 25 22 22 22 Ni 45 47 54 60 Si 1 0. It is carburization resistant at high temperatures.6W 19Fe 12. bar product being relatively uncommon. and very good carburization resistance. sintering muffles. Nickel 45-60%.3Al 0. Compared to RA330. it may be susceptible to catastrophic oxidation under stagnant conditions.4Ti 1Fe 14W 1. 617 alloy is strong. Ni-Cr-Fe alloys. It has also been used in nitric acid catalyst support grids. Using RA 602 CA weld fillers is suggested to address this problem.72 - . and for parts of high temperature vacuum retorts. It was introduced in the 1960’s. the Krupp VDM alloy 602CA. and resists grain growth in high temperature service. 600 is nearly as oxidation resistant but somewhat lower in creep strength.4 C 0. RA600 has poor resistance to sulphidation. In the USA it has been used for kilns operating as high as 2100°F (1150°C). As a consequence 601 fabrications may require frequent rewelding.08 0. RA 602 CA® is a fairly recent development. even in oxidizing atmospheres (sulphur present as SO2).10 Other 3Co 3Mo 3W 18Fe 9Mo 1. It is very strong. carburization resistant and very oxidation resistant alloy. good ductility and resistance to oxidation.4665 2. . 602CA has been used in Germany for steel mill annealing furnace rolls. developed by James Hosier. as shown by both years of experience and long term comparative testing. Because of its 9% molybdenum.5Co 9Mo 1Al 0. and oxidation resistant to reasonably high temperature. Although 601 is very oxidation resistant.

Goetcheus moved on to head up the Rolled Products Division of Michigan Steel Casting Company.08 Other 1. concentrated caustic (sodium or potassium hydroxide) solutions. for carburizing boxes.2 0. sold the first Inconel sheet to Buick Motor Division. “Inconel” was originally sold for corrosion applications. in their terminology) 35Ni 15Cr alloy. 15 to 25% Chromium alloy UNS W/Nr Cr RA601 N06601 2.5 Ni 61. Therefore. and the 35-15 alloy. continued RA600 has good resistance to corrosion by neutral heat treat salts and salt fumes.Nickel over 60%. atmospheres. became RA330. we are fulfilling our slogan.05 0.5 RA 602 CA N06025 2.5 63 76 Si 0.4816 15. READY WHEN YOU NEED THEM”. Nominal Chemistry. working from the Chicago office of Steel Sales. There he worked to promote the use of a wrought (Rolled.2Ti 8Fe This concludes our general discussion of the various wrought materials that might be selected for a given application and those that we have selected to cover the range of temperatures. As an aqueous corrosion alloy. Nickel over 60%.4Al 14Fe 2Al 0.2 -0. A bit of history.08Zr 9. not high temperature.5Fe 0. . 15 to 25% Chromium. Misco Metal.4633 25 RA600 N06600 2. to heat treat 50 pounds of work. It is appropriate for automated salt pot fixturing. Mr. RA600 is resistant to hot. Economics generally favor RA309 or RA330 for the salt pot itself. In 1938 a salesman named Paul Goetcheus. “ALL THE BEST HEAT RESISTING ALLOYS.2 C 0. RA600 has good resistance to dry chlorine and dry hydrogen chloride gas at temperatures up to 900-1000°F (480-540°C).1Y 0. Previously. Goetcheus became the first president of Rolled Alloys. stresses and cyclic conditions.73 - .4851 22. We think one of our alloys will perform to best advantage in almost every application. in 1944. In 1953 Mr. Buick had used cast boxes weighing 200 pounds.

Embrittlement. for example. Selection of cast versus wrought will depend. This is particularly true of the very high chromium alloys. This simply increases the dead weight that goes through each heat treat cycle. 1. They are unable to withstand rough handling when cold. 2. Certain shapes can be cast that are not commonly available hot rolled. A good design in either metal form may outlast a poor one in the other. because they lack sufficient ductility to be worked into wrought forms. Cast grids. In addition there are a number of chemistries that are only available as castings.) Design. cutting and welding of a fabrication.Cast Heat Resistant Alloys2 Heat resistant alloy castings are available in chemistries similar. This is because of the microstructure. Some alloys are available only as castings. Disadvantages of Cast Alloy Delivery. Weight. Compositions. Advantages of Cast Alloy 1. or is bad. and because cast heat resistant alloys are usually much higher carbon than the wrought “equivalent”. 2. In fabrications this usually means the welds. Appropriate design may influence life more than the simple choice of wrought versus cast. With radiant tubes and muffles thicker cast walls increase fuel costs for the same volume of work heat treated. porosity and residual casting stresses. 3. .) Quality. Similar compositions are inherently stronger at high temperature in the cast form than in wrought. With castings it is internal shrinkage. This effect of design may or may not get factored into the user’s evaluation of his own experience. or that cannot be fabricated economically from available wrought product forms. When equipment is down. Initial Cost.74 - . the price per pound of fixture may be lower. economics and delivery time. This is rarely true of castings. are: 1. among other things. upon experience. rolling. Two aspects which influence whether one’s experience with either is good. to those of the wrought alloys. 3. and weld repair is extremely difficult. Creep Strength. although never identical. Shapes. Since cast parts avoid all the forging. may last only a few months. or for many years. Cast parts are almost invariably thicker and heavier than the equivalent fabrication. fabrications can often be delivered in a couple of days to get back on stream. depending on the foundry source. 2. Many cast alloys quickly become very brittle in service. 4.

5. 2. The smooth surface of wrought alloy helps avoid focal points for accelerated corrosion by molten salts or carbon deposits.Cast Heat Resistant Alloys. found in castings. and the inherently greater ductility of wrought metal. Wrought materials are normally free of the internal and external defects such as shrink. Soundness. Surface Finish. and much less unproductive metal goes through each furnace cycle. A pattern must be made for each different part design. Thinner sections that reduce thermal stresses. 5. promote better resistance to thermal cycling and shock. Wrought alloys are available right down to nearly foil thickness. internal shrinkage cavities. Thermal Fatigue.75 - . Disadvantages of Wrought Alloy 1. 28Cr 10Ni or 35Cr 46Ni. With lighter sections the initial cost of a fabrication becomes competitive with. porosity. Section Size. Fabrications are quickly procured to minimize expensive down time. When these defects are open to the surface they are subject to attack by carbon deposits or molten salts. Creep strength. Where creep-rupture is truly important. . Availability. Alloys such as 50Cr 50Ni. Composition. internal oxides and cold shuts. 3. all with excellent hot corrosion and/or carburization resistance. Castings invariably have some degree of porosity. Advantages of Wrought Alloy 1. 4. Pattern cost. Handling the fixture is easier. Soundness. Wrought heat resisting alloys are immediately available from stock in numerous product forms. 2.. Thinner sections often permit weight reduction of 50% or more. Few wrought alloys match the high strength of heat resistant castings. continued 4. are available only as castings. this must be considered in product design. This is all right for production runs but quite uneconomical for one’s and two’s at a time. or less than. etc. a casting.

76 - . When the cast HT (35%Ni 17%Cr) grid was practically new and had been exposed to only a few cycles. oil or brine. quenched in either molten salt. the cast alloy portion suffered surface attack from soot and the quenching salt. continued The effect of cast alloy surface and internal defects versus wrought alloy soundness on service performance is illustrated by our old case history. The wrought alloy RA330 exhibited very little surface attack and no fractures. RA330-108.Cast Heat Resistant Alloys. a particular job required increased working area for the grid. Note the cracks in the center of the cast ribs which occur along the plane of weakness of the dendritic structure. RA330 allo y plate was formed and welded to the outside of the existing cast grid. . The application was a grid for suspending loads in a gantry furnace at a commercial heat treat shop. The work was neutral hardening from temperatures up to 1850°F (1010°C). As can be seen in the photo. and failed from thermal fatigue.

References 1.4840 J94614 -J94605 -J95405 1. Rolled Alloys.8 1.5 0.5 alloy HC HD HE HH-2 Thermax® 40B HI HK HL HT HU HP Supertherm® HOM-3 22H® MO-RE® 40MA IN-657 HX UNS W/Nr J92605 -J93005 -J93403 1.4 0.4.4339 J93633 1.4 0.3 0. 18th Edition.3 0.4 0. .3 0.5 W ----0. Metals & Alloys in the Unified Numbering System . Section VIII. 1998.S. Cast Heat Resistant Alloys3. ASTM DS-56G. continued Nominal Chemistry.5 1 1 1 1. New York. paragraph UNF-56 (page 205).4879 --R20501 2.5 ------5 3 5 ---Co -----------15 3 ----Other 67Fe 63Fe 61Fe 60Fe 59Fe 0. Midwestern experience has been that they contribute to heavy sooting in carburizing furnaces. 1973 4.5Fe 13Fe Where metal dusting is a problem. High Alloy Data Sheets.7 1.7 1. Verlag Stahlschlüssel Wegst GmbH. and on Supertherm for cast fixturing.. Temperance. Warrendale.4 2 C 0.5 1.5Cb 0. However.4837 --J94003 -J94204 1.4 0.A. Michigan 48182 U. Heat Series. ASME.3 1. Inc.5 0. 3.S. Steel Founders’ Society of America. one large captive shop has standardized on RA333 as their wrought alloy. New York. 1998 ASME Boiler & Pressure Vessel Code.5 1 1 1 0. both grades being found extremely resistant to metal dusting (carbon rot).45 0. 5.Cr 28 29 28 25 25 28 25 30 17 18 26 26 26 28 35 50 17 Ni 2 5 9 13 13 16 20 20 35 38 35 35 46 48 46 47. 2. Division 1.5 66 Si 0.5 0. Pennsylvania. German.5 0.4 0. U.45 0.5 0. D-71672 Marbach.4 1.77 - .4 1.Cast Heat Resistant Alloys.06 0. ISBN 0-7680-0407-1 1999 Society of Automotive Engineers. Bulletin 113. Selecting the Alloy. We have been told that nickel-aluminide alloy castings for heat treat service are quite strong.4813 N06006 .4865 J95705 1.A. Stahlschlüssel.3Ti 54Fe 54Fe 47Fe 44Fe 40Fe 36Fe 13Fe 16Fe 3Mo 16Fe 14Fe 1.4857 -----2. 8th Edition.3Cb 1.

there is considerable scatter. the furnace industry often designs to an allowable stress of one half the stress required for a minimum creep rate of 0. under the same load.DESIGN Stresses (compressive. And it is destructive chiefly because the engineer does not include in his design proper allowance for or provision against temperature inequalities or because the operator imposes temperature differentials which cause localized dimensional changes with accompanying stresses greater than the elastic strength of the alloy at the given temperature. It can be surprising how rapidly mechanical strength drops off with temperature. 15 to 20%. These data are obtained under very closely controlled laboratory conditions of constant temperature and stress. Proceedings of ASTM. buckle or crack. . to about 90 per cent of the total number of cases. in rupture data. Fahrenwald. F. designing to either 100% of the extrapolated 0. hence thermal strains.00001%/hour minimum creep rate. If thermal expansion is somehow restrained. Some Principals Underlying the Successful Use of Metals at High Temperatures. of creep-rupture data. in mechanical engineering texts.0001% per hour. are the rule and not the exception in high temperature equipment. When using published average creep-rupture data for design one must include a safety factor. and be clearly aware of the range over which temperature will be controlled in service. yet often dismissed or given but slight consideration in design. nor at least emphasized. at the service temperature. or 67% of the extrapolated 100. or shear) due to unequal temperature distribution and non-uniform temperature gradients. One must design to permit free expansion (and contraction) or the metal will bend.78 - . one should be aware of the significance.000 hour rupture stress. Even so. 1924 V. less than 1/4 that of carbon steel and only 1/30 that of copper. A corollary to this is that most heat resistant alloys have rather poor thermal conductivity. A. and possibly more in creep. 24 High temperature equipment design has certain unique features not commonly found. and the limitations. For example. the resulting stresses will equal the yield strength of the metal at temperature. an increase in service temperature from 1700°F (927°C) to 1800°F (982°C) could drop the life of an RA330 component from 10 years down to only 15 months. cause more failures in high—temperature equipment than all other influences combined amounting . The ASME Boiler & Pressure Vessel Code is more conservative. whichever is lower. . Next. In practice. Thermal gradients. The first and most important is that metals expand in volume with heat. tensile. . This simple statement is so obvious.

above about 1000°F (540°C) stress is no longer proportional to strain. This is because this “strong” design cannot accommodate the relative thermal contraction of the bottom versus the top of the frame. are often designed to much higher stresses than are static components. A 48” (1220 mm) long RA330 heat treat basket. to fatigue from the rotation. bend or warp permanently with each thermal cycle. oil quenched from 1550°F (843°C) will contract 0. Since the bottom of the basket enters the quench while the top frame is still red hot. in typical heat treat service. . for example. Eventually. Although modulus data are published at elevated temperatures. This expansion must be accommodated not only by design but by installation practice as well. the numbers are obtained by a means involving the speed of sound through the material. An item of some minor confusion is elastic modulus.DESIGN. this repeated strain will fatigue the metal and the equipment will break. At such temperatures strain is proportional to both time and stress. such as kilns. at red heat these alloys are simply not elastic. It is important to recognize just how large the total expansion can be. If the metal is not free to expand. A flexible bar frame design may tolerate this.6 mm)—more than 11/16”—in overall length. a mechanically strong and rigid welded angle frame design may be inclined to crack or distort. continued Rotating components. but rarely. when heated from room temperature to 1800°F (982°C). if e ver. Thermal Strain This point is such an important consideration for high temperature equipment design that it must be examined in some detail. A large portion of the many field failures reported to us happen because the designer or user did not appreciate the significance of thermal expansion. This expansion is roughly 3/16” to 1/4” for each foot of length (16 mm per meter). One cannot calculate a simple beam deflection at 1650°F (900°C) using anyone’s published modulus data. it will stretch. In practice. and not simply to stress alone. Kiln failures may be due to hot corrosion. In other words.79 - .692 (17. more often to flite design. the bottom members contract before the top does. But. and the modulus data has no real meaning. Heat resistant alloys expand a great deal when heated.

averages about 37. As well as being the cause of distortion in service. McGraw-Hill. The short-term modulus. New York. So. one may assume that a temperature differential of only 200°F (110°C) in this temperature range would cause permanent plastic deformation. . Theory of Elasticity. for whatever that is worth.5x106 psi (196 GPa) to 19.970 psi.3 x 10-6 inch/inch°F E = 23.80 - .297 The calculated stress = 62. The restraint coefficient in real structures will be some number less than one. a = 9. for example. In general any piece of metal which is hotter on one side will. become concave on what was the hot side.200 psi (256 MPa) at room temperature. drops from 28. rule of thumb is that a 200°F (110°C) temperature differential will yield most austenitic heat resistant alloys. convex to the quench.Timoshenko. when cooled. Assume a plate 1000F on one side and 800F (538 to 427°C) on the other. NY 1934 Apply this formula to RA330. one rough. this principle may be used to straighten metal parts1. but only 40% of that figure. The short-term yield strength of RA330.400 psi (106 MPa) at 1600F (871C).000 psi. but good.8 x 106 psi T = 200°F K = 1 ? = 0. Nevertheless. continued As temperature goes up the metal not only expands but diminishes rapidly in strength.Thermal strain. The combination of differential thermal expansion/contraction and reduction in strength at heat is why quenched grids or large bar frame baskets tend to bow like a rocking chair. Average 0. The equation for calculating thermal stress in the elastic region is: S = aETK 1— ? a = coefficient of thermal expansion T = temperature difference ? = Poisson’s ratio E = elastic modulus K = restraint coefficient The formula may be found in S.2.5x106 psi (134 GPa). or 15.2% offset yield strength of RA330 at 1000°F (538°C) is 25.

The unfused void in this fillet resist weld acts as a stress riser may cause premature failure. The blades may also flutter or vibrate . a small step each cycle. Bar frame heat treating baskets. All welds. just starting and stopping the fan will cause low cycle fatigue failure of incompletely penetrated welds. Eventually. A couple of examples: 1. Each time the fan starts up. This fully welded joint can both thermal and and mechanical fatigue.81 - . This is because centrifugal force. it goes through one fatigue cycle. gas loading and the temperature differential between blade and hub all stress the blades. Incompletely penetrated weld joints will not tolerate thermal strains and are the most common cause of weldment failure in high temperature service. Incompletely fused welds crack a little more each time the basket is quenched. Repeated thermal strains cause the “crack” to grow outward through the weld bead. In thermal or mechanical cycling. Furnace fans. or when the basket is straightened.Weldments Weldments can fail from repeated thermal cycles. there is no warning sign that the part is about to break. Since this crack cannot be seen from the outside. 2. must be completely fused. The weld may break in service. butt or fillet. the unwelded areas behave as large cracks or notches. This happens even though the remaining weld metal is still ductile.

A joint design that makes a good fan in 316L stainless (W. it is also increasing in width and height. 1. Thermal Expansion A simple way to calculate the thermal expansion of a fixture is to use the chart below. It is really a volume expansion. How far will the free end expand? Looking down the RA330 column we find a total expansion of 0. continued during operation. All welds of fan blades to the hub must be fully penetrated. But no weld filler will compensate for inadequate weld joint design.82 - . How wide will it be in the hottest zone? 36 inches + 0. So while the fixture is increasing in length.208 inches/foot at 1800°F (982°C). which causes more fatigue crack growth. Pick the alloy.208 in/ft X 20 ft = 4. (Multiply by 83.208 in/ft X 3 ft = 36. A hole. Incidentally. Example: An RA330 D-muffle 36 inches wide and 20 feet long operates at 1800°F. not just an expansion in one direction.33 to get how many millimeters each meter of metal will expand) Remember that thermal expansion occurs in all three dimensions.Weldments.624 inches. A higher strength weld filler such as RA333 may be helpful in resisting mechanical loads. The result can be that the nickel alloy fan fails even though a stainless fan of same design performed well. it is more difficult to achieve weld penetration by the arc in nickel alloys than in stainless.Nr. which is how much (in inches) each foot of metal will expand. More root gap may be required to achieve full penetration in a nickel alloy. will expand at the same rate as the piece of solid metal that would just fill that hole. . read down the column to the operating temperature and read the number.4404) may well not allow adequate weld penetration in RA330. incidentally. Multiply this figure by the length of the muffle.16 inches total expansion. 0.

144 0.0103 0.123 0.0131 0.144 0.164 0.181 0.00874 0.0145 0.0681 0. times the difference between room temperature and operating temperature.154 0.0297 0.0134 0. such as those given on the next page. multiply by 83.104 0. Note that these coefficients are all multiplied by 10-6.0797 0.0119 0.201 -0.214 0.108 --0.0345 0.209 -0.0859 0.0876 0. which is the same as dividing by one million.173 0.0317 0.0796 0.0225 -0.0104 0.0137 0.227 0.204 0.167 0.193 -0.0370 0. Multiply the length in inches.0937 0. inches/foot RA 253 MA RA310 RA 353 MA RA330 RA333 RA601 RA600 RA 602 CA 0.180 0.160 0.201 0.174 0. continued Temperature Range °F 70-200 -400 -600 -800 -1000 -1200 -1400 -1600 -1800 -2000 Total Thermal Expansion.245 0.137 0.0727 0.0109 ---0.175 0.0710 0.142 0.0281 0.185 --- SA-387 RA446 RA321 RA309 0.0604 0.0949 0.0854 0.0356 0.152 -- The more general way to calculate thermal expansion is to use the mean coefficients of thermal expansion.83 - .0x10-6 = 240 inch X 1730F X 10x10-6 = 4.0566 0.Thermal Expansion.129 0.204 0.237 -0.0526 0.115 0.0348 0.115 0.0141 0.0471 -0.0870 -----0.208 -0.186 0.0566 0.0496 0.133 0.104 --0.0915 0.0372 0.0591 -0.236 0.0341 0.33 to get millimeters expansion per meter of length . For that 20 ft long RA330 muffle operating 1800°F 982°C) this is: 20 ft X 12 inches/foot X (1800-70F) X 10.117 0.0305 0.0502 0.0806 0.0960 0.102 0.152 inches.148 0.224 -0.0610 0. To convert these numbers to the metric system.120 0.106 0.122 0.0710 0.0129 0.0569 0.147 0.174 0.0516 0. times the expansion coefficient.193 0.111 0.0115 0.

4 10.8 for metric units.9 4.1 9.8 -10.4 8.2 9.27 9. .1 --10.56 10.1 8.5 8.9 5.86 10.5 10.5 9.7 10.67 8.95 8.3 -8.0 8.65 8.9 6.87 8.5 9.0 ---5.8 6.56 8.3 8.4 ------------5.11 7.4 ----- 1400 ---10.97 -9.81 --8.59 -8.7 9.57 9.17 7. Multiply by 1.4 10.5 9.8 7.7 ---5.8 AL-6XN® TiGr 2 NOTE: All coefficients are reported as inch/inch °F x 10-6.4 ----9.0 -7.5 6.1 10.6 ------ 8.1 9.3 8.85 -- 1000 10.5 9.61 --8.4 7.14 -5.6 ---------10.0 6.29 8.MEAN COEFFICIENTS OF THERMAL EXPANSION ALLOY 304 316 2205 RA321 RA309 RA310 SA-387 RA 253 MA 410 RA330 ® ™ ® ® 200 9.34 -8.2 6.85 9.3 -10.42 -- 600 9.5 -----9.9 9.14 6.4 --- 1600 ---11.8 8.82 9.8 -- 900 ---------9.8 -10.4 6.95 7.06 5.4 10.3 7.8 8.6 6.0 9.3 9.9 8.2 7.2 -9.7 7.5 --- 1700 ---------9.96 5.7 8.4 9.6 9.8 9.9 8.4 ------------6.8 300 --7.3 9.1 700 ----9.6 -9.05 -10.5 ----6.51 9.5 8.1 10.66 9.95 8.8 ---8.37 -- 500 --7.1 ----- 1900 --------------------- 2000 -----10.05 -7.46 9.3 ----6.3 5.85 9.5 7.4 8.9 -----------8.56 --8.3 8.3 9.9 ---9.09 ---- 1200 10.5 9.9 9.8 ---8.9 7.2 9.0 ----9.2 6.9 -5.33 9.7 -- 800 ---10.7 9.22 9.9 -10.8 -10.5 8.0 9.2 9.2 10.48 7.2 8.4 -10.7 9.8 9.7 9.6 8.3 8.68 8.7 -10.4 8.80 9.0 -9.6 9.07 9.0 ----5.6 7.44 8.0 8.18 9.3 -8.3 8.7 9.84 - .1 8.2 ----8.9 8.0 -9.0 9.5 9.6 9.72 -9.0 9.09 9.4 1100 ---10.5 9.3 7.6 8.19 9.4 6.7 -------9.37 -5.8 10.15 -10.6 1300 ----------------------6.3 8.8 5.24 9.88 ----- 1800 ---11.7 9.3 --9.52 9.5 -9.88 9.4 9.98 9.6 7.6 ---8.6 5.3 --- 1500 -11.3 -10.7 10.5 ---8.3 -- 400 --7.15 9.01 7.7 -9.8 9.9 9.0 --7.6 6.1 ---8.3 9.7 -8.2 -8.87 10.72 9.6 8.9 8.4 8.2 --------------8.1 9.3 8.9 ---6.04 HR-120 RA 353 MA RA800AT RA446 ® RA600 RA601 RA 602 CA RA333 HH HK HT HP E-BRITE® 825 20Cb-3 ® ® ------- 10. room temp to indicated temp.

the effects of repeated thermal shock can be as important as mechanical loading. as when they were constructed of 5/8” (15.9 mm) dia. RA330.7 mm) diameter bar. Quebec Canada H8R 2N9. Stewart.9 mm) dia. 1981 2. Quebec Canada H8R 2N9. Even though this heavier bar should be mechanically stronger. A dramatic example of the effect bar diameter has on quench cracking is shown below. was used for the basket’s top frame. to permit more uniform heating and cooling. Stewart.85 - .9 mm) diameter.Section Size Thin. 1989 . We have seen baskets used for neutral hardening (which see many. RA330 from same heat treat basket A 1/2” (12. bar has cracks extending in depth to one half its radius. In quenching service. bar. Bear in mind that these alloys combine high thermal expansion coefficients with low thermal conductivity. References 1. 9773 LaSalle Boulevard. About 4X 1/2” (12. The lightest possible section size should be used. The basket vertical members were 5/8” (15. LaSalle. This 5/8” (15. on the right. One of these is shown in cross-section. basket top frame About 4X 5/8” (15. Distortion Control. many quench cycles) last twice as long when made of 1/2” (12. Flame Straightening Technology for Welders.9 mm) dia. rather than thick. sections reduce the thermal gradients inherent in heat resistant alloys used under conditions of rapid thermal cycling. LaSalle. John P. John P. it is clearly weaker in resisting thermal shock. 9773 LaSalle Boulevard.7 mm) dia. which shows essentially no cracking.7 mm) diameter RA330 bar.

1.Nr. However the behavior of alloys during long exposure to the many environments and temperatures that may be encountered cannot be completely documented nor described by laboratory tests. One must develop the judgment needed to determine which of the many factors involved are the most important. limited by oxidation. limited by oxidation.86 - .4833) is useful to about 1850-1900°F (1010-1038°C) above which our customers seem dissatisfied with its oxidation performance. difficult to weld. A few points to consider. and move up to RA309 for 1500°F (816°C) service. or strength. weldable. Subject to “885°F” embritlement after long service above about 600°F (326°C). Typically considered 950°F (510°C). Can be hardened by heat treatment.SELECTING THE ALLOY Technical data illustrating the properties of heat resistant alloys are very helpful guides in selecting an alloy suitable for a given application. 1.Nr. One cannot successfully chose an alloy based on temperature alone. 1.4024) 1200°F (649°C). Nr. Formable. whether because of technical advantage over 321 or difference in philosophy we do not know at this time. above which 304H is stronger. W. If product contamination by scale particles is a consideration. limited by oxidation. and is used to 1600°F (1202°C).4571) is used to 1650°F (899°C). In Europe 316Ti (W. Subject to embrittlement after several years’ service above about 600°F (316°C). & EN 1. Experience obtained from many actual installations is most helpful. as a limiting factor one might rate alloys as follows. 410S low carbon martensitic stainless (UNS S41008. W. consider a 1200°F (649°C) limitation. and EN 1. Subject to embrittlement after several years’ service above about 600°F (316°C). 1 Mo).Nr.Nr. W.4541) stainless has about a 100°F (55°C) advantage over 304.Nr. Nevertheless one simple first guide to alloy selection is knowing the maximum temperature at which a given alloy may have useful long term engineering properties. still we’d suggest keeping it below 2000°F (1093°C) . 409 ferritic stainless (UNS S40900. W. RA800H/AT (UNS N08811) is a little more oxidation resistant. Temperature is often the first—and sometimes the only—data point given when we are asked for suggestions regarding alloy selection. Picking oxidation in air. Werkstoff Nr. in plate form. & EN 1.4301 & S31600. & EN 1. Carbon steel. RA309 (S30908. such as ASTM A 387 Grade 22 (2¼ Cr.4512) 1200°F (650°C). 304/304H & 316 stainless (S30400/S30409. W. 1. 321 (S32100. Thin sheet will have a lower limiting temperature due to proportionally greater losses to oxidation.4000) 1200°F (650°C). 410 martensitic stainless (UNS S41000.4401) 1500°F (816°C).

Sometimes parts will diffusion bond themselves to the fixture at very high temperature. RA601 (N06601. Alloys commonly used as fixturing for vacuum heat treating tool or stainless steel include RA330. RA600 (N06600.4854 ) has a melting point similar to that of RA330. RA310 (S31008.Nr. Field experience at this time is with muffles and calciners. 2.Nr. then deposit on cooler areas of the furnace. reducing. etc. Due to its 9% molybdenum content this grade may be subject to catastrophic oxidation under stagnant conditions. RA 353 MA ® (S35315. W. EN 1. inert gas. RA330® (N08330) combines useful oxidation resistance and fairly high melting point so that it will tolerate more extreme temperature abuse than any other fabricable austenitic grade with which we are familiar. RA600 is used at the same high temperatures as RA330. Nicrobraze ® Orange Stop-Off. W. Oxidation resistance does not drop off rapidly with temperature. Occasionally chromium is a concern. is used for this purpose. 2. with better oxidation resistance in laboratory tests. Based on its chemistry and test results we would expect it to tolerate extreme temperature at least as well as does RA330.4851) has deformed more than RA333 in 2150F (1177C) applications and should have a somewhat lower maximum temperature use.87 - . 1. RA330 muffles are regularly used at 2100-2150°F (1149-1177°C). RA333® (N06333.4608) in open air use is limited more by its incipient melting point than by oxidation.SELECTING THE ALLOY.Nr. 2. though stagnant conditions might not be desirable. or in open air above roughly 2150°F (1177°C). W. W. & EN 1. EN 1.Nr. In one exceptional case an 11 gage (3mm) wall RA330 muffle provided six months service brazing with 65% palladium 35% cobalt filler at 2370°F (1300°C).Nr.4845) is reasonably oxidation resistant to about 2150°F (1177°C). RA X (N06002.4665) is designed for gas turbine combustors where the hot gases continually sweep over the metal surface. Know the atmosphere which the alloy must resist—is it air. continued RA 253 MA ® (UNS S30815. 2. although somewhat more creep deformation may occur in service. W. Temperatures to 2200°F (1204°C) may be considered. although the strength is quite low.4893.4835) has superior oxidation resistance to a fairly definite upper limit of 2000°F (1093°C).Nr. We have no experience with this grade at 2300°F (1260°C). Above this temperature the oxidation resistance may be adequate but no longer exceptional. One cure for this is to paint braze stop-off on the parts or fixture. RA600 and RA601.4816) excellent carburization resistance. from Wall Colmonoy Corp.? Or vacuum? Vacuum—obviously. . as it can evaporate from the alloy fixture. metal loss from oxidation doesn’t exist so rather lean alloys may be used to extreme temperature if mechanical properties suit. W.

The vanadium pentoxide formed is very corrosive at red heat. The atmosphere is nominally nitrogen-hydrogen. although it is definitely not as resistant as the 50%Cr alloy. A classic case is a coil annealing cover for carbon steel. reducing products of coal combustion are another matter. sulphidation from both coal and oil fuels can be a serious matter. The only alloy said to resist V2O5 hot corrosion is the cast 50Cr-48Ni alloy (“50-50”).SELECTING THE ALLOY—atmosphere. For example. particularly in oil from Venezuela. electrolytically refined copper. to be neutral to the AISI 4140 or 1045 steel rod being annealed. This atmosphere is actually carburizing to Ni-Cr-Fe heat resistant alloy. one might c onsider RA333. Generally oxidation and strength are the only issues. With respect to oxidizing products of combustion of coal. A less common situation is sulphidation of alloy fixturing used to anneal copper cathodes.4%C. But because scale from this stainless gets onto the glass. The cathodes have residual copper sulphate from the electrolyte used in this process. a major end use of RA 253 MA is for coal nozzles in powdered coal fired utility boilers. This “inert” atmosphere will also mildly carburize the cover itself. That is. But residual palm oil from cold rolling steel sheet vaporizes and makes the atmosphere carburizing enough to deposit soot inside the cover. glass forming operations take place around 1100-1400°F (600-760°C) where 304 stainless might suit as a structural element. and tends to embrittle RA 253 MA. When steel rod coils are annealed the carbon potential of the atmosphere is controlled to 0. In all other atmospheres there may be some potential for carburization or hot corrosion. Short of that. but concern about product contamination from scale is an occasional issue. which do occur in certain areas of the current generation of low-NOx burners. “Oxidation” usually refers to metal wastage. We would not suggest use of any alloy with higher nickel than RA310. This is the source of sulphur. But sometimes the atmosphere as it exists in the furnace is unintentionally different than the pure gas pumped into the furnace. Oxidizing products of combustion from heavy fuel oils may be corrosive due mostly to small amounts of vanadium in the oil. While oxidizing products of combustion of coal can readily be handled by alloys such as RA 253 MA. If the atmosphere really is hydrogen. to minimize sulphidation attack. In reducing atmospheres. UNS R20501.88 - . used for annealing cathodes in a reducing or neutral atmosphere. in particular. or higher nickel grades if one prefers. which would be quite neutral. continued Air—those alloys useful in just plain hot air are also suited for oxidizing products of combustion of natural gas and even coal. argon or nitrogen then no reaction with the alloy should occur. which will attack nickel alloy furnace fans. usually RA309 or RA330. . limit nickel content of the alloy to about 20%. RA330 is used for its much higher oxidation resistance.

at 3 1/2% silicon. RA601 may be useful.89 - . In high chlorine. Under oxidizing conditions chromium. atmospheres high nickel alloys are preferred. Wrought alloys commonly used to resist carburization include RA330. . for practical use in such applications.SELECTING THE ALLOY—atmosphere. When some amount of oxygen is also present. Resistance to embrittlement from carbon absorbtion is largely conferred by the total chromium. RA600 is the usual choice. RA800H/AT is too coarse grained. Of the lower nickel grades only RA85H. or fluorine. has useful carburization resistance in heat treat furnaces. molybdenum and tungsten form highly volatile oxychlorides. RA600 and RA601. with only moderate halogen levels. continued Intentionally carburizing atmospheres are commonly used in heat treatment of steel parts. nickel and silicon content of the heat resistant alloy. RA X has good carburization resistance and is occasionally used. RA333. and too low in silicon.

Good shearing practice cuts about 20% of the metal and fractures the remaining 80%. Plates 1/4” (6. The ferritic grade RA446 does not form well at room temperature.7 mm) alloy plate. both 18-8 stainless and the nickel heat resisting grades will tear or rupture in forming. Our stock materials have all been scientifically annealed. Heating without adequate temperature control is dangerous because of the narrow working range and the possibility of over or under heating. that had been formed into a 4” (100 mm) tube might have had its hardness raised from the original Rockwell B 84 up to RB 96.90 - . and it is well to know the product you are working with to get the most out of it. but before rupturing. range. then cooling quickly with an air blast. A piece of 3/16” (4. It could be returned to RB 84 by heating to 1950°F (1065°C) and holding at this temperature for five minutes.35 mm) heat resisting alloy. will handle 1/2” (12. and their tensile strengths a lot higher. and it were required to be soft to permit further cold work. the mass. while others may be formed successfully. and elongation of 35% and a reduction of area of 60%. and the mill certifications of the material delivered to you are kept on file for ten years at Rolled Alloys. There are some rules to know.5 mm) mild steel. but for the most part designing and fabricating alloys is using common sense based on the properties of the alloys and what you expect them to accomplish. After work hardening. Extremely severe forming may require annealing between operations. but because of good ductility. the yield strengths of heat resisting alloys in the annealed condition are a little higher.8 mm) plate.35 mm) and thicker should be preheated 250-400°F (120-205°C) for any bending or forming. The hydraulic shear. Heavier thickness plate is best cut by abrasive wheels. or red heat. elongation. the material can be restored to its original mechanical properties by annealing. These alloys always harden on deformation and cannot be worked beyond a limit without rupture. which produce a smooth. and reduction of area. It will take more power to form these alloys than it takes to form mild steel. A typical plate might have a Rockwell B hardness of 84. we regularly shear 1/4” (6. than mild steel. In the 1200 to 1600°F (650-870°C). for example. Failure to preheat may result in some plates cracking apart. Every lot of RA material is checked for these properties. rated 3/4” (19 mm) mild steel.CUTTING AND FORMING Mild steel and heat resisting alloys do handle differently. close tolerance surface. has to be about 50% greater. Shearing In the first place. On our shear rated 3/8” (9. Records on your order are kept by RA for six years. Bending and Forming Austenitic heat resisting alloys should almost always be bent cold. There probably would be little reason for annealing this shape. Shear capacity. The process varies with the alloy. for example. . the alloys will take a lot of deformation without rupture. A given size will have limits on hardness. and the hardness. unless it was to be formed again.

Removing the shear burr permitted a 90° bend with some cracks. The ferritic RA446 is less ductile and requires preheating before bending. The first sign of overstretching is an orange peel appearance. the plate cracked after only a 40° bend. by a slight margin RA 353 MA. Occasionally tooling for aerospace requires to be stress relieved after rough machining. likewise they are slightly tougher to work. If severe forming is anticipated. and RA 253 MA are the strongest metals of the group in most temperature ranges. A generous radius is better for keeping the metal solid in service as well as during forming. nearly flat on itself. RA600 is somewhat softer and weaker. The fabricator must perform bends with small radii and his own risk and be prepared to weld cracks that may develop. The work hardened surface of a sheared or punched edge limits the amount of forming possible befo re cracking. For extreme bends or the harder alloys it is better to bend across the grain. but they are not guaranteed to do so. A thermal expansion of some 3/16” per lineal foot (16 mm per meter) is going to occur between room temperature and the average service temperature. the work hardened metal must be removed from the edge to be formed. so it should be pointed in the right direction. material from the same plate was bent 180°. rather than having the grain parallel to the bending axis. After RA333. may be accomplished by heating for one hour per inch (25 mm) of thickness to 1800°F (982°C).Bending and Forming. but the fracture soon to follow with further forming is incurable except by welding. With an as-sheared edge. can be hardened only by cold working. .91 - . continued These solid solution strengthened materials. Its high nickel makes it “gummier” than alloys with more iron.7 mm) RA333 plate. RA 602 CA. It is far better to avoid a design that makes use of minimum radii. the shear burr or drag should be ground off. then air cooling. and furnace cooling until black. therefore. The resulting stresses are great. The photo on page 80 shows the effect of edge condition on formability of 1/2” (12. This in itself is seldom detrimental. which. and softened by annealing. RA309 and RA310 are a little weaker. The austenitic alloys will take a bend of 180° with a minimum inside radius equal to twice the thickness of the material. in the case of RA330. They will sometimes accept a bend flat on themselves. With a ground or bandsawn edge. with no cracking. As a minimum precaution. minimizing the thermal stresses created by heating and cooling. and the metal is going to move. because it gives the structure freedom to expand and contract.

Bent 180° flat on itself.92 - .Sheared edge ground. Right. no cracks.As-sheared. Cracked at 40° bend angle.Shear burr removed. Bend 90° before cracking. burr up.7 mm) plate. Middle .7 Scale RA333 1/2 inch (12. . Left .About 0. formed with different edge preparations.

roughly comparable to 305 stainless. and annealing.93 - . RA330 spins rather well. . Dies for drawing the heat resistant alloys ought not be proofed with 304. as results will be different.SPINNING AND DEEP DRAWING Spinning and deep drawing can be accomplished by taking into consideration the physical properties. None of the heat resistant alloys will deep draw as well as 304 stainless. work hardening. Illustrated below is an 11 gage RA85H spun half for a radiant tube return bend.

Lubricants or cutting fluids for titanium should be carefully selected. Speed Surface ft/min ® Material AISI B1112 ® René 41 25 (l-605) RA188 N-155 WASPALOY RA718 RA625 RA X ® RA333 A-286 RA601 RA800AT Ti 6Al-4V Sol’n annealed Aged ® RA330 TM Speed Surface ft/min 165 12 15 15 20 20 20-40 20 20 20-25 30 25-35 25-35 30-40 15-45 30-45 Speed as a % of B1112 100 7 9 9 12 12 12-24 12 12 12-15 18 15-21 15-21 18-30 9-27 18-27 Material RA 353 MA ® RA 253 MA RA2205 ® 20Cb-3 ® AL-6XN RA309 RA310 304 RA321 RA446 17-4PH Sol’n treated Aged H1025 303 Speed as a % of B1112 25-35 28-35 30-40 40 40 42 42 45 45 45 45 36 60 40-60 45-60 50-65 65 65 70 70 75 75 75 75 60 100 RA333 is a Registered Trademark of Rolled Alloys RA330 is a Registered Trademark of Rolled Alloys 253MA and 353MA are Registered Trademarks of Outokumpu 20Cb-3 is a Registered Trademark of Carpenter Technology . Both workplace and tool should be held rigidly. Slender work pieces of titanium tend to deflect under tool pressures causing chatter. speeding up tool wear and failure. tool overhand should be minimized.MACHINING The alloys described here work harden rapidly during machining and require more power to cut than do the plain carbon steels. Rigidity is particularly important when machining titanium. This information is provided as a guide to relative machineability. Don’t trade dollars in machine time for pennies in tool cost. Feed rate should be high enough to ensure that the tool cutting edge is getting under the previous cut thus avoiding work-hardened zones. Do not use fluids containing chlorine or other halogens (fluorine. to significantly increase tool life.94 - . Such lubricants may be thinned with paraffin oil for finish cuts at higher speeds. Remember—cutting edges. The following speeds are for single point turning operations using high speed steel tools. with chips that tend to be stringy and tough. Slow speeds are generally required with heavy cuts. The metal is “gummy”. Use an air jet directed on the tool when dry cutting. Change to sharpened tools at regular intervals rather than out of necessity. are expendable. particularly throw-away inserts. tool rubbing and tolerance problems. higher speeds are used with carbide tooling. Titanium chips in particular tend to gall and weld to the tool cutting edges. bromine or iodine). Machine tools should be rigid and used to no more than75% of their rated capacity. Sulfur-chlorinated petroleum oil lubricants are suggested for all alloys but titanium. The tool should not ride on the work piece as this will work harden the material and result in early tool dulling or breakage. Make sure that tools are always sharp. in order to avoid risk of corrosion problems. as titanium has a much lower modulus of esasticity than either steel or nickel alloys.

but the working ranges are narrow. It is too difficult to heat nickel alloys uniformly hot enough throughout the section. too cold may cause cracking. and close control of temperature. Heat resistant alloys must be heated throughout the section thickness. 1/2” (12. all will tear when formed at these temperatures. Whether 304 stainless or nickel alloy 600. never attempt to bend or form any austenitic alloy in the 1100-1600°F (590870°C) temperature range. Forging either too hot or. and finish before the metal cools below 1700°F (930°C). the brown temper color in the crack is typical of about 1200°F (650°C) . We know the materials are forgeable. forging should begin when the metal is around 2100-2200°F (1150-1200°C). heating atmosphere and reduction are all important. time.95 - . more likely. heating locally with a torch to make bending easier just doesn’t work. Unlike carbon steel.FORGING Hot forging should be used only if cold pressing cannot do the job. Never. because they all came from large cast ingots. Although the operator thought it was hot enough. Typically.7 mm) diameter RA330 scale: 1 7/8 X Torch heated to bend. The exact temperature ranges vary from alloy to alloy.

96 - .’s 201 & 207 for RA330. Cover or fill in craters. to prevent them from cracking. flat weld beads tend to crack down the center as they solidify. Do not weave. use RA330-04 or RA330-80-15 weld fillers. E312 weldments are not suited for high temperature service. Do not ever preheat.WELDING Welding heat resistant alloys is covered in general in our Bulletin No. . stringer beads. However. as it will be crack sensitive. At red heat E312 welds are very weak. with Bulletin120 covering RA333 welding products. as well as brittle. 2. E312 electrodes. below 212°F (100°C). 202 for RA 253 MA. 209 for RA 353 MA. For our corrosion resistant alloys see Bulletins 203 for AL-6XN® . except to dry moisture off of the metal. Do not use AWS E330 weld wire. 1071 for RA2205. and in more detail in No. They embrittle severely with exposure above 600°F (1100°C). E309. in particular. and a DIFFERENT approach than stainless. 115. Keep the temperature of the metal between weld passes low. or E310 as they will crack. or carbon steel. Make reinforced. Absolutely do not try to weld RA330 with stainless rods such as E308. are often sold under various tradenames for general shop repair welding and dissimilar metal welds. A few important rules: 1. 3. Shallow fillet welds or broad. and Bulletin 205 for 20Cb-3 stainless. Keep heat input low. Heat resistant alloys are readily welded but they do require more time. For RA330 specifically.

or scale. by contrast must be clean and free of any black scale from hot rolling. we will cover the important differences between stainless (under 20% nickel) and the higher nickel alloys. A few users of heat resistant alloys. Shielding Gases C. One can see this in a steel mill when a large ingot is removed from the soaking pit for forging—the molten scale literally drips off of the white hot steel. CARBON STEEL VERSUS STAINLESS Some important differences between welding the carbon or low alloy structural steels and the austenitic stainless and nickel alloys include A. forging or annealing operations. do prefer “black plate”. Of course. plate with the mill hot rolling scale intact. A. Penetration F. or “scale”. that is. on the metal surface). to reduce these surface iron oxides back to metallic iron. stainless normally comes from the mill with a white or bright finish. 2500°F (1371°C)1. Distortion E. The weld fillers normally contain sufficient deoxidizing agents. Surface Preparation When fabricating carbon steels it is common practice to weld right over scale (a socalled “mill finish” is a layer of blue-black oxide. This scale is thought to provide additional environmental protection at red heat. Incompletely welded areas will open up as cracks during normal heat treat thermal cycles. Then. . than does the steel itself. Iron oxide. Incompletely penetrated weld joints are the most common cause of weld failures in service. The resultant Mn-Si slag floats to the weld surface. in particular. and welding either stainless or nickel alloys.97 - . and first describe some of the differences between welding carbon steels.4. red rust and even paint. Let us back up a bit. though. melts at a lower temperature. such as manganese and silicon. Surface Preparation B. Cold cracking vs Hot Cracking D. must be fully penetrated. Make full penetration weld joints. Stainless steel. Weld joints in fans. Fabrication Time.

ENiCrFe-3. as the coating fluxes away most of the scale.k. One exception to this high CO2 prohibition is when using flux cored wire. Both stainless and high nickel alloys which are designed for corrosion resistance are produced to very low carbon contents. are alloy 182 covered electrode. on both sides of the joint. Some of these cored wires are specifically formulated to run best with 75%Ar 25%CO2. grease and paint. These are suitable with carbon or low alloy steel welding wire but far. Also the very high nickel alloys. with gas shielded processes it is difficult to get the weld bead to even “wet”. either stainless or nickel alloy. Even a small amount of that zinc paint overspray on stainless will cause the stainless to crack badly when welded. Incidentally.01% carbon. E309 electrodes are commonly used but may leave a hard layer on the steel side. ERNiCrFe-5. For this reason it is necessary to clean these alloys thoroughly of all trades of grease and oil before welding. far too oxidizing for use with stainless or nickel alloys. . . Metallic zinc paint is a common way to protect structural steel from corrosion. or commercially pure nickel 200/201. Surface Preparation. the appropriate weld fillers for this particular joint. are sensitive to weld cracking from the sulphur in oil. Consider completing all stainless welding before painting the structural steel in the area. free of all rust. and the stainless weld filler chemistry is not capable of reducing this scale back to metallic chromium. clouds of red smoke are coming off when I weld your 310.98 - . which may crack. With SMAW a weld of sorts can be made. or stick to. A fine gas for carbon steel but not for stainless. less than 0. such as 400 alloy (Monel®. heavy spatter. mill scale. to minimize the hard martensitic layer on the steel side. Any higher carbon will reduce the metal’s corrosion resistance. a scaled piece of stainless. The need to clean or grind down to bright metal is more likely to cause trouble when stainless is being joined to carbon steel. As a result. MIG) carbon steel the shielding gases are usually 95% argon 5% oxygen. Alloy 62 bare wire. continued Stainless steel melts at a lower temperature than does its chromium oxide scale. B.03% and sometimes less than 0. 75% argon 25% CO2 (carbon dioxide) or 100% CO2. It is not unknown to hear the complaint “. ENiCrFe-2 covered electrodes are also used.a. and weld metal A.WELDING. That is because in this dissimilar metal joint it is necessary to grind that carbon steel to bright metal. . . . Shielding Gases For gas metal arc welding (a.” and then learn that the shielding gas used was 75%Ar 25%CO2. . ERNiCr-3. UNS N04400). or alloy 82 bare wire. .

about 1%. the weld bead tears rather than stretching. When 75% argon 25% helium is used for GMAW a true arc transfer cannot be obtained. or stress relief. the less time it spends in the temperature range where it can tear. continued Stainless and nickel alloys are often GMAW spray-arc welded with 100% argon. High nickel alloys are susceptible to cracking in restrained joints. molybdenum. There are shops where this is preferred. To prevent such cracking the steel is usually preheated before welding. Austenitic stainless and nickel alloys do NOT harden no matter how fast they cool from welding. This helps burn away the stable chromium oxide film which does impair weldability of stainless and chromium-nickel alloys. . to retard the cooling rate of the weld and avoid martensite formation. That is. or heavy sections. and may damage the corrosion resistance of some grades. etc. Stress relief 1100-1200°F (600-650°C) as applied to carbon steel is ineffective with stainless or nickel alloys. nor to post weld heat treat it. Weldability is greatly improved by adding from 10 to 20% helium. The faster a nickel alloy weld freezes solid. For this reason preheating. it is not necessary to preheat stainless. Cold Cracking versus Hot Cracking Carbon steel weldments may harden. the arc transfer somewhat resembles the globular transfer mode. as it permits more opportunity for hot tearing to occur. Helium provides a hotter arc. will stabilize the arc (prevent arc wander). As a matter of fact preheating stainless. as the bead contracts upon solidifying. This hot tearing/hot cracking has nothing to do with hardness. Rather. but a 90%He 7 1/2%Ar 2 1/2%CO2 “tri-mix” is commonly used. are more likely when the steel contains over 0. Shielding gases. is also applied to some steels. Hydrogen pickup from moisture in the air causes underbead cracking in steels that harden as they cool from welding.25% carbon. which slows down the cooling rate. can make steels of lower carbon content also harden. and crack. A very small amount of CO2. can be positively harmful. C. and the resulting cracking. such as manganese. as they cool from welding. High hardness. beyond what may be necessary to dry it. chromium. is actually harmful. Shortcircuiting arc welding generally requires the 75%Ar 25%He mix. more rarely by aluminum. not a cold crack. possibly by zinc or copper. or for certain applications. Postweld heat treatment.B. This is a hot tearing.99 - . Stainless steel welds generally do not crack unless contaminated. Alloying elements which increase hardenability. So.

The combination of these two factors means that stainless or nickel alloy fabrications distort significantly more than similar designs in carbon steel. hence minimize distortion. tack welds need to be more closely spaced in stainless/nickel alloy welds. Back step welding is also helpful. Among other things.D. Tack welds should be sequenced. . 1 6 4 7 3 8 5 9 2 If the tacks are simply done in order from one end. rather than spread out. only about one fourth that of A 36 structural steel. 1 2 3 4 5 Back step welding helps reduce distortion. Welds should be sequenced about the neutral axis of the fabrication to balance welding stresses.100 - . Distortion2. the plate edges close up and the gap disappears. This means the welding heat tends to remain concentrated.3 Stainless steel has poor thermal conductivity. Stainless also expands with heat about half again as much as does carbon steel.

D. Distortion, continued

3

2

1

E. Penetration The arc will not penetrate a stainless nearly as deeply as it will carbon steel. Penetration is even less in high nickel alloys. Increasing welding current will not solve the problem! Stainless, and especially nickel alloy, joints must be more open, single or double beveled, with a root gap, so that the weld metal may be placed in the joint. Lack of weld penetration is the single most important reason why austenitic alloy weldments fail in high temperature service.

F. Fabrication Time Cleanliness, distortion control measures, maintaining low interpass temperatures and even machining add up to more time spent fabricating stainless than carbon steel. A shop experienced with stainless may require one and a half times as long to complete the same fabrication in stainless, as in carbon steel. A good carbon steel shop encountering stainless or nickel alloys for the first time can easily spend twice as long, maybe even three times as long, to do the stainless fabrication, as it would the same job in carbon steel.

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WELDING AUSTENITIC ALLOYS The fundamental problem to be overcome in welding austenitic nickel bearing alloys is the tendency of the weld to hot tear upon solidification. This matter is readily handled in alloys of up to about 15% or so nickel. In these stainless grades the weld metal composition is adjusted, usually by slightly higher chromium and reduced nickel, to form a small amount of ferrite upon solidification. The amount of ferrite in the weld may be measured magnetically, and is reported as a Ferrite Number, FN. This ferrite acts to nullify the effects of the elements responsible for hot cracking in the Ni-Cr-Fe austenitics. These elements are chiefly phosphorus, sulphur, silicon and boron. In higher nickel grades, about 20% nickel and over, it is metallurgically not possible to form any measurable amount of ferrite. Therefor other means of minimizing hot cracking must be used. Foremost among these is to use high purity raw materials in the manufacture of weld fillers. Simply beginning with low phosphorus alloying elements, and reducing the amounts of harmful sulfur and silicon in the weld metal improves its ability to make a sound weld. Phosphorus, in particular, must be kept below 0.015% in the weld wire itself. Certain alloy additions such as manganese, columbium (niobium), molybdenum and carbon serve in one way or another to reduce the austenitic propensity for weld hot cracking. Manganese ranges from about 2% in AWS E310-15 covered electrodes to 5% in RA330-04 wire & electrodes and 8% in alloy 182 (ENiCrFe-3) covered electrodes. Columbium at the 0.5% level, as in 347 stainless, is harmful whereas 2 to 4% columbium is quite beneficial in many nickel base weld fillers. Molybdenum isn’t necessarily a common addition specifically for weldability but it does enhance the properties of RA333-70-16 covered electrodes. High molybdenum is responsible for the popularity of the various “C type” electrodes (15Cr 15Mo balance Ni) in repair welding. 2% Mo contributes to 316 as being the most weldable of the stainless steels. Carbon is slightly elevated in 310 weld fillers, to about 1/10%. The one welding electrode specifically using very high carbon to promote sound welds is the heat resistant grade RA330-80-15 (UNS W88338). Maintaining a weld deposit chemistry of some 0.85% carbon permits this electrode to make sound welds in either wrought or cast 35% Ni high silicon heat resistant alloys. The distinction between the lower nickel stainless grades, which depend upon ferrite to ensure weldability, and the high nickel alloys, which require high purity weld fillers, is an important one to remember. Most ferrite containing (stainless) weld fillers are useless with nickel alloy base metal, as dilution of the weld bead with nickel from the base metal eliminates this ferrite. Likewise a high purity nickel alloy weld filler, such as ER320LR, may be not quite so crack resistant when contaminated by phosphorus from 316L, cast alloy 20 (CN-7M), or carbon steel base metal. With respect to welding there are some distinctions between those alloys intended for use above 1000°F (540°C), and those meant for aqueous corrosion service. One

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Welding austenitic alloys, continued difference is in carbon content. Corrosion resistant grades are generally limited to 0.03% carbon maximum, and typically much lower. They may also have small additions of columbium or titanium. Restriction of carbon, or tying it up with a stabilizing element (Cb or Ti) is necessary to prevent heat affected zone (HAZ) intergranular corrosion and stress corrosion cracking (SCC) due to carbide precipitation. Heat resistant alloys by contrast typically require 0.04 - 0.010% carbon for good hot strength. RA 602 CA is even higher, at the 0.2% level, while RA330HC belt pin stock and the cast heat resistant alloys have a nominal 0.4% carbon. In the absence of a wet corrosive environment a little intergranular carbide precipitation is not particularly harmful to a heat resistant alloy. In both classes of material, incompletely penetrated welds and open crevices must be avoided in fabrication design. Serious aqueous corrosion can begin in crevices. In high temperature carburizing service crevices are where carbon (soot) can deposit, grow, and pry the joint apart like tree roots in rock. For both classes of alloy, weldability alone is not the entire issue. The weld filler must also have the mechanical and environmental resistance required for its intended service. Usually this point is addressed in fabricating corrosion resistant alloys. It is sometimes overlooked in heat resistant alloy fabrication and even less often considered in repair of high temperature alloy fixturing. ALLOYS UNDER 20% NICKEL Most austenitic grades containing less than 20% nickel are joined with weld fillers that utilize perhaps 4-12 FN (Ferrite Number) to ensure weldability. Heat resistant alloys with 20% or less nickel include 304H, 321, RA 253 MA, RA309, RA85H, RA310, and the cast heat resistant alloys HH and HK. All save RA310 and the cast alloys depend upon some level of ferrite in the weld bead to prevent solidification defects. The cast grades are usually welded with high carbon, fully austenitic electrodes of similar or higher nickel. RA310 stands in an odd position between the stainless and the nickel alloys, having neither ferrite nor any particular alloy addition for weldability. Not surprisingly, 310 welds have a reputation for fissuring. In the past it was possible for 310S (UNS N031008) base metal to contain as much as 1.50% silicon in the ASTM/ASME specifications. Heats on the high side of silicon and phosphorus were definitely a problem to weld (Rolled Alloys traditionally limited silicon in RA310 to 0.75% max). With the advent of 310H (UNS S31009) ASTM limited silicon to 0.75% maximum. To avoid melting two chemistries of 310, in practice all 310 varieties now melted in North America have less than 0.75% Si. Phosphorus in the weld wire may still be an issue with some lots of ER310 welding wire. The current AWS limit for ER310 wire is 0.03%P max. This is far too high. For 310 welding wire to be of practical use the phosphorus must be kept under 0.015%P max. - 103 -

Other nickel weld fillers contain manganese. with no ferrite at all. 556. Constant Potential (voltage) machines are used for GMAW (MIG) welding. silicon and boron. In addition resistance welding. They don’t work well with covered electrodes (SMAW). The cobalt alloys N155. in North America. L605. and HR-160 may be treated in similar fashion with appropriate weld fillers. using spooled bare wire filler. The dial regulates voltage. RA800H/AT. 617. and Constant Potential. sulphur. Techniques include reinforced. RA 602 CA. and is marked with numbers in the 20-40 range. RA330. the stainless weld bead may crack. etc. The most common. particularly cross wire resistance welding. Two other methods are Plasma Arc Welding (PAW) and Submerged Arc Welding (SAW). A constant current machine is used for GTAW (TIG) and SMAW (stick) welding. columbium or molybdenum to improve resistance to fissuring and hot cracking. and Nimonic 75. or just plain “stick” welding. RA333. is Gas Metal Arc Welding (GMAW). RA 353 MA. Stainless steel weld metal (308. Without ferrite. Cleanliness includes NOT using oxygen additions to the GMAW shielding gases for nickel alloys. It is worth repeating here that high nickel alloys can not reliably be welded using stainless steel weld fillers. The least volume of work is done by Gas Tungsten Arc Welding (GTAW). formerly called TIG (Tungsten Inert Gas) and originally trade named Heliarc. the additional nickel melted into the weld bead makes it fully austenitic. The dial on a Constant Current machine reads in amperes. Many nickel alloys are joined with matching composition weld fillers. 803. Haynes alloys HR-120. Practically speaking it won’t work for GMAW (MIG) welding. 600. 601. high carbon. 188. But when a stainless rod is deposited on a high nickel base metal.) depends upon a small amount of deposited ferrite to ensure a sound weld. 230 and 214. Welding technique and attention to cleanliness. alloy X (UNS N06002). 309. formerly known as MIG (Metal Inert Gas). Such chemistry modifications are rarely as effective as is the use of ferrite in the lower nickel stainless weld fillers. There are two basic types of welding machines. Next in popularity is Shielded Metal Arc Welding (SMAW). .104 - . modified only by restrictions on phosphorus. WELDING PROCESSES Five different arc welding processes are generally used with heat resisting alloys. is often used in heat resistant alloy fabrication. Constant Current. Titanium may be added for deoxidation. become increasingly important to ensure the soundness of fully austenitic welds. with covered electrodes. but are not limited to. convex stringer beads and low interpass temperature. then.ALLOYS OVER 20% NICKEL Heat resistant alloys in this category include. and the current is regulated by this dial.

characterized by a noisy arc and low heat input. their BlueShield TM 20 is a nominal 81% argon 18% helium and 1% carbon dioxide. the molten weld metal transfers as large. respectively. A mix of 75%Ar 25%He is also used. but rather a hot globular transfer with a great deal of spatter. Molten weld filler transfers as either a spray of fine drops. Wire is fed continuously through a hollow cable to the welding gun. through the weld torch and around the wire.035” (0. The result can be a tangle of wire known. The arc between weld wire and workpiece melts the metal. direct current reverse polarity). where it makes electrical contact. Oxygen above 2% starts burning out major alloying elements. Choice of shielding gas is important. The GMAW process is fast and well suited to high volume work. or as larger globs. there may be feeding problems.045” (1. This is known as short-arc. Although very small amounts of CO2 may be used in argon. do not use oxygen additions to the gas when welding nickel alloys and NEVER use 75% argon 25% carbon dioxide for GMAW welding either stainless or nickel alloys. ranging from 10 to 15 foot (3 to 4 1/2m) long. usually argon. as is the commonly available 90%He 7 1/2% Ar 2 1/2% CO2 .89 mm) and 0. For spray-arc welding the most common gas is 100% argon. In this mode. For shortcircuiting arc transfer 75% Ar 25% He is used. though 0. individual drops. although the transfer mode will then not quite be a true spray-arc.Gas Metal Arc Welding In this process.105 - . at above 15% CO2 in argon the arc transfer mode is no longer spray. This shuts down the operation until the welder clears it. One such gas from Air Liquide.14 mm). as a “bird’s nest”. CO2 above 5% adds carbon to the low carbon stainless grades.045” (1. welding. or short-circuiting arc. At lower current. Welding with relatively high current. as for welding long tubes. the weld filler metal is bare wire. The care with which the filler metal is wound on the spool affects how smoothly the wire feeds. more often than not proper attention to machine set up will ensure freedom from “bird’s nests”. and argon shielding is used for the spray-arc transfer mode.89 mm) wire. While the manufacturer is often blamed for feeding problems.14 mm) wire. about 190-220 amperes for 0. typically on 2530 pound (11-14 kg) spools. It can be automated. First. molten weld metal crosses the arc to the work as a fine spray. Because the welding wire must be pushed through a cable. To improve bead contour and reduce arc wander. The metal is protected from oxidation by a continuous flow of inert shielding gas.035” (0. . roughly 100 amperes for 0. The most common size is 0. Current is always Electrode Positive (DCRP.59 mm) are also stocked. appropriately. 10 to 20% helium and a very small amount of CO2 may be added to the argon. with 75% argon 25% helium shielding.0625” (1.

2.3m) in diameter. with flux and metal alloy powders inside. and will give more room for the wire to flex. instead of a 0. A rule of thumb is to hold the wire between the fingers as it enters the feed rolls. AvestaPolarit Welding Products. Rise above the flat surface no more than 1 in.9 for stainless. for example. Does this problem occur on more than one machine? How long is the cable—the longer the cable. For 0. occurs the first thing we suggest is to examine machine set-up. will do the following: 1. and therefor require more care to feed smoothly. (380mm) in diameter and not more than 50 in. Inc.14mm) wire. (1. or bird’s nest. Flux Cored Arc Welding FCAW is similar to GMAW except that the wire used is tubular. Many heat resistant alloy weld wires are much higher in strength than stainless wire (e. then give it another half turn beyond that. . U groove for copper or aluminum and serrated rolls for flux cored wire. and the wire may swell into the tip and jam it. When spray-arc welding the tip runs hot. gas shielding may be 75% Argon 25% CO2. Adjust the pressure until you just can not hold the wire. When tangling. and can handle more heat. (25mm) at any location. The oversize conduit won’t hurt.7mm) helix. Use minimal pressure on the feed rolls—more is not better. and the arc is “softer”.14mm conduit. The heavy duty tip simply has more copper. A heavy duty contact tip is preferred instead of a standard contact tip. ER308 or ER316L).045”/1. V groove rolls are used with solid stainless/nickel alloy wire. use a 1/16 inch (1. inlet guide and outlet guide all clean? Incidentally. the more tension in the feed rolls. typically has 36 to 42 inch (915 to 1070mm) cast and 1/2 inch (12. gas metal arc. Are the feed rolls.6mm) conduit.106 – .045 inch (1. As a result there is greater overall productivity with flux cored wire. continued Smooth feeding depends on the cast and helix of the spooled wire. Because this wire contains its own flux. Our RA 253 MA wire. and A5. and should be left in its sealed plastic bag until ready to use. Flux cored wire is sensitive to moisture pick-up.g.14 for nickel alloy wire require cast and helix of wire on 12 inch (300mm) spools to be4 “such that a specimen long enough to produce a single loop. If you can hold it back. The following discussion is based on information from Ron Stahura. when cut from the spool and laid unrestrained on a flat surface. Both AWS A5.WELDING. there is not enough pressure. even with nickel alloys! The advantage of flux cored wire is that welding is easier than when solid wire is used. Form a circle not less than 15 in..

such as manganese. The core wire is usually. a 35%Ni 15%Cr AWS E330 core wire is used. so that the weld bead chemistry will not be the same as the chemistry of the core wire itself. Often. and controls the bead shape Adds more alloying elements. In the case of RA330-80-15 or -16. carbon or chromium Promotes electrical conductivity across the arc and helps to stabilize the arc. 4.107 - . The additional carbon. RA333-70-16 electrodes do use RA333 core wire. 2. continued Shielded Metal Arc Welding Covered welding electrodes consist of an alloy core wire and a flux coating. however. but not always. and RA330-04-15 covered electrodes. Provides a gas that shields the metal crossing the arc from oxidation Produces a molten slag which further protects the molten weld bead from oxidation. various alloy additions are made in the coating itself. During welding. 3. about the same composition as the base metal. important when alternating current (AC) is used .Flux Cored Arc Welding. these additions melt in and adjust the chemistry of the weld bead to the specified composition. manganese and chromium required in the weld deposit are added to the flux coating. affects out-of-position weldability. The electrode coating does four basic jobs: 1.

This means that these electrodes can ONLY be used with direct current. most recently. DC. In a carburizing atmosphere small traces of slag will cause local carburization to proceed rapidly. . the electrode simply won’t run. as well as on direct current. After welding. RA330-04-15 and RA330-80-15 both have DC (Direct Current) lime coatings. but every couple of years someone complains that RA330-04-15 “won’t run”. The AC/DC titania coated electrodes are designated -16. Weld repair with RA333-70-16 covered electrodes is best accomplished using direct current. Under oxidizing conditions this simply results in excessive loss of metal to oxidation. That is. In fact. Coating type is designated by a “-15”. or Electrode Positive). AC/DC electrodes may also be used with direct current. Otherwise the slag destroys the protective chromium oxide scale on the metal. That is.Shielded Metal Arc Welding. In any reducing atmosphere the fluoride flux will scavenge enough sulphur from the atmosphere5. The slag from the electrode coating is extremely corrosive at elevated temperatures. a “-17” after the alloy number. He will not be able to keep the arc going. all traces of this slag must be removed. electrons are emitted from the work and go toward the electrode. They have compounds of potassium and titanium in the coating which stabilize the arc. If the welder attempts to use a DC electrode with an AC (alternating current) setting on the welding machine. a “-16”. These electrodes may be used with alternating current (AC). even a very low-sulphur atmosphere. not unless that AC current is turned up so high that the whole electrode glows red and the coating spalls off. RA333-70-16 and RA330-8016 both have AC/DC coatings. which also operates on alternating current. it will indeed run on DC current.108 - . The newer coating designation is -17. they run better when using DC. prior to using the fabrication at elevated temperature. to cause sulphidation attack of the base metal. DC lime-type coatings are designated -15. but not on AC. This means it will not extinguish itself as the current reverses direction (and goes to zero) 60 times a second on normal 60 cycle current (50 cycle in Europe). This is very basic knowledge. Well. reverse polarity (DCRP). the electrode is positive and the workpiece is the negative electrical pole of the circuit. or. Normally the current is reverse polarity (DCRP. At this writing (2001) RA 253 MA-17 are the only electrodes we stock with this coating. continued There are three types of coatings used on Rolled Alloys electrodes.

it is necessary to add 2 to 2 ½% nitrogen to the argon shielding. Shielding gas must be pure argon or helium. a name still used occasionally. tungsten metal with 1 or 2% thorium oxide added to improve the emissivity of electrons. The work is electrically positive and the tungsten electrode is the negative electrical pole. that is. which protects both the hot tungsten electrode and the molte n weld puddle. just like GMAW wire. Welders sometimes knock the coating off an electrode and use the core wire as GTAW filler. . GTAW is often used to make the root pass in pipes or whenever the joint can only be made from one side. In automatic GTAW the wire is fed into the joint from a spool of wire. For some corrosion alloys. The argon shielding gas. Argon is used for manual welding. A helium addition may be used for automated welding. The arc between the tungsten electrode and the work is what melts the workpiece. where a hotter arc is preferred. and this process makes the best quality weld. The weld filler metal is fed by hand into the molten puddle.Gas Tungsten Arc Welding In GTAW. This may cause some erosion of the tungsten electrode but improves weld bead properties in these particular alloys. the arc is struck between the workpiece and a tungsten electrode. Remember--the core wire of RA330-04-15 covered electrodes is AWS ER330. up to 4% nitrogen is added. Rare earth oxides are also used. such as AL-6XN® or RA2205. This is to resist hot cracking. and was originally patented as Heliarc ®. The rest of the weld may be built up with either GMAW or SMAW. which remains unmelted. used with AC (alternating current). but it is relatively slow. In the case of RA 602 CA. in 10 pound (4 1/2 kg) tubes. GTAW weld wire for heat & corrosion resistant alloys is sold as 36” (914 mm) straight lengths of bare wire. direct current straight polarity. without the benefit of the alloying elements which were in the coating. No oxygen or carbon dioxide can be tolerated or the tungsten electrode would literally burn up. For aluminum welding the electrode is pure tungsten. This process used to be called TIG (Tungsten Inert Gas). The welder has the most control when using gas tungsten arc. For faster welding speed helium is added to the argon shielding gas. For both stainless and nickel alloys the current used is DCSP. is brought in through a nozzle or gas cup which is around the electrode. The electrode is usually thoriated tungsten.109 - . This AWS ER330 will make a crack-sensitive weld. Do not do this with RA330-04-15 or the RA330-80 electrodes. It may be automated for volume production. and not RA330-04 chemistry. both of which are faster.

and has been used to weld RA330 without added filler (with GTAW this would be extremely difficult).5mm). PAW is an excellent welding process for heat resisting alloys. It is this turbulence which causes air to get mixed in with the argon shielding gas. 8 cup (9.7mm) cup.5-12. Look at work to tip distance.4mm) electrode should use anywhere from a No. When using a 2—4% nitrogen addition for welding the corrosion alloys. . shielding gas flow rates.110 - . The longer the arc length.2mm) electrode requires a No. No. Gas cup size depends upon what diameter tungsten electrode is being used.Gas Tungsten Arc Welding. A 3/32” (2. no more than 1/4 to 3/8 inch (6-9. It generates intense heat in a very narrow zone. the shielding gas will be just that much more sensitive to atmospheric contamination. Gas Metal Arc (MIG) Gas Tungsten Arc (TIG) Plasma Arc Welding The plasma arc torch is roughly analogous to a GTAW torch. 6 to No.7mm cup dia). the greater the opportunity to entrain air into the shielding gas. Consider using a gas lens. is a potential cause of porosity. cup size and consider the use of a gas lens. continued Atmospheric contamination. a wire screen which serves to reduce turbulence of the shielding gas flow. 7 (11mm) being about right. 8 (12. Minimize the arc length. as from strong winds or too long an arc length. An 1/8 inch (3.

Wire. much like GMAW. For this reason 1/8” (3.4 mm) are generally preferred. Heat resistance alloys may have twice the yield strength of stainless and considerably higher electrical resistivity. While it is possible to use 0. and markedly from those used for carbon steel. Electrode force.14 mm) dia. a hopper feeds granulated flux into the arc to shield the arc and molten weld puddle. larger sizes such as 1/16 or 3/32” (1. Instead of shielding gas. suc h as Avesta Flux 805 or Böhler-Thyssen’s RECORD NiCrW. and electrode tip contours may all need to be modified accordingly. SAW is a process naturally inclined to high heat input. Resistance Welding6 Spot and seam welding parameters for heat resistant alloys will differ from those used with stainlesses such as 304L or 316L. For nickel alloys such as RA330 a strongly basic flux must be used.045” (1. Heat input must be as low as possible.6 or 2. but this heat must be kept to a minimum to avoid centerbead cracking in fully austenitic alloys.Submerged Arc Welding Submerged arc uses a spool of weld wire.111 – . welding current and time.2 mm) wire is not suggested for submerged arc welding the nickel heat resistant alloys. Absolutely do not use acid fluxes or any flux meant for stainless steel. .

Sandviken. 1968. Sandvik AB. Castro & J. Florida. G. Editor-in-Chief. Pease.J. 1900 Arch Street. to avoid porosity and cracking. Likewise cool time should be sufficient that welded areas are not remelted.S. Cambridge University Press. Ohio. ISBN 0 521 20431 3. de Cadenet. ISBN 0-87171-543-0. ANSI/AWS A5. by Dunod. American Welding Society.34 E. 1977 Specification for Nickel and Nickel-Alloy Bare Welding Electrodes and Rods. Sweden 1989 Berthold Lundqvist. S-74401 Avesta. 6. Philadelphia. 4 Edition. Average dome radius may be 3 inch (76 mm) for material up to 11 gage (3mm). Pennsylvania 19103 U.A. in French. 3. 5. as: Métallurgie du soudage des aciers inoxydables et esistant à chaud. Binary Alloy Phase Diagrams. Paris. -112 - . 1989 th 2. Inf.14/A5.6 to 3mm) a 5 to 8 inch (127 to 203mm) radius dome is sometimes preferred. The metal must be clean and free of all grease. Thaddeus B. ISBN 0-87170-262American Society for Metals. In seam welding heat time should be adjusted to ensure that the wheel maintains pressure until the weld nugget has solidified. 1975. SANDVIK Welding Handbook . or a sound weld cannot be made.S.A. Sandvik publication 0. J.Resistance Welding. September. Miami. Resistance Welder Manufacturers’ Association. 4. Avesta Welding AB. continued A restricted-dome electrode is suggested for spot welding. First published. U. 1986 Avesta handbook for the welding of stainless steel.14M-97. 1956 Resistance Welding Manual. For a larger nugget size in material 16 to 11 gage (1.. R. The best general reference we know for welding this class of materials is: R. References 1. Volume 1. Welding Journal Research Supplement. Metals Park. 8901. Welding Metallurgy of Stainless and Heat-resisting Steels. U. Sweden June. Corrosion of Nickel-Chromium-Iron Alloys by Welding Slags. Massalski.S.A. ISBN 0-09624382-0-0.

. RA330-04-15 General: Do choose the weld filler for its performance under the expected service conditions. The X weld bead may be subject to catastrophic oxidation at the higher service temperatures where RA333 is commonly used.113 - . RA333-70-16 RA800H/AT RA309 RA310 RA446 RA333 556 ER309 ER310 ER309 ER310 RA333-70-16 -E309-16 E310-15 E309-16 E310-15 ERNiCrCoMo-1 RA330-04. HU RA330-80-15 DC lime is the preferred 35% nickel rod for cast heat resistant alloys. HT. RA330. and the welds will crack. *Where sulphidation is an issue. RA601. It is better not to use alloy X (ERNiCrMo-2. RA333. EniCrFe-2 RA330-04* RA330-04* E312-16 HK.g. RA600. do not use high nickel fillers such as RA330-04 . ENiCrMo-2) weld fillers on RA333 base metal. EL-NiCr25FeAlY) RA601 RA333 601 82 RA 353 MA RA 253 MA RA333-70-16 6225 Al 182 RA 353 MA RA 253 MA-17 RA600 RA 353 MA ® RA 253 MA ® RA330-04 -RA333. use cover pass of S 6025) -- RA333 RA 602 CATM S 6025 6225 Al (SG-. as well as for weldability issues. RA800H/AT). Alternates RA333-70-16. Dilution by nickel will eliminate ferrite. RA82 RA333-70-16 ERNiCrWMo-1 ERNiCrCoMo-1 (lacks oxidation resistance. Do not use—any stainless weld filler on nickel alloys (e. RA 353 MA.Suggested Weld Fillers Base Metal bare wire RA330® RA330-04 -RA333 Preferred covered electrodes RA330-04-15 RA330-80-15 RA333-70-16 Alternates RA333® .

blue-black hot rolling scale and paint must be removed before welding with any stainless or nickel alloy weld wires. .316) RA330-04 RA 253 MA RA 602 CA 617A RA333B 617A RA333B 617A Cast Alloys HK. Weld Filler Guidelines Considerations in selecting a filler metal for a dissimilar metal weld joint include the expected service conditions at the joint. and freedom from weld metal hot cracking. HP RA330-80-15 RA330-04 RA333-70-16 RA330 182 RA800H/AT RA333 RA333 182 RA333 RA333 RA330-04 RA333 RA333 RA330-04 RA 353 MA 182 RA 353 MA RA 353 MA RA 353 MA RA 602 CA 82 182 82 182 617 RA333* RA 353 MA RA330-80-15 617 S 6025 6225 Al 617 RA333B 82 182 S 6025 6225 Al 82C 182C 82C 182C 82C 182C RA 253 MA E309-16 RA 253 MA RA 253 MA RA333 RA600 82 182 82 182 82 182 82 182 RA333 RA333-70-16 RA333 RA333-70-16 E309-16 RA 253 MA RA 253 MA -E309-16 ER309 RA333-70-16 RA333-70-16 RA330-80-15 RA333-70-16 RA330-80-15 RA330-80-15 RA601 RA309 E309-16 E309-16 182 ER309 E309-16 E309-16 182 E310-15 E309-16 E309-16 E310-15 E310-15 RA310 RA330-80-15 RA333-70-16 RA333-70-16 -- RA446 Note: The carbon steel joint must be ground to bright metal.Dissimilar Metal Joints. A “mill finish” is not acceptable. B The weldability of RA333 weld filler used on RA 602 CA has not yet been determined.114 - . C These high nickel fillers are not suggested for sulfur bearing environments. HT. relative thermal expansion coefficients of the three metals involved. Base Metals Carbon Stainless Steel (304. All rust. A 617 (ERNiCrCoMo-1) lacks the oxidation resistance of RA 602 CA. The final selection should be approved by the end user and weld procedures qualified by the fabricator. These alloys lack the deoxidation characteristics of carbon steel weld wires.

.115 - .

such as 600. consider stress relief annealing the assembly prior to brazing. Aluminum Brazing From the standpoint of the heat resistant alloy supplier.116 - . The acid chloride flux is corrosive and should be washed off after soldering. Stressed austenitic alloy. The age hardening aerospace grades. BRAZING One of the issues in brazing Ni-Cr or Ni-Cr-Fe alloys is the furnace atmosphere. Silver Brazing Often used to join carbon and low alloy steels. Residual stresses are responsible for cracking during furnace brazing. Somewhat better strength may be obtained by using a tin base solder. If too much flux is applied to the aluminum work pieces. from liquid metal embrittlement. But the nickel alloy is unlikely to last long enough to be worth the higher cost. Technically speaking. To furnace silver braze an austenitic alloy. are commonly joined with nickel-silicon-boron braze fillers. Anything that will flux aluminum oxide will quickly eat holes through stainless. the incoming hydrogen atmosphere should have a dew point1 –80°F (—60°C) or lower. that flux may spill onto the muffle. in the presence of molten silver braze alloy will crack.BRAZING and SOLDERING Heat resistant alloys are normally assembled by welding. These may be alloyed with about 2% of either silver or antimony. has somewhat better resistance to the fluoride flux. Temperatures are low enough that aluminum braze muffles are commonly made of 304 or 316L stainless. Austenitic alloys are prone to crack when silver brazed. whether stainless or high nickel. a high nickel alloy. To be effective with stainless. SOLDERING Copper cooling coils may be lead-tin soldered to heat resistant alloys. by contrast. . This atmosphere must prevent formation of any oxide film which would prevent the braze alloy from flowing. In torch brazing the source of stress is the thermal stress caused by the local heating (which is normal practice when brazing steel). as the braze temperature is not high enough to reduce these stresses. Keep the flux off of the alloy fixturing. Brazing is used on occasion to attach cooling coils or thermocouples. the major issue in aluminum brazing is the flux.

it will not crack. preventing braze flow. Vacuum brazing requires fillers containing neither cadmium nor zinc. Silver braze cracking is not an issue with ferritic stainless steel. in some alloys with up to 3. One approach that has been described to us is to play the torch back and forth about 6 inches (150mm) on each side of the area to be brazed. given time enough. continued The lower melting silver braze alloys may require the use of flux when atmosphere brazing stainless.001 inch (0.Silver Brazing.5% boron. Boron can react with nitrogen. in the alloy as well as the atmosphere. It is not usually chosen to join either heat or corrosion resistant alloys.117 - . The metal should be heated uniformly in the area to be brazed. If there is no stress on the stainless. which would vaporize. Such treatment might include about 0. These temperatures will quickly anneal out residual stresses from the stainless or nickel alloy parts. will penetrate austenitic alloys intergranularly it is unlikely to either crack or seriously attack the metal during the brazing cycle. Pure copper itself melts at 1981°F (1083°C). Nickel Brazing Nickel-base braze alloys are used to join age-hardening nickel base alloys for aerospace applications. This minimizes thermal stress where the molten silver braze will contact the austenitic alloy. Even though copper. Addition of as much as 10% silicon. One indication of nitrogen as the brazing problem is an iridescent bluish-gray color to the base metal. During the braze operation boron from the filler diffuses into the base metal. This may be coupled with rapid heating and short process time to prevent diffusion of nitrogen through the nickel plate. The process temperature for copper brazing is usually 2050°F (1120°C). Successful torch silver brazing of austenitic stainless depends upon technique. Alloys containing more than about 0.03% nitrogen2 can be difficult to braze. With AMS 4777 the brazing range is 1850—2150°F (1010—1180°C). Dry hydrogen may not be sufficiently reducing to chromium oxide at brazing temperatures below 1800°F (980°C). . raising the remelt temperature of the braze alloy. without special treatment.025mm) of nickel electroplate. Copper Brazing Copper brazing is a common means of joining carbon steel assemblies. greatly lowers the melting point. It is the austenitic structure that is sensitive to intergranular cracking by molten braze alloy.

001 to 0. ASM International. of Wall Colmonoy. The braze temperature should not exceed the solution annealing temperature for the alloy in question.Nickel Brazing.118 - . Welding. 2002. Effects on Furnace Equipment Excess silver or copper braze alloys dripping onto the nickel alloy muffle or fixturing will attack that alloy intergranularly. Electroless nickel contains phosphorus.038mm). . Reference 1. 0. by R. Brazing Q&A.A. that prevent braze flow. enough so to depress the melting point to 1610°F (877°C)3 .025 to 0. Peaslee invented the nickel base brazing alloys about 50 years ago. 1993 2. L. even in the best of atmospheres. American Welding Society. September 2001 Welding Journal 3. in ASM Handbook Volume 6. oxides of Al and Ti will form. Nickel base braze alloys simply lower the alloy melting point. Peaslee. Likewise spilled flux is corrosive to the fixturing. in-depth discussion of brazing problems. Otherwise. Brazing of Stainless Steels.. in Welding Journal. Robert L. Brazing Q&A is authored by Dr. An oxide coating on the alloy helps minimize this effect. but of course will not be present in vacuum brazing. continued Alloys containing aluminum and titanium require first to be electroplated with nickel. Dr. Brazing and Soldering.001” (0. This is far and above the best source for thorough.0015” (0.S. This column began in 1989 a nd continues as of this writing. Maimi. January 1991 Welding Journal . Further Information Detailed insight into all manner of brazing issues is available from the Monthly Column “Brazing Q&A”. Hydrogen brazing requires a slightly thicker plate. enough spilled braze can melt a hole through the muffle. The plating does need to be an electroplate and not electroless nickel. For vacuum brazing 0. Brazing Q&A. Florida U.025mm) is sufficient. Peaslee.

450 to 900°F (230 to 480°C). For example. A286. . an age hardening nickel base alloy. RA330 threaded rod. If some of that copper gets carried into an area where the metal is operating above 1981°F (1083°C) it will melt and embrittle or eat holes through any austenitic alloy it touches. A good discussion of fasteners in the chemical process industry has been presented by Robert Smallwood1. NEVER use anti-seize compounds containing copper anywhere near high temperature equipment. that expansion will add to the tensile load in the bolt and may stretch it. A286 and 718. At high temperatures relaxation is the primary limitation to the use of threaded fasteners to maintain a clamping load. one of the grades in ASTM A 193. More of this high temperature bolting experience has been with WASPALOY. even without melting the zinc. Zinc. If the metal to be clamped expands faster than the bolt. or galvanized coatings embrittle austenitics and can also embrittle steel bolts at moderately elevated temperatures. René 41 or WASPALOY. low alloy steel. NEVER. In addition to selecting a strong bolt material it is important to look at the relative expansion coefficients of the alloy to be clamped. nuts and washers are used to assemble high temperature equipment where loose joints are desired to accommodate thermal expansion & contraction during thermal cycling. to about 1400-1500°F (760-816°C) the choices narrow down to René 41® or WASPALOYTM.119 - . a less expensive age hardening stainless. What appear to us as fairly liberal alloy selection suggestions are offered by the Industrial Fasteners Institute as2: Below 450°F (230°C). and the alloy from which the bolt is made. and is not nearly as available in various bar sizes. is sometimes suggested but it does not have as high a temperature capability as does RA718. Above 1200°F up to 1600°F (650 to 870°C). Some cautions. The most common alloy choice for applications up to 1150 or 1200°F (620-640°C) is RA718.APPLICATIONS Bolts Bolts are commonly used at elevated temperature to withstand a shear load. From 900 to 1200°F (480 to 650°C). Above this temperature. so that the assembly is loose once it comes back down to room temperature.

usually with cast HT links. based on high published creep-rupture strength. alloys X and HR-120® pins are also used. At one time Incoloy® 802 was used. Inadequate anneal Belt pins for this service have largely been RA330HC for several decades. that is. due to a wider range of grain size as produced. crankshafted pin.120 - . deforms until it looks like an automobile engine’s crankshaft3. RA333 combines greater strength with better carburization resistance and gives the longest belt life with minimum downtime. With a pin-bearing link the belt pin is heavily loaded in shear. Alloy 120 pins occasionally break after long service at around 1600-1700°F (870-930°C) or so. and interlocking. The best belts use RA333 pins with cast Supertherm® links. If the pin is not strong enough it “crankshafts”. Two RA333SA (top) and one 802 pin (bottom) from the same belt. X grade may not be as consistent.. Ultimately 802 lost out to RA330HC for this market. 1550-1750°F (843954°C) service . Where strength but not carburization resistance is needed.Cast Link Belts The two basic types of cast link belts are pin-bearing.

Using RA333 or RA333SA pins. the links outlast the pin. both RA330 round bar and RA330 hexagonal bar are used to pin interlocking link belts. The links are usually cast HT (35Ni 17Cr 0.121 - . One belt supplier gave us the following examples: Pin RA330HC RA333SA RA333SA Link HT HT Supertherm Typical Life 18-22 month ~30 month 57 mo & running Using RA333SA pins can give a 50% increase in belt life with about 25% increase in belt cost.000 hour rupture strength. although still a relatively strong alloy. 4” (100mm) pitch pin bearing link.34) 802 1750B (12. . RA330 hex bar is used successfully with certain interlocking link designs. On two occasions Rolled Alloys had samples of production 802 tested at Joliet Metallurgical. which is measured in tension.07) A Grade Typical pin lifeA months 30 20 3 max similar to RA330HC in a pin-bearing link . Interlocking links are designed to take up all the shear loading on the casting itself. As pin stresses are low. alloy HT or better. but Supertherm (35Ni 25Cr 15Co 5W) links are also on trial. The optimum.41 N/mm2).24) RA330HC 690 (4.76) RA330 630 (4. 10.5C). The results were not consistent with the published data. state-of-the-art belt uses a 3” (75mm) wide. With HT links and RA330HC pins. Pin life does not necessarily relate directly to conventional rupture strength. 1800°F (982°C). continued Typical belt work loads on the above belt were 25-60 pounds/foot2 (0. B This is the published data. RA333 or RA333SA.17-0. This may be because the pin is loaded in shear. psi (N/mm2 ) RA333 1050 (7. the HT link becomes the weak point.Cast Link Belts. pinned with 3/4” (19 mm) dia.

those parts must be rinsed in water and then dried before running through the furnace. Good furnace design is one reason the 54 inch (1372mm) wide belt example above . Otherwise sodium chromate will form at high temperatures. We understand that another indication is. the alloy components. once the black scale has been scraped away. Hearth rolls must be level and parallel (perpendicular to the belt travel direction). Presence of sodium contamination is indicated by a bright greenish-yellow showing. For maximum belt life the furnace must be designed to minimize stress on the belt. This causes a reaction which will oxidize. the presence of black “cobwebs” hanging off the radiant tubes. and hearth rolls sized to move at the same surface speed as the belt..Cast link belts. Battle Creek. Inc. coupled with brickwork which is white. and not black as might be expected . Contamination by sodium or potassium salts from parts washing operations can cause formation of bulky oxide which shortens the life of a belt by reducing freedom of movement between pin and link.122 - . The following paragraphs are based largely on discussions with Omega Castings. rather than skid tiles. continued interlocking links from a belt misalignment failure For more than 20 years the majority of belt pin failures which we have been called on to examine have been caused by belt misalignment. which fatigues the pin. Michigan. borate or phosphate. When parts are washed in ionized detergents containing sodium. and continue to oxidize. in a carburizing furnace. until the volume of oxide simply freezes up the belt. Suggestions include the use of return rolls. or occasionally by carbon and/or salt deposits which freeze the belt solid. or in sodium hydroxide.

.35 mm) thick. RA330 “D” muffle for copper brazing. Muffles Alloy Selection RA333 . having carried some 180 million pounds (81. RA 353 MA .123 - . Some 3/16” (4. bottom lined with 430 stainless for protection against copper spills. used in the same service. Used for applications from copper brazing to powdered iron sintering. For an iron sintering application 2100-2150°F (1150-1180°C) one shop has gotten 3 year minimum life from RA 353 MA.a first choice for copper brazing muffles. also copper brazing and for brazing stainless 2050-2100°F (1120-1150°C). fabricated in the same shop. RA330 . less than a year with the previous alloy. RA333 is strong eno ugh to be used in 11 gage (3 mm) wall. same design.powder metal sintering muffles. RA330 muffles are most commonly 3/16 to 1/4” (4. Experience to date has been that muffles of 1/4” RA 353 MA plate outlast those of 601.Cast link belts. continued with RA333SA pins & Supertherm links has run 57 months at this writing.650 metric tons) of work.8 mm) RA333 is used. for maximum heat transfer.8 to 6.the most widespread choice for muffles up into the 2100°F (1150°C) and over range.

To minimize leaks in weld seams consider welding with RA 602 CA wire. brass and steel. endothermic atmosphere. Typical life 45 years. RA601 . RA 253 MA . . RA600—competitive with RA330 for very high temperature iron sintering in strongly reducing or carburizing atmospheres. NEVER for a carburizing atmosphere. bright annealing copper. May also suit for the bottoms of brazing muffles. Today we would suggest RA 253 MA here for greater strength. continued RA 602 CA .used for hydrogen and/or nitrogen atmospheres. Can be used for carbon fiber production when sulfur may be a problem.strong. This is an old muffle design. neutral hardening or sintering bronze powder.8 mm) RA309 plate. Muffle of 3/16” (4. Large muffles used for iron powder production are of RA 253 MA. rather than the commonly used 82. oxidation resistant. RA600 is not suited for sulfur bearing environments. Offers greater strength. not suitable for carburizing environments.124 - . under 1800°F (982°C).For longer life in powder metal sintering muffles operating over 2150°F (1180°C). being somewhat more tolerant of spilled copper than are the higher nickel heat resistant alloys. RA309—bright annealing. Gas fired 1200-1600°F (650-870°C).Muffles. perhaps in 11gage for better heat transfer. oxidation and carburization resistance than does 601.

such as Refrasil® silica based insulation. are preferred. The balance of the weld bead may then be made with another process. For electrically heated muffles. Replace the thermocouple at least quarterly. carburizing. The reason for this is lack of full penetration welds in this joint. or with RA330-04 bare wire. RA 253 MA radiant tubes are used in steel mill annealing applications. Type S. platinum. A rule of thumb is to pull on the muffle with about half of its own weight. Ribbon or rod elements may sag and create a hot spot. or separating the SiC plate from the muffle with refractory cloth. regardless of alloy selection one very common failure mode is at the weld of return bend to straight leg. Silicon carbide hearth plates can form a eutectic with high nickel alloys such as 600 and 601. but it absolutely must be free to expand in the other direction.125 - . A type K thermocouple can drift 25°F (15°C) in 4-6 weeks. One furnace maker who uses cast HT tubes commonly welds the return bends with either RA330-80-15 covered electrodes. Common preventatives include painting the hearth plate with alumina castable thinned like paint. silicon carbide elements top and bottom are the least problem. if convenient. The key is to leave them on—it is cheaper to pay the electricity 7 days/week than to replace a muffle which has been periodically shut down to “save” money. melting a hole right through the muffle.Muffles. an RA 253 MA return bend may be used to maximize life. to aid the lengthening caused by thermal expansion. Some shops weld a couple of U-bolts on the flange of the free end and run a chain over a pulley to some dead weights. . One solution would be to purge the tube with argon or nitrogen and make the root pass with GTAW or GMAW. Silicon and nickel form a low melting eutectic at 1767°F (964°C). continued Miscellaneous—The muffle wi ll be fixed at one end. We suggest you consider RA333 weld fillers with RA601 radiant tubes. Most fabricated radiant tubes are RA330. Where 309 suits for the straight leg. Radiant Tubes 11 gage (3mm) RA333 tubes have lasted up to 8 -10 years in captive shops. Whether wrought or cast.

weaker shell from effects of differential thermal expansion. But alloy choice is outweighed in importance perhaps 50 to 1 by how the pot is maintained. This means they will not only expand less. The flight will operate cooler than the shell in an externally fired retort or calciner.) Ensure that there is no salt whatsoever in the combustion chamber of a gas-fired pot or about the elements of an electrically heated pot. 2. The design and attachment of flites inside is very important. Let us examine the reasons behind some of these points. Regarded as “neutral” salts.) Rectify and desludge neutral chloride salts at least daily. RA 253 MA.Rotary Retorts & Calciners Alloy selection covers the range of available high temperature grades—RA309. sodium and barium chlorides are widely used as heating media that neither oxidize nor decarburize carbon.) Do not put oily work or any foreign matter (no floor sweepings!) into the pot. depending upon maintenance and operating procedures. rather than shutting down completely and letting the salt freeze solid. Mixtures of potassium. 3. RA601. Metallic salt pots used to contain neutral heat treating salts may last anywhere from 2 days to 18 months. This is crucial. but they will be stronger than the shell alloy. all welded joints must be full penetration welds.126 - . engineering alloy and tool steels. RA 353 MA and RA333. Best success has been to weld only in the cooler zones. 4.) In both pots and fixtures. they are actually quite oxidizing to the chromium in the Ni-Cr-Fe alloys used for pots and fixtures. RA 602 CA. it may be mistaken for fatigue or rupture failure. The following points are important for good life in a metallic pot for neutral salt heat treating: 1.) Idle the pot with salt still molten. For these reasons the flights must be free to move or they will indeed crack the hotter. 5. Neutral Salt Pots1 The most common industrial use of molten salts is to heat treat steel. RA330. Alloy selection does matter somewhat. . When such cracking occurs. Only after these five points have been addressed should alloy selection be reviewed.

and the hot air or products of combustion provide more than enough oxygen to scale right through the pot. This is somewhat more likely to occur in coarse grained regions. And that is why it is most important to clean out all the spilled salt from the previous pot. and/or barium chromates.Salt Pots. and diffusion voids. the scale is dissolved. The destructive part is that as fast as the alloy forms a protective chromium oxide scale. and permeates the entire thickness of the salt pot wall. forming potassium.127 - . Oxygen is present because the surface of the bath is open to the air. sodium. Eventually the molten salt physically penetrates the grain boundaries. . and because air is always brought into the bath with the workpieces. If a new pot is put into a furnace contaminated with leaked salt from the previous pot. the chloride salts themselves are indeed neutral. Eventual failure in or near a weld does not necessarily mean that weld was defective. that salt will volatilize when heated. the alkali chlorides strip or flux that scale. As fast as chromium from the alloy diffuses to the surface to re-form the oxide scale. but the inevitable oxygen content of the bath is quite destructive. such as the fusion line of the weld or in the weld bead itself. or pores develop in the grain boundaries2. continued Well. Those alkali chloride fumes will attack the chromium oxide scale on the outside of the pot. The chromium diffuses along grain boundaries orders of magnitude faster than through the grains themselves. This occasionally happens in as little as three days. when installing a new one. until the pot begins to leak through to the outside. It is the combination of alkali chloride salts and oxygen that attacks the pot.

that salt must be rectified. In normal operation. oxygen builds up in the salt itself. and the RA330-04-15 weld bead. This may be done by introducing methyl chloride (well away from electrodes and metallic pot sidewalls). 99-66. the oxygen content of the bath must be reduced to low levels. In this case the solution was to replace this blanket insulation each time a new pot is installed. top. ferrosilicon or dicyandiamide are also used. To prevent the steel workpieces from decarburizing. shows corrosion attack and corrosion assisted cracking in the fusion line between RA330 plate. . from Rolled Alloys Investigation No. which converts the alkali oxides back to chlorides. The failure occurred simply because the firebox refractory still contained the spilled salt from the previous salt failure.This photomicrograph. silica.128 - . That is. In this salt pot the attack along weld fusion lines was so bad that entire lengths of the weld bead could be removed with a few blows of a hammer. Operating temperature was about 1700-1750°F (930950°C) using a non-cyanide carburizing salt. Solid rectifiers such as powdered silicon. bottom.

This sludge must be removed frequently. Leaving the sludge in can overheat the bottom to the point that it fails. The inorganic rectifiers form a metallic sludge in the bottom of the pot. This happens even at oxygen levels which will not harm the steel workpieces. the oxygen content will shorten the life of the pot by corrosion from the inside. causing the bottom of the pot to overheat. while the sidewalls are still in good condition. perhaps twice daily. This sludge must be removed frequently. Leaving the sludge in can overheat the bottom to the point that it fails. usually in or near a weld. even without overheating. 3/8” RA309 salt pot bottom 3/4 scale . Alloy Casting Institute 3 studies of salt baths show that corrosion rates in the sludge itself. usually in or near a weld.Salt Pots. If the pot is not rectified well and frequently. This happens even at oxygen levels which will not harm the steel workpieces. continued The inorganic rectifiers form a metallic sludge in the bottom of the pot. If the pot is not rectified well and frequently. while the sidewalls are still in good condition. are increased by nearly a factor of two. causing the bottom of the pot to overheat. lest it act as an insulator. perhaps twice daily. the oxygen content will shorten the life of the pot by corrosion from the inside.129 - Rolled Alloys Report #01-55 . lest it act as an insulator. even without overheating. are increased by nearly a factor of two. Alloy Casting Institute 3 studies of salt baths show that corrosion rates in the sludge itself.

This increase can be about 3/8 to 1/2 inch per foot (31 to 42 mm/metre) of pot depth. in this case over two inches (50mm) deep in the bottom. If one plans a shut-down. Neutral salt pots here were failing by leaks at the bottom weld in 4 to 6 weeks of operation. some after as little as 2 weeks. the volume expansion may cause it to explode through the remaining frozen layer on top. as the salt melts first on the bottom. When salt freezes it contracts in volume. there are a couple of unpleasant possibilities. One is that. that salt will go through a volume increase when remelted on startup. it expands and cracks open the pot.130 - . 6 days per week. either in a weld or along the knuckle radius of a dished head. This sample came from a Western US heat treat shop. once sufficient salt has melted. it is a good idea to ladle out most of the salt before it freezes. Operation was neutral salt at 1400—1600°F (760—870°C) 24 hours per day. . inner weld bead of the RA309 pot above. Etchant: Oxalic Acid Magnification: 25X Crack near the fusion line. Pot idled 1200°F (650°C) on Sundays. continued The photo above is a classic example of pot failure due to metallic sludge buildup.Salt Pots. If the pot is full of solid salt. If a salt pot is shut down and allowed to freeze solid. Alternately.

full penetration welds are necessary. all metallic salt pots would be RA600 or HW. Either RA600 or RA330 is. With respect to fixtures for automated salt lines. or of cast HK. In some shops RA600 has the advantage over RA330. But in practice the majority of metallic pots today are RA330 or RA309. with a very. The same pot should not be used to hold both tempering salts for one operation. high nickel alloys have no advantage in containing molten tempering salts. It is the case that the various ills that may befall metallic pots obscure any theoretical advantages of higher nickel to the extent that 35% or 13% nickel grades are considered more cost-effective. in others there is no clear difference. . in our opinion. the worse the attack. which are mixtures of sodium nitrate and sodium nitrite. the higher the nickel alloy. In all cases. RA330 and RA600. superior to RA309. Both laboratory studies and observations of fixtures are reasonably consistent in showing that the higher nickel grades usually have better resistance to alkali chloride salts. may corrode intergranularly through the pot wall in a rather short time. is disadvantageous in salt. with RA600 distinctly in the minority. If that were all there were to it. More is not better. Almost all submerged or over-the-top heating electrodes are RA446. The combination of the two salts.Salt Pots. Sulphur from whatever will attack the nickel in the pot. and neutral chloride salts for another. Tempering salts. Salt Pot Alloy Selection Since the 1930’s the most popular alloys have been the wrought alloys RA309. Aluminum foil left over from someone’s lunch. very few being RA330 or RA600. We might be inclined to suggest carbon steel for this moderate temperature application. performance often follows the alloy’s resistance to chloride salts. for example. or the cast grades HT (17Cr 35Ni) and HW (12Cr 60Ni). Almost none are pure nickel.131 - . one being residual. will melt and go right through the bottom of the pot. and all electrodes in ceramic pots RA600 or commercially pure nickel. are another matter. This alloy selection discussion is for pots containing chloride salts. Some people use 304 stainless. One of our fabricator customers related an incident in which short life of RA309 pots was indeed traced to the practice of disposing of floor sweepings in the heat treat pots at night. continued Floor sweepings can do interesting things to salt pots. The higher chromium content of RA310. in which some steel piece will be austenitized.

Resistance of Cast Fe-Nf-Cr Alloys to Corrosion in Molten Neutral Heat Treating Salts. . Vol. LaChance. 1954. A. Seybolt. concluded References 1. Transactions of the ASM Vol. Jackson and M. Neutral Salt Pot Alloy Life: Maintenance is the Key. 1970 3. H. pp 157-183. No. H. 2.U. Oxidation of Ni-20Cr Alloy and Stainless Steels in the Presence of Chlorides. Oxidation of Metals.132 - . Heat Treating. April 1990 2.Salt Pots. James Kelly. 46. 2. J.

000psi (MPa) and then held at a constant strain and temperature may after a time period have a remaining stress of only 30.133 - . Corrosion 91 Paper No. Houston.000psi (MPa).E.S. One intentional example of stress relaxation is the reduction of stress in a fabrication due to a stress relief anneal. Use temperature °F 200 500 750 1000 1200 1500 °C 100 260 400 540 650 816 Alloys music wire. Metal Progress August. to 1400-1500°F (760-816°C) René 41® or WASPALOYTM are the remaining practical choices. 3. Philadelphia Pennsylvania . K-500 17-7PH® condition CH900 (50% cold reduction. Fastener Standards. Analyzing Belt Pin Failures. X-750 WASPALOY. Metals Park. 1717 East Ninth Street. RA718 is a practical choice for applications up to 1150-1200°F (620-650°C).Springs Metals used as springs at elevated temperature are subject to relaxation under load. 1505 East Ohio Building. Above that. 1982 ASTM. References 1. guide to alloy selection would be: Max. AISI 6150 chromium-vanadium steel 302 stainless cold drawn. R. René 41 Elastic modulus decreases with temperature. “A bar loaded to an initial stress of say. plus 900°F (482°C) 1 hour age A286 RA718. Bruce McLeod. Cleveland. This time-dependent stress reduction of 10. 1973. Smallwood. but approximate. about a 1% drop in modulus for every 100°F (56°C) temperature increase. The total strain remains fixed but part of the elastic strain is replaced with inelastic strain4. From the standpoint of availability.A. 6th Edition. 40. NACE. ASTM DS-60. 161. available from: Industrial Fasteners Institute. Texas 2. Compilation of Stress-Relaxation Data for Engineering Alloys. Ohio 4. 410. A more complete. Fastener Problems in the Process Industry. Ohio 44114 U.000psi (MPa) is called stress relaxation. ASM.

. is not in itself evidence that the material was defective. It might be interesting to review a few of the types of failures we have encountered. only to have early failure occur. because the tube did not last long enough. and find a generous deposit of soot on the surface and a mass (and a mess) of material looking like stalactites in a cave. we should say—sometimes it is difficult to get the user to accept the fact. He is absolutely correct. and yet the user insists it was never over 1750°F (955°C). We continually hope to add to our knowledge in this respect and thus produce better materials. so we guarantee no performance. At the fabricator’s request. because both think they could not have influenced the performance of the material. however. but we have benefited from certain common denominators found in a series of such failures. that the equipment was improperly operated. It is obvious that a temperature has been reached. however. when pointed out to him diplomatically. and burns very rapidly under the proper conditions. The user immediately refers it to his fabricator. We do guarantee any material we furnish to meet all applicable specifications. Some of these investigations are fruitless. we are happy to replace it. If the material can be found defective in any way.134 - . This mass is metal that was molten. Sometimes it is difficult to diplomatically point out to the user—or. some of which seem to occur periodically and become almost a routine insofar as explaining their occurrence is concerned. Actually. In an effort to constantly improve our knowledge. The metal supplier is always somewhat on the defensive when a premature failure occurs. because he is referring to the temperature indicated by his thermocouple. Soot or carbon burns at a very high temperature. we try to investigate every premature failure reported to us. perhaps more accurately. The fact that it does not last as long as the user thinks it should. The Melted Radiant Tube About once a year someone from somewhere in the United States returns a radiant tube to his fabricator with a request for credit. we examine the tube. which has melted the alloy. who in turn refers it to us. and well saturated with the soot.FIELD FAILURES Every now and then we have a customer who uses a material in exactly the same equipment and presumably under the same operating conditions in which it had previously performed very successfully. both of them might.

Our primary interest is still solving the problem that exists. which is where the soot is. further lowering the melting temperature of that surface. continued When the furnace door was left open.The Melted Radiant Tube. tightly adhering oxide coating but perhaps have a hole or two. and pit-type carburizing retorts. A customer sintering powdered metals had boxes that were manually pushed through a furnace operating at 2400°F (1316°C). The external surfaces usually show a good. This problem is more common when alloy tubes are used to replace ceramic tubes. the metal had a lower melting point than when it was new. to burn out the soot. -135 - . Vertical radiant tube. with a hydrogen atmosphere. About ½ scale. Similar failures have been encountered on endothermic generator retorts. but it could have. a chain reaction resulted. The extremely high localized temperatures from burning soot also accelerated carburization from the soot. These melt on the inside surface only. The net result was melted metal and there is nothing we can do about making a metal stay together if somebody melts it. melted during carbon b urn-out. The furnace was equipped with silicon carbide skid rails for the boxes to slide on. Having absorbed some carbon while in service. The firing and burn-out procedures acceptable with mullite (ceramic) tend to melt metal. The Hole in the Box A very interesting and unusual failure that we had the pleasure of investigating did not concern our material. The photo below is a typical example of a melted radiant tube.

Because of these problems. as the box had been pushed through. because ordinarily we would think of a hydrogen atmosphere as being inert. The cause of the trouble in this case is very clear-cut. The Culprit Copper A very common field complaint. the original fabricator furnished an alloy containing as much chromium and nickel as feasible. although easily solved. and he knew the answer. we called the local representative of the Carborundum Company and asked if they had had experience with this type of problem. After a few cycles. This problem was very intriguing. Where the alloy box contacted the silicon carbide skid rails. The only solution was to change the skid rails to either a refractory that would not give up silicon & carbon. The rest of the bottom and all four sides were perfect. whose entire surface area was exposed to the same operating conditions. were absorbed from the rails into the alloy to lower its melting temperature below 2400°F (1316°C). users change sources on wire-mesh belts. is that of very quick failure of material used in copper brazing fixtures or trays. which occurs two or three times a year. but explaining it to the customer’s satisfaction is more difficult. change sources on fabrications. change materials. the unexpected happened. each box had two holes in the bottom.The Hole in the Box. How could a box. . Solid compounds do not usually carburize readily. continued Because of the high-temperature application. They had. The subsequent laboratory investigation confirmed our suspicions. although at the extreme temperature of 2400°F (1316°C). and. melt at only one point? Before destroying the box for investigation.136 - . the molten metal had resolidified on solid material. and sometimes even change sources for their materials. sufficient silicon. He agreed to have their representative call on the user and suggest a change in the skid rail composition. and carbon. We could not solve this problem by offering an alternate alloy. or to a heat resisting alloy. which was 600 alloy (76Ni 15Cr). The areas of the box not in contact with the rails did not absorb silicon and carbon and therefore were unaffected. Visual examination of the boxes indicated that the metal in the holes had been melted.

continued Regardless of what the austenitic alloy may be. RA446 is. some strips of RA310 had been used in a fixture and failed within two days. This assumes that an exothermic or endothermic atmosphere is used for brazing. the chances are that it will last a long time and ultimately fail from fatigue. they too would not be affected.137 - . of course. and the copper dripping on them rolls off without contacting the metal underneath. the alloy may remain bright and scale-free. within a matter of days. Hence. By holding the strip between your thumbs and fingers. If the equipment does not fail within the first few days. For in such atmospheres the CO. Note that mild steel liners wo n’t work. One way to do this. the material would accept a 180° bend without fracture. The quickest braze failures we know of tend to be in hydrogen or cracked ammonia. This leads us to the means of prevention. far too weak to use as the muffle itself. really) the heat resisting alloy. where the copper had dropped on the alloy. This is the puzzling part to the user. because at the braze temperature carbon steel is also austenitic. By looking at the fracture through the contaminated area. . completely unprotected against braze alloy attack. is to use a bottom liner of a completely ferritic alloy such as RA446 or 430 stainless. where it had been held in the molten state by surface tension. one could see that the copper had penetrated all the way through the alloy and formed a solid layer on the lower surface. cracked ammonia or other hydrogen-nitrogen atmospheres are used. if molten copper is allowed to contact it. Immediately adjacent to the line of demarcation. was very plainly visible. CO2 and H2O present is sufficient to develop a chromium oxide scale on heat resistant alloys. where the muffle is concerned.The Culprit Copper. Had the new trays been allowed to accumulate the same protective coating. a ferritic stainless is largely resistant to copper attack. While copper will penetrate the grain boundaries of any austenitic alloy. you could snap the metal at this point without difficulty. A brownish band on the top surface of the strip. The best means is to prevent copper from contacting (wetting. the copper will be dissolved into the alloy. and susceptible to intergranular copper penetration. since he will usually point to a tray that has been in service for a couple of years and insist that it and the new ones are receiving the same operating conditions and therefor the metal in the new trays must be bad because they are the only ones failing. When dry hydrogen. of course. In one case that we recall. Copper brazing equipment may fail rapidly. The answer. is that the old trays have accumulated an excellent protection in the form of the oxide coating.

the muffle which was supposed to process only iron failed. regardless of composition.The Culprit Copper. even if not 100%. continued The second preventative is to have a good oxide coating on the alloy before it is exposed to the copper. Only iron parts are to be treated in the muffle that failed. though. RA330 has proved by far the most satisfactory of any of the alloys used. of getting somewhat better life if the nickel alloy muffle is made with a lower nickel alloy bottom. or an endothermic atmosphere. but sinters these bronze parts in a separate furnace. RA330 has a very easy job proving itself equal or superior to the higher nickel alloy. such as RA 253 MA. We have customers using RA309. When we find someone using a high nickel alloy.138 - . So. In most cases. such as 600. Then in 15 months he went through five muffles. at less cost. with no change in the product or process. Perhaps we should emphasize again that any austenitic alloy. Visual examination of a jagged foot-long (300 mm) crack in the muffle side showed that molten bronze had dripped out of it. Bronze melts well below the 2050°F (1120°C) iron processing temperature. for copper brazing fixtures. . since fissures do develop in it from expansion and contraction.. and copper just might drop on one of the fissures and penetrate to the alloy. with either a nitrogenhydrogen. however. Sintering temperatures are 2050°F (1120°C) or higher. This plant also makes powdered bronze bearings. and a very effective one. There is a possibility. repeatedly. The oxide is at least a barrier. will fail from copper contamination. Another common problem is with muffles used to sinter powdered iron parts. On one occasion we had a request for assistance from an end user who normally gets two year life from an RA330 muffle. RA310 and RA330 for copper brazing tooling. The oxide coating is not a foolproof preventative. because of a few bronze parts mixed in.

yet has above-average strength at operating temperatures. RA333 A superior product that also costs more. 3% molybdenum and 3% tungsten adds high-temperature strength to a base of 45% nickel. An upgrade over 601.THUMBNAIL BIOGRAPHIES OF RA ALLOYS To conclude this discussion of heat resisting alloys. thermal fatigue and distortion in quenching applications. Can be cut. Good sulfidation resistance. RA309 Preferred for oxidizing atmospheres under 1900°F (1038°C) where resistance to carburizing or nitriding atmospheres is not necessary. because it does more jobs better and for less money. appropriate silicon to resist absorption of carbon and nitrogen. RA 253 MA High strength. with very good carburization resistance. bent and welded without troubles. Oxidation resistance comparable to 601 and RA333. where the hot corrosion resistance of maximum chromium is required. RA330 The work horse of the furnace industry. Resists hot chlorine gas to 1000°F (538°C) RA601 Stronger and more oxidation resistant than RA600. and potential alternate to alloys 617 or 230. glass molds. let us briefly summarize the chief characteristics of each RA product. etc. Field installations have proven it has excellent resistance to carburization. RA 602 CA The strongest and most oxidation resistant high temperature alloy we offer. very low strength and ductility. excellent oxidation resistance to 2000°F (1093°C). copper launders.. 25% chromium and 1% silicon. . Has the best sulfidation resistance but very. RA310 Good oxidation resistance beyond 2000°F (1093°C) under mildly cyclic conditions. excellent carburization resistance.139 - . coal nozzles. melting point about 100°F (56°C) higher. Good oxidation. such as salt bath electrodes. Has enough chromium for good oxidation resistance. The combination of 3% cobalt. Good resistance to sulfidation. Almost always preferred for carburizing atmospheres. Withstands a lot of thermal shock. thermowells. rotary calciners. soot blowers. RA 353 MA Twice the strength of RA330 in the 1800-2200°F (980-1200°C) temperature range. Use for muffles. RA600 Lower strength but more ductility. generally good hot corrosion resistance. enough nickel for good ductility. RA446 Special applications.

Rockwell C is for heat treated steel. 8. and shall not be liable for any direct. Brinell is usually abbreviated BHN (Brinell Hardness Number) on mill certifications. ASTM 3 to 8 grain size would be 125 to 22 µm. This material is subject to revision without prior notice. Small numbers (ASTM 0. Avesta Sheffield report grain size in micrometers. Rolled Alloys makes no warranty and assumes no legal liability or responsibility for results to be obtained in any particular situation. HRB) is most common for our alloys.140 – .CHEMICAL SYMBOLS Al aluminum Ar argon As arsenic B boron C carbon CO carbon monoxide CO2 carbon dioxide CH4 methane Ca calcium Cb columbium (niobium) Ce cerium Cl chlorine (the gas. this material is not intended as a substitute for competent professional engineering assistance which is a requisite to any specific application. special or consequential damages therefrom. 9) mean finer grain size. µm. indirect. 2. . typical for RA 253 MA. O2) P phosphorus Pb lead S sulfur (sulphur) SO2 sulfur dioxide H2S hydrogen sulfide H2SO4 sulfuric acid Sb antimony Si silicon Sn tin Ta tantalum Ti titanium V vanadium W tungsten Y yttrium Zr zirconiuim Hardness is measured by Rockwell or Brinell machines. Grain size is in ASTM numbers. Disclaimer Clause: The data and information in this printed matter are believed to be reliable. The Rockwell B scale (Rb. N2) NH3 ammonia Nb niobium (columbium) Ni nickel O oxygen (as the gas. 3) mean coarse grains. Larger numbers (7. Cl2) Co cobalt Cr chromium Cu copper F fluorine Fe iron H hydrogen HCl hydrochloric acid He helium H2O water La lanthanum Mn manganese Mo molybdenum N nitrogen (as the gas. ASTM 4-7 is about average for RA330. However.

1986 James Kelly.J. ASTM. Added Life for Brazing Fixtures. U.141 - . Automotive Engineering Congress. A.S. p 157—194. JISI July. Performance of Heat—Resistant Alloys in Emission—Control Systems. Burns. Rundell. Vol. Electric Resistance Element. Steel. Neutral Salt Pot Alloy Life: Maintenance is the Key. Heat Resisting Alloys and Their Use in the Steel Plant. A.D. 1923 F. High-Nickel Alloys for High-Temperature Springs. F. Corrosion 86. Fahrenwald.BIBLIOGRAPHY A. and A. Constitution of Iron-Nickel-Chromium Alloys at 650 to 800C. March & April. Industrial Heating. 740093. p 310—347. SPRINGS Magazine. March 17—21. Vol. Chemical and Metallurgical Engineering. Number 2 H. September and October 1972 A. Fahrenwald. Evaluation of Heat Resistant Alloys in Composite Fixtures. 1979 G. 6. Proc. 1924 J. April 26. Cast Heat-Resistant Alloys for High—Temperature Weldments. Cracking in Type 309 High Temperature Fabrications and How to Combat It. M. and J. p 680—681. Industrial Heating. Iron and Steel Engineer. Rees. 1906 F. Understanding Conditions that Affect Performance of Heat Resisting Alloys. Michigan February 25—March 1. Some Principles Underlying the Successful Use of Metals at High Temperatures. 811. Moeller. Bruce McLeod. NACE Paper Number 377. October 1965. L. August. Marsh. 4. Avery. R. Hagen. April. Corfield. D. Patent No. 1949 Charles Emery and Paul Goetcheus. S. Vol. Corwin. 1969 This is the best discussion of heat resistant alloys ever printed. B. June 27.859 Feb. WRC Bulletin 143. Roy. 1955 Ralph H. Cook. 24. April. 28. Heat Treating . 1990 . Metals for High Temperature. Detroit. 1974 James Kelly. SAE Paper No. 1929 W.P. A.

Stainless Steel World 1999 Conference. March 11—15. Industrial Heating. Quebec James Kelly. High-Temperature Corrosion of Engineering Alloys. Oxidation Resistance of Eight HeatResistant Alloys at 870o. July 1993 J.142 - . Conf. 980o. Zutphen. Metal dusting in the heat treat industry. Oxidation Rates of Some Heat Resistant Alloys. 1990 ASM International Gene Rundell and James McConnell. NACE Paper Number 166. 1992 James Kelly. 1981 LaSalle. and 1150oC. Kelly and J. Nos. Tennessee John P. Heat Treating. 3 / 4. NL 1999 . 1991 James Hamer and James McConnell. Flame Straightening Technology. Wilson. Corrosion 91. Of the 2 nd International Conference on Heat-Resistant Materials 11—14 September. Proc. D. KCI Publishing BV. Lai. Heat –Resistant Materials II.BIBLIOGRAPHY. Influence of Composition and Microstructure on Performance of Wrought Heat Resisting Alloys. continued George Y. Kelly. Oxidation of Metals. 1995. Gatlinburg. Steward. April. 36. Heat Resistant Alloy Corrosion—More Problems than Solutions. Vol. C. Heat Resistant Alloy Performance. 1991 James C. 1095o.

HISTORY Austenitic heat resistant alloys and stainless steels as we know them today were invented by Benno Strauss1 of Friedrich Krupp before World War I. Our 35Ni 19Cr alloy RA330 may trace its roots to Nichrotherm® 4, containing 35% nickel and 13-14% chromium, introduced to Germany in 1910 for high temperature applications 1. U.S. patents for Strauss’ alloys were issued on June 25, 1913. What we now call 310 was developed by Adolf Fry, also at Krupp, in 1926. The electrical resistance wire Nichrome®, nominally 80Ni 20Cr, and the European alloy Nimonic® 75, nominal 76Ni 20Cr, would appear to be developments of A. L. Marsh’s U.S. Patent No. 811,859, Feb. 6, 1906, for a 15-25% Cr, balance nickel electrical resistance alloy. Rolled Alloys’ verbal history says that in the early 1930’s the Misco sales manager, John Johnson, loaded an ingot of the cast alloy HT, at that time 35Ni 15Cr, in the trunk of his Buick. He drove it from Detroit to Lockport, New York, to be rolled to the wrought alloy trademarked Misco Metal. The cost included new springs for the Buick & a couple of replacement mill rolls for Simonds Saw & Steel Co. who did the rolling. We have a folder from The Simonds Saw & Steel Company, dated 1934, which includes data and microstructures for a wrought 15% Cr 35% Ni alloy. The Rolled Products Division of Michigan Steel Casting Company initially developed the market for rolled Misco Metal in the heat treating industry. When Rolled Alloys was founded as an independent company in 1953, this alloy was re-named RA330. In 1958 Rolled Alloys lowered the carbon to 0.08% max and, to maintain the strength, raised chromium to the present 19% Cr. The RA330 silicon range was tightened at that time, to 1.00-1.50%. In that same year work began at Simonds, in conjunction with Rolled Alloys, on the stronger and more carburization resistant grade, RA333. All of the ASTM specifications for RA330 were written by Rolled Alloys technical personnel, and shepherded through the committee meetings. In 1975, after several years of creep-rupture and tensile testing, along with Rolled Alloys’ attendance at numerous committee meetings RA330 was approved by AMSE Case 1654-1 for use to 800°F (427°C). A few years later RA330 was approved for use to 1650°F (899°C).

1. The Sorby Centennial Symposium On The History Of Metallurgy, Volume 27, edited by Cyril Stanley Smith, Cleveland, Ohio October 22-23, 1963

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TRADEMARKS RA330 and RA333 are registered trademarks of Rolled Alloys 153 MA, 253 MA and 353 MA are registered trademarks of Outokumpu AB 602 CA is a trademark of ThyssenKrupp VDM AL-6XN is a registered trademark of ATI Properties, Inc. 20Cb-3 is a registered trademark of Carpenter Technology Corporation Haynes and Hastelloy are registered trademarks of Haynes International Kanthal is a registered trademark of Kanthal AB Nimonic, Inconel, Incoloy, Monel, MA956 and 800HT are registered trademarks of Special Metals, Incorporated Refrasil is a registered trademark of SGL Carbon Group, Business Unit Fibers and Composites René 41 is a registered trademark of Teledyne Industries Incorporated Stellite is a a registered trademark of Deloro Stellite, Incorporated MO-RE, 22H and Supertherm are registered trademarks of Duraloy Technologies, Inc. Thermax and Thermalloy are registered trademarks of ElectroAlloys Corporation WASPALOY is a trademark of United Technologies Corporation 17-4PH and 18SR are registered trademarks of AK Steel Corporation

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COMPARISON – German & European Standards with American Grade UNS No. Werkstoff Nr. DIN Designation
1.4002 1.4006 -1.4000 1.4005 1.4016 -1.4362 1.4462 -1.4410 1.4372 1.4305 1.4307 1.4301 -1.4401 1.4404 1.4571 1.4438 1.4541 --1.4818 -1.4835 1.4833 1.4950 -1.4845 1.4951 ------1.4886 1.4854 ----------

EN Number

ferritic stainless 405 S40500 1.4002 X6CrAl13 410 S41000 1.4006 X12Cr13, X10Cr13 410 S41000 1.4024 X15Cr13 410S S41008 1.4000 X6Cr13 416 S41600 1.4005 X 12 CrS 13 430 S43000 1.4016 X6Cr17 446 S44600 1.4763 X8Cr24 duplex stainless 2304 S32304 --2205 S31803 1.4462 X2CrNiMoN22-5-3 2205 S32205 1.4462 X2CrNiMoN22-5-3 2507 S32750 1.4410 X2CrNiMoN25-7-4 austenitic stainless 201 (stainless) S20100 1.4372 X12CrMnNiN 17-7-5 303 S30300 1.4305 X8CrNiS18-9 304L S30403 1.4307 X2CrNi18-9 304 S30400 1.4301 X 5 CrNi 18 10 (X4CrNi18-10) 304H S30409 1.4301 X 5 CrNi 18 10 (X4CrNi18-10) 316 S31600 1.4401 X 5 CrNiMo 17 12 2 316L S31603 1.4404 X2CrNiMo17-12-2 316Ti S31635 1.4571 X6CrNiMo17-12-2 317L S31703 1.4438 X2CrNiMo18-15-4 321 S32100 1.4541, 1.4878 X6CrNiTi18-10, X12CrNiTi18-9 321H S32109 1.4541, 1.4878 X6CrNiTi18-10, X12CrNiTi18-9 347 S34700 1.4550 X6CrNiNb18-10 heat resistant alloys 153 MA® S30415 1.4891 X 4 CrNiSiN 18 10 --1.4828 X15CrNiSi20-12 RA 253 MA® S30815 1.4893 (EN: X9CrNiSiNCe21-11-2) 309S S30908 1.4833 X12CrNi24-12, X 7 CrNi 23 14 309H S30909 1.4833 X12CrNi24-12, X 7 CrNi 23 14 RA85H® S30615 --310S S31008 1.4845 X8CrNi25-21 310H S31009 1.4845 X8CrNi25-21 310 S31000 1.4845 X12CrNi25-21 314 S31400 1.4841 X15CrNiSi25-20 800 N08800 1.4876 X10NiCrAlTi32-20 800H N08810 1.4876 X10NiCrAlTi32-20 ® TM 800HT /AT N08811 (1.4959 similar) (X8NiCrAlTi32-21, similar) Incoloy® DS - -similar to - -1.4864 - -similar to - -X12NiCrSi36 16 RA330® N08330 -(EN: X10NiCrSi35-19) RA 353 MA® S35315 -(EN: X6NiCrSiNCe35-25) 45 TM N06045 2.4889 NiCr28FeSiCe RA333® N06333 2.4608 NiCr26MoW X N06002 2.4665 NiCr 22 Fe 18 Mo 617 N06617 2.4663 NiCr23Co12Mo 601 N06601 2.4851 NiCr 23 Fe 602CA N06025 2.4633 NiCr25FeAlY 603GT N06603 2.4647 NiCr25FeAlYC 600 N06600 2.4816 NiCr 15 Fe Nimonic ® 75 N06075 2.4951 NiCr 20 Ti
weld filler metals —SG designates bare wire, EL is for covered electrodes

RA333 X FM 602 CA FM 617 FM 718

-ERNiCrMo-2 -ERNiCrCoMo-1 ERNiFeCr-2

2.4608 2.4613 2.4649 2.4627 2.4667

NiCr26MoW SG-NiCr21Fe18Mo SG-NiCr25FeAlY SG-NiCr22Co12Mo SG-NiCr19NbMoTi

-----James Kelly 3 February, 2004

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4375 2. S17400 S66286 N07750 N07718 N07263 N07041 N07001 R30188 R30605 N08904 N08926 N08367 N08028 N08031 R20033 N08020 N08020 N08825 N06030 N06007 N06985 N06625 N06455 N10276 N06022 N06690 N10001 N10665 N10675 N10629 N10624 -N02200 N02201 N04400 N05500 C70600 Werkstoff Nr. When the customer requires DIN certification of stock material.4649 DIN Designation X5CrNiCuNb17-4-4 X5CrNiTi26-15 NiCr15Fe7TiAl NiCr19NbMo NiCo 20 Cr 20 MoTi NiCr19CoMo NiCr 19 Co 14 Mo 4 Ti CoCr22NiW CoCr 20 W 15 Ni X1NiCrMoCu 25 20 5 X 1 NiCrMoCu 25 20 6 -X1NiCrMoCu31-27-4 X1NiCrMoCu32-28-7 X1CrNiMoCuN33-32-1 -NiCr20CuMo NiCr21Mo -NiCr 22 Mo 6 Cu NiCr 22 Mo 7 Cu NiCr22Mo9Nb NiMo 16 Cr 16 Ti NiMo 16 Cr 15 W NiCr21Mo14W NiCr29Fe -NiMo 28 -NiMo29Cr ?? ?? Ni 99.4635 2.4668 2.4831 2.B is a general quality specification which can apply to any alloy. RA330 does now have an EN spec. 2004 .4602 2.4373 2.4683 2.4617 -2.4562 1.4702 2. The producing mill can certify to this specification.4638 2.4619 2.4529 -1.4660 2.2 LC-Ni 99 NiCu30Fe NiCu 30 Al CuNi10Fe1Mn SG-CuNi30Fe SG-NiCu 30 Al SG-NiMo16Cr16W EL-NiMo15Cr15W SG-NiCr21Mo14W EL-NiCr20Mo14W SG-NiCr21Mo9Nb EL-NiCr20Mo9Nb SG-NiCr20Nb EL-NiCr16FeMn SG-NiCr25FeAlY EL-NiCr25FeAlY EN Number 1.4858 -2.4710 2. it can be re-certified by the producing mill. DIN 50049 3. JCKelly June.4654 2.146 - . others are not. designation X10NiCrSi35-19.4066 2. EN number 1.4642 -2.0872 2.1.4539 1.4973 2.4806 2.4650 2.4886 2.4621 2.4591 -2.4819 2.4548 1.4856 2. 1.4964 1. EL is for covered electrodes ERCuNi -ERNiCrMo-4 EniCrMo-4 ERNiCrMo-10 ENiCrMo-10 ERNiCrMo-3 ENiCrMo-3 ERNiCr-3 ENiCrFe -3 ERNiCrFe -12 ENiCrFe -12 UNS chemistries generally overlap the German standards shown but they are NOT identical.4068 2.0837 2. Two exceptions are AL -6XN and 20Cb-3.4600 2.COMPARISON—German & European Standards with American Grade 17-4PH A-286 X-750 718 C-263 René 41 WASPALOYTM cobalt alloys 188 L-605 904L 1925hMo AL-6XN® Sanicro® 28 3127hMo 3033 20Cb-3® 3620Nb 825 G-30 G G-3 625 C-4 C-276 C-22 690 B B-2 B-3 B-4 B-10 FM B-10 200 (nickel) 201 (nickel) 400 K-500 90-10 Cu-Ni 70-30Cu-Ni K-500 C-276 C-276 C-22 C-22 625 112 82 182 602 CA 602CA ® UNS No. Many of the EN (European Harmonized Standards) numbers and designations are the same as DIN. or Rolled Alloys can provide a certificate of conformance.4980 2.4887 2.4886.4669 2.4360 2.4610 2.4618 2.4563 1.4542 ----------------------------------- age hardening alloys corrosion resistant alloys ------------- weld filler metals —SG designates bare wire.4620 2. as they have no direct German equivalents.

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