Copyright © 2008 ASM International®. All rights reserved.

Stainless Steels for Design Engineers (#05231G)



ASM International® Materials Park, Ohio 44073-0002

Copyright © 2008 by ASM International® All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the written permission of the copyright owner. First printing, December 2008 Great care is taken in the compilation and production of this book, but it should be made clear that NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, WITHOUT LIMITATION, WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE, ARE GIVEN IN CONNECTION WITH THIS PUBLICATION. Although this information is believed to be accurate by ASM, ASM cannot guarantee that favorable results will be obtained from the use of this publication alone. This publication is intended for use by persons having technical skill, at their sole discretion and risk. Since the conditions of product or material use are outside of ASM’s control, ASM assumes no liability or obligation in connection with any use of this information. No claim of any kind, whether as to products or information in this publication, and whether or not based on negligence, shall be greater in amount than the purchase price of this product or publication in respect of which damages are claimed. THE REMEDY HEREBY PROVIDED SHALL BE THE EXCLUSIVE AND SOLE REMEDY OF BUYER, AND IN NO EVENT SHALL EITHER PARTY BE LIABLE FOR SPECIAL, INDIRECT OR CONSEQUENTIAL DAMAGES WHETHER OR NOT CAUSED BY OR RESULTING FROM THE NEGLIGENCE OF SUCH PARTY. As with any material, evaluation of the material under end-use conditions prior to specification is essential. Therefore, specific testing under actual conditions is recommended. Nothing contained in this book shall be construed as a grant of any right of manufacture, sale, use, or reproduction, in connection with any method, process, apparatus, product, composition, or system, whether or not covered by letters patent, copyright, or trademark, and nothing contained in this book shall be construed as a defense against any alleged infringement of letters patent, copyright, or trademark, or as a defense against liability for such infringement. Comments, criticisms, and suggestions are invited, and should be forwarded to ASM International. Prepared under the direction of the ASM International Technical Book Committee (2007–2008), Lichun L. Chen, Chair. ASM International staff who worked on this project include Scott Henry, Senior Manager of Product and Service Development; Steven R. Lampman, Technical Editor; Eileen De Guire, Associate Editor; Ann Britton, Editorial Assistant; Bonnie Sanders, Manager of Production; Madrid Tramble, Senior Production Coordinator; Diane Grubbs, Production Coordinator; Patty Conti, Production Coordinator; and Kathryn Muldoon, Production Assistant Library of Congress Control Number: 2008934669 ISBN-13: 978-0-87170-717-8 ISBN-10: 0-87170-717-9 SAN: 204-7586 ASM International® Materials Park, OH 44073-0002 Printed in the United States of America

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v


Chapter 1


Chapter 2 Chapter 3 Chapter 4 Chapter 5

Corrosion Theory............................................................................................11 Corrosion Kinetics..........................................................................................19 Corrosion Types..............................................................................................27 Oxidation.......................................................................................................57

Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10

Austenitic Stainless Steels ..............................................................................69 Duplex Stainless Steels...................................................................................91 Ferritic Stainless Steels .................................................................................109 Martensitic Stainless Steels ..........................................................................123 Precipitation-Hardening Stainless Steels ......................................................137


Chapter 11 Chapter 12 Chapter 13

Casting Alloys...............................................................................................147 Melting, Casting, and Hot Processing...........................................................155 Thermal Processing ......................................................................................161

Chapter 14 Chapter 15 Chapter 16 Chapter 17

Forming........................................................................................................173 Machining ....................................................................................................181 Surface Finishing ..........................................................................................193 Welding........................................................................................................201

Chapter 18 Chapter 19 Chapter 20 Chapter 21 Chapter 22 Chapter 23 Chapter 24

Architecture and Construction.....................................................................213 Automotive and Transportation Applications................................................225 Commercial and Residential Applications ....................................................233 Marine Systems Applications........................................................................243 Petroleum Industry Applications ..................................................................247 Chemical and Process Industry Applications ................................................257 Pulp-and-Paper Industry Applications ..........................................................265

Appendix 1 Appendix 2 Appendix 3

Compositions...............................................................................................269 Physical and Mechanical Properties of Select Alloys....................................279 Introduction to Thermo-Calc and Instructions for Accessing Free Demonstration ....................................................................281

Index .................................................................................................................................285


The rate of growth of stainless steel has outpaced that of other metals and alloys, and by 2010 may surpass aluminum as the second most widely used metal after carbon steel. The 2007 world production of stainless steel was approximately 30,000,000 tons and has nearly doubled in the last ten years. This growth is occurring at the same time that the production of stainless steel continues to become more consolidated. One result of this is a more widespread need to understand stainless steel with fewer resources to provide that information. The concurrent technical evolution in stainless steel and increasing volatility of raw material prices has made it more important for the engineers and designers who use stainless steel to make sound technical judgments about which stainless steels to use and how to use them. This book provides design engineers with an up-to-date source of information at a level useful for both metallurgists and other engineers and technicians. It seeks to bridge the gap between the internet where much current, but raw information is available and scholarly books and journals that provide theory that is difficult to put into practice. The content of the book is selected for utility for the user of stainless steel. The first section gives elementary metallurgy and identification of constituents of stainless, the effects of alloying elements and a significant section on corrosion. A second section is oriented toward processes important to users of stainless steel. The third section is about each family of stainless alloys and includes the most recent additions that have come to the market. The fourth section deals in some depth with the major applications for stainless steel. This last part is presented without the promotional bias which is found in many steel producers’, alloy producers’, and trade associations’ literature. While a number of steel producers have provided assistance to the author, there has been no attempt to unfairly bias information in their favor. To the contrary, those producers responsible for generating factual, useful data for the user community are those who should benefit the most by books such as this. The author is particularly indebted to Allegheny Ludlum and John Grubb, and his many colleagues who assisted him, for technical assistance throughout the writing and to Carnegie Mellon University for their support. The author also wishes to thank Professor Sridhar Seetharaman at Carnegie Mellon University for his help in writing the corrosion chapter and others who helped: Roy Matway of CMU, Vittorio Boneschi of Centro-Inox; Paul Mason of ThermoCalc; Bob Drab of Schmolz Bichenbach; Elisabeth Torsner and Chuck Turack Outukumpu, USA; Scott Balliett of Latrobe Steel; Jim Halliday and Fred Deuschle of Contrarian Metals Resources; Professors Tony DeArdo of Pitt and Gerhard Welsch of CWRU; the staffs of Centro-Inox, Euro-Inox, SSNA, The Nickel Institute; and the editorial staff at ASM International, Scott Henry, Eileen DeGuire, Charlie Moosbrugger and Steve Lampman. I would also like to thank the many members of my forum at who have contributed much collective knowledge and perspective to this book.

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there are more detailed treatments of the alloys made of these phases and their properties. alloy steels. subsequent processing or service conditions may alter the carefully established phase structure. silicon. McGuire. The large amount of the alloying elements makes the deviation from the behavior of pure iron greater. and phosphorus. which can have a certain range of compositions. and aluminum. and nickel in thermodynamically meaningful amounts as well as large concentrations of nickel and/or molybdenum.asminternational. Introduction Most widely used alloy systems. In contrast. and martensite. and aluminum alloys. are relatively dilute solutions of several elements in the parent matrix.Stainless Steels for Design Engineers Michael F. CHAPTER 1 Metallurgy Summary COMPARED TO ALLOY STEELS. carbon. manganese. such as carbon. In subsequent chapters on types of stainless steel. stainless steels contain no less than about 11% chromium alone. Stainless steel is an exceptional alloy system in that it is not a dilute solution. niobium. having phases other than the principal one or two phases for which the alloy was designed is undesirable because of the possibility of undesirable variations in mechanical or corrosion performance. The producer of stainless steel controls the chemical composition and thermomechanical processing. as discussed in this chapter. p 1-10 DOI: 10. It is possible to use thermodynamics to calculate which phases may exist at a given tempera* All compositions are given in weight percent unless stated otherwise. Alloy steels may contain several percent of alloying elements. A given structure. and silicon. the calculations that predict which phases will exist are more difficult. stainless steels are chemically complex. In almost every case. nickel. Therefore. with very few exceptions. chromium. just as a gas or liquid is a phase. The result of the large number of alloying elements in relatively high concentrations is that stainless steel can have many stable phases concurrently. However. Most stainless alloys have manganese. Carbon and alloy steels. Aluminum alloys share the face-centered cubic (fcc) structure of pure aluminum. are principally of the magnetic body-centered cubic (bcc) phase or a slightly distorted version of it. phases coexisting simultaneously. www. The wide variety of alloys that exist is based on: • Combinations of these phases • Altering the composition of these phases • Adding secondary phases for particular purposes Metallurgy. The total amount* of these alloying elements seldom exceeds 5%. The three basic phases of stainless steels are ferrite. Alloy steels typically contain very small amounts of titanium. is what is meant by a phase. such as carbon steels. it is necessary to discuss the phases that can exist in stainless steel and the conditions under which they form so that the enlightened user will know which phases to avoid and how to avoid them. In solid metals. in addition to the impurities sulfur. The same is true for most aluminum alloys. consequently. there can be a number of . so that when the processor or end user receives the product it is usually in the correct condition. focuses on phases normally encountered in stainless steels and their characteristics. austenite.1361/ssde2008p001 Copyright © 2008 ASM International® All rights reserved. oxygen. The large number of alloying elements makes possible a larger range of possible phases or basic crystal structures.

Iron does this. may require atomic rearrangements to occur for equilibrium compositions to be reached on an atomic scale.e. The difference between these two is that the equilibrium state.2 / Stainless Steels for Design Engineers ture for a given composition. but others may have free energies that permit them to exist. They are expensive to derive and validate. If diffusion is too sluggish for these rearrangements to take place. Whether the phases will form depends also on kinetic factors. It is assumed that the characteristic equilibrium phases have been frozen and are then identified by various techniques for structure. the strength of the bond. These electrons are of varying energy states and highly mobile. Many metals have a less-dense bcc structure at high temperature and transform to a denser fcc structure at lower temperatures. if energy is applied by mechanical shear. the main concern with thermodynamics is predicting which phases are present both at equilibrium and in the quite frequent metastable state. Thermodynamics of Stainless Steel Pure metals. so the values for the solid state are extrapolations. The attraction determines such macroscopic properties as melting temperature. They are responsible for the ability of metals to conduct heat and electricity well. . For example. It would “rather” be partly ferritic. it is good to become familiar with the principal phases found in stainless steel. however. The prediction involves calculating the free energy of the various possible phases. composition. The topic alone requires a book. mathematical models that can perform the complex thermodynamic calculations. the austenite can transform without diffusion to the lower freeenergy martensite phase. pedantic point. and the like. Also. Hence. the structure may retain the prior metastable structure indefinitely.. Any “what if” extrapolation to a different alloy composition carries the risk of error. to give an adequate treatment of the thermodynamics required to do this. the common alloy 304 (also called 18-8) is normally used in the fully austenitic condition. and quenched to room temperature. This is because thermodynamic values can be measured accurately only in the liquid state. Consequently. are either liquid or solid depending on temperature. A practical tool has been developed that permits phase diagrams to be calculated for arbitrary compositions. equilibrated at the appropriate temperature. with the possibility of some trivial small gas vapor pressure. The solid has a crystallographic structure that may vary with temperature. however. Thermo-Calc. solid) phases equals the number of elemental constituents plus one. The attraction. To do this with accuracy requires databases of thermodynamic values. and elastic modulus. they are proprietary. All thermodynamic properties are based on interatomic attractions. The program allows determination of which phases can exist for any composition and temperature. However. most published phase diagrams are experimentally derived. The phase with the lowest energy is most favored. from a practical viewpoint. This is not a small. a quasi-bcc structure of lower free energy. Most stainless steels are used in the metastable condition. the metal atoms give up valence electrons to the entire mass. In this book. In metals. To determine which phases exist at a given composition and temperature. the interaction between elements is very important in nondilute alloys such as stainless steel. Iron has the curious characteristic of transforming from fcc back to the low-density bcc at still lower temperatures. can be found. A law of thermodynamics is that the number of possible condensed (i. In Appendix 3. The version has a reduced three-element capability but uses the same proprietary thermodynamic database of the full version. The calculation of which phases exist under equilibrium conditions proves to be extraordinarily difficult in complicated alloy systems. These values must be derived from computer analysis of experimental phase equilibrium diagrams. a license to one such program. First. but the substitutional diffusion of chromium in austenite that is required to form a ferrite phase of a separate composition is so slow that it cannot occur in terrestrial time frames. and only a few exist. The necessary knowledge has been embedded in proprietary computer programs that will be used instead. density. These are computer simulated. is proportional to the charge difference and distance. a sample is made. that of the lowest free energy. causing repulsive forces between atoms and requiring a more widely spaced structure. It is not remotely feasible. This is a result of the unpaired 3d orbital electrons (those that give rise to ferromagnetism) that are not given up as valence electrons. This important work is obviously tedious and susceptible to experimental error and applies only to specific compositions.

and sigma phase (σ) are stable. Both are quite soluble in molten iron-chromium alloys and are fairly soluble in ferrite at high temperatures. but even this is . with which they are very reactive. Metals are effective solvents in both the liquid and solid states. it must be emphasized that the influence of an alloying element on structure has zero bearing on its influence on corrosion resistance. This occurs at the grain boundaries. at still lower temperatures. At still lower temperatures. as stated. sulfur. As chromium is added to iron. 1 The iron chromium phase diagram. have no influence on which phase is favored. To preserve the ferrite structure. This is. chromium. Again. chromium.Chapter 1: Metallurgy / 3 Phases Ferrite The basis of stainless alloys is. An important part of steelmaking is refining the molten metal to remove the undesired impurities dissolved in it. but none produces the quality of stainlessness. and titanium all favor ferrite. the approximate level of chromium needed to keep alloys from rusting under ambient conditions. Silicon. The normal technique is to add elements that react selectively with the targeted impurities to form an immiscible reactant that can become part of the slag and physically separated from the refined alloy. manganese. which. This is done for the primary impurities oxygen and sulfur. other elements have similar effects. has the characteristic of stabilizing the bcc structure. The elements that promote ferrite over austenite also have the effect. During cooling as these elements become less and less soluble. Modern refining methods can reduce carbon plus nitrogen to under 0. niobium. solidifies as a bcc alloy before transforming to the denser fcc austenite at lower temperatures. martensite (α' ). phosphorus. nitrogen. at about 12% chromium. such as the impurities phosphorus. tungsten. It is accurate to surmise from this that the free energy of both structures is close. The iron-chromium phase diagram (Fig. the temperature range over which austenite is stable grows smaller until. of promoting intermetallic compounds generally composed of iron. These are discussed separately. carbon and nitrogen can be detrimental impurities. carbon and nitrogen must be eliminated. and some of those alloying elements. These elements have small atomic sizes compared to iron and chromium and. iron. but this effect is not related to whether the structure is bcc or fcc. Carbon. Iron. Fig. Alloying elements that promote one structure over the other can therefore change which one predominates. The most thermodynamically favorable form in which they can precipitate is as a compound of chromium. coincidentally. and depletes those regions of chromium.020%. aluminum. Elements that are insoluble in iron at austenite-forming temperatures. where nucleation is favored. rendering them less corrosion resistant. While chromium is the principal ferrite-promoting alloying element. There are additional reasons to eliminate carbon and nitrogen. A second effect is a loss of toughness due to these precipitates. molybdenum. 1) shows the composition and temperature regions where ferrite (a). The diffusion rates of carbon and nitrogen in ferrite are too high to prevent this precipitation by quenching. is not so easily removed and must be excluded from raw materials to be kept under control. nickel. and copper do not and expand the temperature range over which austenite exists. so they stabilize that structure. has roomier interstitial spaces. Courtesy of Thermo-Calc Software and oxygen. Such interstitial solute atoms profoundly distort the structure. This solubility decreases exponentially with temperature so that it is essentially zero at room temperature. They are much more soluble in the fcc structure. The element that produces the ability to form the passive film that makes stainless corrosion resistant. when dissolved. In stainless steel. it reverts to the bcc structure. of course. austenite (γ). ferrite is stable at all temperatures. A third common impurity. squeeze into interstitial sites within the bcc matrix. they must precipitate. while denser.

Hydrogen and boron are other elements that can be interstitially dissolved in ferrite. in ferrite is about two or three orders of magnitude higher than in austenite. Boron is normally found at levels of around 5 to 10 ppm. molybdenum. as in the case of deepdrawing alloys. Incorrect thermal processing is the main way homogeneity can be lost. The mechanical properties of the ferrite phase are discussed extensively in Chapter 8. distributed throughout the matrix. This is one explanation of. At higher levels. potentially depleting chromium in the vicinity of their precipitation. the solubility of hydrogen increases as the defect structure accommodates hydrogen atoms. This approach is called stabilization and is used for most ferritic alloys today. The first two are controlled by reduction of interstitial levels and refining of grain size. Hydrogen is soluble to several parts per million by weight. and oxygen and the substitutional diffusion of all other elements. So. its success depends to a great degree on maintaining the homogeneity required for proper corrosion-resistant performance. This is thus only an issue for superferritic (high chromium content) alloys or for the ferrite phase of duplex (ferrite-austenite) alloys. other benign carbides and nitrides such as those of titanium or niobium are allowed to form preferentially. is to permit chromium carbides and nitrides to form but then to perform a subcritical anneal to rehomogenize the chromium and coarsen the precipitates so that they have only a small negative effect on mechanical properties. carbon. ferrite may be embrittled by hydrogen. “Ferritic Stainless Steels. above which the sigma phase appears. It shares the following characteristics: • A toughness transition that occurs around room temperature • Notch sensitivity • A yield point phenomenon • Pronounced crystallographic anisotropy of mechanical properties • High stacking fault energies and low workhardening rates These issues are dealt with in the same way as in carbon steel when these characteristics become an issue. which assists in corrosion resistance. nitrogen. The anisotropy is either utilized to advantage by maximizing it. especially if it enters the metal through corrosion processes like pitting. The bcc structure of ferrite allows more rapid diffusion than does the fcc structure of austenite. A by-product of stabilization with titanium is that oxygen and sulfur are also eliminated as compounds of titanium along with carbon and nitrogen. boron substitutes for carbon in carbides. boron. and localized corrosion can occur. If the ferrite is cold worked. it can be picked up during pickling. it is only necessary to note that ferrite in stainless steel closely resembles low-carbon steel in mechanical behavior. whereas they can be in austenite. both interstitial and substitutional. All stainless alloys rely on having a uniform level of chromium and the other element. stress corrosion cracking. Stabilizing makes it much easier to keep chromium from segregating in ferritic alloys. If there are locally low levels of these elements. This is true for both the interstitial diffusion of the elements helium. or minimized by refining grain size and randomizing grain orientation by special thermomechanical processing. and the most likely explanation for. The yield point is eliminated by slight elongation by temper rolling or elimination of interstitial carbon and nitrogen. assuming absolutely dry blowing gases and additions are used. In this condition. as characterized by alloy 430. whose interaction with dislocations causes the yield point. Its strength decreases with temperature more than that of austenite. welding. It does not cause hydrogen embrittlement in annealed ferrite.” Here. The practical implication of this is that precipitation reactions generally cannot be suppressed by quenching in ferrite if they involve interstitial elements. or annealing as well as by corrosion. This becomes an issue only when total chromium plus molybdenum exceeds about 20%.4 / Stainless Steels for Design Engineers too high. Because chromium is a reactive element. localized resistance to corrosion is reduced. These impurity elements would otherwise also precipitate as compounds containing some chromium. While hydrogen is easily removed by argon oxygen decarburization (AOD). Ferrite has a greater thermal conductivity and lower thermal expansion than austenite. Intermetallic phases can form more rapidly in ferrite. The older approach. This can occur by the precipitation of any phase that is richer in chromium or other corrosion-resisting elements. but the good match in thermal expansion between the ferrite and its oxide still makes it an excellent high-temperature . The rate of diffusion of all elements. to avoid the detrimental effects of chromium carbide and nitride formation in ferrite.

which provide ferromagnetism. it cannot benefit from this element. Prog. Nov 1949. such as S34565. Since welds solidify relatively rapidly. These stabilizing factors are mapped in the Schaeffler diagram of Fig. whose purpose is to predict the phase makeup of weld metal. p 98 . Ferrite has very nearly the same corrosion resistance as austenite.Chapter 1: Metallurgy / 5 material. The presence of the bcc structure relates to the unpaired 3d electrons. Vol 77. A Modified Phases Diagram for Stainless Steel Weld Metals. Prog. p 680–688. Constitution Diagram for Stainless Steel Weld Metal. As stated.4 to 0..T. Schaeffler. Met. so even in the small amounts in which they are normally present. As a rule of thumb. The omnipresent carbon and nitrogen have an effect 30 times that of nickel. Delong.. the fcc structure should be considered normal for metals well below their melting temperature as it is a denser structure. One percent nickel can be replaced by about 2% manganese as long as nitrogen is present to maintain the same phase stability. In duplex alloys. iron alloys require about 17% chromium and 11% nickel (or its equivalents) to remain austenitic at room temperature. Austenite The second major constituent phase of the stainless steel alloy system is austenite. 2 Schaeffler-Delong constitution diagram showing phases present in as-solidified stainless steels at room emperature as a function of composition demonstrating carbon and nitrogen contributions to nickel effects. Austenite has an fcc atomic structure. Since all stainless steels contain principally iron and chromium.L. resulting in higher pitting corrosion resistance.6% to be achieved. use 4 to 6 % manganese to permit nitrogen levels of 0. Nickel and manganese are the most prominent alloying elements that do this. Manganese acts largely through its ability to promote nitrogen solubility. and W. Adapted from A. but since ferrite can hold no nitrogen in solution. Vol 56. Adding elements to iron that causes pairing of the 3d electrons diminishes ferromagnetism and promotes the fcc structure. they have a significant effect. The fcc structure is common in many transition metals to the right of iron in the periodic table. no carbides or intermetallic phases Fig. Feb 1960. 2 (Ref 1). but the interstitials carbon and nitrogen are the most powerful austenite stabilizers on a percentage basis. Their use is limited by their solubility and their tendency to form precipitating compounds with chromium. the ferrite is generally the more corrosion resistant phase because it is richer in chromium and molybdenum. Superaustenitic stainless steels. the addition of a substantial amount of austenitizing elements is necessary to transform the structure to austenite. Met.

The interface between these inclusions and the matrix is the locus of corrosion pit initiation. sulfur and oxygen precipitate as primary inclusions before or during solidification. But in the annealed state. A third interstitial solute. This causes poor hot workability and hot cracking of welds. so even interstitial elements cannot move quickly enough to precipitate below about 400 °C (750 °F). Austenite is not embrittled by hydrogen to the extent ferrite or martensite is. This produces solid solution hardening of the austenite. and those with less than about 30% chromium plus nickel will form martensite if deformed sufficiently. hydrogen. make their formation very sluggish. The difference of three orders of magnitude for carbide formation reflects the difference between the diffusion of carbon and that of substitutional elements. but they can reach phenomenal hardness of over Rc 70. only nitrogen is considered a beneficial alloying element. and martensite will be present. quite probably because of chromium depletion occurring during and as a result of inclusion growth. fortunately. The diffusion rates in austenite are quite low compared to ferrite. When an alloy solidifies as austenite. Interstitial elements are much more soluble in austenite than in ferrite. The nickel equivalent (vertical axis) summarizes how nitrogen. for example. 3 Lattice expansions due to carbon. The sulfur and oxygen then precipitate during cooling or subsequent hot working as isolated inclusions. The austenite structure does not discourage the formation of intermetallic compounds such as sigma. causing it to expand about 1% linearly per 1 wt% of solute (Fig. The horizontal axis does the same for chromium and those elements that have a similar effect. austenite. Sulfur and oxygen are considered impurities because they form inclusions. and only ferrite. austenite is normally present in the metastable state. Carbon has a parallel effect. but its tendency to form chromium carbides limits its use and in fact leads to its minimization in most alloys. Fig. Sigma is almost never seen in commercial 316 alloys. Of these. sulfur immediately segregates to the grain boundaries because of its low solubility in austenite. In most austenitic stainless alloys.6 / Stainless Steels for Design Engineers form. but it does. If present in sufficient amounts. 4. The work hardening of austenite is increased by nitrogen. the remainder of these elements are near saturation in the as-solidified ferrite at very high temperatures and then frozen in a state of supersaturation in the austenite when it forms on cooling. Before the AOD was developed and carbon levels in stainless steels were higher. usually chrome/ manganese silicates and sulfides. and it forms a low-strength film with a low melting temperature. This permits carbon and nitrogen to exist in very high degrees of supersaturation if introduced below this temperature. permitting lower levels of nickel to be used in austenitic alloys. but hydrogen does raise its flow stress and hardness while lowering its work-hardening rate.02% would eventually break down into austenite plus carbides. In most common stainless steels. austenitic stainless steels were sometimes stabilized by titanium or niobium to counter the effects of carbon. It both strengthens and improves the pitting corrosion resistance of austenite. Thus. Source: Ref 2 . The low diffusion rates restrict such colossally supersaturated zones to thin surface layers. Interstitial atoms of carbon and nitrogen distort the fcc lattice. they provide useful information about the compositional effects on phase development in nonequilibrium situations. 3) (Ref 2). as is done by various proprietary processes. carbon. the austenite in standard austenitic stainless steels will remain indefinitely as fully austenitic without precipitates unless heated above 400 °C (750 °C) for protracted periods of time or deformed extensively. the retained austenite in alloy steels. Both carbon and nitrogen stabilize the austenite phase. and other elements combine to create a nickel-like effect. The formation of sigma in ferrite is about 100 times faster than in austenite. produces the same effect but to a lesser degree. as seen in Fig. Those with carbon above 0.

nonmagnetic. epsilon. At this temperature. Martensite in stainless steels is restricted to alloy levels at which austenite can form at higher temperatures but at which the austenite is unstable at ambient temperatures. The as-formed martensite to the degree it has significant carbon content is hard and requires tempering to give it adequate toughness. Thus. that all tempering involves carbide formation. Martensite Martensite is a phase that forms from the diffusionless shear of austenite to a distorted cubic or hexagonal structure. the hardness of the martensite increases dramatically with interstitial content because of the huge strain interstitial elements impose on the bcc lattice. have high work-hardening rates. type 2. Austenite can be cold worked to extremely high strengths. Source: Ref 3 . This gives martensite a fairly narrow composition range. The physical properties of austenite compared to ferrite include lower thermal and electrical conductivity and greater thermal expansion. a range that can be encountered in the heat-affected zone (HAZ) at γ/δ boundaries during welding. the ε. it forms at cryogenic temperatures or by cold working.” It is worth noting. This so-called secondary austenite. making it quite hard. Chapter 3. it has the same composition as the ferrite from which it forms and is called type 1. There are two forms of martensite. It is nonmagnetic. It is also. Austenite is characterized by: • Low stacking fault energies leading to high work-hardening rates • Good toughness even at very low temperatures • Low notch sensitivity • Lack of a sharp elastic limit • Good high-temperature strength • Fairly isotropic mechanical properties While there is not a great deal of difference in the yield strengths of austenitic and ferritic alloys of similar alloy levels. another type forms. This secondary austenite is called type 3 and is also poor in chromium. martensitic stainless steels are inherently limited in corrosion resistance to a level no better than a 17 or 18% chromium alloy and often barely qualify as stainless after the chromium tied up as chromium carbide is recognized as not contributing to the corrosion resistance. The most highly alloyed martensites are found in the precipitation-hardening grades. The tempering reaction is the precipitation of carbon in the form of carbides with the concurrent loss of internal strain in the martensite lattice. γ2. It is essentially ferrite that has been formed with a supersaturation of carbon. “Austenitic Stainless Steels. alpha prime. The resulting structure is very fine and highly faulted.2% carbon. Secondary austenite can also coform with sigma as γ/δ grain boundaries are depleted of chromium. and the α'. thus losing some corrosion-fighting chromium. is somewhat enriched in nickel over the ferrite from which it forms but poorer in nitrogen than the primary austenite. γ2. Fig. can form from ferrite below 650 °C (1200 °F). distorting it into tetragonality. 4 Precipitation kinetics in 316 stainless steel. As in carbon steel. This transformation can occur spontaneously on cooling or isothermally with externally applied deformation.” gives a more thorough and quantitative treatment of the mechanical properties of austenite. and therefore have higher tensile strengths. austenitic alloys are more ductile. of course. however.1 to 0. which are primarily the leaner austenitic alloys. Epsilon is formed in steels with low stacking fault energy. a secondary austenite. In duplex stainless steels. The lowest alloy level is that of the basic 12% chromium steels with 0. It appears in martensitic alloys of the precipitation-hardening type. In the 650 to 800 °C (1200 to 1470 °F) range. giving it poorer corrosion resistance. “Martensitic Stainless Steels. has a hexagonal close-packed (hcp) structure. around a maximum of 2000 MPa (290 ksi).Chapter 1: Metallurgy / 7 The mechanical properties of austenite are quite different from those of ferrite. Thus. The complexities of tempering require its discussion in detail to be found in Chapter 3.

B)6 fcc M6C M2N MN Gamma prime Sigma Laves phase Diamond cubic Hexagonal Cubic fcc Tetragonal Hexagonal Chi phase bcc(b) G-phase fcc (a) fcc. The principal intermetallic phases are described next. Fe3Nb3C. Deformation.47 a = 4. Sigma is a brittle tetragonal phase richer in chromium and molybdenum than either the ferrite or austenite matrix around it. so it will not occur inadvertently during thermal processing such as welding or annealing. Fe2Nb Fe36Cr12Mo10 Ni16Nb6Si7. manganese. but fortunately it takes a relatively long time to form. Stabilized alloy grades show more rapid sigma formation than unstabilized alloy grades (e. face-centered cubic. which enhances substitutional diffusion. but they can form in a matter of minutes in alloy-rich grades. This structure is quite brittle. Ni.2 NbC NbN TiC TiN CrNbN Cr16Fe5Mo2C (e.878 a = 11.80 c = 4. causing localized lower corrosion resistance. chromium or molybdenum.e. sites on two intersecting superlattices). It is not surprising that stainless steel with iron.g.40 a = 4.28 a = 2. between 300 and 525 °C (570 and 980 °F). and often molybdenum. M5SiC Cr2N CrN Ni3(Al. Before its true nature was understood.62–11.18 a = 3. This phase forms at chromium contents as low as 15%.59 a = 8. which occurs in the same temperature range but is caused by phosphide precipitation on prior austenite grain boundaries of martensite. rather than random. which makes their precipitation slower than that of carbides.24 a = 3. leading to subsequent sigma formation.4 a = 4. titanium. accelerates their formation. Table 1 lists data on the more common precipitates found in stainless steel. but examination of the iron-chromium phase diagram shows that it is archetypically an equiatomic iron chromium compound. body-centered cubic. Intermetallic phases form by diffusion of substitutional alloying elements. It forms preferentially at ferrite-austenite boundaries in the temperature range 600 to 1000 °C (1110 to 1470 °F) in alloys with more than about 18% chromium plus molybdenum. essentially 25Cr-20Ni. They can render the bulk alloy brittle when they form along grain boundaries.807–8. and niobium should have numerous ancillary phases. chromium.8 c = 4. Intermetallic phases are normally hard and brittle.73 c = 7.Ti) Fe. at which the phase dissolves.57–10. Intermetallic Phases The number of phases that can coexist in an alloy is proportional to the number of alloying elements in the alloy.57–10. The other concern arising from intermetallic phase formation is the depletion from the surrounding matrix of Table 1 steels Precipitate Precipitated phases found in stainless Structure Parameter.391 a = 10. The physical properties are very close to those of ferrite of the same composition. originally called 885 °F embrittlement.13–4. This makes alloys like 310H. Sigma forms much more rapidly from ferrite than from austenite because of the 100-fold .68 a = 10. The mechanical properties of stainless martensite are parallel to those of alloy steels. A Composition NbC NbN TiC TiN Z-phase M23C6 fcc(a) fcc fcc fcc Tetragonal fcc a = 4. This is sometimes confused with temper embrittlement. especially prone to sigma formation. Its composition is sometimes given as (CrMo)35 (FeNi)65. It forms at relatively low temperatures. Mo Fe2Mo.. silicon.33 a = 4. so there is no concern with ancillary phases such as bainite.68 a = 10.) Cr23(C. iron and chromium atoms occupy specific.8 / Stainless Steels for Design Engineers and is very difficult to identify microscopically. alpha prime is an ordered ironchromium phase (i. 347 versus 304). its presence was known through its causing the phenomenon called 475 embrittlement. on the order of hours. In unstabilized alloys the prior precipitation of carbides destabilizes austenite.72 a = 8. Cr.. Ni16Ti6Si7 M23(C.037 c = 7. Not to be confused with martensite. The high quantity of alloying elements in stainless give an extreme depth of hardening. (b) bcc. nickel. The a' martensite is the familiar magnetic variety known in alloy steels that forms both by quenching and by deformation. Alpha Prime. Sigma.B)6 (FeCr)21Mo3C. It is strongly promoted by silicon and suppressed by nitrogen.g. Alpha prime precipitation can cause 475 embrittlement in ferritic or duplex stainless steels and limits their use in this temperature range but not at higher temperatures.54 a = 4.

The precipitation of the carbide from ferrite occurs at grain boundaries. Less than 20 ppm carbon content is required to prevent its precipitation from ferrite. Except for its role in hardening martensite and strengthening austenite at high temperatures. It also precipitates at ferrite-austenite boundaries and has the same deleterious effects. as chromium diffusion permits. Other elements. They precipitate in both the liquid and solid states.10% and at 650 °C (1200 °F) for carbon levels below 0. It is possible for it to form at temperatures below sigma and above alpha prime. but iron can substitute for chromium up to about 50%. titanium. Its beneficial effect on corrosion resistance when it is in solution is negligible because so little of it can be held in solution. sulfur. The ratio of chromium to iron in the carbide increases with time and temperature. M23C6 is the main carbide found in stainless steel. At low levels. but the long times for formation make it rare. carbides may form. While carbon is essentially insoluble in austenite at room temperature. These include M7C3 and M3C. These carbides form preferentially over chromium carbides and thus prevent sensitization. The latter carbide forms during the low-temperature tempering of martensite. Common carbide and nitride precipitating phases are also listed in Table 1. and molybdenum. but they take on a special significance in stainless steel because chromium. It can coexist with sigma and forms in the same temperature range. This makes the phase a useful constituent in wear resistance in martensitic alloys. while the former precipitates at higher temperatures. It forms at 550 to 650 °C (1020 to 1200 °F) over the course of hours. The carbon in these compounds may be replaced by nitrogen or. more carbonrich. although its effect would be deleterious. The Ti(CN) appears as a cube of gold TiN surrounded by gray TiC.10% in supersaturation. additional. in the case of titanium. vanadium. it seldom becomes a practical problem. although up to 50 ppm can be effectively kept in solution by very vigorous quenching. carbide precipitation occurs below about 900 °C (1650 °F) for carbon levels under 0. They affect mechanical properties in ferrite both by their influence on recrystallization and by their ability to act as nucleation sites for brittle fracture Nitrides. Nitrogen has a lesser tendency to form compounds with chromium. It is mainly chromium carbide. the essential alloying element of stainless steel. reacts more vigorously with carbon and nitrogen than iron does. giving rise to the phenomenon of sensitization. Stabilizing carbides are those that are formed by the intentional addition of elements such as titanium and niobium.03%. In the solid state. Thus. quenching can easily preserve up to 0. The Nb(C. precipitation ceases below 500 °C (930 °F) due to the slowing diffusion of carbon. Cold work accelerates precipitation. These elements form carbides of the type MC (metal carbide). carbon is almost universally a detrimental impurity from a corrosion point of view and is minimized. is extremely rapid. Chi. This makes it a much larger issue in superferritic and duplex alloys. and it contains both iron and chromium.Chapter 1: Metallurgy / 9 higher diffusion rate of alloy elements in ferrite. so it is considered a beneficial alloying element in austenite but not in ferrite. or silicon.” Nickel and molybdenum decrease the solubility of carbon and thus accelerate the precipitation. The chromium that combines with the carbon comes from the matrix in the immediate vicinity and therefore decreases the chromium content of that region. At higher nitrogen . Chapter 7. From austenite. Laves Phase. The laves phase has the structure A2B where A is iron or chromium and B is molybdenum. which have high chromium and/or molybdenum levels. In higher carbon grades such as the martensitic stainless alloys. in which it has essentially zero solubility. can also dissolve in this carbide.” contains an indepth discussion of sigma. niobium.N) is less regularly shaped. χ. Chi. and Inclusions Carbon and nitrogen are very important in all steels. Precipitation Hardening. Carbides. It can form at any temperature at which the host austenite or ferrite becomes saturated with carbon. as is commonly seen in type 301 stainless. The carbide precipitation occurs first at grain boundaries. “Duplex Stainless Steels. Its structure is orthorhombic. Carbides. the precipitate normally forms within grains. Nitrogen retards precipitation. is similar to sigma except it contains more molybdenum and less chromium and has a cubic structure. up to a maximum of 4 or 5 to 1. and cannot be suppressed by quenching. The carbide has a hardness of about Rc 72. nitrogen can substitute for carbon in M23C6. For practical purposes. Nitrides. which comes from the original phrase “sensitization to intergranular corrosion. such as tungsten.

which have been linked to both their sulfur ions disrupting the passive layer and their chromium content causing slight local chromium depletion.J. If more reactive elements. or in the solid (type III).R. Precipitation-Hardening Phases. the slight mismatch causes a strain that can significantly restrict dislocation movement and thereby strengthen the matrix. R. Properties and Selection. In these cases. Failures Related to Heat Treating Operations. Kotecki. Welding. Narazaki. fcc phase with the composition Ni3(AlTi). ordered. Inclusions are mainly oxides and sulfides of silicon and manganese. essentially pure copper. Cr2N can form. Inclusions are principally oxides and sulfides that form in the melt (type I). in the solid state either on preexisting inclusions or as micron-size particles. Another nitride CrN can form in HAZs of welds. ASM International. The reader is referred to primary sources. p 16 4. Otherwise. are present. 1990 5. Type II inclusions form in interdendritic spaces as the solubility of oxygen and sulfur drop on solidification. such as company web sites. Welding of Stainless Steels. that is. Siewert. p 677–707 2. Totten. Jarvis. High Performance Stainless Steels. Type III inclusions precipitate the remaining oxygen and sulfur. Nickel Development Institute. ASM Speciality Handbook. Properties of Stainless Steels Physical and mechanical properties of representative stainless steel alloys are summarized in Appendix 2. REFERENCES 1. This can occur in duplex alloys if they are heated to a solution annealing temperature at which the alloy has high solubility for nitrogen.M.J. The secondary hardening of martensite due to the precipitation of molybdenum nitride or carbide is also a precipitation-hardening reaction. up to 100 ppm for normal manganese-silicon killed stainless steels. ASM International. Type I inclusions are the largest and are globular. their oxides and sulfides can also be present. Copper forms the epsilon phase. ASM Handbook. Welding Journal. their presence is detrimen- tal as inclusions have been shown to be the initiation sites for corrosion pits. Cooling from these temperatures can cause the excess nitrogen to precipitate as needles of Cr2N. p 171s–178s . such as aluminum or titanium. G. Except when they are deliberately kept to improve machinability. Sulfides and oxysulfides can be beneficial for machining as solid-state lubricants and chip breakers. Properties are also discussed in chapters specific to each alloy family.10 / Stainless Steels for Design Engineers levels. Inclusions. WRC 1992 Constitution Diagram. Blackwood. at the end of solidification (type II). Brazing. 1996 SELECTED REFERENCES • D. such as Ref 4 and 5. Vol 5. which causes precipitation hardening. 1993.E. they are physically removed by various steelmaking practices. ASM International. Phases that have a very similar lattice match to the parent phase can precipitate coherently. without changing the continuity of the crystal lattice. M. Kotecki and T. D.A. ASM International. Vol 1. and L. and Soldering. p 192–223 3. 2002. ASM Handbook. Vol 11 ASM Handbook. an intermetallic. One such precipitate is gamma prime. Stainless Steels. 1992. Reference Book Series 11 021. Vol 6.

the Nernst equation. Thermodynamics are presented in light of electrochemical potentials as opposed to purely chemical ones. Figure 1(a) shows the arrangement of an experimental setup in which Reaction 1 could proceed. iron is allowed to dissolve according to: 2Fe (s) → 2Fe 2+ + 4 e − (Eq 2) resulting in Fe2+ ions that dissolve in the water-based solution and electrons that are carried to the right side. the reader is referred to texts by Jones (Ref 2). and Pourbaix diagrams. Chapter 4 describes the various forms of corrosion and how they are related to alloy metallurgy.Stainless Steels for Design Engineers Michael F. Ref 1 is recommended. Chapter 5 focuses on oxidation. The examples provided relate these fundamentals to the corrosion resistance of stainless steels. Electrochemical Reactions In electrochemical reactions. Topics covered include an overview of electrochemical reactions. charge is transferred across interfaces of species of different chemistry. electrons have been transferred from the metallic phase. and structure. H+. for example. and Fontana (Ref 4) and to ASM Handbook. An inspection of this reaction suggests that three phases must be present for the reaction to proceed: an ion-conducting phase (water-based solution). CHAPTER 2 Corrosion Theory Summary THIS CHAPTER INTRODUCES THE fundamentals of electrochemical theory as it pertains to corrosion. For an in-depth study of electrochemical kinetics and electroanalytical methods. where they participate in the reaction: O 2 + 2H 2 O + 4 e − → 4 OH − (Eq 3) Inside the water-based solution. and a gas phase O2(g). www. p 11-18 DOI: 10.1361/ssde2008p011 Copyright © 2008 ASM International® All rights reserved. a metallic phase (iron). iron to O2 + H2O. Volume 13A (Ref 5). galvanic versus electrochemical cells. OH . This chapter aims first to provide an introduction to the fundamentals of electrochemical theory as it pertains to corrosion. thereby constituting a so-called ionic current. Second.asminternational. ions (Fe2+. the reaction: 2Fe (s) + O 2 (g) + 2H 2 O → 2Fe 2+ + 4 OH − (Eq 1) Introduction Corrosion—the environmental degradation of materials through electrochemical reactions—is a key subject for more or less all classes of alloys that fall within the broad definition of stainless steels because these alloys were developed with the intention of preventing corrosion. Chapter 3 introduces the formal terms needed to describe electrode reaction kinetics. Consider. or any others) migrate. Faraday’s law. This current together with Reactions 2 and 3 and the transport of electrons from left to right form a closed circuit called an electrochemical cell. On the left. McGuire. For a broader study of corrosion. Uhlig and Revie (Ref 3). The cell is made up of four parts: the two electrodes where the charge transfer Reactions 2 and 3 take place .

Fe / O 2 / OH − and Fe / Fe 2+ . For example. This is given by Faraday’s law: nNF = it (Eq 4) Here. Processes at a single electrode (a ) (a ) + RT ln 4 OH − Fe 2+ 2 2 (Eq 5) aH O PO 2 where G is the Gibbs free energy. and the amount of charge passed per unit time as a result of this current will be linked to the amount of iron dissolved per unit time or the amount of oxygen reacted per unit time by virtue of Eq 2 and 3. and F is Faraday’s constant..g. 1 Schematic illustration of (a) a differential aeration cell involving iron dissolution and (b) the same cell with a variable resistor and voltmeter The Nernst Equation Electrochemical reactions require a transfer of charge. Consider the hypothetical setup in Fig. occurs at the cathode. S is the entropy. R is the gas constant. H is the enthalpy. i * t is the charge passed (in coulombs). This cell is an example of a differential aeration corrosion cell. the Gibbs free energy of the cell is that of Reaction 1: ΔG = ΔH − T ΔS = ΔG 0 (the anode and cathode. As a shorthand notation. n is the ratio of electrons to consumed/produced species. which is essentially the charge in coulombs corresponding to 1 mole of electrons. resulting in the arrangement shown in Fig. Oxidation. Reaction 3. Fig. 1(b). for example. Fe 2+ / Fe . Reaction 2. then a current i will flow from the anode to the cathode. If this is negative. Thermodynamically. gaseous species are written next to their conducting electrode. 1(a) was allowed to proceed and thermodynamics favored to proceed according to the direction in Reaction 1. Faraday’s Law If the cell in Fig. which is discussed later. N is the moles of consumed/produced specie (e. there is a coupling between chemical and electrical energy. in the case of corrosion reactions. respectively). and T is the absolute temperature. The final constituent of the electrochemical cell is a pathway through which electrons can migrate from the anode to the cathode. but at high temperatures it could be a solid oxide. this is most commonly a water-based solution.12 / Stainless Steels for Design Engineers often are described as half cells. 1(a) with the addition of a variable resistor and a voltmeter. which in the case of Reaction 2 will be 2. The thermal heat produced by the system can be divided into two parts: the thermal heat produced by the cell Qt and the heat produced at the resistor QRes. an electrolyte. moles consumed iron in Reaction 2). It should be noted that electrodes are interfaces that require several phases to be in contact. hence. 1(a) would be recorded as Fe / O 2 / OH − . The electrolyte is the medium through which the ions migrate. QRes . Let us assume that this is the case. the reaction would be expected to proceed spontaneously as written in Reaction 1. occurs at the anode and reduction. the cell described in Fig. electrochemical cells are written by separating components within a phase by a comma and separating phases by a slash. and an electron pathway.

The potentials as written in Eq 12 and 13 are called reduction potentials.. this potential is positive for a spontaneous reaction (as opposed to the chemical free energy. On the other hand. which is negative).485 C per mole electrons. the net work gained QRes is maximized and constitutes the rest of the free energy: QRes = ΔG = ΔH − T ΔS (Eq 6) Here.g. Eq 5). By convention. If the resistance approached infinity ( R→ ). It is useful to list reduction potentials for halfcell reactions. this means that the free energy is negative (according to the Nernst equation). the net reaction is thermodynamically favored as it is written in Reaction 1. Reference electrodes are constructed such that they have a stable potential. is Faraday’s constant. Eq 10 would be: 0 Erxn = Erxn − 4 ⎛ RT ⎜ aOH− aFe 2+ ln 4F ⎜ aH O PO 2 2 ⎝ ( )( )⎞ ⎟ 2 ⎟ ⎠ (Eq 11) As mentioned. it can be seen that it is the difference between two hypothetical half reactions. respectively. In this case. It is defined here as Erxn. only potential differences can be measured. If it was not. By inspection of Eq 11. Eq 7 becomes: ΔG = − nFErxn (Eq 8) which corresponds to the reduction Reaction 3 and: EFe 2+ /Fe 4 RT ⎛ ( aFe ⎞ ⎟ ln ⎜ = EFe 2+ /Fe − 4 F ⎜ aFe 2+ ⎟ ⎝ ⎠ 0 ) (Eq 13) and if all elements have unit activities: 0 ΔG 0 = − nFErxn (Eq 9) Equation 8 is the Nernst equation. Reaction 1 would proceed through infinitesimal steps and can be considered thermodynamically reversible. half-cell potentials are measured with respect to a reference electrode. the energy dissipated through the resistance is charge passed times potential difference. 1(b) when a negligible current flows. which means that the electrode Reactions 2 and 3 would be reversed and thus so would the anode and cathode of the cell. and because Erxn = EO /OH− − EFe 2+ /Fe has to be positive for the 2 reaction to be thermodynamically favored as written in Eq 1.) Therefore. ⎠ α α α (Eq 10) which corresponds to the reverse of Reaction 2. n is the number of electrons passed per atom of iron reacted. half-cell potentials (like any electrical potentials) cannot be measured in an absolute sense. in an absolute sense: ΔG = nFE (Eq 7) If the emf according to Eq 11 is positive. In the case of Reaction 1. A common reference electrode in aqueous solutions is . the thermal heat produced by the cell is minimized and according to thermodynamics is given as Qt = Qrev = T S1. and αi and βi are the numbers that are needed to balance the reaction stoichiometrically. The potential difference is referred to as the electromotive force (emf) of the cell. that is. just as it is useful to list free energy data. ( Erxn = EO /OH− − EFe 2+ /Fe ) 2 defined as: EO = EO 0 4 ⎛ ⎞ RT ⎜ aOH− ⎟ − ln 4 F ⎜ aH O PO ⎟ ⎝ 2 2⎠ 2 /OH − 2 /OH − ( ) (Eq 12) Here. hence. thus.. this is discussed further in Chapter 3. and as such they are associated with Reaction 1 rather than a physical cell.. then Reaction 1 would proceed in the reverse direction. and F = 96.. The reversible potential difference E represents the potential difference between the two electrode reactions (cathode and anode). ⎞ ln ⎜ ⎟ nF ⎝ r1β1 r2β2 r3β3 . which in the case of a resistance is given by the product of charge passed times potential difference. and in this case the potential difference is the reversible potential difference E. It is also referred to as the open circuit potential because it is the potential measured by the voltmeter in Fig. if it was a reduction reaction. an expression for Erxn is obtained: 0 Erxn = Erxn − RT ⎛ p1 1 p2 2 p3 3 . hence.Chapter 2: Corrosion Theory / 13 in this case is heat. the reduction potential E O 2 /OH− has to be larger than E Fe 2+ /Fe. pi and ri are the concentrations of reactant and products. However. By virtue of Eq 8 and 9 and the expression for Gibbs free energy of a reaction (e.. but in essence it represents the available energy or work. ( Erxn = EO /OH – − EFe 2+ /Fe can be 2 measured because it is a difference.

a current flows as shown in Fig. also known as the standard hydrogen electrode (SHE). Table 1 (Ref 6) lists half-cell reduction stan0 dard potentials ( EOx/Re) versus NHE that are a result of the emf of the following types of cells (for Reaction 2. normal hydrogen electrode. 2. in which the current is used as electricity. and for other applications.g. In shorthand notation.447 –0. In electrolytic cells (Fig. In electrolytic cells. electrical energy is converted to chemical energy. as an example): Pt / H 2 (a = 1)/ H + (a = 1). It also is the case in fuel cells and batteries (under discharge).828 Fig. NHE(a) (V) Fe 3+ + e− = Fe 2 + O 2 + 2H 2 O + 4e − = 4 OH – (pH = 14) 2 H + + 2 e− = H 2 Ni 2 + + 2 e− = Ni Fe 2+ + 2e− = Fe Cr 3+ + 3e− = Cr 2 H 2 O + 2 e− = H 2 + 2 OH − (pH = 14 ) 0. 3b). 3(a). These types of cells are called galvanic cells. in which chemical energy is converted to electrical energy. 2 The normal hydrogen electrode (NHE) (a) NHE. This is the case in environmentally caused electrochemical corrosion reactions. with a potential set (arbitrarily) as zero at all temperatures. electrorefining and electroextraction (e. Most of the discussion in the following chapters concerns these types of cells. Source: Ref 6 Fig.744 –0. the principle is used for protection against corrosion. an imposed electrical potential counters the “natural” cell potential to drive a reaction in a desired direction. 3 Schematic of (a) galvanic cell and (b) electrolysis cell . The NHE is schematically shown in Fig. it is: Pt / H 2 (a = 1)/ H + (a = 1) . such as electroplating. These types of cells are used for many metallurgical processes. In the case of corrosion.250 –0. Fe 2+ (a = 1) / Fe Table 1 Standard half-cell reduction potentials versus the normal hydrogen electrode Reaction Standard half-cell reduction potential vs.401 0. the Hall-Heroult aluminum smelting cell).000 –0. and the half-cell reaction is: 2 H + + 2 e− = H 2 (Eq 14) Galvanic versus Electrochemical Cells When reactions in a cell occur spontaneously in the direction dictated by the open-circuit potential of a cell that is positive ( Erxn > 0) .. such as charging batteries.771 0.14 / Stainless Steels for Design Engineers the normal hydrogen electrode (NHE).

that is.401 + 0. if the only pertinent reactions were Eq 2 and 3.447 − 0. Similarly.624 V (vs. is discussed in Chapter 3. At room temperature (298 K). NHE Fig. Consider.401 + 0.227 − 0. Figure 1 (with electrode Reactions 2 and 3) can be viewed as an idealized equivalent cell for this situation. If this is positive. cathode. Because a spontaneous reaction requires Erxn to be positive. assuming a Fe2+ activity of 10−6 (this is an arbitrary value but is usually taken to represent a low ion concentration).059 pH V vs. 2 H + + 2 e− → H 2 (Eq 15) (Eq 17) and its reduction potential is (using the definition of pH): 0 EH + / H = EH + / H − 2 2 Here.059 pOH = 0. that the locations of anode(s) and cathode(s) on the iron surface cannot be identified with ease. for example. The rate of corrosion. which is in most cases determined by corrosion kinetics. This is indicated by the region shaded in gray in Fig. however. Eq 12 can be written by assuming unit activity for water and unit activity coefficient for OH−: EO 2 / OH – ing to Eq 13. this means that corrosion (due to iron dissolution to Fe2+ and oxygen reduction) is possible when the line representing EO2/OH− (Eq 15) lies above the line representing EFe / Fe (Eq 16). a case of iron in aerated water. 1 atm oxygen partial pressure. is determined by evaluating Erxn. 4 Reduction potential versus pH for iron and (a) oxygen gas reduction and (b) hydrogen ion reduction . Hydrogen reduction is another possible cathode reaction in water: 2+ = 0. which.059(14 − pH ) = 1. whether a system consisting of anode.0295 log(aFe 2+) = –0. pOH = –log COH− and pH + pOH = 14. It should be noted. the iron dissolution Reaction 2 will have a reduction potential accord- RT PH2 ln 2 nF aH+ (Eq 18) = 0 − 0. becomes at room temperature (using Table 1 for the standard potential): EFe 2+ /Fe = −0. NHE) (Eq 16) Figure 4(a) shows a schematic plot of the two reduction potentials (Eq 15 and 16) versus pH. 4(a).059 pH V (vs. the following definition of pH has been used: pH = –log CH+.Chapter 2: Corrosion Theory / 15 Corrosion Tendency The tendency to corrode. and electrolyte can react thermodynamically. NHE) . then there is thermodynamically a possibility for corrosion. and using Table 1.

pH = 14. Source: Ref 7 . (a) Schematic matching Eq 19 to 21 in text to lines. the following chemical reactions will have to be considered (the pH dependency of these reactions is listed next to them [Ref 7] and since they are not electrochemical. 5 Pourbaix diagram for iron. and they will result in horizontal lines (Fig. The following pH-independent electrochemical reactions need to be considered. pH = 1. several electrochemical and chemical reactions need to be considered when constructing these types of diagrams.810 − 0. 5a): Fe 2+ + 2 e− → Fe. it is noteworthy that hydrogen ions are able to cause corrosion only under relatively low pH conditions. Fig. In Fig. In reality.0591 log aHFeO– 2 ( ) (Eq 20b) ( ) (Eq 19a) The following electrochemical reactions will depend on pH and thus will be sloped depending on this dependence (Fig. pH = 6. (b) Actual complete diagram.613 – (1/3) log(a Fe3+ ) (Eq 19c) The Construction of Pourbaix Diagrams Figures 4(a) and (b) are types of phase diagrams that show the stable phases in an area bounded by pH and potential. 5a).65 − 0. the regions where iron is stable are denoted as immunity (corresponding to immunity from corrosion). − Fe(OH)2 = HFeO 2 +H + . 5a). they will appear as vertical lines (see lines 19a to 19c in Fig. In the case of iron.0295 log aFe 2+ HFeO 2− + H 2 O = Fe ( OH 3 + 2e− .447 + 0. 4(a) and (b).16 / Stainless Steels for Design Engineers Figure 4(b) shows the condition in which corrosion under deaerated conditions (due to iron dissolution to Fe2+ and hydrogen ion reduction) is possible as a gray shaded region. 3 ( ) (Eq 20a) ) EFe(OH) / HFeO2– = −0. Each reaction is represented by a line. When comparing these two figures. they are evaluated from the equilibrium constants): Fe 2 + + 2 H 2 O = Fe(OH )2 + 2 H + . EFe 2+ /Fe = −0. whereas oxygen gas is able to corrode iron in the entire pH range.5 log aFe 2 + Since these are independent of potential.30 + log aHFeO− 2 ( ) (Eq 19b) Fe 3+ + 3H 2 O = Fe(OH)3 +3H + .

W. Fontana. When chromium is added to iron as an alloying element.A.J. D. If iron would be an anode and the tendency to corrode were to be evaluated.. this means that the reduction potential for this assumed cathode lies below any reduction potential of iron. Jones. 6 (Eq 21d) Pourbaix diagram for chromium in water. Wiley.1773 pH − 0. 5(a). The ionic activity was previously arbitrarily set at 10–6. if the reduction potential of the assumed cathode was at point C. Finally.. it forms Cr2O3 over a significantly large region that is of relevance to pH values in water solutions. EFe(OH) 3 / Fe 2+ ) = 1. Faulkner. These types of diagrams are called Pourbaix diagrams. Corrosion and Corrosion Control: An Introduction to Corrosion Science and Engineering. 1996 3. In fact any Fe2+ ions present could plate as iron. Revie. Since Cr2O3 is protective. 3rd ed.H. for example. Eq 15 and 18 (Ref 8). EFe(OH) 2 / Fe ) = −0.. and hence under these conditions iron is immune (since Erxn is negative).G.0591 log aFe 2+ ( ) (Eq 21c) Fe(OH)2 + H 2 O = Fe(OH)3 + H + + e− . Source: Ref 8 = 0. M.495 − 0.0470 − 0. It can be seen that both the oxygen gas reduction reaction and hydrogen ion reduction are able to cause corrosion through the entire pH region.0886 pH 2 + 0. Figure 5(b) shows the Pourbaix diagram for iron overlaid with the common cathode reactions in water. Figure 6 shows the Pourbaix diagram for chromium (Ref 8). Corrosion Engineering. but this means that it also protects the iron alloy due to the properties of Cr2O3. This is the basic design principle behind iron-chromium-based stainless steels. 2 EHFeO. Fe-OH corrosion products are generally not passivating.271 − 0. McGraw-Hill. 2nd ed. one can readily label the regions depending on what iron species increasing pH favors. Unfortunately. Prentice Hall. in A in Fig. it corrodes selectively due to its low reduction potential. corrosion would occur. If this point were to be. 2001 2. it prevents further corrosion. On the other hand. H.0295 log aHFeO– 2 ( ) (Eq 21b) Fe 2+ + 3H 2 O = Fe ( OH 3 + 3H + + e− . Iron or carbon steel alloys are therefore not particularly corrosion resistant in water solutions.R. but from the Pourbaix diagram it can be seen that changes in ion activity do not have dramatic effects on the boundaries. then there is a tendency to dissolve iron to Fe2+ since Erxn is positive. Wiley. but when oxides or hydroxides are formed there is a possibility that this product could form a solid protective layer that kinetically hinders further corrosion. 3rd ed. resulting in Fe(OH)3.Chapter 2: Corrosion Theory / 17 Fe + 2H 2 O = Fe ( OH 2 + 2H + + 2e− ./Fe = 0.0591 pH (Eq 21a) Fe + 2H 2 O = HFeO − + 3H + + 2e− . Principles and Prevention of Corrosion.057 − 0. 1986 . if the reduction potential of the assumed cathode reaction were to lie in point B. REFERENCES 1. Uhlig and R.0591 pH For the pH-dependent reactions (chemical and electrochemical). 2nd ed. While chromium oxidizes even more readily than iron. A. 1985 4. then the reduction potential for a possible cathode reaction would be placed on this diagram. Bard and L. Electrochemical Methods: Fundamentals and Applications. EFe(OH) 3 /Fe(OH)2 Fig..

2001.18 / Stainless Steels for Design Engineers 5. CASTI Publishing. 59 8. Atlas of Electrochemical Equilibria in Aqueous Solutions. p. Testing.. 1974 . Inc.. ASM Handbook. Corrosion Control. 71st ed. 1996.D. ASM International. Handbook of Chemistry and Physics. Pourbaix. Bradford. S.A. Covino Jr. p 41 SELECTED REFERENCE • M. Prentice Hall. 2nd ed.... D. S. Principles and Prevention of Corrosion. Ed. NACE.A. CRC Press.S. 2003 6. Vol 13A. Corrosion: Fundamentals. Cramer and B. and Protection.. Jones. 1991 7. 2nd ed.

www. Source: Ref 1 .485* A* Fe).12 25.485).485).9 8.6 7. McGuire. Fe2+/Fe. the moles of dissolved iron are given as a function of time as N = i* t/(2* 95. respectively. respectively.Mo/3. MFe and Fe are molar mass and density of iron. which in the case of iron loss becomes m = N* MFe = MFe* i * t/(2* 95.22 23. the penetration due to dissolution of element i becomes: r= j t ⋅ Mi ni ⋅ F ⋅ ρ (Eq 1) Introduction Consider the differential aeration cell discussed in the Chapter 2 on corrosion theory. and the magnitude of this current is determined by Table 1 Penetration rates for a current of 1 µA/cm2 (mpy) Alloy Element/oxidation state Density.9 7.41 0. or thickness reduction r.Stainless Steels for Design Engineers Michael F.Ni/2 Fe/2.92 25. i/A is often replaced by j. and molar mass of element i.Ni/2 Fe/2.97 27. the ratio of Mi /ni is computed as an equivalent weight (EW) according to: EW = 1 fi n ∑ Mi i (Eq 2) where fi.46 0. ni.asminternational. This chapter deals with corrosion kinetics. p 19-25 DOI: 10. mpy Fe 304 321 309 316 430 446 20Cb3 Fe/2 Fe/2. Because n = 2 and F = 95. which was introduced in Chapter 2: nNF = it.50 25.Cr/3. which is defined as current density and has the units amperes/square meters.41 0. Fe/ O2/OH–.41 0. and Mi are the weight fraction.41 0. the amount of corroded (dissolved) iron is determined by the current i.1361/ssde2008p019 Copyright © 2008 ASM International® All rights reserved. valence.485 C per mole electrons. 2Fe (S) + O2 + – 2H2O → 2Fe2+ + 4OH .Cr/3. Here. therefore. Erxn = EO / OH – EFe / Fe is positive. that is.9 7. which in the case of iron becomes r = MFe* i* t/(2* 95. Practically. the rate at which corrosion reactions occur is the most important consideration.Ni/2.Mo/3 Fe/2.7 7. this can be readily converted to lost mass m.Ni/2 Fe/2.0 7.13 24. which allows us to understand the rates of corrosion.Cr/3.41 0.) per year. g/cm3 EW(a) Penetration rate. resulting in iron dissolution and consumption of oxygen gas according to the net reaction. A general equation of – 2+ 2 The penetration rates for iron and various stainless steels are listed in Table 1 (Ref 1) in units of mils (0. The magnitude of this current will determine the rate or iron dissolution according to Faraday’s law.Cr/3. As stated.Cr/3 Fe/2.001 in.30 24. If the thermodynamic conditions favor electrochemical corrosion of iron.39 (a) Equivalent weight. It is often the thickness loss (referred to as penetration per unit time) that is useful.42 0. In practice.98 0.87 7.Cr/3. In the case of alloys. or mpy.62 25. then a net corrosion current i will CHAPTER 3 Corrosion Kinetics Summary CORROSION INVOLVES chemical reactions with equilibrium that is known through thermodynamics.Cr/3 Fe/2.Cu/1 7.

the cathode and anode potentials deviate from the half-cell potentials.20 / Stainless Steels for Design Engineers 0 EFe 2+ /Fe = EFe 2+ /Fe − 4 RT ⎛ ( aFe ) ⎞ ln ⎜ ⎟ 4 F ⎝ aFe 2+ ⎠ Schematic illustration of a differential aeration cell involving iron dissolution. These involve: (a) electrode reactions at the cathode and anode. a net current passes through it).i terms are the exchange current densities and represent the equally large cathode and anode currents at equilibrium (zero overpotential) at the electrodes. as such. Similarly. which are defined by the deviation from the equilibrium half-cell potentials. as would be expected in a galvanic cell. at the anode the overpotential is positive. The exchange current densities are a measure of the electrocatalytic ability of the surface to promote/demote the electrode charge transfer reactions. thus producing a net anodic current ia.. and (c) conduction of electrons from the anode to the cathode. (2) ion conduction. (b) conduction of ions in the electrolyte. for the cathode. that is. Ref 2 is recommended): CO (0. (3) electron conduction Fig. Effectively. the overpotential reduces the activation energy for the electrode Reactions 3 and 4. the cathode and anode reactions are: O 2 + 2H 2 O + 4e − → 4 OH − (Eq 3) ja = jc = (Eq 5) and ⎛ (1 − α )nF ηa ⎞ ia = j0 . t ) ⎛ αnF ηc ⎞ ic exp ⎜ − = j 0 . The other two kinetic processes are discussed briefly in this chapter. ηa = Eanode – EFe 2 + Fe. they can vary over many orders of magnitude depending on the surface chemistry and structure and on electrode reaction.a exp ⎜ ⎟ Aa RT ⎝ ⎠ (Eq 6) and 2 Fe ( s ) → 2 Fe 2 + + 4 e− (Eq 4) The Nernst equation predicts an open circuit potential of Erxn = EO / OH – EFe / Fe where – 2+ 2 EO 2 /OH – = EO 0 2 /OH – 4 ⎛ ⎞ RT ⎜ aOH – ⎟ − ln 4 F ⎜ aH O PO ⎟ ⎝ 2 2⎠ ( ) and where the jo. Kinetic steps: (1) electrode reactions.c 2 Ac C O* RT ⎟ ⎝ ⎠ 2 The Butler-Volmer Equation For the case study 2Fe (S) + O2 + 2H2O → 2Fe2+ + 4OH–.e. The corrosion potential is determined by the reaction potential (which was discussed in Chapter 2) and the kinetics of the various steps involved in completing the electrochemical circuit depicted in Fig. The polarization is quantified as overpotentials . ηc = Ecathode – EO2 / OH and for the anode. 1 the corrosion potential. the relation between each electrode current/current density and overpotential is given by the following equations (for a thorough derivation of the current overpotential equation. which results in electrons that are favored to be removed from the solution and transferred into the electrode. 1. and the electrode states are then defined as being polarized. the overpotential is negative. The α-terms are fractions that define the amount to which the . When a cell is not under open circuit (i. If the magnitudes of cathode and anode polarization are large. The conduction of electrons is generally not a problem in stainless steels because the corroding metal (iron) and scale (Cr2O3) provide an easy path for electrons. In the case of a reduction reaction at a cathode. resulting in a net cathodic current ic at this electrode. and driving an electrode toward a lower potential drives electrons from the electrode into the solution. such as Reaction 3.

t ) 2 CO* 2 stands for the ratio of oxygen gas concentration at the electrode/electrolyte interface and the concentration in the bulk. be coupled to the steady-state flux of diffusive oxygen supply through a boundary layer δ. the corrosion current can. t )) 2 2 2 jcorr = (Eq 7) δ (Eq 12) C O* 2 Combining Eq 11 and 12. the flux of an ion i under an electric field φ across a distance L. Eq 7 and 8 would both result in a linear dependence of the overpotentials versus log jcorr: ηc = β c log j0 .a (Eq 10) The ionic transport in the electrolyte phase. when the oxygen concentration is actually zero at the interface.3RT/(αnF) and βa = 2. through Faraday’s law.a 2 (Eq 8) CO * 2 (Eq 13) Tafel Regime: Electrode-Kinetics Control. Eq 7 can be written: ηc = β c log j 0 . they are often taken as 0. They do not have to be the same for the anode and the cathode. icorr = ia = ic. As a limiting case. Migration and Ionic Diffusion and ηa = β a log jcorr − β a log j0 . If the cathode and anode areas are assumed to be equal. the term: CO (0. The concentration terms represent the ratios between the reactant concentration at the electrode/electrolyte interface and bulk. If the electrode charge transfer reactions are rate limiting. the depletion of oxygen will lead toward a zero oxygen concentration at the In an electrolyte with many different ions. the supply of oxygen to the reaction site would be rapid enough to maintain a concentration at the electrode close to that of the bulk. t ) 2 electrode.c jcorr ⎛ j ⎞ + β c log ⎜ 1 − corr ⎟ ji ⎠ ⎝ (Eq 14) The slower the diffusion (small d). When a net corrosion current flows. In Eq 7. an ion current through an area A can be computed by multiplying Eq 15 with zi * A and summing the contribution from all ions: i = FA∑ zi Di + ∂Ci + ( x ) ∂x + F2A RT . In this case. this ratio for the anode would be close to unity because the reactant is iron itself.5. t ) = 1− jcorr jl and j ηa = β a log corr j0 .Chapter 3: Corrosion Kinetics / 21 activation energies are lowered. can be shown to be: J i = − Di ∂ci zi F Δφ − Dc ∂x RT i i L (Eq 15) Mass Transfer Control. one obtains: CO (0. the corresponding equation would be: * DO nF (CO − CO (0.c − β c log jcorr (Eq 9) Thus. then jcorr = ja = jc and Eq 5 and 6 can be rewritten (using βc = 2. If the electrode reaction kinetics are very fast. but due to the uncertainty in evaluating them. and the rate of cathode reaction will depend on how rapidly oxygen molecules diffuse to the electrode/electrolyte interface.c jcorr + β c log CO (0. and no concentration gradient would be expected as a result of the corrosion reactions. which could deviate from unity as a result of consumption/production of species at the interface. This limiting case current is called the limiting current (iL or jL) and can be expressed as: jcorr = jl = * DO nFCO 2 2 δ (Eq 11) In a nonlimiting case. the lower the limiting current and thus a larger contribution from the mass-transfer-dependent second term on the overpotential. sufficiently far away from the interface.3RT/ ((1 α)nF) as: ηc = β c log j 0 . In an iron-based alloy.

as a case study.000 3.. Strictly speaking.447 − 0. a steel corroding under deaerated conditions. 2. to close the circuit.0295 log aFe 2+ + ηa = −0.c jcorr The resistivities of some test solutions are shown in Table 2.c jcorr ⎛ j ⎞ + β c log ⎜ 1 − corr ⎟ ji ⎠ ⎝ (Eq 21) Because the first term is important only at the regions near the electrodes (where consumption/creation of species occur). Consider. The cathode and anode reactions. the electrolyte resistance can be computed as: ⎛ F2A ⎞ Relectrolyte = L / ⎜ ∑ zi 2Ci Di ⎠ ⎟ ⎝ RT (Eq 18) Now.22 / Stainless Steels for Design Engineers × ∑ zi 2Ci Di Δφ / L (Eq 16) and the respective equations describing the overpotentials will be: ηc = β c log j 0 .000 10. the current in the majority region of the electrolyte can be estimated as: i≅ F A ∑ zi 2Ci Di Δφ / L RT 2 and ηa = β a log jcorr j0 .059pH + β c log ⎛ j ⎞ + β c log ⎜ 1 − corr ⎟ ji ⎠ ⎝ Mixed Potential Theory and Polarization Diagrams Viewing the electrochemical cell as an electrical circuit.624 + β a log jcorr j0 . ohm-cm Natural Seawater Fresh (tap) water adjusted with seawater Fresh (tap) water adjusted with seawater Fresh (tap) water adjusted with seawater Deionized water adjusted with fresh (tap) water . Kirchoff’s law can be used to design a so-called polarization diagram. are: 2 H + + 2 e− → H 2 (Eq 19) (Eq 23) Eanode = −0..a (Eq 22) (Eq 17) Using Ohm’s law (R = U/i). in a water solution. the potentials of anode and cathode when current is flowing are in each case the equilibrium potential plus overpotential. respectively. Assume that the pH is such that a passive layer does not form (see the discussion of Pourbaix diagrams in Chapter 2). as shown in Fig.000 Fig. Fe ( s ) → Fe 2 + + 2 e− (Eq 20) Table 2 Test solution Test solution resistivity Ratio by volume Resistivity. 28:1 68:l 950:1 21:10 25 500 1. 2 Schematic polarization diagram . that is: 0 Ecathode = EH+ / H − 2 RT PH2 ln 2 + ηc nF aH+ j0 .a (Eq 24) ( ) A polarization diagram is now constructed by plotting the anode and cathode potentials versus log jcorr. = 0 − 0.

The anode polarization is linear with decade current as predicted by Eq 24 because the overpotential has only a Tafel regime and no mass transfer dependence. In an active (nonpassive) alloy. Effect on Polarization Diagrams. The overall mixed potential of the surface would be at a corrosion potential Ecorr. the exchange current densities (jo. the cathode polarization deviates from the Tafel behavior as a result of the effect of the mass transfer (hydrogen ion supply). A schematic polarization diagram is shown in Fig. 1 does not have a macroscopic anode and cathode. Once the passive layer is formed and offers protection against further dissolution. 3 Corrosion rate and the effect of (a) Tafel slope and (b) exchange current density . which would result in an increase in the limiting current.c and jo. 3. epitaxial to the surface. and in the lack of more detailed knowledge.e.Chapter 3: Corrosion Kinetics / 23 the potential drop across the electrolyte needs to be included.. the corrosion current resulting from the cell depends on the equilibrium half-cell potentials (Ecathode and Eanode). in many cases. The effect of the electrolyte resistance has been ignored. the potential-decade current relation drops to lower currents. On the other hand. dependent on the limiting current in Eq 23. The building up is actually a selective dissolution of iron. that is. When a passive alloy is anodically polarized. Figure 3 shows schematically how decreasing any of the Tafel slopes and increasing an exchange current density increases the corrosion rate.a). it initially behaves like an active alloy (i. which simply equals icorr * Relectrolyte (the electrolyte resistance is evaluated from Eq 18). The polarization diagram for a passive alloy is quite different from those discussed for active alloys. Figure 4 shows the effect of increased mass transfer. this results in an increased corrosion current up to a point. it was identified through the Pourbaix diagrams that there were conditions under which an alloy could be passive. which readily forms a Cr2O3 scale. In effect. The structure is reported to be a nanocrystalline spinel. the Tafel slopes (βc and βa). It is noteworthy that the cell shown in Fig. A schematic of a typical polarization curve is shown in Fig. defined in Fig. Passivation Theory. with a Tafel slope. At some high enough Fig. The grain size may decrease with increasing chromium content. the range of pH and other conditions under which this would occur has been increased thanks to the chromium content. as the passive layer is building up). Researchers (Ref 3) have reported that the constituents of the passive film are alpha Cr2O3 and Cr(OH)3nH2O. a passive layer constituted of adsorbed molecules or thin oxide/hydroxide layers decreases the corrosion current. which causes a greater remaining surface concentration of chromium and other alloying elements. In general. however. etc. This protection by chromium requires a threshold level of 11 to 12% chromium. and any limiting current density (jl). the cathode and anode areas are assumed to be equal.. In Chapter 2. This happens at potentials beyond the passivation potential Epp. this term can be neglected. 5. 2. corrosion current is where the two polarization curves intersect. Different microscopic regions on the surface are assumed to act as cathodes and anodes. In the case of stainless steels.

and the metal becomes active again. At pH = pH2. for example. Finally. 5 Schematic of a passive anode polarization curve Fig. and the passive properties are not utilized.c jcorr (Eq 25) 0 Ecathode = EH+ / H − 2 This will result in a straight line as shown in Fig. it was found that increasing the transport rate of cathode reactants through agitation. the passive layer breaks down. which will be shifted vertically depending on the pH. at pH = pH3. increased agitation in the electrolyte. In the discussion of active anode polarization. 6 in deaerated acidic solutions with different pH. would increase the corrosion rate up to a point but beyond that have no further effect (see Fig. for example. In the case of a passive/active behavior. This could occur with some stainless steels exposed to a very strong alkali solution. an alloy that exhibits the behavior shown in Fig. and low rates of uniform corrosion occur. on the other hand. 4). for example. Beyond the dashed line. If mass transfer limitations due to hydrogen ion supply are neglected. a low-corrosion current is obtained as a result of intersection at the passive regime. Using a similar argument. This is the benevolent case when stainless steel is correctly matched to the environment. the alloy is clearly not optimal because intersection occurs in the active regime. 6 Effect of cathode polarization . the readers can themselves deduce the effects of cathode exchange current density and Tafel slopes. such as with concentrated hydrochloric acid.24 / Stainless Steels for Design Engineers polarization level. 6. This is what occurs when a reducing acid is too strong for a given stainless steel. increasing the limiting current would have no further effect Fig. 4 Effect of increasing the limiting current by. The dashed circles indicate the intersection between anode and cathode polarization curves that would yield the corrosion current. this region is called the transpassive regime. Consider. the resulting corrosion current is again high as a result of intersection occurring at the transpassive region. The design of a structure involving a passive metal should aim at forming a corrosion cell in which the cathode polarization curve intersects the anodic one in the passive regime.059pH + β c log j0 . then the cathode polarization is given by: RT PH2 ln 2 + ηc nF aH+ = 0 − 0. At a sufficiently high pH (= pH1). the effect of mass Fig.

This is the case for jL3. Electrochem. The depleted layer can extend a number of microns in depth and would seriously degrade corrosion resistance if not removed (Ref 4). it is likely that there will be corrosion corresponding to the higher current. What is often called passivation is actually a cleaning process in which contaminants. This is the actual passivation. This is the procedure that should be performed on the oxides formed during welding if full corrosion resistance is to be restored. Maurer. Increasing mass transport. but assuming there are defects present. Simply removing the oxide through mechanical means leaves a chromium-depleted layer that corrodes more readily than is expected of the alloy. M. increasing jl from 1 to 2). It should be noted that there are several intercepts possible (both in the active and passive regime). 7 Effect of mass transport transport is somewhat different.A.J. results initially in an increased corrosion current (e. which happens to be called passivation. Principles and Prevention of Corrosion. are removed from the surface. 2nd ed. During the production of stainless steel. This is then followed by a straight nitric acid immersion. Grubb and J. which ensures complete passivity. NACE International. Jones.. “Corrosion of the Microstructure of a 6% Molybdenum Stainless Steel with Performance in a Highly Aggressive Test Medium.. called pickling. J. achieving passivity takes on several forms. Faulkner.g. Vol 150. 1995 ..R. 2003. such as tramp iron.Chapter 3: Corrosion Kinetics / 25 Fig. 1996 2. p 583–594 4. removes by dissolution both the oxide layer and the chromium-depleted layer below the oxide formed during annealing. Proc. Critical Factors in Focalized Corrosion.. Prentice Hall. the iron removal is really a chemical cleaning operation. Wiley. 7. Electrochemical Methods: Fundamentals and Applications. In the normal use of stainless steel. Soc.P. 2001 3. REFERENCES 1. which does not allow passivation.. after a final anneal another version of passivation is carried out. 2nd ed. A. D. Dilute nitric acid is an excellent vehicle to achieve this. results in a drop in the current because now the only corrosion potential possible is at the intersection in the passive regime. however. Increasing the limiting current beyond the knee corresponding to Epp. Bard and L. Ryan et al. such that the limiting current increases. The oxide from annealing in air is dissolved by a strong mixture of nitric and hydrofluoric acids.” paper 300 presented at Corrosion 95. This treatment. as shown schematically in Fig. This medium has the additional benefit of forming a passive film on an active stainless surface.

chromium. The important difference in the case of stainless steel is that chromium is still a minor constituent. . Yet. it is the composition of the alloy in contact with the specific environment at any microscopic point that determines the corrosion resistance of that particular point. The environment can be too aggressive to allow passivity to be maintained either by being too reducing. The metallurgy and processing of a particular grade are designed to provide passivity in a given environment.asminternational. www. at which uniform corrosion occurs at a very low rate. never more than 30% by weight. Stainless. unlike noble metals such as gold. as with some acid media. Stainless steels are comWhen all parts of a corroding surface have equal access to the corroding atmosphere and the structure of the corroding metal is relatively uniform. does not obtain its excellent corrosion resistance from inertness. by virtue of their passive behavior. How much chromium there is and how uniformly it is distributed have a profound effect on corrosion resistance by virtue of its ability to concentrate into the surface film. such as pitting and crevice corrosion. Stainless steel alloys may have many constituent elements and many thermodynamically possible phases. it is the reactivity of chromium that allows the surface layer of corrosion product to become sufficiently adherent and impenetrable. McGuire. Instead. The former is called dissolution in the active state. they show very low rates of uniform corrosion in many environments. sometimes little more than 10%. This resistance to corrosion is called passive behavior or passivity. Thus. it can also experience various debilitating forms of localized corrosion. form similar layers and also exhibit passivity. Intelligent design and knowledge of the environmental variables for a stainless steel component ensure that the alloy is used in the passive state. p 27-56 DOI: 10. and none of these are necessarily uniform in their composition.1361/ssde2008p027 Copyright © 2008 ASM International® All rights reserved. such as aluminum and titanium.Stainless Steels for Design Engineers Michael F. which effectively stops further corrosion by isolating the base material from the environment. This chapter explores the behavior of stainless steel in media that promote uniform corrosion and the various mechanisms of localized corrosion. while the latter is termed transpassive dissolution. while stainless steels can be made to be essentially immune to corrosion in many environments. the most recognized characteristic of stainless steel is corrosion resistance. Uniform Corrosion Introduction To most designers. Stainless steels are materials of choice because. Other metals. which stem from the failure of this passive CHAPTER 4 Corrosion Types Summary STAINLESS STEEL is unusual among alloy systems in that its corrosion resistance derives from the passivating ability of a minor constituent. plex in their behavior because the influence of processing and alloying variables changes the ability of this layer to form and remain stable in the face of aggressive environments. so that passivating species cannot form or by being too oxidizing so that the oxidized species that normally affect passivity are no longer stable. a uniform thinning of the material is expected. The behavior of stainless steel is further affected by its microstructural complexity.

Environmental Variables Influencing Uniform Corrosion The corrosion of stainless steels is usually the result of contact with an electrolyte. these anions accelerate uniform corrosion. Therefore. the rate-limiting transport through the passive film will not be affected. such as acetic and formic. corrosion in stainless steel are atmospheric and marine environments and chemical environments such as sulfuric acid. Halides are well known for this effect. The main consideration is normally ionic transpor tthrough the passive film. allowing a complex set of partial electrochemical reactions. or acetates. Certain anions have strong effects in media through their well-known. increasing the flow rate of a corrosive fluid does not automatically accelerate corrosion. or transpassive. strong bases.28 / Stainless Steels for Design Engineers Among the important media with which we encounter uniform. rendering it active. These anions seem to intervene in the adsorption of the hydroxyl ions. Of the physical variables of the environment. Fig. both of which act through their influence on the stability of the passive film. The reduction of concentration gradients can be beneficial against localized Fig. accelerated uniform corrosion. This is typically done with 10 to 20% hot sulfuric acid or a mixture of hydrofluoric and nitric acids. such as amines. formates. Increasing temperature may speed the formation of the passive film when thermodynamic conditions are favorable. Anions that form soluble complexes with elements in stainless. while in neutral media they may result in localized corrosion. disruption of the passive film. 1 Reduction potential versus pH for iron and (a) oxygen gas reduction and (b) hydrogen ionreduction . Access to passivating species. if not well understood. In acid media. such as oxygen. can also disrupt the stability of the passive film and thus promote active corrosion. is important in establishing and maintaining passivity. The corrosion rate depends on the current exchanged between the negative and positive electrode (anode and cathode). which may occur sequentially or concurrently. These may be on a macroscopic or microscopic level. and organic acids. pas- sive. 1 illustrates the effect of redox potential on a solution. but sulfides are active. phosphoric acid. nitric acid. Increased diffusion of reacting species in the liquid will normally accelerate the partial reactions. Pickling is an example of controlled. but in general one expects increasing temperature to increase corrosive attack. but acceptably controlled. which after all is what makes stainless so effective against corrosion. The chemical parameters that influence the media with respect to uniform corrosion rate are the acidity and the oxidation-reduction (redox) potential of the electrolytic medium. it should be obvious that temperature is paramount since all the reactions are thermally activated. but if passivity is stable.

as in welds. Increases in chromium can also be seen to lower the current density in the passive region. But. film forms is the subject of ongoing debate. Increased flow rate in a fluid medium is deleterious if it induces mechanical damage to the passive film by erosion. we can say that corrosion resistance is a function of composition rather than structure. molybdenum. but it should be remembered in examining uniform corrosion because corrosion will cease to be uniform when composition becomes nonuniform. So. and the corrosion resistance in that region is diminished. This is consistent with the lower dissolution of noncontributing elements required to achieve a critical surface chromium concentration. but it should be apparent that the success of a stainless steel to a given flow condition will depend mainly on its ability to form and re-form its passive film. These are complex mechanisms. severalnanometer-thick. mainly as inclusions since they have diminishingly small solubility at room temperature. thick corrosion product films. stress-free surface. This is manifest in alloy performance as a reduction in the uniform corrosion rate in a given medium. From an electrochemical point of view. thinner passive films are more protective than thicker films among stainless alloys. In any event. which have soft. as contrasted to copper and aluminum alloys. it combines with chromium. the surrounding matrix is depleted of both chromium and molybdenum. Nitrogen also is effective when in solid solution in austenite but can precipitate as a chromium nitride under certain conditions and cause depletion of the remaining matrix. is also smaller as chromium content increases (Fig. An example is molybdenum. which if elevated by increasing temperature can cause debilitating. they can be present in supersaturation. composition-altering precipitation. This threshold has been attributed most convincingly to the minimum chromium content that permits chromium atoms on surface sites to be linked by adsorbed oxygen atoms (Ref 2). or cavitation. At high temperatures after solidification. If this happens at relatively low temperatures. The tenacity of the thin passive films on stainless (and titanium) make these alloys quite resistant to flow-accelerated corrosion. ready to precipitate as inclusions that alter local composition. of course. Researchers (Ref 1) have reported that the constituents of the passive film are alpha Cr2O3 and Cr(OH)3nH2O. stainless steels are seldom homogeneous or at thermodynamic equilibrium. but we do know that it is enriched in chromium. The foremost element is. which is obviously a great enhancer of corrosion resistance when in solid solution. On an undisrupted. which it promotes. The role of molybdenum is less clear. local composition does quite precisely determine corrosion resistance. 2).Chapter 4: Corrosion Types / 29 corrosion. The structure is reported to be a nanocrystalline and epitaxial to the surface. such as chromium. Somewhat counterintuitively. and nickel. The grain size may decrease with increasing chromium content. The tendency of carbon and nitrogen to form precipitates is controlled by diffusion rates. we must quickly add the qualifiers to this statement. however. This protection by chromium requires a threshold level of 11 to 12% chromium. The even more slowly diffusing substitutional alloying elements. The same element may under some conditions not be in solution and have a contrary effect. chromium. as measured during polarization. As a generalization. have strong tendencies to form phases that disturb their uniformity in the austenite or ferrite matrix in which they are intended to work. abrasion. The observed action of molybdenum is to greatly reduce the critical current density required for passivation. this is explained as a manifestation of the stability of the Cr(OH)3 nH2O. and flow can bring to the surface an increased supply of passivating species. the mechanism by which this thin. any discussion of the influence of alloying element on corrosion resistance of a phase like austenite or ferrite must recognize that alloying elements exert their effect when they are in solution in that phase. This is also seen as accelerating the formation of the passive films and as increasing the resistance of the alloy to depassivation at . This becomes more important to localized corrosion. When it precipitates as a con- stituent of sigma phase. as discussed later. and that it is thinner for higher chromium alloys. Local structure and composition are paramount. Then. The critical current density j. Impurities such as oxygen and sulfur are usually present. The compositional material variables that influence uniform corrosion are not exactly the same as those that will be seen to influence localized corrosion. Material Variables Stainless steels have a great variety of alloying elements and microstructures.

A summary of the known major alloying effects in acidic chloride media is shown in Fig. The action of molybdenum as an alloying element is complicated by the fact that molybdate ions are known to impede pit growth as a separate effect from their action within the alloy matrix (Ref 4). and to a degree that cannot be explained by their presence in the film. nickel. however. Nickel does not actively help passive film formation and can actually hinder film stability in highly acidic/oxidizing environments. This also may be the result of the stronger bond between nickel and chromium reducing the anodic dissolution rate of the alloy by permitting the anodic enriching of the surface by selection iron dissolution. Nitrogen. 4 (Ref 7). While nickel and copper provide no benefit to the stability of the passive film once it is formed. which would promote a surface richer in chromium (Ref 3). Pure molybdenum is itself not passive. Its action does not appear to be via a product of reaction. From this. it can be seen that chromium. Molybdenum and nitrogen act both to enhance the enrichment of Fig. The role of molybdenum is not to enrich in the passive film itself. Copper has a similarly complicated effect. Its potency is far more than its presence can take into account. Note the alloying composition is measured by a crevice corrosion index (CCI). Nickel also lowers the critical current density for passivation without contributing directly to the passive film’s stability. while chromium. appears to be more like molybdenum in its effect. molybdenum. 3 in acidic chlorides. 2 Schematic illustration of polarization behavior for a passive alloy with and without pitting occurring Influence of alloying element on corrosion rate as explained by the effect on polarization. it seems to reduce the dissolution rate of elements other than iron. copper. and nitrogen all assist in the active region. both nitrogen and molybdenum do. Source: Ref 7 chromium in the passive layer and to decrease active dissolution of noniron alloying elements. which is discussed in the section Localized Corrosion. An example of the influence of these alloying elements on the uniform corrosion rate of stainless steels in a sodium chloride/carbon dioxide environment is shown in Fig. molybdenum. This may then relate to their thermodynamic action within the alloy itself. 3 Fig. although it can be found in the film. Instead. Alloying elements provide benefits in the part of the chart where they appear (Ref 6). and nitrogen expand the region of passivity and diminish the corrosion current. . with copper ions gettering sulfide ions and redepositing as metallic copper (Ref 5).Source: Ref 6 lower pH. 4 Influence of alloying elements on uniform corrosion rate in 20% sodium chloride solution with carbon dioxide pressure of 20 MPa.30 / Stainless Steels for Design Engineers Fig. thereby promoting both the formation and stability of the passive film.

and it is highly recommended that it be used. although other empirical relationships exist or can be generated. Corrosion rate legend: 0. which contains a “Steel Professional Tool. Free sites tend to promote proprietary alloys.0 mm/yr (material not recommended). 6. the alloy chemistry is chosen such that the passive-active behavior favors corrosion in the passive regime.1–1 mm/yr (useful in certain circumstances). 2.1 mm/yr (corrosion resistant). 5 Corrosion table for stainless steels and titanium in sulfuric acid plus copper sulfate. These tables are supplemented by isocorrosion diagrams such as that shown in Fig. 1. The serious engineer will consult multiple sources and unbiased sources before making alloy decisions. Source: Ref 8.” refer mostly to corrosion in these aqueous solutions. as these charts suggest. we need to discuss some of the more commonly encountered severe environments. This information is available to guide the designer in selecting appropriate steels for various environments. None is more accessible than the Web site of Outukumpu. Straight 16% chromium grades such as 430 fare poorly. Sulfuric Acid.asp (Ref 8). while it is useful and necessary to have these experimental data. Because the influence of alloying element varies with environment. These data can be obtained from a number of sources. “Corrosion Kinetics. Many of the isocorrosion charts in this book are reprinted from this source. see source for interpretation of data. < 0. http://www. Courtesy of Outukumpu Stainless Unfortunately. it is also helpful to understand the peculiarities of some of the major alloy-environment pairings. such as the National Association of Corrosion Engineers (NACE) and ASM Handbook volumes. in which the slow thinning rate of the chosen alloy can be determined through the mixed potential theory and polarization diagrams. In the case of stainless steels. The influence of alloying element is by no means the same in all environments. while the nickel-containing . it cannot be assumed that this relationship is true for other environments. > 1. Corrosion in Acids and Bases The examples discussed in Chapter 3.outokumpu.Chapter 4: Corrosion Types / 31 Fig. Figure 5 shows an example of one such table. 0.” a lookup table in which the corrosion rate of many stain- less steels in a great number of environments can be obtained. These diagrams show constant corrosion behavior under varying environmental conditions such as temperature and solution composition. Stainless steels require more than a minimum amount of alloying to resist sulfuric acid. The corrosion rate of the various stainless steels in the myriad possible environments has been measured in probably all practical cases.

The corrosion behavior of sulfuric acid varies greatly with concentration. nickel-molybdenum-copper-bearing stainless steels begin to exhibit useful corrosion resistance. the solution begins to show oxidizing behavior. C-276. If passivity cannot be established. As acid concentration increases beyond 50%. In the 96 to 100% sulfuric acid concentration range. etc. especially in sulfuric acid-manufacturing . the solutions become more corrosive.) can provide acceptable corrosion rates. At about 50% acid. sulfuric is a classic reducing acid. and oxidation- Fig.32 / Stainless Steels for Design Engineers Fig. AL-6XN. and even these alloys are restricted to use at near ambient temperatures. Alloying with molybdenum is also very effective. the oxidizing character is quite pronounced. At acid concentrations above 80%. Figure 7 (Ref 9) shows the isocorrosion rate curves for several common alloys. increasing chromium content actually increases corrosion rate. Courtesy of Outukumpu Stainless 304 has more than an order of magnitude better corrosion rate in either dilute or concentrated sulfuric acid at ambient temperatures. It dissociates in water to create hydrated hydrogen ions (H3O+) that release hydrogen gas bubbles during the corrosion reaction. as is alloying with copper. At low concentrations.Source: Ref 8. and progressively more highly alloyed stainless steels are required to provide adequate corrosion resistance. 6 Isocorrosion curves for 17-12-2. carbon steel can be used to hold sulfuric acid at ambient temperatures. at elevated temperatures. Source: Ref 9 resistant high-chromium (type 310S) and highsilicon (MECS ZeCor UNS S38815 and Sandvik SX S32615) stainless steels are frequently used. although stainless steels provide better performance at elevated temperatures or if flow-erosion can occur.5 stainless steel and titanium in sulfuric acid plus copper sulfate. As the acid concentration increases. In the 93 to 98% sulfuric acid concentration range. only the most highly alloyed stainless alloys (alloy 20. 7 Isocorrosion rates of various stainless steels in sulfuric acid.

e. Studies (Ref 10) have shown that in sulfuric acid molybdenum is highly enriched in the passive film. Chromium additions . but reducing impurities such as halides have an extremely negative effect.Chapter 4: Corrosion Types / 33 Fig. The uniform corrosion rate in contaminated sulfuric acid may be more important than in pure acid since this represents a potentially likely failure mode because contamination is a constant hazard. Figure 8 shows the corrosion rate of various alloys in sulfuric acid contaminated with chlorides and iron. Highchromium stainless steels (i. act like aeration to diminish the corrosive attack. Hydrochloric acid is very destructive of the passive film on stainless. Oxidizing impurities.) Aeration has a major influence on corrosion rates because oxygen stabilizes the passive film. 8 Influence of alloying element on corrosion rate in contaminated sulfuric acid. This is a manifestation of selective dissolution of other elements in the matrix.mtiglobal. These researchers (Ref 11) found that the resistance to attack correlated to the alloy content by the formula shown. Their superiority in deaerated solutions is much less marked. Figures 9 and 10 show how isocorrosion rates vary with alloy and contamination level. An alloy like 304 is not suitable even in a deaerated 1% HCl solution at room temperature. Molybdenum-alloyed stainless has dramatically lower corrosion rates in aerated solutions than non-molybdenum-bearing alloys. type 310S) are among the very few materials that exhibit corrosion resistance in oleum. These effects are not linear and underscore the value of these for more information. and when molybdenum is an alloy. (See MTI Materials Selector Volume 3—Sulfuric Acid at www. 9 Isocorrosion curves for various alloys in sulfuric acid equipment. Sulfuric acid-containing dissolved sulfur trioxide is called oleum. chromium also is enriched. as the corrosion tables will show. and such solutions are often identified as sulfuric acid of greater than 100% concentration. Source: Ref 11 Fig. such as ferrous ions.

14) (Ref 8). 11 are only modestly helpful. This can be seen in Fig.34 / Stainless Steels for Design Engineers Fig. Courtesy of Outokumpu Stainless Fig. is deleterious in this case because it forms soluble compounds. molybdenum. This superiority appears above the azeotropic composition of about 67%. Figures 11 (Ref 8) and 12 (Ref 12) show how even the most highly alloyed grades can withstand only dilute concentrations and low temperatures.0%) beneficial. and copper is even better (Ref 8). Stainless steels are not good materials for contact with hydrochloric acid. This oxidizing acid behaves more like sulfuric acid in that simple iron-chromium alloys have only moderate resistance to uniform corrosion in them. which is a common commercial concentration. consequently. Phosphoric Acid. Nitric acid is strongly oxidizing. Silicon is unusual in that normal levels (0. 12 Isocorrosion curves for various stainless steels in hydrochloric acid.05%) or very high levels (4. while alloying with molybdenum and copper produces major improvements. When this is a possibility. which augments the true passive layer. The addition of molybdenum. resistance to lesser amounts of chlorides is important because of the possibility that an acidic environment may be contaminated with chlorides. This actually promotes the passive film formation. 15 for high-silicon austenitic stainless steels (Ref 13). High silicon levels contribute to a general protective silica surface layer in concentrated acid. In the commercial production of phosphoric acid. It is useful to keep carbon. as shown in Fig. in which alloys with increasing nickel (18-10) show clear benefits over a chromium-molybdenum alloy (18-2). which is the usual locus of attack. copper. which is so generally helpful. Figure 13 shows a correlation between alloy content and resistance to the general corrosion (GI) by sulfuric acid contaminated with hydrochloric acid (Ref 11). then proper alloy selection must guard against it. The low levels of silicon contents of these alloys are useful for their action in minimizing grain boundary segregation. with very low (0. while 904L with nickel.4 to 1. halide impurities may be present. and the added molybdenum in 317 (17-14-4) is better. silicon. while nickel. While a stainless steel vessel may not be intended to be used for hydrochloric acid. and molybdenum are more beneficial. in which . Source: Ref 12 Fig. 10 Isocorrosion curves for various alloys in sulfuric acid with chlorides Isocorrosion curves for austenitic AL-6XN (UNS N08367) and 904L (UNS N08394) stainless steels in hydrochloric acid. Source: Ref 8. and phosphorus as low as possible. 16. even low-chromium alloys remain passive at all concentrations at ambient temperature (see Fig.0 %) are worst.

Increasing chromium levels provide increased resistance. The weakly dissociating organic acids are normally not aggressive against stainless steels. . nickel is detrimental. Adding molybdenum and nickel does little to further improve performance as the underlying resistance is due to chromium. In strong bases. 15 Corrosion behavior of high-silicon alloys in concentrated nitric acid. chromium.Chapter 4: Corrosion Types / 35 Fig. The difficulty lies in the hightemperature solubility of nickel complexes and is best addressed by the use of ferritic or duplex alloys. copper. If halides are present in organic acids and liberated by contact with water. This phenomenon is also seen in the production of urea via the intermediary ammonium carbamate. the stainless steels are generally quite resistant to uniform corrosion. Figure 18 shows isocorrosion curves for sodium hydroxide (Ref 8). 17 (Ref 8). Courtesy of Outokumpu Stainless case alloys with higher molybdenum. Strong Bases. It should be noted that in formic acid. Courtesy of Outokumpu Stainless Fig. 13 Influence of alloy content on corrosion rate in hydrochloric acid Fig. Straight chromium (17%) alloys are usable at any concentration up to 50 °C. which does dissociate more strongly. as illustrated in Fig. Organic Acids. Attack when it does occur can be manifested as grain boundary attack. The exceptional dangerous environments are those that include high temperature and the presence of chloride contamination. 14 Isocorrosion curve for nitric acid. and nitrogen may be required. which could then become nonuniform. then pH and chloride concentration will govern the corrosive attack. Alloying with molybdenum seems to provide the greatest resistance to uniform corrosion in strong organic acids.

Source: Ref 8. Courtesy of Outokumpu Stainless In the pulp-and-paper industry. Courtesy of Outokumpu Stainless Fig.1 mm/yr for titanium and 17-12-2. Courtesy of Outokumpu Stainless Atmospheric corrosion is an example of uniform corrosion that occurs when a thin layer of water condenses on a metal surface and as such . 16 Isocorrosion curves in phosphoric acid: (a) 0. and ferritic or duplex alloys are preferred.36 / Stainless Steels for Design Engineers Fig. chemical pulping is called the kraft or sulfate process.5 stainless steel. (b) formic acid. nickel can be quite detrimental. 17 Isocorrosion curves in organic acids: (a) acetic acid. 18 Isocorrosion curves for various materials in sodium hydroxide. 19. (b) 0.1 mm/yr for various stainless steels. In the presence of sulfur. Atmospheric Corrosion Fig. SCC. This can be seen in Fig. which shows a 26-1 (chromiummolybdenum) alloy significantly outperforming higher alloys that contain nickel and molybdenum (Ref 12). This again is caused by the solubility of nickel complexes formed in the presence of sulfur-containing compounds. stress corrosion cracking.

F is the faraday constant. Without washing or the natural rinsing by rain. and therefore has two contradicting effects of temperature. M is molar mass. Source: Ref 12 depends on humidity. the rules of corrosion of aerated aqueous solutions are followed by stainless with respect to atmospheric corrosion. they are found far inland. The most deleterious impurity in the atmosphere for stainless is the chloride ion. and ρ is the density). The difficulty is accurately estimating the solution that constitutes the aqueous solution. red rust stain will occur. and in relatively pure atmospheres. which means that for a given corrosion current. 19 Corrosion rates of various alloys in simulated evaporator liquid. and the reason that certain structural features assume the roles of cathode and anode can be used to categorize and exemplify different cases. In the case of stainless steels. In localized corrosion. The access of oxygen to the bare metal limits the cathode reduction reaction rate. while identifiable. sulfur dioxide impurities in the atmosphere react with water to form sulfuric acid. temperature. where coastal conditions prevail throughout. the corrosion rate is negligible due the protective nature of the oxide. the anode and cathode are clearly identifiable locations. In general. Borne from oceans by normal climatological processes. and PREN is an index to pitting resistance. surface chloride concentrations can become very high. unrinsed architectural purposes.. localized corrosion involves a large-area cathode and a small-area anode. the tendency for corrosion was introduced as a positive value for an . Localized Corrosion Localized corrosion is in general more damaging from a structural integrity point of view than uniform corrosion since the corrosion current is limited to a small area and the penetration distance is large. Much experience has shown that if coastal and road salt effects are minimal. the corrosion current density at the anode is very large. In steels. they are also seen in high concentrations from road salts.Chapter 4: Corrosion Types / 37 Fig. Interestingly. unlike uniform corrosion. n is valence. Pitting is a form of localized corrosion. “Corrosion Kinetics. from distinct macroscopic components or parts to microstructural features. zero pitting) (Ref 14). If the same alloy is used in an unrinsed coastal environment. the cathode and anodes. much research has been done that has shown that a pitting resistance equivalent number (PREN) of 25 is necessary for freedom from corrosion (i. the corrosion products are (a) an outermost layer of porous rust (FeOOH) characterized by low water content but easy access to oxygen and (b) an inner layer of magnetite (Fe2O3) in which pores are filled with water. then 18% chromium alloys such as 304 experience such negligible visible corrosion that they can be used for exposed. The rate of corrosion measured as defined in Chapter 3. In Chapter 2. However. and other atmospheric conditions. temperature increases the exchange current density and transport properties and thus the kinetic rates involved in corrosion. increasing temperatures may reduce the concentration of dissolved oxygen in the electrolyte and eventually will dry the surface and thus limit the electrochemical corrosion due to the access to an electrolyte. can vary across scales. Thus. This is the corrosion product from metastable and possibly stable pitting. to a wide enough region in terms of pH (see Pourbaix diagrams in Chapter 2) that atmospheric corrosion can in effect be prevented. Chlorides are pervasive. These concepts are examined in the next section. t is time in seconds. that is. which tends to dissolve the protective oxide. the passive region is extended due to chromium. This contrasts to a requirement of about PREN 35 to resist pitting in seawater. In Japan. In many colder climates.” as dissolution r of element i as r= j t ⋅ Mi ni ⋅ F ⋅ρ where j is current density. On the other hand.e. Often.

Resulting corrosion currents are shown in Fig.250 + 0. in our case a corrosion reaction.. is dependent on the polarization behavior. Different stainless steel alloys have minor differences when passive. Erxn is obtained as: 0 Erxn = Erxn − α α α RT ⎛ p1 1 p2 2 p3 3 ... in which a metal is partially immersed in water. and occurs when two metals/alloys are in contact that have elements in them that are dissimilar in the electromotive force (emf) series (see Chapter 2) and there is an electrolyte present. 20(b). and thus anodic iron dissolution is slow. where oxygen is readily replenished. pi and ri are the concentrations of reactant and products.197 V The distance at which this occurs is balanced by being large enough to limit the rate of oxygen transport but not too long to be strongly influenced by ion transport that is needed to complete the electrochemical cell. as discussed in Chapter 3. Dissimilar Metals and Differential Aeration Cells The case of dissimilar metals and differential aeration cells is perhaps more important in active alloys than for stainless steels. For example. the more significant occurrence of this type of cell occurs when a crevice. Sufficiently far away from the surface. A classic example is the use of carbon steel fasteners for joining stainless sheets. For example. such as at locations 1 and 2. surface defects or scratches) or has broken down as a result of. Fe2+ ions remain and .38 / Stainless Steels for Design Engineers electrochemical cell potential (Erxn) corresponding to a spontaneous electrochemical reaction forming a galvanic cell. This type of degradation is called waterline corrosion. Near the surface of the water.. Less-noble alloys. exists. This gives rise to a differential aeration cell. and αi and βi are the numbers that are needed to balance the reaction stoichiometrically. Transport distance of oxygen increases with depth. but if the environment is such that one alloy is active while another is passive. there is thermodynamically a tendency for an electrochemical reaction. In many cases. In effect. for example.447 = 0. Crevice Corrosion. if nickel and iron pipes are connected and water flows though them containing some traces of Ni2+ ions.. ⎠ arises in which access of oxygen is not the same to different areas of a sample. consider Fig. ⎞ ln ⎜ β β β ⎟ nF ⎝ r1 1 r2 2 r3 3 . These regions become anodes where the following reaction occurs: 2Fe (s) → 2Fe 2+ + 4e − (Eq 4) RT ⎛ aFe 2 + ⎞ ln ⎜ ⎟ 2 F ⎝ aNi 2 + ⎠ (Eq 2) In this case. This region assumes the role of the cathode. this results in that the cathode reaction: O 2 + 2H 2 O + 4e − → 4 OH − (Eq 3) (Eq 1) Here. can fail rapidly if coupled to stainless. passivation is likely to be fast. such as carbon steel. The rate of corrosion. the corrosion tendency is primarily caused by the first two terms on the right side of Eq 2. As a result of the geometry. the limiting current would then vary with depth. 20b. This is normally important for alloys joined to stainless that are themselves less noble. and cathode polarization curves as a result of this are schematically plotted in Fig. which are generally passive. 20(a). In stainless. the dissimilarity in the standard half-cell reduction potentials: 0 0 ENi 2 + / Ni − EFe 2 + / Fe = − 0. if there are regions where passivation is incomplete (e. then: 0 0 Erxn = ENi 2 +/ Ni − EFe 2 +/ Fe − is limited from proceeding in some areas but not others. repassivation does not readily occur since oxygen transport is too slow. from whatever cause. then the galvanic differential could be harmfully large.g. and reactions within the crevice or pit cause the accumulation of iron ions by: 2Fe (s) → 2Fe 2+ + 4e − (Eq 5) This tendency is caused by the galvanic dissimilarity between the metals. respectively. Any time that Erxn is positive. and reaction 1 occurs. a situation The regions adjacent to the drop that maintained their passive layer and have access to oxygen act as cathodes where the oxygen reduction reaction takes place: O 2 + 2H 2 O + 4e − → 4 OH − (Eq 6) This reaction maintains an alkali solution. Cl− (see section on pitting).

(c) The presence of Cl– prevents repassivation. the reaction: 2Fe ( OH 2 + O 2 + H 2 O → 2Fe ( OH ) ) 3 (Eq 8) further consolidates the isolation of the pit and impedes the ingress of oxygen. Cl– migrates into the pit. such as if leaks of toxic materials were to result from perforation. At the outside. The greatest contributions to this field have been electrochemical studies. Its consequences may be only cosmetic. all pitting is crevice corrosion” (Ref 15). 20 Schematic illustration of (a) sample partially immersed in water. and localized corrosion is the local loss of passivity. Whether the consequences are major or not. This causes the following reaction: Fe 2+ + 2H 2 O + 2Cl − → Fe ( OH 2 + 2HCl ) (Eq 7) which has several consequences: (a) Hydrochloric acid further acidifies the pit and increases the rate of iron dissolution since decreasing pH increases cathode half-cell potential. Pitting corrosion is important to designers because it is corrosion under conditions at which corrosion may not have been anticipated. Stainless steels are designed to be passive. and as a result the pit grows in depth. which is still the subject . (b) resulting polarization behavior for two different passivating alloys (A and B polarization curves) enrich in the water-filled pit. This is to say that the electrochemistry of cavities such as pits and crevices is quite similar and has been well modeled. “In a sense. Thus. however. What do we know for certain about pitting? We know quite a lot. it is always undesirable. which increases corrosion rate (see polarization diagram construction in Chapter 3. Pitting Corrosion Pitting corrosion is the most intensely studied and debated form of corrosion of stainless steel. such as on a building or appliance facade. “Corrosion Kinetics.Chapter 4: Corrosion Types / 39 Fig.”) (b) The formation of porous Fe(OH)2 further helps to isolate the pit. These same tools. and good design allows it to be avoided. or potentially catastrophic. have been much less successful in clarifying the mechanism of pit initiation. really. to maintain charge neutrality. thereby separating anode and cathode regions in the differential aeration cell. the dissolution rate becomes autocatalytic. it is both a materials selection and an environmental control problem. The local environment within pits has been sufficiently measured and correlated with cavity geometry that some experts can say. Experts now conclude that since the early 1970s the local chemistry of pitting has been understood (Ref15). The tools of electrochemistry have been especially successful in elucidating the mechanism involved in pit growth and pit stability (Ref 16). As a result of increased acidification.

The dissolution parameters..4 0. 0. A key point to understand when considering inclusions as initiation sites for pitting is that inclusions are not simply inert debris but precipitates that are seeking thermodynamic equilibrium with the steel in which they have previously been dissolved. Their effect on sulfur is similar to that on oxygen. .. 0. 0..02 1. 1. 1600 °C Stainless steel.022 0..15 0..05 9. What are the typical inclusions in stainless steel? Inclusions in steel are normally the residue of normal deoxidation and desulfurization taken during steel refining usually done in an argon oxygen decarburization (AOD). 0. which most authorities (Ref 18) have concluded are associated in some way with pit initiation. called metastable pitting. In the absence of inclusions.01 1.24 0.45 1. cause the generation of iron ions and local pH reduction. Aluminum is a powerful deoxidant in carbon steel but is less effective in stainless.. but that this process occurs in both the liquid and solid states. . Different researchers assume dissolution of the inclusion.05 . which if left in solution would later precipitate as low-meltingpoint iron compounds that would make the steel fragile and unworkable at high temperatures. 0. 8 1. That it carries over significantly into the solid state means that diffusion has a major role in determining if equilib- Table 1 Typical values of activities and activity coefficients in liquid steels: activities in the 1 mass % solution: ai = fi .. small spikes in corrosion current occur.3 1. depend on variables not of the inclusion chemistry but of the matrix composition.93 0.01 0..006 0. .0 0.45 0. stable or not. After removal of the carbon.0 . To the extent these remain concentrated in a small volume.. while others continue to grow as stable pits. %i Metal Al C Mn P S Si Ti H N O Cr Ni Carbon steel..02 0. Pitting events..372 0... which is in keeping with the reduction in dissolution of the matrix that these alloying elements confer. The question of what causes the initial dissolution that causes both stable and metastable pits focuses on inclusions. they will affect subsequent events. ....45 0. and the potential at which pitting occurs is the beginning of the transpassive regime.45 1....17 ... These spikes measure local dissolution.32 0... The reactions in stainless steel differ thermodynamically from those in carbon steel because of the presence of high chromium concentrations..0 8. . .0 0. 1600 °C %i fi ai %i fi ai . The potential at which stable pitting occurs is the pitting potential. As potential increases. .. The dissolution during metastable pitting is located at the matrix-inclusion interface.93 ..053 0.046 0. .1 0.40 / Stainless Steels for Design Engineers of debate...05 0.345 0.6 .06 0.. while metastable pitting can occur at much lower potentials.0 0.05 1. Inclusions in stainless steel are typically oxides and sulfides..49 0.. .025 0. Figure 21 depicts a polarization curve for stainless steel in a chloride-containing solution..47 .66 0. Fig..5 . It also alters the efficiency of deoxidizing elements. possibly indicating that the root causes are more metallurgical than electrochemical. 3. The bottom line is that oxygen and sulfur are generally removed by silicon/manganese deoxidation. metastable pitting events are not noted. 1.3 1... making them more soluble..85 .. This lowers the activity of oxygen and sulfur. .007 0. .01 0. as measured by current transients. while titanium becomes a stronger deoxidizer in stainless... the subsequent objective is to remove or render less harmful the dissolved oxygen and sulfur. as Table 1 indicates (Ref 19).0 .21 ..97 . Some such sites complete their dissolution and repassivate.. Pitting occurs in the zone in which passivity is expected. 21 Schematic of a passive anode polarization curve Inclusions. 18 0.. while others assume dissolution of the matrix. 0.97 17.. notably molybdenum and nitrogen levels (Ref 17).05 0..

some manganese sulfides can precipitate during solidification interdendritically. its activity) makes it more favorable. In austenitic steels. to form. such as silicate present from the deoxidation process. Manganese is a strong sulfide former. That equilibrium is easily achieved in the molten state. the supersaturation of sulfides is pushed to a lower temperature. Such alloys have elevated resistance to pit initiation. which results in the most thermodynamically favorable species. manganese is generally present at a level of around 1. but achieved more slowly once the material has solidified. The solubility. In a well-deoxidized and well-stirred melt and with a basic slag. but it can act indirectly by reducing a small amount of Ca2+ in the slag. which is high in the liquid state. Oxide inclusions also are common.5% as a deoxidant and as a substitute for some nickel. We will see that they do not. causing its growth. and often does. Manganese sulfide precipitates as an inclusion as a function of manganese and sulfur concentrations and temperature. cerium. as seen in Fig. calcium. and titanium. Otherwise. They are formed as the products of the reactions of silicon and manganese with dissolved oxygen. low-manganese alloys can be free of manganese sulfide inclusions even at somewhat high sulfur levels. and other rare earth metals (REMs). also at amounts in the neighborhood of 100 ppm depending on deoxidation . The greatest amount of sulfur removal is obtained by the addition of cerium or other REMs. These include aluminum. These reactive elements typically form oxysulfide particles in the melt that may be trapped in the slag before metal solidification. Inclusions form not only in the molten metal but also in the solidified metal. nucleate on a preexisting inclusion. manganese sulfide. calcium dissolved in the metal will react with dissolved sulfur to form calcium sulfide. Elements more effective than silicon and manganese are now in use for deoxidation and desulfurization. and it is the main agent used to tie up sulfur. The thermodynamics of the reactions determine at any time how much oxygen can be dissolved in the steel at equilibrium. It may. forming low-melting oxysulfides that diminish hot workability. 22 Pseudo-binary-phase diagram for iron and sulfur at 1. Titanium can sequester some sulfur as titanium carbosulfide precipitates. 22. is less effective directly in desulfurization. while a potent deoxidizer.Chapter 4: Corrosion Types / 41 rium reactions occur and whether they go to completion. Aluminum. Oxygen is normally dissolved in solidifying stainless steel. Sulfur is a very surface active impurity that assists in weld penetration in stainless by virtue of its effect on weld pool circulation. Thus. while normal alloys with less than 100 ppm of sulfur form their inclusions after solidification. lowering chromium depletion around manganese sulfide/chromium sulfide inclusions. at which lower diffusion rates hinder or prevent the precipitation. in which diffusion is very rapid. where it precipitates as an oxide of silicon or manganese to the extent that these are locally present or of chromium when its local concentration (or more properly. decreases on solidification. allowing the formation of calcium sulfide.8% manganese and 18% chromium the liquid. The action of calcium is notable. The inclusions in the solid state grow by the diffusion of oxygen to inclusion sites. Only resulfurized free-machining stainless steels have sufficient sulfur to precipitate manganese sulfide in Fig. An inclusion formed in the molten metal does not cause alloy depletion around it. which will be incorporated into the slag phase. Lower manganese levels also thermodynamically reduce the chromium sulfide coprecipitation in inclusions. it is a detrimental impurity. These oxides are often the nucleation sites for manganese sulfide inclusions. One that forms or grows in the solid state does cause depletion of the elements that are precipitating. The distinction is important because precipitation in the liquid state permits rapid diffusion. usually in the form of the alloy mischmetal. At high sulfur and manganese concentrations. If manganese is lowered to very low levels.

wrought material has better pitting resistance than cast or welded material. Thus. if the alloy solidifies in a ferritic mode (FA. which. ferrite forming first on solidification as opposed to austenite first. This causes existing inclusions to grow and new ones to nucleate. as is more the case for alloys solidifying in an austenitic mode. This precipitation is similar to that which carbon undergoes in stainless. However. FA. Inclusions that precipitate from the liquid. The inclusion growth necessarily depletes the surrounding region of reactants. Solidification can also occur in a mixed ferriticaustenitic mode. AF. 23 and 24 (Ref 23). except carbon is generally not supersaturated until below 1200 °C at the highest in most alloys. Thus.. AF). as is almost always the case with commercial alloys. The ratio of chromium and chromium-like elements molybdenum and silicon to nickel and nickel-like elements carbon. 24 Influence of sulfur level on pitting resistance of welds without homogenizing anneal. allowing depleted zones around the inclusion in the reduced dimension to be more rapidly homogenized during annealing. These zones are altered in size and shape by thermomechanical processing in wrought alloys but exist fairly undistorted in welds. manganese. manganese determines the mode of solidification. and thermal cycles of steel production are rarely sufficient for the equilibrium to be attained. Pitting resistance is still affected to a degree by alloy depletion due to solidification segregation. precipitation continues since sulfur and oxygen are decreasingly soluble with temperature. Hot rolling and cold rolling followed by annealing elongate manganese sulfide inclusions and flatten them. do little to diminish the chromium content around them. pitting resistance is lowered proportionately to the sulfur level (Ref 22). 23 Influence of sulfur level on pitting resistance of unannealed welds for different solidification modes. i. to virtually nil at room temperature. and have a small effect on lowering pitting resistance. But precipitate they must. nitrogen. As the alloy cools after solidification. inclusions grow via diffusion of oxygen and sulfur. ferrite forming first on solidification as opposed to austenite first. in which case each microstructural component behaves according to the chart. as interstitials. greater than 1μ. Inclusions based on oxygen and sulfur formed in the liquid or during solidification are relatively large. Thus. and chromium (Ref 20). and there is little negative effect from solidification segregation.e. diffuse much more rapidly than the silicon or manganese with which they have the greatest thermodynamic affinity. silicon. It Fig.42 / Stainless Steels for Design Engineers methods. whereas sulfur and oxygen are normally near saturation even at freezing or almost always when the solidifying ferrite transforms to austenite. Source: Ref 23 Fig. Inclusions thus formed are nonequilibrium in nature. inclusions can grow with chromium substituting for either silicon or manganese as the precipitating partner for oxygen and sulfur. more sulfide precipitation happens in the solid state. are at equilibrium with the surrounding matrix by virtue of the faster diffusion in liquids. The chromium enrichment of such inclusions and corresponding chromium depletion of surrounding regions has been measured (Ref 21) and corresponds to the depletion seen next to chromium carbide precipitates at grain boundaries in sensitized alloys. Source: Ref 23 . even if the silicon and manganese in the vicinity of their inclusion are exhausted. as is shown in Fig.

However. Pitting Resistance. Such precipitates have a much lower tendency to allow chromium to join in the precipitation since the higher the temperature of precipitation the more that diffusion allows the more favorable reaction to occur. Long-term annealing of welds has shown that sufficient time and temperature to achieve some rehomogenization the alloy result in better pitting resistance (Ref 24).Chapter 4: Corrosion Types / 43 can also be altered by freezing rate. and their correlation is shown in Fig. The initiation of pitting is also affected by stress and inclusion orientation (Ref 25). Faster cooling favors austenitic solidification. which. 22 indicates that the precipitation of sulfides that cause chromium depletion occurs in delta ferrite on freezing when sulfur exceeds 0. Titanium. which is often added to form carbides and nitrides.3 % Mo (Eq 10) For duplex alloys. For austenitic alloys: PREN = % Cr + 3. since it is clear that the surface is not homogeneous. Whenever fast-diffusing elements such as oxygen. and if the depletion zone shape and size are favorable.3 % Mo + 16 % N (Eq 11) These equations are useful. Pitting has been extensively correlated with environment and compositional variables. The influence of stress was to cause cracking at otherwise unfavorably shaped inclusions. These hypotheses deal with how a passive film on a homogeneous surface could break down. if . for instance. which are about 10.007% and in austenite when sulfur exceeds 0. This fundamentally is due to the high ratios of the diffusivities of oxygen and sulfur to chromium. these hypotheses are not necessary to explain the behavior of everyday stainless steels.000 and 680. if approximate. carbon. which have a strong affinity for chromium and a solubility that decreases strongly with temperature. neither of which matches the bulk composition: PREN = % Cr + 3. these mechanisms presuppose a stainless steel surface that is homogeneously passive and try to explain the observed inhomogeneous behavior of the passive film. which unfortunately have abundant inclusions and chemical inhomogeneities capable of locally diminishing the integrity of the passive film. Metastable pitting is diminished by the presence of these elements. The most well-known and useful correlations are between the PREN and the critical pitting temperature (CPT) and by extension to the pitting potential. especially with regard to the passive film. also forms sulfides and oxides more strongly than manganese and therefore does so at higher temperatures. This will be relevant to later discussions of stress corrosion cracking (SCC). More research in understanding the exact nature of the inhomogeneity of stainless steel surfaces is necessary for a complete understanding of pit nucleation and therefore prevention. Examination of the decreasing solubility of sulfur in stainless in Fig. are present in steel. There have been numerous proposed mechanisms for the breakdown of a passive film in chloride-containing media. 25 (Ref 26) They do not include tungsten. Certain other types of inclusions/precipitates are less harmful in this regard. The low chromium around inclusions is a sufficient condition for the local dissolution measured as metastable pitting.3 % Mo + 30 % N (Eq 9) For ferritic alloys. then stable pitting would ensue. these have been summarized in other publications (Ref 23). which have two phases. approaching that of the wrought alloy. and nitrogen. They include: • Adsorption of chloride ions • Penetration of the passive film by chloride ions • Film breakdown by electrostriction • Formation of stable metallic chlorides • Coalescence of cationic vacancies • Random localized thinning of the passive film • Local variations in the composition of the corrosive medium By and large.01% in manganese/silicon deoxidized steels. which then provided a crevice capable of sustaining stable pitting. Rare earths also behave the same way. Oxygen behaves in a parallel manner and is usually present in sufficient quantities. sulfur. about 0. their precipitation will result in some degree of chromium depletion around the precipitation site because chromium diffuses too slowly to be replenished.003%. to cause the same phenomenon. respectively. which the researchers correlated to the dimensions of the inclusion-derived cavity being able to sustain a sufficiently low pH due to iron dissolution to maintain stable pitting. which hold no nitrogen in solution: PREN = % Cr + 3.

It should also be noted that the critical PREN values vary with crystallographic structure. and improve pitting resistance (Ref 29). How is a metallic sample suspended in a solution without creating any crevices and without exposure at the liquid-gas interface? The development of the flooded gasket technique (used in ASTM G150) was a milestone. Research on very pure sputtered films of iron-chromium alloys have demonstrated that both titanium and niobium in solution diminish active dissolution. which seldom varies enough to have a visible effect but has been shown when in colossal supersaturation to have a factor of about 10. 25 Variation of critical pitting temperature with pitting resistance equivalent number (PREN) of austenitic steels in water plus 6% FeCle. so welded alloys have different CPTs for the same PREN (Fig. carbon. do not contribute to increasing the resistance to the onset of pitting. Ferritic alloys require somewhat lower PREN values to exhibit similar pitting resistance as austenitic alloys of somewhat higher PREN. They neglect carbon. 26) (Ref 13).44 / Stainless Steels for Design Engineers Fig. and the 3. Nitrogen seems to act by concentrating at the passive film-alloy interface rather than by buffering the solution by ammonia formation.1N NaCl. Pitting in a given medium capable of causing pitting does not occur below a temperature that is characteristic of the medium and the material. In most practical cases. which is primarily a function of local chromium content. has half the effectiveness of molybdenum. Molybdenum and nickel thus seem to bolster local chromium content in the passive film.5% NaCl solution of the ASTM G 150. which has been proposed (Ref 36). not unlike nitrogen. While the PREN approximates the pitting resistance of an alloy. While pitting is of great theoretical and practical interest. It also does not include the negative influence of elements such as sulfur. with which they form compounds. which are beneficial against uniform corrosion and which slow the growth of pits by this same action. with the myriad exceptions of stress state. but it also has some problems—most notably the potential for dilution of the test solution. It is noteworthy that the elements copper and nickel. FeCl3 testing benefits from the fact that the solution creates a reproducible positive potential. especially during prolonged testing. microstructure. the . This is another manifestation of pitting initiated by the local stability of the passive film. there is a standard test by which the CPT is measured. allows the ECPT. another interstitial that it resembles in solution thermodynamically (Ref 27). 26 Differential variation of critical pitting temperature of several stainless steel alloys for unwelded wrought and welded material. assist repassivation. and nitrogen. there are significant problems in actually conducting good tests. The latter. sulfur. These equations are all-other-thingsbeing-equal equations and are useful for gross alloy behavior predictions. etc. The most commonly used test media are the unacidified 10% FeCl3. these elements are not found in solution because of their affinity for oxygen. Monitoring of the electrochemical potential during the test is considered mandatory by most researchers. surface finish. if modified to 0. the equations cannot deal with inhomogeneity issues. Likewise. Source: Ref 13 present. which is used in the ASTM G 48 practice B. Source: Ref 26 Fig.

given as the crevice corrosion resistance equivalent number (CCREN). 27 (Ref 11). Materials are characterized as having a critical depassivation pH. and the aggressiveness of the environment can reach a threshold at which active corrosion occurs. alloy selection. such as nickel. but this presumed effect is not strong enough to be reflected in this actual behavior Eq 12 represents. and critical crevice corrosion temperature (CCT). The interior reactions become increasingly anodic. shown in Fig. so it is a greater danger in that sense. The countermeasures against crevice corrosion are cathodic protection. It is especially the inhibition of the cathodic reaction inside the crevice by the dearth of oxygen. then active corrosion will begin within the crevice. Crevice corrosion occurs at lower temperature than pitting in the same environments. If crevice conditions are such that the reactions over time allow the pH to be reduced to this level. design. under faulted coatings. It is logical to think that alloying the elements that contribute to lowering the critical current density for passivation and the uniform corrosion rate. etc. Designing to avoid crevices should include maximizing the volume of unavoidable crevices. metastable or stable. Crevice Corrosion In the case of pitting. passive film stability seems to be the critical factor rather than corrosion rate after initiation. maintenance. engineering flow to enhance transport in and out of crevices. The relationship between the alloy content. is similar to that of PREN (PI) to CPT except for the molybdenum factor being more important: Cl = %Cr + 4. although it is generally acknowledged that austenitic steels perform better than ferritic steels in the absence of molybdenum. the geometry that makes up the pit is essential in creating the differential aeration cell and to cause the autocatalytic dissolution process. under bolt or screw heads. The dissolution of iron during passivation itself as well as the differential oxygen cell created by the crevice contribute to the process. a geometry that retains and acidifies water is already present in crevices in different types of structures such as gaskets. Thus. Crevice corrosion occurs because zones have restricted access of reactants and restricted exit of corrosion products.1%Mo + 27%N (Eq 12) Since a crevice has a preexisting favorable geometry for pit growth. would reduce the creation of the reactants that start the crevice corrosion process. 27 Variation of critical crevice corrosion temperature with alloy content . while the situation exterior to the crevice is safely passive.Chapter 4: Corrosion Types / 45 electrochemical pitting potential. Crevices are thus incubators for corrosion triggered by metastable pitting events. In many cases. and Fig. can initiate ongoing crevice corrosion. any pitting event. of course. which sets up a more aggressive environment within the crevice than without. of lower alloys such as 304 to be measured (Ref 30). Preventing Crevice Corrosion. and.

biofouling will create crevice sites. such as marine exposures. When a stainless steel is heat treated. primarily chromium. Gasketed joints are another severe crevice location. whereas the larger cathodes reduce oxygen. In these situations. 28 Schematic illustration of sensitization due to chromium-rich precipitates that deplete adjacent regions of chromium. resulting in a localized corrosion along grain boundaries. Thus. Figure 29 shows a TTT (timetemperature-transformation) curve for precipitation of the unwanted phase. Figure 29 shows schematically the temperature versus time due to welding and the resulting sensitization. the smaller chromium-depleted nonpassive anodes dissolve. whereas far away from the weld (C) the temperature experienced is too low. 28. Cr)23C6. however. depending on the time-temperature history and precipitation kinetics of the unwanted phase. 29 Schematic illustration of how a heat treatment relates to sensitization due to precipitation kinetics. judicious use of very expensive. resulting in a depletion of chromium in the adjacent regions. TTT. Sensitization can occur at any temperature at which carbon is supersaturated in an alloy. a risk for sensitization. S32205 is a benchmark alloy of sorts. Welds are particularly vulnerable surface sites. there is. as shown in Fig. These phases tend to form at grain boundaries where nucleation is favored. crevices are almost impossible to eliminate. In the various grades of stainless steels. Current austenitic stainless steels have carbon levels of under 0. Any maintenance or design procedure that prevents formation of deposits is beneficial. highly corrosion resistant materials is justified. such as from shellfish and barnacles. and their usage should be curtailed to the minimum practical extent. grain boundary Fig. Sensitization/Grain Boundary Corrosion The maintenance of a passive layer in a wide range of pH conditions in stainless steels is dependent on the alloying elements. the chromiumdepleted regions near the grain boundaries are sensitized in that they behave as active anodes compared to the larger interior of the grains that are still passive. and design and operational controls to preclude the formation of deposits and the prompt removal of sludge and the like are necessary. Microscopic biofouling causes the special form of crevice corrosion called microbiologically influenced corrosion (MIC) discussed in a separate section). The use of smooth welded joints is thus generally preferred.46 / Stainless Steels for Design Engineers avoiding stagnation. It has just sufficient alloying to resist pitting in seawater.10% normally Fig. But in some situations. Near the weld (A). but it is susceptible to crevice corrosion. there is a risk that the unwanted phases may form. As a practical matter. In a more general consideration. deposition and fouling create crevice sites. An example of such a phase is chromium carbide (Fe. This fouling may be macroscopic. there are many intermetallic phases that are thermodynamically stable but kinetically slow to precipitate that are enriched in chromium. In an aerated corrosive environment. At location B. the time spent in the temperature region where precipitation occurs is too short. Any heat-treating or welding procedure of stainless steels should thus be tailored to avoid sensitization. so any combination of welds and crevices or crevices caused by poor weld geometry must be avoided. Austenitic. Threaded fasteners and joints represent severe crevices and should be avoided in aggressive environments if possible. or it may be microscopic. time-temperature-transformation . GB.

niobium. H is the heat of dissolution. There are a number of candidate elements. and the fast diffusion in the ferrite keeps austenite from becoming depleted. but the diffusion rates of chromium in austenite as so slow that it is impractical in most real cases. Duplex steels have a subtle near immunity to carbide sensitization. Effect of Alloying. Here.97 − 6780 T (Eq 13) log[ Nb][C ] = 4. and nickel promote carbide formation by increasing the thermodynamic activity of carbon and make alloys more susceptible. in which carbon is much less soluble but is much more mobile. thus aggravating sensitization. Thus. While they are typically low carbon anyway. However. Low-carbon grades avoid sensitization because they are not sufficiently supersaturated at temperatures at which carbon is mobile enough to diffuse to grain boundaries. but below about 500 °C diffusion of carbon is too slow for carbon to move to grain boundaries and cause the damaging combination with chromium that causes sensitization. Besides determining basic phase structure. no carbon will form chromium carbides under equilibrium conditions. The carbon in the martensite can precipitate and cause sensitization if reheated to the 300 to 700 °C region. Nitrogen lowers the tendency for carbide formation and slows sensitization. Fortunately. Annealing over 900 °C can put enough carbon in solution to cause sensitization even at the lowest carbon levels attainable in an AOD and even at the fastest possible quench rates. the carbides that do form do so at ferrite-austenite grain boundaries. The thermodynamic affinity tool can be used to prevent chromium carbide formation in another way. Another situation exists in ferritic stainless steels. The caveat with titanium is that it forms oxides. The supersaturation increases with decreasing temperature. The damaging chromium depletion caused by this very rapid precipitation can be undone by a simple rehomogenization anneal of the remaining chromium. the rapid formation of intermetallic phases at the ferrite-austenite interfaces can lead to a rapid loss of corrosion resistance and a severe loss of toughness if exposure to temperatures within the intermetallic precipitation range is not controlled.55 − 9350 T (Eq 14) These equations follow the form of the general equation for precipitation reactions: log[ M ][ X ] = A − H / RT (Eq 15) in which A is a constant. starving chromium of sufficient carbon to form damaging precipitates. It is possible to defeat the stabilization reactions by quenching the alloys from temperatures at which titanium carbide or niobium carbide is dissociated. silicon. tantalum. Decreasing grain size and therefore increasing grain boundary surface area decreases the amount of precipitate per unit area of grain boundary and therefore the amount of chromium depletion per unit area. Ferritic. This is a purely thermodynamic effect. the diffusivity and affinity for carbon of niobium and titanium make them the best for this purpose. sufficient quantities must be used to accommodate the prior formation of these phases. Of these. most prominently. Each forms stable carbides at much higher temperatures than chromium. and nitrides preferentially to carbides. heating to above 700 °C rehomogenizes the chromium and eliminates sensitization. leaving the austenite intact. R is the gas constant. If the amount of titanium or niobium is stoichiometrically sufficient. Those elements that reduce the tendency of chromium carbides to form also reduce the susceptibility to sensitization. The solubility products of these precipitation reactions are: log [Ti ][C ] = 2. and titanium. vanadium. and T is the absolute temperature. Cold work accelerates diffusion and makes precipitation more rapid. Niobium tends more toward carbide than nitride formation but is a weaker carbide former than titanium. chromium is consumed from the chromium-rich ferrite phase. If free carbon is . Their large grain boundary area keeps carbide concentration per unit area low. Martensitic steels are quenched as austenite to and through the Ms temperature without time for carbon to precipitate in austenite. Molybdenum. zirconium. sulfides. This is theoretically possible with austenitic alloys also.Chapter 4: Corrosion Types / 47 and under 0. Therefore.03% for low-carbon L grades. Introducing alloying elements that combine with carbon more strongly and rapidly than chromium can exhaust the supply of carbon available to precipitate as chromium carbide. normal grades sensitize below around 800 °C. Nonthermodynamic effects are those of austenite grain size and prior cold work. alloying plays a role in susceptibility to sensitization.

as in most prolonged arguments. Welding. a crevice. suggesting an appreciable electrochemical effect. no attempt is made to address an all-encompassing theory. this effectively precludes this chromium carbide precipitation in most cases. Intergranular corrosion sites. by what mechanism. This introduces us to what is perhaps the most controversial technical subject in all of stainless steel research. rather than the most thermodynamically favorable element. The latter is a zone that exists in alloys that have zones of chromium depletion. Stress corrosion cracking has always been among the most controversial subjects among metallurgists and electrochemists. cracks can be seen to initiate at surface defects and irregularities. Obviously. and region II. In stainless steels. Is the cracking zone locally softened. The debate centers on whether the critical mechanism is dissolution or fracture. but there is room for convergence. Such SRA treatments are typically in the sensitization temperature range for austenitic stainless steels. such as chromium. 30: region I. where pitting and breakdown of the passive layer occur. that no hypothesis is completely correct. Even then. transformed. SCC. elements of many may come into play.48 / Stainless Steels for Design Engineers left free in the matrix by quenching. Stress Corrosion Cracking The key cause for SCC is the cooperating effects of tensile stress and a corrosive environment. there is no general agreement on which type mechanism is the fundamental cause. in some cases. This can occur when a stabilized alloy such as 321 is welded. Corrosion Combined with Fatigue or Fracture Environmentally induced failure occurs when brittle failure under tensile mechanical loading occurs at a lower stress when a material is subjected to a corrosive environment than what would happen in a noncorrosive environment. In passive metals. This problem has nearly ceased to exist as modern 321 has low levels of carbon and nitrogen for economic reasons. 30 Zones of susceptibility to stress corrosion cracking . to a more brittle phase or embrittled by hydrogen? As of this writing. Stress lowers the anodic potential at which pitting occurs and permits metastable pits Fig. and even pure metals. construction code rules usually require that the carbon steel component be given a stress relief annealing (SRA) treatment. In stainless steel. which were thought to be more or less immune. which would be titanium or niobium. It is likely. Use of low-carbon or stabilized grades is necessary in such cases. In these situations. Many of the most severe problems of sensitization arise when stainless steels are welded to carbon or low-alloy steels. We will try to fairly set out what is known and agreed on as fact and then present researchers’ views in an unbiased manner. Such cases can be identified in most alloy systems. as are seen in sensitized material. locally hardened. where the protective layer is not fully developed. A zone away from the weld may experience a high enough temperature to put carbon into solution and then cool just rapidly enough to not form only the equilibrium titanium carbide but also Cr23C6 at grain boundaries. can also provide the conditions for SCC initiation. then on reheating it may form carbides with the most locally accessible favorable element. and if a fracture. The interrelationship between pits and SCC cracks has been studied (Ref 25). but since we concern ourselves only with stainless steel. Crack Initiation. also have had cases of SCC reported. use of the lowest allowable temperature SRA treatment for the shortest allowable time is preferred. causing the type of sensitization called knife-line attack. two sensitive potential regions for the occurrence of SCC have been identified and are shown in Fig. it must be agreed by all that the preponderant initiation site is a corrosion pit or.

which has been reported as between 25 and 50% of the yield strength in austenitic stainless steel. The ferritic steels.Chapter 4: Corrosion Types / 49 to become stable via the generation of cracks. and they vary in their degree of susceptibility to . while austenitic alloys begin their sensitivity above room temperature and increase in susceptibility with increasing temperature. ferritic. and that the mixed potential that arises because they are in intimate contact is outside the potential range for SCC on either phase. ferrite remains as a crack-arresting phase. SCC can occur in all types of stainless at room temperature. Rates of crack propagation are exponentially increased by increasing temperature. the sensitized grain boundaries themselves can be depleted of chromium to a degree they are not stainless and have a much less stable austenitic structure.. In environments of mixed chlorides and sulfides. The propagation path may be intergranular or transgranular. in which chloride ions can condense on the stressed steel and cause pitting and SCC. and overall rate limiting. martensitic. This has been seen in the SCC of austenitic stainless steel in swimming pool environments. Ferritic alloys. The crack propagation rate has been seen across a range of alloys to be linearly proportional to the average current density that alloy experiences when its surface is strained. Material Variables. This susceptibility increases with hardness. The crack growth gives off acoustic emissions as cracking steps occur. they have a plateau rate that is fairly constant until the stress level at which catastrophic failure occurs at very high propagation rates. Despite the controversy surrounding the mechanism of SCC in austenitic stainless steels. indicating that reactions at the crack tip are strain sensitive. These steps of growth are brittle and are seen as facets on fractographs with cleavages corresponding to crystallographic planes. Ferritic stainless steels of low and medium chromium are generally not susceptible to SCC. Crack growth is discontinuous with individual steps of growth many times the average rate. and embrittling heat treatments. molybdenum. They will crack at threshold stresses equal to 50% of yield strength. The most common example is that of sensitized 304 in high-temperature water or caustic media. by definition. there is almost complete agreement that SCC of body-centered cubic (bcc) stainless steels. and nickel. having their martensite start temperature Ms. The presence of α'( or high-temperature embrittlement also increases susceptibility. This fits with the resistance to SCC of wrought alloys with a lamellar structure and the lesser resistance of cast alloys that lack that structure. Duplex stainless steels have low susceptibility to SCC. which is similar to that seen with gaseous hydrogen embrittlement (HE).g. however. Martensitic stainless steels and martensitic precipitation hardened stainless steels are quite susceptible to SCC. should be considered martensitic for SCC purposes. and pH is simply a manifestation of HE. The temperature at which SCC is initiated ranges from ambient to under 100 °C for martensitic materials. A second explanation of the resistance of duplex alloys to SCC is that their two phases have different corrosion potentials. yield strength. have their maximum susceptibility in the same range as martensitic steels. Cracks propagate very slowly below specific certain stress intensity levels. but not necessarily the mechanism of cracking. showing almost no evidence of plastic deformation or dissolution. Austenitic stainless steels are the type of stainless steel generally associated with SCC. raised by the loss of chromium. The crack facets match with high perfection. the austenite is a crack arrester. The relevance of this to the normal case of stainless steels must be questioned since. active corrosion within a pit) or cathodic reactions. The stress at which SCC initiates has a threshold. while under conditions that cause SCC in highly alloyed ferrite. but once that intensity is reached. while considered nearly immune to SCC. Grain boundary propagation in stainless steels usually corresponds to conditions under which grain boundaries are less corrosion resistant because of either material or environmental variables. These alloys can be tempered at sufficiently high temperatures that they become soft and tough enough to have very good resistance. with hydrogen provided by either anodic (e. they can become susceptible. Their dual-phase microstructure ensures that under conditions that crack austenite. once formed. If purely ferritic alloys are alloyed with copper. as does cold work. Cracks. which can have a martensitic structure. presumably have favorable geometry to duplicate pit internal chemical reactions and must be considered to be described by the models that apply to pits and crevices.

However. of course.50 / Stainless Steels for Design Engineers SCC. but least stably so. There are three key types of environments in which SCC occurs in stainless: • Chloride-containing solutions • Caustic solutions • Polythionate and thiosulfate solutions The cases of polythionate and thiosulfate solutions are industrially important but can be adequately explained as simply the stress-assisted intergranular corrosion of sensitized material. This is simply the delay of initiation. if pitting can be delayed indefinitely. It is mitigated by material variables such as cold work and by alloying elements that increase austenite stability. However. which we already know helps prevent pitting and crevice corrosion. The minimum in the curve corresponds to the nickel level at which the structure is entirely austenitic. is not occurring. alloying elements that delay or prevent localized corrosion do the same to delay SCC. such as chromium and molybdenum. 32 Variation of resistance to stress corrosion cracking with nickel (and other) content and structure . impurity. also increases the threshold stress for SCC. Resistance to general corrosion is proportional to nickel content. All other things being equal. more harmful localized corrosion. if metastable or stable pitting is occurring. the threshold stress has been reached. Chloride containing environments are the main ones that induce SCC. Hot caustic solutions are aggressive against stainless steels. 32. Molybdenum. its role seems mainly to be as an austenite stabilizer and as a retarder of active corrosion. but ferritics and duplex alloys are less prone to SCC. often referring to the data from Fig. as shown in Fig. and dissolved oxygen can cause SCC as well as other undesirable corrosive attack. Environmental Variables. Certain combinations of concentrations. while higher levels promote austenite stability and correspond to alloys having more alloying elements. Water can cause Fig. Lower nickel levels produce better immunity through the duplex structure. temperature. Many publications cite nickel as beneficial in enhancing resistance to SCC. assuming. But. and the temperature is sufficient. 31 Influence of molybdenum on resistance to stress corrosion cracking (SCC) in austenitic steels Fig. such as that due to intergranular chromium depletion. then SCC will proceed. then SCC can also. 304 has been reported to have no meaningful threshold stress for SCC in hot caustic solutions. 31 (Ref 31). leading one to question whether such a failure should even be classified with SCC of the typical chloride-induced type or belong with the previous polythionate and thiosulfate solutions. which are probably the greater cause of resistance to SCC.

which comes into equilibrium with the solution within the crack.. Mechanisms. 33 Variation of susceptibility to stress corrosion cracking (SCC) with media oxygen and chloride content for 304 stainless steel. Only in alloys such as Fe-3Si are steps small enough to make this mechanism plausible. looks to the parallels between liquid metal embrittlement and SCC to explain the mechanism of SCC as the action of adsorbed species weakening atomic bonds on the crack tip surface. above 100 °C) if there are even very low combined concentrations of chloride (greater than 0. also known as stress-sorption. that tests crack propagation against electrochemical events will absolutely support this model. There have been many mechanisms proposed for SCC in stainless steel. Fig. The crack does advance discontinuously. Decreasing pH lowers the temperature at which SCC occurs in a given time. So. and after time it fractures by an unspecified mechanism. Failure times decrease exponentially with decreasing chloride content. Research (Ref 34) showing that metal dissolution at the crack tip is isotropic rather than crystallographically oriented make dissolution models incapable of being reconciled with the crystallographic fracture surface facets. and after each advance there is fresh surface. The weakness of this model is that it does not provide a mechanism for brittle fracture. We focus only on those that address the failure in chloride-containing media. It is axiomatic that films must rupture and reform as cracks advance discontinuously. It simply proposes that at a crack tip a passive film forms. The models that have found some support are: • Slip dissolution • Adsorption-enhanced plasticity • Adsorption-induced brittleness • Hydrogen embrittlement Slip dissolution (anodic dissolution) was the earliest proposed model for SCC. Adsorption-induced brittleness. the main concern for users of stainless steel.1 ppm) dissolved (see Fig. The strength of this model is that it actually does describe what is happening. any experiment. 34 (Ref 33). and the very brittle features of transgranular SCC fracture surfaces do not show any supporting evidence of dissolution.Chapter 4: Corrosion Types / 51 SCC at sufficiently high temperatures (i. brittle cracks which characterize SCC. however. Crack growth rate increases by a factor of ten with each 30 °C rise in temperature. If the action is on the surface. The fresh active surface may or may not repassivate. the mechanism cannot produce the observed discontinuous. such as that shown in Fig. after which the process repeats itself.1 ppm) and oxygen (greater than 0. Source: Ref 32 . 33) (Ref 32).e.

52 / Stainless Steels for Design Engineers Fig. 34 Crack propagation rates of various metals plotted versus current density. It has been proposed and supported by calculations that hydrogen lowers the energy required or vacancy formation. The main question is whether it causes damage by creating porosity. It has been demonstrated that hydrogen is absorbed into the material at the crack tip. HE is implicit in all these models. Source: Ref 33 Adsorption-enhanced plasticity/hydrogen embrittlement encompasses a number of models that observe that adsorbed species enter the lattice in the vicinity of the crack tip and then cause failure by one of several mechanisms: • Dealloying and porosity • Adsorption-induced brittleness • Coalescence of voids formed by cross slip enhanced by the adsorbed species Since hydrogen is the only species that is produced in quantity and is capable of diffusing into the lattice. It has been observed that where SCC occurs there is a large concentration of vacancies. This has led to speculation that porosity is a weakening mechanism responsible for SCC (Ref 35). The lowest energy . All of the models have support in that they have some experimental observations that show that the phenomena they propose as causal actually take place. There is support for each. but none is specific enough to have been tested by critical experiments to prove or disprove it. or causing lattice decohesion. altering dislocation mobility.

This has been observed to occur and has caused deformation to become concentrated in Luders bands in austenitic alloys. accounting for about 1% strain per 0. But. however. as shown in Fig. In stainless steels. so there is no basis to challenge the enhanced vacancy formation. however. While not formalized as a proposed hypothesis for SCC. This pairing of hydrogen solute atoms to dislocations is very reasonable given the major distortion the interstitial hydrogen causes to the lattice.1% concentration by weight. while hydrogen causes dislocation motion and lower work hardening. The largest measurable effect of hydrogen has been a slight acceleration of stress relaxation in martensite. This has been observed distinctly in single crystals of austenitic stainless alloys. looks to the parallels between liquid metal embrittlement and SCC to explain the mechanism of SCC as the action of adsorbed species weakening atomic bonds on the crack tip surface. Hydrogen. also known as stress sorption. in HE in the more general case. that for SCC. to show how this mechanism could account for the temperature and stress dependence observed. Adsorption-induced brittleness. which of course do not show such behavior without hydrogen (Ref 36). Source: Ref 36 in Fig. At hydrogen levels of over 1000 ppm. 35 (Ref 36). which would be considered stable without hydrogen and deformation. But. so it can diffuse to sites where it can alter mechanical properties. Only in alloys such as Fe3Si are steps small enough to make this mechanism plausible. the mechanism cannot produce the observed discontinuous.Chapter 4: Corrosion Types / 53 configuration is calculated as two hydrogen atoms per vacancy. causing strain to be localized on certain slip systems. although . The major influence of vacancy formation due to hydrogen may be to enhance the volume expansion due to hydrogen. which are thought to exist around growing SCC crack tips. The effect is not small. the role of hydrogen as a generator of very high stresses has been pointed out as a factor that cannot be neglected when evaluating other proposed mechanisms. This theory encounters a problem. This also precludes the necessity of hypothesizing hydrogen-induced phase changes. there could therefore be hydrogen concentration gradients capable of producing additional tri. has about half the distorting effect and half the hardening effect. 36 (Ref 38).or biaxial stresses on the matrix ahead of the crack tip that may approach the yield stress and account for some or all of the difference between the normal fracture toughness KI and the KISCC. as the smallest of them. with the fact that the same studies showed that hydrogen actually strengthens the matrix by solid solution hardening. If the action is on the surface. so this theory by itself cannot account for the role of hydrogen in SCC and. its small size makes it mobile at ambient temperatures. by inference. and more important. 35 Stress-strain curve for single crystals of stable austenitic stainless steel with and without hydrogen. It acts in much the same way as carbon and nitrogen do. there seems to be nothing to support this proposed mechanism. brittle cracks that characterize SCC. Hydrogen has been shown to distort the lattice in proportion to its concentration. as shown Fig. it does not weaken austenite. Whether the effect is large enough to cause failures has not been demonstrated. The relevance of hydrogen-induced vacancy agglomeration as the principal cause of failure must be considered questionable until some further critical experiments link the vacancies to the observed instances of failure quantitatively. Adsorption-enhanced plasticity has become known recently as HELP or hydrogen-enhanced localized plasticity. The underlying mechanism at work in this model is the hydrogen-induced shielding between microstructural defects. This also produces ε-martensite in austenitic alloys. The quandary of hydrogen finally having been shown to have a clear effect on mechanical properties but having that not account for either SCC or HE may be put to rest by the additional observations of hydrogen’s role as a lattice distorter (Ref 37). The Cottrell atmosphere of hydrogen around dislocations causes mutual repulsion. All these interstitials strain the lattice and therefore harden in proportion to their atomic size.

and stress dependence of SCC. which can quantitatively differentiate among the above effects and measure the contribution of each. The observations that make a given model plausible as a mechanism for SCC lack traction for the same materials in HE. which is hardened by cold work or alloying. whereas void coalescence by vacancy creation seems more likely to account for the observed behavior. This in- volved distinguishing among the same mechanisms. they would result in the same lattice expansion. Hydrogen Embrittlement Like SCC.54 / Stainless Steels for Design Engineers Fig. Austenite is somewhat diminished in ductility by hydrogen. in fact. it will be from critical experiments. . The main difference between HE and SCC in stainless steel is that HE is limited to ferrite. The growth of this stress over time with increasing hydrogen-producing corrosion would account for the observed kinetics. It hard to envision enhanced plasticity involved in the completely brittle fracture of high-strength martensitic stainless steels. and martensite. In both cases. discontinuous cracking of bcc stainless. If nothing else. namely: • Decohesion • Enhanced local plasticity • Adsorption embrittlement • Void coalescence The identification of the operative mechanism for HE involves again distinguishing what role each of the above contributes to HE in a given situation since all are known to be real metallurgical phenomena. the failure would occur at a region ahead of the crack tip and beyond the highest hydrogen concentration. but not subject to the completely brittle. locus. Source: Ref 38 were they to exist. The next few years may finally see the resolution of the lengthy debate over the causes of SCC. 36 Dilation of austenite due to hydrogen in solution. If it comes. there has been debate about HE that has produced more heat than light. may account for much of the observed SCC behavior of stainless steels. the main models for SCC and the experimental results on which they are based should be reexamined in view of the fact that the stresses induced by hydrogen are not negligible and. which is what is observed to occur.

or peroxide. The precipitated deposits of manganese dioxide can accelerate pitting corrosion even in low-chloride waters in which alloys such as 316 would otherwise be safe from pitting attack.Chapter 4: Corrosion Types / 55 The resolution of mechanism here also must account for the contribution of hydrogen-induced stress as well as hydrogen effects on mechanical processes. an initiation site that is the weakest link in a combined mechanical and metallurgical sense will be the initiation point after which conditions that may not cause SCC can help propagate fatigue cracking at lower stresses than would be expected in more benign environments and in environments that may not cause SCC or pitting under static loads. Some materials show a combination of both. crack propagation rates are elevated above those in air at all stress levels. The cracks are transgranular. The importance of the environmental interaction is reflected in the sensitivity to frequency of stress application. especially since the observed susceptibility to HE is proportional hardness. can cause manganese to be oxidized to manganese dioxide. Among the anaerobic bacteria that are known to [16] (Ref 40) affect stainless steels can be counted: Desulfibrio and Desulfotomaculum. which increase the anode dissolution reaction: Fe → Fe 2+ = 2e − (Eq 18) by converting the ferrous iron-ion product (Fe2+) to less soluble ferric (Fe3+). while the last two seem to indicate an SCC–type behavior. and the collaborative effect of corrosion and fatigue is that corrosion accelerates the plastic deformation that accompanies the evolution of extrusions and intrusions. such as ozone. The bacteria that are known to influence corrosion can be sorted as aerobic bacteria that lie in aerated water and anaerobic bacteria. In some materials. However. which provide enhanced hydrogen solubility where it can aggravate the applied crack opening with a wedge effect from hydrogen dilation. . Corrosion Fatigue Just like SCC. Biocorrosion is most commonly encountered in ambient aqueous environments. The same uncertainties that cloud our understanding of SCC necessarily disguise the precise mechanism of corrosion fatigue. Biocorrosion and Microbiologically Induced Corrosion There are many cases for which biological organisms contribute to initiating or enhancing rates of corrosion. which are the environments in which most microorganisms have evolved to thrive. The stress. microbiologically induced corrosion. which are used in these environments. however. This is called biocorrosion or MIC. it tends to be a problem for the medium-alloyed steels such as 304 and 316. This can occur in natural environments such as ground or seawater as well as domestic and industrial environments such as the nuclear and chemical processing industries. failure will occur at a lower N under the corrosive environment. Due to this. The first case seems to be merely fatigue assisted by corrosion. therefore to the amount of hydrogen a given material can hold both in normal interstitial solution and the amount it can trap at lattice defects (Ref 39). Both of these are so-called sulfate-reducing bacteria (SRB). an obvious pit corrosion site may not be necessary because of the combined action of cyclic stresses and the environment. for example. is cyclic and in a test of stress versus number of cycles (S vs. In corrosion fatigue. So. Oxidizing biocides. especially the dislocations within the plastic zone at the crack tip. Countering MIC with biocides can cause problems in manganese-containing waters. while in others a threshold stress intensity must be reached before an acceleration is noted. which must be viewed as a combination of SCC and fatigue. corrosion fatigue causes brittle failure under a combined environment of corrosion and a tensile stress component. Examples are the iron-oxidizing Gallionella and Sphaerotilus. macroscopic so-called tubercules form that can cause crevice-type shelters where differential aeration and pit initiation can occur. High-frequency loading gives less time for corrosive attack and brings crack propagation rates down closer to those in air. chlorine. which means that they promote the reaction: SO 2− → S2− + 4 O 4 (Eq 16) which in turn accelerates the cathode reaction: 2H = + 2e − → 2H (Eq 17) Aerobic bacteria flourish under oxygen (Ref 40). N).

Critical Factors in Localized Corrosion. Corros. Microbiologically Influenced Corrosion. Kawasaki Technical Report 31. Feb 2001.alleghenyludlum. p 195–200 30. Metal. S. Metals Institute. Vol 47 (No.G. M. A. B. 1997. Tagashi et al. 2001.. Sci.Kurkela.pdf 13. Vol 13A.O. p 332 36.. Hydrogen Effects on Materials Behavior. A. p 1489–1494 38. Vol 28. Vol 384. Institute of Metals. Proc. Stainless Steels ‘87. Lee. Stinner.E. Sedricks. Vol 161. Suutala and M.J.pdf 14. Corrosion of Stainless Steels. p 4171.56 / Stainless Steels for Design Engineers The more chemically or thermally hostile environments in which higher alloyed grades are used are also hostile to bioorganisms and thus minimize the problem.C. Trans. Newman. 2005. 1993 24. Feb 2002. 2003. 1985. p 240–247 25. 5). TX. Truman. and T. Electrochem Soc. Hakkarainen... 1999. Hoelzel et al.. S. p 779 32. Bohni. and R. Webb. Grubb. 1985. Nippon Steel Tech. Vol 5. Les Editions de physique. and this turbulence can cause flow erosion in copper materials. 1988. p 93–103 40. Scr. Corrosion: Metal/Environment Interaction. p 268 11. A. A. Proc. Stainless ‘84. Wiley. Pitting Corrosion of Metals. Br.. p 398–413 . Sci. Critical Factors in Localized Corrosion. J. H. the action of microbes in raising the corrosion potential is key to understanding why natural seawater is so much more corrosive than sterile sodium chloride or synthetic seawater solutions. F.M. Sci. B. G. and Protection. 1976. Spiedel.E. K. Met. Documents/AL-6XN_sourcebook. Corrosion. Hanninen et al. J.C. Met. TMS. A.J. Soc. June 2001.N. Y. Adv. p 247–252 27. Nature. Metals Institute. L. Ryan. p 533–540 18. H. B.F. R. They create crevices and sites where microfouling can start early. Newness-Butterworths. K. Proc. p 1771 17. REFERENCES 1. Tobler and S. Institute of Materials.C. Soc. Williams. 1986 19. These represent a differential aeration cell that acts just like a severe crevice. Hydrogen Effects on Materials Behavior. Z. Met..alleghenyludlum. Fujimoto . J. H. Eng. Trans. And. 1993. 1979. S.G.T. JFE Technical Report 7. Laycock and R. Sci.J. H. Michal.. T. Hahhinen. Electrochem Soc. 2003. M. Testing. Dec 2001. p 770–777 22. Corrosion. p 1097–1117 6. http://www. Mimura et al. Tahtinen. Fundamentals of Steelmaking. F.. http://www. M.Virtanen. Cao. p 255–261 39. Y. Brewer. Vol 32A. 1968. 1979. Corros. Vol 148 (No. Houston. 1986. Ernst. Audouard. Vol 1. http://www.. High Cr Stainless OCTG with High Strength and Superior Corrosion Resistance. Vol 39.C. Stainless Steel ‘84. Corros. At the same time. KCI. D.P. V. B174–B185 26.W. Kobyashi. ASM Handbooks.P. J. 2004. Dexter. p 115 4. p 1519 21. Vol 32A.outokumpu. P01488. Grekula et al. p 5 34.. Bohni. H.J. 1981. 5). Electrochem. 40.S. M. Stainless Steels. Mater. Stainless Steel World. Science. Acta Mater. E. Vol 12A. R. Mater. Documents/al610_611. Szlarska-Smialowska. 1996 20. p 137–153 29. 1994 15. The development of microbiological consortia allow anaerobes to flourish under biofilms that form in an aerated environment.. July 2004. Spiedel. Stainless Steels Les Editions de physique. 1984... W. p 158 33. Pound. 2003. E. 2004. Vol 150. p 1980 3.J. Kim and H. p 352 10. Electrochem.P. Jan 2006 8. Newman. Fritz. Turkdogan.Virtanen.. p 143–148 35.O. Vol 51. J. Baroux et al. J. and C. J. London. Also. 2003.. making use of stainless steels more attractive. N. Corrosion: Fundamentals.. p 1030–1041 16.C. and H. 2001 31.. Kimura et al. p 201–210 37. 2003. 2003.. Vol 14. Parks. Electrochem. 2006. they are sources of turbulence in flowing systems. Trans. et al.. Lothongkum et al. Nagumo et al. Report 90.Suter. M. Parkins. http://www. macrofouling organisms are important..alleghenyludlum. Sci. Ryan et al. html 7. Alkire..P. 28. Technol. p 284–294 2. 1993. p 583–594 5. N. Corros. NACE. M. p 94–99 12. products/xq/asp/T. p 569 23. Vol 415. Vol documents/start. Gadgil. and G.1/qx/productCategory. A.asp 9. Sieradski and R.D. Newman. Vol 133.

plays an important role as a heat-resisting material. The electronegative gaseous oxidant X could be sulfur.1361/ssde2008p057 Copyright © 2008 ASM International® All rights reserved. 1 that the major alloying element in stainless steels. This is partly due to its ability to retain strength at higher temperatures at which many otherwise useful alloying systems.5 yX 2 ( g) → MX y (Eq 1) Due to the high temperatures involved. chromium. and even titanium. than those of the base alloy iron (FeO. soften. Fe3O4.5 y ⎟ ⎝ ⎠ 2 (Eq 2) Introduction High-temperature oxidation is a form of environmental degradation of metals and alloys that results from the following chemical reaction in which metal atoms M react with gaseous oxidants: M (s) + 0. chlorine.. the chromium content determines the oxidation behavior of stainless steels. the free energy G is decreased by a lower nobility of the metal (or a higher activity a of a metallic alloying element). Birks. hydrogen would be added as a product in Eq 1. forms a thermodynamically significantly more stable oxide. these reactions are generally rapid and thus are a concern for high-temperature applications such as components for power generation. Stainless steel retains strength and has excellent oxidation resistance from room temperature to nearly 1000 °C. The Effect of Chromium. Thermodynamics of Oxidation As discussed in Chapter 2. p 57-68 DOI: 10. 1 (Ref 4). for which temperatures are high enough to form mixed oxides or spinels. and Pettit distinguished between two basic types of behavior: (a) a noble matrix . The standard Gibbs free energy ΔG0 is often presented in Richardson-Jeffes (Gibbs free energy-temperature) diagrams such as the one shown in Fig. Kinetics of their growth is complex because metal solute diffusion in the metal phases varies. often considered mainly as a corrosion-resisting material. at which other economical alternatives are lacking. and a higher partial pressure P of the oxidizing gas according to: ⎛ aMeX ⎞ y ΔG = ΔG 0 + RT ln ⎜ ⎟ ⎜ aM PX0. as do metal and oxygen ion mobilities in the different oxide phases. www. but the discussion here mainly is limited to oxidation by oxygen or water vapor (in the latter case. such as aluminum. a lower temperature T. referred to Ref 1 to 3). and Fe2O3) or the major ternary element nickel (NiO). Cr2O3. the activities of the oxide species also need to be considered. and there might be degrees of solubilities of oxides in one another. McGuire. Meier. etc. It is evident from Fig. The oxidation of multicomponent alloys is a complex process from both thermodynamic and kinetic points of view. and to a great extent. A range of oxides may form with various degrees of thermodynamic stabilities and stoichiometries (including complex ones with different cations).asminternational. a reaction will be possible when the net free energy In the case of alloy oxidation. In Eq 1. CHAPTER 5 Oxidation Summary STAINLESS STEEL. For a thorough study of oxidation.Stainless Steels for Design Engineers Michael F. Corrosion Theory. is negative.

The progressive change in oxidation behavior as chromium is added to iron has been described in the literature (Ref 1). It can be seen here that Fe2O3 and Cr2O3 are soluble in each other. where FeO would form next to the metal. Isolated pockets of spinel may form within the FeO layer. The oxidation of iron proceeds predominantly due to the rapid ionic diffusion of Fe2+ cations on the FeO layer.).5O4 (with a solid solubility with Fe3O4) and FeCr2O4 form. in which oxidation takes place under significantly oxidizing conditions. 1.58 / Stainless Steels for Design Engineers Fig. which leads to growth of this layer. 1 Standard Gibbs free energy of formation of some metal oxides as a function of temperature. silicon. At lower chromium contents and above a minimum temperature. aluminum. an iron-chromium alloy would behave as pure iron. an element for which the free energy defined by Eq 2 is negative is nonnoble. A high-temperature Fe-Cr-O phase diagram is shown in Fig. 2. Source: Ref 4 metal with less-noble alloying elements and (b) both matrix element and alloying elements are nonnoble. then gradually Fe3O4 and Fe2O3 would form toward the gas as oxygen potential increases. it can be seen from Fig. and that the spinels Fe1. that is. etc. If chromium . We first discuss the more common case (b). The concept of nobility is decided by the thermodynamic conditions of Eq 2. molybdenum.5Cr1. In such a situation. such as air. manganese. that the matrix iron is nonnoble and so are many of the solutes (chromium.

Above 16%. The solubility of Fe3O4 in the spinel will eventually result in continued iron oxide formation. and 446) is that they are relatively inexpensive. At chromium contents less than about 16 wt%. silicon. which has . and this is the reason that these elements are used as alloying elements to reduce oxidation rates for alloys in high-temperature applications. A is the area exposed to the oxidizing atmosphere. A chromium limit of roughly 20% is needed to achieve a permanent Cr2O3 scale. an outer layer of Cr2O3 is formed.Chapter 5: Oxidation / 59 Fig. This amount decreases if nickel is added. the parabolic rate constant for the oxides of chromium. and km is the parabolic rate constant. The subscript “m” is added here to denote that the reaction is measured as added mass (it can also be defined for oxide thickness X). While the thermodynamic driving force is important. as the iron-chromium system is not an optimal basis for high-temperature oxidation resistance. the oxidation rate is influenced by the rate of supply of chromium from the alloys beneath the oxide. This gives them an advantage in cyclic oxidation applications even though their strength at high temperatures does not rival that of austenitic alloys. and thus the scale is not yet protective. by which the mass change per unit area due to oxidation (incorporation of oxygen) is given by: ( m / A) 2 = km t (Eq 3) Here. the chromium content of the alloy can override because the supply of chromium to the interface becomes dominant. and aluminum are low compared to others. 309. 3. As chromium content is increased further. As shown in Fig. The ferritic stainless steels are the most widely used alloys based on their low cost. the supply of chromium is fast enough that chromium gradients are low enough that instead transport in the oxide layer controls the rate. The value of ferritic alloys (such as 409. The major stainless steels used for oxidation resistance fall into two categories: the ferritic stainless steels and the austenitic. although it might be an option from an economical standpoint compared to other alloy systems such as superalloys. The rate of oxidation then follows a so-called parabolic law (this is explained in the next section). 439. Table 1 lists some of the more significant alloys commonly encountered in applications for which oxidation resistance is paramount. Source: Ref 6 Fig. m is the added mass. t is the time exposed. and 310). the spinel pockets increase. and the oxidation behavior becomes similar to that of chromium. 2 The iron-chromium-oxygen phase diagram at 1300 °C. and that they have a thermal expansion coefficient that is closer to that of the oxide than do austenitic alloys (such as 302B. 3 Parabolic rate constants for the growth of several oxides. As chromium content is increased further. The high mobility of both iron and manganese in the spinel structure is also an important factor. Source: Ref 5 in the base alloy is increased. and the mobility of Fe2+ decreases. Iron diffusion through the mixed spinel is significant. a mixedspinel scale is formed.

0–3.25 .. ...0 24... 0. . 0.. 1..015 0. 0.75 0..15 0. 1 .25 .. through which ions are transported. 4(a).. 0... at high oxygen potentials.75 11. through which electronic defects are transported. 0. either or both metal or oxygen ions can migrate... .. scale-gas surface.10 0.04–0..0–10....25 0.0 17....25 .35 12 17.0–22. and the chromium is oxidized at the metal-scale interface. 0. Transient Oxidation The oxidation of a clean metal surface on exposure to an oxidizing environment will initially lead to all the nonnoble components of the alloy being oxidized together.04 Ce . In principle. 1 .. the oxide will grow at the 3 ''' ''' ⎡VCr ⎤ p3 = K 2 pO/ 4 → ⎡VCr ⎤ = K12 K 2 Po4 ⎣ ⎦ ⎣ ⎦ 2 2 (Eq 4) The electron holes that form as charge-compensating defects serve as the “electron lead” in the electrochemical cell in Fig.7 1.015 0. . then the scale would continue to grow at the oxide-metal interface.02 0. The Cr2O3 scale serves as both electrolyte..0 0. as shown in Fig.0 . As these oxides thicken. 0... 0...02 0.0–2... The free energy of Reaction 4 determines the concentration of mobile defects and thus the diffusion coefficient and electrochemical mobility (Be) of the cation according to: ⎛ ΔGm ⎞ DCr 3+ = ⎡VCr 3+ ⎤ γΛ 2 υ ⋅ exp ⎜ − ⎣ ⎦ ⎝ RT ⎟ ⎠ ⎛ ΔH m ⎞ = ⎡VCr 3+ ⎤ ⋅ cons tan t ⋅ exp ⎜ − ⎦ ⎣ ⎠ ⎝ RT ⎟ (Eq 5) ..... the partial pressure of oxygen at the scale-metal interface falls until only the most reactive element present in high concentration can be oxidized..35 0.0 12. The defect can be described as an interaction with oxygen..01 0.2 0. .55 .2 Al .0 18 17. Similarly. through Kroger-Vink notations as: 3 3 x ''' O ( g) = VCr + OO + 3h • 2 2 2 −3 3 The Electrochemical Nature of Oxidation Once an inner scale of Cr2O3 is formed. 1. whereas if chromium ion mobility dominates.04 .. and electron lead.6 ...2 0.0 19...3 18 23.. If oxygen ion mobility dominates.0–15. Note: All compositions include Fe as balance.0–19..07 0. unless otherwise specific (a) Indicates typical analysis made them the standard alloys for automotive exhaust systems. The case will be determined by the equilibrium defect structure of the oxide. 1.0–19...0–26.0 9.. chromium cations are the predominantly mobile defects (Fig. In stainless steels..6 8.0 18.0 20..0–10.25 .0 22.0 . forming mixed oxides having composition similar to the base alloy. leading to metal deficiency. .. . ..0–12...3 0. . .. 0..0 ..60 / Stainless Steels for Design Engineers Table 1 UNS Oxidation-resisting grades of stainless steel in common use Composition.8 0..25 . .5 .05–0..0 1 0..12–0..14–0.06 0. 2.5 0... 4b) as a result of a very small degree of deviation from stoichiometry in the cation lattice. ... Single values are maximum..3 0. For stainless steels..0–27. . . the electric charge can be carried by either n-type (electrons) or ptype (electron holes) electronic defects. Cr2-5O3. . .20 . 0. these initial oxides are typically Fe-Cr-Ni-Mn mixed oxides. 0..3 1 0.08 0. that is.. 1 0. .015 0. The contribution of chromia grain boundary diffusion is large and probably dominates the process at temperatures of interest..08 0. 4b..0–22. This is called transient oxidation.75 ..5 2 0..20 + 4X(C + N) to 0.0–19. this means that a layer of Cr2O3 is eventually established in contact with the alloy...0 Al ..5–11.0–24. the oxidizing gas is reduced at the gas-scale interface. 10.2 . . 1. In the case of Cr2O3..4–2.. which depends on temperature and oxygen partial pressure.18 0.0 10..8 2 2 1 S43935 S44600 S30215 S30415 S38150 S30900 S31000 6X(C + N) to 1.04 Ce 0.7 Al 1..10 1. % Name C N Cr Ni Mn Si Ti Nb Other S40900 409 11Cr-Cb(a) 12SR(a) 439 18Cr-Cb(a) 18SR(a) 4742(a) 446 302B 153MA 253MA 309 310 0.45 0.3 .

(b) Schematic of electrochemical oxidation through a protective oxide scale that serves as electrolyte and electron lead. This treatment follows the derivation in Ref 1. and thus the transport of Cr3+ through its scale is much slower than the transport of Fe2+ through FeO and thus the difference in parabolic rate constants in Fig.. let us assume that the mobile ion defect is cations due to metal vacancies in the scale. as shown in Fig. The case is for mobile cations e BCr 3+ = 3FDCr 3+ RT (Eq 6) where zi is the ion charge. and the theory is explained in most of the monographs on oxidation.e. F is Faraday’s constant (96. defects are in thermal equilibrium throughout the scale).s) of a particle i in an electrolyte subjected to an electrochemical potential gradient was shown to be: Ji = − ci Bi ∂ ( μ i + zi Fφ ∂x ) (Eq 7) Kinetics and Oxidation Rates: Wagner’s Theory The parabolic oxidation rate was introduced without explanation in Eq 3. (a) A protective scale that prevents gas access. It was first described in terms of oxide defect structure and resulting transport properties by Wagner (Ref 6). 4 Metal with oxide scale.eq–1). and (d) double-layer where zi is the ion charge. Consider a general case. scales are relatively thick compared to range of space charge effects). Compared to wustite (FeO). The molar flux J (moles/m. 3. resulting in a low degree of nonstoichiometry in Cr2–δO3 compared to Fe1–δO (where δ can be as large as 0. such as Chapter 3 in Ref 3 and Chapter 4 in Ref 1. (b) electrode reactions are rapid enough to be in equilibrium at the interface and surface.. F is Faraday’s constant (96.05). 4 under the assumptions that (a) the scale is compact and adherent.Chapter 5: Oxidation / 61 Fig.457 C. effects are ignored (i. (c) nonstoichiometry is small and uniform throughout the scale (i.e. The electronic or ionic conductivity κ in an electrolyte can be computed through: κ = F 2 ∑ zi Bi ci 2 (Eq 8) The contribution of a given ion specie type or electron defect type to this conductivity is denoted as the partial conductivity and computed as: κ i = F 2 zi Bi ci 2 (Eq 9) Inserting Eq 9 into Eq 7 yields: Ji = − κi F zi 2 2 ∂ ( μ i + zi Fφ ∂x ) (Eq 10) . and φ is the electric field (V). As a case study. the equilibrium constant of Eq 4 is quite low.457 C/gram equivalent).

one obtains κ c = F 2 zc 2 Dc c RT c and inserting this into Eq 21 results in: 1 k= RT μ 'M μ" (Eq 16) μ '' M ∫ D dμ c M (Eq 22) Now. if the growth of the oxide scale is controlled by the flux of cations: ∂C dx ∝ JC = − DC C ∂x dt (Eq 17) It is often more convenient to express Eq 22 in terms of oxygen potentials rather than the metal potentials. an expression for the parabolic rate constant is obtained: 1 k= 2 2 zc F CC μ 'M μ '' M ∫κ κ cκ e dμ + κe M c (Eq 20) μ M = μ c + zc μ e (Eq 14) Combining Eq 11 to 14. at all times: dx k = dt X (t ) (Eq 18) ∂ ( μ c + zc Fφ ∂x ) (Eq 11) and Je = − κe F ze 2 2 ∂ ( μ e + ze Fφ ∂x ) (E q 12) The constant k is the parabolic rate constant.g. then two fluxes are present: Jc = − κc F zc 2 2 assumed. then Eq 20 can be simplified as: 1 k= 2 2 zc F CC μ 'M κ cκ e ) ∂μ M ∂x μM ∫ κ dμ c M (Eq 21) (Eq 15) To obtain an explicit function for the cation flux. and the chemical potential gradients can be replaced by the metal (M) potential gradient. M κκ 1 Jc = − 2 2 ∫ c e dμ M κc + κe zc F x μ ' M Since from diffusion theory we know that Dc = BcRT. If quasi steady state is .62 / Stainless Steels for Design Engineers Now. Cr3+) and electrons. μM = μ′′M) to the scale-metal interface (x = X. Integrating from the gas-scale surface (x = 0. Eq 15 needs to be integrated after variable separation. the anode reaction is in equilibrium. μM = μ′′M) one obtains.. that is. that is: z + M = M + zce − and therefore. A mass balance can be written where the flux of cations for a period of time dt is equated to the amount of metal being accumulated as cations inside the scale of thickness dx: Jc ⋅ dt = CC dx (Eq 19) Electrical neutrality requires that: Jc Z c + Je Z e = 0 (Eq 13) And at the oxide-scale/metal interface. It was assumed at the onset of this analysis that the deviation from stoichiometry is small and constant throughout the scale. the potential gradient is eliminated. if the mobile particles are a single type of metal cations (e. and the following equation results: Jc = − 2 zc F 2 ( κ c + κ e If the mobility and thus partial conductivity of electrons is significantly higher than that of the ions (a reasonable assumption). c By combining Eq 18 and 19 and inserting Eq 16 for the flux. keeping in mind that conductivities and metal chemical potential may vary within the scale. Therefore. and inserting this in Eq 9. a linear drop across X. the oxide potential is constant and: zc μ + μ M = μ MO = constant zC / 2 4 O2 (Eq 23) The concentration drop across the scale is constant since interface and surface reactions are at equilibrium.

the subscript m stands for molar volume. The different causes of stress generation are described in Chapter 5 in Ref 1.S. rendering it nonprotective. CrO2(OH)2 ) (Ref 11. Eq 4 and 5 inserted into the diffusion coefficient in Eq 24 for C = Cr3+. with large deviation from stoichiometry.g. In Eq 27.. Grain boundary diffusion has however been identified to be important in the case of Cr3+ transport (Ref 8). Spalling and Cracking of the Scale At elevated temperatures or during temperature cycling. instead. Therefore. stainless steels that depend on a protective chromium oxide layer are limited in use to temperatures up to 900 to 1000 °C. Environmental Protection Agency (EPA). The effect of this reaction on the oxidation kinetics can be described as follows: The thickness change described through the parabolic rate constant in Eq 18 is corrected for by the * Hexavalent chromium is now considered a human carcinogen and is rigorously regulated by both the Occupational Safety and Health Administration (OSHA) and the U. if bulk diffusion is dominating. the formation of a gaseous hexavalent chromium oxide CrO3* could lead to thinning of the Cr2O3 scale according to the following reaction: 3 Cr2 O3 (s) + O 2 ( g) = 2CrO3 ( g) 2 (Eq 26) Figure 5 shows the vapor pressure of the superoxide as a function of temperature and partial pressure of O2. grain boundary diffusion would be expected to dominate (Ref 9). results in: '' PO 2 2 P 3/ 4 dPO = ∫ P −1/ 4 dPO 2 2 PO P' 2 O2 '' PO k∝ ' PO ∫ 2 = 3 ⎡ '' P 4 ⎢ O2 ⎣ ( ) − (P ) 3/ 4 ' O2 3/ 4 ⎤ ⎥ ⎦ (Eq 25) Thus. The last is perhaps the most commonly mentioned and is characterized by the Pilling-Bedworth ratio. which is described by a first-order reaction kinetics expression with rate constant ke. this means that dx/dt = 0. Thus. While at first this seems to suggest that it does not affect the oxidation process in that the rate of oxidation does not increase. 6). consequently.Chapter 5: Oxidation / 63 And thus. there are multiple ways in which stresses can develop that may crack and blister the scale. and at a critical oxide scale thickness X( the rate of thinning due to evaporation equals the rate of thickening due to oxidation. The observed growth rate of Cr2O3 polycrystalline films is far too fast to be accounted for by bulk diffusion of chromium ions. As a result of evaporation losses. (Eq 28) Here. The presence of water vapor promotes the formation of even more volatile oxyhydroxides (e. PBR = Oxide VOxide Vm = Metal VMetal Vm * ν The Volatile Nature of Cr2O3 At high enough temperatures and high enough oxygen partial pressures. recrystallization. and υ is the number of metal atoms needed to form a stoichiometric unit of the oxide (in the . X = k/ke. abbreviated as PBR (Ref 13). alloy depletion in the metal. point-defect gradients in scales containing oxides such as FeO. the formation and evaporation of chromium oxides results in greater chromium consumption in the alloy compared to what would be the case if evaporation did not occur. This results in a so-called paralinear (as opposed to parabolic) rate for the oxide thickening (Fig. 2 2 Eq 22 can be written: '' ln PO k∝ ' ln PO ∫ 2 '' PO Dc d ln PO = 2 2 ' PO ∫ 2 Dc dP PO O2 2 thickness loss due to evaporation. These include differences in lattice mismatch. the parabolic rate constant would be predicted to vary with the power of three-quarters of the external oxygen partial pressure. dμ O = dRT ln PO ∝ − dμ Me. the thickness change becomes: dx k = −k dt X (t ) e (Eq 27) (Eq 24) 2 In the case of Cr2O3. and volume differences between the oxide and metal. So-called growth stresses arise due to changes caused by the oxidation process itself. 12).

partly because the stress state often depends more on the mechanisms and conditions of the oxidation process rather than the properties of metal and oxides. α is larger for the metal than the oxide. In general. it is 1). Here. and ΔT is the temperature change. Effect of Silicon. however. α is the coefficient of thermal expansion. many exceptions to this. and Molybdenum. υ is 2. There are. where both sides on a metal undergo oxidation. and the stresses generated in oxide scales can be estimated: σ Oxide = − EOxide ( α Oxide − α Metal ΔT Fig. σ is the stress. 6 Schematic of paralinear oxidation as a result of evaporation of chromium superoxide ( ⎛ ⎞ t E 1 − ν p ⎜ 1 + 2 Oxide Oxide ⎟ t Metal E Metal ⎠ ⎝ ) ) (Eq 29) The equation is written for a case shown schematically in Fig. stresses are caused by differences in thermal expansion between the oxide and metal. Aluminum. Source: Ref 10 case of Cr2O3. whereas if it is less than 1. 5 Chromium-oxygen system species volatility as a function of temperature and oxygen pressure. Due to concerns about the cost of chromium and its (former) classification as a . during cooling the stresses are expected to be compressive and during heating tensile. and it is most severe under cyclic conditions. and in the case of FeO. t is thickness. thus. the oxide is in tension and thus nonprotective. When PBR is greater than 1. Thermal stresses can cause spalling of the protective oxide layer. υp is Poisson’s ratio (it has been assumed that there is no mismatch). 7. then the oxide is expected to be in compression and is likely to be protective. E is the modulus of elastic- ity.64 / Stainless Steels for Design Engineers Fig. Thermal.

Cerium. due to the low oxygen potential needed to form Al2O3. this SiO2 layer seems to promote oxide spalling. but this can oxidize further to form the low-melting and volatile MoO3. and preventing spalling of the oxide scale during thermal cycling. Rare earth additions have been suggested to have a multitude of beneficial effects. the aluminum-bearing alloys provide the greatest oxidation resistance attainable in engineering alloys. In consequence. the surface aluminum-oxide layer flakes off. Aluminum forms a very stable thin outer layer of Al2O3 that initially reduces the oxidation rate.Chapter 5: Oxidation / 65 tox Oxide tm Metal tox Oxide Fig. Silicon additions of 1. Also. The improved adherence could be because these elements getter tramp elements such as sulfur and suppress void formation at the interface. which can enhance the rate of initial Cr2O3 formation. lanthanum. The effect on the growth kinetics could be because the reactive element ions collect at grain boundaries and block fast path diffusion.5 wt% or more have the effect of forming a continuous amorphous subsurface layer in iron-silicon and Fe-Cr-Si alloys that is relatively impervious to transport of ions. an addition of 4 wt% Si to a Fe14wt%Cr14wt%Ni alloy resulted in a 200-fold reduction in weight gain at 900 °C However. internal oxidation may result below the metal-scale interface in alloys in which formation of a continuous alumina scale film does not occur. but if its volatilization is inhibited by low atmosphere circulation. . Molybdenum normally forms MoO2 oxide. an internal Cr2O3 layer forms and thickens. the aluminum content is not sufficient to force alumina scale formation at the scale-metal interface. An understanding of these fundamental issues would help to develop optimum alloy chemistries for selected high-temperature and pressure applications and to further develop the surface infusion process. the SiO2 layer is formed. The precise role of the rare earth additions to Cr2O3 oxide protection and the mechanism by which they are incorporated into the scale during the surface treatment processes remain unknown. The mechanism for the evolution of such a layer is as follows: (1) The more readily available iron or chromium first forms a surface layer. The lack of fundamental understanding of how rare earths improve oxidation resistance has not stopped the development of several alloys that benefit from the effect. If the MoO3 evaporates. especially in cyclic service.and iron-based alloys (Ref 6). and yttrium additions are known to improve oxidation resistance of high temperature nickel. there is little problem. Eventually. The explanation for any of this does not seem clear. 7 stresses Schematic of a cross section of oxidized sample indicating dimensions in Eq 29 for predicting thermal strategic material. however. liquid MoO3 can accumulate and dissolve the protective Cr2O3 scale. Furthermore. It has been reported that alloys with chromium content as low as 6 wt% and silicon content of 1.5 wt% perform in terms of oxidation as well as commercial stainless steels. increasing adhesion. Molybdenum is suggested to strain the lattice due to its larger size and consequently increase the rate of bulk diffusion of elements (Ref 11). there were efforts to try to substitute less-expensive elements such as aluminum and silicon that also are known to form protective layers (Ref 14). giving it an extremely low diffusion rate. and this causes an enrichment of silicon at the oxide-metal interface. Molybdenum is usually considered detrimental for oxidation resistance. if sufficient aluminum is present to maintain the protective alumina scale. leading to catastrophic oxidation. If. such as reducing the growth kinetics of Cr2O3 scales. they might form so-called oxide pegs at the interface (Ref 16). Also. but some hypotheses have been suggested. even though they have significant metallurgical and mechanical drawbacks. Alumina is among the most stable and defect-free oxides. Effect of Rare Earth Additions. (2) As sufficient silicon is enriched. stabilizing Cr2O3 scales at lower chromium levels.

during annealing for microstructural control. Beyond X. the oxide of the reactive element can. Assuming a quasi-steady-state situation as shown in Fig. and separating variables results in: XdX = S N O DO O υN B dt = S N O DO 3 0 N 2 Cr (Eq 32) Integrating Eq 32 from x = 0 to x = X results in an expression for the internal oxidation depth X: ⎛ 2N S D X =⎜ O0O ⎝ υN B ⎞ t⎟ ⎠ 1/ 2 ⎛ ⎜ 2N S D =⎜ O O 0 ⎜ 3 N Cr ⎝ 2 ⎞ ⎟ t⎟ ⎟ ⎠ 1/ 2 (Eq 33) Schematic of two cases in a less-oxidizing atmosphere. However. etc. The molar volume Vm is used to obtain the flux in units of moles per square meter. Let us discuss the conditions that promote one or the other of these by starting with a situation in which (a) no surface oxide exists and (b) the oxygen atmosphere is such that the solubility of oxygen within a distance X is enough to thermodynamically render Cr2O3 stable according to Eq 2 but none of the iron oxides. 9. 8. Assume for a start that the DO >> DCr. 9 . and thus while oxygen diffuses into the alloy. Fig. which is in equilibrium with the gas phase. the oxygen solubility is such that Eq 2 is negative enough that Cr2O3 forms.66 / Stainless Steels for Design Engineers Oxidation Under Less-Oxidizing Atmospheres The two types of alloy oxidation behaviors. for which case a will apply. the flux can be written: JO = S N X − NO NS dm = − DO O = DO O dt Vm X Vm X (Eq 30) Within the depth X. form either on the surface (as has been discussed so far) or internally as discrete oxide particles in a metal matrix through oxygen diffusion into the metal. (a) Adsorption of oxygen leading to internal oxidation and (b) external oxidation as the B element migrates. it is not. Within the layer 0 < x < X. equating to Eq 3. For simplicity. In this case. At the distance X. The flux of oxygen inward into the metal is then the cause of increased mass. steels are exposed to furnace gases at high temperatures that have relatively low oxygen or steam contents. the accumulated mass due to oxygen addition: o 3 0 N B υX N Cr 2 X m= = Vm Vm (Eq 31) Differentiating Eq 31 with time. and most of the discussion has been devoted to this. case b is perhaps the most relevant. all the chromium is assumed to be oxidized. molybdenum. chromium does not counterdiffuse. The derivation is done in terms of both a generic system A-B causing an oxide BOν and for iron-chromium causing Cr2O3. Counterdiffusion of B is assumed to be negligible Fig. Both cases are shown schematically in Fig. were mentioned. depending on the concentration of the reactive element and atmosphere. (a) a noble matrix metal with less-noble alloying elements and (b) both matrix element and alloying elements are nonnoble. therefore. that is the atmosphere does not cause iron (or nickel) to oxidize but chromium (and aluminum. in principle. the oxygen concentration is negligibly low compared to the surface composition. When designing against oxidizing environments. silicon.) does. assume a binary system A-B of “noble” iron and “reactive” chromium. 8 Quasi-steady-state approximation of the moving boundary problem of internal oxidation.

if the ratio were increased there would be a slowing of the inward penetration of the internal oxide front and an enrichment of BOυ in the internally oxidized zone. Metal dusting is often characterized by the generation of large.D.A. 1988. K. PA. Sproule. New York 2. Grünewald. Peterson Memorial Symposium. Vol 40B. Z. Combust.B. 1938. oxygen can be depleted to the point that oxidation essentially ceases. in products of combustion atmospheres.S. Pettit. and S. King. Flame. Now. C. Wagner and K. It was assumed in the derivation of Eq 33 that counterdiffusion of chromium does not occur. Richardson and J. 1993. there is a transition from internal to external oxidation. p 119–137 . AIME. Cambridge University Press. Birks. 1998. but if the oxygen is depleted before all surfaces are oxidized. P. Norman L. which manifests itself as the breakup of bulk metal to metal powder. If DCr was not negligible. Vol 93. niobium. S. 1948. D. Elsevier Applied Science.. Under reducing conditions. smooth pits that look as if metal had been scooped from the surface. (b) decreasing S NO . When considering Eq 33. REFERENCES (Eq 34) If more than one reactive elements were present (such as is the case in stainless steels in which aluminum. Phys. Oxidation of Metals. Phys. Grünewald. 2006. let us see what causes this to transition into an external scale. London 3. Oxidation of Metals and Associated Mass Transport. p 261 5. For a more rigorous derivation (without assuming quasi steady state). J. During oxidation in air. N. Jeffes.. 1938. p 455 8. The Effect of Reactive Element on Self-Diffusion in Cr2O3. is clear that the rate of penetration of the internal oxidation front will 0 decrease with (a) increasing NB . Dayananda. Warrendale. and F. 10). Rothman.E. Vol 160.I. 10 Temperature dependence of metal dusting of iron. The underlying phenomenon is the formation of metal carbides. Plenum Press. Effect of Oxide Grain Structure on the High Temperature Oxidation of Cr. Meier. Kofstad. this happens when: ⎡ πg* S DOVM ⎤ N >⎢ NO ⎥ DBVOx ⎦ ⎣ 2ν 0 B 1/ 2 Fig. p 455 6. F.L. edited by M. N. oxidation and carburization may occur simultaneously and at a higher rate than exhibited in pure oxidation. Wagner and K. Introduction to the High-Temperature Oxidation of Metals. Rothman. the remaining material can be rapidly nitrided by the residual. Peterson. Iron Steel Inst.E.Chapter 5: Oxidation / 67 This expression predicts a parabolic dependence of X with time. C. Chem. when the volume fraction of BOυ versus volume metal in the internally oxidized zone reaches a critical value g*. Caplan and G. and W. Source: Ref 18 trogen absorption. Oxid. if large surface area is present under conditions of restricted air supply. nitrogen atmosphere. p 103–107 7.H. 2nd ed.J. 1975. B. Metal Dusting. refer to Appendix B in Ref 1. Hauffe.. Gradually. New York. Vol 40B. may be present). Park. G..I. Met. J. essentially pure. King. Oxide films inhibit ni- 1. silicon. specifically. W. Ebbinghaus. and thus the transition to external may occur at a lower solute 0 (CCr ) concentration than what is predicted by Eq 34. molybdenum.E. based on that at some point. High Temperature Corrosion. This occurs at temperatures at which the carbide is most stable (Fig. the condition called metal dusting may occur.. Z. Wagner developed a model (Ref 16). etc.H. Vol 9. 1965 4.. p 459–472 9. Under even more reducing conditions. and (c) decreasing DO. there would be a gradual change in oxida0 S tion morphology if the ratio (NB DB)/(NO DO). Chem. this will decrease the inward flux of oxygen.H. just as Eq 3 did for the external oxidation.

J. 1998. S. 1956. Felten. J. JECS.M. C. Hilpert et al.D. Vol 147. 2000. Stress Effects and the Oxidation of Metals. Warrendale. Oxidation of Metals and Associated Mass Transport. Soc.E. J. Vol 143/11. J. Peterson Memorial Symposium. Understanding the Oxidation Protection of Fe-Cr-Si Alloys. J. PA. Pilling and R. Rothman. p 3680 . and T.V. p 200 13. AIME.. Chun. AIME. New York.A. edited by M. p 3642–3647 11. C. 1996.. Rawers. Vol 103. and W. Vol 108. ed. Wagner. Met. Mumford. p 571 16. p 323–340 14. Electrochem. King. 1975.K. Oxide Spallation Mechanisms.E..68 / Stainless Steels for Design Engineers 10.I. Cathcart. Dayananda. p 490 15. Soc. Soc. Tien and J. J.B.J. Davidson. J. 1961.M.A. 1923. Vol 29. K. Electrochem. N. Norman L. p 529 12. Electrochem. J. E. Inst.. Bedworth.. Ramanarayanan.

Stainless Steels for Design Engineers Michael F. McGuire, p 69-90 DOI: 10.1361/ssde2008p069

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Austenitic Stainless Steels
AUSTENITIC STAINLESS STEELS are the most common and familiar types of stainless steel. They are most easily recognized as nonmagnetic. They are extremely formable and weldable, and they can be successfully used from cryogenic temperatures to the red-hot temperatures of furnaces and jet engines. They contain between about 16 and 25% chromium, and they can also contain nitrogen in solution, both of which contribute to their high corrosion resistance. Were it not for the cost of the nickel that helps stabilize their austenitic structure, these alloys would be used even more widely. because their greater thermal expansion coefficient tends to cause the protective oxide coating to spall. 2. They can experience stress corrosion cracking (SCC) if used in an environment to which they have insufficient corrosion resistance. 3. The fatigue endurance limit is only about 30% of the tensile strength (vs. ~50 to 60% for ferritic stainless steels). This, combined with their high thermal expansion coefficients, makes them especially susceptible to thermal fatigue. However, the risks of these limitations can be avoidable by taking proper precautions.

Austenitic stainless steels have many advantages from a metallurgical point of view. They can be made soft enough (i.e., with a yield strength about 200 MPa) to be easily formed by the same tools that work with carbon steel, but they can also be made incredibly strong by cold work, up to yield strengths of over 2000 MPa (290 ksi). Their austenitic (fcc, face-centered cubic) structure is very tough and ductile down to absolute zero. They also do not lose their strength at elevated temperatures as rapidly as ferritic (bcc, body-centered cubic) iron base alloys. The least corrosion-resistant versions can withstand the normal corrosive attack of the everyday environment that people experience, while the most corrosion-resistant grades can even withstand boiling seawater. If these alloys were to have any relative weaknesses, they would be: 1. Austenitic stainless steels are less resistant to cyclic oxidation than are ferritic grades

Alloy Families in Perspective
The fundamental criterion in the selection of a stainless steel is generally that it can survive with virtually no corrosion in the environment in which it is to be used. Good engineering practice sometimes requires that materials be selected for sufficient, but finite, service life. This is especially true for high-temperature service, for which creep and oxidation lead to limited life for all materials. The choice among the stainless steels that can be used in that environment is then based on the alloy from which the component can be produced at the lowest cost, including maintenance, over the intended service life. The ferritic stainless steels are less expensive for the same corrosion resistance but sometimes are found lacking because of: • Lack of toughness, as is the case at subambient temperatures or in thicknesses greater than about 1.5 mm • Lack of great ductility, specifically if more than about 30% elongation is needed

70 / Stainless Steels for Design Engineers

• Susceptibility to high-temperature embrittling phases when moderately alloyed The less-expensive martensitic grades are used instead of austenitic when high strength and hardness are better achieved by heat treating rather than by cold work, and mechanical properties are more important than corrosion resistance. This is also the case for the more expensive PH grades, which can achieve corrosion resistance only matching the least corrosion resistant of the austenitic alloys. Duplex grades match austenitic grades in corrosion resistance and have higher strength in the annealed condition but present the designer with challenges with regard to embrittling phases that can form with prolonged exposure to elevated temperatures and only moderate ductility like the ferritic alloys. So, the austenitic grades are the most commonly used grades of stainless mainly because, in many instances, they provide very predictable levels of corrosion resistance with excellent mechanical properties. Using them wisely can save the design engineer significant costs in his or her product. They are a user-friendly metal alloy with life-cycle cost of fully manufactured products lower than many other materials.

The austenitic alloys can have compositions anywhere in the portion of the Delong diagram labeled austenite shown in Fig. 1 (Ref 1). This diagram was designed to show which phases are present in alloys in the as-solidified condition, such as found in welds. Thus it also applies to castings and continuously cast products. As a practical matter of castability, the composition of most commercial alloys falls along the zone of several percent ferrite as cast. The salient feature of austenitic alloys is that as chromium and molybdenum are increased to increase specific properties, usually corrosion resistance, nickel or other austenite stabilizers must be added if the austenitic structure is to be preserved. The traditional way of displaying the austenitic stainless steels is to present 302 as a base. Figure 2 shows one such diagram. Diagrams such as these treat alloys as an evolutionary family tree and subtly mislead. Many alloys were pushed toward obsolescence because of advances in processing. For instance, 321 was developed as an alloy in which the detrimental effects of carbon were negated by addition of titanium. The widespread adoption of the argon oxygen decarburization (AOD) in the 1970s made this alloy unnecessary, except for special circumstances, since carbon could be cheaply

Fig. 1

Schaeffler-Delong stainless steels constitution diagram. Adapted from Ref 1, 2

Chapter 6: Austenitic Stainless Steels / 71

Fig. 2

The austenitic stainless family. Source: Ref 3

removed routinely. Likewise, 302 gave way to the lower-carbon 304, for which the even lowercarbon 304L is commonly substituted and dually certified to qualify as either grade. While low carbon prevents sensitization, stabilized grades may still be preferred for special applications such as type 321 in aerospace and type 347 in refinery service. Similar inertia keeps the higher-nickel 300 series as the de facto standard when the more cost-efficient high-manganese 200 series is the logical basic grade. The relevant types of austenitic alloys can nonetheless be rationalized with this diagram. As chromium is added, oxidation resistance and corrosion resistance increase. Because

nickel equivalents (manganese, nitrogen, carbon, etc.) must also be added in matching amounts, austenite stability is also increased. If molybdenum, a chromium equivalent, is added, corrosion resistance but not oxidation resistance is enhanced. And, if nitrogen is the austenite stabilizer added to balance increases chromium or molybdenum, then corrosion resistance is also increased. With small exceptions, that is the rationale of austenitic grade design. Silicon is used as an alloy to promote oxidation resistance and resistance to corrosion by oxidizing acids. Copper is used to promote resistance to sulfuric acid. Rare earths make a more stably oxidation-resisting scale. Niobium increases

72 / Stainless Steels for Design Engineers

creep resistance. Sulfur and selenium increase machinability. In this chapter, austenitic alloys are classified into three groups: • Lean alloys, such as 201 and 301, are generally used when high strength or high formability is the main objective since the lower, yet tailorable, austenite stability of these alloys gives a great range of work-hardening rates and great ductility. Richer alloys, such as 305, with minimal work hardening are the high-alloy, lowest work-hardening rate grade for this purpose. The general-purpose alloy 304 is within this group. • Chromium nickel alloys when the objective is high temperature oxidation resistance. This can be enhanced by silicon and rare earths. If the application requires high-temperature strength, carbon, nitrogen, niobium, and molybdenum can be added. 302B, 309, 310, 347, and various proprietary alloys are found in this group. • Chromium, molybdenum, nickel, and nitrogen alloys when corrosion resistance is the main objective. Alloys such as silicon and copper are added for resistance to specific environments. This group includes 316L, 317L, 904L, and many proprietary grades. Wrought alloys generally have cast counterparts that differ primarily in silicon content. Versions that require enhanced machinability have a high content of controlled inclusions, sulfides, or oxysulfides, which improve machinability at the expense of corrosion resistance. Carbon is kept below 0.03% and designated an L grade when prolonged heating due to multipass welding of heavy section (greater than about 2 mm) or when welds requiring a postweld stress relief are anticipated.

Lean Alloys
Lean austenitic alloys constitute the largest portion of all stainless steel produced. These are principally 201, 301, and 304. Alloys with less than 20% chromium and 14% nickel fall into this unofficial category. Since they are stainless, it is generally taken for granted that these alloys will not corrode, and these alloys have sufficient corrosion resistance to be used in any indoor or outdoor environment, excluding coastal. These grades are easily weldable and formable and can be given many attractive and useful surface finishes, so they are very much generalpurpose alloys. Table 1 lists some typical compositions of the most commonly used lean austenitic alloys. These typical compositions vary with end use, raw material cost factors, and the preference of a given manufacturer. The compositions of standard alloys are often finetuned to the intended end use. In this table, the word drawing indicates higher nickel for lower work hardening, while tubing indicates alloys with higher sulfur to facilitate gas tungsten arc welding (GTAW) penetration. Tensile indicates lower alloy levels to increase the work-hardening rate for material that is intended to be used in the cold-worked, high-strength condition. 316L is included in its most common tubing end use chemistry even though it is a corrosion-resisting alloy because it is so pervasively used as a service center sheet item. The main difference among the lean austenitic alloys lies in their work-hardening rate: the leaner the alloy, the lower the austenite stability. As unstable alloys are deformed, they transform from austenite to the much harder martensite. This increases the work-hardening rate and enhances ductility since it delays the onset of necking since greater localized

Table 1 Typical compositions of the most commonly used lean austenitic alloys
Alloy Designation C N Cr Ni Mo Mn Si Other Other Other

201 201 drawing 201LN 301 tensile 301 drawing 303 304 304 drawing 304 extra drawing 304L tubing 305 321 316L

S20100 S220100 S20153 S30100 S30100 S30300 S30400 S30400 S30400 S30403 S30500 S32100 S31603

0.08 0.08 0.02 0.08 0.08 ... 0.05 0.05 0.06 0.02 0.05 0.05 0.02

0.07 0.07 0.13 0.4 0.04 ... 0.05 0.04 0.04 0.09 0.02 0.01 0.0

16.3 16.9 16.3 16.6 17.4 ... 18.3 18.4 18.3 18.3 18.8 17.7 16.4

4.5 5.4 4.5 6.8 7.4 ... 8.1 8.6 9.1 8.1 12.1 9.1 10.5

0.2 0.02 0.2 0.2 0.02 ... 0.3 0.3 0.3 0.3 0.2 0.03 2.1

7.1 7.1 7.1 1.0 1.7 ... 1.8 1.8 1.8 1.8 0.8 1.0 1.8

0.45 0.5 0.45 0.45 0.45 ... 0.45 0.45 0.45 0.45 0.60 0.45 0.50

0.001 S 0.001 S 0.001 S 0.001 S 0.007 S ... 0.001 S 0.001 S 0.001 S 0.013 S 0.001 S 0.001 S 0.010 S

0.03 P 0.30 P 0.03 P 0.03 P 0.03 P ... 0.03 P 0.03 P 0.030 P 0.030 P 0.02 P 0.03 P 0.03 P

0.2 Cu 0.6 Cu 0.5 Cu 0.3 Cu 0.6 Cu ... 0.3 Cu 0.3 Cu 0.4 Cu 0.4 Ci 0.2 Cu 0.4 Ti 0.4 Cu

Chapter 6: Austenitic Stainless Steels / 73

deformation is more than offset by greater localized strain hardening. These grades are best viewed as a continuum with a lower boundary at 16%Cr-6%Ni and an upper boundary at 19%Cr-12%Ni. This represents the range from minimum to maximum austenite stability. Since that is the main distinction within this grade family, let us examine its basis. Martensite and Austenite. Stability. The formation of martensite at room temperature may be thermodynamically possible, but the driving force for its formation may be insufficient for it to form spontaneously. However, since martensite forms from unstable austenite by a diffusionless shear mechanism, it can occur if that shear is provided mechanically by external forces. This happens during deformation, and the degree to which it occurs varies with composition according to (Ref 4):
Md30 (°C) = 551 – 462(%C + %N) – 9.2(%Si) – 8.1(%Mn) – 13.7(%Cr) – 29(%Ni + Cu) – 18.5(%Mo) – 68(%Nb) – 1.42 (GS – 8) (Eq 1)

such as occurs when they are sensitized or when solute segregation occurs, as from welding, then the equation applies on a microscopic scale. Sensitized zones (i.e., the regions near grain boundaries where chromium carbides have precipitated) will have a much higher tendency to transform to martensite. Figures 3(a) and (b) show the changes in phase structure as a function of composition over ranges that encompass these alloys. Martensite can be present in two different forms. The α′-form is the bcc magnetic form, while ε is a nonmagnetic, hcp (hexagonal closepacked) version. The formation of ε versus α′ is related to the stacking fault energy of the alloy, which is given by (Ref 6):
Y300SF (mJ m-2) = Y0SF + 1.59Ni – 1.34Mn + 0.06Mn2 – 1.75Cr + 0.01Cr2 + 15.21Mo – 5.59Si –60.69(C + 1.2N)1/2 + 26.27(C + 1.2N) (Cr + Mn + Mo)1/2 + 0.61[Ni•(Cr + Mn)]1/2 (Eq 2)

This is the temperature at which 50% of the austenite transforms to martensite with 30% true strain (Ref 5). It should be noted that even elements that are chromium equivalents in promoting ferrite are austenite stabilizers in that they impede martensite formation. This temperature is the common index of austenite stability. This regression analysis was generated for homogeneous alloys. If alloys are inhomogeneous,

Epsilon martensite formation is favored in alloys of lower stacking fault energy. The fcc structures deform by slip between (111) planes. Viewed from these planes, the structure is a series of ABCABC atom arrangements. Slip between planes can result in an ABCA/CAB structure. This so-called stacking fault generates an hcp structure. With lower stacking fault energies, these are more readily

Fig. 3

(a) Iron-chromium phase diagram at 8% nickel; (b) iron-nickel phase diagram at 18% chromium

74 / Stainless Steels for Design Engineers

Fig. 4

Variation of martensite formation with temperature and true strain for 304. Source: Ref 7

formed, and ε predominates. The stacking fault can also be viewed as two partial dislocations with the material between them faulted. These partial dislocations, when generated in abundance, cannot readily slip past one another and thus pile up, increasing work-hardening rates. As in carbon and alloy steels, the martensite transformation can take place simply by cooling, but in the lean austenitic alloys the temperatures are well below ambient. The more stable alloys do not transform even with cryogenic treatment. Figure 4 shows the variation of martensite formation with temperature and true strain for 304. Martensite formed in these alloys is quite stable and does not revert until heated well above the temperatures (Fig. 5) at which it was formed. The carbon levels of austenitic stainless steels are always relatively low, so strain-induced martensite is self-tempering and not brittle. Martensite has been found to form in unstable austenite due to the electrochemically induced supersaturation by hydrogen (Ref 9). Under conditions of cathodic charging, superficial layers were found to transform to ε under conditions of intense hydrostatic compression. During subsequent outgassing, α′ was found to form due to reversals in the stress state. Martensite thus formed is, of course, susceptible to hydrogen embrittlement. Mechanical Properties. The tensile properties in the annealed state not surprisingly relate well to composition. The 0.2% yield strength

and tensile strength, respectively, are reported (Ref 10) to follow the equations:
YS( MPa) = 15.4[4.4 + 23(%C) + 32(%N) + 0.24(%Cr ) + 0.94(%Mo) + 1.3(%Si ) + 1.2(%V) + 0.29(%W ) + 2.6(%Nb) + 1.7(%Ti ) + 0.82(%Al ) + 0.16(%Ferrite ) + 0.46(d −1/1/ 2 ) (Eq 3)

TS ( MPa) = 15.4[29 + 35(%C) + 55(%N) + 2.4(%Si ) + 0.11(%Ni ) + 1.2(%Mo) ( + 5.0(%Nb) + 3.0(%Ti ) + 1.2(%Al ) + 0.14(%Ferrite ) + 0.82(d −1/ 2 ) (Eq 4)

In each case, d is the grain diameter in millimeters. Another researcher (Ref 11) gave the relationships as:
YS ( MPa ) = 120 + 210 N + 0.02 + 2 Mn + 2Cr + 14 Mo + 10 Cu + (6.15 − 0.054δ)δ
+ (7 + 35(N + 0.2))d −1/ 2 TS = 470 + 600( N + 0.2) + 14 Mo + 1.5δ + 8d −1/ 2 (Eq 6) (Eq 5)

Again, d is grain diameter in millimeters, and δ is percent ferrite. The claimed accuracy for the latter set of equations is 20 MPa and is said

either by slow strain rates or use of heat sinks. Thus. Equation 3 must also be favored over Eq 5 in that it accounts for carbon explicitly. it can provide very high strength while keeping impressive ductility. Austenitic stainless steels have exceptional toughness. Very lean 301 can be cold worked to yield strengths on the order of 2000 MPa because of its unstable austenite transforming to martensite. Source: Ref 8 to apply to both austenitics and duplex stainless steels. (b) duplex. What is most remarkable is the absence of a transition temperature. even with accepted norms and standards. in which tensile strength increases with decreasing alloy content because of the effect of increasing alloying causing less transformation to martensite. This again is due to the multiplicity of slip systems in the fcc structure and the fact that they do not require thermal activation. This is simply due to the influence of adiabatic heating during testing increasing the stability of the austenite. 5 Reversion of martensite formed by cold work. reported tensile strengths should not be taken as an absolute value but a result that can be significantly changed by changes in testing procedure. produce lower tensile strengths. aluminum) for strengthening. that is. Most precipitation-hardening stainless steels are unstable austenite. Even highly coldworked material exhibits this phenomenon. As a rule of thumb. such as 301. 6 Variation of impact strength with temperature for (a) austenitic. behavior at less than half the yield strength is considered fully elastic and stresses below twothirds of the yield strength produce negligible plastic deformation. those with Md30 temperatures (Eq 1) near room temperature. This makes the austenitic stainless steels. which inarguably produces higher tensile strengths in austenitic stainless steels. This quasi-elastic behavior is a consequence of the many active slip systems in the fcc structure. are very strain rate dependent. One commercial alloy. and that is precipitation hardening. which is transformed to martensite before the precipitation hardening takes place. One other hardening mechanism is possible in austenitic stainless steels. When cold worked to lower degrees. and (c) ferritic stainless steels Fig. is entirely austenitic and employs the precipitation within the austenite matrix of Ni3 (titanium. Austenitic stainless steels do not have a clear yield point but can begin to deform at as little as 40% of the yield strength. but clearly the tensile strength relationship must break down for leaner alloys. especially the 200 series. Highly cold-worked austenitic stainless steels are often used for their robust mechanical properties. although stress-relieving cold-worked material will cause dislocations to “lock in place” and form more stable dislocation arrays that break loose at a higher and distinct yield point. The ambient temperature impact strength of austenitic stainless steels is quite high. This is dealt with in a separate section. Figure 6 shows impact strength of the various stainless steel types versus temperature. This is not surprising in view of their high tensile strengths and high elongations. A-286. Tests run under constant temperature conditions. which characterizes ferritic and martensitic materials.Chapter 6: Austenitic Stainless Steels / 75 Fig. The tensile properties of austenitic stainless steels with unstable austenite. the optimal cryogenic . Few metallic materials can match the very high strengths they can achieve.

surpassing the 9% nickel martensitic steels in cost. of course. even the 0. 7 Carbon solubility in 18–10 austenitic stainless. which is found in most 304. Precipitation of Carbides and Nitrides. At room temperature. and grain boundaries provide excellent nucleation sites. Because of this affinity. Fig. form whenever carbon reaches levels of supersatura- tion in austenite. Source: Ref 13 The equilibrium diagram for carbon in a basic 18%Cr10%Ni alloy is shown in Fig. supersaturation increases exponentially. and diffusion rates are sufficient for carbon and chromium to segregate into precipitates. so precipitation occurs along grain boundaries. At these temperatures. M23C6.06%. supersaturation is reached below about 850 °C. Below this temperature. The absence of carbides in austenitic stainless is due to the slow diffusion of carbon and the even slower diffusion of chromium in austenite. chromium carbides.03% of L grades is mostly in a supersaturated solution. because carbon diffuses several orders of magnitude more rapidly than chromium. while diffusion decreases exponentially. Carbon is normally considered as an undesirable impurity in austenitic stainless steel. The solubility is given by (Ref 12): log (C ppm ) = 7771 − 6272 T (°K ) (Eq 7) Fig.76 / Stainless Steels for Design Engineers material. toughness. 7.4% at solidification but decreases greatly with decreasing temperature. At a carbon level of 0. The solubility of carbon in austenite is over 0. and. And. very little carbon is soluble in austenite. grain boundary diffusion is much more rapid than bulk diffusion. it has a great thermodynamic affinity for chromium. depleting the grain boundaries of chromium in solution. While it stabilizes the austenite structure. 8. carbon diffuses to and combines with chromium essentially in situ. 8 The precipitation rates for Cr23C6 as a function of carbon content . This results in precipitation rates that vary with temperature and carbon level as shown in Fig. corrosion resistance.

Underneath chromium-rich oxide scales is a layer depleted in chromium and lower in corrosion resistance. Nitrogen is much more soluble than carbon and does not give rise to sensitization phenomena as does carbon even though Cr2N can be a . Molybdenum and nickel accelerate the precipitation by diminishing the solubility of carbon. 9 Depletion of chromium from the austenite near grain boundaries due to chromium carbide precipitation. This is why not only scale from welding must be removed. because it is lower in chromium. Source: Ref 16 Fig. The key observation is that any solid-state precipitation of a chromium-rich precipitate will necessarily cause local chromium depletion and a resulting loss of corrosion resistance. Much longer term heat treatment is required to eliminate these depleted zones by rehomogenization of slowly diffusing chromium than the short time required to form them. primary carbides. Chromium precipitates that form in the liquid alloy do not cause depletion of chromium locally because no chromium gradients are set up around them during precipitation as diffusion in the liquid is very rapid. This is very evident for carbides. if the same compounds form and grow in the solid state. Alloying elements can have a major influence on carbide precipitation by their influence on the solubility of carbon in austenite. This zone. also has very unstable austenite and is quite prone to martensite formation. Increasing austenite grain size accelerates precipitation. as does cold work. Nitrogen is especially useful in this regard (Fig. chromium depletion occurs (Ref 15). But. Carbon relatively far from grain boundaries in the interior of grains remains in supersaturation until much longer times and much greater supersaturation since bulk diffusion is required for the nucleation and growth of these precipitates. Thus. Figure 10 shows how the locus of precipitation changes with time and temperature. 11). oxides. but also true for oxides. Source: Ref 14 Figure 9 shows that the local chromium depletion is such that the chromium level can become low enough that it has not even enough to be stainless and certainly much lower corrosion resistance than the surrounding area.Chapter 6: Austenitic Stainless Steels / 77 Fig. especially in the interior of grains. and sulfides. and sulfides are not per se harmful to corrosion resistance. where diffusion is enhanced by increased defect density. 10 Variation of carbide precipitation locus with time. Chromium and nitrogen increase the solubility of carbon and thus retard and diminish precipitation. nitrides. but also the underlying chromium-depleted zone. Other precipitation processes that give rise to chromium depletion are α and χ and the solidstate precipitation of oxides.

11 Delay in carbide precipitation induced by nitrogen level. If quenched from this state. it was found that adding more powerful carbide formers than chromium could preclude the precipitation of chromium carbides. Carbon has always been considered totally undesirable from a corrosion point of view because of its tendency to form chromium carbides. Stabilization. Source: Ref 17 stable phase when the solubility limit is exceeded. although this is not observed at normal concentrations. we can see that carbon.3(%Mo) + 30(%N) + 10(%C) (Eq 11) This is consistent with the similar thermodynamic interaction coefficients that carbon and nitrogen share with regard to chromium. High temperatures. after accounting for the oxygen and sulfur. This socalled colossally supersaturated austenite results in very high hardness (Fig. such as encountered in welding. is actually beneficial to corrosion resistance in solid solution. however. Titanium and niobium are the most useful elements in this regard. there must be sufficient titanium or niobium to combine stoichiometrically with all these species present. The solubility is over 0.97 − 6780 T 9350 T (Eq 9) log [ Nb] [C] = 4. They form carbides with solubility that follows the following equation type: log [ M] [ X] = + A − H RT (Eq 8) Fig. the respective solubilities are: log [Ti ] [C] = 2. Recently. for which solubility is much lower. which can be done quite readily. any additions made to form carbides must be sufficient to account for the prior formation of these compounds. Before carbon was easily lowered to harmless levels. Thus. for successful gettering of all carbon. like nitrogen. so its precipitation seldom has the possibility of occurring. Nitrogen also competes with carbon for available titanium or niobium. new processes have been developed to supersaturate carbon in austenite below the temperatures at which it has sufficient mobility to form carbides. Manganese and chromium increase the solubility of nitrogen in austenite. It would be a mistake to ignore the titanium-consuming capacity of oxygen and sulfur unless they have been minimized by refining.15% in austenite. kinetic considerations may result in that not occurring. It is possible to see that if it could be kept in solution it would be appropriate to give it a factor of around 10 in the pitting resistance equivalent number (PREN) equation: PREN = %Cr + 3.55 − (Eq 10) Oxides and sulfides are more energetically favorable than are carbides and nitrides of these metals. From this. but it does become an issue in ferritic stainless steels in this regard. 12 Variation of hardness with depth and therefore carbon content in colossal supersaturation For titanium carbide and niobium carbide. . however. Thus. carbon can be free to form Cr23C6 if it is reheated to temperatures above 500 °C. 12) and corrosion resistance over limited depths. This requires in rough terms that titanium exceed four times the carbon plus nitrogen.78 / Stainless Steels for Design Engineers Fig. or that niobium exceed eight times. dissociate carbides. Even if sufficient titanium or niobium is present to combine with all carbon.

Aluminum’s strong ferrite-promoting tendency restricts its utility in austenitic grades. shown in Fig. with 25Cr-20Ni composition. as can be seen in Fig. Figures 14. 14. and niobium produces the greatest strength at elevated temperatures. sulfur. then the oxygen penetrates beyond the interface and forms Cr2O3 in situ. and 16 display this relationship. 153MA. oxidation rates decrease with increasing nickel content. the parabolic rate is maintained. is reached by the commercial alloy 310. The rate increases exponentially with temperature since diffusion governs this phenomenon. This generates the parabolic-type oxide growth rate that characterizes these alloys. rare earths can yield even greater benefits from mere trace additions. The scale acts as a barrier to oxygen and greatly slows further oxidation of metal below the scale. Source: Ref 18 in which the rate is in units of mass gained per unit of surface area and time. nitrogen. the path to the interface lengthens. halogens. While the gains from using under 3% silicon are impressive. The rate drops dramatically as chromium reaches the concentration necessary to generate the protective Cr2O3 layer. This discussion concentrates on their resistance to hightemperature environments. leading to breakaway oxidation. The rate of oxide growth is expressed simply as: R = kt (Eq 12) Fig. Below the composition at which complete Cr2O3 coverage occurs. which is where the oxidation reaction occurs. If there is insufficient chromium flux. nitriding. Aluminum forms a layer of Al2O3 that is more restrictive to oxygen diffusion than is Cr2O3. The breakaway temperature increases with increasing chromium level. Resistance to oxidation comes from the protective Cr2O3 scale that forms on the surface of the material. and 253MA all use elevated silicon levels. The oxide will change to the less-protective FeCr2O4. Above about 18% chromium. as does silicon through the formation of SiO2. For a given chromium level. Some elements form more protective oxide layers than Cr2O3. This rate is a strong function primarily of chromium level. however. carburizing. Above this sufficiency level. Oxidation Resistance. The optimal range for the iron base stainless steels. 13 Variation of parabolic oxidation rate with chromium level and temperature. They are often called on to resist attack by oxygen. they mainly provide a reservoir of chromium to re-form the Cr2O3. Alloying can alter the oxidation-resisting performance of the austenitic stainless steels. The Cr2O3 scale is more protective because it better restricts the diffusion of oxygen to the interface between the scale and the base metal. which is their salient characteristic. further increases in chromium are not as beneficial. The austenitic alloys benefit over the ferritic alloys from the presence of nickel. a continuous scale forms. Refer to the properties database for comparisons among the grades. 13. Cerium appears to act at the metal-scale interface such that the oxides . Aluminum and silicon are most useful in this regard. and the rate of oxidation slows. As long as chromium can diffuse to the interface at a sufficient rate to satisfy the incoming flux of oxygen. Alloying with carbon.Chapter 6: Austenitic Stainless Steels / 79 High-Temperature Alloys The austenitic stainless steels can have an exceptional combination of strength and corrosion resistance at temperatures above 500 °C. and molten salts. 15. Austenitic stainless steels are the most creep resistant of the stainless steels. 153MA (UNS S30415) is a variation on 304 using silicon and cerium. the film will also contain the less-protective spinel FeCr2O4. and the scale growth rate will increase beyond the parabolic relationship. The alloys 302B. As the oxide grows.

. 15 Isooxidation curves. 18 (Ref 21). tougher. 14 Influence of nickel on oxidation of iron-chromium alloys. they stress their scale more during thermal cycling. This can fracture the scale. This serious performance flaw also is remedied by rare earths. Source: Ref 20 formed are thinner. Because austenitic stainless steels have a greater thermal expansion coefficient than fer- ritic alloys. 16 Corrosion rates for various stainless steels and nickel base alloys. as shown in Fig. Figure 17 shows the improvement quantitatively (Ref 21). more adherent. Source: Ref 19 Fig. Source: Ref 20 Fig. causing spalling and rapid subsequent oxidation of the underlying metal. although there is no consensus on the mechanism. and more protective.80 / Stainless Steels for Design Engineers Fig.

lowmelting oxides (MoO3 and WO3) that promote catastrophic oxidation (Ref 22. especially cyclic oxidation. form volatile. during heat treating. At 10%. or during welding the surface. The compositions of some of the main high-temperature austenitic alloys mentioned here are given in Table 2.Chapter 6: Austenitic Stainless Steels / 81 Fig. The formation of an oxide on stainless steel should be understood to imply de facto the depletion of chromium from the underlying metal surface. which are refractory metals and are beneficial to aqueous corrosion resistance. which has significant vapor pressure above about 1100 °C. 4833 = 309S. there will be less chromium than the bulk alloy. Other Environments. which melts at 660 °C and can also cause catastrophic oxidation. but also the underlying metal which is depleted in chromium. As a generalization. forms a manganese-chromium spinel that is less protective than the Cr2O3. It acts by increasing the porosity of the oxide scale and by promoting formation of the volatile CrO2 . water vapor will increase oxidation by a factor of ten. Vanadium also forms an oxide. 18 310S (4845) versus rare earth-modified 253MA in cyclic oxidation. Source: Ref 21 While the mechanism by which rare earths make the scale tougher and more adherent are vague. At the very highest temperatures. their effect in making austenitic alloys much better at resisting high-temperature oxidation. an even more potent oxide former than chromium. This is why welds must have not only their heat tint removed. The most common addition species that aggravates high-temperature oxidation is water vapor. Molybdenum and tungsten. are undeniable. it can be said that changes that promote the diffusion of chromium assist in the formation of a protective scale and improve oxidation resistance. to a depth on the order of 10 μ (Ref 24). V2O5. Microstructure can also affect oxidation resistance. Thus. 4845 = 310S. often by a very significant amount. Manganese. Whether the scale is formed in service. once the oxide is removed. cold work and finer grain size are positive factors via their enhancement of chromium diffusion. 23). and therefore the corrosion resistant will be less. Source: Ref 21 Fig. 17 Comparison of rare earth-alloyed stainless alloys to conventional stainless alloys. Cr2O3 can be further oxidized to CrO3. Alloying elements can also be detrimental to oxidation resistance.

07 0. on the order of 100 h or more..50 0. followed by some loss of corrosion resistance. (Å) Composition NbC NbN TiC TiN Z-phase M23C6 M6C σ-phase Laves phase χ-phase G-phase fcc(a) fcc fcc fcc Tetragonal fcc Diamond cubic Tetragonal Hexagonal bcc(b) fcc a = 4.05 Ce . 0.Ni.5 23. The resistance of a material to creep is generally measured by the creep rupture strength.5 0.4 1. i.0 8. It can contain as little as four iron to one chromium or molybdenum in a tetragonal structure.. The most relevant is σ..1 9.. If the temperature at which the alloy is to be used is one in this temperature range.8 18. Transition elements may combine to form intermetallic phases in which the formula can vary from B4A to A4B.06 0.72 a = 8.391 a = 10.5 12.06 0. which is the stress that causes Notable high-temperature austenitic alloys Designation C N Cr Ni Mo Mn Si Other Max temp.57–10.17 0. so alloys such as 153MA are less prone to it.60 . maximum service temperatures should be reduced by 50 to 100 °C in the presence of steam.. Austenitic alloys have no advantage over ferritic in this regard. M5SiC Fe. Carburization and nitriding are best prevented by an oxide layer that forms at very low oxygen partial pressures as chromium and silicon contents are increased. Sigma formation is retarded by nitrogen. .8 18.1 2.05 Ce .68 a = 10.47 a = 4.5 1.15 0. which will form first at triple points and then throughout grain boundaries....6 25..7 1.05 Ce . stress rupture.80.5 . 0. such as 310.0 35. Because of this morphology.0 21. 0.90 0.05 0.8 17..40 Nb 950 820 820 1000 1040 1040 1100 1090 1200+ 1200 1200 Table 3 Precipitate Secondary phases in austenitic stainless steel Structure Parameter.0 24..08 0. . c = 4.Mo Fe2Mo. 600 to 1000 °C service.50 2.8 1.Cr. As a rule of thumb.. apart from austenite and ferrite..04 17.07 0. °C 302B 304H 321H 153MA 309S 309Si 253MA 310S 353MA 330 332Mo S30215 S30409 S32109 S30415 S30909 DIN 1.08 0.28 a = 8. c = 7.2 11. then their toughness will be seriously reduced by the brittle σ.0 34.807–8.. 0. 0. . Fe2Nb Fe36Cr12 Mo10 Ni16Nb6 Si7. times can be as short as several hours..05 0.6 Ti 0..5 19. formation times are relatively long.6 1.03 0. ... then some σ is a foregone conclusion. The greatest risk from these phases is the loss of room temperature toughness.1 9.54 a = 4. face-centered cubic.0 1.08 0..07 0.0 19.08 0.33 a = 4.40 a = 4. If such alloys are intended for use near room temperature... as is molybdenum.. Silicon and aluminum are detrimental. just a few percent intermetallic phase can cause toughness to decrease by an order of magnitude. Lower chromium and higher nickel are beneficial. 2. Table 3 lists the most common secondary phases encountered in austenitic stainless steels.. 1.73.8 21.50 1.7 1.8 0. Ni16Ti6 Si7 (a) fcc. σ is an even greater concern as these are prone to its formation and can inadvertently form some during processing. .. long-term properties such as creep.3 0...037. .82 / Stainless Steels for Design Engineers (OH)2 species. High-Temperature Mechanical Properties. Thus.. it can exist in many conventional austenitic alloys.15 0.1 10. ... . and while σ will have little detrimental effect on short-term properties at these temperatures. Intermetallic Phases. and especially rupture ductility are degraded by σ.40 .878 a = 11. c = 7.05 0.2 NbC NbN TiC TiN CrNbN Cr16Fe5 Mo2C (e. Halogens can attack oxide scales and cause their degradation or volatilization. In richer alloys. yield strength is less appropriate than creep strength in assessing the adequacy of an austenitic stainless steel for structural purposes..0 18.0 Al.03 0.. Above about 500 °C.08 0..6 1. .. Table 2 Alloy In lean austenitic alloys used in high-temperature.1 8.e..15 .5 0. Other relevant phases are χ and Laves.04 0.8 1.2 35. Fe3Nb3C.8 0.4828 S30815 S31008 S35315 S33000 S35125 0. (b) body-centered cubic .g.6 1.62–11. ... For alloys..) (FeCr)21Mo3 C. . 0.24 a = 3.

000 or 100. Figures 19 to 22 compare mechanical properties of the major high-temperature austenitic alloys (Ref 25). Thus. can be used as a basis for design. that is. are quite useful. however. Nitrogen is the better addition in this regard.000 or 100. the creep deformation strength. Fig.000-h creep strength . the stress that results in a strain of 1% after 10. plus it has the collateral benefit of strongly retarding intermetallic phase precipitation. 20 Relative 100. Cold work and precipitates tend to be ineffective strengtheners at temperatures that produce solution annealing and precipitate coarsening (overaging). solid solution hardening is preferred. such as carbon and nitrogen. but interstitial solid solution elements. If deformation is a greater concern. 19 Charpy V toughness after 200 hr aging Fig.000 h.000 h.Chapter 6: Austenitic Stainless Steels / 83 rupture after 10. Substitutional elements have limited effect.

In normal atmospheric conditions. short-time yield strength Corrosion-Resistant Austenitic Alloys Stainless steels are almost always chosen at least in part for their corrosion resistance. 22 High-temperature.000-h creep rupture strength Fig.5% chromium do not rust. . Austenitic alloys require higher levels than this to stabilize the austenitic structure at room temperature. thus giving the common perception that they are superior in corrosion resistance.84 / Stainless Steels for Design Engineers Fig. That is the key aspect of the more modern austenitic stainless steels that have come into use in the last two decades. alloys with more than 10. 21 100. The main advantage austenitic alloys have is their ability to utilize the powerful and inexpensive alloying element nitrogen.

It is. The obvious paradox is how can elements that are not active in the passive film be so effective in maintaining its integrity. Crevice corrosion is. such as oxidizing acids. YUS 270 = S31254. If this is highly localized because of a local weakness in the passive film. on roads. 23 Critical pitting temperature versus pitting resistance equivalent number (PREN). Pitting in stainless steels is in most instances the threshold level of corrosion. The main factors in the resistance of austenitic alloys to pitting attack are generally given by: PREN = %Cr + 3. Crevices can exist not only in deliberate joints but also under environmental deposits. then active corrosion ensues. in food. and acidity are sufficiently aggressive to break down the film. corrosion-resistant austenitic stainless steels all look like they were designed to resist chloridepitting attack. We do know that the essential chromium in the matrix of stainless steels is quite reactive and will form compounds with carbon.3(%Mo) + 30(%N) (Eq 13) Pitting resistance is measured by ASTM G 48 (practice C) in which the lowest temperature at which pitting occurs in a 6% FeCl3 is measured. it is no longer effective as a passive film former. The function of chromium in the passive film is intuitively clear. As the chromium content of an alloy increases. It is the subject of much research. Source: Ref 26 . There are other environments in which the resistance follows different rules. the ready reservoir of chromium to form the chromium-rich layer is facilitated. The roles of molybdenum and nitrogen are subtler and are still subject to controversy. weld splatter. 23 (Ref 26). which has been summarized in reviews. bases. then pitting occurs. but they are less ubiquitous. etc. Because of the specific virulence of the chloride ion and because of its universal presence. If the conditions of chloride concentration. but also in the rain. Chlorides destabilize the passive film. paint films. oxygen. Other halides have the same effect. The regions from which the chromium diffused to form the chromium-rich phase will be poor in chromium unless subjected to a lengthy homogenizing anneal. This is the critical pitting temperature. temperature.Chapter 6: Austenitic Stainless Steels / 85 The ion that is most aggressive against stainless steel is one of the most pervasive in our environment. Most theories of pitting founder at the start because they assume Fig. The relationship between PREN and CPT is shown in Fig. and other transition elements. in seawater. The chloride ion is found in abundance over the entire earth. When it does. SUS 329J4L = S31260. of course. and even in our bodies. sulfur. more severe and usually design limiting vis-à-vis corrosion. but these are best regarded as exceptions. however. and organic acids. CPT. or it may grow without limit. Such a pit may be unstable and repassivate.

06 0. ..45 0. . as oxide layers do.0 24.0 18.02 0..5 13.0 25.. The advances are quite appreciable and made stainless steel a viable material for many applications for which previously nickel base or titanium alloys had been required..20 0. at least in part because they rapidly formed brittle grain boundary σ-phases in as little as several minutes at some temperatures.03 0..50 0. This was found to increase PREN by another five units..5 10..8 6. also suppressed σ formation to times that permitted thicker sections to be welded without embrittlement.4 6. and 904 without the high levels of nickel and molybdenum that render these alloys so expensive.7 1.7 24.7 1..01 0.02 0.2 6.5 0. This was exploited in the alloys UNS S34565 and S32654.. Early grades were based on alloying with chromium and molybdenum with sufficient nickel added to preserve the austenitic structure.02 0. . The corrosion-resistant austenitic stainless steel grades range from 316 to the various highmolybdenum.3 Cu 0.20% from nominal levels of 0. This permitted even higher levels of total alloying to be achieved... 0.4 18. these alloys were resistant to seawater at ambient but not at elevated temperatures.02 0.3 0.5 0.. These alloys were also very difficult to process.1 2. 0.02 0. First.06 0.. which is an impossible goal in reality..5 19.5 Cu 0.02 0.7 1.4 19.3 Nb . .. Table 5 lists the performance of the various popular corrosion-resistant austenitic stainless steels.5% molybdenum. but that silicon was helpful under such conditions. which contain 3 to 6% manganese and about 0..5 20.8 Cu .2 6. . .03 0. Allegheny’s AL-6X™ is representative of this group.2 Cu .02 0. Then..1 4.4 0..1 3.4 . Nitrogen was increased to around 0. As the alloy content of chromium and molybdenum increase.2 Cu 0.05%. 0.0 20.. The obvious question in view of the success of the use of high manganese levels in conjunction with high nitrogen levels in the most highly alloyed austenitic stainless steels is when this approach will be used for the medium-alloyed austenitics to make alloys superior to 316.. the most notable of which are listed in Table 4 with their typical analyses.06 0..5 0. With PRENs of around 40. 317.4 18. This left a great deal wanting in corrosion resistance..8 1. 0.0 18.1 4.5 21. Table 4 Alloy The discovery that nitrogen was beneficial against corrosion permitted a breakthrough in alloy development by the 1980s.5 0. In view of these trends in Typical compositions of corrosion-resistant austenitic stainless steels Designation C N Cr Ni Mo Mn Si Other Other 316L 316Ti 317L 317LM 904L JS700 254SMO 4565 654SMO AL6-XN Al6-XN Plus S31603 S31635 S31703 S31725 N80904 N08700 S31254 S34565 S32654 N08367 N08367 0.. .50% nitrogen.06 0. The PRENs of these alloys are over 50...0 24.02 0. and the class of alloys known collectively as the 6%Mo alloys was commercialized.40 . and the current density required to form the film is correspondingly reduced.02 0.0 22..5 7.4 16. Research into the thermodynamics of nitrogen in austenite showed that manganese increased the solubility of nitrogen appreciably. Copper was beneficial against sulfuric acid.24 16.1 4.4 0.0 0.5 12..86 / Stainless Steels for Design Engineers a homogeneous passive film..22 0. but more importantly. The chapter on corrosion deals with this topic in more depth..5 0.5 0. It does not take much imagination to envision alloys equal to 904L in PREN with less nickel and molybdenum than 316L that would be almost totally resistant to intermetallic phase precipitation and have much greater resistance to SCC because of higher austenite stability.8 1...0 3. The same case could be made for a 317-equivalent alloy in corrosion resistance with less than 7% nickel and 0.7 1. Further experimentation showed that molybdenum was not beneficial under highly oxidizing conditions. high-nitrogen alloys commercialized in the last ten years.4 Cu 0. Alloy development came in stages. 317 was the most significant corrosion-resistant alloy. . the film is thinner.0 25. Each of these elements facilitates the formation of the passive film and reduces the corrosion rate in the active state..8 10. which gives them a critical pitting temperature around 100 °C.01 0.7 0.3 2.4 . . more chromium and molybdenum were added.1 4. It is on the order of 1 to 10 nm thick. Its formation does not cause chromium depletion beneath it. The passive layer is extremely thin compared to oxide layers.0 24. This limited chromium and molybdenum levels to a total of about 30%. . essentially a 301 in alloy cost. . 1.

What can be said about SCC in austenitic stainless steels with consensus? • Risk of SCC is low at room temperature and increases exponentially with temperature. is lower than the CPT. metal loss. the future use of 316 and 317 should be numbered. • Stress must exceed a threshold for a given set of conditions for SCC to occur. The threshold stress varies with alloy and thermomechanical history. abundant replacements like manganese and nitrogen are available. but also exists in caustic environments. . the environment to initiate SCC must be sufficiently severe to cause localized corrosive attack. The key is to choose an alloy that is resistant under the conditions of use. It is almost entirely lacking in plastic deformation with little. The reason for this lowering of resistance to localized attack has been thought to be related to alloy depletion caused either by dendrite coring during solidification or chromium depletion around inclusions. The mechanism of SCC has been a subject of intense academic controversy for many years. Stress corrosion cracking is the bane of austenitic stainless steels. The use of 316 as a standard alloy should in the future be eroded by more cost-effective alloys such as the lean duplex alloys like 2003. The relation to crevices would thus seem to be that surfaces contain numerous flaws with respect to corrosion resistance. or it may cause SCC in environments in which it would not otherwise occur. It is the lowest temperature at which crevice corrosion occurs. As a rule of thumb. All stainless steels suffer from SCC under some set of conditions of environment and material thermomechanical history. or both. SCC occurs when there is both a tensile stress of a sufficient magnitude and a sufficiently aggressive environment. which has an incubation time. GTAW a wrought alloy also lowers the CPT to about the level of the CCT. much of the literature has focused on arguing a case rather than clarifying the phenomenon. the CCT (critical crevice temperature). • Fracture may be transgranular. this means using an alloy that will not pit under the conditions of use. The critical temperature for crevice corrosion is also measured in 6% FeCl3 (ASTM G-48 B or D). Because of this. pitting resistance equivalent number. • Anodic or cathodic polarization may prevent SCC under conditions at which it would otherwise be expected. then designing its Table 5 Corrosion resistance ratings of various austenitic stainless steels. which. can in a crevice dissolve and alter the environment sufficiently that the new harsher environment can generally destabilize the passive film and proceed autocatalytically. if any. and then proceeds in a discontinuous manner. A crevice is a volume in and out of which diffusion is restricted to a degree that corrosion products accumulate and cause the contained environment to become increasingly aggressive in pH and [Cl–]. intergranular. To a first approximation. • SCC is aggravated by increased chloride concentration and acidity.Chapter 6: Austenitic Stainless Steels / 87 alloy development. • SCC is preceded by localized corrosive attack. The same environments that cause pitting corrosion also cause crevice corrosion. using 30 factor for nitrogen Alloy Designation PREN(a) CPT oC CCT oC 316L 316Ti 317L 317LMN 904L JS700 254SMO 4565 654SMO AL6-XN AL-6XN Plus S31603 S31635 S31703 S31726 N80904 N08700 S31254 S34565 S32654 N08367 24 23 30 34 35 36 46 53 63 50 50 min 15 15 25 30 40 43 73 90 105 78 95 –3 –3 0 4 15 15 38 50 75 43 60 (a) PREN. while not capable of sustaining pitting. This temperature. The most dangerous situation is one in which the expectation of pitting is marginal. • Alloying or treatments that delay localized attack or stabilize austenite can delay SCC up to the point of virtual immunity. Austenitic stainless steels are not alone in their susceptibility to SCC. There is no justification for the use of scarce and expensive resources such as nickel and molybdenum when cheap. Conditions that are below the threshold for pitting can cause crevice corrosion.

Only the most highly alloyed austenitic alloys. Hence. aggressive. These elements are kept low for nitric acid The following discussion presents just the principles of the resistance of austenitic stainless steels to specific. is quite aggressive against stainless steel. and silicon can lower chromium locally. where such information is available freely. The 25% chromium alloys such as 310 or an equal Fig. phosphorus. Hydrochloric acid. resistance to hydrochloric acid is simply an extreme case of resistance to pitting in chlorides with resistance given by Eq 12. refer to the publications of organizations such as the National Association of Corrosion Engineers (NACE) or to the Web sites of companies such as Allegheny Ludlum or Outukumpu. while not beneficial against pitting. Sulfuric acid is common. assuming that the metal will have residual stresses equal to 100% of the yield strength is the prudent engineering approach. So. 17% Cr. Source: Ref 28 . Otherwise. Each contains several percent copper that. The more reputable producers will give assistance on specific questions. while 304L can be used to 90 °C. should be considered and then under conditions that are tolerable. 904L. 25 Isocorrosion in pure sulfuric acid. but 304 NAG with low carbon. chromium and nickel are beneficial. such as www. Pitting is not a risk. 310 is most resistant. should it take place. Molybdenum and tungsten are also very beneficial for resistance to sulfuric acid. It is very effective in destabilizing the passive film. Strong bases such as NaOH and KOH are not especially aggressive against stainless. especially a low carbon version. 24 Threshold stress for stress corrosion cracking (SCC) for various alloys. while molybdenum is counterproductive. • Around the 65% aziotrope. phosphorus. attack. and silicon is more often used. The 17% chromium alloys can be used up to 50 °C. and must be contained. Thus. should also be considered a resource. Figure 25 shows the isocorrosion curves for several alloys in pure sulfuric acid. such as those shown in Fig.eng-tips. Source: Ref 27 Fig. 18% Cr. not surprisingly. This information is extensive since it must correlate many environments and temperatures for many materials. concentrates in the passive film and diminishes general corrosion.88 / Stainless Steels for Design Engineers use to be below the threshold stress completes a sound design approach if residual stresses can be accurately known. alloys with 4% Si. where segregation of elements such as carbon. Standard usage is: • Below 50% concentrations and below 100 °C. Nitric acid is not particularly aggressive against stainless steels. such as AL6XN®. As is the case with nitric acid. is preferably at grain boundaries. Phosphoric acid is similar to sulfuric acid in its effect on austenitics but somewhat less aggressive. Alloy 20. Figure 24 shows threshold stress for a number of alloys. • For 98% solutions or for lower concentrations that contain other stronger oxidizers. Engineering forums on the Internet. 304L and 17% Cr ferritics are used. and 17% Ni (UNS S30600 and S30601) have been developed. Resistance to it is proportional to chromium content. Special Corrosive Environments. 26. Knowledge of the ability of the various stainless steels to resist specific environments is essential to the design process. more common environments. and alloy 825 were developed specifically for sulfuric acid service. and 15% Ni or 5% Si.

Austenitic Stainless Steels. Les Editions de Physique. Paris. as are other stainless steels. Marshall. Very fine abrasive polishing causes little residual stress and has very minimal crevice creation. Microstructure and Mechanical Properties. Vol 56. or when they dissociate strongly. Studies have shown chromium depletion of a maximum of 6% extending 10 μ before reaching bulk chromium levels.. H. p 40 14. Organic acids are generally less aggressive against stainless than are mineral acids since they are less dissociated in solution.217 12. p 566 13. Aciers Inoxidables.” paper presented at Stainless Steel ‘84. They become hazardous when they contain chloride ions. 26 Resistance to hydrochloric acid. equal to a reduction in chromium content of 5%. When exposed to the surface. Chin. Les Editions de Physique. The increase in attack rate from this depletion is huge. refer to the various corrosion tables.” paper presented at Stainless steels ‘77 5. Phys. High-chromium ferritic stainless steels are also very good choices.. that is. F. p 680–688 2. P. Paris. Les Ulis. Met. Vol 48. Vol 77. Delong. p 579 11. W. Aciers Inoxidables.T. Dai et al. Les Editions de Physique. p 98 3. Schaeffler. has a major detrimental effect. J Res. surface abrasion. but they do not enhance corrosion resistance as does electropolished mirror finishes. K. such as with formic acid. Met. McGuire. REFERENCES chromium duplex can be used to 150 °C. Les Ulis. p 564 8. Oxide formation depletes surface chromium. This is equivalent to the depletion seen in sensitization. Design Guidelines for Selection and Use of Stainless Steel. Paris. exposure of MnS inclusions. such pores act as crevices and lower the pitting potential also. Aciers Inoxidables.J. Rolled finishes are much preferred. M. 1993. Q. All of these factors are operative and can act in unison. Aciers Inoxidables. p 565 9. Blom. p 3 4. Les Ulis. mirror-type polished finishes do not degrade corrosion resistance. S. Stand. SSINA. The 120 grit #3 finish often seen on stainless reduces pitting resistance by as much as the equivalent of 5 PREN. Irish. “Press Formability of Stainless Steels. Vol 11.1998. Nov 1949. and residual stress have been cited as possible 1. 1952. A 1000fold increase in weight loss in the ASTM G 48 B test has been seen by a superficial loss of 6% chromium. Paris. at high temperatures.Chapter 6: Austenitic Stainless Steels / 89 Fig. “A Diffusion Model for the Influence of Oxygen and Sulfur on the NonEquilibrium Distribution of Chromium in . p 410 15. “Physical Metallurgical Developments in Stainless Steel.B. p 2. doi:10. The mechanism for this has not been clearly established. Les Editions de Physique. Likewise. Nordberg. Elsevier.-J. Surface Finish.. A. especially coarse abrasion. 2002. Nat. Prog. Powder injection-molded stainless components often have porosity that is generally spherical. Source: Ref 28 contributing causes. Bar. Prog. 1993. 1993.. Constitution Diagram for Stainless Steel Weld Metal. Thus. p 596–600. above which temperature nickel base alloys are required. Les Editions de Physique. Treatments that enhance surface concentrations of beneficial elements or remove detrimental constituents can greatly alter performance.L. 1993. 1993.R. the microcrevices abrasion produces. which can initiate pitting.. 1993. Goteborg 6. Rosenberg and C. Because of the large number of organic compounds that may be considered. Pickering. which remove chromium-depleted sites. Mechanical Properties of Austenitic and Duplex Stainless Steels. Paris. A Modified Phases Diagram for Stainless Steel Weld Metals. Les Ulis. so strong pickling or electropolishing of the descaled surface is especially important. Les Ulis. The corrosion resistance of austenitic stainless steels is quite dependent on surface condition. 1984 10. Aciers Inoxidables.1088/1009-1963/11/6/315 7.-X. Feb 1960. Innovation in Stainless Steels ‘93 (Firenze).

2004. Allegheny Technologies. p 448 Aciers Inoxidables. 1961. July 2004 27. Les Editions de Physique. Accelerated Oxidation of Metals at High Temperature. Les Ulis. Les Editions de Physique. Vinckier. p 128–137 24. Grubb. A Super-Austenitic Stainless Steel for Tubing and Piping Applications. Paris. Les Editions de Physique. 18. Austenitic Stainless Steel Welds and Slabs. Okamoto et al. Trans. paper 04291 presented at Corrosion 2004. Les Ulis.F. 1993. p 568 Aciers Inoxidables.outukumpu.outukumpu. N. www. High Temperature Stainless Steels. p 453 Aciers Inoxidables.. 1993. p 1–15 25. J. 1993. “AL6-XN® Alloy” . NACE. Paris.2004 R. 20. ASM. p 454 www. 21. p 1213–1219 23. Paris. Stickler and A. Les 28. Mechanism of Rapid Oxidation at High Temperature. ACOM W. Nippon Steel Technical Report 90. 1958. J. Vol 44. 22. Trans.90 / Stainless Steels for Design Engineers 16.outukumpu. Les Ulis.. p 362 Aciers Inoxidables. 17. Vol 54. Vol 41.C. www. Trans. J. 19. Grant. Les Editions de Physique. ACOM Files.” paper presented at Proceedings MS&T ‘04. Leslie. Paris. 26. 1993. High Temperature Stainless Steels. 1961. ASM.

as seen in Fig. Their limitations lie in their lack of cryogenic toughness and their inability to withstand temperatures much above 300 °C without forming embrittling phases. 1 Wrought 2205 duplex microstructure . they languished in a suboptimized and underutilized state until recently. They also display exceptional resistance to stress corrosion cracking (SCC) and corrosion fatigue. They should largely replace alloys such as 316L and317L in the future. p 91-107 DOI: 10. toughness. Discovered in the 1920s. The leaner grades. while the higher alloy grades like 2507 compete with the 6% molybdenum superaustenitics in corrosion resistance while still possessing much greater strength. Whether these duplex alloys will grow to the full extent of their potential depends on several factors: • Will high nickel and molybdenum prices be sufficient motivation to drive designers to explore alternatives to traditional austenitic grades? • Will producers overcome their inhibition to aggressively market these grades through their cost-saving potential? • Will producers perfect the techniques to produce these grades reliably so that their availability is unquestioned? • Will design codes change to correctly reflect the duplex materials’ higher ratio of yield strength to tensile strength? Why are there such issues with a family of alloys that has been successfully used for 20 years? The concept of duplex stainless steels is simple: islands of austenite in a continuous matrix of highly alloyed ferrite. This Introduction Duplex stainless steels are the newest and fastest-growing alloy group in the stainless steel family. so they are considered as highly corrosion-resistant alloys but not high-temperature alloys because of embrittling phases.asminternational. Duplex alloys have at least 20% chromium. they are exceptional materials. Their low nickel content makes them more economical than austenitic alloys of the same level of corrosion resistance. especially when their greater strength can be utilized to reduce the amount of material CHAPTER 7 Duplex Stainless Steels Summary THE NEWEST FAMILY of stainless steels is the duplex alloys. McGuire.1361/ssde2008p091 Copyright © 2008 ASM International® All rights reserved. ferrite and austenite. correspond to 316L in corrosion resistance but have double the yield strength. But between –100 and 300 °C Fig. They are called duplex because at room temperature they consist of two phases. www. such as 2304.Stainless Steels for Design Engineers Michael F. and corrosion resistance. The mixture of ferrite and austenite in their structure gives them higher strength than either phase by itself. They possess excellent strength. 1.

keeping the ratio of ferrite to austenite more nearly constant with temperature. Ferrite contains a great deal more chromium than austenite. its pitting corrosion resistance contribution from chromium is much greater than the resistance of the austenite because in duplex grades: PREN = %Cr + 3. 2 The Fe-Cr-Ni phase diagrams. At this point. This lowers the activity of chromium and thereby effectively attracts more chromium to the austenite phase than would otherwise be present.92 / Stainless Steels for Design Engineers combination in principle offers high strength because of the possibility of refining the dual-phase grain structure and thereby raising yield strength according to the Hall-Petch relationship as well as by solid solution hardening. in the ferrite matrix. The shaded area results from nitrogen additions . the control of nitrogen in the refining by the argon oxygen decarburization (AOD) process allowed the control nitrogen content up to the solubility limit. and each phase would have equal corrosion resistance despite having different compositions. Why this was so important can be seen by studying the structure of these alloys. The optimization of the alloy system had to wait for two events. hence. Second. The salient points are that the typical successful alloys nearly bisect the two-phase field for austenite and ferrite. The austenite would be islands If one were to add molybdenum to increase pitting resistance. the understanding of the thermodynamics of the alloy system became understood and reduced to a computer model. and new grades with higher nitrogen vastly improved the performance and user friendliness. It took a long time for that to be accomplished. especially with nitrogen. Additions of nitrogen concentrate nearly entirely in the austenite.3 × %Mo + 16 × %N (Eq 1) Structure and Alloy Design The ideal structure of a duplex grade would be a stable 50-to-50 ratio of austenite to ferrite at all temperatures at which it is to be used without other phases. the alloys developed over the first 50 years of development became obsolete. First. the absence of a continuous austenite phase provides relief from SCC by having any propagation of cracks in austenite arrested by the ferrite phase. This is where nitrogen saves the day. The pitting resistance of the austenite increases signifi- Fig. Figure 2 shows a simple Fe-Cr-Ni constitutional diagram (Ref 1). it would preferentially partition to the ferrite. further exacerbating the differential between the two phases. both related to nitrogen. It is also obvious that the composition of the austenite and the ferrite must be quite different. In addition. This stabilizes the austenite.

6 Variation of partitioning ratio with temperature.Chapter 7: Duplex Stainless Steels / 93 cantly to approximately that of the ferrite. The partitioning tendency is a strong function of temperature. 5 Partitioning tendencies of various elements between ferrite and austenite. 4 The iron-nickel diagram for 25% Cr. Source: Ref 2 . This composition includes the important 2507 alloy. and 0. The 2205 is the workhorse grade of duplex. α is ferrite. Conversely. and molybdenum. Figure 6 shows that as temperature Fig. leaner alloys can be devised that save cost based on reduced molybdenum and nickel.25% N: N is a nitride. developed by the Swedish Royal Academy. ThermoCalc. with the same diagrams varying nickel for a higher molybdenum level. more corrosion-resistant alloys with higher PRENs can also be mapped. and below the 6% molybdenum grades. with PRENs of around 45. greater than 317L stainless. and γ is austenite Fig. Partitioning of elements (Fig. the nitrogen solid solution strengthens the austenite and retards the formation of intermetallic phases. 3 The iron-nickel diagram for 22% Cr. it would be impossible to project the partitioning of the various potential alloying elements. such as AL-6XN alloy. Without being able to computer model the thermodynamics of the system. Figure 3 shows isopleth diagrams for a basic 2205 composition in which nickel is varied. It has a pitting resistance equivalent number (PREN) of about 35 and fills a niche in corrosion resistance where austenitics and ferritics are lacking. such as Fig. In addition.15% N Fig. χ is chi. 3% Mo. has been an especially valuable tool in helping us understand and design better duplex stainless steels. 4% Mo. 0. 5) between austenite and ferrite is an important issue. Ferritics have a gap between 442 (18Cr-2Mo) and the super ferritics (28Cr-4Mo). By varying the chromium. PREN = 30. which is not bad for an element that costs nothing. Source: Ref 2 Fig. σ is sigma. 4. nickel.

If the heating time does not permit this. of which the most prominent and dangerous is σ. with high chromium and molybdenum encounter the σ problem fairly equally and in proportion to their alloy content (Ref 2). so its precipitation has the immediate effect of lowering toughness. but for the major reduction in rate of formation of sigma. the tendency is to increasingly segregate to austenite as temperature increases (Ref 2). For nitrogen. While duplex grades have good oxidation resistance and high-temperature strength. The nitride Cr2N can form when saturated ferrite is quenched from a high temperature.94 / Stainless Steels for Design Engineers increases. by which ferrite undergoes spinodal decomposition into the iron-rich α. with its bad consequences. this so-called secondary austenite will have low nitrogen and therefore low pitting corrosion resistance. Table 1 lists the major grades of duplex stainless steels. so the alloy’s resistance to localized corrosion is compromised also. This helps keep welds from becoming excessively ferritic and disturbing the desirable 50-to-50 ratio of austenite to ferrite. These are of more research than practical interest because σ. A danger in these alloys is that austenite formed from ferrite on heating. which has a formation that follows an Arrhenius-type curve with a maximum at around 400 °C. will contain only the low amount of nitrogen that was in the ferrite from which it was formed. however. including austenitic. This is the reason that the use of nitrogen instead of molybdenum is so beneficial to the leaner alloys. The point is generally moot since all modern duplex grades contain less than 0. A crucial aspect of alloy design in the duplex alloys involves the avoidance of unwanted phases. as can occur in the welding process. Table 1 lists the duplex grades currently available commercially. ferritic. as shown in Fig. Ferrite and austenite both form intermetallic phases. Figure 10 shows the large reduction in σ formation enjoyed by the lean alloy AL 2003™ material compared to the higher molybdenum 2205 alloy (Allegheny Ludlum).030% carbon. The areas around the newly formed σ are naturally somewhat diminished in chromium and molybdenum. Mechanical Properties In many ways. Carbide formation does not as easily cause chromium depletion in duplex alloys because the precipitation at the ferrite-austenite grain boundary does not deplete the austenite as greatly in chromium locally because of the neighboring ferrite having a much higher diffusivity for chromium. The duplex stainless steels have all the potential problems with embrittling phases of the ferritic and austenitic stainless steels combined since they contain both as phases. . making austenite stable to higher temperatures. Alloys of all structures. 7(e). austenitic. R. They offer high as-annealed strength with good toughness and ductility. such as during welding or annealing. It is possible that this would result in nearby chromium depletion and a decrease in corrosion resistance. Secondary austenite with low nitrogen is remedied by diffusion if the phase forms at higher temperatures at which diffusion of nitrogen can rehomogenize the nitrogen level. Carbides and nitrides can also form in duplex alloys. a tetragonal phase richer in chromium and molybdenum than the ferrite from which it forms. normal ferrite. the α′ problem restricts their use to below about 315 °C. the duplex stainless alloys represent a best of both worlds in combining traits from the austenitic and ferritic alloys. They include χ. There are other intermetallic phases in addition to σ. forms sooner and in greater quantity under the same conditions compared to the others. not just in cost. and the chromium-rich α′. the partitioning diminishes until at just above 1300 °C it approaches unity for all normal substitution-alloying elements (Ref 2). until diffusion can restore equilibrium. Higher levels of chromium or the presence of copper or molybdenum exacerbate this reaction. Ferrite forms two main embrittling phases. π. Cold work accelerates the precipitation process by up to an order of magnitude by virtue of its dual effect on nu- cleation and diffusion. which is a brittle ordered alloy. α′ and σ. Figure 7 shows a series of duplex photomicrographs. and duplex. Nitrogen alters the phase stability. Figure 9 shows the TTT (time-temperaturetransformation) diagram for various high-alloy stainless steel. and duplex. It is brittle and forms at grain boundaries. Figure 8 shows the α′ formation kinetics for five duplex alloys (Ref 2). ferritic. and τ. The α′ is generally believed to be a result of the miscibility gap that exists in the ironchromium system.

7 Table 2 lists typical and minimum properties for the major duplex alloys and those of some comparable ferritic and austenitic alloys for comparison. (b) 2205 annealed. (e) 7-Mo Plus with ( (dark areas) that has induced the formation of secondary austenite (arrows) Fig. more than double that of comparable austenitic grades. austenite in a ferrite matrix.Chapter 7: Duplex Stainless Steels / 95 (a) As-cast duplex structure. austenite phase contains twins. (d) Same weld as (c) after homogenization anneal. (c) 2507 as-welded. The most striking and unexpected characteristic of the duplex grades is their high yield strength. . weld is highly ferritic because of rapid cooling rate.

It owes its strengthening primarily to: • Solid solution hardening by nickel. below 0. and results are in megapascals. chromium. 9 Sigma formation kinetics at various alloy levels Rp0.2 = 120 + 210 N + 0.5δ + 8d −1/ 2 (Eq 4) (Eq 2) (Eq 3) Fig. 8 Kinetics of ( formation The strength of the duplex grades is driven by the strength of the continuous ferrite phase.15 − 0.54δ)δ + (7 + 35( N + 0. and manganese • Interstitial solid solution hardening by carbon and nitrogen • Strengthening by grain refinement These components have been related to the mechanical properties by the following equations (Ref 3): Fig..02))d −1/ 2 Rp1.02 +2( Mn + Cr ) + 14 Mo + 10 Cu + (6.g. The influence of nitrogen is interesting in that at lower levels (e. but additional ni- .2 + 40 ± 9 Rm = 470 + 600( N + 0.96 / Stainless Steels for Design Engineers Fig. 10 Delay in ( precipitation in lean duplex 2003 where δ is the ferrite content in percent. d is the lamellar spacing. copper.02) +14 Mo + 1.1% nitrogen) austenite is the weaker phase. molybdenum.0 = Rp0.

03 0.0 2.0 0..23–0.0 1..0–23. . 40 .. .8 .0 24.8 .5 19.0–4.030 0.5–6.35–1.20–0.0–23. 0.5 .2% nitrogen..0 2.25 0.5–8.70 4. The most deleterious effect on toughness comes from the precipitation of intermetallic phases.0 21.040 0.17 0.020 0.30–0.030 0..0 0.0 4.5 2.020 0..040 0. 0.75 1.0 0.5 2.040 0.5 1.0 0.5 1. such as 100 J at –100 °C in the solution-annealed condition. toughness improves with decreasing grain size and deteriorates with cold work.0–8.1–0.03 0.0 24.33 23.5–3.30 0.. 0.10–0.75 1.0 5.0 1.0 1.030 0....0 1.1–0.40 0. .03 0. Because use of these alloys above 300 °C is not recommended..0–5.03 0... 0..2 1...0 21.5 1..25–5.5–3.35 0.0 22. with the austenite taking on a (110) [223] texture and the ferrite (100) [011] to (211) [011] (Ref 2).0– 6.0 5. .0 1.0 0.32 0.24–0. 0. ..03 0.5–5.040 0.5 4.010 0.. 0.030 0.010 0. The two phases are elongated parallel to the major strain axis of working such as from hot or cold rolling.030 0.03 0. .5–3..5–21.5 24.0 6. J S31200 S31260 S31830 S32003 S32001 S32101 S32205 S32304 S32520 S32550 S32750 S32760 S32960 44LN DP3 2205(old) 2003 19D 2101 2205(new) 2304 Uranus 52N+ Ferralium 2507 Zeron 100 7-Mo Plus 450 485 450 450 450 450 460 400 550 550 550 550 485 690 690 62 620 640 650 640 600 770 760 795 750 690 25 20 25 25 25 25 25 25 25 15 15 25 15 293 290 293 290 290 290 290 290 .03 0...5 3..0 1.0–6.0 2.035 0.030 0.2–0... the microstructure and properties become increasingly anisotropic.8 .035 0..0 24.5 .03 0.030 0.0 2.0 0.040 0. Toughness is a significant consideration when using duplex alloys to replace the extremely tough austenitic alloys.0 2.10 0.025 .0 0.25 2.020 1..0 2.5–3. the austenite becomes the stronger phase.20 0. .14–0.08 0.0 5.030 0.03 0..0–5.030 0.8–1.0 0. .1–0.14–0.5 1.0 5.5–3.0 6.0 26.0 24.0 18. Duplex alloy low-temperature toughness is intermediate to that of ferritic and austenitic alloys. . it should be noted that the duplex alloys can have excellent toughness levels.. Impact Strength.04 0.0 .5–2.6 0.. such as α′ and σ.0–5. the dependence of these properties on temperature is significant since flow in body-centered cubic (bcc) structures is thermally activated. .20 0. .020 0.2 Table 2 Grade Duplex mechanical properties Name Rp0..5–2.0–27..0–3.5 2.20–0.5–23. ..0 21.9 3.040 0.0–26.5 3.Chapter 7: Duplex Stainless Steels / 97 Table 1 UNS Duplex compositions Name C N Cr Ni Mo Mn Si Cu W P S S32900 S31200 S31260 S31500 S31830 S32001 S32003 S32101 S32205 S32304 S32520 S32550 S32750 S32760 S32906 S32950 S39274 S39277 329 44LN DP3 3RE60 2205(old) 19 D 2003 2101 2205 2304 Uranus 52N+ 255 2507 Zeron 100 2906 7–Mo Plus DP3W AF 918 0. they also are not well suited to cryogenic use.0 1.5 0...0–30.20–0.0–8.030 0.030 0. .5–8.0 0.25 0.8 0.0–2. ...5 1.0–26.0 1. Since they have a ductile-to-brittle transition.040 0.0 24..0 .05–0.2–2.6 0.08–0.5–21.030 0.020 0.0–26.20 0.0–26.20 0.8–7..14–0. 40 .030 0.0–19.0 24..5–5. 302 310 270 293 31 31 31 30 25 32 32 31 28 32 32 .030 0..30 0.. 0.0–4.0 4.0 3..030 0. ..0 28.8 .0 2.0 1.0 6.20 0.5 1.30 0.03 0. .0–3.0–26. ...0 1.2 6.0 3.0–2.0 2.4–2.0–5.5–2.. which cause a sharp decrease .2–2.0–28..5–6..0 1.0 19. 0.0 1. Figure 11 shows the variation of yield and tensile strengths of various grades along with that of austenite and ferrite of similar composition.8 3. Because the ferrite phase controls mechanical properties. .5–7.040 0.5–1..9–3.030 0.020 0.05–0. As would be expected.03 0..0–26.03 0.035 0.8 1.. ..0–8.8 1.10–0. 40 40 40 .. As working increases.20–0.030 0...8 1.30 0..8 0.03 0. no highertemperature properties are shown.0–26.2 Rm A5 HB RC Charpy-V –40 °C..2–0..5–3. 32 .0–29.15–0.0 24.0 1. trogen strengthens the austenite so that above 0.0–6..0–22.5 3. This having been said..... 0. .5–1.6 1.05–0.0 2.5–3.35 0.05–0.5 3.04 0.0–8.8–1.2–2.0 1.0 0.

11 Variation of ferrite. Lean alloys such as 2001.e. Fig.. While this is intuitively reasonable. 11. Fatigue tests on duplex stainless steels indicate that they possess a fatigue limit of about 50% of the yield strength when tested in air (Ref 4). austenite. Source: Ref 4 . Source: Ref 4 in toughness level and a concurrent increase in transition temperature. Fatigue.98 / Stainless Steels for Design Engineers Fig. and 2101 have a much slower rate of formation of α′ and are much less at risk for loss of toughness from exposure in the 300 to 600 °C range. The combined effect of cold work and α′ can be seen in Fig. its fatigue limit in a given environment approaches that in air. strength and corrosion resistance). it is not diminished because the duplex reward the user with a higher level of yield strength and fatigue strength in air. indicating simply that corrosion plays an increasingly small role in fatigue crack propagation as corrosion resistance increases. 12. The ratio of the fatigue strength in a hostile environment to that in air is a useful measure of the complementary strong points of the duplex grades (i. As an alloy’s resistance to corrosive attack increases. as was shown in Fig. 12 Increase in transition temperature with α′ formation with aging for (a) annealed 2705 and (b) coldworked 2205. 2003. and duplex with temperature. Figure 13 shows that ratio for various alloys plotted versus their PREN. so the net useful strength under cyclic loading is much greater than that of equivalent-PREN austenitic alloys.

because of the greater partitioning of the chromium and molybdenum to the ferrite. it enriches the austenite phase preferentially until the corrosion resistance of the austenite phase reaches that of . had higher corrosion resistance than the austenite. each must carry its own weight in resisting corrosion. ferrite and austenite. Heavily formed sections should be fully annealed. Source: Ref 2 Forming and Machining The higher strength and lower ductility of the duplex grades compared to austenitics gives them correspondingly less ability to be cold formed. Tubing can be expanded into tube sheets. 13 Influence of pitting resistance equivalent number (PREN) to fatigue strength in NaCl solution versus in air. Tubing bend radii should be at least twice tubing outside diameter (OD). not just stress relieved. Operations such as bending. duplex alloys can be cold formed like austenitic alloys. drawing. they behave like ferritics or austenitics of similar alloy level. and pressing can readily be performed. is an alloy level at which excellent formability is seldom expected. however. whenever there is a potential for SCC in the service environment. Nevertheless. but care must be taken to produce tight roller-expanded joints. Early alloys that were lacking in nitrogen generally had a ferrite phase that. Bend radii should be at least twice sheet thickness. This. As nitrogen is added. Duplex alloys have sufficient ductility to be cold drawn. Corrosion Resistance Because duplex alloys are made up of two phases.Chapter 7: Duplex Stainless Steels / 99 Fig.

it has only a minor effect on the copper-alloyed duplexes (Fig. sodium hydroxide. Source: Ref 5 Fig. General Corrosion The duplex alloys offer important advantages in performance over the austenitic grades in a number of significant aggressive media. Source: Ref 5 Fig. Here again. Hydrochloric Acid. more highly alloyed duplex grades. The net result is a type of alloy that has most of the highly desirable corrosion resistance characteristics of superferritic grades without their limiting lack of mechanical properties.5%) gives them much better performance than the otherwise similar S32750. Sulfuric Acid. 14 The 0. Source: Ref 6 . In real-life situations. phosphoric acid. the Fig. 16).5%) and S32760 (0. 16 Isocorrosion (0. 15 The 0. including sulfuric acid. While this contamination is deadly to 316 and 317. mainly toughness. This performance extends to situations in which the aggressiveness of these media is enhanced by contamination. and organic acids.1 mm/yr) performances of several austenitic and duplex alloys.100 / Stainless Steels for Design Engineers the ferrite. such as seen in flue gas desulfurization. hydrochloric acid. Figure 15 shows additional.1 mm isocorrosion curves. Historically stainless steels have had their poorest performance when confronted by hydrochloric acid. which has primarily higher nitrogen.1 mm isocorrosion curves. The use of copper as an alloying element in S32550 (1. Figure 14 shows the behavior of S32304 compared to 304 and 316 in sulfuric acid. This approach is common to all more recently developed alloys starting with the revision of 2205 from UNS S31803 to S32205. sulfuric acid can be contaminated with chlorides.

17 Isocorrosion (0. which was one of the first uses of stainless steel. Indeed. This extends the usefulness of stainless steels to an environment that had previously been off limits. Nitric Acid. in all other instances a very beneficial alloying element. has a strongly negative influence on resistance to this highly oxidizing acid. Consequently. Much of the older published data on the behavior of stainless steel has seemed to promote the notion that higher nickel levels were beneficial in strong bases. Sodium Hydroxide. Phosphoric Acid. Molybdenum. and even then no advantage can be claimed. as is the case of the white liquors of kraft digesters. as seen in Fig. that the duplex alloys with their relatively low nickel levels significantly outperform the higher nickel 304L and 316L. Figures 18 and 19 clearly indicate. 17. respectively. such as S32304.1 mm/yr) performance of duplex in HCl compared to 316L. should be considered for use with nitric acid. Source: Ref 7 Corrosion rates in white liquors plus chlorides. depends almost entirely on the chromium content. It is fairly well known and accepted that resistance to nitric acid.Chapter 7: Duplex Stainless Steels / 101 copper/tungsten-alloyed duplexes show exceptionally good performance. Source: Ref 6 Fig. Source: Ref 8 . While pure phosphoric acid is not a very corrosive medium for stainless Fig. 19 Corrosion rates in boiling NaOH. There seems now to be little to support that notion. The advantage is magnified when the environment is contaminated with chlorides. with performance improving with increasing chromium content. only the leanest-molybdenum duplex alloys. the duplex stainless steels in general can be said to be relatively indifferent to the pH of chloride solutions and are affected rather by the chloride concentration and temperature. 18 Fig.

1 mm/yr) performances of various alloys. Organic Acids. 22. PREN. Source: Ref 9 In combinations of acetic and formic acid. the most aggressive organic acid. Duplex alloys perform particularly well in organic acids and have an excellent record in industrial plants. Alloys such as S32205 perform well. Figure 20 shows the substantial improvement in performance of the duplex alloys over 316L when contaminants are present. and nitrogen levels. contaminants again can render it so. In formic acid.3%Mo (Eq 5) Fig. 21). Pitting Corrosion The different analysis of the two main phases in duplex alloys means that each has its own pitting resistance equivalent number. These relationships are incomplete in that they only address the major alloying elements.127 mm/yr. 304L handles lower temperatures and concentrations. In acetic acid.3(%Mo + 0. Halides are particularly common and aggressive contaminants.102 / Stainless Steels for Design Engineers Fig. molybdenum. S32750 shows virtual immunity. 20 Minimum temperatures for wet phosphoric acid (WPA) with an isocorrosion rate of 0. Even the lower alloyed S32205 can offer an order of magnitude improvement over S31703 in hot contaminated acetic acid. Source: Ref 9 steel. 21 Isocorrosion (0. S32750 is resistant at all concentrations almost to the boiling point. The ferrite phase has the relationship common to ferritic grades: PREN + %Cr + 3. Performance again improves with increasing chromium.5 × %W) + 16%N (Eq 7) .3%Mo + 30%N (Eq 6) The duplex grades partition these critical elements in such a way that the overall PREN of most alloys comes out to be approximately Eq 1. Tungsten has half the value of molybdenum and is frequently included: PREN = %Cr + 3. If one has the actual analysis of each phase. as seen in Fig. while in mixtures contaminated with halides its performance ranks very closely to expensive nickel-based superalloys such as N06625 and N06455. then the proper relationship to use is Eq 2. the superiority of duplex alloys is quite evident. while the austenite obeys the more familiar: PREN + %Cr + 3. outperforming even titanium (see Fig.

22 Corrosion rates for various alloys in 50% acetic plus formic acid. The critical pitting temperature (CPT) of welds often decreases to near the critical crevice corrosion temperature (CCT) of the parent metal. The duplex alloys stand up very well in comparison to corresponding superaustenitic alloys. Crevice Corrosion Crevices exist both by design and inadvertently. which can have higher sulfur levels to increase weld penetration.or molybdenum-rich second (third. Tube welds can be reequilibrated by high-temperature annealing. has very little nitrogen. with pitting potential dropping fairly rapidly with temperature and at different rates for different alloys. These tests are best for judging relative performance of alloys and must be used cautiously when extrapolating lab results to service performance. So. This is because nonequilibrium-diminished concentrations of chromium are often found around precipitates. Figure 23 shows how CPT varies with PREN. The precipitation of chromium. respectively. boiling. This austenite. such as σ or α′ inevitably results in diminishment of these key alloying elements in the region surrounding the precipitate. as in ascast and welded alloys. which forms from ferrite. which will make it more prone to localized corrosion. 12) and because of lower alloy content locally due to solidification segregation. The influence of chloride concentration is strong over a wide range of concentrations. the rankings show a minor variation with pH and a rational relationship to alloy content. This ranking is not always linear. as Fig. but field girth welds will show diminished corrosion resistance if unannealed. reflect long-term performance has not been well established. in this case) phases. This is most significant in welded tubing. 24 shows. Source: Ref 10 If nonwrought material is involved. especially (manganese. untreated welds can have PREN’s 5 to 15 lower than the parent alloy. which equates to the localized lowering of chromium levels.Chapter 7: Duplex Stainless Steels / 103 Fig. principally of molybdenum. which clearly lowers its pitting corrosion resistance. 26). The degree to which short-term tests. whether potentiostatic or strictly immersion. Crevices are occluded volumes of liquid . these relationships greatly overstate PREN. In 3% NaCl (Fig. This can also occur when secondary austenite forms during the heating of alloys to high temperatures. Figures 25 and 26 show the influence of pH and chloride concentration. chromium) S inclusions (Ref 11.

Only soft ferritic stainless steels are immune to it. 24 Variation of pitting potential with temperature. Thus. Stress Corrosion Cracking Stress corrosion cracking (SCC) has long been the Achilles’ heel of stainless steels. the tighter the crevice is. SCE. as can be seen in Fig. 27. the difference is approximately the same as is the difference in CPT between the wrought alloy and the welded alloy. the greater the restriction of diffusion between the crevice and the bulk and therefore the greater the chance of crevice corrosion occurring. 23 Critical pitting temperature in seawater measured potentiostatically versus pitting resistance equivalent number (PREN). Source: Ref 14 in which oxygen and corrosion products reach levels quite different from the exterior environment and become highly corrosive. Source: Ref 13 Fig. An alloy’s susceptibility to crevice corrosion is proportional to its resistance to pitting corrosion under the same conditions. The CCT is lower than the CPT by about 10 to 30 °C.104 / Stainless Steels for Design Engineers Fig. The difference increases with total alloy content. It . saturated calomel electrode. Interestingly.

if not solved. So. SCC has both its initiation and propagation mechanisms still open to debate. saturated calomel electrode. we can map out the conditions under which duplex alloys are susceptible to SCC. Other ferritic and martensitic alloys display pronounced susceptibility to these failures modes when their hardness . While duplex alloys behave in many regards like ferritic alloys in their SCC or hydrogen embrittlement response. This is in spite of their higher yield strength. while we cannot state the mechanism for SCC. The temperature at which SCC occurs at the fastest rate increases with nickel content. and cold work accelerates failure and lowers threshold stress values. Ferritic stainless steels are known for their resistance to SCC in the annealed condition. whose initiation mechanism has not been identified. Source: Ref 5 Fig. The arrival of duplex stainless steels has to a very large degree ameliorated. 26 Critical pitting temperature (CPT) as a function of NaCl concentration. 30). 29) than austenitic alloys. Figure 28 shows the remarkable advantage the duplex alloys have over the comparable austenitic alloys with regard to the temperatures at which they may be used without SCC. In ferrite. Source: Ref 14 Fig. The duplex alloys in this regard are governed in their behavior by their ferrite matrix. But the duplex alloys have good strength mainly through fine grain size and solid solution hardening. 25 Variation of critical pitting temperature (CPT) with pH. 27 Critical crevice temperature (CCT) and critical pitting temperature (CPT). H2S also accelerates failure in chloride environments (Fig. Source: Ref 15 occurs at temperatures and in environments where stainless would be a perfect material if only it did not stress corrosion crack. SCE. The duplex alloys show a higher threshold stress for SCC as a percentage of their yield strength (Fig. which seems to avoid the hydrogentrapping dislocation types that seem to be associated with hydrogen failures. through which cracks must propagate (Ref 16). that problem. SCC susceptibility is a maximum below 100 °C. The major environmental factors that affect SCC are chloride concentration and temperature. Like pitting.Chapter 7: Duplex Stainless Steels / 105 Fig. again giving these alloys more usable strength. they do not have the same relationship between susceptibility and bulk hardness. The advantage of the duplex lies in their composite-type microstructure with the crackarresting austenite phase and the toughening fine grain structure. while in austenite susceptibility appears to begin around 50 °C and increase monotonically with temperature. SCC is unfortunately poorly understood. This is also characteristic of ferritic and martensitic materials and mirrors their hydrogen embrittlement behavior.

it is very important to understand duplex SCC behavior as a separate study and not interpret it in terms of austenitic or martensitic SCC. Testing duration 1000 hr. 30 Suggested chloride and pH limits for cold-worked duplex alloys. Source: Ref 5 exceeds Rc 22. The duplex alloys have annealed hardness over Rc 30 without being in danger. Source: Ref 17 Fig. . This probably simply indicates that hardness as a measure of susceptibility is valid only insofar as it reflects a certain yield strength threshold as it does in tempered martensite and is not valid for ferrite/austenite composite structures.106 / Stainless Steels for Design Engineers Fig. Source: Ref 5 Fig. Thus. 28 Stress corrosion cracking (SCC) in neutral aerated NaCl. 29 Constant load stress corrosion cracking (SCC) tests in aerated MgCl2 at 150 °C.

217–2. Vol 412.47 11. E. B. Werkstoffe und Korrosion. 1990 16. 1991. Conf. Kudo. Proc. AIM. TWI. Williams. Stainless Steels. Les Editions de Physique. 1993. p 1237 7. Innovation of Stainless Steel. J. R. NACE. Walden et al. and G.229 4. Francis. Corrosion Handbook for Stainless Steels. Las Vegas. NACE. P..N. p 511–519 8. Charles. D. paper KIV . The Institute of Metals. April 1992. H.V. Florence. MS&T Conf. p 3–48 5. Beaune. Nordberg H. Houston. Nederlands Instituut voor Lasteckniek. J. Beaune. McGuire. Avesta Sheffield. Horn. R. H. 2003 2. Lacombe. 1986. Bernhardsson. Audouard. Nature. Paper 164 presented at Corrosion ’90. M. Vol 1.. R. M. Duplex Stainless Steels ’91. Duplex Stainless Steels. AIM. C. Beranger. Abington Publishing.-M.M. 1994 10. and A. p 168–175 17. 1990 15. S. Duplex Stainless Steels ’91. Tsuge. 1991. Vol 3. Why Stainless Steel Corrodes. Les Editions de Physique. Nichols J. p 831–846 12. Paper 270 presented at Corrosion ’90. Vol 1. Vol 42. McPhail. Stainless Steel Europe.Chapter 7: Duplex Stainless Steels / 107 REFERENCES 1. Chater. The Hague. Glasgow. Stainless Steel ’93. Duplex Stainless Steels ’86. 1991. Roscoe et al. Ryan. 1988. Gunn. Baroux. Seki. 1994. B. 2004. Les Editions de Physique. p 3. 12th International Corrosion Congress. p 28 3. Duplex Stainless Steels ’94. p 126–135 14.F. p 137–150 6... 1994. Las Vegas. Drugli et al. NACE.. p 45 9. p 2. p 770 13. and D. B. 1997. Bernhardsson. Proc. Hutton. T. Florence. S. Stainless Steel ’87.P. J.

the first commercial use of argon oxygen decarburization (AOD) changed the world for ferritic stainless steel. which combine strongly with carbon and nitrogen and effectively remove them from solution. Introduction Ferritic stainless steels are simplest. Their carbon levels cause them to form some high-temperature austenite. which can render them brittle. reduced the carbon plus nitrogen levels sufficiently that their effect could be nearly negated by small additions of titanium or niobium.and oxidationresisting alloys in existence. 434.Stainless Steels for Design Engineers Michael F. They are useful mainly as light-gauge sheet since their toughness drops off rapidly for heavier sections. to develop the fully ferritic structure. which requires a lengthy subcritical anneal to avoid martensite and to evenly distribute chromium after all carbides have stably formed. The mechanical properties of ferritic stainless steels appear similar to austenitics strengthwise. The lower thermal expansion coefficient of ferritics makes their scale more compatible with the base alloy and provides them with a lesser tendency to spall.04%. It was not until carbon and nitrogen levels were brought down to AOD levels that it became truly practical for ferritic alloys. CHAPTER 8 Ferritic Stainless Steels Summary THE FERRITIC STAINLESS STEELS are the lowest-cost highly corrosion. This makes their welds brittle. and the . rendering it useless as a corrosion fighter. they contain simply enough chromium to overcome their inherent level of carbon impurity and hit the 11% chromium in solution required for “stainlessness. and 446 and the more modern stabilized alloys led by 409 and 439. p 109-122 DOI: 10. So much extra chromium was required because during annealing. www. The older. they could still economically displace the popular but expensive 304 for many routine applications. To be used. In October 1967.1361/ssde2008p109 Copyright © 2008 ASM International® All rights reserved. 430 came into being. They are ferritic at all temperatures (excluding for the moment the possibility of extraneous phases such as (α' and σ) and can be easily welded without fear of unwanted phases. McGuire. technology was documented long before AOD was invented (Ref 1). carbon combines with chromium. This process. The level of carbon plus nitrogen was lowered from around 0. This makes them excellent for high-temperature applications with thermal cycles. and less-expensive high-carbon ferrochromium could be used instead of expensive low-carbon versions. In their minimal form. lowestcost stainless steels. there exist two types of ferritics: the early high-carbon types such as 430. This process is called stabilization. Even as they have grown in use more than any other type of stainless. which transforms to martensite if quenched. and they are limited at low temperatures by brittleness and at high temperatures by softness.” Early in the 20th century. they are normally in the annealed condition. unstabilized grades are not always fully ferritic. and the attainable levels of carbon removal required 16% chromium for this to occur. Stabilization does not preclude excessive grain growth in the fusion or heat-affected zone (HAZ) of welds. but they lack the ductility of austenitics. provided their strength is adequate. The newer stabilized alloys behave as if they are interstitial free.10% to around 0. 436. in which argon and oxygen are blown through the molten metal to selectively remove carbon without removing chromium (described in detail elsewhere in this book).

Now. The historical archetype of ferritic stainless steels was 430. relatively low cost. The main attraction of ferritic stainless steels over austenitics is their cost. The new archetype for this medium-chromium level is 439. A similar predecessor was 410S. A modern offshoot of these alloys. such as appliances. this alloy overcomes the problems of 430 and can readily replace 304 in most applications with significant cost savings. both of which can cause local chromium depletion and pitting. But.110 / Stainless Steels for Design Engineers The corrosion resistance of ferritics is hampered by their inability to utilize nitrogen. opening up what eventually became the largest single market for stainless steel. There are a few exceptions. it is generally used instead of 439 whenever the part can be designed to be formed from it. the predecessor of 409. In North America.02% and the use of dual stabilization by titanium and niobium. then the total cost of 304 versus 439 is doubled by its presence. are essentially free from stress-corrosion cracking (SCC) since they are below the threshold hardness for hydrogen embrittlement in body-centered cubic (bcc) ferrous alloys. The key issue of the 11% chromium ferritics is how to deal with carbon and nitrogen. heat exchangers. It was made possible by the very low carbon plus nitrogen levels the AOD process provided and the use of stabilization. moreover. The 405 and 410S take the approach of minimizing it and live with annealing. This alloy has roughly the corrosion resistance of 316L but is fully resistant to SCC in the welded or annealed condition. Its drawbacks are lack of weldability. Ferritics. compared to carbon steel. The low-chromium ferritic stainless steels began with the development of MF-1. which characterizes these alloys.5 to 12. This has largely been overcome by better refining techniques to reduce carbon plus nitrogen to levels below 0. a low-carbon version of 410 to which some understabilizing amount of titanium is added but that still requires annealing for full ferritic properties. No design engineer can afford to ignore this level of incentive to learn to use ferritic stainless steels. medium (16 to 19%). the amount of titanium required to combine with it can reach levels at which the first TiN precipitates in the molten metal. which has existed since the 1920s and is still widely used. The hidden problem with using only titanium is that unless nitrogen levels are made very low.and beverage-processing equipment. causing casting problems and surface defects. Ferritic Stainless Alloys The ferritic stainless alloys generally group in low (10. 434 and 436 are little used as their historical application in automotive trim finds little place in today’s automotive styling. 468 (UNS S40930) is such an alloy. These distinctions are somewhat imposed after the fact. Rather than giving them an order that they truly do not possess. A fair comparison might be between 439 and 304. There. is 444. The absence of nickel. Both the nominally 11 and 18% chromium alloys are sometimes modified to enhance their high-temperature strength or oxidation . The titanium stabilization of the modern alloys has quite a beneficial effect since titanium is a powerful deoxidizer and desulfurizer. which are basically molybdenum enhanced 430. 439 is mainly used as a higher-temperature automotive exhaust alloy. and low carbon suppressed martensite. 409 was an improvement on 405 in which aluminum performed a quasi stabilization. and formability permitted it to replace aluminized carbon steel and cast iron in automotive exhaust systems. They can be stabilized or not. and modest formability. Its excellent corrosion resistance. With 17% chromium and single (439) or dual stabilization (468). This makes it especially useful for applications such as hot water heaters. This gave 409 a reputation as a grade unsuitable for applications that required good appearance because the titanium streaks were difficult to avoid and greatly highlighted by polishing. and food. This slaggy precipitate agglomerates. if nickel is selling for $7 per pound. The corrosion resistance of these two alloys is barely distinguishable under normal ambient conditions. and high (greater than 25%) chromium. They are both very formable and weldable. relatively poor corrosion resistance because so much of its chromium is tied up as carbides. The 409 uses full titanium stabilization. but in Europe 430Ti is used extensively in more visually challenging applications. is not a problem since nickel adds little to corrosion resistance. Thus. good welding. The old comparison of 430 versus 304 is a bit unfair since 304 is richer in chromium. in the 1960s.0%). The vast majority of the objects made commercially from 304 could be switched to 439 with no adverse consequence. the most significant alloys are all listed in Table 1 with their compositions.

. ...75 1 1 1 0.08 .4 .. 0.04 0. .... .04 0..03 . 0.5 . .....04 0.025 .06 0. 10.....10 0.04 0. 0.. 1 .03 0. 0...5 0.. 0.7 409Ni S40975 0..02 0. 0.03 0.08 0. . .. . .....5 439 439LT S43035 S43932 0..0–20... 13...45 ..03 0. . ... 1 0... 0. ...03 17..02 10.....04 0. .. 0.. .3 0.7 Al 1 Al ..75 Nb 0... ..3 0.. ....25 1 1 1 0.03 0.75 10...2 0.05 0.. 0.03 ...5–11...01 17.. 13 4724 0. .5 0. .. 1 1 . 0. .3 Chapter 8: Ferritic Stainless Steels / 111 4742 AK alloy typical AK alloy typical Outukumpu typical 0.15 Al ... ....5 0.75 ..04 . ...0 430Se S43023 0.06 0. ....75 409 ultraform AK alloy 0...7 466 409Cb S40930 S40940 0... 0..20 + 4x(C+N) to 1.15–0..... ..0–18.0–16..12 0..015 11..35 Ti + Nb: 0..Table 1 Cr Ni Mn Si Mo P S Other Ti Nb Ferritic stainless compositions 0. .. 18 18SR 0...17 .75 0.12 0. .....0 18 Cr-Cb 0.015 .. ... .. 17. .0–18..35 12 SR 0. 1 ..025 .5 0.3 .. ....08 .02 .02 6x(C + N) to 0... ..03 10.03 0..25 0. .35 1 0. .7 409 S40920 0..... .. 0.03 .45 0.02 0..04 0.04 0..10–0. 0...75 Ti+Nb 0. 10.20 + 4x(C+N) to 0....08 .20 + 4x(C+N) to 1.035 0.03 .02 0..7 1 0. 0... . 0. 1.5–1 0.035 0.04 0.5 0. ..5–11.2 .25 . 0..12 .... .....0 16.50 1 .02 0.0–13...5–11...10 0. 0.75 409 S40910 0.. ..3 .. 1 1 ..15 min 0..0–18. 1 1 1 1 0.5–11....04 0.03 10..1 0.20 + 4x(C + N) to 1.. 16..0–19.75 ..001 0.....45 1 1 1 . 1..01 0.15 Al .03 . ..5 1 0.. 18... AK alloys S46800 0...01 0. 0.04 0....0 16.015 12 Alfa I 0.10 0.. 0.. .45 6x(C + N) to 0.25 . .. 0..04 16..5–11..7 11 Cr-Cb 0. .. .6 . 1 1 1 ..5 0. ..5–11.04 .. .. ... . ..5 429 430 430F AK alloy typical AK alloy typical ATI alloy typical ATI alloy typical Outukumpu typical S42900 S43000 S43020 0...55 ..... (continued) 0. 18 1. 14..03 0.02 . 11..2 Al 3 Al 4 Al 1 Al .7 1 1 1..01 8x(C + N) 0.. 13 Alfa II 0....07 0..5–14.25 .... ..25 1..0–19 439 HP 439 ultraform 468 ATI.. .06 .03 0. 0..05 ...4 .0 430Ti S43036 0. 0.5 0.3 0.03 0. 1..0 17.8 + 8x(C+N) Ti + Nb 10xC to 0... 0.04 0. .6 ...5 12.. .5–11.30 Al 0.03 10... . .3 . 0. ..0–19... ..... .. . 1 ..15 Se 0. .35 0.. 1 .. ...04 0.. 1 .06 0.04 ..12 . . .03 0..0 409 S40900 0... ... . ..03 0.25 Al Alloy Designation C N 405 400 S40500 AK alloy 0.02 8x(C + N) to 0.5 0. . ..01 0. 1 0....03 .

..5–0..025 0. 430J1L 0.75–1.015 ...5 .. 20 10x(C + N) ...25 0. . 112 / Stainless Steels for Design Engineers 442 436S 444.80 1 1 1 0.. .2 0.01 0..Table 1 Cr Mo P S Ti Ni Mn Si Nb Ferritic stainless compositions (continued) Other Alloy Designation C N 434 436 441.... S44627 0.4 ..25 . 0. 22 E-Brite..04 .04 0..6 0...3 .4 . . .2 0. S44200 ATI alloy typical S44400 0.25 0.025 0. S43400 S43600 S44100 0...04 0. .0–27.04 0. .20 + 4x(C + N) to 0.04 0..01 . . 0. . . .5–3.... ....5 433 0.5 . 26-1 3.5–4....025 0. 1.3 8x(C + N) min Ti + Nb: 0. Nb + Ta 5xC 0. 24 453 ATI alloy typical Outukumpu typical ATI alloy typical 0.20 + 4x(C + N) to 0.... 0... 0..6 0.02 0. 9xC 0..20 + 4x(C + N) to 0.3 0. YUS 190-EM 0.0 28.0 26....12 0..5 Cu + Ni ..01 .035 . . 0.3 .04 0.5 0.5 3. 0.03 .03 0.5–19. ... . ..20 + 4x(C + N) to 0. .....0 .02 0.1-0. .04 0.03 0.80 Ti + Nb: 0.. .0–27.03 1 0...75–1.04 0...5 1.0–18..5 0....... 0.12 0.. . .2 Cu 0.03 ..2 0. .02 0..3–1.8 17..5 0.80 .. ..7 .025 0.03 0. Ti + Nb: 0.5 0.25 0.. 4509. .5–3. 0.5–26.. 16...001 ... ..5 3.03 ..20 Monit Sea-cure 29-4C 446 CC-50 S44635 S44660 S44735 S44600 Cast alloy 0.. 0.. . ..0 25.5–4.001 .4 0..... .4 0... 1.0–27.035 17..0–18...3 0.2 1 0..7 1.6 4 1 1 1 1..0 16.03 0. .1 REM 0.03 0.80 Ti + Nb: 0.015 18. .5 Al 0.5 ...0 17.04 0. 0.03 0.5 2. .5–18. ..4 .25 . 4762 0. ..60 Al 0..04 0. .5 1 0. .. 24.0–30 23.25 . 1 1 1 1 1 1 0.08 .... ..5–4.0–30 0.02 0..02 0.0–23..75–1.035 0.3 0.015 25.75 1 1.02 0..75–1..75 1 0..

To obtain high toughness. which would lead to breakaway oxidation.e. The use of silicon and aluminum decreases formability and can accelerate (formation.e. while additions of chromium. 0... The performance of 446 has been exceeded by lower alloyed grades. It is difficult to say ferritic stainless steels are underutilized since they account for about half the world’s production of stainless. This was the purpose of the earliest highchromium ferritic stainless. these are usually developed for specific automotive needs and employ all or some of these alloying variations. it was vacuum refined to very low carbon plus nitrogen levels. As with other ferritics. Alloying with niobium and molybdenum adds to the high-temperature strength. exhaust manifolds). 1 Iron-chromium phase diagram from Thermocalc . The high-chromium alloys. Alloys with more than 20% chromium are used specifically for high-oxidation or corrosion resistance. are usually called superferritics. rare earths act as very powerful oxide and sulfide formers that concentrate at the metal-oxide interface and stabilize it. As in austenitic alloys. Ferritic stainless steels are a viable alternative to nickel-bearing austenitics when thickness is 2 mm or less and drawing and bending instead of stretch forming is permitted. but there are many applications in which more expensive austenitic stainless steels are used needlessly. There are many applications where the longer corrosion life of low-chromium ferritics should economically replace carbon steel. (E-Brite now has a new life as a fuel cell material based on its oxidation resistance and very low thermal expansion coefficient. There exists an array of proprietary alloys as shown in Table 1. In the 1960s. less than several millimeters). so their use involves trade-offs. This alloy and its close neighbor SeaCure® are used primarily in tubing where corrosion resistance is most important.Chapter 8: Ferritic Stainless Steels / 113 resistance. Despite the relative lack of hightemperature strength. when used for corrosion resistance.) These alloys saw success as replacements for 316L when SCC was a problem. 2 with the level Fig. It is also used in heat ex- changers and extensively in condensing portions of high-efficiency residential furnaces. It was developed for welded condenser tubing where seawater or brackish water is involved. A prime example of the state of the art is 453. as seen in Fig. this alloy was stabilized and became the still-popular AL 29-4C®. Later. the driving force has been the requirements of the hot end of exhaust systems (e. The lower-alloyed Seacure had a slight toughness advantage that permitted it to be used at wall thicknesses of 1/16 in. silicon. such as the aluminum-alloyed ferritics. There are no technical barriers to obtaining these savings. so early metallurgists saw the diagram shown in Fig. austenite does not exist at any temperature in pure iron chromium alloys. It was followed by the more capable 29-4®. Metallurgy of Ferritic Stainless Steels Chromium stabilizes the ferritic structure at high temperatures.1%). Thus. Again.. E-Brite® was developed. as they have in automotive exhaust systems. these alloys are particularly useful because of their high-oxidation resistance. This type of alloys finds use in high-temperature applications such as planar oxide fuel cells. 446. above about 11% chromium. when AL29-4C® was too brittle. However.6% aluminum but also rare earths in trace amounts (i. The close match between the thermal expansion coefficient of the scale and the alloy prevents spallation of the oxide.g. design engineers need to learn how to use these alloys. iron-chromium alloys devoid of carbon are not practical. these alloys are generally only suitably tough when used in thin section size (i. which they derive from the tight adherence of their oxide scale. which has not only 22% chromium and 0. 1. again preventing spallation. and aluminum increase oxidation resistance.

20%. 3 Iron-chromium diagram at low carbon levels Source: Ref 2 . but they are treated later as a variation from the normal ferritic alloys. This is called high-temperature embrittlement because it comes from putting carbon and nitrogen into solution at a high temperature and then causing it to precipitate in a harmful manner. 3. So. which are fast-diffusion paths. This severely embrittles the material and does not avoid sensitization. unstabilized fully ferritic alloys are not feasible below 20% chromium without extreme refining techniques. chromium is combined in situ. such as electron beam refining. Thus. The introduction of AOD refining permitted much lower levels of carbon. Carbon and nitrogen added together produce about the same effect as carbon alone. These alloys were only ferritic at room temperature if they were given a subcritical anneal to transform austenite to ferrite. This can be eliminated by a Fig. such as 430. especially along grain boundaries. Rapid cooling of unstabilized alloys causes carbon and nitrogen to precipitate within grains. at room temperature they would be ferrite plus martensite. Carbon is essentially insoluble in ferrite at ambient temperatures. and the alloy is sensitized. nearly all modern ferritic alloys Fig. which represented the purity level attainable in arc furnace refining.114 / Stainless Steels for Design Engineers of carbon at 0. as seen in Fig. This locally depletes chromium. which are not commercially viable for low-cost alloys. This is standard in the processing of unstabilized ferritic stainless steels. Otherwise. opening the door for fully ferritic stainless steels. and carbides of chromium and iron will form to the extent carbon is available. 2 Iron-chromium phase diagram at 0. Since carbon diffuses interstitially much more rapidly than chromium can substitutionally. There are alloys that are intended to use a mixed ferrite/martensite structure.20% carbon sufficiently long homogenization anneal at a low enough temperature that carbon and nitrogen have very little solubility.

the removal of oxygen begins in the molten state with the formation of titanium sulfide and nitride and next in the molten or solid state. “Austenitic Stainless Steels”). and sulfur in that order. Carbon in austenite can be retained in supersaturation for extended periods of time. In ferritics. TiC forms. It is desirable to keep sulfur and nitrogen low enough that precipitation is in the solid state so that precipitates do not agglomerate and cause large primary inclusions that become unsightly surface defects. since carbon mobility is quite high. TiCS forms in the solid state if sulfur is present. and sensitization is alleviated by prolonged heating in the 600 to 850 °C range to allow chromium to equalize where carbide precipitation has previously made it inhomogeneous. 4 430 time-temperature-transformation (TTT) curve. This will be seen to have a major influence on corrosion resistance as the MnS inclusions generally associated with the initiation of pitting are not found in titanium-stabilized grades of normally low sulfur. such as 321. it is not practical to quench alloys quickly enough to prevent carbide precipitation as is possible in austenitics (detailed in the Chapter 6.” This means that a strong carbide former such as titanium or niobium is added in sufficient quantity to combine with all the carbon plus nitrogen. Because of these factors. This is why austenitic L grades do not sensitize even though they are slightly supersaturated.40 T (Eq 5) (Ti )( N) = (Eq 6) It must be noted that titanium has an even higher affinity for oxygen and sulfur than for carbon. the heat treatments to avoid sensitization are essentially reversed. carbideSource: Ref 3 . Stabilization causes nonchromium carbides to form at high temperatures. The thermodynamic driving force for carbide and nitride formation is given by (Ti )(C) = −7700 + 2. Figure 4 shows the time-temperaturetransformation (TTT) curve for an unstabilized 430-type alloy with carbon plus nitrogen of 0.Chapter 8: Ferritic Stainless Steels / 115 are “stabilized. so that the removal of carbon from solution is preceded by the removal of oxygen. Fig. The latter effect was real in early austenitic alloys.08% (Ref 3). 1. depending on concentrations. nitrogen. K. The rate of diffusion of carbon in ferrite is around 100 times greater than that of carbon in austenite. Sensitization occurs at higher levels of carbon by prolonged heating at 600 to 850 °C.e. The net effect is that modern stabilized ferritic alloys behave as interstitial free and can be mapped using the pure iron-chromium diagram shown in Fig. greater than about four times the carbon plus nitrogen). precluding chromium carbide precipitation. The solubility of carbon in ferrite is vastly lower than it is in austenite. leading to knife-line corrosion attack after welding. The stabilization formula in various specifications is more than four times the carbon plus nitrogen because experimentally it has been found that sometimes understabilization occurs. removing them from solution. But. This is due to the influence of oxygen and sulfur having prior compound formation with the titanium and less importantly that kinetic factors prevented TiC formation. carbon cannot be kept in supersaturation even by the most rapid quenching. which have much greater diffusion rates than austenitic alloys. Essentially all carbon is removed from solution below 1250 °C if carbon and nitrogen are kept as low as possible and a stoichiometric amount of titanium is available (i.. if not. but does not exist in low interstitial ferritic alloys. These reactions are simply: Ti + C = TiC Ti + N + TiN Nb + C = NbC Nb + N = NbN (Eq 1) (Eq 2) (Eq 3) (Eq 4) Titanium is the stronger getter for carbon and nitrogen. In practice.75 T −15790 + 5.

Before the nature of α' was known. its formation causes chromium depletion of the adjoining ferrite. can form intermetallic phases.e. but regaining full homogeneity is not immediate. The most prominent is σ. The σ may be redissolved by solution annealing. as does nitrogen. Since cold work enhances substitutional diffusion. The α' is the ordered equiatomic chromium iron phase that forms by spinodal decomposition. Thus. and this causes it to have a major embrittling effect. it is a hard. Temper embrittlement is the segregation of phosphorus to prior austenitic grain boundaries and does not occur in fully ferritic alloys.000 psi. Figures 5 and 6 show the hardening effect of α' and the resulting loss of toughness. like austenitic alloys. The σ forms preferentially along grain boundaries for diffusion reasons. Formation requires substitutional diffusion of chromium so is slower to form than carbides. The influence of substitutional alloying elements is also quite significant. which occurs in martensitic alloys at the same temperature. Because the lattice so closely matches that of ferrite. which can be seen to form in higher-chromium stainless steels (i. Pure iron is an extremely soft material with a yield strength well under 10. 5 Influence of α' formation on hardnessSource: Ref 4 . Mechanical Behavior Ferritic stainless steels are quite similar in their mechanical behavior to carbon steel. it accelerates σ formation.116 / Stainless Steels for Design Engineers Ferritic alloys. minutes rather than seconds. This was named 885 °F or 475 °C embrittlement before its cause was understood. According to Fig. it was confused with temper embrittlement. Another embrittling phenomenon is the formation of α'. it has the same composition as σ but exists at a lower temperature with the same structure as ferrite but with the chromium and iron atoms in an ordered bcc matrix in which iron and chromium occupy sites equivalent to two interlocking simple cubic matrices.. The main influence of chromium is to produce some solid solution hardening. It also causes a loss in corrosion resistance via the chromium depletion of that part of the matrix that surrenders chromium to the α'-phase. respectively (Ref 6). Let us review the strengthening mechanisms of bcc iron. the precipitate is coherent and causes hardening. Formation of σ occurs when such alloys are held between 500 and 800 °C. The α' embrittlement causes an extreme loss of toughness as well as hardening. brittle tetragonal phase with equal parts iron and chromium. This softness is not seen in practice because steel is never pure. those with chromium plus molybdenum of 20% or more). Carbon has an extremely powerful effect on hardening.

The worst toughness-inhibiting effects come from interstitial elements to grain boundaries: oxygen. Stabilizing removes the interstitial carbon and nitrogen.Chapter 8: Ferritic Stainless Steels / 117 Fig. but the lack of an austenite-to-ferrite transformation in stabilized ferritic stainless steels negates this benefit for them. This mechanism also increases the impact transition temperature unfavorably. Manganese and silicon are normally deoxidizers. Fig. To maximize softness and formability. They contain as little manganese. . so its presence at around 0. along with oxygen and sulfur. 7 Influence of substitutional elements on hardness of iron alloys The softest ferritic stainless alloys are the 409 variations made for highly formed exhaust system components. Elements that produce a refining of grain size are the exception to this general rule in carbon steel. carbon. and nitrogen. 8 (Ref 8). The effect of carbon plus nitrogen on transition temperature is profound.02% is normally a given unless low-phosphorus raw materials are used as a starting point. the misfit of solute atoms causes lattice strains proportional to the amount dissolved and provides strengthening through the lattice friction term. as seen in Fig. from solution. so that the resulting precipitate fraction after titanium addition is as low as possible. titanium and niobium in excess of that required for stabilization must also be minimized as they will cause solid solution hardening. because the precipitate itself has a hardening effect. but in titanium-stabilized alloys. nickel. titanium takes over the deoxidizing role so their presence can be limited. This does not produce a major softening. Phosphorus is virtually impossible to refine from stainless steel. Figure 7 shows that fairly common ingredients and impurities have strong hardening effects (Ref 6). and other substitutional elements as possible and have a minimum of carbon plus nitrogen. silicon. however. 6 Influence of α' formation on toughness Source: Ref 5 Paxton (Ref 7).

6 × N (Eq 8) As titanium and niobium are added to alloys. Titanium combines with carbon and nitrogen stoichiometrically by: Ti = 4 × C + 3. but without proper heat treatment even alloys of this purity can incur debilitating loss of toughness due to carbide and nitride precipitates (Ref 9). so stabilization is the correct engineering answer. through which both weld and base metal toughness and corrosion resistance are optimized. 9 Corrosion of titanium-stabilized 29% Cr plus 4% Mo alloys in ASTM A 763 Y test. It was not known until about 1980 just what the mechanisms of embrittlement were in the ferritic stainless steels. Excess amounts of the stabilizing elements have negligible effect. 11 and 12) (Ref 11). Source: Ref 11 Fig. Maximum improvement in corrosion resistance levels off once full stabilization is reached. 8 Influence of interstitial carbon and nitrogen on toughness transition temperature Source: Ref 8 Stabilization Stabilization is essential to ferritic stainless steels to avoid the precipitation of grain boundary carbides. Source: Ref 11 Niobium requires a greater weight percentage: Nb = 7. Stabilization is generally considered as the simple gettering of carbon and nitrogen by a suitable carbide and nitride former. 9 and 10) (Ref 11). The upshot of this understanding was the introduction of dual stabilization. The distinguishing of α' from those related to interstitials and their stabilizers (Ref 10) permitted stabilizing elements to be optimized. This toughness reduction is more pronounced with titanium.4 × N (Eq 7) Fig. Toughness improves for niobium-stabilized alloys up through full stabilization and then begins to decline. however. 10 Corrosion of niobium-stabilized 29% Cr plus 4% Mo alloys in ASTM A 763 Y test. This is a result of excess stabilizing alloy acting as a solid solution hardener and therefore a toughness reducer.118 / Stainless Steels for Design Engineers Fig.7 × C + 6. These levels are not economically attainable for commercial alloys. which is a stronger solid solution hardener (Figs. their corrosion resistance is improved (Figs. The same study recommended that dual stabilization follow the following formula: . Combined carbon plus nitrogen levels below 100 ppm are necessary to avoid both sensitization and embrittlement. This is probably due to titanium’s ability to eliminate sulfur and oxygen from solution. but titanium-stabilized alloys have a lower rate of corrosion than niobium-stabilized alloys.

there is no automatic grain-refining transformation as exists in carbon steel. there would be few instances when the use of the much more expensive nickel-bearing grades would be justified.Chapter 8: Ferritic Stainless Steels / 119 (Ti + Nb) ≥ 6 × (C + N) (Eq 9) Fig. Stabilized ferritic stainless steels are seldom used in thicknesses of over several millimeters because of decreasing toughness. 13) (Allegheny Ludlum). 13 Toughness of dual-stabilized low-alloy ferritic stainless. AL 466 is recognized as S40930 . 11 Charpy V-notch impact ductile to brittle transition temperature (DBTT) of titanium-stabilized 29%Cr plus 4%Mo alloys test. Source: Ref 11 Fig. They also have too great a tendency to form intermetallic compounds. If grains grow large from annealing at high temperatures or welding. Section size also has an effect. then the transition temperature increases. Figure 14 shows how transition Fig. Because stabilized alloys are ferritic at all temperatures. Toughness in ferritic stainless steels is a major consideration. If ferritic alloys enjoyed the same toughness as austenitic alloys. 12 Charpy V-notch impact ductile to brittle transition temperature (DBTT) of niobium-stabilized 29%Cr plus 4%Mo alloys test. Other strong carbide formers such as zirconium and vanadium are ineffective stabilizers because their mobility at the temperatures at which they are thermodynamically capable of forming sufficiently large percentages of carbides and nitrides is too low to rid the matrix of these elements. Source: Ref 11 The toughness of these alloys has a broad optimum that takes advantage of the corrosion-resisting benefits of titanium (Fig.

A combination of careful chemistry design and thermomechanical processing is required to keep it under control.120 / Stainless Steels for Design Engineers tion. have pronounced mechanical anisotropy. This same phenomenon means that they cannot be stretch formed since plain strain quickly results in fracture because of the resistance to deformation in the thickness direc- When this expression equals 1. Furthermore. They resist thinning. They are subject to ridging. This is an artifact of texture in the material. This puts niobium in solution during hot working where it can interact with dislocations. which is the formation of visible ridges parallel to the direction of elongation. When ferritic stainless steels are deformed. Thus. with ferritic stainless steels with elongations in tensile tests in the mid-30% range being nearly equal to austenitic stainless steels with over 50% elongation. the drawability increases. certain crystallographic slip systems predominate. high stacking fault energy. which can translate to finer grain size and less anisotropy. But. The ferritic stainless steels in sheet form have LDRs of around 2. The lack of dissociation of dislocations encourages cross slip. the anisotropy does result in remarkable drawing characteristics. randomness of grain orientation is never achieved.2 compared to 2. as measured by the limiting drawing ratio (LDR). 14 Change in transition temperature with thickness for 29Cr-4Mo-2Ni alloy. when ferritic stainless are deformed. Hot working merely reorients these similarly oriented grains en masse. So. The good formability of ferritic stainless steels has some drawbacks. the ratio of the diameter of a disk to that of the deepest cylinder into which it can be drawn. This is because titanium carbides and nitrides form at higher temperature and are therefore coarser. alloys at least partially stabilized with niobium can achieve greater recrystallization. they contract in the width direction while keeping virtually the same thickness. The measure of anisotropy is the Lankford ratio. and lattice anisotropy. This minimizes dislocation tangles and work hardening. . Heavily cold-rolled and annealed ferritic stainless steels draw quite well. then a material is isotropic. Texture and Anisotropy The deformation of ferritic bcc materials is characterized by limited slip systems. When elongated. As the value increases from 1. Titanium-stabilized steels show more texture and recovery versus recrystallization than do niobium-stabilized alloys. Without phase changes or enough stored energy to provoke full recrystallization. It is expressed as: R= r0 + 2r45 + r90 4 (Eq 10) Fig. Source: Ref 12 temperature can increase with thickness (Ref 12). This effect is due simply to stress states transitioning from biaxial to the more embrittling triaxial with increasing thickness. niobium precipitates tend to dissociate to a greater degree than those of titanium. This preferred deformation along easier slip planes results macroscopically in overall mechanical properties varying with direction with respect to the prior deformation. They thus present less obstruction to dislocation motion than finer niobium precipitates. like low-carbon steels. The ferritic stainless steels even carry forward some of the preferred grain orientation that come from initial solidification when growth of dendrites is along preferred crystallographic directions.0 for 304. so that large deformations mechanically bring different grains via rotation into closer crystallographic alignment. The approach centers on variables that increase stored energy from deformation to promote recrystallization over recovery during annealing. dislocations tend not to dissociate as they do in austenitic stainless steels. ferritic stainless steels. Thus. This is manifest in their deep drawing characteristics.

both substitutional and interstitial. the precipitation of chromium carbides that depletes grain boundary regions of chromium. This has led to considerable development of high-temperature properties. are about two orders of magnitude higher than in austenite. . so ferritic stainless steels behave just as do other stainless steels of the same crucial alloy content. The relatively high insolubility of TiC causes this. and crevice corrosion are chromium. 102 h or so. and cobalt are kept below 0. primarily for the automotive market. and nitrogen. Cold work sufficient to raise their hardness above Rc 20 to 22 can make them susceptible to both SCC and its cousin. such as copper and nickel. whose tendency to form chromium carbides causes areas around such carbides to be partially depleted of chromium. are almost always seen to be the locus of pitting corrosion (Ref 15). As with martensitic stainless steels.5% in aggregate. Niobium is concurrently made available for high-temperature solid solution strengthening. Adding titanium to niobium-stabilized steels stabilizes the type of carbide. Because ferrite has a non-close-packed structure. and sulfur can also form chromium compounds and cause localized loss of corrosion resistance. the carbides form on preexisting TiN particles and result in coarser overall precipitate arrays since finer. copper. Even in environments that cause pitting. B)6. other elements can have a negative effect. but their high-temperature strength is lower than that of austenitics. but they are of secondary importance compared to chromium and molybdenum. Alloys cannot be quenched rapidly enough to forestall sensitization. The net result is coarser grain size and no major improvement in mechanical properties over the use of titanium alone (Ref 13). for instance. Likewise. Either of these with about 50% chromium will cause adjoining ferrite to have lower chromium levels. The ferritic stainless steels are valued for their resistance to SCC. The main alloying elements that provide resistance to localized corrosion. Corrosion and Oxidation Resistance Corrosion resistance is chemistry dependent rather than structure dependent. or the chromium depletion must be removed by homogenization in longbox anneals. molybdenum. whose growth decreases strength. lower-temperature precipitating TiC or TiCS precipitates are at least partially precluded. The most notorious of these is carbon. The more highly alloyed superferritic alloys are even susceptible to hydrogen embrittlement in the annealed condition (Ref 17). it cannot contribute to the corrosion resistance of ferritic stainless steels as it can in austenite. Since nitrogen is essentially insoluble in ferrite. More careful examination has shown that such sulfides grow in the solid state as chromium/manganese sulfides and deplete their very close surroundings of chromium. can add to corrosion resistance in special cases.Chapter 8: Ferritic Stainless Steels / 121 Boron additions to ferritic stainless steels result in the formation of grain boundary carbides. especially preventing the formation of the coarse M6C. oxygen. Other alloying elements. Instead. the normal initiation step for SCC. Other factors that lead to loss of localized corrosion resistance are the formation of chromium-rich phases such as α' and σ. inviting corrosion to begin at the inclusion-matrix interface. carbon must be neutralized by stabilization. High-Temperature Properties High-temperature mechanical properties of ferritic stainless steels are often important to their successful use because their oxidation resistance is excellent and better than austenitics. where chromium levels in solution are reduced (Ref 16). M23(C. Research has determined that high-temperature strength and creep resistance are best served by stabilizing grain size and having niobium in solid solution. annealed ferritic stainless steels do not undergo SCC as long as alloying elements such as nickel. general corrosion. However. hydrogen embrittlement. Manganese sulfides. Additions of boron to niobium-stabilized steels does cause finer precipitates and grain size than would niobium alone (Ref 14). Any element that can combine with chromium or molybdenum can detract from corrosion resistance by their removal of these essential elements from solution. diffusion rates. nitrogen. Note that the latter technique is also possible in austenitics but would require annealing for excessively long times. That means that any deleterious chromium-depleting reaction can happen more rapidly. If added to titanium-stabilized steels.

Int. Les Editions de Physiques.M. ASTM. H. and K. Nippon Technical Report 71. Yamamoto.. Oct 1996 15. Grubb and J. Ohmura. Les Editions de Physique. McPhail. Grubb. 1998. B. 5–12 7. p 483 3. Newell. 5). El-Kashif. Trans. p 126–143 2. Sato. as opposed to austenitics. Alloying. Suter. Williams. Hutton.W. Webb. T. This limits these alloys’ ability to employ cathodic protection safely to –0.. and R. reduced to very low levels (Ref 18). H. Met. N.D. Grubb. Conf. Why Stainless Steel Corrodes. J. E. and A. p 213 8. Stainless Steel ‘77 9. Vol 148 (No. Shibata. Soc. “Hydrogen Embrittlement of Superferritic Stainless Steels. September 1984 18. J. Grobner.122 / Stainless Steels for Design Engineers this susceptibility is a maximum near room temperature and declines with increasing temperature.” Special Publication 706. Stainless Steels. Detroit. p 770 17. ASM.. ISIJ. High Chromium Irons. New Orleans. Chater. E. Stainless Steel. Wright. Stainless Steels. The Role of C and N in the Brittle Fracture of Fe-26Cr. Nature. A. Handbook of Stainless Steels. p 1568–1575 14. which see their maximum susceptibility above room temperature. Pit Initiation in I M NaCl With and Without Mechanical Stress. 1980 11. T. and P. F. p 27 13. Vol 4. p 617–626 5. K. Sept 1979. Wright. R. Streicher. Beckett and R. J. Paxton. and D. The 885 °C (475 °C) Embrittlement of Ferritic Stainless Steels. 1973. Ryan. Chiba.” paper presented at 1984 ASM Int’l Conference on New Developments in Stainless Steel Technology. P. D. Grubb. Proc. Metall. April 1984 . McGraw Hill. April 1947. Trans. Fujita. Asakura. 1991 12. if not eliminated. p 5–9. Vol 113.J. B174 16.80 Vsce. Abo et al. p 251–260 6.. M. Bohni.. 1977. Peckner and Bernstein. J. REFERENCES 1. J. Met. H. Koseki. M. Grubb and R. Electrochem. R. 1934. ISIJ Int. Alkire. Franks. Stabilization of High-Chromium Ferritic Stainless Steels.A. Trans AIME. Stainless Steel ‘77. Farrar. p 1247–1255 10. E. K. “Micromechanisms of Brittle Fracture in TitaniumStabilized Stainless Steels. Prog. 2004. Vol 10A. 2003 4. J. 2002. H. at which point corrosion in seawater is. 1992. Vol 412. 2001. Vol 44. “Use of Cathodic Protection With Superferritic Stainless Steels in Seawater. Maurer.” paper presented at Corrosion 84.

0% carbon. high-temperature CHAPTER 9 Martensitic Stainless Steels Summary THE SMALLEST CATEGORY of stainless steels in usage volume is the martensitic stainless steels. The presence of ferrite in a martensitic structure is detrimental to strength. Ferrite can appear in the as-cast structure and be formed during austenitizing or tempering. vanadium. they fill an important niche as a strong. Table 1 lists the most significant of the martensitic stainless steel alloys. The additional concerns one must have with stainless martensite relate mainly to those that are due to the strong ferritizing influence of chromium. Martensitic stainless steels are the most marginally corrosion resistant of all the stainless alloys. All the usual concerns inherent in any martensitic alloys are still present. p 123-135 DOI: 10. stable. Those martensitic stainless steels in which elements such as copper and titanium are added to produce additional hardening through precipitation are discussed in Chapter 4.” The designers and engineers already familiar with martensitic carbon and alloy steels will find nothing confusing about martensitic stainless steels. In addition they are always susceptible to stress corrosion cracking (SCC) when their hardness exceeds about Rc 22.Stainless Steels for Design Engineers Michael F. Relatively small amounts of nickel. This was the first commercial use of stainless steel and cutlery with the same basic analysis is still sold today. hard. www. temper embrittlement. some of the martensitic alloys containing molybdenum or Introduction Nearly 100 years ago cutlery was first sold in Great Britain with a composition of 13% chromium and 0.25% carbon. retained austenite. McGuire. and tough alloy of fairly good corrosion resistance and as a strong. Nearly all the precipitation-hardening stainless steels are used in the martensitic state. which restricts the temperature and composition ranges over which it is possible to obtain a fully austenitic structure from which to form martensite.1361/ssde2008p123 Copyright © 2008 ASM International® All rights reserved. . etc. This is mainly because these alloys are limited in corrosion resistance because of the necessity of keeping alloy levels low to produce the martensite structure. hardness. Even so. but their special hardening mechanism of precipitation within a martensitic matrix causes them to be categorized separately somewhat arbitrarily. Much of the carbon in them detracts from the effective chromium content by forming chromium carbides. “Corrosion Types. By this conventional logic. The useful alloys of martensitic stainless steel contain from roughly 11 to 18% chromium and up to 1. Their high strength and hardness for their relatively low cost ensure their place as a very useful engineering material. The reader should be aware that some alloys which are quite similar are discussed primarily in other chapters dealing with specifically PH stainless steels or primarily ferritic stainless steels. Chromium strongly promotes the formation of ferrite. The distinction between martensitic stainless steels and some other stainless alloy families is sometimes vague. tungsten. The requirement that they be fully austenitizable limits the amount of corrosion-resisting chromium and molybdenum they can contain. molybdenum. and toughness. There is no aspect of martensitic steels that does not apply directly to stainless martensitic steels. and niobium are also added at times for specific purposes explained in this chapter. These limitations combine to make their excellent properties usable in only mild environments compared to other stainless steels.asminternational.

..25 1 0.. . 1. .70 0.. .... ..12 N .15 min 0..00 3.25 1.50-3. ..5-13.5 10...15 max 0.5 1 .50-4.. 4 418 420 4116 0.5 1 .50 4..0 13.80-2.00 1 1 1 0. .03 0.. .15-0.5-14. 2.25 0... ....15 max 0.0 14...03 0.15 min Se 0.5 11.5 11. 1.512.00 .30-0.03 1 1 1 1.30V ...030 max 124 / Stainless Steels for Design Engineers 414 414 mod S41400 S41425 Wrought Wrought 0...5 12. .60 1 1 1 .. .15 min 0. 0.0 -14 13 13 12. .50 ..65 0. .0-14.. 420F 420FSe 422 424 425 425mod Trinamet S41800 Wrought S42000 Wrought DIN Wrought 1.00-2.0-16. .5-1.08-0.70 0..00 Cu .50-1.. .6 0.0 14.030 max N . 0.....15 V .30 max HP13Cr-1 Wrought 0. .......06-0.25 0....50-5. .0 12.25 1...015 11.5 .0-14.03 0.... 0. .025 0.05 415 416 416Se S41500 S41600 S41623 Wrought Wrought Wrought 0. 0.0 12.5 0.50 W . .15 max 0. .5 1 0.5 0.512..00 -3 1 2 1.06 0..25 0.45 0.5 1 1. . Alloy UNS Form C 403 410 410S S40300 S41000 S41003 Wrought Wrought Wrought 0..06 0.03 . .45 0... 0.03 .6 .Table 1 Mn S Si Cr Mo Ni Other Other Compositions (wt%) of martensitic stainless steels 0.75-1... 1 1 0. .5 11.75 0.4116 Nominal S42020 Wrought S42023 Wrought S42200 Wrought S42400 Wrought Wrought S42500 .30-0....5 1 ....20 ..03 0.50-1.. .08 410Cb S41040 Wrought 0.5 Cu HP13Cr-2 Wrought 0..25-2....03 0...03 0.....0 12.6 1 1 0.. 1..45 1.00 -3..18 max 412 S41003 Wrought 0.513. 1. ..6 0.025 .014 12. . 1..005 0.. 0.07 3..30 Nb 0.7 0. 0. ...30 Cu ...15 min 0. Wrought .20-0..... Wrought 12.20 0..55 0.5 11.00 0.. 0.. .0-14.15 min 0.0-14.0 11. . N 0.. (continued) .03 410 S41008 Wrought 0... 5 4.80-1.. 0.75-1.03 .03 0..5-13.6 0...15 max 0.5 . ..50-1.01 0.50-1.03 .0 12.03 0. .. .. .15 max ...5 12.03 0. 1.06 max 0. . . 1. .. 1 1 1 1 0.0 0.040 N NT-CRS JFE Nominal JFE Nominal Nippon Nominal Wrought 0... . .03 0..0 12..5 10.15 min Se 2..52 0. .5-13...05 max 0..20 0.0-14..05-0..0-13.....25 W ..20 1.0-14. ......50-0..513......50 1.00 1.0-14.03 0.15-0.30-0.. 0.5 11.4 .15-0...5 .30 0.

75 0....0 14.0 10.75 ..35 0.0 V 5. ..20 0.5 0.5 0.0 V .95-1.5 14 14 .6 4 4 4 ..40-0..20 0.. .03 .05 1.75 0..8 1.. .95-1.20 max 0.03 0..25 0.. .0 16. . . .4 . .... . ... .10-0.4 Wrought 0.50 0.0 16. ...020-0. .90-1.... 0.00 11..95-1..5 1.05 1. 1 1 1 1 1 1 0..00 0.. .25-2.0-18.5-14.2 V . 0.. 1 1 1 1 0. 2..00 . 4.. 0.. ......50-12....20-0. .. .60-0.2 Chapter 9: Martensitic Stainless Steels / 125 J91150 J91151 J91153 J91154 J91650 J91540 J91422 Cast Cast Cast Cast Cast Cast Cast 0.15-1.28 ....5 1 1 1 17 13 11.... .03 0.04 0..0 16. .75 0.00 0.06 max 0. ..20-0. 0...20-0..15 min Se 1... .03 . .. ....40 0.50-1.5 Cu 0.75 0.. .5-14.0 16..15 max 0..... 12 2 5. .4 0...3 2 5..0 16.0-18.02 0.5 1 0. 0.. ...05 Nominal Nominal Wrought PM 1. .3 14 14 4 2 0...5-14.01 Wrought Wrought Wrought Wrought Wrought Wrought Wrought Wrought Wrought 0.35 0...04 0.0-17...0-18.....3 0.06 max 0.5 0.5-14..25 W 0.03 0. .... .50 .0 11. .95 0...45 .20 1....040 0. .. .0 11. .. 0.. ..15 1. .015 N 0. 0.5 Cu . 12.. . . .00-12.....20-0..90-1. .5 0.. .45 Nominal PM 2.......25 1..50 11.65 1..3 15.25 . . .50 0..5 V 9.50-14......02 2 .50-4..5 0..75 0.. 11 .0-18.. .. 1.40-1.010 N . ...01 Nippon Nominal JFE Nominal JFE Nominal S43100 S44002 S44003 S44004 S44020 S44023 Nominal Nominal Nominal Wrought 0.75-0.50-1.0-18...Table 1 (continued) (wt%) of martensitic stainless steels Compositions Mn S Si Cr Mo Ni Other Other Alloy UNS Form C NT-CRSS ...30 V KL-12Cr Wrought 0. .010 N 0.15 max 0.60 0..15 KL-HP 12Cr 431 440A 440B 440C 440F 440FSe BG-42 ATS-34 14-4 CrMo 154 CM CPM S30V CPM S60V CPM S90V CA-15 CA 15M CA-40 CA-40F CB-6N CB-6MN CA-28MVW Nominal PM 2.00 0.4 1 0. .03 0. ..03 0. . .. 1 1 1 1 1.40 0.04 0...5 1..0 11.... 1 1 1 1 1 3.

This free-energy differential increases with decreasing temperature. The formation of martensite is essentially mechanical (i. At a certain temperature. The amount is given by the Koistinen and Marburger equation (Ref 1): 1− Vα ′ = exp{β (Ms − T )} (Eq 1) The martensite is coherent with the parent austenite and resembles the passage of slip dislocations through the crystal. The austenite may be supersaturated with carbon or nitrogen. 1 Martensite platelets emerging from the surface. Greninger and Troiano determined that the close-packed planes of the austenite {111} varied from the {011} of the martensite by only 0. There is regularity to the relationship between the parent austenite and the martensite. This is shown diagrammatically in Fig. ac . not diffusion). but they customarily are not and will not be in this work. The martensitic alloys themselves can be made to be partially ferritic by forcing their carbon contents to low levels as is customarily done with 410S (UNS S41003). the martensite start temperature Ms. involves a great deal of strain energy that must be taken into account. but that is not necessary for the transformation. on temperature. 2 (Ref 2).7° from the <1 bar 11 bar> of the martensite. Martensite Formation Martensite as a phenomenon deserves a brief review.126 / Stainless Steels for Design Engineers tungsten should also be considered precipitationhardening alloys. The ferritic alloys often have compositions that allow them to be partially martensitic under some conditions. Source: Ref 2 Fig.e. which can be attributed largely to large mutual repulsion between iron atoms that possess unpaired outer electrons with the same quantum number and magnetic polarity. The sum of many such dislocations is shear. Martensite forms essentially independent of time and the fraction transformed depends only Fig.2°. These relationships define the habit plane that constitutes the austenite martensite boundary. about 4%. 430 (UNS S43000) and 3CR12 (UNS S41003) can contain some martensite if their heat treatment is such that austenite is allowed to form and is followed by rapid cooling. and this can be macroscopically visible as in Fig. 1.. 2 The martensite reaction ab contrasted to the nucleation and growth-type transformation of austenite to ferrite. The composition of the martensite is identical to that of the parent austenite. the transformation occurs spontaneously via the coordinated movement of atoms in a shearing-type mode at very high speeds approaching the speed of sound in the material. the direction of the <101 bar> of the austenite was only 2. The shear and volume expansion. Not understanding these alloys can lead to unexpected consequences in mechanical properties or corrosion performance. The driving force for the transformation is simply the much lower free energy of the ferrite phase over the austenite phase. which accompanies the transformation. Further. Even 409 (UNS S409XX) can form some austenite if chromium is at the high end of its possible range and nickel and manganese residual levels are high. Martensite forms as result of the diffusionless transformation of austenite. via deformation.

These interstices are considerably smaller in the bcc structure even though it is expanded from the fcc. leaving the parent martensite less strained. the carbon diffuses from these inter- stitial sites and forms various carbides. and Fig. but above about 0. the untransformed austenite is hindered from transforming by the compression it receives from the already-formed martensite. softer. Nitrogen behaves similarly to carbon in both austenite and martensite.5% chromium to qualify as stainless and even more for better corrosion resistance. 3 Change in size of the octahedral interstitial site with the change from face-centered cubic (fcc) to bodycentered cubic (bcc). These criteria are somewhat challenging.86 by 2.018% carbon this can no longer be accommodated and a tetragonal distortion occurs (Ref 3). Indeed. The distortion is accommodated by accommodation from site to site at low carbon levels. 5 (Ref 4) shows how hardness varies with carbon content. and it is less significant as an alloying element accordingly.86 by 3. • The temperature at which austenite forms on heating should be sufficiently high to permit tempering above the temper embrittlement range. 3 (Ref 3). Figure 4 shows that the large strain energy in martensite varies with the carbon content. as shown in Fig. Phase Structure Figure 6(a) to (h) shows a series of photomicrographs of various martensitic alloys (Ref 5). However. as interstitials. Fig. and tougher. A stainless martensitic alloy should have the following characteristics: • It must have at least 10. 4 Strain energy of martensite dependence on carbon content. the body-centered cubic (bcc) phase becomes preferable energetically. The amount of distortion is proportional to the amount of carbon in the interstices of the structure. above which some δ-ferrite tends to be stable at all temperatures below the melting point. At the Ms temperature. Applied strains affect the transformation. but this temperature is too low for diffusion transformation. and a slight shear in the austenite lattice causes a rearrangement of the atoms from a face-centered cubic (fcc) to a distorted bcc structure.86 A. Thus. but its solubility is lower. also raise hardness. Increasing carbon slightly expands the chromium level at which full austenitization can occur (Fig. The carbon is in a state of supersaturation in the as-formed martensite.05%) levels austenite is stable up to about 12% chromium.56 A to 2. • It should be fully austenitic at some temperature. Source: Ref 2 Fig. The octahedral sites change from 2. metastable austenite can readily be transformed to martensite by deformation. Hydrogen and boron.Chapter 9: Martensitic Stainless Steels / 127 This energy differential between ferrite and martensite is stored in the high-strain energy matrix. When the martensite is tempered. Figure 7(a) shows that at low-carbon (0. 7b) (Ref 3). some residual austenite is commonly found between lathes of martensite. Source: Ref 2 .

Nickel greatly expands the . in which it becomes clear that for higherchromium alloys the range over which full austenitization can occur is further restricted. but fortunately nickel again can make an important contribution. 5 Variation in martensite hardness with carbon content The interplay between chromium and carbon is further explained in Fig. 8(a) and (b).128 / Stainless Steels for Design Engineers Fig. The variety of martensitic stainless steels would be very limited if only chromium and carbon were available as alloying elements.

(d) 420 quenched and tempered showing fine carbides in a martensite matrix. (b) 410 quenched and tempered. (e) 420 quenched and tempered showing surface decarburization. (f) 440A annealed displaying primary and smaller secondary carbides in a ferrite matrix. 6 .Chapter 9: Martensitic Stainless Steels / 129 (a) Annealed 410 showing carbides within an equiaxed ferrite matrix. (g) 440B quenched and tempered displaying both primary and secondary carbides. (c) 416 quenched and tempered: white ferrite and gray sulfides in a martensite matrix. (h) 440C quenched and tempered displaying significant primary carbides plus finer secondary carbides in a martensite matrix Fig.

4 0. are increased. with the exception of cobalt. This is because as the main corrosion fighters. 9 (Ref 3).3 0.3 0. all depress the Ms temperature.4 0.9 1. so must austenitizers such as nickel.6 0.2 0. which are ferritizers. It can be seen that the elements that promote austenite.9 1.130 / Stainless Steels for Design Engineers Fig. %C 1000 800 α + carbide 600 0 0.2 0.8 0.0 Mass. (b) iron-chromium diagram at 17% chromium chromium levels and temperatures at which austenite is stable as is shown in Fig. °C 1400 γ 1400 γ γ + carbide 1200 1000 γ + carbide 800 α + carbide 600 0 0. %C Fig.5 0. chromium and molybdenum.0 Mass. °C α+γ 1200 Temperature. 8 (a) Iron-chromium phase diagram at 12% chromium. 7 Iron-chromium phase diagrams at two low-carbon levels 1800 1800 1600 Liquid 1600 L+α σ α+γ Liquid Temperature.5 0. Table 2 quantifies the influences of the various possible alloying elements on the key properties of martensitic stainless steels.1 0.1 0.6 0.8 0. This puts a limit on the amount of total alloy that can be used and in the end puts an upper limit on the ability of martensitic stainless steels to achieve high corrosion resistance. The coordinated increase in these elements lowers the Ms to such a degree that the .7 0.7 0.

if transforming martensite to austenite during tempering caused subsequent untempered martensite or other undesirable phases. Ms. should be heated gradually through stage heating to avoid cracking due to thermal stresses. resulting in much lower surface hardness. Phosphorus precipitates at prior austenite grain boundaries during tempering with a maximum effect at 475 °C. Fig. The higher-carbon grades. Since carbon solubility varies strongly with temperature at austenitizing temperatures (Fig. an example of which is shown in Fig. those above 0. Carbon or nitrogen pickup could also occur if the atmosphere was rich in these elements. so achieving low phosphorus levels depends mainly on restrictions on raw materials for melting. This affects Ms. The carbon potential of the furnace atmosphere must be controlled to avoid potentially serious problems.Chapter 9: Martensitic Stainless Steels / 131 alloys become stably austenitic before much higher corrosion resistance is obtained. but more importantly it influences subsequent toughness. Soaking at 800 °C until uniform temperature is achieved minimizes this risk. Figure 10 (Ref 3) shows the significant toughness change that occurs as increasing austenitizing temperature increases austenite grain size and permits greater phosphorus concentrations at grain boundaries. This loss increases with base carbon level and austenitizing temperature. Obviously.. If hydrogen atmospheres are used the Influence of alloying elements on ferrite. Copper has become an important alloying element in martensitic stainless steels because it greatly improves corrosion resistance in certain environments without diminishing an alloy’s ability to be tempered. grain size control is the main tool for controlling temper embrittlement. Refining phosphorus from any chromiumcontaining steel is quite challenging thermodynamically.. Ms. 6(e). and austenite start N C Ni Co Cu Mn Si Mo Cr V Al Lowering of % ferrite per % element Lowering of MS per % element Change of AC per % element –220 –475 –210 –475 –20 –17 –7 0 to 10 0 –7 –17 0 –6 –30 6 –11 5 –21 14 –17 18 –46 54 . Thermal Processing The main concerns with processing martensitic stainless steels are austenitizing. Because this is difficult or costly. tempering/stress relieving. Austenitizing temperature also determines austenite grain size. This limits the use of nickel while encouraging the use of elements like molybdenum. quenching. 0 to 280 0 to 250 –30 to –115 –25 to –66 25 to 73 25 to 60 0 to 35 50 to 290 30 to 750 . and mechanical properties. control of temperature is vital to have the correct balance of carbon in solution versus carbon as carbide since carbon in solution has such a strong influence on ferrite content. and annealing.10% per hour. The ability to temper without austenite reversion is an important trait. 9 Table 2 Element The expansion of the range of austenite stability with nickel content Austenitizing is complicated in martensitic stainless steels because many grades contain carbon at levels intended to produce carbides for wear resistance purposes. this would limit one’s ability to temper at a high enough temperature to achieve desired toughness. Heating in air to 1050 °C can cause surface carbon to decrease by approximately 0. This is the infamous temper embrittlement.20% carbon. Another concern during austenitizing is superficial carbon loss. 7a and b).

stress relief. The hardening reduction with stress relief and tempering for a 12% Cr alloy is shown in Fig. The high chromium content of these alloys renders them very deep hardening. and tungstenalloyed grades will resist softening during tempering because of the strength of the secondary hardening they undergo due to precipitation . The microstructural changes at these temperatures are the above-mentioned loss of carbon from solid solution. Thus true tempering is conducted above this temperature. stress relieving should be immediate to avoid cracking.003-0. Stress relief without delay would be mandatory. it may decompose to ferrite and carbide with a negative effect on toughness. This results in a slight decrease in hardness.035% P: 0. The molybdenum. If the material contains retained austenite. vanadium. 10 Influence of austenite grain size and phosphorus level on toughness danger of embrittlement after quenching must be recognized.132 / Stainless Steels for Design Engineers +120 [ ] +80 [ ] P: 0. At 500 °C. This is accompanied by a pronounced softening. °C +40 P: 0. vanadium. and tungsten.047% P: 0. a further precipitation of M2X and M7C3 as well as the transformation of M3C into M7C3 can result in a secondary hardening. Avoiding quench cracking and excessive warpage is almost always a greater concern than depth of hardening so air quenching is standard. Because the quenching and the transformation it causes are inevitably accompanied by residual stresses in a brittle material. Oil quenching which is faster may be slowed by heating the oil.021% Transition temperature. the previously mentioned phosphorus segregation to prior austenitic grain boundaries occurs. there is a slight growth in the number of fine cementite particles and a corresponding decrease in the amount of carbon in solid solution. Separately at the 475 °C range. the M2X carbide can become the more stable species and be responsible for the secondary hardening. This effect begins to disappear above 550 °C. a true precipitation-hardening effect. Air hardening is generally sufficient. 11 (Ref 6). Pickling should never be done on asquenched material because this could easily result in hydrogen uptake and delayed cracking by hydrogen embrittlement. The result is a pronounced softening and toughening. of course. In the presence of strong carbide-forming alloying elements such as molybdenum. and.004% [ ] 0 [ ] [ ] −40 [ ] −80 5 10 20 50 100 200 Austenite grain size. Higher-carbon grades should not even be allowed below room temperature before stress relief. Heating as-quenched material to between 150 and 400 °C produces stress relieving. At 400 °C. μm Fig. carbide precipitation and coarsening. Besides the normal flow on a microscopic scale. coarser M23C6 and M7C3 begin to grow at grain boundaries. which we understand as stress relieving.

A high-profile use of martensitic stainless steels is in cutlery. While 420 is the common alloy and is quite serviceable. The martensitic alloys have a tendency toward centerline segregation during solidification as well as toward the formation of primary carbides. 440C was the maximum step up from 420. The higher-carbon. further alloying with molybdenum for corrosion resistance and vanadium for hardness of the carbide phase has led to improvements. Powder metal techniques . Electroslag remelting (ESR) or vacuum induction melting-vacuum arc remelting (VIM-VAR) provides the cleanliness required. 11 Influence of tempering on hardness hardening of carbides and nitrides. The basic 12 % Cr martensitic alloy has been the basis of alloying improvements that were done to produce better high-temperature performance. as shown in Fig. and chefs’ cutting tools are highly valued items and contain some of the most sophisticated martensitic stainless alloys. 12 (Ref 3). which can be introduced into the matrix in conventional production. Nickel seems to amplify this action by its influence on diminishing the solubility of carbon in the matrix. The wear resistance of a blade is largely determined by the hardness and amount of carbides while the toughness is governed by the matrix properties.Chapter 9: Martensitic Stainless Steels / 133 500 Initial hardness 450 300°C 350°C 400 400°C 450°C 300°C 350°C 400°C 450°C 500°C 350 Hardness 550°C 600°C 650°C 300 500°C 250 550°C 600°C 650°C 200 700°C 750°C 150 11 12 13 14 15 16 17 18 19 20 21 22 23 700°C 750°C T (20 + LOG t) × 10−3 Fig. Thus. Hunting knives. both of which form much more stable carbides than chromium. higher-chromium grades are typically only stress relieved because the removal of chromium from solution by carbide formation at higher temperatures causes an unacceptable loss of corrosion resistance.and corrosion-resistant alloys exist. The nominal analyses of some prominent grades are shown in Table 3. Applications High-Temperature Use. sport knives. Tool and Cutlery Alloys. which measures the ability to withstand chipping in use. These alloys are used at very high hardness levels. especially for turbines. results in alloys that have vastly improved creep resistance in the 550 °C range. while powder metallurgy is optimal for obtaining very fine carbide size and uniformity. The addition of vanadium and niobium. much more wear. At one time. This has produced limitations in the amount of highly wear-resistant constituents such as vanadium carbide (hardness Rc 75). the tempering of the higher-alloy martensitic stainless steels can truly be considered a precipitation-hardening reaction. however. so cleanliness is very important to toughness.

.15 min 0.0 V 5.03 0.134 / Stainless Steels for Design Engineers 4 50 2 45 40 Applied stress.60-0.5 0...15 V . maintaining it in solution for corrosion resistance..05 1.15 2.. 0.75 4 4 4 4 2 0. 9% V.5Cr-0..4 0.15 1. Oil Country Tubular Good and Line Pipe.. The third alloy is a near match for the precipitation-hardening stainless Custom 450 (UNS S45000) (Ref 8).2C-10.0 14..0-18. .05 1.. . kg/mm2 35 3 30 1 25 20 1 (0. ..... 0.3% C...0-14. .75 0... . .. 1 1 . Low carbon and nitrogen levels give good toughness without tempering and minimize the loss of chromium to carbides..45 ...1V-0..5Cr-0... 12. The addition of nickel and molybdenum yields full austenite and martensite transformation and improves corrosion resistance..4116 Nominal S44002 S44004 Nominal Nominal Nominal Nominal Nominal Nominal Nominal Wrought Wrought Wrought Wrought Wrought Wrought Wrought Wrought PM PM PM 0.1Nb) 3 10 30 100 300 1000 3000 10. . 1 1 0...03 .5 0.. . ... The need for corrosion resistance in oil production tubulars has grown as the quality of petroleum deposits has become less optimal... ..75 0.. 4.. 0... 1.2 V ... are not subject to the same limitations as continuous casters and have alloys the production of alloys with high volume content of VC.5 14 14 14 14 17 13 . .0 V .1Nb) 3 (0.. . . ...0 16...35 0....4 1 . Like other precipitation-hardenable steels..... .. 1% Mo. .0 14.. ...5Cr-0. This alloy has equal or better toughness and corrosion resistance as 440C but has ten times the wear resistance at the same macrohardness. Use of stainless can eliminate for corrosion inhibitors in H2S and CO2 environments... ..5 V 9.65 0.. h Fig.. .. 1 ..2 1 . One such alloy is Crucible CPM 90V with 14% Cr. it shows excellent resistance to SCC at high strength levels.. ..03 . 12 Table 3 Alloy Influence of vanadium and niobium on high-temperature properties Tool and cutlery martensitic stainless steels alloy compositions UNS Form C Mn S Si Cr Mo Ni Other Other 420 4116 440A 440C BG-42 ATS-34 14-4 CrMo 154 CM CPM S30V CPM S60V CPM S90V S42000 DIN 1.. .2C-10.3 . This has led to the use of low-carbon martensitic stainless steels..1V) 4 (0. .000 16 Rupture life... Figures 13 and 14 show the improvements in corrosion resistance .45 2. .3 0. Table 4 lists several such alloys by JFE: the first two can be made to meet L80 specifications and produced as seamless... .2C-10........ ... .2C-10.0-18. ..000 tons per year of this product (Ref 7)......95-1. JFE reports production of over 100. 0.20 1.5Cr) 2 (0.5 16.05 1...4 . 0. and 2. . ... .. 0.3 0. . .

p 386–405 7. . Irvine et al. p 7–13 . . Les Editions de Physique les N 0. This does not diminish their importance.” Acta Met.. p 59 2.. ..03 0. then the strength improvement.. Aciers Inoxidables. . M..5 . Kimura et al.025 0.. “High CR Stainless OCTG with High Strength and Superior Corrosion Resistance. Transportation and Storage of Energy. JISI. Lower carbon levels permit the use of field welds without tempering so that similar alloys can be used for line pipe..025 0. . p 481 4.5 Cu 0.. 1985.3 11 12 1 2 1. .html 3.45 1. 1993... The stainless can resist this failure mode at higher strengths.asminternational.. Koistinen... 2 4 5 4.5 5.” JFE Technical Report ( 2002/martensite... These are corrosion resistant and yet meet X70 and X80 class specifications. . . . Paris. As specifying bodies such as the American Petroleum Institute (API) approve the use of stainless tubulars at higher strength levels than carbon steel tubulars are safely capable of handling. Carbon steels are limited in sour envi- 1. .... 14 Corrosion rates for stainless oil country tubular goods (OCTG) alloys under severe operating conditions over carbon steel L80 oil country tubular goods (OCTG) under test conditions representative of difficult real-use environments (Ref 7).010 N Fig..E. Deshimaru et al.01 0.45 2 .040 N 0. . JFE Technical Report (No... These uses of martensitic stainless steels for oil production represent possibly the greatest growth area for any kind of stainless steel in the first decade of the 21st century. 1. R.. D. will cause a great increase in their use.8 2. ... K. The improvements in martensitic steels for these applications are hardly more than a thorough revisiting of the developments of the 1950s and 1960s.. 13 13 12. 1959. 2)... .. . “A General Equation Prescribing the Extent of the Austenite/Martensite Transformation in Pure Iron. March 2004 p 55–67 8.. coupled with the orders of magnitude improvement in corrosion resistance.J. .msm.45 0. Vol 195. ASM Handbook Desk Edition.01 0. “Steels for Production. Marburger..5 Cu . 13 Corrosion rates of stainless versus carbon steel ronments to about Rc 22 to avoid SCC by the hydrogen embrittlement mechanism. . These alloys are the last two in Table 2.Chapter 9: Martensitic Stainless Steels / 135 Table 4 Alloy JFE Steel/Nippon Steel oil country tubular goods and line pipe alloys UNS Form C Mn S Si Cr Mo Ni Other Other HP13Cr-! JFE Nominal HP13Cr-2 JFE Nominal NT-CRS Nippon Nominal NT-CRSS Nippon Nominal KL-12Cr JFE Nominal KL-HP JFE 12Cr Nominal Wrought Wrought Wrought Wrought Wrought Wrought 0. http://products. Vol 6.. p 28–9 5.4 5... Jan 2006. REFERENCES Fig.4 2 .5 Cu 1.R. http://www.. 7)...7 12....015 N 0. 0. S.02 0... ISIJ International 1960.

Primarily used as forgings. Introduction The PH stainless steels exploit the low austenite stability possible in the chromium/nickel stainless steels by making the alloys so lean in composition that they can be made to transform nearly entirely to martensite by thermal or mechanical treatment. or even phosphides. McGuire. The fully austenitic PH alloys fill a small niche where high mechanical properties are required at temperatures above or below which the other PH grades are found lacking. elemental copper. then martensitic stainless steels should be considered for applications where strength and hardness over that of annealed ferritic and austenitic stainless is required. Here. microstructure through the elimination of residual δ-ferrite and retained . although not with the flatness expected from non-PH stainless. Some authors have astutely treated them as a single group. which are used in many forms. we treat them separately because they are traditionally considered as separate alloys. p 137-146 DOI: 10. www. In no case is corrosion resistance better than that of normal 304 found in PH stainless steels. This precipitation hardening can also be made to occur in a fully austenitic matrix. or when the higher thermal expansive coefficient of an austenitic material is desired. If cost is a greater concern than corrosion resistance or toughness. they can be fabricated in a relatively soft state and then hardened with very little dimensional change. with Stainless W (UNS S17600) by CHAPTER 10 Precipitation-Hardening Stainless Steels Summary THE PRECIPITATION-HARDENABLE (PH) grades are a highly specialized family of stainless steels whose existence derives from the need for very high-strength materials with good corrosion resistance. strip. The PH grades were developed at the beginning of World War II. when a nonmagnetic material is required. then the designer should look to duplex stainless steels for the optimal material. The advantage of the PH alloys over the strictly martensitic stainless steels is that they attain great strength with higher toughness and corrosion resistance than can be obtained through the hardening of martensite through carbon. If enhanced strength and very high corrosion resistance are required. bar. and wire and are designed for applications that require extensive forming before hardening. and the PH alloys is indeed vague. which undergo secondary hardening during tempering. But.Stainless Steels for Design Engineers Michael F. The semiaustenitic alloys are more amenable to production as sheet.1361/ssde2008p137 Copyright © 2008 ASM International® All rights reserved. they can also be obtained in cold-rolled sheet and strip. The increased use of titanium alloys and advanced composite materials may occur at the expense of the stainless PH alloys and at the same time may create some new niche applications for them. In addition. nitrides. the martensitic PH grades are by far the more common. The border between the more highly alloyed martensitic stainless steels. and other hot-worked forms. and therefore tougher.S. Steel generally acknowledged as the first. The workhorse alloys are the martensitic PH grades. The later-developed grades are distinguished from the first by their more uniform. and this also provides a commercial PH alloy. This martensite can then be further hardened by the coherent precipitation of intermetallic compounds.

The presence of some fine bands of δ-ferrite promotes easier and more reproducible precipitation of chrome carbides at the δ/γ interface during the “austenite conditioning” or “trigger anneal” heat treatment step for semiaustenitic alloys (17-7. The mechanical properties of the final microstructure depend on the initial strength of the matrix before aging. This allows not only coherency but also strain. the amount of precipitate. properties. The aging temperatures can also be high enough that reversion of martensite to austenite occurs. The precipitation has the dual function of stress relieving the martensite while further hardening the matrix through the precipitation of the coherent precipitate. wt% 4 γ + Ni3Ti + Ni3(AlTi) Cellular precipitation Fig. While the presence of persistent. The precipitate that causes the hardening is normally nickel (aluminum/titanium) (Ref 1). which also lowers subsequent tensile properties. Overaging causes the precipitates to lose coherency. 1 Possible aluminum/titanium precipitates . the zones can grow to sizes that cannot accommodate the small size differential. These enriched zones are called Guinier-Preston (GP) zones. are compromised. large bands of either δ-ferrite or γ-austenite is undesirable. it is the presence of residual interlath γ + Ni(AlTi) + Ni3AlTi 4 Ni(AlTi) Ni(AlTi) + Ni2AlTi Ni2AlTi Ni2(AlTi) + Ni3AlTi Ni2AlTi Ni3Ti σ Limit of austenite ferrite region in solution treated conditions γ + Ni(AlTi) Aluminum. but both also have benefits. Although bands of stable austenite are undesirable. especially yield strength and toughness in the transverse direction. Figure 1 shows the compounds that can form from the precipitation of supersaturated aluminum and titanium in an iron alloy matrix. and softening follows. coherency is lost. a hardening may be produced by the precipitation of Cr2N (Ref 3).138 / Stainless Steels for Design Engineers austenite and by more astute alloy design and chemistry control. The ideal microstructure for the initial matrix is 100% martensite. The coherent precipitate is a effective barrier to dislocation movement. To the extent there is δ-ferrite or retained austenite. In nitrogen-bearing alloys.). The mechanism of precipitation hardening is parallel to that used to strengthen aluminum alloys in which the precipitation of a coherent second phase from a supersaturated solid solution is produced by an aging heat treatment. The differential should be on the order of a percent. The coherent precipitate strains the lattice and impedes the motion of dislocations. As time and temperature of precipitation increase. AM350. etc. producing strengthening. Close dimensional matchup between the precipitating species and the parent matrix is required. and with it the hardening effect diminishes. wt% 3 γ + Ni2AlTi 2 γ + Ni2(AlTi) + Ni3AlTi γ + Ni3(AlTi) 1 γ γ + Ni3Ti 0 1 2 3 Titanium. and the coherency of the precipitate. It is also possible to produce a hardening reaction by the precipitation of elemental copper (Ref 2). The precipitation begins with the diffusion of the precipitating species to sites on the existing matrix.

These grades in the normally furnished condition A are fully austenitic. 40 20 70 25 70 60 180 8 25 13 28 .. and alloys were designed that had minimal δ-ferrite and still transformed entirely to martensite. fully martensitic at room temperature.. Table 2 shows Mechanical properties of martensitic precipitation-hardenable alloys UNS Condition Yield. Last. which was developed for welds.. This was done first by trial and error and more recently by using thermodynamic computer models.. The austenitic PH strength is better above 750 °F. The complexity of PH steels comes from the processing involved in producing the martensitic structure in which the precipitation will occur. The precipitation takes place in austenite and therefore results in lower room temperature Table 1 Alloy strength than that of which the martensitic or semiaustenitic alloys are capable. 1240 1210 1210 930 1450 1270 460 1515 1205 1650 1500 1855 1315 1565 1340 1310 1300 1025 1550 1350 970 1585 1310 1765 1600 2005 1572 1985 14 14 15 17. and it has the possibility of superior corrosion resistance because of higher chromium content. cryogenic treatment. The most advanced PH alloys are martensitic PH grades by Cartech. to predict the phase composition of alloys that have been homogenized by hot working. also called the martensitic PH alloys. A second major group of PH grades is the semiaustenitic.g. or a destabilizing anneal to cause the matrix to become martensitic before its precipitation aging treatment. After the material is fabricated. Custom 465 and 475.05%) martensite as opposed to the higher carbon found in the martensitic stainless steels. and nickel.. low-carbon (less than 0. such as more chromium. H-950 ( 510) H-925 (495) H-925 (495) H1100 (595) H-950 (510) H1050 (565) H-900 (480) H1100 (595) H-950 (510) H1050 (565) H-950 (510) H1000 (535) H-975 (525) H 1100 (595) . The most straightforward alloys are the martensitic. The austenite is more formable than martensite.. This would be expected from the Schaeffler-Delong diagram. or condition A. % HRC Toughness. it is subjected to an aging treatment designated by the aging temperature in Fahrenheit (e. if the austenite is made very stable by further alloying additions. It is this work hardening that gives the PH alloys. This is balanced by the need to use either cold work.. 18 . This development was very significant for making the alloy family useful as a high-strength/hightoughness material for demanding applications requiring high mechanical properties and corrosion resistance. Their martensite is a relatively soft. a precipitation reaction can still be made to occur by the same type of aging treatment without martensite ever forming. which caused poor through-thickness toughness.50 12 14 23 10 14 11 13 5 13 14–16 42 41 41 34 47 42 . The early alloys of this type. Table 1 shows the more significant of these alloys compared on a strength basis.. This is confusingly called the annealed condition. Martensitic Precipitation-Hardenable Stainless Steels The martensitic PH alloys are. This is accomplished by adding elements that lower the martensite start temperature. These aging temperatures range from 950 °F (510 °C) to 1150 °F (620 °C). if not at room temperature. The inaccuracy of the diagram for more complex systems was overcome.... MPa Tensile. as stated. contained up to 10% δ-ferrite stringers... but this is asking too much of the Schaeffler-Delong diagram. 48 40 49 48 54 48 54 . especially the semiaustenitic ones. CVN ft-lb Stainless W 17-4 PH 15-5 PH 13-8 PH Custom 450 Custom 455 Custom 465 Custom 475 Ferrium S53 S17600 S17400 S15500 S13800 S45000 S45500 S46500 . 17–7 PH and 17-4 PH. at least at a reasonably attainable subzero temperature. MPa Elongation. such as ThermoCalc. H-950). even though the matrix is untempered martensite. their unusual combination of high strength plus ductility and toughness in the fully hardened state. . to predict equilibrium phase composition. molybdenum.Chapter 10: Precipitation-Hardening Stainless Steels / 139 austenite that provides the work-hardening ability in many of these PH alloys. These steels are supplied in the fully martensitic condition with hardness in the low Rc 30s.

. .2 0. .....4 0.1 0. 0.3 8. 0.2 0. . 2 0. .... and earliest..1 0. .1 .3 4...2 0. .. in Stain- less W to the latest in Custom 475 besides the elimination of δ-ferrite is in the volume fraction of the precipitating phase and the elimination of retained austenite. 1 2 2 ...140 / Stainless Steels for Design Engineers Table 2 Alloy Composition of martensitic precipitation-hardenable alloys Designation C Mn Si Cr Ni Mo Al Cu Ti Other Stainless W 17-4 PH 15-5 PH 13-8 PH Custom 450 Custom 455 Custom 465 Custom 465 (275) Custom 475 Ferrium S53 S17600 S17400 S15500 S13800 S45000 S45500 S46500 . 1.2 ... P 0.5 ... .3 0....3 Nb .. 2 their nominal compositions. 3...5 6 8. . .6 0.. . .. (d) 17-7 PH showing residual ferrite stringers and inclusions Fig.3 Nb 0.. 0.3 V 14 Co Typical microstructures of precipitation-hardenable (PH) stainless steels: (a) 15-5PH as-quenched martensite. (b) 13-8 PH solution treated and aged displaying fine martensite.5 . 1 1 5 2 0.0 Co 1W 0. ..... 1....6 0.2 .6 0. 1 .. The main advancement metallurgically in these alloys from the top..3 0..3 4. ..4 0....1 0 0 0 0 0 0 0 0 0..6 0. 1... .3 ...2 0. Figure 2 shows a series of photomicrographs of PH alloys.5 2...1 0..5 11 11 8 5. Alloy designers found that to ...1 17 16 15 13 15 12 12 12 11 10 6. . .5 0.8 ....2 0...3 0..2 3.5 0.3 0..2 Nb 8.. (c) 17-7 PH displaying ferrite stringers in a martensite matrix.. ..2 0 .. ..

so the resistance to pitting is given by: PREN = %Cr + 3. Rapid quenching of these alloys is not required. The precipitation hardening mechanism is the precipitation of Mo2C. the corrosion Table 3 Element Influence of alloying elements on key transformations N C Ni Co Cu Mn Si Mo Cr V Al Lowering of % ferrite per % element –220 –210 –20 –7 –7 –6 6 5 14 18 54 Lowering of MS –475 per % element Change of AC 0 to 280 per % element –475 –17 0 to 10 0 –17 0 –30 –11 –21 25 to 60 –17 0 to 35 –46 50 to 290 30 to 750 0 to 250 –30 to –115 –25 to –66 25 to 73 . no chromium is rendered ineffective by the formation of Cr23C6 since carbon is either held low or stabilized by titanium or niobium. microstructural cleanliness is essential. It has been established that this hardening mechanism optimizes resistance to stress corrosion cracking (SCC) for a given strength level. But. MS. which also happens to reduce the temperature at which martensite forms. To minimize δ-ferrite requires reducing chromium or molybdenum. Last. As a result. Custom 465 and 475.Chapter 10: Precipitation-Hardening Stainless Steels / 141 reduce δ-ferrite they also tend to stabilize austenite. the remaining austenite tends to stabilize. but air melting and argon oxygen decarburization (AOD) refining are quite adequate. nitrogen. The newest alloy is Ferrium S53. and full transformation to martensite does not occur. which also reduces corrosion resistance. corrosion resistance is compromised. so this is viewed as an acceptable compromise. one of the recent alloys designed by computer-assisted thermodynamic calculations. Thus. As with any alloy used at such high strength levels. as alloy strength increases. The alloying characteristics of these grades are: • Low carbon. During delays after the start of martensite transformation has occurred. 4340. Corrosion Resistance. the cooling of these alloys must be completed expeditiously through the final stages of martensite formation with minimal delay. The martensitic PH stainless steels obey the same rules as other stainless steels with regard to corrosion resistance. silicon. They are air hardenable. from a utility point of view. The alloys with the greatest strength potential.3%Mo (Eq 1) In the martensitic PH alloys. Its composition superficially seems deficient in chromium to provide “stainlessness. This is summarized in Table 3 in terms of the influence of the element on different factors measured in degrees Centigrade for a 12% chromium alloy. the higher levels of molybdenum reduce the tendency to form secondary austenite during aging. and AerMet 100 on an equal mechanical properties basis but also provide the corrosion resistance necessary to be used in aircraft components without cadmium plating. the higher levels of austenite reduce subsequent mechanical properties after aging. to increase the temperature at which austenite forms. and manganese because these elements lower MS without contributing to age hardening • Low chromium to suppress δ-ferrite • Sufficient nickel to suppress δ-ferrite and provide for precipitates without excessively depressing MS • Molybdenum to offset loss of corrosion resistance by minimization of chromium. It was designed to replace 300M. The martensite carries no nitrogen in solution. When this happens. But. and to form another hardening precipitate in the presence of cobalt • Cobalt to stabilize austenite while raising MS • Aluminum or titanium to form intermetallic precipitates with nickel or copper to precipitate as elemental copper It is possible to quantify these various influences on phases.” but the cobalt level raises the thermodynamic activity of chromium sufficiently that the equivalent of 12% chromium in a non-cobalt-containing alloy is achieved. these alloys are designed to have maximum mechanical properties with adequate corrosion resistance. barely qualify as stainless with around 11% chromium.

Also. while higher aging temperatures (above 540 °C) producing lower strengths renders the materials immune at stresses near the yield strength. for martensitic alloys. giving the austenite the stability of a normal 301-type alloy. permit them to be manufactured as coldrolled sheet and strip. which is considered to be the threshold hardness for susceptibility to SCC in body-centered cubic (bcc) ferrous alloys. while the highest strength of the condition C route reflects the compound influence of cold work and martensite hardness with similar subsequent contribution from age hardening. while the last two have no apparent precipitating components. This has been accomplished for a group of alloys called the semiaustenitic PH grades. The lower strength levels achieved by the condition T route in Fig. in solution. Depending on the temperature at which the anneal is done. the PH alloys are susceptible to SCC if used at a high strength level. This permits extensive forming. If the austenite could then be transformed to martensite by cryogenic treatment. These alloys are complex metallurgically because of the technique used to make the austenite stable at room temperature after a full solution anneal. A greater concern is the risk of SCC in these alloys. SCC is simply a manifestation of hydrogen embrittlement in which the hydrogen is provided by local corrosion. Examination of the chemistries in this table shows that the first two alloys rely on the precipitation of Ni3Al for the hardening. This would make the alloy softer and more fabricable and. if not necessary. 3 reflect the lower carbon content of the martensite. These permissible hardness levels are significantly higher than allowed in non-PH martensitic alloys. the austenite could be made stable at room temperature. While the mechanism of SCC in austenitic alloys is still debatable.142 / Stainless Steels for Design Engineers resistance will equal that of stabilized ferritic alloys of the same pitting resistance equivalent number (PREN) for which voluminous data are available. the use of S17400 is permitted if it is double tempered at 620 °C and its hardness is 33 HRC or less. approximately 1170 MPa. The suitability of high-strength alloys for use in potential SCC-provoking environments containing H2S is regulated in many locales by National Association of Corrosion Engineers (NACE) International Standard MR01-75. in solution in the austenite. cold work. This causes a higher Ms temperature because of the lower amount of carbon. it should be noted that these semiaustenitic alloys usually contain some δ-ferrite in their predominantly austenitic microstructure after annealing. and chromium. The existence of pitting is a sufficient. In marine environments. The material susceptibility is largely a function of resistance to crack propagation in any given alloy that is measured by fracture toughness. The key is to apply a subsequent lower-temperature anneal so that less carbon goes into solution. Some of it will thus form M23C6. then it could be age hardened just like the martensitic PH grades. The 1050 °C anneal of the condition A mill anneal puts all the carbon in solution. a powerful austenite stabilizer. In it. The austenite is rendered stable by fairly high levels of carbon. which reflects the fact that the martensitic matrix has the toughness of a lower-hardness martensite. The “semi” signifies that the austenite in these alloys is metastable rather than stable at ambient temperatures. The amount of carbon that can be held in solution is a function of annealing temperature. The main alloys of this group are listed in Table 4. it has long been clear that. The martensitic PH grades have excellent toughness and low rates of crack propagation. condition for SCC to occur if the temperature is within the range of susceptibility and the material is inherently susceptible. but the sensitization takes place at such a high temperature that chromium deficits around precipitated carbides are minimized by diffusion. most importantly. 22 HRC. Figure 3 shows a chart of these heat treatment options. the Ms temperature can be controlled so that a transformation to martensite can be raised to either room temperature or some attainable cryogenic temperature. S17400 aged at 480 °C with a yield strength of 1240 MPa is susceptible to SCC. or special heat treatment. Their hardening is a more subtle . but none should be considered immune to SCC since their hardness is never below the Rc 22 level. This is in a sense deliberately sensitizing the alloy. while S45000 can be used if it has been aged at 620 °C for 4 h and its hardness is 31 HRC or less. Semiaustenitic PrecipitationHardenable Stainless Steels If a martensitic stainless steel were alloyed more strongly with austenite-stabilizing ele- ments. The threshold strength for ordinary martensitic stainless steels would be 1030 MPa (Ref 4).

1 secondary hardening from the tempering of martensite rather than the classic precipitation hardening via precipitation of intermetallic compounds.1 0. 0 0 0.3 0.4 0.3 4.4 17 15 17 16 7. it is the precipitation of . 2. 3 Processing routes for S15700 Source: Ref 5 Table 4 Alloy Compositions of semiaustenitic precipitation-hardenable alloys Designation C Mn Si Cr Ni Mo Al N 17-7 PH 15-7 PH AM-350 AM-355 S17700 S15700 S35000 S35500 0. In AM350 and AM355.3 0.3 . aluminum rather than titanium is the precipitating agent because titanium would preferentially deplete the alloy of carbon and nitrogen.. .1 0..5 0.8 0.8 1 1 .1 0..1 0.2 2.Chapter 10: Precipitation-Hardening Stainless Steels / 143 Fig.1 7.1 0.. which relies on manipulating the amount of carbon in solution. precluding the action of the conditioning heat treatment.5 0..1 4.9 0.8 2. In 17-7 and 15-7..

Fe)2N within the martensite phase that is responsible for age hardening. This gives the alloy the .144 / Stainless Steels for Design Engineers Table 5 Alloy Mechanical properties of semiaustenitic precipitation-hardenable alloys UNS Condition Yield. and nitrogen can remove chromium as a nitride. . The fact that the semiaustenitic alloys are typically sheet products generally makes their service toughness requirements less onerous. then the alloy and heat treatment that yields the greatest amount of chromium in solution should be chosen. TH 1050 (565) RH 950 (510) CH 900 (480) TH 1050 (565) RH 950 (510) CH 900 (510) SCT 850 (450) SCT1000 (540) SCT 850 (450) SCT 1000(540) 1100 1380 1585 1380 1550 1720 1210 1020 1250 1035 1310 1520 1655 1450 1650 1790 1420 1165 1510 1124 10 9 2 7 6 2 12 15 13 22 42 46 49 45 48 50 46 40 48 38 (Cr. Thus condition CH is better than RH. Corrosion Resistance.. especially if double aging is performed. it is best to assume that all carbon is present as chromium carbide. In addition. The martensitic PH grades have somewhat better strength because they have a more uniformly martensitic structure. around 700 °C. the order of ascending solution annealing temperature and ascending Ms. carbon can remove some molybdenum in the form of carbides. This means it is very formable and nonmagnetic. This benefit is offset by the necessity to condition anneal before age hardening. because the precipitation takes place in an austenite matrix. so that their retained δ-ferrite is not a crippling drawback because of its detrimental effect on through thickness toughness. These two early alloys did not possess the hardening potential that alloys employing copper-. . And.. molybdenum produces a secondary hardening in carbon-bearing martensite. Austenitic Precipitation-Hardenable Stainless Steels The austinitic PH class consists of just one important commercial alloy. they have very good resistance to SCC compared to ordinary martensitic stainless steels.. AM-355 in the SCC (850 °F) condition can withstand stresses of 75% of 0... titanium-. which is better than TH. While the general and pitting corrosion resistance of the semiaustenitic PH alloys are never quite as good as most austenitic stainless. The mechanical properties of these alloys are not greatly different from the martensitic alloys. the precipitation takes place at a higher temperature. MPa Elongation. The thermal processing of these alloys causes a significant portion of the chromium to be removed from solution as chromium carbide. The semiaustenitic PH alloys tend to higher values of PREN than the martensitic alloys inherently since they are alloyed to have lower Ms temperatures. and they employ a tougher.. and that the chromium content is diminished by that amount before applying Eq 1. The δ-ferrite and the generally well-tempered martensitic matrix provide a crack-arresting feature and good inherent toughness that resist SCC at higher strength levels than in straight martensitic stainless steels. In addition.. lower-carbon martensite. or aluminum-based precipitates enjoy.. MPa Tensile. % HRC 17–7 PH 15–7 PH AM-350 AM-355 . . The effective corrosion resistance of these alloys thus is similar to ferritic 430. If corrosion resistance is a high concern. From an engineering point of view. as can be seen in Table 5. This lowers the corrosion resistance from what would be expected based on the bulk composition. A-286. The importance of the alloy is that it is entirely stable austenite in both the solution-annealed and the age-hardened condition. The designer is thus advised to consult with producers about corrosion resistance depending on the thermal processing that will be used.2% offset yield strength in salt spray without SCC failure. Their separate existence is due to the need for alloys that are more fabricable at room temperature than are the alloys that are martensitic at room temperature. which can cause some degree of chromium depletion at grain boundaries.

so aging treatments are typically 16 h. It has slightly . as is shown in Fig. 16 h aging. 4 A-286 properties as a function of test temperature. The hardening mechanism of A-286 is the precipitation of Ni3 (aluminum. unaged condition • High toughness at all temperatures and strength levels • Excellent creep and stress rupture properties • Excellent oxidation. corrosion. even at the higher temperatures. the nickel.6 0. 5. Source: Ref 5 potential to be used to near 700 °C without fear of overaging. which has the following advantages: • High ductility and therefore high formability in the soft. Diffusion.3 3 0. The corrosion resistance of A-286 is comparable to that of 304 and 316. compared to nickel-base PH alloys.15 1.. These last alloys can attain greater strength and creep resistance than A-286.05 0..5 15 14 25.5 26 1. 2. Thus.. The toughness of the austenitic matrix is abundant and quite temperature insensitive. 0. The lower cost of the A-286 alloy. effectively ending further development of austenitic PH alloys. austenitic PH stainless represents a way to strengthen the austenite matrix.5 0. 4 shows some typical properties as a function of temperature for a standard 980 °C solution treatment followed by a 720 °C.04 1.Chapter 10: Precipitation-Hardening Stainless Steels / 145 Table 6 Alloy Austenitic precipitation-hardenable composition UNS C Mn Si Cr Ni Mo Al V Ti A-286 Discalloy S66286 S66220 0. Table 6 gives the typical composition of A-286.3 . Charpy V-notch values of over 60 J are typical from –200 to 800 °C.7 Fig. The mechanical properties can be greatly enhanced by cold working prior to aging. makes it attractive for a variety of aerospace and nonaerospace uses. titanium). and Fig..5 1.and cobalt-based superalloys.15 . is slower in austenite. and SCC resistance This alloy is rightly considered an ironbased superalloy and is the root of the group that succeeds it in properties.

Stainless ’84. thesis. paper presented at the Twenty-fourth Meeting of the AGARD Structures and Materials Panel (Turin. REFERENCES 1.E. 3. 1967. “Stress Corrosion Cracking of High Strength Stainless Steels in Atmospheric Environments”.146 / Stainless Steels for Design Engineers Fig. G. 5. Y. 1984. Ph. April 17–20. Goteborg. Vol 30A. Carnegie Mellon University 4. E. 5 The influence of cold work on aging response in A-286. Pickering. Murayama. Italy). Microstructural Evolution in a 17-4 PH Stainless Steel After Aging at 400 °C. Aggen. Katayama. Hono. Sept 3–4. Allegheny Technology Blue Sheets . and K. Physical Metallurgical Developments of Stainless Steel. Met- allurgical and Materials Transactions A. F.B. Source: Ref 5 better resistance to SCC despite its higher strength level. DPH. diamond pyramid hardness. M. 2. Feb 1999.D. p 2–28. Denhard.

are notably absent from the cast alloys. “H. and C for columbium (niobium).asminternational. These are explained. titanium. stabilized ferritic stainless steels are seldom used as castings. As with other ferrous alloys.5% silicon. and nitrogen and carbon in solution. such as Cu for copper. The inclusion of a number after the first two letters indicates the center of the carbon range expressed in hundredths of a percent by weight. p 147-154 DOI: 10. casting is often the most convenient method by which to produce components. refer to the chapters on the individual alloy families. which constitute almost half the tonnage of all stainless steel used. F for free machining. tungsten. the Alloy Casting Institute) for cast alloys that is significant. The number following the hyphen for “C” alloys designates the maximum carbon in hundredths of a percent.Stainless Steels for Design Engineers Michael F. www. Also. from a minimum of 0 to 1% for “A” up to 30% nickel for “N” alloys.” indicates corrosion resisting. is too readily oxidized for normal foundry practice to avoid the loss of this . Thus. This cross reference to wrought equivalents is helpful when looking for data about an alloy that may be more easily found for wrought alloys than for cast. which occurs when precipitates Stainless Steel Casting Alloys Essentially any wrought stainless alloy composition can be modified to be made as a cast alloy. The systemic difference between cast alloys and their wrought equivalents is that cast alloys generally contain between 1. these designations are currently assigned by ASTM as grades and are added to ASTM specifications. Silicon has strong metallurgical effects. This is true for stainless steels—both for corrosion-resisting and for heat-resisting applications. which should be understood by the user of cast stainless steels. Foundry methods are discussed to the degree they are specific to the stainless alloys. The second letter indicates the relative amount of nickel.1361/ssde2008p147 Copyright © 2008 ASM International® All rights reserved. this is done to increase the fluidity of the melt to make it cast more effectively. The suffix letters designate additional alloying elements. molybdenum.0 and 2. The heat-resisting. This chapter discusses primarily the alloys used for stainless steel castings and their metallurgy. as well as general corrosion resistance. To learn more about the influence of alloying elements. essential element. McGuire. This makes them quite lacking in toughness as CHAPTER 11 Casting Alloys Summary WITH TYPICAL ALLOY SYSTEMS.” alloys have generally only a second letter designating relative nickel level on the same scale as “C” alloys but going past stainless steels all the way to nickel-based alloys. • Localized corrosion is caused by chromium depletion. This is because these alloys are single phase at all temperatures in the solid state and because they have large as-cast grain sizes that can only be refined by heavy cold work followed by annealing. see Section 3. we briefly summarize: • Pitting and crevice corrosion resistance. the casting alloys listed in Tables 1 and 2 (Ref 1) are recognizable as approximate counterparts of the co-listed wrought alloys (AISI grade). both beneficial and detrimental. the standard stabilizing alloy. M for molybdenum. “C” or “H. Here. are enhanced by chromium. The first letter. Since heavy cold work defeats the purpose of casting to achieve a nearnet shape. A second general observation is that the stabilized ferritic stainless steel alloys. The High Alloy Product Group of the Steel Founder’s Society of America employs a naming system (ACI. N for nickel or nitrogen.

0–15.00 1.5–5.18–0.00 1.0 1.0–3.00 2.0 17.04–0. 0.0 0.03 0.0 9.0–21.0–22.5–14.35 Se 0.03 0.50 1.0 1.50–1. 0.20–0.25 2.50 1.0–6.0 4.75–6.15 1.08 0.0–18.0–12.50 1.0 10.5–1.5 0.30 N 2.10 0.00 2.03 0.0 9.50 0.2 Cu.0 9.33 N 3.0 2.00–9.0 4.0–26.6 0.0 22.5–17.0 9.0–13.00 1.0 8.5 26.10–0.00 1.50 4.0 2.70 1.00 0.5–3.24 N 4.10 0.0–25.5 24.30 0.25 Cu.0 4.0 16.0 3.65 1.10 0.25 N 1.50 18.04–0.00 2.5 24.0 8.00 21.0 17.20 0.2–0.50 2.0–8.5–1.30 0.25 2.12 0.0–26.0 20.0 18.50 1.50 0.0–3.10 0.0–15.5–30.0 23.50 1.1–0.25 1.0 12.0–27.20–0.0 8.0–26.0–23.0 0.50 1.5–2.0 20.5–6. 0.0 13.08 0.0–18.0 18.5 Nb (a) Balance Fe for all compositions.25 W.30 N 2. 0.5 Cu.50 1.0 10.0 0.50 2.16 0.0–11.0–16.0–34.0 11.5 0.9–3.50 0.0 18.0 0.0 18.0–22.0–13.00 1.0–21.5–14.00 1.0–22. 0.0–15.50 1.0–12. 0.0 8.05–0.0–21.00 2.5–1.0 2.00 1.70 1.50 2.15 0. 0. 0.0–21.0 22.0 8.20 N Nb 2.0 6.0–11.0 9.50 1.0 4.0-22.6–4.50 0.0–20.0 8.4–1.24 N 3.0 15.0 Cu.5 4.0 6.5–8. 0.5–14.75–2.0 18.0 18.442 CC-50 446 Chromium-nickel alloys CA-6N CA-6NM S41500 CA-28MWV 422 CB-7Cu-1 J91150 J91151 J91153 J91154 J91803 J92613 J91650 J91540 J91422 0.25 17-4PH (AISI 630) J92180 CB-7Cu-2 15-5 PH (XM-12) J92110 0.00 1.3 V 2.5–13.0 26.2–0.0 17.0 max Cu.7 1.00 24.0–21.0 20.40 Ss 0.0–3.20 2.0 0.5–25.50 3.2–0.0 17.0–21.50 1.50 1.00 1.0–23.0 22.03 0.5–3.06 0.0–13.0 (10xC)–1.00 1.10–0.06 0.5 max 1.0–7.05 N max 2.22–0.00 2.0–12.35 Nb.9 Cu.50 7.50 1. 0.5–4.0–22.0 1.5–1.0–12.0–26.50 1.0–15.5–3.2 Cu.18–0.5–14.9–1.50 1.0–21.7 24.03 1.00 0.148 / Stainless Steels for Design Engineers Table 1 Compositions of cast stainless corrosion resisting alloys Composition(a).00 2.00 1.3 V.00 2.0–26.50 1.5 11.0–21.00 1.5 CD-3MWCuN (S32760) CD-4MCu CD-4MCuN CD-6MN CE-3MN CE-8MN CE-30 CF-3 CF-3M CF-3MN CF-8 CF-8C CF-8M CF-10 CF-10M CF-10MC CF-10SMnN CF-12M CF-16F CF-20 CG-6MMN 2507 (S32750) 312 304L 316L 316LN 304 347 316 304H 316H 316H NITRONIC™ 60 316 303 302 NITRONIC™ 50 J93370 J93372 J93371 J93404 J93345 J93423 J92500 J92800 J92700 J92600 J92710 J92900 J92590 J92901 J92971 J92972 J92701 J92602 J93790 0.0–21.03 0.00 2.5–26.50 1.50 2.75–3.50 1. 0.00 2.50 1.5–12.0–21.08–0.04 0.10–0.0–30.5 23.00 2.0 9.0 11.00 1.08 0.00 1.0–9.0 W.9–1.5–3.0 27.7 6.00–6.0 20.4–1.00 1.0 12.15 0.0 12.0–12.3 Nb.00 1.0 19.25 Cu 1.0–27.10–0.5 0.50–1.15–1.0–3.2–0.07 0.15–1.0 22.0 3.00 1.5–5.00 1.00 1.00 0.0–8.00 2. 0.0 22.50 3.0 6.12 0.0 8.50 1.0–4.07 1.0 23.50 1.0 8.25 N 4.5 19.20–0.00 11.0–12.5 4.00 1.20 0.0–21.03 0.0–3.0 1.20 0.28 0.03 0.0 11.00 1.025 0.5 24.7–6.0-26.00 1.50–4.30 0.00 1.1–0.5–1.50 2.5 15.00 1.2–0.5–26.25 2.0–11.5 5.75–2.2 Nb 0.00 1.07 0.04–0.50 1.10 1.6–6.0–4.5–19.0–30.0 31.0 11.5 CD-3MN CD-3MCuN 2205 (S32205) 255 (S32550) J92205 J93373 J93380 0.06 1.50 1.0 19.20 1.0 Cu 1. 0.06 0.0-27.5–23.75–2.15–0.10 0.03 0.35 Nb.5 6.0 0.0 19.5–20.08 0.75–2.00 1.0 9.0 2.0–12.0–12.0–11.75–3.0–21.08 0.18 N 0.08 0.0 18.00 1.0 18.00 1. Source: Ref 1 .0 1.0–4.0 24.0–21.30 N 3.0 2.8 1.10–0.50 0.0 18. 0.0 Cu.04 0.0 Cu 0.0–3.00 14.00 0.50 1.75–2.50 1.5–3.00 1.0 11.5–14.05 N max 2.0–7.4 0.07 0.40 N CG-8M CG-12 CH-8 CH-10 CH-20 CK-3MCuN CK-20 CN-3M CN-3MN CN-7M CN-7MS CT-15C 317 308 309S 309H 309 254SMO™ 310 904L AL-6XN® 320 J93000 J93001 J93400 J93401 J93402 J94653 J94202 J94652 J94651 N08007 J94650 N08151 0.0 18.40 0. wt%—maximum or range Nearest AISI grade UNS %C %Mn %Si %Cr %Ni %Mo %Other ACI designation Chromium alloys CA-15 410 CA-15M CA-40 420 CA-40F 420F CB-30 431.50 1.2–0.50 1.0–11.0–27.5 1.30 N 1.0–5.

Chapter 11: Casting Alloys / 149

Table 2

Compositions of cast heat-resistant stainless and nickel base alloys
Composition(a), wt%—maximum or range Nearest AISI grade UNS %C %Cr %Ni %Si max

ACI designation


504 446 327 312 302B 309 310

J82090 J92605 J93005 J93403 J92603 J93505 J94003 J94224 J94203 J94204 N08604 J94213 N08705 N08605 N08603 N08005 N08006 N06050


0.20 max 0.50 max 0.50 max 0.20–0.50 0.20–0.40 0.20–0.50 0.20–0.50 0.20–0.60 0.25–0.35 0.35–0.45 0.20–0.60 0.20–0.50 0.35–0.75 0.45–0.55 0.35–0.75 0.25–0.35 0.35–0.75 0.35–0.75 0.35–0.75

8–10 26–30 26–30 26–30 19–23 24–28 26–30 24–38 23–27 23–27 28–32 19–23 24–28 24–28 13–17 13–17 17–21 10–14 15–19

4–max 4–7 8–11 9–12 11–14 14–18 18–22 19–22 19–22 18–22 23–27 33–37 33–37 33–37 33–37 37–41 58–62 64–68

1.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 1.75 1.75 2.00 2.00 2.00 2.50 2.50 2.50 2.50 2.50 2.50

(a) Balance Fe for all compositions. Manganese content: 0.35–0.65% for HA, 1% for HC, 1.5% for HD, 2% for the other alloys. Phosphorus and sulfur contents: 0.04 (max) for all but HP-50WZ. Molybdenum is intentionally added only to HA: 0.90–1.2%. Maximum molybdenum for other alloys is 0.5%. HH contains 0.2% N (max). HP-50WZ also contains 4–6% W, 0.1–1.0% Zr, and 0.035% S (max) and P (max). Source: Ref 1

form in the solid state. These precipitates are carbides, oxides, and sulfides as well as intermetallic phases richer in chromium, molybdenum, or nitrogen than the matrix. • General corrosion resistance follows the above guidelines but is also helped by copper and nickel, which do not assist in pitting resistance. • High-temperature oxidation resistance is enhanced by increasing chromium and silicon. Wrought alloys employ aluminum and rare earths to help oxidation resistance, but the difficulty of keeping these elements from being oxidized requires special techniques such as vacuum induction melting and inert refractories for molds. • Iron-chromium (ferritic) alloys have better thermal fatigue resistance but poorer creep resistance than iron-chromium-nickel (austenitic) alloys. The alloy designation system largely ignores the wrought alloy distinctions by microstructure (i.e., ferritic, austenitic, duplex, PH [precipitation hardening], and martensitic). One reason is that the most widely used wrought-stabilized ferritics (e.g., 409, 439) do not exist as common casting alloys, and nominally austenitic alloys in the cast form contain enough ferrite to be significantly magnetic. Thus, the distinctions based on phase are not as well defined for casting alloys. The high ferrite content in the nominally austenitic casting alloys is to avoid or at least

minimize solidification hot cracking or to allow weld repair of cracks that do form. It has been shown that the existence of ferrite can increase the resistance to stress corrosion cracking.

Metallurgy of “C” Alloys
The corrosion-resistant “C” series have wrought counterparts from which they differ essentially only in silicon content. This silicon has no significant influence on corrosion resistance or mechanical or physical properties, so an understanding of these alloys by approximating them to their wrought counterparts is justified. The main difference between the cast and wrought product forms of these alloys is the grain structure. In wrought grades, the grain structure can be manipulated by deformation and heat treatment. The use of deformation is not an option in cast alloys; consequently, the opportunities for grain refinement in cast alloys are limited. To counteract the problems of lower corrosion resistance of cast grades, a homogenizing solution heat treatment is necessary to counteract the chromium depletion that occurs due to solidification segregation and precipitating phases. Representative mechanical properties for “C” alloys are listed in Table 3 (Ref 1). Martensitic. CA alloys are martensitic. The metallurgy is straightforward and equivalent to their wrought counterparts. The mechanical

Table 3
Tensile strength MPa J ksi MPa ksi Elongation % in 50 mm, 2 in. ft-lb Reduction in area, % Hardness, HB Yield strength, 0.2% offset Charpy toughness Specimen

Room temperature mechanical properties of corrosion resisting cast stainless alloys


Heat treatment(a)

150 / Stainless Steels for Design Engineers

CA-6NM CA-15 CA-40 CB-7Cu CB-30 CC-50 CD-4MCu 896 669 531 600 531 586 531 552 621 552 531 531 565 607 524 770 476 ... 97 77 87 77 85 77 80 90 80 77 77 82 88 76 112 69 434 248 290 255 310 248 262 310 290 262 276 303 345 262 365 214 63 36 42 37 45 36 38 45 42 38 40 44 50 38 53 31 ... ... ... ... ... ... ... ... ... ... ... ... ... ... 18 60 50 55 50 50 55 45 50 39 52 45 38 37 50 48 190 140 160 140 156 163 150 170 170 149 150 176 190 144 185 130 130 634 92 ... 20 305 35.3 9.5 149.2 135.6 100.3 94.9 81.4 162.7 135.6 94.9 40.7 101.7 108.5 40.7 67.8 190 94.9 26 7 110 100 74 70 60 120 100 70 30 75 80 30 50 140 70

827 793 1034 1310 655 669 745 120 115 150 190 95 97 108 689 689 862 1172 414 448 558 94.9 27.1 2.7 33.9 2.7 ... 74.6

100 100 125 170 60 65 81

24 22 10 14 15 18 25

60 55 30 54 ... ... ... 269 225 310 400 195 210 253 70 20 2 25 2 ... 55

V-notch Keyhole notch Keyhole notch V-notch Keyhole notch ... V-notch V-notch Keyhole notch V-notch V-notch Keyhole notch Keyhole notch Keyhole notch V-notch V-notch Keyhole notch Keyhole notch Keyhole notch V-notch Keyhole notch Izod V-notch V-notch Keyhole notch

CE-30 CF-3 CF-3A CF-8 CF-8A CF-20 CF-3M CF-3MA CF-8M CF-8C CF-16F CG-8M CH-20 CK-20 CN-3MN CN-7M

>955 oC (1750 oF), AC, T 980 oC (1800 oF), AC, T 980 oC (1800 oF), AC, T 1040 oC (1900 oF), OQ, A 790 oC (1450 oF), AC 1040 oC (1900 oF), AC 1120 oC (2050 oF), FC to 1040 oC (1900 oF), WQ 1120 oC (2050 oF), FC to 1040 oC (1900 oF), A 1095 oC (2000 oF), WQ >1040 oC (1900 oF), WQ >1040 oC (1900 oF), WQ >1040 oC (1900 oF), WQ >1040 oC (1900 oF), WQ >1095 oC (2000 oF), WQ >1040 oC (1900 oF), WQ >1040 oC (1900 oF), WQ >1065 oC (1950 oF), WQ >1065 oC (1950 oF), WQ >1095 oC (2000 oF), WQ >1040 oC (1900 oF), WQ >1095 oC (2000 oF), WQ 1150 oC (2100 oF), WQ 1150 oC (2100 oF), WQ 1120 oC (2050 oF), WQ

(a) AC, air cool; FC, furnace cool; OQ, oil quench; WQ, water quench; T, temper; A, age. Source: Ref 1

Chapter 11: Casting Alloys / 151

properties are governed by the thermal processing, and strength, hardness, and toughness can be varied over a wide range. The CB 30 and CC 50 alloys are ferritic and, as such, have negligible toughness but effectively deliver corrosion resistance. The toughness of CB 30 can be improved by balancing the chromium and silicon to a lower part of the range and the carbon and nickel to the higher end to render the microstructure partly martensitic. Precipitation Hardening. The cast PH alloys include CB-7Cu-1, which behaves in a similar way to 17-4PH, which has an overlapping composition range. Note that most other major wrought PH grades rely on titanium and aluminum to form coherent strengthening precipitates and so do not have cast counterparts. Copper, which can harden ferrite but not austenite, is thus the only strengthener available. There is one cast PH alloy that has no wrought counterpart. It is CD-4MCu; however, it is rarely used in the precipitation-hardened condition and is most commonly classified as a duplex stainless steel in which the nitrogen level is closely controlled. This is a highly alloyed duplex grade that contains copper to precipitation harden the ferrite phase. Oil field CO2 corrosion is resisted by alloys that resemble the martensitic PH grades. These alloys are discussed in Chapter 22, “Petroleum Industry Applications” and can be considered castable alloys. Duplex. The cast equivalents of alloys 2205 and 2507, J 92205, and J 93380 have similar properties and corrosion resistance. Modern wrought duplex alloys rely on nitrogen to partition the alloy with uniform corrosion resistance in each phase and to suppress intermetallic phase formation. Cast alloys are effectively limited to 0.25% nitrogen before gas porosity becomes excessive. Porosity can be reduced by replacing some nickel with manganese, which increases nitrogen solubility. Doing so would expand the most promising area of stainless steel development, lean duplex alloys such as 2101 and 2003, to the cast grades. Alloy 2101 with 4 to 6% manganese provides the corrosion resistance of CF8M or 316L with total nickel plus molybdenum of only 2% versus the 12% required for the austenitic alloy. The duplex alloys also have greater strength and are nearly immune to stress corrosion cracking. These alloys represent significant cost-savings potential for the foundry and for its customers. CE-30 is duplex steel, which is fairly simple metallurgically and uses only chromium for corrosion resistance. However, its

high level of nickel negates much of the potential cost savings duplex alloys offer. All castings are solution annealed and quenched to eliminate embrittling intermetallic phases. The cast duplex alloys may offer a better engineering approach than the equivalent austenitic cast alloys because they have greater strength and lower alloy cost for the same level of corrosion resistance. They do not have the same problems of hot cracking that make casting austenitic steels difficult. The poor hot workability of duplex steel is not an issue for castings. It is important for designers to understand that cast duplex steels are totally compatible galvanically with wrought or cast austenitic alloys of the same corrosion resistance. Mixing components with different microstructures does not create a galvanic differential when corrosion resistance levels are similar. Reluctance to mix alloys for galvanic reasons can be an expensive error when their similar corrosion resistances makes them compatible, even if they are quite different microstructurally. Austenitic-Ferritic. The typical CF alloys, which make up about two-thirds of U.S. stainless steel castings, are nominally austenitic but always contain ferrite. This is not detrimental and improves resistance to stress corrosion cracking and sensitization. Homogenization annealing can reduce the amount of ferrite and result in lower yield and tensile strength and higher elongation and toughness. The composition balance is the main determinant of ferrite level. Increasing the nickel, nitrogen, manganese, or carbon content decreases ferrite. Increasing chromium, silicon, or molybdenum content increases ferrite. Increasing the solidification rate will increase the ratio of austenite to ferrite in duplex or austenitic-ferritic alloys. The predominantly austenitic matrix has a very high toughness even at cryogenic temperatures. Ferrite, if continuous, decreases toughness. Fortunately, it is seldom present as a continuous phase. The loss of toughness associated with high ferrite content can be aggravated by heating the ferrite above 475 oC (885 oF) for a sufficient time for the ferrite to decompose to the brittle α and α'. At higher temperatures, development of the σ phase would have a similar embrittling effect. These phases thus formed are quickly redissolved and removed by annealing. Note that sometimes copper is added to austenitic alloys to improve corrosion resistance in sulfuric acid environments. It has no precipitation hardening effect in austenite, as it does in ferrite. When

152 / Stainless Steels for Design Engineers

used as a precipitating hardening agent, copper does not increase corrosion resistance. Virtually any non-titanium-bearing, corrosion-resistant, austenitic, wrought alloy can have a cast counterpart. Curiously, the 2xx lownickel alloys are not found in most cast alloys lists. If a specific wrought alloy cannot be found to have a published cast counterpart, the designer should not avoid requesting a producer to supply a version that the foundry is confident of making. The designer must thoroughly understand the design of the alloy desired so that any alterations to its composition necessary to allow castability will not compromise expected performance.

Metallurgy of “H” Alloys
The heat-resisting “H” alloys are principally austenitic. Alloying elements and impurities diffuse more slowly through the face-centered cubic (fcc) austenitic structure than the bcc ferrite structure, making the austenite more resistant to diffusion-controlled creep. Austenite

has higher thermal expansion and lower thermal conductivity than ferrite, which aggravates thermal fatigue and oxide spalling. Nevertheless, the better high-temperature strength of austenite generally is the predominant consideration, and most “H” alloys are austenitic. Tables 4 and 5 list properties of “H” alloys (Ref 1 to 3). Ferritic HA, HC, HD. Of the ferritic alloys HA, HC, and HD, HA with less than 10% chromium is not quite stainless but is useful to 650 oC (1200 oF) for petroleum refinery applications. HC and HD are very high chromium ferritics that have very low toughness and creep resistance but are quite oxidation and sulfidation resistant. They can be cost-effective materials when high-temperature strength is not an overriding concern. Austenitic HE-HP. The predominant hightemperature grades are the austenitic HE through HP, after which come the nickel alloys, which are not generally classified as stainless steels because they contain less than 50% iron. The high material cost of the nickel base alloys restricts their use to those specific environments where maximum carburization or nitriding

Table 4

Mechanical properties of heat-resistant cast stainless alloys at room temperature
Tensile strength Condition MPa ksi Yield strength MPa ksi Elongation, % Hardness, HB

Standard grades HA HC HD HE HF HH, type 1 HH, type 2 HI HK HL HN HP HPNb(d) HPNbTi(e) HT HU HW HX

N + T(a) As-cast Aged(b) As-cast As-cast Aged(b) As-cast Aged(b) As-cast Aged(b) As-cast Aged(b) As-cast Aged(b) As-cast Aged(c) As-cast As-cast As-cast As-cast As-cast As-cast Aged(c) As-cast Aged(f) As-cast Aged(g) As-cast Aged(f)

738 760 790 585 655 620 635 690 585 595 550 635 550 620 515 585 565 470 490 450 450 485 515 485 505 470 580 450 505

107 110 115 85 95 90 92 100 85 86 80 92 80 90 75 85 82 68 71 70 75 70 73 68 84 65 73

558 515 550 330 310 380 310 345 345 380 275 310 310 450 345 345 360 260 275 220 220 275 310 275 295 250 360 250 305

81 75 80 48 45 55 45 50 50 55 40 45 45 65 50 50 52 38 40 40 45 40 43 36 52 36 44

21 19 18 16 20 10 38 25 25 11 15 8 12 6 17 10 19 13 11 8 8 10 5 9 5 4 4 9 9

220 223 ... 90 200 270 165 190 185 200 180 200 180 200 170 190 192 160 170 ... ... 180 200 170 190 185 205 176 185

(a) Normalized and tempered at 675 °C (1250 °F). (b) Aging treatment: 24 h at 760 °C (1400 °F), furnace cool. (c) Aging treatment: 24 h at 760 °C (1400 °F), air cool. (d) ISO 13583-2 specification minima. (e) ISO 13583-2 specification limits for microalloyed grade. (f) Aging treatment: 48 h at 980 °C (1800 °F), air cool. (g) Aging treatment: 48 h at 980 °C (1800 °F), furnace cool. Source: Ref 1

Chapter 11: Casting Alloys / 153

Table 5

High-temperature mechanical properties of “H” alloys
Yield strength ksi, MPa Tensile strength ksi, MPa Creep rate 0.0001%/h psi, MPa 1% in 100,000 h psi, MPa Stress to rupture in 1000 h Stress to rupture in 10,000 h




1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 800 oC 800 oC 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF 1400 oF 1800 oF

16 8.7 2.1 10.5 2.5 36 15 1.3 3.6 3.5 1.0 3.5 1.0 6.0 1.6 (est) 3.0 1.1 7.0 2.1 6.6 1.9 6.8 2.7 7.0 2.8 (est)

27 1.3 0.6 7.0 2.5 11.0 2.5 9.1

35 17 6.3 18 7 33 9 35 11



6.3 0.9

50 18.7

8.0 1.6 8.5 2.6 12.0 2.8 15 5.2



2.4 2.1 51 MPa 54 MPa 8.0 2.0 8.5 2.2 6.0 1.4 6.4 1.6


... ... 26 8 6.2 23 8 19.5 6.9

... ... 35 11 40 10 32 10 42 10.7

... ... 12 2.7 2.9 7.8 2.6 2.2

55 MPa 64 MPa 1.7 1.8

(a) Data from ISO 13583-2. Source: Ref 2, 3

resistance is mandatory. For oxidation and sulfidation resistance, the iron base alloys are preferred. These cast stainless steels derive their oxidation resistance from their chromium level. The chromium near the surface acts as a reservoir to replenish the protective iron/chromium oxide scale as explained in Chapter 6 in the section on oxidation. Silicon, another stable oxide former, assists in forming this protective scale and resistance to carburization. Other typical alloying elements do not aid in oxidation resistance. If it were possible to cast these alloys with aluminum or rare earth additions without them being lost to oxidation before solidification, there could be some impressive benefits. Such alloys exist in wrought form, for example, 153MA and 253MA. The metallurgical basis of the benefits from aluminum and rare earth

alloying also are discussed in the oxidation section of Chapter 6. The major problem that all producers of stainless steels face is that of transferring molten metal from the furnace to the mold cavity. This problem is heightened when the foundry makes complex shapes. Methods developed to protect the molten stream from exposure to air to prevent reoxidation have shown great promise and have been demonstrated by the wrought alloy producers who tend to produce much simpler shapes than the foundry. Protection of the molten stream could result in castings with much better hightemperature performance that could be used instead of some use of higher nickel alloys. High-temperature strength is modestly improved by higher levels of chromium and nickel. Molybdenum improves high-temperature

154 / Stainless Steels for Design Engineers

strength, but its detrimental effect on oxidation resistance and its promotion of intermetallic precipitation limits its use. Carbon is very effective for promoting high-temperature strength and suppression of intermetallic phase formation. All “H” alloys, therefore, employ much higher carbon levels than the “C” alloys. This does, however, directly imply that the corrosion resistance of “H” alloys, should it be an issue, is significantly degraded over otherwise similar “C” alloys. The HP grades have undergone significant development over the last 30 years. This development has come about through the addition of niobium to increase creep and rupture properties. The use of microalloying additions has delivered creep and rupture properties some 30% higher than the HP grade without niobium microalloying. It is unfortunate that these HP grades have not at this time found their way into ASTM standards; however, work is under way to remedy this omission. Currently, the most upto-date collection of these grades can be found in ISO 13583-2.

higher-performance grades. It is also possible to use AOD-refined master melt stock to achieve the same benefits as AOD refining while using induction melting. Welding of cast stainless alloys is a common practice and does not present problems when using approved weld procedures and qualified welders. Chapter 17 describes joining methods in detail. The same precautions about sensitization apply to castings. Welding of non-niobiumstabilized “C” alloys with carbon levels above 0.03% will require postweld annealing to redissolve chromium carbides, which will otherwise make the alloy susceptible to corrosive attack in the chromium-depleted regions of the heataffected zone. Iron and nickel base “H” alloys that are fully austenitic can suffer from hot shortness due to sulfide films that precipitate along grain boundaries even at low bulk sulfur levels. This makes them susceptible to hot cracking of welds. Alloys with some ferrite are less susceptible to hot cracking, so most “C” alloys are highly resistant to this problem.

Foundry Practice
While the scope of this book does not extend to the production of castings, certain aspects are important to the user of castings. For the last 50 years, virtually all stainless has been refined in argon oxidation decarburization (AOD) vessels or versions thereof. For “C” alloys, this refining method should be considered a basic requirement for good quality where the carbon levels are restricted to low levels (e.g., CF3M). “H” alloys are less refined inherently and can be simply arc or induction melted; however it may be necessary to use refining techniques for the

1. Cast Stainless Steels, Metals Handbook, desk ed., J.R. Davis, Ed., ASM International, 1988, p 386–390 2. International Organization for Standardization,, ISO 13583-2 3. Steel Founders Society of America, online documents: index.html


This process was not only very expensive. p 155-160 DOI: 10.1361/ssde2008p155 Copyright © 2008 ASM International® All rights reserved. this flexibility allows scrap of all types to be used. This process is based on the following chemical reaction: Cr3O4 (Solid) + yC = yCO (gas) + Cr (Eq 1) Introduction The manner in which stainless steel is made at the producing mill can have a great impact on its final properties. reacts more strongly with the purifying agent.Stainless Steels for Design Engineers Michael F. early stainless steel making.asminternational. than does carbon. It is this carbon whose removal is the primary focus of refining. widespread engineering materials they are today. the low processing cost of stainless steel has spurred demand and made some of its ingredients. was a lengthy process that necessarily involved high chromium losses to the slag as carbon was removed. oxygen. Melting and Refining The arc furnace is nearly universally used for the first step in the production of stainless steel. Since the charge materials for stainless steel are typically carbon steel and stainless steel scrap. and it is seldom beneficial for the end user to specify processing paths. ladle metallurgy. Ironically. making most of today’s stainless steels. The vast majority of stainless steel is made by arc furnace melting followed by argon oxygen decarburization (AOD) refining and continuous casting. impossible to produce. The necessary chromium is added as ferrochromium. www. even more costly. The fundamental difference is that the basic decarburization step. the carbon levels that could be achieved were not much below 0. McGuire. and powerful hot rolling mills has led to stainless steels of much higher quality produced at lower cost. The arc furnace is quite flexible in the types of charge materials it can accept. and hot processing are invisible to the end user.10%. The carbon content of the heat of steel is roughly 1. These production methods have undergone a major evolution over the last 50 years and are mainly responsible for stainless steels becoming the practical. chromium. Thus. forcing the cost of many alloys to spike even higher than in earlier years. be knowledgeable and require the producer to document the process and the producer’s control of it. whose cost is inversely related to its carbon content.5% when it is melted and ready to charge into the separate refining vessel. whose carbon levels range from CHAPTER 12 Melting. however. of removing nearly all the carbon from molten stainless steel without significant loss of chromium. continuous casting. which is common to all steel making. In the 1960s. is thermodynamically very difficult in stainless steel because the essential element. Traditional carbon and alloy steel-making methods are not suitable for stainless steels. The end user should. Union Carbide engineers perfected a method.5 to 2. Casting. The advent of AOD. done in an arc furnace. which are relatively scarce and expensive commodities. It is not normal. the previously mentioned AOD process. and Hot Processing Summary THE PRIMARY PRODUCTION PROCESSES of melting. casting. austenitic alloys. such as molybdenum and nickel.010% in stabilized ferritic alloys to about 0.07% in normal The equilibrium for this reaction is: Ln (K ) = −ΔG 4575T (Eq 2) .

is based on cost and final nitrogen content desired. it exists in almost all stainless steel at levels close to its normal specification limit. and G is the Gibbs free energy. and this excellent purity level is commercially furnished without additional price premium. and welding methods. Titanium is believed to reduce hot working defects.925 log p CO T %C (Eq 3) Thus. other impurities can be removed from the molten stainless. Titanium. In both processes. Also note that even if no intentional addition of metallic calcium is made. Any known process to remove it first removes chromium. A typical starting ratio is 3 to 1 oxygen to argon/nitrogen by volume. argon or nitrogen. which are . Sulfur.020% or less in ferritic alloys. Stabilized stainless steels require low carbon and nitrogen levels. sulfur can be readily removed by contact with a basic slag. By increasing the ratio of argon to oxygen in the injected gas as the refining proceeds. This mixing not only allows the CO-producing reaction to reach equilibrium.800 =− + 8. and CO (Ref 1): Log = %Cr 13.015%) for tungsten inert gas (TIG) welding penetration (see Chapter 17) and at high levels (0. This is similar in principle to the basic oxygen furnace (BOF) process for carbon steel in which oxygen is injected into molten steel to remove carbon by oxidizing it. increasing the temperature works to increase the elimination of carbon as CO.15%+) for machinability (see Chapter 15). stagnant. Phosphorus is an impurity for which no practical removal technology exists in stainless steel. whose product integrity is compromised. can be used in many cases to eliminate the need for the weld penetration enhancement of sulfur while increasing welding speeds. although a harmful impurity from a corrosion standpoint. The key to the AOD process. can be used when required. and consequently small amounts of it are sometimes used as a supplementary deoxidant in alloys even though an alloy specification may not call for any. so the more expensive argon must be used. is the injection of oxygen and argon into the bath to keep the partial pressure of CO (pCO) very low. for instance. There are processing methods for which higher levels of sulfur are not necessary that are preferable to the end user while not compromising welding or machining costs. This is done at a temperature consistent with economic refractory life. which evolves from the melt. More active deoxidants.001% in the AOD. is often deliberately kept at moderate levels (0. though. is enhanced as a deoxidizer in chromium-iron alloys. Once the steel has been deoxidized. Sulfur can be reduced to less than 0. This could be further reduced by aluminum.030% in austenitic alloys and 0. chromium. For example. such as laser welding.008 to 0. should be viewed with skepticism by end users. The VOD process can achieve slightly lower carbon levels but does not achieve cleaner steel as some believe. The ending ratio can be as low as 1 to 9. so its role as a deoxidizer is less valuable in stainless steels. oxygen to argon/nitrogen. after final carbon content has been achieved ferrosilicon is added to reduce the chromium in the slag and have it return to the molten steel. producing measurable calcium content in the metal. This is the vacuum oxygen decarburization (VOD) process. Working through the thermodynamics yields the relationship that summarizes the important relationship among carbon. Besides carbon and oxygen. Thus. but aluminum-based inclusions are generally undesirable. but also the mixing of the slag and metal also permits desulfurization. such as calcium and magnesium. the carbon is selectively oxidized without concurrent chromium oxidation. The thermodynamic activity of aluminum is considerably reduced in iron as chromium levels increase.76 − 0.156 / Stainless Steels for Design Engineers where K is the equilibrium constant. which would never happen in the flat. It is possible to use a vacuum system to keep the partial pressure of CO low when refining with injected oxygen. strong deoxidation with aluminum or titanium can reduce small amounts of calcium from the CaO in the slag. The injection and the reaction cause extremely thorough mixing. The excellent mixing of the slag and metal in the AOD permits this to be done efficiently. These trade-offs. The choice of which inert gas to use. arc furnace bath. The silicon plus the manganese in the steel combine to reduce the oxygen content of the steel to around 100 ppm. machinability can be improved by calcium additions that produce malleable oxides to replace the deleterious sulfides (see Chapter 15). about 0. The injection is done through tubes called tuyeres in the bottom of the barrelshaped vessel. which are beneficial to processors. on the other hand.

The activity coefficient γ varies with the concentration of alloying element x by: RT lnγ i = RT lnγ i0 + on interstitial solubility.01 0.01 .01 –. and little refining is possible.06 .02 –. This is a nearly slag-free process. nitrogen.03 .27 –. There are two principal remelt processes: vacuum arc remelting (VAR) and electroslag remelting (ESR).03 –.03 –. This technique is very effective for the finetuning of reactive elements such as titanium.08 .11 0.05 –. and oxygen J i Al C Cr Mn Mo N Ni O S Si Ti W O N S 0 . A manganese/silicon deoxidized stainless steel will still have about 100 ppm of dissolved oxygen at the freezing temperature as opposed to the less than 10 ppm of oxygen found in aluminum-killed carbon steel.45 –. but there are subtle differences because of the difference in the thermodynamics of dilute solutions like carbon steel and highly alloyed. The deleterious effects of phosphorus on corrosion are not avoided unless much lower levels are achieved..14 .05 . Vacuum induction melting (VIM) is another method of melting stainless steels. Table 1 shows the factors by which additions of various elements to stainless steel (j) alter the thermodynamic activity of other alloying elements (i). The tapped molten steel generally has excess heat from the highly exothermic refining process.006 –.02 –.. Consequently.01 . This allows the composition to be measured and adjusted before it must be cast.34 .04 –.13 . Melt purity is largely controlled by the purity of the starting material. which solidifies in a bottom-up fashion.. –.0 . Volatile constituents escape from the molten drops.13 .11 –. its presence is tolerated since it has no differential effect over the range in which it is found. Casting. and the molten drops fall through the intervening vacuum.05 . Remelting Some stainless steels and related alloys are remelted to refine composition or ingot structure. Heavy metals are eliminated by high-temperature AOD blowing.39 .05 –.13 . –.005 –.06 –. nondilute solutions like stainless steel. Limited decarburization is possible via injection of oxides such as Fe3O4 or SiO2 to create CO evolution inside the vessel.Chapter 12: Melting.01 . This can be done very precisely by wire feeding of alloying elements through the slag into the heat. has a powerful effect Table 1 Influence of alloying elements on the thermodynamic activity of carbon. The higher solubility of carbon. nitrogen. and oxygen in stainless steels is significant. and the purified drops collect to form a molten pool on top of the starter plate.003 . n ∑ n RT δ ln γ i δxj (Eq 4) This calculation is best left to computer programs such as Thermo-Calc that have been perfected for these lengthy procedures. VAR parameters are adjusted to maintain a shallow pool.. as is hydrogen. Alloy adjustment can be done in the AOD or preferably in a treatment-and-transfer ladle. Equation 4 is used to calculate the activity of elements in steel. Care must be taken not to reintroduce such impurities after refining.. This oxygen precipitates as oxides in the solid state. which is always present in nondilute quantities. sulfur. Using this technique.20 . Use of VIM is generally limited to high-value. very low carbon levels (less than 50 ppm) are achievable commercially.53 –. A high-current direct current (dc) arc is established between the electrode and a starter plate at the bottom of the chamber. which is a risk when using damp or contaminated scrap for coolant.01 –.003 .0 .. high-purity.07 –. and Hot Processing / 157 made from a higher percentage of low-phosphorus carbon steel scrap.001 .04 –. In VAR.02 –. the material to be remelted is cast into a cylindrical electrode and placed inside a cylindrical water-cooled vacuum chamber.6 –.01 .01 –.01 –. and use of AOD master melt stock for VIM remelting is common. The refining treatments used for carbon steel and stainless steel are very similar. The shallowness of the molten pool produces a refined grain j =1. which can be stirred by argon bubbling via porous plugs. It should be noted that chromium. The end of the electrode is melted.01 –. or low-tonnage melts.

seldom-recognized effect. to prevent fluctuations in level that may entrap slag in the slab surface. called the submerged entry nozzle. Continuous casting produces slabs directly. and the molten drops fall through the slag. which detracts from hot workability. A high current is used to melt the slag. The metal feeds through another ceramic tube. they may be held at high enough temperatures prior to hot rolling to stay above the temperature range in which embrittlement can occur or to stay above the temperature at which an embrittled slab can fracture. into a ceramic tube into the large tundish situated over the caster mold. The initial portion of slab cast in a sequence is seldom of adequate quality to be used because of exogenous inclusions. The metal in the tundish is covered with a protective slag cover. which is covered with a consumable protective and lubricating slag cover.158 / Stainless Steels for Design Engineers structure with less solidification segregation than found in typical cast product. which in turn melts the end of the electrode. whose hot rolling from slab can be both expensive and problematic.). called a mold powder. Producers generally apply first slabs to less-critical uses or discard suspect sections of them. oxidizing potential. and certain alloying elements concentrate at the centerline. There are a . This deformation has a crucial. The pinch rolls apply enough pressure to slightly deform the slab. it can cause excessive grain growth. or preferably a stopper rod gate. Elimination of hot rolling could be quite valuable in stainless steel. This deeper pool produces a grain structure between that of VAR and typical cast product. entrapped mold powder. and non-steady-state solidification structure. replacing the obsolete ingot method. The strand is bent from an initial slightly curved shape to flat and cut into slabs. Some end users stipulate that no first slabs be applied to their orders. slabs are of sufficient quality that they require no surface conditioning before being hot rolled. In ferritic alloys. The level of the molten metal should be carefully controlled by ultrasonic measurement. this slag is calcium fluoride-based with high lime (CaO) content. In properly executed continuous casting. A gap between the electrode and a starter plate at the bottom of the mold is filled with a prepared slag. In ESR. and bloom casting have become the standard methods of making stainless steel primary products. This is ideal economically and for quality reasons since initial and final segments of a casting can contain more inclusions and aberrant structure. the material to be remelted is cast into an electrode of similar shape. If casting conditions are not optimal. Carbon and molybdenum are examples of alloying elements with this tendency. Casting Continuous slab. and flow patterns within the tundish are designed to minimize dead spots and encourage removal of inclusions by impingement with the slag cover. The mold powder. and carbon. and the molten pool is deeper. however. There has been great interest for decades in producing stainless steel coils directly from the melt in so-called strip casters. copper alloy mold oscillates in a precise pattern as the solidifying strand of steel is withdrawn from the mold bottom by pinch rolls and sprayed with water to cool it. which melts in the mold as it is added. and the purified drops collect to form a molten pool on top of the starter plate. It causes a beneficial recrystallization that improves hot working characteristics of austenitic and duplex alloys. There are some alloys that cannot be continuously cast. billet. Typically. into the mold. The entire water-cooled. Reaction of the molten drops with the slag removes sulfur and some other impurities. but slightly smaller than the water-cooled mold. contains ceramics. the result can be slabs with poor surface quality that must be surface ground. the ladle feeds by a slide gate. Slabs are sometimes quenched to avoid precipitation of phases. The segregation in continuous casters is less than in ingots because of the smaller section size. fluidity. Additional ingredients control the basicity. but these represent a miniscule percentage of stainless production. where they defy homogenization. The defective portion must be identified and scrapped or diverted to low-quality requirement end uses. Slabs range in thickness from 13 to 63 cm (5 to 15 in. fluxes. thus removing the costly soaking and slabrolling processes. Ferritic and martensitic alloys are especially prone to these problems. It is not eliminated. with commensurate intermediate segregation patterns. and other properties of the slag. In a well-executed continuous casting operation. or other methods. More than one heat of steel may be cast sequentially without restarting the process. ESR melting typically is done at a higher rate than VAR. however.

such as roll shifting. having been quenched extremely rapidly. very high carbon/vanadium stainless tool steel components can be made by encapsulating powder in an evacuated canister in which it can be sintered and hot worked to 100% density and virtually complete homogeneity.06 in. Hot Rolling Hot rolling remains an essential process for the vast majority of stainless steel used. it seems unlikely that strip casting will soon become a major factor even if it is perfected technically. These particles. Hot Steckel mills have become the favored method of hot rolling stainless steel because their throughput better matches stainless steel melt shop production outputs. and Hot Processing / 159 number of such machines in pilot or limited production. the refined molten metal is atomized by gas or liquid and made to freeze into small particles. Martensitic stainless steels roll like their carbon and alloy steel counterparts since their microstructure during hot rolling is a moderately alloyed austenite similar to alloy steels. although rolling stainless on hot tandem mills used primarily for carbon steel can be an excellent production method. Since their development is only being undertaken by those large stainless steel producers who already have the hot rolling assets that strip casting would replace. Hot strip tandem mills powerful enough to successfully roll high-quality stainless steel hotrolled bands are massively expensive and are seldom justified for the tonnage of stainless steel rolling a given melt shop produces. This is the same justification for using Sendzimir mills to cold roll stainless. In either case. Furthermore.) can struggle to attain 4. the hot-rolled band must then be annealed and pickled since the as-rolled hot-rolled band . This increases mill loads. This permits the melt shop and caster to be adjacent to the hot mill. singlephase structure at hot rolling temperatures. which if not countered by roll bending or roll shifting schemes can lead to significant variation in thickness across the sheet.2-in.) thickness for 316 stainless. Then. Powder technology methods allow for the design of alloys that would otherwise freeze with too much segregation and too coarse a structure with conventional production methods. Hot rolling characteristics of stainless steels vary greatly. not to have to be duplicated among many stands. or roll bending. Hot-rolled bands vary in thickness along the length of the coil because the tail end of the slab is colder and harder to roll. embedded scale that must be removed from the surface before further processing in most cases.Chapter 12: Melting. Another method of shortcutting the casting/ ingot step has been perfected: the powder metallurgy approach. In hot Steckel mills. In both cases. Casting.18-in. Powerful hot strip tandem mills that routinely roll carbon steel to 1. Chapter 9 on martensitic alloys discusses these materials. are quite homogeneous. If normal cold rolling or use as hot-rolled coil is foreseen.) thick. Coil boxes (on reversing mills) address this problem to a degree by permitting the semirolled coil to equalize in temperature. Some alloys can be cold rolled in the “black band” state at a cost of coarser surface finish and greater rolling mill roll wear. Ferritic stainless steels are extremely easy to hot roll since they have a soft.).01 in. More impressively. the logic applies more to austenitic alloys than to the easily rolled ferritic stainless alloys. avoiding most of the costly machining steps. The microstructure during hot rolling is the crucial factor. Austenitic stainless steels have high strength at hot rolling temperatures. as much as 0. powder technology is also used to produce massive components. typically a fourhigh reversing rougher rolls slabs to about 3-cm (1. roll crossing. They have not had sufficient commercial or technical success to have become a factor in the industry. The economy of having only two mill stands makes these mills ideal for typical stainless production quantities and permits the cost of sophisticated mill capabilities. The high separating forces on the hot rolling mill stands also cause greater roll deflection and compression. For example.5 mm (0. the transfer band is rolled to final gauge on a separate reversing four-high finishing mill with coil boxes to preserve temperature.25 mm (0. This variation as a percentage of thickness is not reduced by cold rolling and is a major cause of tolerance loss in sheet and strip. and lower reductions must be taken than for alloy steels.5-mm (0. which permits energy-saving hot charging of slabs. the low diffusion rates in austenite slow recrystallization so that the steel does not always soften between stands in tandem mills. the hot-rolled band carries a heavy. Traditional powder metallurgy production methods are used to make small near-net shape components. In powder metallurgy.

They do have repercussions on delivery. Handbook of Stainless Steels. which facilitates diffusion of sulfur and oxygen to the grain boundaries and also encourages very large grains. This is true of all hot mill scratches. a skid mark from a slab-heating furnace will remain through the hot rolling. Inclusion-related defects are all essentially avoidable by using state-of-the-art technology. REFERENCE 1. Defects Stainless steel hot-rolled bands can contain many types of defects. Hot ductility defects are more subtle. 1977. This poor hot ductility manifests itself as “slivers. even alloys such as 304 and 316 can have very poor hot ductility if they contain much sulfur and oxygen or if they are reheated for long times or at temperatures above 1250 °C (2280 °F). etc. as well as slab surface working in the caster pinch rolls. The major categories are: • Hot mill defects • Inclusion-related defects • Hot ductility-related defects Stainless steel is less forgiving of hot mill faults because its surface is not removed by oxidation to the degree carbon steel’s surface is. and the phases can exhibit mechanical incompatibility at certain temperatures.” which can require grinding of the entire hot band surface. Bernstein. and cold rolling processes. Edge cracks are simply a lack of ductility at the colder strip edge.160 / Stainless Steels for Design Engineers has poor corrosion resistance. The former has a mixed-phase structure. These tendencies are fought by low oxygen and sulfur levels and minimal slab-reheating temperatures and times. where they form very weak films. gouges. very poor hot working alloys are given a single hot reduction pass on a hot mill to produce a full recrystallization that disperses grain boundary-weakening elements on subsequent reheat. The latter alloys reject sulfur and oxygen during solidification and slab reheating to the grain boundaries. These are seldom seen by the end user because they are removed when they are not prevented. Stainless hot ductility often has a narrow temperature window. The most inherently challenging alloys for hot working are the duplex alloys and the alloys that solidify in the fully austenitic state. as well as a heavy oxide layer. Rolling stainless requires a different mindset than rolling carbon steel. Peckner and I. They arise from many causes and are manifest prima- rily as edge cracks and slivers. annealing. Protecting metal from reoxidation and keeping precise mold-level control in the continuous caster prevents all inclusions of a size that can produce a defect. residual cold work and hardness variations. digs.M. p 3–13 . Thus. poor mechanical properties. and many factors can affect the size of that window depending on alloy type. Sometimes. which argues against the benefits of rolling stainless on a mill built and primarily used for carbon steel. But. McGraw-Hill. D.

www. and some are potentially very detrimental. Normally. Each of the alloy groups of stainless steels has radically different thermal processing objectives and requirements. It is not simple in concept or in practice. There is no substitute for understanding the processes that are occurring when stainless steels are heated for successful heat treating to be achieved. McGuire. Before attempting to carry out any thermal processing on stainless steel. less-obvious. and atmosphere can have complex and easily unintended consequences. The soaking had two functions. each is discussed separately. Stainless also reacts with its environment at high temperatures. The obvious one was to equilibrate at the right temperature for hot working. and continuous casting helped make the stainless Introduction The thermal processing of stainless steels can have many purposes. times at temperature. The lack of homogeneity comes from the solute segregation that occurs as solute elements are rejected from the material that was first to freeze. The thermal processing then must be designed and executed in a planned. controlled manner. and processing history of the material in question. desirable. the objectives are simple: heating for hot working. p 161-171 DOI: 10. the practitioner must understand the alloy design.Stainless Steels for Design Engineers Michael F. one was to achieve greater chemical homogeneity. Stainless steels have many alloying elements in large amounts. Austenitic Stainless Steels Thermal processes applied to austenitic stainless steels include: • Soaking for homogenization and preparation for hot working • Annealing to remove the effects of cold work and to put alloying elements into solid solution (solution annealing) • Stress relieving The temperatures at which these processes are carried out are shown in Table 1 for typical austenite compositions. solution annealing to homogenize. The consequences of failure in thermal processing can become catastrophic to mechanical properties and corrosion resistance. The practical consequence of this is that many phases are thermodynamically possible at different temperatures. Solute segregation was exaggerated by the slow solidification of CHAPTER 13 Thermal Processing Summary THE THERMAL PROCESSING of stainless steel is a topic the end user should approach with great respect. Soaking Because virtually all stainless steel is continuously cast. or to stress relieve. The second. heating to temper martensite. Some of the resulting phases are . therefore. 6–10) to familiarize themselves with these phases.1361/ssde2008p161 Copyright © 2008 ASM International® All rights reserved. annealing to soften after cold working. the processes that occur are anything but simple. heating and cooling rates. Variations in temperature. Readers are encouraged to review the earlier chapters on phases in stainless steel (Chap. However. composition.asminternational. even if the objective is simple. Many of these elements are highly reactive thermodynamically. causing changes in surface alloy content. the older soaking process of holding ingots in soaking pits for many hours is rarely used.

305. . It is important to soak at the highest temperature at which delta ferrite is not a stable phase so that it will dissolve. steel more homogeneous... (a) Standard specification for general requirements for flat-rolled stainless and heat-resisting steel plate. by reducing grain boundary area. °F Stress relieving.. . that is. °F ASTM A480(a) 2006....... lower sigma alloys... . about 1250 °C (2280 °F) for most austenitic stainless steels. exacerbates this effect. JS700 Highly alloyed. to the extent it is done. New grains nucleate and grow.. annealing returns into solution solute that has been precipitated as unwanted phases.. 202. soaking times are best minimized and closely controlled... Annealing Annealing serves two main functions in stainless steel: It removes the effect of cold work by replacing strained microstructure with new strain-free grains. 815–870 . Welds that are unannealed have such precipitated inclusions in an unequilibrated state. Creq<26 S31725. 1000–1600 . 201LN 301. 310. 1900 min 1900 min 1900 min 1900 min 1900 min . which also must be equilibrated with the sur- rounding matrix by sufficient soaking. leaving the same grains relieved of stress.162 / Stainless Steels for Design Engineers Table 1 Alloy Recommended thermal processing temperatures for austenitic alloys Annealing temperature.. Thus. 955–1065 980–1025 925–955 1120–1175 1120–1175 .. high N AL6-XN.. all versions 316. 654SMO. occurs as they are reheated to the appropriate temperature for hot working. The oxygen and sulfur trapped in the ferrite during solidification precipitates in the solid state as inclusions. as happens often with ferritic stainless steels. negating the homogenization and causing very poor hot workability. .. plastic films that also degrade hot workability. 1205–1230 2200–2250 Various Not recommended . 1750–1950 1800–1950 1700–1750 2050–2150 2050–2250 . principally carbides.. . . 309S... . 316L. If stored strain energy is insufficient.. Soaking dissolves the few percent of residual delta ferrite that are present on slab solidification.. 317. making the composition more homogeneous. 309.. .. Various Various 1500–1600 non-L. sheet. This leaves the surviving grains with the same crystallographic orientation that deformation produced and may or may not be the desired outcome. 348 20Cb-3 Moderately alloyed. Alloys are therefore designed to have only a slight amount of delta ferrite to be redissolved during soaking. Ferrite is useful because it has a high solubility for oxygen and sulfur. The homogenization process is accelerated by the reduction in dimensions from hot and cold working. Soaking at higher temperatures causes ferrite levels to increase. sigma-prone alloys. . and the result is diminished chromium concentration and poorer pitting resistance. 540–870 .. 304L. 540–870 L grades . 1900 min 1900 min ... which results in the worstpossible hot working characteristics. 301LN. Creq>30. cast slabs and blooms must be soaked to eliminate as-cast segregations. and the annealing process may only produce recovery without recrystallization. Nevertheless. and strip. Having none would result in impurity rejection of these elements to grain boundaries during solidification. °C Annealing temperature.. 1850–2050 1850–2050 1850–2050 1900–2150 1900–2150 . true recrystallization is difficult to achieve. °F Stress relieving. 1010–1120 1010–1120 1010–1120 1040–1175 1040–1175 ... oC Standard alloys 201. Longer times at temperature than the minimum required for thermal uniformity also cause problems as any sulfur and oxygen impurities are rejected from austenite and can diffuse to grain boundaries. recrystallization. low N AL6-X . where they form weak.. . 316N. but also intermetallic phases.. N08028. Second. 4565. 310S Stabilized alloys 321 347.. 925–1010 1500–1600 Not recommended 815–870 non-L. 1000–1600 L grades .. ... 254SMO Highly alloyed. Annealing also may help to reduce solute segregation remaining from the casting process.... all versions 304.. A reduction in dimension by a factor of two reduces the time to achieve a given degree of homogenization by a factor of four. This process.. Creq>30... 317L 308.... Grain growth. .

End use determines whether a fine or coarse grain size is preferable. the temperature selected should be determined by the desired grain size. The overall interplay between prior cold work and annealing temperature on mechanical properties of annealed material can be summarized as (Ref 3): • Grain size of a given alloy is the most important parameter in characterizing mechanical properties. • Maximizing elongation comes from maximum prior cold work and medium annealing temperatures • Anisotropy coefficients. The strain energy in a given material is proportional to the square of the material’s flow stress. require higher temperatures to dissolve all the carbon. which r45 and rn increase sharply. Solution annealing requires longer-range diffusion and thus can require much longer times. while rt decreases. Hot-worked material often has a composite structure that may have already had some recrystallization depending on the final reduction temperature. recovery occurs first. for instance. • Yield and tensile strength are essentially constant for a given grain size regardless of the amount of prior cold work. Table 1 lists recommended annealing temperatures for austenitic stainless steels. but this does not mean that all composition gradients have been reduced to zero. it is instantaneous. The annealing temperature for a given alloy is chosen based on the temperature required to put all alloying elements into solution. the elongation depends on the prior reduction. This leads to earing during drawing. in which transit time can be short enough. to limit the grain size attained. Annealing may not produce a clear recrystallized structure in this case. The nucleation of new grains occurs at highangle grain boundaries and proceeds by the movement of roughly hemispherical growth fronts into strained areas. This may not be the case for continuous annealing lines. It should be noted that precipitates can be redissolved and not apparent in the annealed microstructure without full homogeneity being achieved. and hardness are essentially linear functions of grain size. As the material is heated. • Yield strength. Within the recommended range. Annealing after lower amounts of cold work is characterized by scarce nucleation sites and can result in very large and nonuniform grain size. This is one of the principle values of accurate phase diagrams. The relative rapidity of recrystallization annealing is due to the fact that it is rate controlled by short-range diffusion. carbides can be redissolved and carbon diffused away from the carbide. Even at the lower range of annealing temperatures. Others have seen homogenization in as little as 10 min (Ref 2). • The increase in properties for a one ASTM grain size increment is: a. It is normal for the time to fully recrystallize to be rather less than the time to attain that temperature. 13 MPa (2 ksi) for tensile strength b. Thirty percent cold work should be used as a rough threshold for the required amount. Higher carbon levels. less than a minute at temperature. however. To a first approximation. once a sufficient temperature is reached. do not recover completely from their loss of corrosion properties that arise from local alloy depletion unless they have been annealed for times on the order of 1 h (Ref 1). The percentage recrystallized. • Elongation decreases with finer grain size and at an increasing rate as grain size becomes finer as long as cross-section size of the test specimen is not extremely small. This is the change in physical and mechanical properties associated with dislocation annihilation and polygonalization that occurs before the nucleation and growth of new grains. 20 MPa (3 ksi) for yield strength c. Wrought materials can require much shorter times because reductions during hot working have reduced diffusion distances. times are generally less than 1 min. and the results are merely a function of the maximum temperature attained. The driving force for recrystallization is the strain energy stored in the lattice from deformation. If it were simply a consideration of recrystallization. tensile strength. 2 HRB for hardness . all alloys could be annealed at similar temperatures at the low end of the recommended range. for instance. grows sigmoidally. This is not true for very coarse-grained material.Chapter 13: Thermal Processing / 163 Annealing to recrystallize is fairly rapid. Some studies have shown that welds. For example. or plastic strain ratios r are constant up to about 40% reduction after. Recrystallization will not occur if the lattice contains insufficient strain energy. This means that precipitates may re-form more rapidly in such a material than they would in a completely homogeneous alloy.

which can cause distortion or lead to stress corrosion cracking in service. It can also form from slow cooling of slabs or hot bands. and annealing times should be generous. Newer alloys have higher nitrogen contents to suppress formation of sigma and other deleterious inter- metallic phases. Last. This latter sigma forms at grain boundaries and will cause embrittlement and reduced corrosion resistance. The chromium-depleted zone.164 / Stainless Steels for Design Engineers Atmospheres for annealing are important. so must the chromium-depleted layer. Stabilizing anneals are sometimes conducted on stabilized alloys such as 321 and 347. then is done to permit the carbon to combine with the stabilizing element rather than leaving it available to form chromium carbides. present a special problem because these alloys have significant sigma-forming tendencies. which renders this stabilizing unnecessary. form oxide scales. If vacuum is used. The dew point must be –40 °C (–40 °F) or lower. This Bauschinger effect. If this is not done. For this reason. and even alloys like 317. the key consideration is moisture content. of course. Even hard water deposits can cause differential oxide growth. Cold-worked austenitic stainless steels have a markedly diminished proportional limit. with times doubling for each 100 °C (180 °F) decrement as decreasing diffusion rates. which arises from the easy mobility of dislocations. which can cause etched spots on the surface. Superaustenitic stainless steels. Use of high-chromium andmolybdenum alloys without enhanced nitrogen is no longer recommended. Austenitic stainless steels heated in air. so that residual stresses may be relieved by creep. it should be less than 2 × 10–3 torr (0. and the use of lowernitrogen alloys should be reexamined and questioned if specified.and molybdenum-depleted regions will still exist. which while done commonly. . vacuum. which provides the thermal energy for dislocation interactions to lock into place. so it must not only be redissolved. chromium. Sigma forms initially because solidification segregation causes local enrichment of sigma-promoting elements. the metal matrix becomes significantly depleted of chromium (Ref 4). can be eliminated by stress relieving at around 350 °C (660 °F) for 2 h. hydrogen. If forced air or water quenching are impractical or if section size prohibits rapid cooling. which govern creep. may not be practical for many stainless users. Alloys used for high-temperature service benefit from the creep-resisting contributions of higher carbon levels. This produces a sharp yield point without premature nonproportional elastic deformation. More stringent levels may be required if mirror finishes are desired. Austenitic alloys that are subject to sensitization must be cooled rapidly enough from annealing temperatures to avoid carbide precipitation during cooling. They are commonly stress relieved at temperatures slightly below the annealing temperature. such as molybdenum. Vacuum or inert gas is preferable to hydrogen for alloys containing stable oxide formers such as aluminum or titanium or for alloys containing boron. but also the alloy must be homogenized to remove the residual concentration gradients from the sigma. A second anneal at lower temperature. particularly in compression. are encountered. stainless surfaces should be scrupulously clean before annealing. then using stabilized or low-carbon grades is indicated. however. Cool down must be rapid as oxidation potential increases as temperature decreases. Lower temperatures require exponentially longer times for the same stress relief. One hour at 900 °C (1650 °F) reduces residual stress by about 85%. Stress Relieving Austenitic stainless steel weldments often contain residual stresses. If an inert gas or hydrogen is used.). or inert gas atmospheres may be used. This requires aggressive pickling. does pickle rapidly precisely because it does have less chromium. So. where the postanneal pickling attacks the different oxide more strongly.3 Pa). and sigma will re-form much more rapidly during subsequent exposure to high temperatures. often more than 5% lower in chromium and to a depth of as much as 10 µ (395 µin. Current preferred practice for these alloys is to maintain carbon and nitrogen below 0.03% for corrosionresistant service. the higher ends of the annealing ranges are recommended. This is useful when carbon levels are sufficiently high that significant dissociation of carbides occurs at annealing temperatures. about 900 °C (1650 °F). Beneath this oxide. not only must any oxide be removed. Carbonaceous materials left on the surface are even more objectionable because they can cause carburization and subsequent loss of corrosion resistance. To avoid oxide scale formation.

which are ferritic at all temperatures. First are the modern. also shows which grades fit into which category. in solution to cause them to form austenite at what would otherwise be a good annealing temperature. or the formation of austenite at higher temperatures would make martensite formation on cooling virtually unavoidable. at temperatures below annealing temperatures. 446 870–925 705–790 1010–1065 760–830 1600–1700 1300–1450 1850–1950 1400–1525 phases that require dissolution. which have enough austenitizing elements. Thus. This is not a concern with IF alloys. This makes them truly quasi-martensitic alloys. Seacure. except in rare cases. At this temperature. In the second category are the older ferritic steels. 444 Unstabilized. which lists heattreating temperatures for ferritic stainless alloys. do not have intermetallic Table 2 Recommended annealing temperatures for ferritic alloys Alloy Annealing temperature. Stabilizing anneals are normally unnecessary for stabilized ferritics as their high diffusion rates ensure freedom from knife-edge attack due to sensitization from free unbonded carbon combining with chromium at grain boundaries. Whether stabilized or not. which greatly reduces toughness. The interstitial-bearing ferritic stainless steels must be annealed subcritically. Alloys with high chromium and molybdenum contents can form σ and/or α'. no debilitating phases occur. The driving force for recrystallization in these alloys is limited by the lower stored energy from deformation inherent in the bcc structure. This cycle also precipitates essentially all the carbon and nitrogen as mixed Cr/Fe carbides and nitrides and homogenizes chromium content. The stabilizing additions of titanium and/or niobium tie up the carbon as stable TiC or NbC. oC Annealing temperature. Table 2. 434. The high diffusion rate inherent to the ferritic structure makes homogenization easy. usually carbon. The major concern is to avoid excessive annealed grain size. so rapid cooling is prudent when chromium plus molybdenum exceeds 20%. In addition. This necessarily slow process permits subsequent subcritical annealing for mechanical properties (to alleviate the effects of cold work) to be done in a few minutes since carbon has been eliminated from solution by the formation of fairly stable carbides. these alloys are heated to the 1000 to 1100 °C (1830 to 2010 °F) range for hot working. The objective of annealing is generally simply to remove the effects of cold work. These alloys retain this texture after annealing. Cr+Mo<20 405. Anneal at the higher end of the range only if the loss of toughness associated with large grain size is not a concern. and ductility is good. The superferritics can be heated to up to 1300 °C (2370 °F). from an annealing point of view.Chapter 13: Thermal Processing / 165 Ferritic Stainless Steels Ferritic stainless steels. must be discussed in two categories. 436 Stabilized. a typical primary anneal cycle for a typical alloy such as 430 would be nearly 24 h at 750 °C (1380 °F). and they must be treated accordingly. Monit. the brittle. the pronounced deformation texture leads to annealing responses that are more accurately characterized as recovery and grain growth with diminished recrystallization. good hot ductility is expected. the majority of which is thermal equilibration of the large coil mass. 439. stabilized alloys. These alloys behave as interstitial-free (IF) alloys because the interstitial carbon and nitrogen are removed from solution as a stable precipitate. oF Stabilized. Soaking Heating of ferritic stainless for hot working is straightforward. Cr+Mo>20. . As long as hot working is completed at temperatures above that at which austenite forms. Cr+Mo<20 409. The actual time at temperature required is less than 1 h. 430. which does not redissolve during annealing. which do not form austenite. Continuous annealing is not practical because the diffusion of carbon is too slow to occur in the dwell time at temperature typical in continuous annealing lines. ordered body-centered cubic (bcc) phase. This is because they do not need to have carbon put into solution and. and this characteristic anisotropy is exploited for good drawability. Since the material is generally purchased in the annealed condition. Annealing The IF ferritics do not undergo any phase change with temperature during the course of properly executed heat treatment.18 SR Unstabilized. Cr+Mo>20 29-4C. the user need never be concerned with such lengthy anneals.

high range.20 440A.B. Unstabilized grades should not be welded. low range. they will not transform to martensite. Full austenitizing is crucial to producing a microstructure that is fully martensitic. and tungsten promote secondary hardening and tempering resistance. Martensitic alloys have lower corrosion resistance in the annealed condition than in the hardened condition because in this state they have the maximum amount of chromium tied up as chromium carbide. If the alloy level is such. 410. austenitizing. This is a characteristic of the so-called super 12Cr alloys. oC (oF) Tempering. difficult process. Nickel reduces the temperature at which austenite is stable as shown in Chapter 9. Fig. Temperatures for this are listed in Table 3. such as the 440 group.20. Austenitizing Table 3 lists the austenitizing and tempering ranges for martensitic stainless steels. Other additions like vanadium. then only subcritical annealing is feasible. If other constituents. o C (oF) Austenitizing. such as δ ferrite or carbides. The martensitic stainless steels form essentially 100% austenite on heating and have very high hardenability. exist during the austenitizing heat treatment before quenching. The more highly alloyed newer alloys are. 9. which directly determines strength and corrosion Recommended annealing. o C (oF) Tempering. 431. More recently. C<0. 414. o C (oF) Full anneal. full subcritical annealing is required. 416. Annealing Martensitic stainless steels can be annealed by subcritical anneal and sometimes by full anneal depending on alloy level. sometimes with a small amount of nickel and/or molybdenum. so their ability to be softened by annealing is limited. 425. molybdenum. even for nickel-free alloys the hardenability is so great that annealing by slow cooling is quite difficult. oC (oF) Straight Cr. so subcritical annealing is always recommended for these alloys. C>0. Martensitic Stainless Steels The martensitic stainless steels resemble the unstabilized ferritic stainless steels described. alloys have been developed for petroleum applications that contain high copper. Only austenite transforms to martensite. Forging and hot working should always be followed by annealing to avoid stress cracking due to the deep hardening of these alloys. Soaking Hot working should be carried out in the austenitic range. The nickel-bearing alloys have such high hardenability that annealing in the critical range cannot produce softening by any practical cooling rate. The traditional martensitic stainless steels are iron/chromium/carbon alloys. the more economic subcritical anneal is the predominant annealing heat treatment.403 Ni/Mo. in fact. Stabilized grades have no need for postweld heat treatment. that Table 3 Alloy martensite cannot be avoided by furnace cooling from austenitic temperatures. The principles of heat treatment of the two alloy categories are the same. as in the nickel-containing grades. C<0. have enough carbon that the austenitizing temperature determines how much carbon is put into solution. simpler to heat treat because their low carbon and nitrogen levels alleviate the need to temper.20. Martensitic alloys are put into the annealed condition for processing before they are quenched and tempered for their final use. But. Lowtemperature heat treatment runs the risk of α' formation and is best avoided.166 / Stainless Steels for Design Engineers Stress relieving is rarely a concern for any type of ferritic stainless. The carbon in solution in the austenite will become the carbon level in the martensite.C F. and subcritical annealing of these alloys becomes a slow. 415. nickel. Thus. 420 650–760 (1200–1400) 620–705 (1150–1300) 675–760 (1245–1400) 830–885 (1525–1625) Not recommended 925–1010 (1700–1850) 980–1065 (1800–1950) 1010–1065 (1850–1950) 205–370 (565–605) 205–370 (565–605) 150–300 (300–700) 400–700 (1050–1125) 400–700 (1050–1125) Not recommended 845–900 (1555–1650) . Some alloys. and if they are. and tempering temperatures for martensitic alloys Subcritical anneal. and/or molybdenum and low carbon.

The PH steels. which occurs more severely in alloys with higher chromium levels. Heating to even low temperatures allows carbon enough mobility to diffuse and precipitate as carbide. requiring a second tempering operation. Oxidation during austenitizing can cause serious carbon loss on the surface. which will result in serious loss of surface hardness. which is caused by the precipitation of phosphorus and other species. called secondary hardening. as can low levels of carbon. The ferrite is a generally undesirable phase that can be produced by temperature excursions or composition variations. Niobium and vanadium also form carbides that result in higher hardness at all tempering temperatures. the austenite boundaries maintain the microcompositions they have at high temperatures. The strain energy associated with the lattice strain of the bcc martensite caused by the poor fit of the carbon in the tetragonal interstices is very large. which can lower hardness and cause problems with dimensional stability. chromium. Lower tempering temperatures and higher austenitizing temperatures are best for corrosion resistance because both minimize the amount of chromium tied up as carbide. such as Cr23C6. more thermodynamically stable carbides. The existence of temper embrittlement is the reason that Table 3 recommends avoiding certain temperature ranges for tempering. The growth of carbides reduces strain and hardness. higher tempering temperatures lead to lower hardness. This phenomenon is distinct from the precipitation of α'. it tends to precipitate with the abundant iron atoms first. Carbide formation is a complex function of temperature.Chapter 13: Thermal Processing / 167 resistance because undissolved carbides contain chromium. If this occurs. may have retained austenite. which causes the so-called 475 °C embrittlement. It will cause lower hardness and toughness if present. to avoid precipitation of carbides in the austenite during quenching since the sensitization would persist in the final microstructure. At higher temperatures and longer times. Heating 410 in air for 10 min at 1100 °C (2010 °F) can cause surface carbon to decrease by one-half. such as. then they should be promptly . Austenite has low solubility for impurities such as phosphorous. where its solubility is a steep function of temperature. The nickel-bearing alloys have a restricted upper tempering temperature because of the danger of re-forming austenite. Heating rates should be such that a uniform temperature is attained before the allotropic transformation from bcc to face-centered cubic (Fcc). carbides. AM-350 and AM-355. but some. There are exceptions. Excessive austenitizing temperatures can cause its formation. Had this been understood early on. which involves a more than 1% linear dimension change and can cause distortion or cracking. time. at prior austenitic grain boundaries. Stress Relieving If quenched martensitic steels are not immediately tempered. so phosphorous is more highly concentrated in the grain boundary regions. The quenching rate must be sufficient. form. lowering hardness from HRC 45 to under 20. which diminishes that available for corrosion resistance. however. and composition. Quenching rate is not a significant issue for the martensitic stainless steels since they have such high hardenability. or other carbide formers. Austenitizing temperature and holding time become most significant when carbon exceeds 0. but not limited to. whose morphology produces a precipitation hardening (PH). Because the formation of martensite is diffusionless. these steels could have been correctly included in the PH stainless group. which combines with the phosphorus and prevents the embrittlement. such as the precipitation of Mo2C. During tempering. carbon is precipitated from the supersaturated state it is in when it is quenched into the bcc martensite structure during the diffusionless transformation. Since carbon diffuses 106 times as fast as iron. This compositional inhomogeneity can be eliminated by higher tempering temperatures or by the addition of molybdenum. In all other cases. both derive their PH from the precipitation of Mo2C and Mo2N.20%. Intermediate temperatures can lead to the phenomenon of temper embrittlement. a subzero treatment at below –75 °C (–100 °F) should be undertaken immediately after quenching. which may be originally present in the alloy or arise from decarburization. which would then transform to untempered martensite during cooling. Quenching from higher temperatures also enhances toughness. Tempering Untempered martensite has insufficient toughness to be a useful engineering material. especially those with higher carbon levels.

the residual stress from quenching could result in stress corrosion cracking even in seemingly benign environments. many with some molybdenum substituting for part of the chromium.0005 in. The semiaustenitic grades are more complicated than the martensitic PH alloys. The time and temperatures required to produce this precipitation are also given in Table 4. The classes are martensitic. The as-quenched state is called condition A. enhances dimensional stability but diminishes toughness. the hardness and strength of these alloys is derived from a subsequent tempering-type heat treatment during which various constituent elements form extremely fine coherent precipitates that greatly strain and therefore strengthen the matrix. These alloys essentially resemble a lean 301 austenitic alloy. as mentioned. the martensitic PH alloys are carefully designed to produce a nearly fully austenitic structure at high temperature that quenches to a nearly fully martensitic structure on cooling. The condition code itself tells the temperature at which the aging is conducted in that the code numbers are based on thermal processing temperatures expressed in degrees Fahrenheit (oF). This stabilization of the austenite comes mainly from higher chromium and carbon levels. The key to these grades is making them behave as a martensitic alloy. Stress relieving is simply a low-temperature tempering operation. Otherwise. so it is relatively soft and not prone to brittleness. Most alloys may retain some austenite after quenching to room temperature. All aging treatments are above the temper embrittlement range to which these alloys are susceptible. are optically invisible and cause very little dimensional change. The constituent elements are easily dissolved. from aging is typical. Service temperatures in this range would result in embrittlement. Martensitic PH Grades Solution treatment of these alloys is conducted to achieve a fully austenitic structure. The presence of retained ferrite is mainly a function of alloy and composition within the allowed range. by eliminating retained austenite. The most straightforward alloys are the martensitic PH grades. often permitting machining to final dimensions in condition A. Table 4 lists the solution treatments for all PH grades. and it permits them to be highly formable. Higher temperatures and longer times produce greater stress relief and maximize elastic properties. This is done by precipitating some of the carbon as chromium carbide at a temperature at the high end of what would normally be consid- . The subsequent alloys are substantially ferrite free. Precipitation Hardening Stainless Steels There are three classes of PH steels. so use above 350 °C (660 °F) should be avoided. The result is a very tough microstructure. allowing some austenite to re-form. which would be detrimental to final mechanical properties. These alloys are designed so that they are austenitic when quenched from the solution heat treatment temperature. The precipitates. Lower temperatures result in higher possible hardness but lower toughness. Aging. This is also called condition A. This is the normal condition in which the material is supplied from the mill and is intended to be soft enough for machining and some forming. All require the shortrange diffusion of substitution elements to form these optically invisible precipitates. The final properties are a function of both aging time and temperature. So./in. semiaustenitic. but optimal toughness is obtained at intermediate times and temperatures. and austenitic. but some elimination of residual stress does occur.168 / Stainless Steels for Design Engineers stress relieved. Like the plain martensitic alloys. for example. The subsequent aging then overages that martensite while retaining some stable austenite. and they are described in detail in the PH chapter (see Chapter 10). so excessive temperature or time is unnecessary and could be counterproductive if it were to result in ferrite formation or surface oxidation. The martensite is low in carbon. Molybdenum-bearing grades should be selected to minimize this phenomenon if high-temperature use is contemplated. TH 900 means transformed to martensite (T) and aged at 900 degrees Fahrenheit. and each requires totally different heat treatment. There are numerous precipitates that can provoke this effect. If softer material is required. in which case subzero treatment should be done within 24 h to avoid further stabilizing the austenite. the H-1150M condition exists in which the material is first highly overaged at 760 °C (1400 °F). Earlier grades such as 17–4 and the obsolete stainless W intrinsically contained some ferrite. Solution Heat Treatment and Conditioning. Contraction on the order of 0. Subzero treatment.

xxx °F for 4 h xxx °F for 4 h xxx °F for 4 h . Cold reduce 955 °C (1750 °F) 10 min.. 930 °C for 90 min. .. air cool.. room temperature.. .. precipitation-hardenable. air cool 1065 °C for 30 min. air cool –75 °C 8 h –75 °C 8 h . air cool.. oil or air cool below 15 °C 1035 °C 30 min.. water quench 1035 °C for 1 h. This material. air cool 1065 °C for 30 min.. .. air cool.. . . oil or air cool below 15 °C 1035 °C 30 min. oil/water quench 900 °C 120 min. The highest conditioning temperatures of 955 °C (1750 °F) cause a sufficiently ... xxx °F for 180 min 440–470 °C for 180 min 540–590 °C for 180 min . oil or air cool below 15 °C 1035 °C 30 min.. oil or air cool below 15 °C 925 °C 15 min. .. cool rapidly 925 °C 1 h. 760 °C (1400 °F). 15-7 A T C R THxxx CHxxx RHxxx 1065 °C for 30 min... This process is called austenite conditioning... air cool.. .. oil/water quench 900 °C 120 min. air cool 1065 °C for 30 min.. . oil or air cool below 15 °C 1035 °C for 1 h. 730 °C 16 h 730 °C 16 h.. The carbide precipitation occurs at the interfaces of the small amount of residual ferrite these alloys have and also at grain boundaries..... RT.. 180 min at –75 °C 930 °C for 90 min. The higher the temperature of the conditioning. oil/water quench 980 °C 120 min. air cool 930 °C for 90 min. 180 min at –75 °C 930 °C for 90 min... .. water quench 980 °C for 1 h. air cool 925 °C 1 h. oil/water quench 980 °C 120 min. water quench 830 °C for 1 h. 730–760 °C 180 min ... 275 475 A RHxxx Hxxx A Hxxx A Hxxx A Hxxx A Hxxx A Hxxx A Hxxx 925 °C 15 min.... . 180 min at –75 °C 930 °C for 90 min. air cool AM-350 A 1010–1065 °C L (equivalent to T) 1010–1065 °C SC (equivalent to R) 1010–1065 °C SCTxxx 850 °F or 1000 °F DA (double aged) 1010–1065 °C . 450–540 °C 180 min ..Chapter 13: Thermal Processing / 169 Table 4 Alloy Recommended annealing and stress-relieving temperatures for martensitic PH grades Condition code Solution anneal Conditioning Aging Martensitics 13-8 15-5 17-4 450 455 465. air cool to RT for 30 min.. air cool 1065 °C for 30 min. oil or air cool below 15 °C 1035 °C 30 min. water quench 830 °C for 1 h. . The deletion of carbon and chromium from the matrix changes the matrix composition sufficiently that the temperature for the start of the martensitic transformation (Ms) of the depleted austenite increases from below zero to about 65 to 100 °C (18 to 212 °F). air cool. The heat treatment scheme just described would be condition A-1400. 180 min at –75 °C 930 °C for 90 min. xxx °F for 180 min . air cool 930 °C for 90 min. oil/water quench PH.. air cool to RT for 30 min Cold reduce 955 °C (1750 °F) 10 min. cool rapidly 980 °C for 1 h. oil or air cool below 15 °C 925 °C 15 min.. air cool. chill to –75 °C for 8 h ... air cool.. ered sensitization. . chill to –75 °C for 8 h 760 °C (1400 °F) 90 min. the less carbon is precipitated and the lower the resulting Ms. 650 °C 8 h 730 °C 16 h Am-355 A 1025–1040 °C L (equivalent to T) SC (equivalent to R) SCTxxx 850 °F or 1000 °F DA (double aged) Equalized and overtempered Austenitic A-286 ST1650 ST1650A ST1650DA ST1800 ST1800A 900 °C 120 min.. 730–760 °C 180 min 930 °C for 90 min. 930 °C for 90 min. The martensitic transformation finishes (Mf) near room temperature.. after quenching to room temperature. . –75 °C 8 h –75 °C 8 h –75 °C 8 h –75 °C 8 h xxx °F for 4 h xxx °F for 4 h xxx °F for 4 h xxx °F for 4 h xxx °F for 4 h xxx °F for 4 h xxx °F for 4 h xxx °F for 4 h Semiaustenitics 17-7. would be said to be condition T. air cool 1065 °C for 30 min. air cool. air cool..... . 730–760 °C 180 min . 760 °C (1400 °F). . 90 min. air cool 1065 °C for 30 min.

The highest-temperature solution and carbide precipitation treatments provide the best corrosion resistance. The subsequent precipitation aging requires higher temperatures and longer times because diffusion is much slower in austenite. 255 1010–1100 1040–1100 1050–1150 1850–2010 1900–2010 1925–2100 Various 1040 min Various Not recommended Not recommended Not recommended . The resulting mechanical properties vary in a complex fashion with the alloy composition and thermomechanical treatment history before aging. °C Lean duplex. Cr+Mo<26. It is even possible to obtain the fully martensitic structure by cold work from full condition A. °F Stress relieving. as do the lowest aging temperatures. are: • Carbon level of the quenched martensite • Amount of cold work of austenite prior to aging These factors do not come into play with the martensitic PH grades because all of the carbon is in solution. Cr+Mo<23. The aging treatments of the semiaustenitic alloys are identical to those for the martensitic alloys because the treatments are standardized. have an equally variable chromium content. besides the strain induced by the precipitate phase. soaking should proceed the same as for ferritic stainless alloys since ferrite constitutes the continuous phase to be worked. Their strengthening reaction comes from precipitation of titanium. so corrosion resistance will vary accordingly.and aluminum-nickel intermetallic phases within the austenite matrix as occurs in superalloys. The semiaustenitic PH alloys. Table 5 lists the normal annealing temperatures for these alloys. °F ASTM A480 2006 Stress relieving. Because these alloys always contain high chromium and generally high molybdenum. Solution treatment is very typical Table 5 Alloy for a normal solution anneal of non-PH austenite. they should be cooled as rapidly as possible from high temperatures to avoid formation of sigma or other intermetallic phases.170 / Stainless Steels for Design Engineers low Ms that subzero treatment is required to obtain the fully martensitic structure required for age hardening. 2507. because of the variable amount of carbide precipitation. it would be called condition R-100. and they are not significantly cold worked prior to aging. 19-D-2304 Medium alloy. Zeron 100. 2205 Cr+Mo>26. It is extremely important to drive sulfur to the lowest possible levels. the austenitic PH alloys are austenitic under all conditions. Otherwise. Austenitic PH Alloys In contrast to the martensitic and semiaustenitic PH alloys. The principles at work that determine the mechanical properties. making their hot workability quite poor. 52N+. 2003-2101. approximating the overlap between what each of the two constituent phases would be annealed at separately. which is quenched from 1065 °C (1950 °F). After subzero treatment at –73 °C (–100 °F). This is called condition C and requires heavy cold rolling to accomplish. less than 0. Since there is no heat treatment to precipitate carbon from the austenite matrix. °C Annealing temperature.001%. The use of nitrogen as a key alloying Recommended annealing and stress-relieving temperatures for duplex alloys Annealing temperature. so their heat treatment combines the same elements and principles as their principle phases. Soaking Duplex alloys are multiphase at all useful working temperatures. the resulting martensite is the hardest. to achieve satisfactory hot ductility. This would be called A-1750. Annealing The function of annealing in the duplex alloys is generally to: • Remove the effects of cold work • Restore the balance between the volume fraction of ferrite and austenite • Achieve equilibrium composition within both the austenite and ferrite • Dissolve unwanted intermetallic phases The annealing range of duplex alloys is somewhat restricted. Duplex Stainless Steels Duplex stainless steels are both ferritic and austenitic.

Data courtesy J&L Specialty Steel. A. Stress relief would have to occur at temperatures at which embrittling reac- tions. causing ferrite-austenite equilibrium to be attained very rapidly.Chapter 13: Thermal Processing / 171 element has improved the annealing behavior of these alloys since its diffusion is quite rapid. Vol 35 (No. Grubb. 1979. No strengthening heat treatments are used. J. which takes over at 600 °C (1110 °F). June 4. p. Corrosion. which can form after quenching from welding temperatures and cause regions of poor corrosion resistance. Nitrogen also hinders (formation and facilitates the dissolution of secondary austenite. 1998 4. J. October 2. Grubb. personal communication. REFERENCES 1. 2006 3. either from ' beginning at 350 °C (660 °F) or from / . the guiding principle in annealing is simply to achieve phase balance and avoid cooling so slowly that intermetallic phases may form. would occur and so is not indicated for these alloys. The strengthening of duplex is normally achieved by the strong grain refinement and solid solution hardening. Garner. 108–114 2.F. The Effects of Autogenous Welding on Pitting Corrosion in Austenitic Stainless Steel. 1991. Thus. Chiba. 3). ISIJ . These alloys are not very susceptible to carbide sensitization and normally have very low carbon content. Proceedings of the International Conference on Stainless Steels.F.

the process is normal. For steels with equivalent corrosion resistances. so lubricant is not normally used. Bending is a simple operation. This higher strength requires greater sophistication in tooling and lubricants.Stainless Steels for Design Engineers Michael F. formability increases with the level of austenitizing alloying elements. These steels are formed by bending. stabilized stainless alloys contain abrasive carbide microconstituents. The various types of stainless steel have very different deformation characteristics in terms of strain hardening and anisotropy. the best forming economies can be gained. Stainless steel has lower thermal conductivity than carbon steels. If the dies significantly restrain the periphery of the blank so it cannot move. The higher yield strength and work-hardening rates of most stainless steels will result in greater springback than would be experienced in carbon steel. Last. if the specific structural anisotropy of ferritic alloys. spinning. Material properties determine whether a material is most successfully formed by stretch forming or drawing. The higher initial strength is also accompanied by a higher work hardening rate in austenitic stainless steels. thereby decreasing lubricity. However. In neither of these forming methods is there large motion of the formed material across the die surface. p 173-180 DOI: 10. roll forming. which gives particularly good deep-drawing characteristics for a given level of ductility. stainless products are flat products. or ordinary. drawing. can be exploited. least expensive. McGuire. especially. shown that it is important to understand and exploit these characteristics to optimize forming of stainless steels. Roll forming is most commonly used to produce welded pipe and tubing and is simply bending done in a continuous manner. and least formable. and austenitic steels are the most formable but most expensive. and it requires more powerful forming equipment. Galling also must be recognized as a danger and prevented. The ferritic alloys are the least alloyed. Deep drawing is the foremost of these. stretch forming occurs.asminternational. and deep drawing. Tooling must be adjusted to compensate for this. A round blank is held between dies over a cavity. The reader is referred to the Forming and Forging in Volume 14 of the ASM Handbook for detailed charts on bend radii and springback related to bending. Figure 1 (Ref 1) shows schematically what occurs during drawing. duplex steels are next. www. Flat. Rolled Stainless Steel The vast majority of carbon steel and.1361/ssde2008p173 Copyright © 2008 ASM International® All rights CHAPTER 14 Forming Summary STAINLESS STEELS RANGE in formability from the extremely formable austenitic alloys to the hard-to-form martensitic alloys. which further distinguishes them from carbon steel. which can cause it to retain heat from deformation and friction. The primary difference is the higher strength of all types of stainless steels compared to drawingtype carbon steels. and there is no meaningful change in thickness of the sheet during the operation. Other forming techniques employ more complex deformation processes. It will be . Introduction The technology for forming stainless steel is quite similar to that for forming carbon steels. hydroforming. If the dies pinch the blank to only a small degree. and a punch pushes the material into the cavity to produce the part.

As long as the work-hardening rate keeps the flow stress below the through-thickness yield strength. This nonrandom crystal structure can cause the material to have higher strength in the through-thickness direction. For drawing. Deep Drawing. Austenitic materials have the face-centered cubic (fcc) crystal structure with many slip systems and low stacking fault energies. So.174 / Stainless Steels for Design Engineers Fig. the material is constrained from moving wholly into the die. again redistributing the deformation away from the potentially thinning area. adjustments to the drawing process (i. In stretch forming. without stretching requires a different material characteristic. referred to simply as drawing. This directional variation in properties is called anisotropy. If the material were constrained from contracting while being stretched. there will be no thinning. some hold-down pressure is required to prevent wrinkling of the blank before it is pulled into the die. In many forming situations.. This is more pronounced for thinner blanks and for material with higher work-hardening rates. The geometry of deep drawing with constraint fits such materials’ capabilities. ferritic material has one other advantage: Body-centered cubic (bcc) alloys have more slip systems than fcc alloys. Whether the material becomes so thin locally that it fails is governed by its work-hardening rate. it flows in the stretching direction and contracts laterally at lower stresses than are required to initiate plastic flow in the throughthickness direction. a low work-hardening rate is desirable so that the material can compress in the circumferential direction while elongating in the radial direction. They can also transform during stretching to the much harder martensite. Thus. Even without stretching. the tensile strength would be exceeded before through-thickness flow occurred and the material would fracture with little deformation. and local failure is prevented. the section that enters the die is stretched more and must become thinner. called texture. Obviously. This is why carbon steels and ferritic stainless steels deep draw well. these materials cannot be stretch formed.e. But. a high ability to elongate is always useful regardless of any other characteristic. the strain is distributed. This makes austenitic stainless steels particularly suitable for stretch forming. for which the deformation is greatest. This means that they can generate many complex arrays of tangled dislocations. Deep drawing. they may retain a preferred crystallographic orientation. When a material with desirable texture is stretched. hold-down force adjustment. draw . If it work hardens faster than it becomes thinner. which cause strain hardening. as a result of the deformation. 1 Deep drawing schematic. When bcc alloys are rolled to become flat stock. Source: Ref 1 Stretch Forming.

Optimizing the material/drawn component combination is far from simple. but values between 1. This diagram shows the locus of failure under varying strain states.Chapter 14: Forming / 175 bead contour.10 2.9 26. It should noted that the very ductile 304 fares no better than carbon steel because of the advantage of a beneficial anisotropy. R determines the average depth (that is. End users are encouraged to deal directly with the producing mill early in the design stage of any new highproduction.2 31.7 26. The measure of anisotropy is the Lankford ratio (Ref 2).01 2.8 34. The material properties that are important to formability are ductility. When this expression equals 1. are certainly reservoirs of knowledge of current practice.67 1. r45 is the strain ratio measured at 45° to the rolling direction (of the sheet metal-forming operation). which is the instantaneous slope of the true stress.0. The ability to be deep drawn is measured by the limiting drawing ratio (LDR). blank size.5 9. such as cost and material performance in service must be factored in. the material properties are the same for all crystallographic orientations.7 28. % Hardness HV Lankford value n value ro r45 r90 r ¯ Erichsen value.20 0. the best-performing deepdrawing stainless steels are low interstitial ferritic steels with boron added. developed by Keeler and Backofen (Ref 5). the drawability increases because the material tends to maintain a constant thickness while changing shape from a flat blank to a cup shape. as measured by tensile test elongation.92 1.77 0. the Lankford ratio equals the ratio of the lateral strain to the through-thickness strain during the tensile test of a sheet specimen.76 1.07 1.24 0.66 1.94 0.7 8.2% proof stress.44 1. The ferritic stainless steels in sheet form have LDRs of around 2. It shows that when comparing different types of materials. deep-drawn component. mm YUS 190 YUS 436S (B-added) YUS 436S (B-free) YUS 4O9D SUS 430 SUS304 Source: Ref 2 343 275 284 239 308 281 497 459 483 424 472 705 33. then a material may be considered isotropic. As a first approximation.63 1.8 34.5 27. the work hardening rate.83 1. N/mm1 Tensile strength.11 l. that is.12 2.83 1.) may be more important than material properties in determining whether the desired part can be made successfully. For austenitic steel.19 2. Figure 2 shows the LDR as a function of the Lankford ratio. A number of stainless steels are compared in Table 1 (Ref 4). especially when other considerations. Figure 3 shows a comparison of the FLDs for austenitic stainless steel and carbon steel.22 0.2 compared to 2.0 are more common. expressed as: r0 + 2r45 + r90 4 R= (Eq 1) where R is the average strain ratio.21 0. the wall height) of the deepest draw possible.47 1. The FLD tells Fig. Indeed. which the ferrous bcc structure has. true strain curve and is called n.9 12.0.0 for 304.5 26.79 1. Source: Ref 3 Deep-drawing materials comparison 0. 2 Limiting drawing ratio variations with Lankford ratio. the ratio of the diameter of a disc to that of the deepest cylinder into which it can be drawn.8 64. and r90 is the strain ratio in the transverse direction.91 1.8 9.21 0. the ratio is about 1. As the value increases from 1.60 1.0 . The most widely used summary of a material’s formability is contained in its forming limit diagram (FLD).5 Table 1 Steel and 2.8 9. some tests are not good predictors of deep-drawing performance.8 26. while for flat-rolled carbon steel and ferritic stainless steel. The producing mills.0 173 135 137 116 159 172 0. r0 is the strain ratio in the longitudinal direction. mm Conical cup value. etc. it can be greater than 2.90 1.5 37. die radii. while not necessarily exhaustive sources of information. lubrication. N/mm2 Elongation.51 0. and the anisotropy.03 9.49 1.50 0.

There is much more variety within the families of stainless steel than within carbon steel. HAS. Quite often. This comes with a cost penalty as the easiest way to improve formability is to increase the nickel level. This can be used as an index of formability and is the elongation possible for plane strain conditions. One is to eliminate extra operations or components by consolidating them into one more complex deep-drawn part. Figure 4 shows generalized FLDs for austenitic. although replacing the expensive nickel with copper or manganese. ferritic-austenitic stainless steel. making them an optimal material for objects such as sinks. highstrength ferritic stainless steel. carbon plus nitrogen) and by thermomechanical working to give a fine-grained. fully recrystallized. Figure 5 shows how the FLD of an enhanced 409 ferritic stainless steel. This gives 201 and 301 the ability to redistribute deformation from thinning areas elsewhere and stretch extensively. such as the household appliance industry. Certainly. which is the precursor of failure. Many austenitic components are made by stretched deep drawing. This has been accomplished by reducing the total interstitial content (i. maximum drawability is obtained by low work-hardening rates coupled with maximum elongation. FA(50). yet beneficially anisotropic. Source: Ref 3 the point of failure for a given sheet material with a given thermomechanical history over a full range of combined strain states. 4 Fig. The specific alloy composition is often finely tuned for a given part and tooling design. ferritic. and duplex stainless steels. Source: Ref 3 Forming limit diagrams for categories of stainless steels.e. This value within a given class of materials is proportional to the strain-hardening exponent because a higher work-hardening rate causes higher localized resistance to thinning. Martensite has a 4% greater volume than the austenite from which it forms and a much greater strength. In this case. austenitic stainless steel. A. Even such minor process changes as blank temperature variations due to ambient temperature can alter work-hardening rates enough to cause breakage problems. as many components as possible are deep drawn from ferritic stainless alloys and the more costly austenitic alloys are used only when the part cannot be made from a ferritic. this can occur when designs push the . high-strength ferritic. as exemplified by 305 and high-nickel 304. There are various drivers that cause this. as in 204Cu. Another is to use the least-expensive alloy. it is necessarily a high-volume application. compares to the already highly evolved 409. 409 Ultra Form. designers push component design to the limit of a material’s ability to be formed. high-strength austenitic stainless steel. There has been much research to develop ferritic stainless alloys with improved formability. For austenitic stainless steel. These alloys form martensite more rapidly than do 304 and 305 during stretching.176 / Stainless Steels for Design Engineers Fig. the preferable alloys are the leaner austenitics. has been shown to be effective. ferritic stainless steel. Deep drawing of components is seen as a way to obtain near-net shape. These diagrams are generated by examining circle grids printed on material that is deformed to failure in various modes. microstructure. 201 and 301. HSF. F. and small deviati ons can dramatically increase breakage rates. Since tooling is costly. 3 Forming limit diagram of carbon steel compared to austenitic stainless steel. The single most important value on the curve is the intersection of the curve with the major strain axis at zero minor strain. In some industries. high-strength austenitic.

The hydroforming process avoids friction between . When drawing. a variation on deep drawing in which hydrostatic pressure forces a blank into the die cavity. Austenitic steels experience the opposite effect if they are susceptible to martensite formation. Bright-annealed alloys with high martensite levels from forming can fail by hydrogen embrittlement with just the residual hydrogen from annealing. A last key variable in which practice and material interact is strain rate. can improve the degree to which stainless steels can be deep drawn. Adiabatic heating can retard the martensitic transformation and reduce the workhardening rate. 5 Optimized 409 for forming versus normal 409. this is good.Chapter 14: Forming / 177 Fig. changing their forming characteristics. Stainless steel in the as-drawn condition will have residual stress and may have sufficient hardness to be susceptible to delayed failure if placed in a corrosive environment. Ferritic steels flow more easily at lower strain rates and are thus more formable. intermediate annealing may be required to either enhance ductility or reduce required pressure. but for stretching it may not be. the use of bright-annealed lean alloys such as 301 is not recommended. On very severe forming. Therefore. Source: Ref 5 envelope of a material’s capability. Hydroforming. but cost pressures generally drive designers to this extreme.

It should be noted that deformation always produces some surface relief. One measure of the earing tendency is derived from the Lankford r measurements: Δr = r0 + r90 + 2 r45 2 (Eq 2) The left side of Eq 2. This behavior is contrary to the general behavior of single-phase alloys. r. and temper passing (i. Austenitic stainless steels can also develop anisotropy. reportedly up to 15% lower in the longitudinal direction than in the transverse direction required for tensile tests (Ref 7). Deformation is spread more evenly across the blank. Flatrolled stainless should be fully annealed and pickled so that the surface holds lubricant well and yields as readily as possible. so its use is justified mainly when it is not otherwise possible to make a certain design in one drawn component. such as Koolline. Tooling for stainless must be strong and wear resistant. The difference in yield strength is sufficient. They also have significant rolling anisotropy. Productivity using this technique is relatively low. but the time and expense of buffing increase dramatically if orange peel or roping (a similar surface defect) is excessive. The steel producer can minimize the phenomenon by keeping cold roll reductions above about 60%. thereby vastly improving wear resistance without harming toughness or even raising overall hardness. Orange peel is prevented by keeping grain size fine so that the surface relief is too small to be seen. This has been an issue for items such as automotive bright trim. while values significantly above or below zero indicate increased tendency toward earing. D2 tool steel must be hardened to HRC 60 to 62 and must have smooth surfaces. six-. is a measure of the variation of plastic strain ratio r with direction in the plane of a sheet. One of the most important material considerations for deep drawing is surface finish. Besides failure by breakage. and low tendency to gall. Ferritics undergo a more specialized surface relief because their anisotropic grain structure can yield in a more concerted fashion and give even greater surface relief. Traditional tooling materials are D2 tool steel and high-strength aluminum bronze. the result of slip planes within a grain disrupting the surface. An example of this may be the production of a complex exhaust manifold that requires a higher-alloyed ferritic stainless with relatively low formability. The use of powder metal techniques to produce tool steels for dies has permitted much higher volume fractions of ultrahard microconstituents such as vanadium carbide to be introduced. there are other less-severe defects found on deeply drawn parts. They are preferred when finished part surface appearance is more important than .178 / Stainless Steels for Design Engineers the blank and the tool. Duplex stainless steel flat products exhibit significant in-plane anisotropy that can cause forming difficulties and lack of compliance with mechanical property requirements. called ridging and roping.” in which round blanks deform nonuniformly in a four-. or cloudy. Temper passing will drastically reduce the drawability of stainless by smoothing the surface (rather than increasing the yield strength). Temper passing with roughened rolls does not significantly harm drawability. achieving full recrystallization versus just recovery during annealing. elongation of about 1% on a cold-rolling mill) to suppress the yield point phenomenon that is characteristic of ferrous bcc materials. after plastic deformation.. or eight-fold symmetry.e. retain lubricant well and can be drawn with minimal distortion. Mechanical buffing can restore the luster. high thermal conductivity. Values of r near zero generally indicate minimal tendency toward earing. which causes the yield strength transverse to the rolling direction to be consistently higher than it is in the rolling direction. The surface finishes that are produced by temper rolls with special finishes. so highly reflective surfaces become spectrally diffuse. Austenitic steels can develop a surface condition known as orange peel. causing excess ear-shaped material to extend beyond the intended dimensions of the component. and the material forms close to its theoretical best. Material is wasted because larger blanks have to be used. The benefits of cast aluminum bronzes are low friction. A combination of a high R value from Eq 1 and a low r value provides optimal drawability. that it is both serious design and forming considerations. which while less severe than ferritic steels. can cause “earing. End users should always make their use of the material known to the producing mill so that the correct thermal processing path can be employed for the manufacturing process the material will undergo. This is minimized by refining grain size.

nuts. (c) Water emulsions of soluble oils.Chapter 14: Forming / 179 Table 2 Lubricant Suitability of various lubricants for use in forming of stainless steel Blanking and piercing Pressbrake forming Press forming Multiple-slide forming Deep drawing Spinning Drop hammer forming Contour roll forming Embossing Fatty oils and blends(a) Soap-fat pastes(b) Wax-base pastes(b) Heavy-duty emulsions(c) Dry film (wax or soap plus borax) Pigmented pastes(b)(d) Sulfurized or sulfochlorinated oils(e) Chlorinated oils or waxes(f) highviscosity types(g) Chlorinated oils or waxes(f) lowviscosity types(j) Graphite or molybdenum disulfide(k) C NR B B B B NR B NR B C C B B B A A A A NR C B B B B A B B B A C C C NR B B B B A NR B C A B A B A NR A A B+ B A A C C NR NR A NR B NR A A(h) NR A NR A NR A(i) A NR B+ A A A B NR A(i) A A NR (l) (l) NR (l) NR (l) NR NR A. such as 384. Ratings consider effectiveness. (b) May be diluted with water. the stabilized ferritic alloys. and additions of mineral oil. NR. degree of chlorination. C. The martensitic. an optimal ferritic such as 430 can tolerate upsets up to about 2.000 SUS. (l) For hot forming applications only. lists common lubricants as shown in Table 2 (Ref 1). rivets. may contain emulsifiers for ease of removal in water-base cleaners. Stainless Long Products Cold heading. The ferritic stainless steels are the most easily cold headed. or water. cleanliness. acceptable. PH. (j) Viscosity (200 to 1000 SUS) is influenced by base oil or wax. The ASM Metals Handbook. not recommended. (k) Solid lubricant applied from dispersions in oil. one of the most important forming operations conducted on stainless long products. The process is widely used to produce a variety of small. SUS. (i) For cold forming only. The use of the most formable stainless alloys for flat products. austenitic. the maximum possible deformation an alloy can tolerate is expressed in terms of the length of long product exposed beyond the die that can be successfully forged into the upset. (h) For heavy plate. (e) EP types. As with flat-rolled forming operations. (a) Vegetable or animal types.08 in. can tolerate 3. precipitation-hardenable (PH). and other suitability factors. the nonstabilized ferritics. the primary difference between carbon/alloy steels and stainless steels comes from the higher yield strength and higher work-hardening rates of stainless. and richer duplex . when applied to the surface at a density of around 1 g/m2 (0. Desk Edition. and duplex grades are all cold formable.25 diameters. In cold-heading terminology. (d) Chalk (whiting) is most common pigment. B.0. is limited for long products because of the severe lack of toughness these alloys show for cross sections greater than about 2 mm (0. such as screws. solvent. Say-bolt universal second.004 oz/ft2). excellent. may contain some mineral or fatty oil.and medium-sized hardware items. contain a high concentration of extreme pressure (EP) sulfur or chlorine compounds. is a forming process that increases the cross-sectional area of a room temperature blank at one or more points along its length. ease of removal. Not listed in the table are the newer thermoplastic acrylic polymers that. and specialized fasteners. absolute die life and forming pressures are moderate. while a very low workhardening austenitic. the martensitic.). (f) EP chlorinated mineral oils or waxes. Anisotropy is not a significant consideration for long products.000 to 20. Lubricants for stainless steel forming must be able to prevent metal-to-metal contact under higher pressures than those seen with carbon steel. So. good. But. bolts. mineral oil is used for blending. provide a dry film with lubricating properties surpassing any of those listed in Table 2. This is measured in the number of diameters of initial stock. others sometimes used. Cold heading is typically a high-speed process in which the blank is progressively moved through a multistation machine. (g) Viscosity of 4.

Tanoue. 14..5 to 2.-R.” Product Data 4. the initial pressure requirements for a given deformation range for 304 can be three times what is required to deform carbon steel and up to five times for higher molybdenum alloys.R. 163). Strip. Keeler and W. Source: Ref 1 alloys are in the 1.. all stainless alloys can be forged. Q.. 17-7 PH) that have high levels of ferrite in austenite or austenite in ferrite at the hot-working temperature exhibit reduced hot ductility compared to either fully austenitic or fully ferritic stainless steels and are more difficult to hot work. ASM International.25 diameters maximum. 1998. R. Cambridge. TWI conference. 56 (No. Tomé.180 / Stainless Steels for Design Engineers their work hardening is not instantly removed by annealing. Glasgow..0 range of formability. www. while the austenitics require much more because of their high hot hardness and because 1. Ed.F. p 782–829 2. As much as possible. REFERENCES Fig. Backofen. October 1996 5.g. 1963. 7. Martensitic stainless steels require 10 to 100% more force than 4340 alloy steel. ASM Trans. 6a and b). desk ed. For greater deformation.. ASM International. 1988 . 6 Forces required for hot working. 1994 SELECTED REFERENCE • ASM Handbook.P.A. p 25–48 6. Nippon Steel Technical Report 71. Vol. For example. should resemble 430 with 2. H. UK. Forming and Forging. J. The lean duplex. Kocks. when they find their way into wider use.” Paper 109. all alloys should be hot worked in a single phase field of the phase diagram to avoid mixtures of ferrite and austenite since the great difference in their great strengths can cause failures.” ACOM Technical Paper. Wenk. 1998 3. Austenitic stainless steel loses ductility when heated above 1280 °C (2335 (F) because of low melting phases in the grain boundaries. “Duplex Stainless Steels.AKSteel.outokumpu . E. S. in Metals Handbook. Hot forming of stainless steel is done as an integral part of their production. Forming of Sheet. The main issue is that the high hot strength of stainless requires much more force than would be required for carbon steels. Cordewener et al.A. and Plate: Deep Drawing. C. this multiple increases (see Fig. Texture and Anisotropy. Cambridge University Press. Davis. H. Sumitomo and T. therefore. Vol. U. Duplex stainless steels and other alloys (e. Schedin. “409 Ultra Form Stainless Steel. Ed. “Forming Stainless Steel.

org CHAPTER 15 Machining Summary MACHINING STAINLESS STEELS is a complex operation. both of which are reducing machining costs and keeping shops competitive.Stainless Steels for Design Engineers Michael F. Cost per part: What is the cost of the final geometry? 5.1361/ssde2008p181 Copyright © 2008 ASM International® All rights reserved. The incorporation of complex oxides has led to the development of materials that allow higher machining speeds and increased productivities. Some of the variables can affect the appearance of the material. Surface finish: How smooth or shiny is the part? 7. castings. www. its ability to be machined and the factors that affect its ability to be machined. This fundamentally involves the removal of a layer of material from the workpiece with a cutting tool one or multiple times until a finished or semifinished part is produced. hours. Chip control: Are the chips manageable? 8. shift. Cycle time: How fast can a part be completed? 6. in itself. Fig. Optimum machinability is obtained when each of these sectors come together. Technology in the production of a more machinable stainless steel is advancing. it is helpful to consider a material’s machinability. From a more focused viewpoint. Any change in one of these sectors can change the behavior or efficiency of a machining job. plate. Rather than attempt to understand all aspects of machining. making machining an art as well as a science. and management. Machining. Minimal operator intervention: Does the operator need to constantly adjust setup? Introduction Stainless steel forgings. or days. or day? 4. providing the best possible conditions for efficient machining. machine. methods. Not only does a shop need the correct supporting equipment and supplies. In Fig. Productivity: How many parts were made in an hour. is a complex topic with many variables.asminternational. 3. and long products all are frequently machined. Maintaining tolerances: How long can the machining operation continue before adjustments are made? 10. Maximum cutting speed: How fast can the part be cut without affecting tool life? 9. p 181-191 DOI: 10. that is. a better understanding of the metal itself is advantageous. shifts. McGuire. while others affect the performance of the piece. 1. 1 The 5 M’s of machinability . material. the machinability of a material is further described by: 1. a macroview shows how the machinability of a material is influenced by the interaction of humans. Tool life/wear: How long does the tool last in the machining operation? This could be minutes. Consistency: Does the material machinability stay the same when bundles are changed? 2.

182 / Stainless Steels for Design Engineers This list is somewhat empirical or job related. However. will machine very differently from the martensitic. Armed with an understanding of the material and how it is made.) in Cincinnati. gummy material that has high workhardening characteristics. coolant. Chromium strengthens and reduces ductility of stainless steel. typical in ferritic stainless steels. Rather than simply reproducing data. as carbon content increases. and the cross-section size of the stock. and slight deviations may be encountered depending on the stainless grade. the amount of carbon in a martensitic stainless can change tool wear characteristics. Iron is the base element in a stainless steel. cleanliness. cross section) Each variable contributes uniquely to machinability. Chromium allows chips to begin breaking. this is like comparing brass to carbon steel. 3rd edition. Carbon content increases strengthen stainless steels and promote carbide formation. for example. structure. Machinery’s Handbook. but it provides guidelines for defining a job since cutting conditions can be very different for each material and part. there will be differences in machinability of a steel grade provided by different mill suppliers. and cutting fluid for a given material/material condition (thermomechanical history) can be found in readily available published tables. machining involves much more than simply cutting a piece of metal. or the Machining Data Handbook. Clearly. processing. many of the concepts could be applied to forgings as well as castings. Increasing amounts of carbon to greater than 0. The effects of the elements as described next are general. the focus of this chapter is the metallurgical factors governing the machinability of stainless steels. Physical and Mechanical Properties The machinability of stainless steels is very difficult to characterize in definitive terms because of the broad nature of these materials. with no one factor more important than another: . both will be the basis the material’s machinability. martensitic. and setup of the machining job. however. Because no two mills are exactly identical. it may be necessary for chip control and tool life to be sacrificed. if the surface finish of a part is very important. and it has a high tendency toward tool built-up edge (BUE). s structure. Combined. Chemistry The role of chemistry is to define not only the different grades of stainless steel (ferritic. but the chemistry and structural differences create diversity in machining characteristics. However. Low carbon levels. by the Machinability Data center at the Institute of Advanced Manufacturing Services (IAMS. or a change in nickel content within specification limits can alter the stringiness of a chip.08% will aid in chip breakability and reduced BUE in these grades. Each of the elements used to produce stainless steels will contribute some general machining attributes. However. In some sense. Machine shops and users generally have very little influence on these material variables. include much of the data used in industry today. Let us take a closer look at these variables. tool material. A typical guide from ASM is shown as Table 1 (Ref 1). these effects of these alloying elements are fairly accurate. For example. published by Industrial Press. Machine and tool setup require more rigidity. The machinability of stainless steels can be thought of as a function of the steel’s chemistry. one can determine the tooling. Material manufacturers are also a source of valuable machining data. cleanliness. for the more common stainless grades used today. published by McGraw-Hill Book Company. but also how the grade is chemically balanced within the specific grade. such as type 430. The recommended feed rate. Iron is characterized by surface finishes that are difficult to obtain and chips that are stringy. processing history. depth of cut. Books such as the ASM Handbooks. do not help machinability much. A ferritic stainless steel. Marks’ Standard Handbook for Mechanical Engineers. Machinability of stainless steels = ƒ(chemistry. Both type 410 and type 430 are stainless steels. formerly known as Metcut Research Associates Inc.). Machining is a very empirically mature subject. OH. It is a soft. having an understanding of how these variables contribute to machinability is invaluable. Most of the information regards machining stainless bar products. etc.

150 0. 347. Chips can be more difficult to break. 304. thus creating hotter cutting conditions.Chapter 15: Machining / 183 Table 1 Machining setup recommendations for turning wrought stainless steels Uncoated High-speed steel tool Hardness. M3 T15.020 0.007 0.. Feed. 305.150 0. fpm Feed. While the molybdenum helps in chip breakability. manganese has the same relative effect as nickel when used in greater amounts.020 0.015 0..020 .007 0.150 0.. which acts as a self-lubricant and improves machinability. M42(b) T15.040 0.020 0.015 0.030 0.300 155 125 100 80 145 115 90 70 95 75 60 65 50 40 0.015 0.020 0. M3 M2. 275-325 Quenched and tempered 375-425 Quenched and tempered 0. 135-185 Annealed 302...040 0.. M3 M2.020 M2. 310S. CC-3 CC-3 CC-2 . Copper improves ductility and reduces the strain-hardening or work-hardening rate (with the exception of participation-hardening alloys.007 0.015 0.020 .040 0. This causes chips to be more difficult to break. M42(b) T15.300 0. M3 M2..030 0.. 0.007 0...020 . 410..007 0. 304L. Manganese is generally added to combine with sulfur to form manganese sulfide (MnS). M3 M2.020 . such as duplex and 200 series alloys. 429. M42(b) T15. duplex 314. CC-7 CC-6 CC-6 . M3 M2.040 0. 317. 700 450 375 475 300 250 0. 850 550 450 .007 0.. M3 M2.015 0.030 0. M42(b) 475 400 320 240 460 385 300 235 360 280 225 290 225 180 620 480 380 300 570 450 350 265 465 360 280 320 250 200 0. M3 M2. 202. 309. material Brazed Indexable ipr AISI fpm ipr grade grade Material Condition Ferritic steels 405.015 0.625 150(235) 120(190) 95(150) 75(115) 95 75 60 45 80 65 50 40 0.. in.150 0. 309S.020 0.300 0.007 0. 442. Source: Ref 1 (a) Caution: check horsepower requirements on heavier depths of cut.150 0.. M41–M47).015 0..015 0. M3 M2. the amount of carbide increases.040 0.015 0.015 0. CC-7 CC-6 CC-6 . precipitation-hardenable.007 0. Nickel will have a tendency toward increased BUE. 2507 295-310 Annealed Martensitic and PH steels 403. ipr Speed.300 0. 135-175 Annealed 422.020 0. 321. 420. 501.020 CC-7 CC-6 CC-6 . In high-manganese grades.030 0.007 0.020 0. 308. material Speed. 409.020 .150 0. in the 200 series stainless steels.030 M2.007 0.015 0. Sulfur reduces mechanical and corrosion properties and can be a cause of hot cracking in the resulfurized grades.007 0. M3 M2.015 0..007 0. Molybdenum increases the strength and elevated temperature mechanical properties.015 0. fpm Coated Tool Tool Tool material Feed. 135-185 Annealed 430. It is best known as a free-machining contributor that promotes better tool life and greater machining speeds. (c) Free machining versions..040 0.150 0..040 0.. 348.015 0. (b) Any premium high-speed steel (T15. 436..007 0. M42(b) 575 450 350 275 325 300 225 175 300 250 290 140 650 500 400 310 375 325 250 200 325 275 215 165 0. . 301. 0.. 316. 434..030 0. M42(b) T15.030 0.030 C-7 C-6 C-6 C-6 C-3 C-3 C-2 C-2 C-3 C-3 C-2 C-2 850 650 525 . 385(c) 2205. however.. M42(b) T15.625 0. the structure changes to martensitic. M42(b) T15. M3 M2.007 0. for instance. 384. 500 425 325 .015 0. 446(c) Austenitic and duplex steels 201.020 0. 0.300 0. Nickel also increases elevated temperature mechanical properties.007 0. 0. 302B. 502(c) 175-225 Annealed 0. M33.007 0.625 0. 425 350 275 .... M3 M2.040 0.625 0.020 0.020 0. CC-3 CC-3 CC-2 .015 0.. M3 M2..625 0. and the wear on tools increases. 330. better tool life will generally result.007 0.300 0. annealed 316L.007 0.040 0. M3 M2. which increases the tendency of BUE and promotes better tool life.030 0. as. for which copper is used as the precipitant). M42(b) T15. This increase in hot hardness and strength means more energy will be needed to cut the material.007 0.020 C-7 C-6 C-6 C-6 C-7 C-6 C-6 C-6 C-7 C-6 C-6 C-7 C-6 C-6 800 625 500 . M3 T15.300 0. CC-7 CC-6 CC-6 CC-7 CC-6 CC-6 PH.007 0. Speed.015 0. Nickel increases the toughness and ductility of stainless and reduces the work hardening rate. 0.030 0. 225-275 Cold drawn or 310.015 0. M42(b) T15.015 0.015 0..015 0. it will require more rigid setups and will reduce tool life. HB Depth of cut(a).007 0.. M3 M2.040 0.

machinability can vary when the same-size material is drawn across two different draw benches using different pulling mechanisms and two different straightening mechanisms. etc. For example. Many times. finer grain sizes yield better surface finishes and smoother roll thread crests. Cleanliness The cleanliness of steel is determined by the amount and type of inclusions it contains. The melt type. Titanium promotes carbide formation and increases tool wear. requiring adjustments in the machining setup to remedy the situation. Mills that promote machining consistency pride themselves by practicing manufacturing consistency. It aids in chip breakability and reduces BUE but increases tool wear. Whether the material is continuously annealed or batch annealed can cause different strain distributions across the material cross section as well as material strength differences. Each type of stainless steel belongs to a larger family. It is entirely possible for the grain size difference between two lots of material to be large enough to prevent both lots from being effectively machined with the same setup. Structure Material structure consists of both the phases that are present and the microstructure of those phases. cause hotter cutting conditions. The microstructure of a given alloy is independent of the grade type and composition and is mainly influenced by grain size. the culprit is equipment operational procedures or practices that can vary one day to the next. Vacuum and argon oxygen decarburization (AOD) melting and refining along with proper steelmaking techniques can reduce the inclusions to negligible levels. The material’s grain size results from the thermal and mechanical history during manufacturing and from the mill’s equipment capability and practices. while a third bundle performs differently from the first two. It is beneficial to machinability to avoid hard inclusions. the manufacturing sequence. The beneficial effect of controlled inclusions is discussed in this chapter. UNS. processing affects how consistently the material can be machined. Since today’s mill technology can meet very tight elemental targets within the grade specification. martensitic. However. These specifications are all defined with fairly broad elemental chemical compositions.184 / Stainless Steels for Design Engineers Nitrogen strengthens stainless steels. hot rolling parameters. an AISI 304 has a 2 wt% window for the nickel content. Process The type of equipment used by the stainless manufacturer. . On the brighter side. thermal treatments. and duplex (see the chapters on stainless steels. that is. Chapters 6 to 10. The grain size of a particular product can dramatically change its machinability. but more important. A type 304 with 8% nickel can have different machinability characteristics from a type 304 with 10% nickel. and the practices employed by the mill can affect machinability as well as mechanical properties. and sequence of these operations can affect how consistently a material machines. Tolerance variation will be tighter and machining costs will be lower with their products. in this Volume). austenitic. This 2% difference alters chip morphology and surface finish capability. Grain size is not normally specified or reported on certifications. and have a higher tendency of BUE. These are ferritic. precipitation hardening. manufacturing consistency can be a great asset in machinability. certain inclusions are plastic and act as solid-state lubricants and chip breakers and prevent adhesion of the material to the tool. EN. this grade can have a nickel level of 8 to 10%. A machine shop can adjust when a material is consistently bad. Niobium promotes carbide formation and increases tool wear. but it is very difficult when one lot is easy to machine followed by a lot that is tough to machine. With all this in mind. how the mill balances the grade’s chemistry will provide the foundation of its machinability characteristics. Their machining characteristics are described in the next section. however. cold-finishing parameters. mills measure and control it to varying degrees. For example. such as AISI. Finer grain sizes strengthen the stainless steel. Various annealing lines vary in time/temperature profiles and therefore result in different grain size and mechanical properties. The production of stainless steels is identified by industry specifications. JIS. Equipment types can also play a role in machinability. which is characterized by a single predominant phase or a combination of two.

and difficulty breaking chips are familiar scenarios for this class of Machinability of the Stainless Steel Families Comparing the machinability of stainless steels with other materials such as carbon steels. Austenitic stainless steels are more highly alloyed and are more prone to higher work-hardening rates. and the second is simply a straightening-turning operation. chips . stainless steels have: 1. Low thermal conductivity High work-hardening rates High tensile strengths High toughness High ductility Large spreads between the yield and tensile strengths Each stainless steel family (ferritic. Precipitation Hardening Precipitation hardening stainless steels are characterized by higher strength and toughness. and a close yield-to-tensile ratio. are more difficult to machine than the ferritic and martensitic families. 2. necessitating tooling with higher heat resistance. while larger diameters are straightened/cut/turned. Martensitic stainless also has a small yield-to-tensile ratio. sizes greater than 1 in. and surface finishes will be somewhat of a challenge. These grades will have a high tendency to BUE. Further alloying of these families. This leads to the need for higher horsepower and more rigid setups. martensitic. The mechanical properties of the straightenedturned bars will be softer than the bars made by cold drawing. Typically. Ferritics are the easiest of the stainless steels to machine. making chips hard to break. This can have an impact on machining performance despite all other factors being the same. The difference is that the martensitic grades have much higher carbon levels. Higher horsepower requirements. Cold finishing of stainless steels can be accomplished via a couple of general manufacturing routes. with virtually no strain in the product. These grades generally exhibit lower strengths. Smaller diameters are cold drawn. Chips in this family of alloys tend to be long and stringy.Chapter 15: Machining / 185 Cross-Section Size Mill processing equipment dictates a manufacturing route based on size. The first is by cold drawing to bar. The higher strengths will require more horsepower to cut and will need more rigid setup than ferritic steels. These grades are very prone to BUE and hence are prone to poorer surface finishes and tend to tear. and will generally have higher speed and feed capabilities than other stainless families. such as with a sulfur addition. higher tool wear. high tendency to BUE. Martensitic Martensitic stainless are also very basic straight chromium stainless steels. Ferritic Ferritic stainless steels are the most basic stainless steels and are part of the 400 series grades. Austenitic The austenitic grades. there are some striking differences. The yield-to-tensile ratios of austenitic stainless steel is very large. This is especially true if the material is being machined in the hardened condition. The solution-annealed hardness of AISI 630. One must keep in mind that these are general characteristics. do not require much horsepower. and are similar to the ferritic grades. for instance. brass. 3. which will lead to higher tool wear. In general. 4. The higher strength and higher ductility of these grades also tend to increase cutting temperatures. yielding a softer product. the 300 series stainless grades. will tend be stringy but can be broken through aggressive chip breaking. or aluminum. is HRC 36 versus HRC 23 for a 304. 5. have a low workhardening rate and better tool wear. which further strengthen the materials and allow these materials to be hardenable by heat treatment.) brings its own general set of machining rules. more ductility and softness. etc. Their basic chemical composition is iron and chromium. These grades will have higher carbide levels. (25 mm) are annealed/turned and straightened. This is mainly due to the chemistry of these families and its resultant effect on the physical and mechanical properties. The work-hardening rate of martensitic stainless is lower than for ferritic stainless. 400 series stainless grades. making chips easier to break. 6. A general description of the machining behavior is provided next. can result in a radical change in machining behavior.

These particles provide a solid-state lubricant between the chip and tool or a discontinuity in the material to aid in chip breaking. like the duplex alloys. Sulfur It became obvious very early to metallurgists that higher sulfur levels correlated to better machinability.186 / Stainless Steels for Design Engineers stainless. Between the duplex structure and high-strength levels.8%.8%. a high manganese-to-sulfur ratio is desired. Two basic sulfide forms are found in stainless steels—manganese sulfides and chromium sulfides—and the form the sulfide will take depends on the manganese content. These grades. The tool will alternate cutting between soft and hard grains of the duplex structure. and incompatibility with stainless. It was once a leading addition to carbon steels. comparatively pure manganese sulfide will be found. The manganese-to-sulfur ratio is also important. This elongation increases the Role of Inclusions Metallurgists have long known that the presence of a soft second phase dispersed in the matrix of a parent metal can improve its machinability. always a serious consideration in stainless steel design. Lead additions probably are the best source for improving . However. as well as cold working. Many carbon mills are looking at other machining agents to replace lead. The challenge to the alloy designer has been to develop second phases that produce these beneficial effects with a minimal of degradation to the material itself. For manganese levels beyond 1. and sulfur remains the popular additive choice. sulfur combines with manganese to form manganese sulfide inclusions. Tellurium The range of additions possible to stainless steel is the same as for carbon steel. leading to an automatic tendency to initiate chatter in the cutting system. highly alloyed carbide tooling with high hardness and high heat resistance. Duplex The duplex is a unique class of stainless characterized by a dual-phase structure. driving machinability downward. chromium-rich manganese sulfides are present. but its reported environmental toxicity has diminished its role. Selenium and tellurium have similar characteristics to lead as additives but also are noncompetitive due to cost. Lead. Lead. the precipitation-hardenable (PH) grades are all martensitic alloys and can be treated as such for machining purposes. Sulfur is a natural impurity and has negative effects on mechanical and corrosion properties. are being developed to increase corrosion performance parameters to meet some of today’s increasing performance requirements. and highly rigid setups are required. The role of sulfur as a machinability agent in stainless steels is very complex and not necessarily straightforward. has not been a large factor for stainless steels because of the extremely negative effect it has on hot workability. toxicity. but in general sulfur has been extremely beneficial in increasing the machinability of stainless steels. Selenium. however. Sulfur is cost-effective as a machinability additive and can be easily removed with modern refining methods. discussed separately here. chromium sulfides and chromium-rich sulfides will be present. if corrosion resistance is desired. thus. two hardness materials with different hardnesses coexist side by side. As manganese levels reach 0. should be used. Duplex alloys have a structure that is roughly a 50% mix of austenite and ferrite. Super Stainless Steels Super stainless steels are today’s highly specialized stainless grades.4%. Except for alloy A-286. high horsepower is necessary. For highest machinability levels. Sulfides form initially as spherical inclusions within the cast structure. a low manganese level is preferred to encourage the formation of chromium sulfides or chromium-rich manganese sulfides since these sulfide forms have superior corrosion resistance. such as the C7/C8-type carbides. Generally. as the molten metal cools to solid form. Some work at Ugitech found that to effectively machine these grades. Strength levels are higher and toughness is greater. elongates these inclusions as shown in Fig. machinability of a material. Strength levels of duplex alloys are quite a bit higher than austenitic grades.4 to 1. These alloys are more highly alloyed than the duplex materials. 2. Hot working. Manganese becomes a very important variable during this reaction. When manganese levels are less than 0.

it seems that sulfides that are too large or too small can be detrimental to machinability. Courtesy of Ugitech surface area of the sulfides and will form weak planes that mechanically weaken the steel. the curve flattens out. Source: Ref 2 Fig. Ingot casting.10%. homogeneously dispersed sulfides are better than the other types for enhancing machinability in both carbon and stainless steels. The coarsest type I sulfides.028% sulfur. However. That small addition of sulfur has a dramatic effect. The discussion of the combination of manganese and sulfur revealed that there is a particular balance of manganese to sulfur to achieve desired needs. there is more to this than just adding sulfur. Sulfides are defined into four categories based on morphology: type I to IV sulfides.030%. And.Chapter 15: Machining / 187 Fig. An additional benefit of these manganese sulfide stringers is that when these stringers touch and pass the cutting tool. This reduces friction. solidification rates are much faster. 3. the size and shape (relative elongation or globular nature) of sulfides contributes to the machinability of stainless steels.023% and one with 0. shown in Fig. With the transition to continuously cast blooms. Type I sulfides form from the melt as large globular sulfides and are assumed to be best for machinability. In addition to chemistry (manganese-sulfur balance). improving machining productivity. 2 Typical AISI 303. permitting chip breakage. The effect of sulfur on the machinability of stainless steels is more effective in smaller amounts than in larger amounts. a small amount of manganese sulfide is deposited on the tool surface. Type II sulfides generally form as a eutectic-like distribution of finer rod-like sulfides in interdendritic regions. stainless steels can be classified into three groups based . providing a lubricating layer between the chip and tool. From a machining perspective. Machinists readily can see differences in tool wear between a 316 with 0. Consequently. thus reducing heat to the tool. This also can be proven with a 304 or 316 stainless steel. Much has been written about the benefits of sulfides in a machining operation. It is easily seen that small additions of sulfur have the greatest effect at sulfur levels <0. The deformation caused by the severe bending of the chip during cutting causes the chip to break at the sulfide striations. It has been shown that the larger. Type III sulfides form as angularshaped particles. with the slow cooling and solidification rates. is beneficial to the creation of the coarser type I sulfides. 3 AISI 303 chip breaking at the sulfides.20%. once thought to be best for machinability. Type IV sulfides form from the melt as plate-like sulfides in a ribbon-shaped pattern. Figure 4 shows a graph of drill penetration results in varying amounts of sulfur in an 18-9 stainless. On the opposite side of the scale. A metallurgical perspective shows the more complex nature of sulfides. machining speeds can be increased. effectively creating a finer type I sulfide. for which sulfur levels are inherently lower than 0. more globular (less-elongated) type I. are difficult to attain with today’s stainless manufacturing equipment. with sulfur levels greater than 0.

These manganese sulfide inclusions become exposed on the surface of the bar and become initiation sites for pitting corrosion. This group of stainless steels still holds corrosion resistance. The question of performance of the finished component is another issue. 4 Effect of sulfur on stainless machinability. And. Hot workability is also hurt by sulfides. Figure 5 shows that small amounts of calcium can greatly increase tool life. any cold deformation can lead to cracking along the sulfide stringers. Outokumpu’s Prodec materials. This has led to the development of alternative methods of improving machinability. The benefits of sulfur to improve machinability outweigh the losses due to defective parts. In the first group. 1. The beneficial effects of sulfur are undeniable. Oxides The basic machinability-enhancing agent discussed thus far has been sulfur. a susceptibility to longitudinal cracking can become an issue. 321.15% are considered resulfurized grades. This has led steel producers to look at other inclusion systems for a viscoplastic inclusion without the negative effects of sulfur. 430F. 420F. Product offerings include Ugitech’s Ugima and Ugima XL (Ugima 2) materials. Sulfur levels are generally 0.15%. The third group with sulfur levels 0.010 to 0. complex oxides that act as freemachining agents with high-temperature lubricating capabilities. With these stress risers in place.188 / Stainless Steels for Design Engineers Fig. especially in the transverse direction. As a general rule. 304/304L. sulfur is a major negative factor for corrosion resistance. malleable. Passivation of the components will help. among others. Sulfides in stainless steels have a dark side. which lead to reduced mechanical properties in notch-sensitive alloys. These calciumbased oxide formulations have been commer- . with some grades reaching 0. the sulfides found in stainless steels are very effective in improving machinability. many duplex and super stainless grades.45%. the higher the sulfur.35%. The second group has sulfur contents ranging from 0. 410. or mechanical properties are more important than machinability. for the end user. Manganese sulfides form stress risers within the material. The grades in the third group include 303. at least from the machinist’s viewpoint. which concerns the end user. Sulfur tends to form segregated films with low melting points during solidification. Sulfur increases the hot shortness of materials during hot-forming operations. and 430. but the amount of sulfur is not the grading criterion. since these films are low strength. This is where mills will rebalance chemistries and processing to enhance machinability beyond what the first three groups offer to create enhanced machining grades. A fourth group of grades can be included in this classification. especially in austenitics.030%.25 to 0. weldability. and others. 347. The oxide inclusion chemistry is based on the CaO-Al2O3-SiO2 system. Sulfur hurts corrosion resistance by locally depleting chromium from the matrix to precipitate as a sulfide. corrosion resistance. 430FR.4570. they may induce the formation of microcracks brought on by solidification shrinkage stresses. Source: Ref 2 on the sulfur additions. Other sulfide inclusions that form on the grain boundaries contribute to intergranular corrosion. Despite these deficiencies. It is well documented that sulfides negatively affect corrosion resistance and mechanical properties of stainless steels. the smaller the bar. Sandvik’s Sanmac materials. and mechanical properties as critical but has the advantage of increased machinability. but the hole left behind by the sulfide becomes a collection site for contaminants. where contact forces are very high. welding.010%. and Carpenter’s Project 70+ materials. and the higher the strain produce a high probability for a crack to initiate. As the amount of sulfides increases in stainless steels. Grades in this group are 316LVM and other remelted stainless grades. Since the 1900s. Grades in this group include 316/316L. For these stainless steels. but the detrimental effect is equally evident. leading to poor processing yields. especially when sulfur levels exceed 0. steelmakers have known that injecting calcium into the melt converts refractory inclusions into soft. sulfur content is limited to 0. Further processing of these materials can induce cracking even further.

The Ugima oxide performs synergistically with sulfur. However. Courtesy of Ugitech Fig. not standardized as this process is difficult to reproduce consistently from heat to heat. The Ugima oxide works similarly to sulfur by coating the cutting tool and acting as a lubricant. the manganese sulfides in the stainless are the dominant machin- . 7 X-ray examination showing manganese sulfides and Ugima oxides coating the tool surface. but the machinability agent is. 5 Effect of calcium on machinability of 303. Ugitech SA (formerly Ugine Savoie and now part of Schmolz and Bittenbach) developed a proprietary and patented process sold under the trade name Ugima and Ugima XL (Ugima and Ugima 2 in Europe and Asia). EDAX. proving the existence of coatings of manganese sulfide and Ugima oxide. 6 Fig.Chapter 15: Machining / 189 Fig. energy dispersive analysis by x-ray. Figure 6 shows the Ugima oxide coexisting with sulfur in AISI. Since the oxide alone has limited lubricating abilities at slow machining speeds. at this point. Source: Ref 2 Complex Ugima oxides populating the 303 matrix. Courtesy of Ugitech cialized for stainless steels. Figure 7 shows EDAX (energy dispersive analysis by x-ray) spectra of the surface of a carbide tool.

8.190 / Stainless Steels for Design Engineers ing agent. The cutting tools themselves are the main variable other than the Fig. sharp cutting tools. the chip is shearing along complex oxide stringers. Feed rates need to be sufficiently more aggressive than with carbon steels to prevent work hardening and glazing of the material as well as to avoid reducing tool life.025% sulfur level.3. as seen in Fig. Like sulfur.30%. Machining tests at Ugitech and many field experiences have shown increases in machining performance of 30% with the addition of 1.3 mm of tool wear in 30 min. VB30/0. helping the chip break. which seems to contradict the experience of many machine shops.30%. Figure 9 exhibits cross-sectional photomicrographs of 304L chips with a 0. As shown. Machine and tool rigidity.8% copper to a 303 stainless steel with the Ugima oxide. Ugitech has seen synergistic effects with copper additions as well. Tool lubrication is only one function the complex oxide performs. The grade chemistry meets EN 1. Data generated at Ugitech as well as data generated by other producers have shown that once sulfur content reaches 0. High-Speed Tool Steels. 8 Comparison of machinability of AISI 303 at different sulfur levels with and without the Ugima oxide. and the oxide acts as a high-temperature lubricant that will allow faster machining speeds without the need to use specialized tooling. Tooling and Coolants The machining of stainless steels can be much more complicated than for other materials. the contribution toward machinability flattens and possibly decreases. The vertical axis. manganese sulfide eventually loses its lubricity. the combination of sulfur and the Ugima oxide extends the machinability range for sulfur levels beyond 0. and optimum lubrication type and amounts are very important.4570 and is sold under the trade name 303 Ugima UX (4570 Ugima in Europe). As machining speeds increase.4 to 1. the Ugima oxide is a discontinuity and will aid in chip breakage. Courtesy of Ugitech . However. Fig. Further additions of copper up to 4% have exhibited even better machining performance. machine power requirements. represents 0. 9 Comparison of 304L chips with and without the Ugima oxide.

There are always exceptions. in ASM Handbook. semisynthetic. With time. Today. . there are certain coatings that are more beneficial than C8type carbides. its limiting factors are heat and wear resistance. It is always a good idea to discuss the options with the coolant supplier. Davis. has high frictional forces.Chapter 15: Machining / 191 material in determining the quality of the machined part. These classes of carbides are harder and have more heat resistance. Tooling manufacturers such as Kennametal. high wear resistance coatings such as titanium carbonitride (TiCN) coatings are good. Iscar. The wrought HSS tooling was very versatile. Like the carbide. for which machine speeds are limited. ASM International. In the past. These tools are usually subjected to higher temperatures from high speeds. Powder metallurgy techniques produce even more highly alloyed high-speed tool steels with properties approaching those of carbide tooling. the carbide grades to be used when machining stainless steels are the C5. Ney. water soluble. unless it was possible to feed hard. and the new type: vegetable based. The earliest cutting tools were those made of the high-speed steels (HSSs). For example. etc. deep cuts. and C4-type carbides when using the older cam-operated multispindle and Swiss machines.R. and has tendencies of the metal to stick to the tools. form cutting. and is still a preferred choice in many shops.. Machining of Stainless Steels. it is possible to use the C2. a material with higher hardness and better thermal resistance. but many correspond to the C5 to C8 types. REFERENCES 1. 1989. Stainless cutting is hot. Vol 16. The aluminum in the coating breaks down and combines with the surrounding oxygen to form aluminum oxide (Al2O3). carbide tooling was a good choice. properties that are needed when cutting stainless. synthetic. petroleum-based oils need high C4-type carbides are not well suited for stainless steels because they do not have the heat resistance needed. Coolants available are petroleum based. Cutting materials that withstand these circumstances are needed. The C2.. Single-point tooling is now able to withstand the punishment of an interrupted cut. When tooling will not be subjected to much heat. Carbides. Although high-speed tool technology has improved. The discussion in this chapter has stated that the cutting of stainless is more difficult and generates more heat. and drills are able to withstand some flexing.. Generally. T. Carbide tooling is the next generation of tool materials after HSS. and limited coolant. Machining. 2nd ed. Ed. Titanium nitride (TiN) was a great coating when it was first introduced. Coatings.P. Micrograin and nanograin carbides are providing carbide tooling with increased toughness. chlorine. 1998. The other coolants need highpressure additives. Coolants need to remove this heat and provide lubrication to reduce friction and minimize BUE. drills. p 917–950 2. but further development in this area has created other coatings that work even better. in Metals Handbook. cutoff. allowed resharpening of the tools many times. Kosa and R. Tool coatings have contributed to machining improvements. grooving. Coolants. J. p 681–707 SELECTED REFERENCE • www. have their own proprietary grade designations. For example. ASM International. such as with taps. Sr. and have uninterrupted cuts. tools are being made with a powder metallurgy process.. All of these coolants need to be highly fortified for use in stainless machining. maintain fast speeds. desk ed. although it tends to be hard and brittle. mills perfected their ability to produce more highly alloyed tool steels to meet the increasing demands of the machining industry. Grades like titanium-aluminumnitride (TiAlN) and aluminum-titanium-nitride (AlTiN) are great coatings for turning. Sandvik. and fat levels for lubricity at higher temperatures. Coatings add a very hard layer on the tool surface that will provide additional lubricity between the tool and chip as well as potentially providing heat resistance for the tool.ugitech. reamers. again to help lubricity. allowing better machining performance. carbide tool technology has come a long way in grades and technology. Use of HSS tooling still limits machining speeds and performance. by which ingots of compacted high-speed tool steel powders have more structural homogeneity and thus better wear and heat resistance. Machining Data Recommendations.

The acids commonly used are nitric (HNO3). joining. Scales deplete chromium.. The underlying economic justification for using stainless steel is that it does not corrode if properly specified for the environment it faces. and the choice and application of surface finishes. coated. hydrofluoric (HF). H2SO4 is used alone. so the surface of the steel under the oxide is chromium depleted and therefore has lost possibly a significant amount of corrosion resistance. This is because the chromium in the steel oxidizes much more readily than other elements. Thus. Function of Surface Treatments Removal of Oxide Scale Introduction Surface finishing is usually very important for stainless steel. which is a characteristic for which the end user pays dearly. one can also create surfaces on the stainless that enhance its beauty and performance. hot-forming. They include the proper cleaning of stainless. McGuire. ground or mechanically patterned. The cost ramifications of improper or suboptimal surface treatments are immense because of the possibility of them compromising corrosion performance. even in an industrial setting. It can be treated chemically or electrolytically. This combination allows good control of pickling rates by varying the ratio of the two acids. The surface can be made reflective or matte. its surface appearance remains normally intact throughout its life.Stainless Steels for Design Engineers Michael F. is not recommended for stainless because it locally attacks (i.e. or oxidized. Removal of this scale is important to proper corrosion resistance. or hot forming • Accumulated ambient foreign material • Applied process materials. Even so. An oxide scale is quite different from a passive film. especially iron. It is used in combination with HF to modulate the attack by the strongly reducing action of the HF. and joining operations. plated. and sulfuric (H2SO4). pits) the surface. Beyond such considerations.1361/ssde2008p193 Copyright © 2008 ASM International® All rights reserved. It is often . All of these are discussed in this chapter. www. Oxide scales form on stainless steel during annealing. Pickling is the chemical dissolution of the oxide scale. sometimes producing profoundly different mechanical and corrosion-resistant properties. Raw stainless surfaces resulting from rolling and annealing operations are not considered attractive and are used only for functions in which aesthetics are a negligible consideration. painted. which is commonly used to pickle carbon steel. passive films enrich the surface in chromium by selective loss of iron. and the surface finish should not detract from its CHAPTER 16 Surface Finishing Summary SURFACE TREATMENTS are extremely important to the end user. etc • Contamination from other materials. and they are totally within the end user’s control and specification.asminternational. HCL. there are surface treatments required for stainless steel intended for such uses. HNO3 is an oxidizing acid that by itself does not pickle stainless. p 193-199 DOI: 10. fluxes. Oxide scales are arguably best removed by pickling. the various means of descaling after thermal treatment. This appearance should therefore be aesthetically pleasing. The surface can be altered on an atomic basis. such as forming lubricants. The stainless surface must be freed of: • Oxides resulting from annealing.

The HF provides: • a complexing agent for iron and chromium • destabilization of the passive film • stabilization of the redox potential The HNO3 provides: • • • • • a source of H+ ions stabilization of the passive film elevation of the redox potential an oxidizing agent of the base metal a dissolving agent for the scale The nitrates carried off from this pickling process are an environmental problem. making it more easily removed by subsequent pickling. and undissolved constituents can remain on the surface as “smut. so neutral solutions can be used. or electrolytic conversion treatments such as electrolytic sodium sulfate. The attack of H2SO4 on the base metal can be severe. however. Hexavalent chromium (Cr+6) is much more readily soluble in aqueous solutions. Annealing and shotblasting are required before pickling so that the acid can penetrate to the chromium-depleted region under the scale and selectively dissolve this layer. oxidizing treatments such as Kolene. Simply removing the scale mechanically may be insufficient if only the oxide is removed and the compromised (depleted) metal surface is left. The low solubility of trivalent chromium (Cr+3). It is also vital that this layer be removed as it diminishes the corrosion resistance of the surface. This process uses alternating positive and negative polarization in baths using sulfates or nitrates. Higher temperatures cause excessive HF evaporation and can also lead to visible emission of nitrogen oxides. HNO3 concentrations are normally from 10 to 25%. The strong oxidizing action of such a bath chemically alters the chromium oxide in the scale to a more soluble oxide without attacking the metal. makes such scale hard to remove. Use of strong acids and complexing agents is required to get pickling to occur at an economically acceptable rate. and the bath must be replaced for efficient pickling. patented UG3P process developed by Ugine (Ref 1) or Henckel’s “CleanOx” process. permitting it to be cleaned by many aggressive agents. The rate of NO2 formation increases at higher temperatures. lead to environmental problems as hexavalent chromium compounds are toxic and heavily regulated. Both treatments convert the trivalent chromium to hexavalent form.* a molten mixture of nitrate salt and hydroxide. The NO2 (nitrogen dioxide) produced during the reduction of the HNO3 (oxidation of the metal) is visibly brown-red. The H+ ions are produced by the polarization instead of by an acid. and 1% sodium chloride bath. as seen on two-dimensional flat-rolled material. The HF/HNO3 pickling is carried out between 120 and 140 °F (50 and 60 °C). It has been shown that the HNO3 can be eliminated and replaced by hydrogen peroxide (H2O2). and this leads to “ditching” of the grain boundaries during pickling. sensitized material will undergo grain boundary attack if pickled. simply using the cleaning agent appropriate for * Kolene is a registered trademark of Kolene Corporation. Their use may. Metal removal rates are proportional to the chromium level. Electrolytic pickling is commonly used in the production of cold-rolled stainless.194 / Stainless Steels for Design Engineers used as a preliminary pickling because of its aggressive. pickling can be considered a deliberately imposed corrosion process. Nearly all the action of pickling derives from undercutting of the oxide scale and dissolution of the chromium-depleted layer. HF concentrations can vary from 1% for light scales to 8% for maximum aggressiveness and difficult-to-pickle alloys.” This smut must be physically removed or dissolved by subsequent HF/HNO3 pickling. for example. This is the proprietary. The rate of pickling decreases rapidly as iron builds up in the bath. and less-controllable. resulting in the matte appearance of a pickled surface. Typical concentrations for H2SO4 pickling are 8 to 15% by weight. allowing for easy scale dissolution. Because contamination is “on” the surface of stainless rather than “in” the surface as is the case with many materials. typically found in oxide scale. action. Thus. Bath temperatures are generally 150 °F (65 °C). . Pickling involves both scale dissolution and metal dissolution. The scale formed during hot rolling may be an embedded scale with a minimal chromiumdepleted layer beneath the scale. All stainless has slightly greater oxidation in the grain boundaries when it is oxidized. Pickling may be assisted by prior treatment of the scale in molten 85% sodium hydroxide (NaOH). Thus. 14% sodium nitrate. Cleaning Stainless steel is very resistant to chemicals of many kinds.

Field experience has shown that stainless steels with less than 16% chromium can be harmed by hypochlorite bleaches. In fact. or oxalic-containing cleansers If severe. such as 201. and dry. But. and domestic uses of stainless. dry with forced air or a dry cloth. and rust stains Hard water scale. but film formation can be accelerated by controlling the environment. Table 1 summarizes some cleaning recommendations based on the contaminant to be cleaned. or nonscratching cream or polish Alkaline. but does not occur on roll-finished or bright-annealed surfaces. The stainless surface will not be harmed by cleaning as long as strong halides. Do not use HCl-containing products. The surface to be passivated should first be cleaned by one of the methods discussed. mortar Oxides. is resistant to some level of chloride concentration at a given temperature and pH. particularly in crevices. Sanitation concerns in the food service industry take precedence over this prohibition. This allows uniform passivation and avoids contamination of the passivating solution. discolorations. Neutralize with ammonia. room temperature use of hypochlorite bleaches will generally not harm most types of stainless steel if well rinsed after application. The film forms of its own accord when a clean surface encounters moist air. as explained in the “Corrosion and Oxidation” section of this Volume. Precipitation-hardenable (PH). are not attacked unless concentrated chloride solutions are permitted to stay on the surface. heat tint Nonscratching creams or polishes 10–15% phosphoric acid. trisodium phosphate. Thus. leading to localized corrosion. Do not use HCl-containing products. Wax and oil polishes minimize fingerprinting. iron utensils. especially by chlorides. The greatest controversy regarding cleaning stainless steels involves the use of sodium hypochlorite. short-term. Follow manufacturer’s directions Paint . such as 430. Scotchbrite©.Chapter 16: Surface Finishing / 195 the contaminant will permit very thorough cleaning of the stainless surface. or hydrocarbon solvent Use a soft cloth or sponge.2 g/L sodium dichromate added to that solution to avoid attack. notably iron. Hypochlorite bleaches must be well rinsed to avoid pitting. and straight chromium grades with less than 17% chromium should have 2. or dilute ammonia Detergent and warm water or a hydrocarbon solvent Hydrocarbon solvent More severe stains. sulfamic acidcontaining. or semiconductor applications. stainless scouring pad. Damage occurs mainly on abrasively polished surfaces in alloys with 16% chromium. 301. Blasting the surface with carbon dioxide pellets is a rapidly growing process for removing paint and other adherent. The user is encouraged to test whether a product meets this requirement by testing it on a small. rinse. treat by pickling. they should blend with existing surface finish in size and direction. clean water. and to form a passive film. They should be immersed in 5% NaOH for 30 min at 75 °C (165 °F) followed by a rinse before the Recommended cleaning methods Cleaning recommendation Comments Exterior soiling Fingerprints Grease. Stainless steels with slightly higher chromium and nitrogen. These cleaning recommendations apply to industrial. Many highly qualified experts flatly disapprove of its use because it can easily leave a residue of chloride on the stainless surface. martensitic. area. and abrasives that alter the surface finish are avoided. Glass cleaner is appropriate for mirror finishes. Passivation is a very commonly used surface treatment to remove surface contamination. Alkaline cleaners may also be used in severe cases but may require cleaning the entire surface to maintain visual uniformity. If abrasives must be used. every stainless steel. preferably unexposed. The recommendation not to use abrasives does not include soft abrasives such as calcium Table 1 Contaminant carbonate or brush material that is sufficiently soft not to mar the stainless surface. The free-machining grades are the most easily attacked of all types. oil Soap. pharmaceutical. health considerations make this position untenable. which can cause a rapid attack. and 304. refer to the chapters dealing with those applications. For special levels of cleanliness required for medical. architectural. Those stainless steels with more than about 17% chromium can be pickled in 20% HNO3 at 50 to 60 °C (140 °F). detergent. soft coatings and deposits without damaging the surface of stainless steel. in reality.

Oxide films are thicker and through optical interference can cause different colors. The resulting surface is bright and cleanable and provides the optimal corrosion resistance that a given alloy can achieve. When stainless steel first appeared on the market. as well as Federal Specification QQ-P-35. The hotrolled or cold-rolled annealed and pickled surface finish is nonuniformly dull and unattractive to most observers. which is a function of the time at a given temperature. the more economical abrasive polishing became the standard. The most prominent is the International Nickel Company (INCO) process. like pickling. Electropolishing.0 amp/m2. Table 2 Parameters for oxide film coloring of stainless steel Heat treatment time Color Oxide film thickness. and a final rinse. The most commonly used electropolishing solution is 40% H2SO4 and 45% phosphoric acid (H3PO4).196 / Stainless Steels for Design Engineers nitric/dichromate passivation is performed. and it had the benefit of removing the many cosmetic defects that then were common to the manufacture of stainless. Coloring Stainless steel passive films are so thin that they are quite invisible. also selectively removes any exposed chromium-depleted regions. Apparent pitting resistance is thus increased. another 30-min NaOH treatment. The colors produced are correlated to thickness and treatment parameters (Ref 2) as shown in Table 2. nm 10 15 20 25 30 35 40 50 Gold brown Brown/red/blue Brown/blue Green/blue Green/gold/blue Gold/green Gold/green/brown Red/brown 70 100 120 140 165 185 210 250 . two parts H2SO4. as showcased on the Chrysler Building in New York City (Fig. The colors typically range from light yellow formed at 300 °C (570 °F) through violet formed at 420 °C (790 °F) and dark blue formed at 600 °C (1110 °F). it is often for aesthetic rather than functional reasons. A 380-99. Rocha-Fila et al. citric acid has become a popular replacement for HNO3 because it avoids the problem of toxic nitrates and hexavalent chromium. The color depends on oxide film thickness. Reproducibility is sometimes a problem. The reflectivity of the surface is a function of the preelectropolished surface. Aesthetic Surface Finishes When steel is used in other than the asannealed and pickled state. Refer to ASTM documents A 967-01. The use of NaOH before and after is still recommended for lowchromium and free-machining alloys. Electropolishing is the most effective means of accomplishing this. It causes the surface roughness to decrease by approximately one-half in Ra (the arithmetical average of surface peaks and valleys as measured over a straight line). Soon. When citric acid is used. balance water. Electrochemical methods permit more uniform and reproducible color and tougher films. Much higher levels of surface quality were made possible with the development of the Sendzimir mill to the bright anneal process permitted much higher levels of surface quality. well metal composition. This should be followed by a rinse. a highly polished surface was the paragon. This surface finish was very expensive to produce since it had to be done by polishing and buffing. which selectively dissolves the surface in such a way that it becomes microscopically smoother. used at 90 °C (194 °F) with a current density of between 1. confirmed that these coloring treatments did not degrade the pitting corrosion resistance since their formation mechanism more closely resembles passive film formation than oxidation. Brightening Stainless steels can be brightened by chemical or electrolytic action. but whose normal use is strictly functional. The films are formed thermally in a process known as heat tint. In this two-step process. which has a bright surface from cold rolling. B 91200. a 10% solution is applied for the same time and temperature as with HNO3. the steel is first immersed in a mixture of one part chromic acid. leaving only the bulk alloy with the intended corrosion resistance on the surface. and one part water at 30 °C (85 °F). The major exception to this is temper-rolled strip. 1).0 and 3. Other baths using perchloric acid are technically good but carry the risk of explosion. and oxygen partial pressure. This is followed by an electrochemical treatment with the same bath or with H3PO4 substituted for H2SO4. In recent years.

Table 3 Polished finish designations based on grit sizes to achieve target surface roughnesses Finish number Grit number Ra max.15 40 30 8 4 . ©iStockphoto. Thus.. in which abrasives are bonded rigidly to each other on a rigid backing. µm Ra max. Neither the producer nor the customer is protected by a clear specification as of this writing. µ Mirror finishes could be achieved with cold rolling followed by bright annealing.30 0. wet polishing) gives sharper cuts and less heat tint from frictional heating. This is distinct from grinding. The latter are superior in uniformity and corrosion resistance. Buffing is done by very fine abrasives. • High surface hardness influences which abrasive will be effective.75 0. Lubrication during polishing (i. is quite visually apparent. This has not entirely replaced sheet buffing to obtain mirror finishes. The difference can be more than 10 μin.e. Table 3 shows the varying surface roughnesses that are typical of polished stainless. but sheet buffing has been relegated to those few applications where a high degree of perfection is demanded. • Low thermal conductivity can cause excessive temperatures during processing and distortion. medium-sized abrasives that are bonded to a flexible backing. ASTM merely describes the finish by a grit with which it is typically made. and will make adjacent pieces of stainless from the same coil look different.Chapter 16: Surface Finishing / 197 Stainless steel surface finishing is governed by: • High strength and high work-hardening rate require more power for metal removal. and the customer should specify minimum and maximum Ra values for his purpose. but the polished finishes are still more common. (0. resulting in more surface brightness. the producer is encouraged to publish standards. especially appliances and architectural panels. • Oxidation (heat tinting) that occurs over about 250 °C (480 °F) • Residual stress due to surface working. The length of the grit line varies with the speed of the material as it passes the rotating abrasive belt. There are no official roughness values for the various surface finishes. The standard rule is that materials used in finishing must not permit iron or iron oxide particles to come in contact with the stainless surface or passivation layer. 3 4 7 8 60–120 120–180 240–320 500 1. Polish appearance varies also with the presence or absence of lubricant. Polishing for aesthetic purposes is generally done with abrasive coated belts and is done to both coils and sheets. which are loose and do their work by being forced along the surface by a soft material. Polished Finishes Polishing is carried out with coarse. 1 View of the Chrysler Building in New York. Polish appearance also depends on the length of the grit line caused by an individual particle of abrasive. The main methods of producing aesthetic surface finishes on stainless steel are abrasive finishes and rolled finishes.25 μm) in Ra.0 0. The typical number 4 polish varies in roughness from the beginning of the coil to the end because of the wear of the abrasive particles on the belts. This may be objectionable for certain products. especially in austenitic alloys Grinding is a relatively coarse procedure with usefulness that is largely confined to defect removal.

If the repaired area is small. this composition is prepared by mixing gases. many other designs such as replicating fabric or leather. and elastic flattening of the roll and the stainless cause about 50% less Ra on the stainless than on the roll. where corrosive conditions require a PREN (percentage chromium equivalent) of 25. The better producers have proprietary methods of prior pickling. or matte finishes can also be made. • They retain the enhanced corrosion resistance of bright-annealed material. Bright-annealed sheet will only be as bright and flawless as the cold-rolled sheet that is annealed. These finishes can be applied to all the normal sheet alloys. There are also instances for which polished UNS S31600 was corroding in coastal . If the pickling is kept mild enough to retain surface brightness. Final brightening occurs with temper passing after bright annealing. In theory. The benefits of rolled finishes are: • They can be made identically from coil to coil since roll engraving is quite precise. This combination of variables. but for large areas. The pattern on the roll is impressed into the stainless surface. many older bright-annealing facilities are narrower than normal sheet width. in addition. Repair of a polished surface damaged. a quality product. These finishes are called “hairline” in Japan and “grainline” and other names in the United States. must be produced with great care. which can take on any appearance and can be engraved onto a temper mill roll. while seemingly controllable. Some of the finishes produced by rolling are shown in the architectural chapter (see Chapter 18). Therefore. Bright annealing is annealing in a very low oxygen atmosphere. generally as mirror-like as possible. annealing. This process was originally developed as a means of producing bright ferritic trim for automobiles. Bright Annealing Aesthetic finishes that do not depend on abrasion are derived from bright annealing. But. usually at significant expense. repolishing of the entire surface is often the best remedy. These finishes also permit type 430 stainless steel to be used successfully in restaurant applications without corrosion issues where polished type 430 material previously had corroded. if not undetectable.198 / Stainless Steels for Design Engineers and the rotational speed and diameter of the backup roll for the abrasive belt. and a decrease in corrosion resistance are the chief drawbacks of polished finishes. A perfect match and blend to the surrounding original surface is an art. This variability also causes problems in field repair. only correct pressure and grit size are required to achieve good visual matching. and no practitioner of that art can accomplish it perfectly. but the process itself is intrinsically superior to annealing in air because no oxide is formed only to be later removed. For many stainless steels. by welding or scratching is quite challenging. but finishes applied by roll to two-dimensional surfaces that have been dulled by pickling are somewhat gray and indistinct. • They are less expensive to produce. usually varies enough so that no two polished sheets look identical to the trained eye. so the final product is generally priced lower than polished material. the 3:1 H2:N2 can be varied without difficulty. Today. Qatar. more modern lines are high speed and wide enough to produce bright sheet. This has permitted rolled finishes to be used on UNS 32003 for building exteriors in Doha. Because the original product was strip. difficulty of repair. geometric designs. All polished finishes can be duplicated as rolled finishes. including the lean duplex alloys. “dissociated ammonia” referred to a 3:1 (mole ratio) mixture of hydrogen and nitrogen produced by the catalytic decomposition of anhydrous ammonia. either dissociated ammonia* or hydrogen/argon. This can be done with a belt sander. That use has largely passed out of favor. * At one time. then it can be acceptable. The wider. Lack of uniformity. and rolling by which the surface is made flawless and very smooth. such finishes can be made from airannealed material. By eliminating the variable of grit length. A solution to the problem of matching polished surfaces is to use very long grit lines for finishes of the same roughness. or it can be used as a basis for rolled finishes. then it is possible insufficient prickling has occurred to remove the chromiumdepleted layer caused by the air anneal. This effect increases with the yield strength of the stainless being processed. for example. The most critical applications from a surface perfection point of view use rolled finishes rather than abrasively finished number 4 polishes. Rolled Finishes The bright-annealed and temper-passed surface may be used in its mirror-like condition.

15 (No. dramatically reducing the corrosion resistance. there was no further corrosion. the corrosion resistance increases significantly. Ernst. Braz. F.Chapter 16: Surface Finishing / 199 architectural applications in the United States. and G. The properties of this layer are phenomenal. p 4171–4181 . Cao. Acta Mater. p 472–480 3. C. Because alloying is such a high component of cost in stainless. Les Editions de Physiques. Simply using these processes on stainless cannot be done because these elements combine too strongly with chromium as carbides or nitrides.. surface chemistry can be changed to affect certain properties. Michal. Vol. 4). In addition. REFERENCES 1. its corrosion resistance may be reduced. Stainless Steels.% carbon in supersaturation can be achieved without carbide formation.. There have been modifications to carburizing and nitriding that permit austenitic stainless steels to have very high carbon levels implanted to a thin surface layer. Rocha-Filo et al. These processes are at the very initial stages of commercial use. like nitrogen. Only by such supersaturation with carbon could it be determined that carbon. Soc. J. 2003. Y. 2004. When the abrasively polished surface was replaced with rolled finish UNS S30400 (Koolline). Vol 51. Carburizing and nitriding are examples of such processes. the hardness is 1000 Vickers 25 compared to 200 for the base alloy (Ref 3). Surface Alteration In carbon steels. 1989 2. Chem. By exposing an activated stainless surface to a high carbon fugacity at 470 °C (880 °F) for around 200 h a 50 nm thick layer with 12 at.. is a powerful antipitting alloying element when kept in solid solution. it makes sense to employ rolled finishes whenever possible. it must be noted that when manual polishing is used to repair scratches or other damage in rolled finish material. However.

since TiC can dissociate at elevated temperatures and not be able to Welding Characteristics of Stainless Steels Austenitic stainless steels are readily welded by nearly all welding techniques. The older method of preventing sensitization is to stabilize the alloys with titanium. toughness. This is foolproof only if carbon levels are low.1361/ssde2008p201 Copyright © 2008 ASM International® All rights reserved.04%. The welding process must. which must be respected as a process that combines melting.asminternational. corrosion resistance. of course. • Stainless steels contain readily oxidized chromium. This prevents rapid precipitation by reducing the supersaturation of carbon. for the intended service conditions. it is complex in theory and practice. • Surface oxidation during welding depletes chromium in all types of stainless steel from the underlying surface. refining. The main objective is to show how standard welding technology is correctly applied to stainless steels. which is what makes it stainless. characteristics of austenitic stainless steels that distinguish them from ordinary carbon steels in welding are: • Austenitic stainless steels have lower thermal conductivity and higher thermal expansion than carbon steels or ferritic stainless steels. so that: 1. This chapter gives a basis for understanding the influence of alloy composition and metallurgy on the welding process. must be protected from oxidation. The foremost special consideration of welding stainless steel as opposed to carbon steel is that the chromium in stainless steel. www. p 201-212 DOI: 10. produce a sound joint. but it must also result in the weld and its surrounding affected metal having correct strength. resulting in reduced corrosion resistance unless this layer is removed. as in 347.Stainless Steels for Design Engineers Michael F. thus increasing the potential for residual stress and therefore hot cracking. • There are thermodynamically metastable conditions due to the low diffusion rates in the face-centered cubic (fcc) matrix. which must be protected. Knowledge of each aspect is required for the process to be designed and executed properly. less than 0. which can localize the heating. It does not form refractory oxides that would diminish weld soundness. • The possible precipitation of intermetallic phases in the HAZ can lower toughness and corrosion resistance. This chapter does not attempt to teach welding. The welding and joining of stainless steels requires knowledge of both the technology of the welding or joining process and the response of the steel to the thermal and mechanical effects of the process. McGuire. The influence of carbon has been well addressed using low-carbon versions of all grades whenever welding involves significant time between 600 and 900 °C (1110 and 1650 °F). • The possible formation of chromium carbides in the heat-affected zone (HAZ) can cause susceptibility to grain boundary corrosion (sensitization). 2. The .org CHAPTER 17 Welding NEARLY ALL WELDING of stainless steel is done by end users or processors. • There is increased microsegregation in the fusion zone with increasing alloy content. and thermal processing. It stays in solution as a corrosion-resisting element. etc. Like thermal processing. as in type 321. or with niobium.

The Schaeffler diagram has been improved by the Welding Research Council’s adoption of the modification shown in Fig. where it forms weak films. a useful empirical mapping of weld metal phase composition shown in Fig. if present. 2.) material or when the HAZ is drastically reduced. which does not reject the sulfur. Another serious threat posed by thermal stresses is hot cracking. Very rapid cooling. as with laser welding. normally between 3 and 10%. This is avoided only in thin-gauge (>1.03%) unstabilized alloys must be annealed after welding to redissolve chromium carbides if the cooling was sufficiently slow for the carbides to have formed. tends to make austenitic welds less ferritic and has the opposite effect in duplex alloys. 1.202 / Stainless Steels for Design Engineers recombine successfully with titanium during cooling. which super- Fig. The higher carbon-stabilized alloys and the high-carbon (>0. Welds of less highly alloyed austenitics.5 mm. This weakness occurs when the steel solidifies in an austenitic mode. Faster or slower cooling will change the relative amounts of ferrite and austenite because of the need for diffusion to achieve the most stable phase balance. This can occur to material that has just solidified when geometric constraints to contraction imposed by the surrounding material imposed act on weak grain boundaries. In such alloys. 0. 1 The Schaeffler diagram. Source: Ref 1 . which may require annealing to eliminate.06 in. forcing it to precipitate as sulfide inclusions within the grains. This is not harmful since the ferrite is richer in chromium and in molybdenum. sulfur and other contaminants. must be excluded from the weld zone. permitting a thin zone of sensitization called knife-line attack. Fortunately. The amount of ferrite expected can be measured by magnetic devices and estimated from the Schaeffler diagram. and copper. The high thermal expansion of austenitic stainless steel can cause high residual stress around welds. which are balanced to freeze in a ferritic mode. most 321 and 347 are produced with carbon levels below 0. This diagram has an arbitrary cooling rate resembling that of tungsten inert gas (TIG. as in laser welding. When austenite freezes. This approach is highly effective but cannot be used for some highly alloyed grades with compositions that do not permit a ferritic solidification mode. such as phosphorus. generally those with less than 20% chromium. oxygen. retain some ferrite at room temperature. it strongly rejects sulfur to the intergranular areas.03%. described in a separate section of this chapter) welds. zinc. This is solved by balancing the composition so that alloys solidify first as ferrite.

Thus. the welds have lower resistance to localized corrosion. while the addition of 3 to 5% by volume of nitrogen gives the necessary partial pressure to ensure that welds will not be depleted of vital nitrogen content. Thus. Inert gases provide the barrier. oxygen-free gas mixtures are used to exclude the ambient atmosphere from the molten pool during electric arc welding. Restricting heat input to under 16 kJ/mm (400 kJ/in. Austenitics at the alloy level of 316 and above should not have sulfur above 0. which delineates those compositions that solidify in a primary ferrite mode. Another problem particular to the more highly alloyed grades is the formation of intermetallic phases from long cumulative exposure to temperatures in the 600 and 900 °C (1110 and 1650 °F) range (coincidentally.) and interpass temperature to under 150 °C (300 °F) helps to minimize each of these risk factors inherent to the more highly alloyed austenitic grades. creating slag and depleting the alloy of needed elements. The austenitic stainless steel weld metal composition can be altered by the gases to which the molten base metal is exposed. Lack of shielding can lead to oxygen combining with chromium and other elements. Note that the influence of microsegregation of alloying elements is separate from and in addition to the negative influence of sulfur on the corrosion resistance of welds. so these alloys are recommended if extensive welding is planned. This is addressed by using more highly alloyed filler metal or by solution annealing the welds. This adverse precipitation is largely prevented in the modern. precluding the problem of intergranular solidification cracking. The slow diffusion of alloying elements in austenitics makes this a lesser problem than in ferritics or duplex. Figure 3 (Ref 1) shows the influence of nitrogen content of the shielding gas .001% for these alloys to deliver the expected corrosion resistance.Chapter 17: Welding / 203 Fig. This causes austenitic dendritic cores to have lower chromium and molybdenum content and consequently lower corrosion resistance. 2 Welding Research Council’s (WRC’s) 1992 constitution diagram imposes the solidification mode as a function of the composition. the same as for carbide precipitation). nitrogen-alloyed grades. The more highly alloyed grades also suffer from greater microsegregation during solidification. The crucial line on this diagram is dotted-dashed line AF.

If the weld cannot be annealed. and corrosion resistance from their nearly equal percentage of ferrite and austenite. the key precaution in welding duplex alloys is to prevent the formation of embrittling phases while preserving as close to a 50/50 austenite/ferrite structure as possible. so welds did not become so ferritic. and since nitrogen is a crucial alloying element. The nitrogen also decreased the speed at which intermetallic phases form.. • While carbide sensitization is not an issue with the duplex alloys. • Cleaning before and after welding is equally important in duplex as in austenitics. the stronger will be the effect. the darker the tint. hot shortness is not a problem. so minimizing the total time at high temperature is the overriding concern. toughness. like all stainless types.g. The rapid cooling of welds produces welds and HAZ with more ferrite than the parent metal by quenching in the high-temperature ferrite. the addition of high (>0. The heat from welding can produce a surface oxide composed mainly of iron and chromium. it must be a component of the gas mixture. 2209 with 2205 base metal) should be used. compared to austenitic stainless steels. which is richer in chromium and molybdenum. The additions of larger amounts of nitrogen stabilized the austenite to higher temperatures. So. • Duplex. . Modern duplex alloys derive their impressive strength. joint preparation must be done correctly and not left to the welder to correct using timeconsuming remedial procedures. This should be followed by acid pickling. which completes the removal of the oxide and depleted zone. Thus. Excess nitrogen in the shielding gas (e. Nitrogen additions partition to the austenite and thus both strengthens it and increases its corrosion resistance to close to that of the ferrite. sufficient time must be spent above about 1000 °C (1830 °F) to promote the formation of sufficient austenite. duplex stainless steels have the following distinguishing factors: • The ferritic solidification mode of duplex stainless steels provides very good hot cracking resistance. The nitrogen content of the austenite brings its corrosion resistance up to that of the ferrite phase.g. • Duplex alloys are more sensitive to problems in the HAZ because their generally high chromium and molybdenum content plus their ferritic content make the precipitation of embrittling intermetallic phases more rapid than in austenitics. and since ferrite rejects little sulfur on solidification. 3 on corrosion resistance of a highly alloyed austenitic grade. must be protected from oxidation by shielding gas. enlarging the time window for welding without their precipitation. Despite these advances. especially in duplex alloys. The early duplex alloys had a tendency to form excessive ferrite when welded and formed embrittling intermetallic phases rather rapidly.. But. Duplex stainless steels differ from austenitic stainless steels in their metallurgical response to welding mainly because their approximately 50% ferrite causes greater thermal conductivity at lower temperatures. These alloys solidify in a completely ferritic mode. the area must be ground to remove the oxide and any depleted base metal. increased nickel filler metal (e.204 / Stainless Steels for Design Engineers Effect of weld shielding gas composition on crevice corrosion resistance of autogenous welds in AL-6XN alloy tested per American Society for Testing and Materials (ASTM) G-48B at 35 °C (95 °F) Fig. Minimizing time at red heat temperatures (500 to 900 °C. 930 to 1650 °F) is the objective. For heat-tinted surfaces. Pits can start in this thin layer and propagate into sound metal beneath. and ferrite has greater diffusion rates. more than 10%) can cause porosity in the weld. by promoting greater austenite formation at high temperature. To fully restore corrosion resistance.12%) nitrogen actually reduces the tendency for chromium nitride precipitation. and greater than 5% is detrimental to the life of the tungsten electrode. the formation of intermetallic phases can cause loss of corrosion resistance. The underlying surface can be significantly depleted of chromium because of the loss of chromium to this scale and therefore significantly lower in corrosion resistance. And.

However. more slowly than can be done in welds. rendering the alloys ferritic at all temperatures.08 in. In practice. The reason is that the welds are invariably partially martensitic and thus normally brittle.6 kJ/cm (Eq 2) and D = 75 × E – 350 above 6. which must dwell in σ-forming temperatures for some period of time. If for some reason they must be used and welded. this can be achieved by limiting heat input to less than 6 kJ/cm. the relationship is: D = 206 × E – 585.6 for up to 6. Niobium can replace some titanium. which otherwise would cause the formation of the high-temperature austenite. because of their moderate thermal expansion and higher thermal conductivity. The stabilized grades commonly use titanium or niobium to combine with the carbon and nitrogen. These alloys form appreciable amounts of austenite when heated above 800 °C (1470 °F). then the techniques for welding martensitic stainless steels should be employed. The stabilized group should not be exposed to nitrogen. • The grades more highly alloyed with chromium and molybdenum can form α' and σ. successful welding is simplified to making a sound.11 in.08%. the austenite transforms to martensite. The semiferritic alloys such as 430. heat inputs that are too high lead to the formation of embrittling intermetallic phases.08 + 8(C + N). Ferritic stainless steels can be split into two groups for purposes of welding: the older semiferritic group and the more prevalent stabilized ferritic group. The first group. and these are not generally available commercially. • The stabilized group can lose toughness via excessive grain growth. Thus. These are empirical relationships that take into account that some titanium oxidizes before it can stabilize carbon and nitrogen. While the technical remedy for this is simply annealing. which is very brittle.Chapter 17: Welding / 205 Duplex stainless steels. In the fusion zone. and 436 are seldom welded and often called unweldable. it is: D = 29. which requires annealing to eliminate. The key is to limit the time at those temperatures by not permitting interpass temperatures to exceed 150 °C (300 °F) because workpiece temperature has the greatest influence on time at σ-forming temperatures. Postweld stress relief is not needed for duplex weldments and indeed could be harmful because of the danger of embrittlement. • The semiferritic group will form martensite.6 kJ/cm (Eq 3) The light gauges ensure sufficiently short times at high temperature that precipitation of . leading to embrittlement. Full annealing can be done and can restore the original phase balance and composition that gives the optimal toughness and corrosion resistance found in wrought material. can tolerate relatively high heat inputs since these factors determine the stress intensity that will be generated by thermal gradients. Only very specially controlled compositions of 430 can be welded successfully. Because of the low toughness these alloys have in large cross sections. It is rare to see any welding more extensive than spot welding of unexposed surfaces with these alloys.6 (Eq 1) In the HAZ. The stabilized ferritic stainless steels are commonly welded. For 409.) and normally have sections less than 2 mm (0.). while the requirement for the higher chromium 439 is 0.6 × E – 50. is exemplified by the alloy 430. The salient metallurgical characteristics for welding of the two groups are: • Both groups offer good thermal conductivity and low thermal expansion. An empirical relationship between grain diameter D and heat input E (kJ/cm) has been reported (Ref 2). At the other extreme. It is prudent to impose this limitation when qualifying the weld procedure and then monitoring the production welding interpass temperature electronically to ensure qualifying procedures are not more lenient than are those of production. the required titanium level is Ti > 0. well-shielded weld without producing excessive grain growth in the HAZ. This issue concerns the HAZ. Unless they are cooled extremely slowly. excessively low heat inputs can result in fusion zones that are predominantly ferritic. This is discussed in detail in Chapter 8 on ferritic stainless steels. these alloys are only rarely seen with minimum section size of more than 3 mm (0. 434. it is seldom economically viable. with a resultant loss of toughness and corrosion resistance.20 + 4(C + N). The levels of stabilizing elements required to prevent austenite formation and sensitization are well known and are reflected in the alloys’ chemistry specifications. in which chromium is between 16 and 18% with carbon up to 0. • Both groups require protection from oxidation by shielding gases.

precipitation-hardening (PH) stainless steels. The considerations in welding them are: • Shielding must be sufficient to prevent loss of oxidizable alloying elements such as titanium. If mechanical requirements permit.10 and 0. such as 309L. • Austenitic PH grades are fully austenitic and subject to hot short cracking.20% carbon. Material Selection and Performance Stainless alloys that are prone to precipitation of intermetallic phases require special prewelding consideration. a final heat treatment is required to achieve the quenched and tempered properties for which these alloys are designed. Especially in the superferritics. Extraordinary surface cleaning at and near the weld will pay dividends in final quality.10 to over 0. but between 0. distortion may be encountered. • Postweld heat treatment solution annealing must be adequate to homogenize weld solidification segregation. then austenitic filler. crevices. even though they can form.206 / Stainless Steels for Design Engineers intermetallic phases should not be a concern. But. If mechanical properties equal to that of the base metal are not required in the weld. which is even more readily oxidized than chromium. The impact properties of ferritic stainless steels are always a concern because their transition temperature can become elevated to ambient levels. preheat can be omitted. those of low-alloy stabilized ferritic stainless steels with regard to cleanliness and shielding. It is prudent to consult with the manufacturer’s data sheets for specific recommendations on alloys that they produce as they are often privy to test data and user experience that cannot be found elsewhere in the literature. the desired approach is to start with a well-tempered or annealed material and then preheat and maintain high interpass temperatures. Any amount of time for which these alloys have been exposed to temperatures at which inter- .30%. Aside from the cracking consideration. of course. Last. Table 1 summarizes the major metallurgically important parameters for the various types of stainless alloys. while very complex metallurgically. any heat treatment to achieve the properties of which these alloys are capable must be a final step. are straightforward from a welding perspective. especially in superferritic alloys. • The high aluminum or titanium contents of many PH alloys cause their welds to be “slaggy. superferritic. and superaustenitic alloys. but less stringent than. chromium. Such alloys include duplex. oxygen must be rigorously avoided because it will quickly deplete the essential titanium. Their carbon content ranges from 0. It has been determined that there exists an optimum level of titanium around 0. because these alloys are designed for extreme mechanical performance. ranging from 11 to 18% chromium with small amounts of nickel and molybdenum. martensitic welding considerations are similar to. Martensitic stainless steels vary little in alloy content. Even with preheating. • Filler metal must match the base metal if like properties are required. which ensures this minimum transition temperature (Ref 3). For all normal uses of martensitic stainless steels. Obviously.10%. These alloys are easily welded and not prone to cracking or developing embrittling phases. dual stabilization with titanium and niobium as well as not having excessive heat input are the best way to ensure weld toughness. which is most likely to occur in the HAZ from stresses caused by the austenite-to-martensite transformation on cooling. it is essential to preserve their correct chemistry by shielding with a fully inert gas mixture. the major challenge they present is avoiding the potential cracking. Thus. maintaining the benefits of having the fairly precise balance of carbon plus nitrogen to the stabilizing elements titanium and niobium requires that neither carbon nor nitrogen come into contact with the weld pool. preheating to 250 °C (480 °F) is advised and for higher carbon levels. Since this transformation cannot be avoided. For low carbon levels. The soft joint may deform to accommodate thermal strains and thus minimize weld cracking. The problem becomes more severe with increasing carbon level because the transformation takes place at lower temperatures in more brittle material. 300 °C (570 °F). Likewise. can be used.10%.” and these slaggy welds have are irregular with objectionable recesses. aluminum. Because it is difficult to have low enough carbon plus nitrogen to stabilize at this titanium level. the use of austenitic (309L) weld filler metal should be considered. or prominences. below 0. and. Precipitation-Hardening Stainless Steels.

Unfortunately.. .a.5%Ar+2. 2304. 4.5%Ar+2.. 19-D 2205 25 Cr duplex 2507 superduplex Same as base alloy 20–40 Ar+2% O2. 308. Slow cool Anneal .5%Ar+2.. . 310 310 316L. 309L 439L. ..Chapter 17: Welding / 207 Table 1 Alloy group Welding parameters for various stainless steels Filler Heat input kJ/cm(max) Shielding gas Preheat Interpass max Postweld heat treat Austenitic .5%Ar+2. 2101. .5 CO2 Ar+2% O2. 20–40 301.. 308L 22.005 to 0. n. as shown in Fig. Once a welding procedure is qualified for an alloy with given nitrogen content. shooting the hottest metal to the bottom of the weld pool. accurate knowledge of material history is vital. 276 Same Same Same Same Same Same 16 PH grades Martensitic 410 420 440 Supermartensiic Ferritic 430 434 409 439 Superferritic 2003. He+7. 675...0 6. 308... 100 oC . Ar/3% CO2/2% H2 He+7..5%Ar+2. 308..5%Ar+2. Likewise. . which is a good thing. 347 Superaustenitic 308.a. He+7. He+7. 308.. 309L.5 CO2 Argon/helium Argon + 3% N2 Argon + 3% N2 Argon + 3% N2 Argon + 3% N2 no no no no no no no no no . He+7. .. 310 Same as base metal 20–40 20–40 20–40 20–40 Ar+2% O2.. 316Ti 321. This effect exploits the temperature-dependent surface concentration of sulfur in the weld pool... .5 CO2 Same Same Same Same Same Same Argon/helium or argon + 3–5% N2:no O2 Argon/helium 150 oC 150 oC None or full anneal .. 308L 308L 309. 150 oC 150 oC 150 oC 150 oC Subcritical anneal Subcritical anneal none none None or full anneal None or full anneal None or full anneal None or full anneal None or full anneal PH. . 302. .. The effect on corrosion resistance is less desirable since the abundant MnS inclusions that result from the higher sulfur levels decrease pitting resistance. use of lower nitrogen alloys would not be prudent engineering practice. He+7.a.... He+7... 310 440..5 CO2 Ar+2% O2.0 5–25 5–25 5–25 5-25 Ar+2% O2. . precipitation hardenable metallic phases form without full subsequent homogenization anneal is time that the welder cannot use to complete a satisfactory weld before precipitation occurs. . Thus. n.5 CO2 Ar+2% O2. 317L 347. .. None or full anneal no ..... 309L....5%Ar+2.015%.. He+7. ..5 CO2 Ar+2% O2.5 CO2 Ar+2% O2. causing the molten pool to flow toward the center on the surface and then flow downward... . . This is done to improve weld penetration through the so-called Marangoni effect. 309L.. 50 oC .. Austenitic stainless steels that are intended for autogenous welding are often specified with elevated sulfur levels. Full solution anneal 410... .5 CO2 Argon/helium 250oC 250 oC 250 oC no 250 oC min 250 oC min . . the pipe purchaser cannot know if the pipe has had a sufficient anneal. 304 304L 309 310 316L. This decrease in corrosion resistance can only be eliminated by a long anneal. variations within specification of nitrogen content influence the time it takes intermetallic phases to form. Full solution anneal 430.0 6... 309L 420. This speeds welding and minimizes weld and HAZ width. on the order of 0. which causes a decreased surface tension toward the hotter center of the pool..... 309L 309 Mo L 410L. n. 316L 29-4C 2209 2209 25Cr-10Ni-4Mo-N 25Cr-10Ni-4Mo-N 20–40 20–40 6..5%Ar+2.. ...

2 in. aim to ensure full penetration without burn through. and variations in joint geometry impede the swift completion of the weld. It can produce very highquality welds. are especially detrimental and should be removed completely prior to welding. paint. 5. as shown in Fig. The chemistries of both base metals and filler metals are carefully formulated to produce the mechanical and corrosion properties that these alloys have been designed to produce. Gas tungsten arc welding (GTAW)/tungsten inert gas (TIG) is commonly used for the automated production of stainless steel pipe and tube. Source: Adapted from Ref 5 Welding Processes All stainless steels should be very clean prior to welding. It is versatile and generally used when thicknesses are less than 6 mm (0. Joint design does not differ in principle from that of other steel weldments.). This is called the unmixed zone. Preheating is never strictly forbidden since it is required to eliminate moisture. good welding technique. Furnace anneals of about an hour are required. For alloys like 304L and 316L. however an increased need for dimensional uniformity for the alloys susceptible to intermetallic precipitation since minimizing time at temperature is a priority. and nitrogen. It is best performed with the DCSP (direct current straight polarity) electrode negative Critical pitting temperature in 6% FeCI3. solidification segregation can also cause microscopic regions to be poorer in corrosionresisting alloying elements chromium. roughly the difference between 304 and 316 in performance. This is also true for alloys that are susceptible to excessive grain growth. This effect is minimal for low-alloy material. or to sensitization. the corrosion resistance is lower depending on total alloy level and sulfur content. which means up to 10 °C (18 °F) decrease in critical pitting temperature.003% are going to result in decreased pitting resistance of 1 to 5 PREN (pitting resistance equivalent number). These. oil. This also applies to girth welds done by the pipe user. In addition to inclusions decreasing weld corrosion resistance as mentioned. 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 −5 1 Welded 2 3 4 5 6 Molybdenum. Source: Adapted from Ref 4 In-line induction annealing is insufficient for this purpose. wt% 7 Fig. but for highly alloyed austenitic grades. including the more sensitive alloys. which in turn can alter corrosion and mechanical properties and compromise the entire structure.208 / Stainless Steels for Design Engineers Fig. Moisture. that is. A constant-current power supply is preferred. °F Unwelded 194 185 176 167 158 149 140 131 122 113 104 95 86 77 68 59 50 41 32 23 Critical pitting temperature in 6% FeCI3. 4 Metal flow directions in a weld pool with (left) and without (right) sulfur. it is a major effect. Welds are essentially a casting in the midst of wrought material. Figure 6 shows some joint designs appropriate to stainless steels. molybdenum. Eliminating this effect requires a thorough homogenization anneal. Cutting fluids. 5 The influence of molybdenum on critical pitting temperature. and good procedural qualification. the user should always require material chemistry certifications and assume that any sulfur levels above 0. The use of filler metal with higher corrosion resistance does not totally offset the influence of welding on corrosion resistance because some of the base metal melts and is not altered in composition by the filler metal. There is. such as the stabilized ferritics. °C . It is essentially a zone with properties equal to that which would occur in an autogenous weld. dirt or grease. like all joint designs. especially sulfurized oils. as well as manual short runs. Virtually any contaminant can either interfere with the welding procedure or detrimentally alter the composition of the welded joint. and oxides all can negate good material.

. mm (in. The weld pool exposes a great deal of surface area to the atmosphere in a very turbulent manner. GTAW. The weld metal alloys are not necessarily the same as the parent alloys but are chosen based on their ability as weld metals to provide the most acceptable corrosion and mechanical properties. mm (in. If consumable electrodes are used. 1–2 1–2 1–2 1–2 2–3 1–2 2–3 1–2 . mm (in. Intermittent wire addition can lead to creation of zones of essentially autogenous weld.. 1–2 1–2 1–2 5 1–3 1–3 3–5 1–3 1–3 3–5 .A. For manual GTAW using a filler wire..) Root K... SMAW. the wire should be fed continuously into the weld pool. Moving the tip of the wire in and out of the protection of the gas shield is especially . shielded metal arc welding Fig. ..) Bevel α(°) GTAW t d 3–5 3–5 3–4 4–15 3–8 5–12 9–12 >10 >10 >10 >25 >25 >25 >3 >3 >3 3–15 25–8 3–12 4–12 12–50 >8 >12 >10 1–3 1–3 1–3 1–3 1–3 1–3 0 1.....7 to 2. ... SAW. 6 Joint designs. submerged arc welding....) Gap d. usually 12 to 18 L/min. .Chapter 17: Welding / 209 Groove Process Thickness th. Gas flows. Thoriated electrodes containing 1. . negating many of the benefits of filler metal addition. 55–65 60–70 60–70 60 55–65 60–70 80 10–15 10–15 10–15 ... It is helpful to incorporate a highfrequency circuit to aid in establishing the arc. .. the shielding gas precludes the need for coatings. Courtesy Ugine S.. technique.5–3 0 1–3 1–3 0 0–2 0–2 0–2 2–3 2–3 2–3 2–3 1–2 1–2 1–2 1–2 . This sometimes means using austenitic filler with a ferritic base or higher nickel content in an austenitic or duplex base to compensate for the solidification rate or inherently lower corrosion resistance of the weld. 60–70 60–70 60–70 70–80 10–15 10–15 10–15 10–15 GMAW SMAW a SMAW GTAW GMAW d SAW a SMAW GMAW SAW SMAW GMAW SAW GTAW t k d a k d r = 6-8mm GMAW SMAW d a SMAW GTAW GMAW d SAW SMAW GTAW GMAW a d r = 6-8mm SAW GMAW.. must be adequate to prevent air infiltration by aspiration or turbulence before arc contact. gas tungsten arc welding.5–3 1. ideally until temperatures cool to below oxidation temperatures... The shielding gas must replicate the controlled gas mixtures used to refine stainless steel and establish the original composition... gas metal arc welding.2% thoria are recommended because they have better emissive properties and provide better arc stability at higher currents. . . .

Short-circuiting transfer uses arc contact with the workpiece at low power to melt the electrode. and therefore limits the technique to horizontal orientations and thick material. However. it resembles resistance welding in that both have minimal HAZ and very high quenching rates.210 / Stainless Steels for Design Engineers bad. gases can be argon/25% carbon dioxide for horizontal welding with current and voltages from 150 to 200 amp and 22 to 38 V. This method has great versatility with some trade-off in cost and quality. the FCW filler metal. The effect is to undercool the molten metal and suppress the transformation that would normally occur. which can be detrimental to toughness. the flame can be made nonoxidizing for low-alloy steels. Metallurgically. freeze in their high-temperature ferrite structure because the fast quench prevents the nucleation and growth of austenite. uses oxygen to accelerate fuel (typically acetylene) combustion to produce temperatures that can melt steels. excessive protrusion of the wire should be avoided. Unless this ferrite is heated to permit austenite to form. Shielded metal arc welding (SMAW) is done manually with short lengths (“sticks”) of coated electrodes. The equipment is the same as for GMAW. and gravity deposits the molten metal to the workpiece. In fact. Resistance welding is readily done on most types of stainless steel. both of which can have a pronounced effect on some types of stainless steel. Thus. the shielding requirements are reduced. and material transfer ceases. It is possible to get high-carbon welds. Because of the flux. It is restricted to horizontal orientations and requires postweld slag (flux) removal. Flux cored wire (FCW) welding is a method that is able to accommodate a large range of thickness and orientations while providing high deposition rates. “torch” welding. This is done with high power. have deep. after which the short circuit is broken. an austenitic alloy that normally solidifies in a ferritic mode before transforming to austenite freezes directly as austenite. including corrosion evaluation. defeating the action of the shield gas and impairing weld quality. Spray transfer uses a high current to form a stream of fine drops from the end of the electrode. Thus. Gas metal arc welding (GMAW) is arc welding in which a consumable electrode provides larger amounts of filler weld metal than practical in GTAW. Vertical welds can use 100% carbon dioxide with amperage of 60 to 110 amp and voltage of 20 to 24 V. as for pipe and tube or high-production manufactured items. SAW may be preferable to multipass techniques for alloys such as duplex for which time at temperature is limited. Most resistance welds. but the consumable electrode. lower-toughness welds will result. Submerged arc welding (SAW) employs a consumable electrode immersed in a conductive flux that acts as a protective shield from the atmosphere. otherwise. The arc is struck through the flux. It is a low-heat process suitable for thin material but may cause lack of penetration defects if used for thick-section welding. laser welds quench the material so rapidly that corrosion resistance is enhanced since inclusions cannot nucleate and grow. So. Ferritic. such as air-bag canisters. and PH alloys are not harmed by the rapid quench. but the lack of shielding gas may introduce oxygen to the weld metal. The possibility of crevice . Flow rates of gas are 20 to 25 L/min. including both seam and spot welds. on the other hand. is critical. tight crevices adjacent to the welds. The large weld pool has high heat input and can deposit large amounts of metal relatively quickly. Oxyfuel gas welding (OFW). the full benefit of the inert gas shielding may be lost. resulting in a large fluid weld pool. martensitic. This last aspect is arguable. The freezing is so rapid that the normal hot shortness of austenitic solidification is avoided. Laser welding has become a major production method when it can be automated. respectively. which may not resist corrosion as well as desired. the OFW process is not suitable for use with stainless steels. By controlling the fuel-air mixture. The hot tip can carry oxides and nitrides into the weld. so as always. There are three GMAW techniques: • Pulsed arc transfer • Spray transfer • Short-circuiting transfer Pulsed arc transfer employs a power source that is switched rapidly to provide transfer of weld metal droplets at regular intervals. Duplex alloys. weld qualification. For all GMAW processes. Allowance must be made for the lower thermal and electrical conductivity of stainless steels compared to other common materials. these “neutral” flames can simultaneously oxidize and carburize stainless steels. has a flux core that supplements the shielding gas. so quality is not compromised. The technique creates a minimal weld pool and is viable in many orientations.

welding of stainless steels presents a special hazard: hexavalent chromium. while the iron oxide helps flux the refractory chromium oxide. All of the standard NDE techniques used with other materials are applicable to stainless steel weldments. Soldering and brazing are possible with all stainless steels. pharmaceutical production. the flux must be thoroughly removed to prevent subsequent pitting corrosion. Exposure to and inhalation of stainless steel welding fumes must be avoided. silver. This is opposite from the situation in low-alloy steels. Hexavalent chromium is a carcinogen and regulated by the Occupational Safety and Health Administration (OSHA). Thermal cutting of stainless steels also generates hexavalent chromium. The best range can be determined from examining temperature ranges to be avoided in the thermal processing chapter (Chapter 13) of this book. The fume created by welding stainless steel contains significant concentrations of chromium trioxide and other forms of hexavalent (Cr+6) chromium. Positioning and operation of the fume extraction device must be done precisely to ensure effective fume removal while avoiding excess turbulence. low-carbon martensitic alloys for line pipe have been developed with . Combustion of the iron increases the temperature. Nondestructive Evaluation (NDE) is used almost universally to ensure weld quality. The high temperatures attainable with lasers or plasma arc torches provide good cutting action. and other contaminants is advisable. Fluxes are typically acid type with chlorides. lead. and careful attention should be given to the potential for galvanic and other forms of corrosion when considering the use of soldered or brazed joints with stainless steels. Thermal cutting of stainless steels is routinely practiced. typically by grinding or milling. or antimony or combinations of several of these. In addition to the normal hazards (which are not discussed here) associated with welding. The possibility of entrapment of foreign material and the difficulty of removing it from such crevices should also be considered. Brazes and solders rarely match the corrosion resistance of stainless steels. Thermally cut edges of stainless steel usually require subsequent cleaning. Brazing temperatures must be chosen to avoid ranges at which unfavorable phases form. Stainless steels may also be cut using oxyfuel equipment if supplemental iron powder is used. Solders are generally alloys of tin and bismuth. High-frequency induction welding of stainless steel is more difficult than for lowalloy steel because of the refractory nature of chromium oxide. supplemental oxygen or nitrogen blast jets may be used. for which the iron oxide melts at a lower temperature than does the iron base metal.Chapter 17: Welding / 211 corrosion in these regions should be considered when contemplating the use of spot welds in stainless materials. and appropriate reference defect standards must be provided. fume deposits. Soldering is done below 450 °C (840 °F). etc. However. one technique—magnetic particle inspection—is problematic. while brazing is done above 450 °C (840 °F). Recent developments in stainless steel have been made with weldability as a major consideration. The chromium-rich oxide coating must be removed by a suitable flux for bonding to occur. Brazes are normally either silver based or nickel based. Allowance must be made for the differing physical properties of stainless steels. 2008. To expand the range of thicknesses that can be cut or to increase cutting speed. and similar procedures are required to minimize exposure during such operations. Refer to OSHA for further updates on this limit. The presence of this refractory oxide on the surfaces to be joined makes it more difficult to obtain a defect-free weld. Welding Practices Safety must always be considered when welding. especially in equipment for food handling. which can cause loss of effective inert gas shielding of the weld pool. which has a higher melting temperature than does the stainless base metal. but the processes and parameters used are determined by the refractory nature of the chromium oxides that form on stainless steels. The presence of bands of persistent austenite in martensitic or PH stainless steels can lead to spurious defect indications. Use of fume extraction equipment is generally the preferred method of minimizing hexavalent chromium exposures. and these processes are frequently used. The product exposure limit for hexavalent chromium is 5 μg/m3 as of December 31. Chemical cleaning of all surfaces of cut pieces to remove heat tint. magnetic particle examination of stainless steel welds is best avoided. For this reason. Thus. Highly alloyed. after the soldering or brazing.

REFERENCES 1. The friction stir welding (FSW) process offers the promise of reliable solid-state joining. issues associated with solute redistribution are eliminated. such as S31803. The low carbon makes welds of this material that are tough and do not require tempering. ASM International. Chiba. Stainless Steels. A. ASM Handbook. New developments in welding also have an impact on stainless steels. The relatively low temperatures involved essentially eliminate generation of weld fume (see the discussion of safety). p 786 5. 37.212 / Stainless Steels for Design Engineers the express purpose of use in the as-welded condition. By avoiding melting and resolidification. Aziez and R. Proc. ISIJ 4. such as multiple (GTA or GMA) torch welding. 1992. This makes welding of these alloys much more foolproof than with the early duplex alloys. Corrosion. p 28–34 3. Brazing. 1983.F. Kotecki.J. p 178 . p 677–707 2. Other new welding processes. 1.D. promise greater productivity. Welding. B. laserassisted GMA or GTA welding. Les Editions de Physiques. Sheet Metal Ind. Grubb. the lean duplex alloys have very delayed precipitation of intermetallic phases because of their higher nitrogen and lower chromium and molybdenum contents. Garner. 1981. Feen. D. Int’l Conf on Stainless Steel. 1993. and Soldering.. Vol 6. so girth welds in the field are possible. Likewise. The dual-stabilized ferritic alloys have tougher welds than those stabilized with only titanium or niobium. Welding of Stainless Steels. S. Washko and J. 1991. etc.

and these grades have varying strengths. Used with permission . they come in many different grades (chemical analyses). as does wood. www. Despite the rather crude methods of early production. However. art. This chapter deals with the technology of stainless steel as it pertains to its proper use in architecture. paint. bronze. Stainless steel by definition must contain slightly more than 10% Cr. Stainless steel’s unique combination of beauty. p 213-223 DOI: 10. This is explained in greater technical Corrosion Resistance Corrosion is the life-limiting factor for architectural metals. it re-forms by itself. The ability of stainless steel to resist corrosion resides in its chromium-rich superficial passive layer.1361/ssde2008p213 Copyright © 2008 ASM International® All rights reserved. plastic. say by abrasion. and if it is removed. completed in 1930. one Fig. The passive layer forms spontaneously in air or water.Stainless Steels for Design Engineers Michael F. and other alloys react with the environment and degrade over time. a discipline that must balance aesthetics. stone. the domed top of the Chrysler building still shines undiminished by the harsh coastal and urban climate (Fig. 1). aluminum. lead. strength. and construction. stainless steels are complex. With today’s technology. 1 The Chrysler building with its famous bright stainless details. can choose from a variety of stainless alloys with sufficient corrosion resistance to withstand any environment. With stainless steel. and structural integrity. economy. and lack of application experience involved in its construction. Copyright © iStockphoto. Steel. the material can itself be viewed as a metaphor for architecture. copper. resistance to corrosion. and economy makes it a remarkably appropriate material for uses as diverse as sculpture and concrete reinforcing bar. McGuire. and costs. Allen. appearance. limited alloy options. it is possible to choose a material that can withstand attack from the environment indefinitely. One of the first major uses of stainless steel in architecture was in New York’s Chrysler building. and even CHAPTER 18 Architecture and Construction Summary STAINLESS STEEL IS OFTEN EMPLOYED as an architectural material.asminternational. The success of a building project involves careful planning for the appropriate use of materials.

proper design should be used to exclude the possibility of crevice corrosion. a nobler grade of stainless steel. Stainless steel 2003 (UNS S32003) or an equivalent lean-duplex grade can replace 316 at a cost advantage during times of high alloy cost Table 1 Ranking of common stainless steels by pitting resistance equivalent number (PREN) Alloy 430 PREN 15 439 17 201 17 304 19 316 24 2101 2003 2205 2507 26 28 35 38 PREN stands for pitting resistance equivalent number. • In close proximity to deicing salt use. but the key aspects are that the chromium atoms on the surface of the metal react with oxygen in air and water to form with neighboring iron atoms into a tight. and nitrogen. As alloys become richer in the alloying elements mentioned. even on nearby roadways where vehicle traffic can create airborne particles. The acidity within the crevice increases because of restricted diffusion in and out of the crevice. ionically nonconductive layer that prevents any further oxygen penetration. and high salinity. which mirror these traditional views: • Type 304 should be used for most exterior applications. The strength of the layer in resisting corrosive attack is proportional to several key alloying elements: chromium. including type 430. can be prevented by proper choice of alloy. such as 2101 or 2003. If dependable maintenance is not predicted. such as 2101 or 2003. their ability to maintain the passive layer can overcome the chlorides’ ability to destroy it. just as happens within a pit. Crevice corrosion occurs when recessed spaces are small enough to act like a corrosion pit. Pitting occurs in environments that contain chlorides. A leading architectural metals company (Ref 1) makes the following recommendations. micron-size parts of the surface and then grows by virtue of the more aggressive media that form within them because of the corrosion reaction’s products. The decision criterion for material selection with stainless steel should then be. if the building is subject to saltwater spray. Pitting corrosion. less than 0. These guidelines are based on the admittedly easy availability of these alloys and a lack of concern for cost during times of peak raw material prices. finish. Higher PREN values indicate greater pitting resistance. . • Type 316 should be used within ten miles of saltwater bodies. low rainfall. They contribute according to the following formula: PREN = %Cr + 3. • In the most severe environments—high heat and humidity. Chloride ions compete with oxygen and disrupt the integrity of the protective passive layer. pitting corrosion. This number can be related to resistance to the mildest form of corrosive attack that stainless steel undergoes. and Economy The rule of thumb for grade selection is usually somewhat oversimplified to recommend the use of types 430 and 304 on interior applications. Which grade and finish will exclude the possibility of pitting corrosion at the lowest cost? Then. and 316 where road salts or seacoast effects make a more corrosion-resistant grade necessary. may be used in interior applications. This layer is mere atoms thick and completely invisible. Table 1 ranks a number of stainless alloys by pitting resistance. For projects where quick availability is not more important than cost. Other factors involving strength and fabrication should also be considered.214 / Stainless Steels for Design Engineers detail in this book in the chapters on corrosion. type 304 on exteriors where salt is not a problem. should be used. The buildup of iron and chloride ions makes a very corrosive medium that disables the passive film formation. Pitting is a “weakest link” phenomenon in which corrosion begins in small.3(%Mo) + 16(%N) (Eq 1) Balancing Corrosion Resistance. and design. such as are found in Middle Eastern countries—a grade with a PREN of 25 or above is recommended. However. should be specified. type 316 should be used. and another similar form of corrosion called crevice corrosion.030%. A design that avoids crevices is the best defense. • Specify types with low carbon. and nitrogen to withstand any environment the structure will experience. if welding will be employed. If periodic rinsing will not occur on all exterior surfaces. • Any grade. molybdenum. a nobler grade of stainless steel. Processing Characteristics. molybdenum. 439 and 201 should be considered as viable replacements for 304. The key is to choose an alloy rich enough in chromium. these areas must be washed each spring.

4 polish behaves like 304 with a 2B mill finish. they are extremely uniform from batch to batch. The average atmospheric chloride levels collected in rainwater are shown in Fig. which change in grit coarseness with use. Abrasion has a similar effect. any competent architectural metals supplier will not shy away from the use of specialty grades where appropriate. in times of high nickel prices. or embossed. that both the low-nickel 201 and the nonickel 439 can be used in place of 304. Type 316 welds have the corrosion resistance of wrought 304. It is valuable to know. Further. These architecturally useful surface finishes are produced by the preferred rolled-on. this is not an issue. but it has a significant influence on corrosion resistance and must be factored into grade selection. Balancing Service Environment. Type 316 with a No. To avoid unwanted complications related to grade selection. such as abrasive polishing and embossing. An un-heat-treated weld has lower resistance to corrosion in proportion to the alloy content of the grade. such as during the period of 2004 to 2007. for applications requiring severe forming. unlike finishes produced by abrasive-coated belts. If panel designs call for 90° bends. 2 The decrease in corrosion resistance with increasing surface roughness by abrasion. have correct corrosion resistance for their alloy content. these grades can provide a challenge to the fabricator/installer. this compounds the effect. The Nickel Institute. formerly the Nickel Development Institute. To obtain these grades usually involves working with a producing mill since they are not typically stocked in service center inventories. It should be noted that the leaner alloys suggested (439. Very smooth abrasively polished finishes mitigate this reduced corrosion resistance. this method of surface finishing is recommended. However.Chapter 18: Architecture and Construction / 215 as have been experienced on occasion. and lean-duplex alloys such as 2003) can be somewhat more difficult to form. while 2101 (UNS S32101) and 2003 (lean duplexes) can replace 316. and maintenance on grade selection (Ref 3). 4. 5 (Ref 5). Because welds are abraded. and Maintenance Considerations An expert system has been developed that enables designers and specifiers to analyze the trade-offs of climate. This effort will ensure a viable specification is written that will balance cost with the necessary performance attributes to make the part as well as resist corrosion once installed. 3 for a particular application yields a score that can be used to identify an appropriate alloy according to the scale shown Fig. the specifier should consult a competent architectural metals supplier. In addition to their advantage in corrosion resistance. Answering the questions in Fig. as shown in Fig. these leaner grades can pose challenges with certain finishing methods. design requirements. Source: Ref 2 . 201. Design Requirements. However. 2. method. Reviewing a map of the salinity of rainwater in the United States is instructive of the degree to which geography influences corrosion severity. The highest levels occur along the coastlines of the Atlantic and Pacific Oceans and the Gulf Surface Finish and Corrosion Resistance Surface finish is usually an aesthetic choice. for this reason alone. resistance in abraded stainless steel surfaces is not seen on finishes that are produced by patterns imprinted by hard-rolling mill rolls that have been engraved with the desired pattern in reverse. The effect of reduced corrosion Fig. Welding or abrading the surface degrades the corrosion resistance by a significant amount. also offers excellent publications on topics related to alloy selection for specific service environments and design requirements (Ref 4). as in the case of a double-lock seam on a standing seam roof. Mill finishes such as 2B and 2D are inconsistent because they are annealed and pickled to remove oxides. These unattractive surfaces. however.

Source: International Molybdenum Association (Ref 3) .216 / Stainless Steels for Design Engineers Fig. 3 Stainless steel selection expert system.

while Fig. will stay new looking indefinitely. Surface finish aesthetics are arguably more important architecturally than the influence surface finishes have on corrosion. the height above sea level. The maximum corrosion rate is related to the maximum chloride in the atmosphere. Aesthetic Considerations A correctly chosen grade of stainless steel will have no degradation over time and. 7 shows special finishes created by one manufacturer. . and subtlety. Source: International Molybdenum Association (Ref 3) Fig. and the prevailing winds (Ref 6).Chapter 18: Architecture and Construction / 217 Fig. Finishes vary in reflectivity. Numerous finishes have been developed to try to meet various objectives. 5 Average chloride concentration (mg/L) in rainwater in the United States. This will be related to the distance inland. directionality. Figure 6 shows some of the finishes that go beyond the familiar brushed look (Ref 7). if prop- erly maintained. Source: Ref 5 of Mexico. 4 Grades recommended based on the expert system.

(b) Rolled-in no. 4 finish (InvariBlend). Finish No.8 µm (15 to 30 µin.4 to 0. 3 has a surface roughness average (Ra) of 0. Finish No. Specular gloss at 85° is typically 40 to 60 (per ASTM D 523. 4 calls for 120 to 150 grit abrasive. where the discovery of . (c) Rolled-in moderate-glare finish (InvariLux). 6 Various rolled-on stainless steel finishes. which are traditionally produced by abrading the surface with different grit size abrasives.218 / Stainless Steels for Design Engineers Fig. There is considerable difference in appearance from sheet to sheet. This is crucial in architecture. These are American Society for Testing and Materials (ASTM) designations for abrasively produced finishes. 3 and 4 are directional. and manufacturer to manufacturer. 8 finish.). No. 8 is a mirror finish obtained by final polishing with 800 grit abrasive. coil to coil. 7 The classic abrasively produced finishes are No. “Standard Test Method for Specular Gloss”). with grit lines typically 1 cm (0. The greatest consistency of appearance comes from specifying a brand of rolled-on finish from a given manufacturer. 3. Any of the traditional finishes can be replicated by a rolled-on finish with greater uniformity. Courtesy of Outokumpu Special finishes for 304/304L and 316/316L stainless steels available from one manufacturer. and 8. 3 calls for 80 to 100 grit abrasive.4 in. (a) Rolled-in low-glare finish (InvariMatte). Finishes No. Finish No. Source: Contrarian Metal Resources (Ref 8) Fig. only the method of producing them. with the possible exception of bright annealed having a difficult time matching the mirror quality of a No. 4. Source: Ref 7. The standards for appearance do not exist within specifications.) in length.

such as slightly concave panels or panels with a die-pressed design. D.. in 8 ft. or the Pittsburgh Convention Center (Fig. The degree to which this is objectionable is a function of design. as is normally the case with exterior components.C.Chapter 18: Architecture and Construction / 219 unacceptable visual nonuniformity on large areas can be disastrous.” can cause a very shoddy appearance./–0 in 10 ft or less../–0 in 48 in. Mirror finishes are often used for high impact. such as at Reagan Airport in Washington. such as by “oil-canning. A good standard for flatness that precludes visible distortion is five I units. small deviations from flatness can be very visible. Sometimes. Deviations of sheets from squareness and straightness (camber) are also objectionable because such deviations can cause gaps between panels. Reflectivity or gloss can be a major consideration in the choice of a surface finish. the latter having been developed for airport roofing. Flatness is measured in I units. Maximum camber is 3/32 in. while length is held to +1/8 in. Closer tolerances can be negotiated. Fig. 8 The Pittsburgh Convention Center with low-gloss finish stainless steel roof . Flatness (Iunits) = 2 (πH / 2L) × 105 (Eq 2) where H is the height of the deviation from flatness. but more diffusely reflecting surfaces are more common. Steel producers have various means to produce this level of flatness. Another option to ensure flatness is to back light-gauge stainless steel with a stiff material. especially when this appears late in the construction process. assuming a sinusoidal wave. rather than aiming for high flatness a controlled deviation from flatness is used. 8). Flatness is a special consideration for panels where lack of flatness. Patterned surfaces provide consistent reflectivity from a moderately reflective 40 to 60 specular gloss at 85° to a dull matte of less than 20. and L is the distance between peaks of deviations. the most extreme of which is actually stretching the steel sheet or coil until all distortions are eliminated. and tolerances can be held tightly at a cost. Because stainless in sheet form is usually reflective. Width tolerance is normally +1/16 in.

Rain does not completely clean the surface. Nonscratching cream or polish. The typical remedy is to clean stainless steel with a solution containing light oil and a detergent. such as horizontal surfaces and recesses. alternatively. and it does benefit from proper maintenance. The second reason is that it may harm the surface by allowing corrosion agents to concentrate. Table 2 Requirement polymer coatings are applied to stainless steel at some producing mills to permanently provide a film to which additional fingerprint oil cannot add a noticeable discoloration. the whole surface may need to material and dry. or soft-fiber brush. should be avoided. however. If the oil from a hand contacts the uniformly thin film of cleaning oil. Nylon-type pad Use on brushed and polished finishes along the grain. stainless exteriors should be washed during routine window washing operations. There are two reasons for this. Detergent and warm water. One of the great values of stainless steel is its low cost of ownership. soft cloth. neutralize with diluted ammonia surfactant additions. water marking. Rinse off residues with clear water and dry. no visible mark is left. but it does dilute any harmful contaminants and forestall corrosion from accumulated chlorides. or dilute (1%) ammonia Satisfactory on most surfaces solution in warm clean water. Stainless steel can be abused. A fine abrasive paste as used for car body May brighten dull finishes. • Sheltered areas and areas subject to splatter. nylon or bristle brush on pretreated material. Carbon steel wool and water rinses) pads that have previously been used on carbon steel should not be used. One of the most common complaints about maintenance of stainless is the work involved in removing fingerprints. and light discoloration. 10–15 vol% solution of phosphoric acid. A test should be carried out to ensure that the original surface finish is not damaged. Apply Suitable for most finishes. The obvious first reason is that whatever is soiling the surface is probably not attractive. Avoid the use of solution. nonscratching creams and polishes. light rust staining Localized rust stains caused by carbon steel contamination Adherent hard water scales and mortar/ cement splashes Heat tinting or heavy discoloration Badly neglected surfaces with hardened accumulated grime deposits Paint. Proprietary spray-applied polishes available to hydrocarbon solvent clean and minimize re-marking Hydrocarbon solvent Alkaline formulations are also available with surfactant additions. Avoid chloridecontaining solutions. Use soft. then rinse in clean water and dry. especially roadside spatter. Table 2 provides recommended practices for removing various substances from stainless steel surfaces (Ref 9). Proprietary solutions or solvent paint stripper Apply as directed by manufacturer depending on paint type. The oil from fingerprints makes an easily visible interference film on the reflective stainless surface. rinse with clean water and dry hydrochloric acid-based mortar removers. with soft cloth or soft sponge. Without the benefit of cleansing by rain.220 / Stainless Steels for Design Engineers Maintenance and Repair Maintenance is a significant cost of any structure. the following design considerations are recommended: • Designs that can collect dirt. • Designs that create uneven flow or drainage patterns producing uncleansed areas should be avoided. stains. Apply with a clean sponge. Cleaning methods for uncoated stainless steel Suggested method(a) Comments Routine cleaning of light soiling Fingerprints Oil and grease marks Stubborn spots. Rinse clean to remove all paste appearance. The greatest ally of stainless on building exteriors is the cleansing action of rain. Mild. (a) Cleaning agents should be approved for use under the relevant national environmental regulations and should be prepared and used in accordance with the company’s or supplier’s health and safety instructions. Proprietary formulations available with Use warm. graffiti Soap. rinse Cream cleaners are available with soft off residues with clean water and dry. detergent. Proprietary gels or 10% phosphoric acid Small areas may be treated with a rubbing solution (followed by ammonia and water block comprising fine abrasive in a hard rubrinses) or oxalic acid solution (followed by ber or plastic filler. be treated. To avoid a patchy refinishing. Source: Adapted from Ref 9 . Apply with soft cloth or soft sponge. calcium carbonate additions. Alternatively. should be designed so that they are easily cleanable. Avoid cleaning pastes with abrasive additions. The main objective of the maintenance of stainless is keeping it clean. Given the importance of cleaning.

Austenitic stainless steel keeps the same atomic structure and remains much stronger than carbon steel at elevated temperatures. Fabrication Considerations Fabrication and joining of stainless steel employ the same techniques as for carbon steel and other metals. Thus. This can be remedied by passivation. floor systems. Repair of more severe damage done to surfaces. and austenitic stainless steel ladders under load and exposed to flame temperatures of more than 1000 °C (1830 °F). • Separation of tools and work areas between those used for stainless steel and carbon steel is prudent. Certain processing principles related to architectural and building applications of stainless steels should be emphasized: . The specifics of cutting. as carbon steel is. Fasteners should not be permitted to cause distortion of flat panels. If a decorative surface pattern has been damaged. Even welds can be removed and reblended to be indistinguishable from the surrounding original surface. The plastic and aluminum ladders failed in less than a minute. Contamination of stainless surfaces with carbon steel from welding. forming. and aluminum will corrode more readily than the stainless. gratings.Chapter 18: Architecture and Construction / 221 • Contamination by rust from carbon steel is corrosive and must be removed. catastrophic failure ensues. austenitic stainless steel has great value as a material for structures that must retain structural integrity in a fire. and welding are described in the processing section of this book and are not repeated here. The ability to be repaired should be a top criterion in the choice of a surface finish whose appearance is critical and that may be subject to damage. and proper weld finishing is essential. A second aspect of higher strength and lighter gauge is greater spring back in forming operations. The main distinction in the use of stainless steel in this regard is that its higher strength and corrosion resistance permit the use of lighter gauges. such as scratching. While any structure would benefit from these guidelines. the usual tool available for field repairs. • Fasteners used with stainless steel should also be stainless steel. The resulting corrosion products are also harmful as well as unsightly. It is used on offshore oil platforms for stairways. galvanized steel. and cutting can stain the surface of stainless steel and result in corrosion. Galvanized steel. grinding. Ordinary carbon steel undergoes a phase change at about 760 °C (1400 °F). and it is virtually impossible to match the pressure. such as press braking. walkways. aluminum. and arc of contact that created the original surface. handrails. and this corrosion is aggravated by galvanic contact. The ability of contactors to produce sound. stainless steel becomes the material of choice. This in turn permits designs in hollow or rolled-formed sections. joining. attractive welds is an indicator of their overall competence with stainless steel. soldering. grit size. which has a very consistent grit length and depth. they are especially valuable in maximizing the benefits of stainless steel. These have very long grit lines. ladders. • Welding is better done in the shop than in the field. Correct filler metals must be used. • Designs should facilitate easy access for cleaning. so grit length is easily duplicated with a belt sander. but it is much better to avoid it in the first place. while the stainless steel remained intact (Ref 10). The reason for that is mainly that abrasive finishes are applied by rotating belts. the challenge is in trying to replicate it in the field. Stainless steel is the only common building material that remains strong and tough at temperatures encountered in fires. If the need for fire resistance is serious. The galvanized carbon steel lasted 5 min. This can literally pull a building apart. which have higher stiffness and low weight and potentially lower overall cost than using less-expensive metals. Additional Service Considerations Fire resistance is an important consideration in buildings. It can be more nearly done to a surface with a rolled-on finish. The exception to this rule are abrasively applied or rolled-on long-grain finishes. When this occurs to a structure already weakened by heat. Very few surface finishes are wholly repairable in the sense that they can be repaired in a spot so that the repair is invisible. Tests have been conducted on glass-reinforced plastic. This change in atomic structure results in a sudden shrinkage of more than 1 linear percent. is difficult. carbon steel.

9 Graphic depicting low release of metal ions from two grades of stainless steel (304 and 316) to the environment. 430. In bridges. lead coatings. low-nickel grade. such as 409. and Michigan. because it does not corrode when properly used. based on a 4-yr multidisciplinary research project involving both field research and laboratory studies. Stainless is a material that will never come back to haunt an architect years later. The use of even these alloys reduces the longterm cost of these structures. living modules. New Jersey. Ecological considerations are never trivial when considering a construction material. the expansion of the corrosion products spalls the concrete. can be used. Concrete Reinforcing Bar Concrete reinforcing bar is one of the least glamorous uses of stainless steel in structures. does not enter the environment. or 201. which affects a tiny percentage of the steel volume. so the future adoption of less-expensive stainless steels holds great promise.222 / Stainless Steels for Design Engineers Fig. Canada. and so forth. Ontario. the stainless in the structure will be recycled. it has been the object of interdisciplinary studies that have demonstrated its innocuousness even under conditions of heavy acid rain on freshly abraded surfaces (Fig. If the internal rebar corrodes. A more certain approach is to use stainless steel rebar. such as 316 and 2205. usually by corrosion. leading to the failure of the structure. . and others are once-accepted materials whose long-term effects have been dangerous and costly. Stainless steel. 9) (Ref 11). Its intrinsic raw material content value ensures that even with the end of the life of a structure. and other concrete structures. and enter the general environment. and moderate cost. parking garages. resistance to corrosion and SCC. Asbestos. Therefore. Many materials used in buildings degrade environmentally. saltwater can penetrate the cement over time. The lean duplexes are ideal for this application because of their high strength. Source: Ref 11 firewalls. This can be delayed by treating the concrete to repel the incursion of water or by coating the carbon steel rebar with epoxy. blast walls. While this seems obvious. The stainless steel for this duty need not resist pitting corrosion. These are less than 100% effective. an inexpensive. The more enlightened transportation departments in the United Kingdom. lead-based paints. and Oregon in the United States have led this development. Most of the work to date has been with more expensive grades.

nickelinstitute. ASM International. www.Chapter 18: Architecture and Construction / 223 REFERENCES 1. 9. www. Nickel and Iron from Stainless Steel Exposed Under Atmospheric Conditions and the Environmental Interaction of These org. accessed June 2008 D.l-v.H. accessed June 2008 .metalresources. John Wiley and Sons. Ailor. 2. www. Atmospheric Corrosion. 2005. Griffin. accessed June 2008. p 42–60 Guide to Stainless Steel Finishes. Guttman. Ed. “Which Stainless Steel Should Be Specified for Exterior Applications?” International Molybdenum Association. www. The Nickel Institute. accessed June 2008 Contrarian Metal Resources.metalresources. accessed June 2008 5. www. Stainless Steel Selection Contrarian Metal Resources. 1982. Atmospheric and Weathering Factors in Corrosion Testing. accessed June 2008 The Nickel Institute. Euro Inox. org. Houska. ASM Handbook. Release of Chromium. Vol 13C. W. www. imoa. accessed June 2008 Care and Maintenance of Stainless accessed June 2008 4. 1985. 8.eurofer. H. org. Leda-Vannaclip.euro-inox.. p 3–12 3. Corrosion: Environments and In- 7. R. Corrosion in Marine Atmospheres.B. 2006. C.. dustries. p 51 6.nickelinstitute. Berggren et al. 10. 3rd ed. www. Bulletin of the National Dairy Federation 189.. Oct 2004. www. net. European Confederation of Iron and Steel Industries.

as automobiles became more sophisticated technically and as durability and environmental demands grew. Soon. lighter weight. Exhaust systems constitute the largest use of stainless steel in the automotive market. and Laws enacted in the United States in the 1970s mandated automotive emission standards that could be met only with catalytic converters. So. The compelling need of the automotive industry for economy drove the widespread adoption of argon oxygen decarburization (AOD). hose clamps. However. hardware. p 225-232 DOI: 10. Exhaust Systems Introduction The use of stainless steel in automobiles used to be mainly a story of decorative applications: wheel covers and trim with a minor amount used for valves and hose clamps. they would last the life of the vehicle. thermal fatigue resistance. the role of stainless became increasingly functional and less ornamental. seat belt and air bag components. Stainless alloys in common automotive use now are generally highly engineered for their specific application and represent some of the most highly evolved applications engineering in any use of stainless. and filters. This has required subsystems. or resistance to the corrosion of new fuels. the auto manufacturers have become the largest users of stainless steel. since exhaust systems currently predominate. An examination of the preferred practices in materials selection in automotive systems is an excellent example of the rule of using the simplest and lowest alloy content grade that can do the job. and formability. there will be new applications that respond to new socioeconomic needs. to resist more corrosive environments for longer periods of time. McGuire. tubing. Because automotive and steel-producing engineers have collaborated so well. www. rendering obsolete an entire muffler replacement industry.asminternational. both parties have benefited greatly. they are covered first. even while the traditional automotive uses . stainless steels may be required to endure the corrosive environments. and other highvolume methods of the carbon steel industry. oxidation resistance. emerge. From AlleghenyLudlum’s MF-1 evolved a succession of ferritic alloys that grew in sophistication to meet the increasing needs of corrosion resistance. but there are other important applications that cannot be ignored: valves and CHAPTER 19 Automotive and Transportation Applications Summary THE ADEQUATE DURABILITY and life span of cars.Stainless Steels for Design Engineers Michael F.1361/ssde2008p225 Copyright © 2008 ASM International® All rights reserved. often. the continuous caster. entire exhaust systems were made of stainless. such as fuel cells and ethanol. such as for greater crash worthiness. or any transport system requires freedom from corrosion. But. The only practical materials that could withstand the temperatures of the hot end of an exhaust system using a catalytic converter were stainless steels. The main result has been a strong growth in the use of the leaner ferritic stainless steels in many components. trucks. such as those for exhaust and fuel. And. As more exotic propulsion systems and fuel. creep. as have consumers.

are optimal for oxidation resistance. it should be noted that ferritic stainless steels. The temperature of this breakaway increases as chromium content increases. but also the oxygen and sulfur from solution. Their formability is further enhanced. resistance to external corrosion. aluminum. The stainless steel industry was changed from a boutique industry to a mass production industry by its embracing the needs of the automotive market. • Ferritic stainless steels have very anisotropic forming properties. They resemble highformability carbon steels in that they tend not to thin when stretched. which the designs of exhaust system components require. we revisit only the main points that are relevant to alloy selection for exhaust systems. which could preclude successful catalytic conversion downstream. • The σ phase does not readily occur in alloys containing less than 20% Cr. especially those containing molybdenum and aluminum. Cold work accelerates the formation of this phase. and ductility decreases. and a muffler. Niobium is used to costabilize and fight creep. and molybdenum also increases oxidation resistance.226 / Stainless Steels for Design Engineers of stainless steels—wheel covers and other ornamental trim—faded to nearly nothing. Special thermomechanical processing is also used to optimize texture and grain size. We will see that other alloying elements can also improve this performance. At the outset. brittle phase called α’ in a process commonly called 885 °F (or 475 °C) embrittlement. but these elements have the same detrimental effect on ductility while increasing hot strength. . At the breakaway temperature level. a catalytic converter to reduce NOx and CO emissions. scale growth is no longer parabolic with time but becomes linear and therefore no longer protective. The intact scale of ferritic stainless is thus protective up to the temperature at which oxygen diffusion through the scale becomes great enough so that “breakaway” oxidation occurs. but yield strength also increases. each of these are connected by piping. An exhaust system normally consists of a manifold to collect exhaust gases. resistance to oxidation. and mechanical properties. • Niobium above that needed for stabilization is a powerful solid solution hardener and is effective at high temperatures. This prevents the fracturing and spalling of the scale. Rather than reexplain these concepts here. The exhaust manifold must possess good high-temperature strength and resistance to thermal fatigue. Titanium stabilization greatly improves corrosion resistance by removing not just the carbon and nitrogen. and copper. It must also be able to resist oxidation at the exhaust temperature. Because the alloys have evolved so well to fit the individual requirements for each component. which greatly assists in formability. combusted gases from the engine and delivers them to the front pipe. resistance to internal corrosion. which can reach 950 (C (1740 (F). so does resistance to oxidation and corrosion. • Alloying with silicon. This prevents sensitization and makes all the chromium content useful as alloy. so it is not a consideration for exhaust systems unless silicon or molybdenum are also elevated. Exhaust manifolds had previously been heavy castings but are generally now formed from stamped sheet stainless steel or formed from welded tubing that may have a double-wall structure to insulate the gases from heat loss. It is not a difference in the oxide scale. • Coating ferritic steel with aluminum is effective in preventing oxidation and corrosion. nickel. Not only are the steels in exhaust systems almost exclusively ferritic. when necessary. The metallurgy of ferritic stainless is discussed in depth in Chapter 8. These alloys are therefore essentially interstitial free and have excellent formability. the use of stainless in automobiles grew to about 30 kg (65 lb) per vehicle by the turn of the century. they are also stabilized by titanium or niobium. • Ferritic alloys can form a hard. The reason is that the thermal expansion of ferritic stainless more closely matches that of the oxide scale than does that of austenite. Each component of the system has different requirements for formability. we discuss them segment by segment through the exhaust system. This is only a factor in alloys with chromium of 18% or more. • As chromium level increases. This sharply improves resistance to pitting corrosion. by low additions of tramp substitutional alloying elements such as manganese. The exhaust manifold collects the hot. as opposed to austenitic. All these factors come into play in the design of exhaust systems. especially cyclic oxidation.

• formability • • • Oxidation resistance. • formability. dual-stabilized T409) • 409 ALMZ (aluminized 409) Source: Adapted from Allegheny Technologies Inc. Table 1 lists a number of the grades of stainless steel commonly used in exhaust systems and where they are used.4509. from inner and outer surface • 409HP (UNS S40930. oxidation resistance.4509. dual-stabilized T409) 409 ALMZ (aluminized 409) T439HP (UNS S43035. common name (related designation) High-temperature strength. thermal shock resistance Salt damage resistance Catalytic converter substrate 1000–1200 1830–2190 • ALFA-IV (FeCrAl) Center pipe 400–600 750–1110 Muffler 100–400 210–750 Corrosion resistance. 18CrCb) Type 304/304L (UNS S30400. salt • attack resistance • High-temperature • strength. thermal • fatigue strength.4509) 18CrCb (DIN 1.4509) 18CrCb (DIN 1. formability Flexible pipe 600–800 1110–1470 Catalytic converter shell 600–800 1110–1470 • • • • • • • High-temperature • strength. S30403. 18CrCb) 444 (UNS S44400. The alloys are listed in order of increasing severity of the requirements for each major system component. T441) 433 (T443) Front pipe 600–800 1110–1470 High-temperature strength. S30409) 321 (UNS S32100) 309S (UNS S30908) 310S (UNS S31008) 332Mo (S35125) 600 (N06600) 601 (N06601) 625 (N06625) 409 ALMZ (aluminized 409) T439HP (UNS S43035. 18CrCb) 444 (UNS S44400. Risk of such damage is due to the intermittent use of vehicles. 18CrCb) 441 (DIN 1. oxidation resistance. which causes cyclic oxidation and the ensuing spalling of the oxide scale. • oxidation resistance. from inner and outer surface • • • • • • • • • • • • • • 409HP (UNS S40930. T441) 433 (T443) 409HP (UNS S40930. There are numerous alloying approaches for optimizing the ferritic stainless alTable 1 Component loys for spalling resistance. thermal fatigue strength.4509) 436S (type 436S) 444 (UNS S44400. S30403) Tailpipe 100–400 210–750 Corrosion resistance. 18CrCb) 441 (DIN 1. . dual-stabilized 409) T439HP (UNS S43035. the exhaust manifold must possess the greatest resistance to high-temperature oxidation damage. All approaches involve raising chromium content but use different techniques to enhance the effect of chromium.4509) 18CrCb (DIN 1. T441) 433 (T443) 304/304L (UNS S30400.4509) 304/304L/304H (UNS S30400. salt • attack resistance. S30403) T321 (S32100) 316/316L (S31600/S31603) 316Ti (S31635) 332Mo (S35125) 625 (N06625) 409HP (UNS S40930. dual-stabilized T439) 436S (T436S) 441 (DIN 1. dual-stabilized 439) 441 (DIN 1.4509. formability • • • • • • • • • • • T439HP (UNS S43035.Chapter 19: Automotive and Transportation Applications / 227 As the highest-temperature component of the exhaust system. dual-stabilized T439) 441 (DIN 1. dual-stabilized T409) 409 ALMZ (aluminized 409) T439HP (UNS S43035. Alloys normally used for the major elements of automotive exhaust systems Service temperature Exhaust manifold ºC 750–950 ºF 1380–1740 Requirements Alloys currently used. thermal fatigue strength. dual-stabilized 439) 18CrCb (DIN 1.4509.4509. dual-stabilized 439) 18CrCb (DIN 1.

aluminum. The tailpipe is exposed to view in most vehicles. The catalyst itself is supported by a ceramic and ferritic stainless steel carrier that must resist thermal shock and possess low heat capacity for rapid heating. the housing. the basic type 439 (UNS S43036) Either of these basic alloys can enjoy enhanced oxidation resistance by additional alloying with molybdenum. the worst of which comes from road salt or coastal salt sources. We attempt to simplify the choices. whereas aluminum or silicon additions do not improve that trait. To reduce exhaust noise. The material used must have exceptional formability to be formed into a bellows. It consists of a double-wall pipe in a bellows configuration with an outer covering of braided stainless steel wire. The object here is to avoid visible corrosion. Chromium or molybdenum alloy additions increase corrosion resistance. This is an exothermic reaction at temperatures equal to those in the exhaust manifold. an austenitic such as 304 can be used. The function of the flexible joint is to prevent vibration from the engine from being transmitted to the rest of the exhaust system. and it has the aesthetic benefit of not showing red rust. Aluminum coating is a powerful corrosion fighter. Use of molybdenum or niobium enhances high-temperature strength. but not the same risk of thermal fatigue. All alloying additions detract from formability and toughness. the basic alternatives for exhaust system alloys are: • Straight chromium alloying at 11 to 12% with stabilization by titanium or niobium. as can chromium plating or aluminizing. On short runs. and its appearance is therefore important. the objective must be to use only those alloying elements that are indispensable to performance. but the condensing water vapor creates an internal corrosion risk. After startup. The muffler must withstand corrosion from the outside. acidic environment. Exotic alloys of 20% Cr with 5% Al are used for the carriers. For this reason. making thermal fatigue a problem. this may not occur. they can be coated with hot-dipped aluminum-silicon alloy to increase oxidation resistance. Internal corrosion is also a major consideration because condensing exhaust gases create a hostile. while not requiring great hot strength. The housing is generally made of a 17% Cr ferritic stainless. and internal corrosion ebbs. so a heat shield of type 409 is used to separate it from the floor. so it must resist hot salt corrosion. This represents a worst case for internal corrosion. or silicon. The flexible joint is also exposed to road salt in some regions. a double-wall pipe is sometimes used for this component. which complete the combustion of the gases to form less-noxious compounds. The cooling exhaust gases no longer present a major oxidation threat. must resist oxidation. Alloys with these additions are thus useful for manifolds with a design that constrains expansion and contraction. next in line. This may force the use of 316L versus the normal choice of 304L. However. The converter is usually directly beneath the passenger compartment. In addition. It must have very good high-temperature fatigue strength to withstand the cyclic stress of the vibration it absorbs. a simple grade such as 409 should generally provide sufficient resistance to this environment. . they do not present any challenges not already confronted and solved for passenger vehicles. It exposes the exhaust gases to noble metal catalysts. Thus. Truck exhaust systems are beginning to require similar technical sophistication as their emissions come under increased regulation. The flexible joint is the one segment of the exhaust system for which austenitic stainless steels are preferred. The dual internal and external corrosive attacks require the use of aluminized stainless for best performance. Thus. as well adding to basic material costs. presents only a corrosion issue. The muffler. The greater hot strength and formability of austenitic steels thus prevails. the basic type 409 (UNS S40920) • Straight chromium alloying at 17 to 18% with stabilization by titanium or niobium. the heating of the muffler to temperatures above 100 °C (212 °C) evaporates these condensates. Thus. and road salt presents an external one.228 / Stainless Steels for Design Engineers The best choice for a given design is not obvious. However. The catalytic converter is the next component of the exhaust system. The center pipe conveys the converted gases to the muffler. The front pipe connects the exhaust manifold to the flexible joint and experiences nearly the same temperatures as the exhaust manifold.

Type 301 in the annealed condition is actually the original transformation induced plasticity (TRIP) steel as it can be tailored to have a controlled level of austenite stability.131 1.e. those that most easily transform to martensite during deformation) is shown in Fig. The value of a material as an energy-absorbing structure (i. but this characteristic would be insufficient in many cases without considering mechanical properties.726 364 269 . then this characteristic makes 301.16 1. it has become the standard material for seat belt anchors and hose clamps. Table 2 Comparison of tensile properties of carbon steels and stainless steels for automobile structural components Type Thickness. 201 and 301. j/m3 Carbon steels TRIP 700 DP 750 DP 800 Austenitic stainless steels HyTens X HyTens 1000 Source: Ref 1 0.. even if stainless steel were not corrosion resistant. or aircraft aluminum alloys.4 8.3 38. Indeed. Tables 2 and 3 show the properties of specific variations on basic 301 developed by Outokumpu and how they stack up against the most competitive carbon steels. and TRIP steels (Ref 1).55 306 639 937 1068 1429 1377 52.48 1. Across the board. titanium. When crash worthiness becomes a prime consideration. giving not only a very high work-hardening rate but extraordinary resistance to localized thinning.e. The kinetic energy of a collision that a structure can absorb in deformation is proportional to its strength multiplied by the amount it can deform before fracturing.58 1. This allows it to transform at a known rate to martensite during deformation. Austenitic stainless steels are the toughest and stiffest practical materials available to the automotive engineers. The superiority of metastable stainless steels (i.8 9. more varied applications for stainless in automotive engineering. Even with its lower density.Chapter 19: Automotive and Transportation Applications / 229 Structural Components The driving forces of durability.536 1.9 1.2% proof strength. MPa True stress at ultimate tensile strength. or less formable.. less durable. In this higher-strength condition.9 59. necking. % Carbon steels TRIP 700 DP 750 DP 800 Austenitic stainless steels HyTens X HT 1000 Source: Ref 1 1. and weight reduction have spawned other. J/m3 Toughness. MPa Ultimate tensile strength. or its low-nickel counterpart 201. energy-absorbing components since austenitic stainless can be rivaled for such applications only by heat-treated alloy steel.4 13. Common 301 can be cold worked to yield strengths anywhere from its annealed level of about 300 MPa (44 ksi) up to 2000 MPa (290 ksi). all of which are more expensive.32 105 101 74 0. one that enhances crash worthiness) is measured by the energy it can absorb per unit of mass.6 Table 3 Comparison of resilience and toughness of carbon steels and stainless steels for automobile structural components Type Resilience.9 17 18.5 28. an ideal material for structural.996 1. safety. % Total elongation. and therefore fracture. 1. the main distinguishing trait of stainless that qualifies it as the optimal material is its corrosion resistance. MPa Uniform elongation. its superior strength and toughness would qualify it for many automotive applications. aluminum falls far short of austenitic stainless in energy absorption per unit weight.44 473 513 573 703 811 896 818 920 976 16. mm 0. dual-phase steels.

Source: Ref 1 These exceptional strength-to-weight and energy absorption-to-weight characteristics permit automotive engineers to reduce weight and increase crash worthiness while designing vehicles with greater life span—because corrosion resistance “comes along for the ride. if the entire system is stainless and the investment is avoided. but the initial cost of the bus was lower. The design key was to use rectangular 304 stainless structural tubing. Audi. 1 True stress-true strain curves for 301 variants (HyTens X and HyTens 1000) versus two duplex carbon steels (DP750 and DP800) and a transformation induced plasticity (TRIP) steel (TRIP700). The use of stainless steel in strategic components enables greater weight reduction than that which the vehicle would have in all aluminum. engineered various components of austenitic stainless steel into its otherwise aluminum-intensive A6 series. However. Designers began the conversion to gain the normal advantages the stronger stainless gives: over 10% lighter weight and over 10% improvement in crash worthiness of the passenger compartment. not only was the long-term cost of operating the bus lower. Another manufacturer. and lower rear wishbones in its Carrera GT. The incremental savings of eliminating coatings on individual body components is thus essentially nil.230 / Stainless Steels for Design Engineers Fig. Now. stiff sections to be welded into space frames. buses are 80% stainless. While it is probably apparent to the reader that essentially any body component can be made in stainless and be made better in stainless. Volvo and Saab have designed austenitic stainless steel bumper systems that also serve to reduce overall vehicle weight. then the initial cost of a stainless body actually can be lower than one in coated carbon steel. internal push rods on front and rear axles. the accompanying savings in fuel consumption. the question of when doing so is a better engineering decision involves economic considerations. coating and painting could be eliminated. Now. which allowed strong. The economic analysis is shown in Table 4 (Ref 2). Porsche uses austenitic stainless steel for front and rear side members. Large automotive companies generally have large fixed investments in painting and coating systems to protect entire bodies from corrosion. This is the experience of Italian bus manufacturers. This swung the economic pendulum to stainless in a major way. A stainless bus body is shown in Fig. .” as it were. 2. Some components in which these virtues are most readily exploited are bumper systems (Ref 2). and the virtual elimination of body maintenance. who began in the 1980s using 304 stainless steel in buses. It is only a matter of time until this is improved on by the use of 201 (with 3 to 4% Ni instead of 8 to 9% Ni) to lower cost and cold working of the tubing to achieve higher strength levels. With essentially the entire body now in stainless.

391 28. The engineering basis for this is the same as for buses: high strength. Manufacturers of trailers would be well advised to consider upgrading to duplex grades such as 2003 or 2205 or to cold-worked austenitic stainless. These vehicles are prized for their ability to be driven and parked in very small or congested locations.838 10.322 2. no coating costs.023 1.00% 4. which reach maximum load at a volume limit rather than a weight maximum.897 57 0 4. have installed stainless steel fuel tanks in their vehicles (Ref 2). while tanks may also be 316L for corrosion resistance when the transported material requires it. such as Volkswagen. These tanks contribute more to the required maximum 2 g/day of hydrocarbon emissions than is tolerable. Source: Ref 2 Table 4 Life-cycle cost calculation (LCC) for stainless steel versus carbon steel for a bus application Cost of capital Inflation rate Real interest rate Desired LCC duration Downtime per maintenance/replacement event Monetary unit Value of lost production Material costs Fabrication costs Other installation costs Total initial costs Maintenance costs Replacement costs Lost Production Material-related costs Total operating cost Total LCC cost Source: Ref 2 Stainless steel 3.S. $/day Carbon steel 1. The design by the famous design house Pininfarina employs a stainless frame to give maximum torsional stiffness and crashworthiness while eliminating painting entirely. Tank wrappers are often made of bright annealed and buffed 304.0 day U.425 . This weight reduction would directly translate into greater load-carrying capacity because the payload of liquid-carrying trailers is limited by total gross weight.S.76% 20. Normal cargo-carrying trailers also use some stainless where corrosion is problematic.Chapter 19: Automotive and Transportation Applications / 231 Microcars are now a familiar sight in Europe. Trailers used for hauling foodstuffs or corrosive materials are now constructed almost entirely of stainless steel. which would permit major weight reduction. so a Fig.331 25.185 30. Structural members in trailers are typically 304. led in the United States by the state of California.050 32.402 36. and a product with long life and low maintenance costs. Trucks Over-the-road trailers are an excellent example of stainless steel being used for utilitarian purposes.00% 5. lined carbon steel tanks are now largely obsolete. Weight reduction is less important in these trailers. such as in doors and door frames. Figure 3 shows a stainless steel microcar frame.0 years 1. These considerations combine to make stainless the best material for many of their components. have made manufacturers reexamine the suitability of polymeric fuel tanks. few manufacturers. Other Automotive Components Stringent emissions controls regulations. $ 101 U. 2 Stainless steel bus bodies.838 0 0 0 0 0 30.582 4. The ability to add a few thousand more pounds of payload would quickly pay back a small premium in material cost. Their economy of operation is also a major attraction.448 2.

Andersson. Hopper cars made of 12% Cr martensitic stainless steels. Ergonomics. a 5 to 10% increase in economy could be achieved if type 201 were used instead of 301. Low-Weight. Schedin.232 / Stainless Steels for Design Engineers Fig. J. 3–4. No. The transition to 201 has not occurred simply because of inertia and resistance to change on the part of designers and producers. Persson. Vehicle Architectures: Evolution Towards Improved Safety. AvestaPolarit AB. has not been carried over into trucks and buses even though it is technically feasible to economically produce structural sections in very high-strength stainless. Curiously.” paper presented at Florence ATA 2005. Magnusson. F. R. which has been successful for decades. and A. obviating the need for painting and lowering maintenance costs. ACOM. Ocklund. 2002 2. www. Source: Ref 2 Rail Transport Passenger trains have exploited the high strength-to-weight and toughness qualities of the 301 family of stainless steels for many years. “Stainless Steel: A New Structural Automotive Material. No loss in performance would occur. typically 409Ni and 3Crl2. Viganò. The Applicability of Stainless Steels for Crash Absorbing Components. Capelli. the use of coldworked austenitic stainless in railcars.centroinox. 9th International Conference (Florence). accessed June 2008 . E. have excellent abrasion and corrosion resistance as well as high strength and therefore greater loadcarrying capacity. May 2005. 3 Microcar frame fabricated from stainless steel. REFERENCES 1. V. and Flexibility. As with any other major use of type 301. The corrosion resistance of these alloys makes them corrosion free in long use. Boneschi. and P.

Stainless has been increasingly identified with highquality. Plastic is weak. and cleanable and able to be disinfected. laundry. Medical knowledge is not sufficiently advanced to convince consumers of the harmlessness of such contaminants. The case for using stainless in appliances of all types. Whether this is a fad of an increasingly affluent consumer or a reflection of more design engineers and consumers being more interested in lasting value than they were in the “throwaway” society that preceded that period remains to be seen. Its lack of need of coatings often makes components made from stainless less expensive to produce than equivalent designs that must be coated with paint. esthetics. the case for value rather than fad seems to be stronger if the lessons of the harshly pragmatic automotive industry. even more important. Last. with respect to food. and sterilized.asminternational. . stone. high-end products. But. and manufacturing considerations. p 233-242 DOI: 10. and health care professionals and have increasingly carried over into equivalent domestic areas as consumers have become more aware of the benefits of stainless. in which decorative use of stainless has virtually disappeared while utilitarian uses have mushroomed. porcelain. heating. www. This has become an increasing concern as the effects of ions or chemicals released from food preparation materials have been viewed as potential toxic or disease agents. Introduction The last 20 years have seen the long-standing pervasive commercial use of stainless steel for food preparation and serving. and laundry because it combines strength and durability with an unexcelled ability to be cleaned. it provides minimal harbor for unwanted biologic growth as do more porous materials. The second. whether they are commercial or residential. and ceramics break. stainless is very amenable to nearly all manufacturing techniques. Stainless also competes quite well esthetically with other materials. and air conditioning (HVAC). or metal. Chemical neutrality is achieved by a material when the material does not enter into the food with which it comes in contact.Stainless Steels for Design Engineers Michael F. so it is preferable to demonstrate the absence of contamination if one is to win the public confidence in a food contact material. disinfected. health care. Steel and aluminum corrode. both chemically and biologically. a food contact material must first meet three criteria: It must be chemically inert. Stainless steel itself is inert. Stainless is without rival for ruggedness and durability. Further. Food Contact Qualifications Setting aside cost. biologically inert. are any indication. relates to stainless being able to provide the best value over the intended service life. reason is that stainless steel is essentially benign from a hygienic viewpoint. CHAPTER 20 Commercial and Residential Applications Summary STAINLESS STEEL HAS BECOME the essential material for products related to food. McGuire. offering the designer numerous surface finishes. ventilation. and other appliances penetrate the domestic market for the same types of goods. laundry. These qualities have long been apparent to commercial food.1361/ssde2008p233 Copyright © 2008 ASM International® All rights reserved.

7 24.19 ≤ 0.350 2. water. Nickel levels of various foods before and after cooking have been scientifically measured to assess the possibility of leaching of that ion from 304 stainless steel (Ref 2).22 0.12 ≤ 0. Table 1 shows the vastly lower rates of metal ion release from stainless than from aluminum and carbon steel.700 62. So. and 444.87 0. if not optimal. however. which can have 15% salt.22 0.010 mg/cm3 of iron.12 ≤ 0. based on pH. This is complemented by other studies showing that the transfer of ions from food contact vessel to food is diminishingly and negligibly small. food contact materials.160 15. and temperature. Referred to chapters in this book on both corrosion and individual alloy families for guidance in choosing an alloy based on resisting pitting in a given environment. no alloy greater in pitting resistance than 304 is required in residential or commercial cooking food contact.0 7.93 3. are projected to last 20 years before pitting.71 0.12 0. is the responsibility of the design engineer.40 0. Under such conditions. the 6Mo alloys. Stainless therefore is effectively inert.40 6.19 ≤ 0.12 ≤ 0.4 4.12 ≤ 0. In food production. more extreme levels of acidity and salinity can be encountered. The distinguishing characteristic of stainless.3 8. which is so stable chemically. Choosing the proper grade of stainless.42 5.12 ≤ 0. Aluminum releases aluminum ions into solution of both cooking oil and 3% acetic acid at nearly equal rates of 15 mg/cm3 in 30 days. µg/cm3 Material Time Iron Chromium Aluminum Nickel Austenitic stainless Ferritic stainless Aluminum Carbon steel 30 min 10 days 20 days 30 days 30 min 10 days 20 days 30 days 30 min 10 days 20 days 30 days 30 min 10 days 20 days 30 days 2. Stainless.6 6.82 14. alcohols. and 3% acetic acid.12 ≤ 0.9 31. Carbon steel releases iron at over 100 mg/cm3 in the same period. it is necessary to apply the correct assessment of the corrosivity of the foodstuff in question.0 36.12 ≤ 0.19 0. that had both industrial finishes (2B and BA) as well as freshly abraded and air-aged finishes.40 0.19 ≤ 0. These sample steels were subjected to boiling solutions of oils.28 0.12 ≤ 0.19 930 5. is the spontaneous passive film.62 7.12 Source: Ref 1 .12 ≤ 0.22 ≤ 0.3 3.000 0.900 112. one must still verify the corrosion due to a particularly aggressive food ingredient. such as those promulgated by the National Science Foundation (NSF). Tests have been conducted on stainless steels. must withstand prolonged contact at 45 °C (115 °F). No increase was noted from the natu- rally occurring level of up to 0.31 ≤ 0. as opposed to preparation for serving.6 4. while guidelines exist for the minimum alloy content permissible for normal food contact.7 26. Were they to enter the food with which the stainless came in contact.3 8. These negligible levels of leaching simply indicate that foodstuffs are a benign chemical to stainless steel. The higher alloy requirements come from the more aggressive Table 1 Net metal migration into acetic solution (3%) Metal migration during indicated time.2 2.12 0.00 ≤ 0. Nevertheless.12 ≤ 0.19 0. then stainless would be a poor food contact material. This is significant because only pitting corrosion is likely to release metals ions into a food substance.22 0. salinity.12 0.1 ppm level (Ref 2).9 18. This having been said.9 ≤ 0.3 μg/g in cereals to 1.300 7. 316 stainless pits in about 1 day.43 0. releases less than 0.430 57.234 / Stainless Steels for Design Engineers Stainless steel contains many constituent elements.2 17. of which their YUS 270 is one (equivalent to UNS S31254).12 ≤ 0.7 2. both of which are permissible. None caused the transfer of either chromium or nickel to exceed the statutory 0.58 12. while higher alloy grades. This film acts as a barrier to corrosion.1 μg/g in meat and fish. 439.19 ≤ 0. Tests have been made of the rates at which metal ions can enter foodstuffs (Ref 1). types 304. which would result in metal release. however. Nippon Steel reported (Ref 3) that materials used in the manufacture of soy sauce.

enamel. There is some technology to go beyond biological neutrality in the use of coatings that actively discourage or eliminate growth of microorganisms. These are often organic acids such as citric acid or oxalic acid and amine acids such as sulfamic acid and ethylene diamine tetraacetic acid (EDTA) or salts of these compounds. Alternative alloys. This includes the removal of both organic and inorganic substances. Cleanliness. microorganisms adhere to this film and. The ability to maintain a microscopically smooth surface is an asset in stainless that polymeric. It contains trace amounts of copper. Stainless steel is primarily composed of iron. or other surface active agents. Some precautions are worth mentioning. silicon. such as can occur when unattended pans have their liquids boiled away. The abrasive size and hardness must be chosen . which are vaporized at the temperatures at which stainless is refined. Stainless is essentially devoid of heavy metals. 6. form a biofilm. All these factors combine to make stainless the most chemically neutral metal found in food contact. Very high temperatures. Various stainless manufacturers and associations have identified a number of effective of cleaning products (Ref 2. which protects the colony from cleaning and disinfecting.This will be seen to influence its ability to be cleaned and disinfected. The most complete form of disinfecting is sterilization. However. which dissolve fats and oils • Chelating or sequestering agents. Even if toxic metals were somehow to be made to contaminate stainless. Silver ions. This process is distinguished from disinfection. actively leach into foods. Geometric factors also can protect these colonies. as colonies of them grow. The purpose of cleaning stainless steel is to rid it of contamination. Rough surfaces are intuitively more difficult to clean. The combination of cleaning and disinfecting is important. The most important objective of cleaning is to remove the visible and invisible materials that can provide a growth medium for microorganisms. true bacteriological cleanliness is obtained only after disinfection. Polymeric coatings impregnated with silver ions have been developed and com- mercialized (Ref 5). aluminum phosphorus. such as lead and mercury. Microorganisms adhere to solid surfaces. although cleaning can and does reduce the population of microorganisms. which is the reduction of the microbial population to a satisfactory level. whose objective is the complete removal of all microbial life and viruses. Each can be found in a typical multivitamin/multimineral supplement. 7): • Alkalines. and molybdenum. and mineral surfaces lack. which emulsify • Dilute oxidizing acids like nitric acid • Mild acids such as phosphoric acid The effectiveness of a cleaner relates mainly to the contaminant to be removed.Chapter 20: Commercial and Residential Applications / 235 concentrations and exposure periods that can be found in food-processing plants. This film consists of layers of microorganisms that can produce an exocellular polymeric matrix. like copper ions. which agglomerate contaminants. Some trial and error may be required for a given contaminant. trisodium phosphate. Abrasive cleaners should be used with caution. A necessary quality in any material considered for food contact is the ability to be cleaned. When a clean surface comes in contact with food. Stainless steel is much less roughened by abrasion. such as copper and aluminum. the passive film would prevent their release. although there are no specific studies on this. and nickel along with small amounts of manganese. The film may also contain molecules left from previous cleaning and disinfecting. Each of these elements is naturally occurring in food. detergent. What this level is depends on the standards of hygiene in force. Copper and aluminum have been linked to but not demonstrated to cause Alzheimer’s disease. Biological Neutrality. can damage stainless but are more harmful to less-rugged alloys such as copper and aluminum. The formation of this film is presumably influenced by material characteristics such as roughness. The combination of such a coating with stainless as a corrosion-proof substrate may represent the maximum in hygienic and chemical protection and is already being used in medical applications where such concerns exceed those in ordinary food contact situations. are powerful antimicrobial agents. chromium. keeping the surface smooth (Ref 4). • Hydrocarbon solvents • Water with soap. Studies have shown that the efficacy of disinfectants is weaker on bacteria that have been established in a surface biofilm than on bacteria in suspension. And. and sulfur. Certain abuses can even damage stainless cookware. a surface deposit is formed from the food.

The ability of stainless to be cleaned is best measured by the actual removal of bacteria colonies. Abrasion did not degrade the ability of stainless to be cleaned as it did softer materials.. Taking this into account requires that commercial and residential food equipment be able to withstand some chloride level greater than otherwise projected. even with the seemingly protected recesses due to abrasive polishing. mineral resin. Stainless can be disinfected quite readily. especially in crevices. permits bacterial colonies to be removed. etc. If chloride-containing cleaners are used. Industry practice in the United States has shown that corrosion problems occur at an unsatisfactory level with mechanically polished 430 but not with bright-annealed 430. So. The surface of stainless. This has been done to compare unabraded and abraded (to simulate new vs. Care should also be taken to clean with the polish grain if a polished surface is being cleaned. used) stainless steel. the underlying finish can be disturbed. then thorough rinsing should be conducted to avoid chloride concentration through evaporation.g. Their use is not recommended on stainless. and aluminum all required about one to two orders of magnitude greater concentrations of disinfectant for the same result. (Ref 4). enameled steel. and that polyesters. 1 Bacterial retention as a function of material and cleaning time. food prep tables. polyurethanes. Numerous studies have been published (e. The effectiveness of sodium hypochlorite as a disinfectant is inarguable. If the abrasive is harder than the stainless or coarser than the stainless surface roughness. Also. despite its potential corrosivity. also. Use of hydrochloric (muriatic) acid is especially detrimental. counters. cleaners containing chlorides are common. The greater roughness of the other materials may serve to protect the bacterial colonies from shear forces and provide greater specific surface area on which the colonies can bond. rubber. Fig. Steel wool or steel brushes should not be used on stainless under any circumstances as iron residue interferes with the integrity of the passive film. it will be commonly used. which allows the great invisible liability of food-borne diseases to be minimized. These results indicate why stainless is so essential to the food industry. Ref 8–10) showing that glass and stainless steel have equal aptitude for disinfection. Source: Ref 4 .236 / Stainless Steels for Design Engineers so that the stainless surface finish is not affected in an unwanted manner. which can be used for sinks. and polycarbonate materials. Disinfection. The ability of a surface to be disinfected is measured by the concentration of a given disinfectant required for a specific reduction in bacterial population. Figure 1 shows that the reduction in bacteria count by the same cleaning technique is ten times more effective on stainless than on the other material types.

Nonstick coatings. Alloys such as 436 have been used for this application. The qualities discussed make aluminum and copper less desirable. Above 350 °C (660 °F) these coatings give off toxic fumes. These two metals do have one advantage over stainless. Higher chromium grades such as 304 can be used even with mechanically polished surface finishes. Aluminum and copper are nearly equally effective as inner conductive layers. because many commercial appliances are visible to the customer. made of stainless steel. with an inner layer of copper or aluminum effectively spreading the heat. as are premium domestic kitchen appliances. The ferromagnetism of ferritic stainless steel makes it ideal for induction heating. the choice of the non-foodcontacting stainless is less stringent. A larger drawback is the expense of retinning copper utensils. The uniformity is the more important consideration than the absolute thermal conductivity or even the thermal diffusivity. alloys with less than 16% Cr should not be used unless corrosion can be accepted. such as wok cooking or blackening. Lustrite. The food industry. Sometimes. and 201 as their standard alloys as well as by specifying nonabrasive finishes. stainless is the material of choice. and usually is. such as polytetrafluorethylene (PTFE). As was noted that 430 is marginal for kitchen use. 4 finish. It is also possible to produce a magnetic carbon steel core with stainless bonded to both sheet surfaces. The exposed edges are rolled to shield them from corrosion.. Koolline. the rolled-on replicas of No. could do more than any other industry to help conserve nickel by specifying alloys such as 430. Both of these are preferable to mechanically polished finishes. Every type of commercial kitchen appliance can be. From a cost-effectiveness point of view. permitting better control of the cooking process. since cookware must be flexible enough to handle any potential food. Kitchen Appliances. This is a necessary trade-off required to achieve high hardness for good cutting edge retention. etc. In North America. And. but more likely to be encountered by accidentally high temperatures above those intended. This can be done with no loss of functionality or change of appearance and could save 23% to 50% in material cost. Aluminum is known as a toxic metal. This is a danger for certain types of cooking. unless it has been bright annealed. the choice of material for cookware must be the most conservative. Only glass and stainless are excellent food contact materials. Alloys containing 16% Cr can be used with optimal surface finish. while in Europe the bright-annealed finish has been preferred. Alloys as low in carbon as 12% are used for cutlery applications where slight corrosive attack can be accepted. Applications Cookware. Premium cookware features them both. while 304 is the pervasive choice for the food contact surface. however: their thermal conductivity. there is no reason to use more expensive alloys than 430 or 201 in the vast majority of commercial and residential kitchen and laundry applications from a corrosion standpoint as long as surface finishes that have not been produced by abrasive polishing are specified. All austenitics . This is despite the fact that 201 or 301 are quite adequate for this application. which allows the stainless to be on both the food contact surface as well as the exterior. aesthetics are also a driving force. The tin also corrodes over time but has very low toxicity. Copper can be tinned to combat this.Chapter 20: Commercial and Residential Applications / 237 Thus. because of the prevalence of chloride-containing cleaners. their use does not alter the choice of the material to which they are applied. This choice is based on durability and ease of cleaning and disinfecting. the exterior is made of a ferritic stainless steel. Since they can be scratched and are not impermeable. Both leach into food. 439. are quite common. The solution to the problem of thermal conductivity is to make composite materials. Stainless can be bonded to copper and aluminum. an immense consumer of stainless steel. Many such finishes are widely used. And. For this reason and because of the brittleness of glass. Any interaction between a food contact material and the food is most likely to occur during the cooking process when temperatures are greatest. Choice of alloy for a given appliance is a crucial cost factor. In a triple layer. are very popular because of their nonstick qualities. High thermal conductivity in a cooking utensil minimizes differences in temperature across the surface in contact with the food. The “sandwich” is the optimal design because it optimizes heating uniformity even more than using aluminum or copper alone would since the high conductivity inner core functions as an isotherm. with its toxicity causing symptoms similar to those of Alzheimer’s and osteoporosis (Ref 11).

For Fig. This choice is supported by decades of use by the major manufacturers of commercial appliances. which were exposed to coastal salt and humidity for 10 years in North Carolina (Ref 12). This applies to inland conditions or coastal conditions where interior environments are protected by air conditioning or adequate cleaning of the stainless is practiced. and the use of 304 represents wasteful overengineering. Figure 2 shows how different alloys withstand coastal conditions. I recommend following American Society for Testing and Materials (ASTM) A240 and specifying UNS S20100 when substituting for 304 as this has very similar performance in forming. which cannot be passed on to their customers. coastal salinity is not a problem. while that on the 201 and 304 is acceptable given that some routine cleaning would have prevented the corrosion that is present on these samples. 2 Stainless steel samples exposed on a North Carolina beach for 10 yr. which can be a much larger savings than the base price savings. practice of service centers not stocking 201 despite its being the most costeffective general-purpose stainless grade. Under these conditions. These are the same guidelines used for architectural applications. Smaller manufacturers are often precluded from these savings because of the general. This is normally the case for commercial equipment. In the high ambient salinity of coastal climates. The extended nickel price elevation from 2004 onward has a good chance of changing that situation as end users rebel against surcharges. The corrosion on 430 would be considered excessive. It has been pointed out that there is an array of 201-type grades. welding. Designers seem to generally neglect the possibility that their equipment may be used in coastal climates. and appearance to 304 and can be most easily interchanged without complications in manufacturing and field performance. if inexplicable. In the vast majority of ambient conditions. Use of 201 versus 304 reduces surcharges by almost 50%. 201 is quite adequate. and that this is a drawback to their wider adoption. corrosion will occur unless 304 with a bright-annealed finish or a brushed finish rolled onto a bright-annealed 304 is used. Source: Ref 12 .238 / Stainless Steels for Design Engineers are satisfactory under normal use. Many who are large enough to specify their desired grade on bills of materials rather than simply buying from service center inventories have routinely used 201 and realized an approximately 8% lower cost before surcharges. Mechanically polished 304 stainless is inadequate for coastal environments.

0 16..00 1. In the case of dishwashers.5–5.00 1. .0 1.0 1.10 0.00 1. Use of dual stabilization permits keeping titanium levels to a minimum.0 16.00 1. There are important precautions..15 0.9 18. from using ferritic grades. are generally made from austenitic stainless steel... . since most appliance components experience little more than cutting.0–18.10 . Stainless steels commonly used for appliances Composition. This can be solved by specifying rolled-on finishes. drawers. ice cream. These include refrigerators. which can be welded without adverse corrosion effects and has high formability and corrosion resistance at as little as half the cost of 304 when alloy surcharges are factored in..0 18. and welding. but deep-drawn grades are more finely tuned to specific process paths and must be more tightly specified than general-purpose grades. Nb + Ta: 5 × C.0 17. 0.08 0. to 0.0 .0 8.. serving pans. This occurrence is strictly a thermodynamic phenomenon related primarily to the titanium and nitrogen levels.Chapter 20: Commercial and Residential Applications / 239 parts made by deep drawing. This yields very consistent forming characteristics. Not a small reason for this is that this finish requires only a single temper pass to both flatten and provide the finish.5 6. The more commonly used alloys for appliances are listed in Table 2.. .20 + 4 × (C + N).15 0.75 0.. The greatest savings comes.030 . There are important visual considerations in these applications.20 + 4 × (C + N). C N Cr Ni Mn Si Mo Ti/Nb 201 301 304 316 430 439 468 436 444.030 0. This is especially true of dispensing machines. stoves..12 0.. bending.75 . etc.0–10. forming requirements are often severe enough to require the use of austenitic stainless. durability. 0.50 Ti + Nb: 0.0 16.0–20..0–30.. Appliance facades are increasingly using stainless..07 0.00 1.025 16.00 2.0–18.00 1. . to the degree they require high cleanability or contact food.0–18. Ti + Nb: 0.80 . which is usually a very important quality criterion for appliance manufacturers.0–18..00 1.0 1..5–7. which is the majority of the time.0025 when Table 2 Alloy concentrations are in weight percent. YUS190 29-4C S20100 S30100 S30400 S31600 S43000 S43035 S46800 S43600 S44400 S44735 0.20 + 4 × (C + N). substitution is still very possible.00 1. Interior or working parts of appliances. etc.0 0..025 0. This is difficult to achieve for 17% Cr alloys if stabilization is by titanium alone.00 1.. to 0.. to 0. Consistent. 2. and esthetics.0–19.04 0. It is still preferable to use a dual-stabilized grade such as 468. 0. which look the same on ferritics and austenitics.5–4.0 17. to 1.50 .10 .00 1.5 28. 1. microwaves. which occur if significant TiN precipitation occurs before solidification in the original steel production. Coatings are rarely used. which should be minimized so that the product of titanium times nitrogen is less than 0. however. are also often made of stainless...0 16.75–2. .0 0. is put side by side with an austenitic such as 201 or 304.00 1.00 1.5 5. Rolled-on finishes are generally preferred. Shelves and exhaust hoods also benefit from being made of stainless.0-3. and ice. . This subtle difference can be magnified to objectionable levels when a mechanically polished ferritic stainless.0–18. which lends itself to the typical deepforming operations used in their manufacture.80 3..12 0..80 ....5–19. chafing dishes. These finishes also supply the added corrosion resistance that makes alloys such as 430 acceptable.0 3. and the low work hardening rate of ferritics causes the mechanical polish to take on a different color shade.5 2. such as for beverages. Mechanical polishing results in unacceptable corrosion resistance. Rolled-on finishes also have very high visual consistency. to 0. Food preparation tables also fit into this category.025 0. this would be an ideal application since already cooked food is most often in the intermediate temperature danger zone at which bacteria can multiply. making it possible to avoid TiN-caused surface defects..00 2. and they should be used whenever forming requirements permit. .20 + 4 × (C + N). . such as 430..70 1.. 0.0–14.08 0. Stainless interiors are often found in refrigerators and dishwashers.0 0.5 Ti + Nb: 0.. The drivers here are cleanability.25 ..0–20..5 10. of course. Canisters.035 0.0–8. If antimicrobial coating were to be used in food contact.. meaning much lower breakage during press-forming operations. % UNS No.50 0.

The corrosion resistance of martensitic grades cannot be improved above modest levels. which was hard but whose rusting was an obvious problem. as is found in 440A and to a greater extent in 440C. Stainless filled the gap between carbon steel. The addition of higher levels of carbon ties up chromium so that it cannot add to corrosion resistance. The chromium carbides of these straight-chromium martensitic stainless steels are very hard. Maximum corrosion resistance is achieved in the as-quenched condition. Outdoor cooking grills. which would cause excessive δ-ferrite retention if it were raised. reflectivity. These problems can be circumvented by the use of powder metallurgy. are almost always 304 or a similar grade. vanadium and tungsten have even harder carbides. as is often the case for products such as hoods and counters. only a small amount of these carbides can be introduced into the matrix. Hard particles are much more useful for wear resistance if they are small and widely dispersed. and color. Gas burner manifolds are also stainless. Improved corrosion resistance of these alloys is achieved by adding molybdenum at the expense of chromium. which permits the solidification step on a macroscale to be skipped. Heat tint does not occur with these to a problematic degree. this refinement of the primary carbides can be achieved by raising nitrogen levels. some toughness is a valuable but not crucial characteristic. so most cutlery is tempered at low temperatures. material is stamped or forged and then finished. such as heating element sheathing (American Iron and Steel Institute [AISI] type 334). Depending on the shape of the final utensil. Freedom from fingerprinting can be another valuable attribute for faÁade applications. smooth cutting edge.240 / Stainless Steels for Design Engineers defect-free surface finishes are paramount. they tend to be coarse and to embrittle the alloy. ferritics are required because of the need for extreme high-temperature oxidation resistance and the desirability of a low coefficient of thermal expansion. making a ragged rather than a fine. This can be obtained on stainless by the mill application of a thin. The problem is that if primary carbides form during solidification. but this criterion is secondary to hardness because of the need to keep a sharp cutting edge. However. which was soft and whose cost prohibited its use to all but the wealthy few. for low-cost flatware. At the high end is 304. however. such as 430. Although very high alloy stainless steels are used for high-temperature kitchen applications. This again can really only be achieved by rolled-on finishes since abrasively polished finishes vary excessively in roughness. bonded polymer film. Table 3 lists the martensitic alloys used for cutlery. it is seldom used for oven interiors because it does take on a heat tint when exposed to temperatures above 300 °C (570 °F). If visible welds are required. The wear resistance added by carbides is proportional to their hardness and amount. 2800 and 2100 HV. which see lower temperatures. All bare stainless finishes show fingerprints. Cutlery is the domain of martensitic stainless steel. it is best avoided by using mineral oil-based cleaners. These large carbides can pull out during edge honing. and silver. The preferred alloys are those developed for automotive exhaust systems. It is reasonable to say that most of these alloys far exceed the requirements of food preparation. at high carbon levels. The vast majority of requirements for high-quality cutlery are satisfied by 420 stainless. are normally stainless. variations on 409 and 439. Flatware and cutlery were among the original uses of stainless. This is a practical impossibility with abrasively polished finishes and very difficult with rolled finishes. 1800 HV. so that it can become barely rust resistant. In this case. type 301 is commonly used also. never reaching that of 304. because they must endure exterior environments without corrosion. . But. Flatware has no hardness requirement. However. which has all the corrosion resistance that could be needed for flatware. Panel flatness is often very important and another benefit from rolled finishes. then special finishes with very long polish grains have a major advantage in that the weld can be ground and polished with a belt sander of the appropriate grit size so that the weld blends imperceptibly with the adjoining original surface. Through conventional casting and hot working. This is done by adding more carbon and chromium. Range tops. Furthermore. as are ferritic steels. This can be seen in alloys above the basic 420. versus the 1100 HV hardness of iron carbides. so grade selection is based on the need for perceived quality. To a degree. If greater cutting edge retention is desired. then more or harder carbides are engineered into the martensitic matrix. respectively. carbides precipitate in the liquid and are much coarser. Larger volume fractions of hard carbides such as vanadium carbide and tungsten carbide can be added and dispersed. With uncoated stainless.

.0 4.. 12.. The intermediate efficiency furnaces (80 to 90%) require the use of corrosion-resistant vent pipe to prevent corrosion from condensation in the flue. stainless has come into domestic use as a heat exchanger material. .75 4. forced-air furnaces.15 2. Dryers are less challenging. 1. while porcelain becomes quite abrasive over time as wear opens voids with edges that can be quite sharp and cause significant damage to clothing... The stresses induced by the high spin speeds.... 1.0–18.45 .... .. and austenitics can be 201. 0.. 0.... 0.5 14..0 0.. ..4116.. . .60–0... Porcelain-coated carbon steel obviously can be strong. This trend began in Europe with the development of high spin speed..75 0. Given the number of units produced and .05 1. In the end. Some manufacturers have always used lower-alloyed stainless steels.. should never be used in welded applications.0 14. .030 . 0.0 13.40 .. horizontal axis washing machines. but the coating is cracked by strains that the steel itself easily tolerates.0 14...0 14. along with the implied quality of stainless. The selection is based on forming requirements rather than corrosion or strength.00 .0 .030 0. 1.2 V .0 V Many kitchen utensils are also made entirely or in part with stainless. .05 1.0 16... This condensate can. nominal UNS S44002 UNS S44004 Nominal composition Nominal composition Nominal composition Nominal composition Nominal composition Nominal composition Nominal composition Wrought Wrought Wrought Wrought Wrought Wrought Wrought Wrought PM PM PM 0. These features have eroded the share enjoyed by vertical axis..0 .0 14. or 304..00 0.4 0.00 ..15 1.0–14. These washers use far less water and energy to achieve higher levels of cleaning with less damage to clothing. High-temperature plastics were tried.0 V 5.5 16. The proper handling of combustion products is an interesting problem in materials selection. and grade selection depends on forming and joining requirements.75 0.. which are necessary in horizontal axis machines to take water removal from 80% to 95%.. but failed joints in them caused their recall after several fatalities were reported. . contain corrosion elements.. .0 14..Chapter 20: Commercial and Residential Applications / 241 Table 3 Stainless steels commonly used for cutlery Composition.. 29-4C alloy is nickel free) and probability of failure.00 1.. 0. Ferritics should be a 17% stabilized grade.3 . Alloy 29-4C (UNS S44735) was the original alloy used nearly universally in the United States. High-efficiency (90% or higher) furnaces can use low-temperature plastic pipe.00 . .45 2.. ..030 .. If components can be made by bending rather than stretching. 0.. but at least one used alloy 6XN (UNS N08367) alloy for formability.95–1.20 1. . depending on incoming air.... % Alloy Designation Form C Mn S Si Cr Mo Ni Other 420 4116 440A 440C BG-42 ATS-34 14-4 CrMo 154 CM CPM S30V CPM S60V CPM S90V UNS S42000 DIN 1.. .05 1. Heating and Water Heating.5 0. Alloy 29-4C was the original choice for most secondary heat exchangers. These furnaces gain their extra efficiency by condensing water from combustion gas exhaust. so pitting corrosion must not be allowed.. .. but these units require the use of a corrosion-resistant secondary heat exchanger to recover the latent heat of vaporization of the water from combustion. then the lowercost ferritics can be used.. . 4... 1.. . .15 min 0..5 V 9.. . Type 304 is the alloy most commonly used..0 4.. such as 439 or 468. .. such as 430. An additional benefit to stainless over porcelain is that stainless starts smooth and becomes even smoother with use.. With the development of high-efficiency. The worst consequence of perforation by pitting could be the release into the home of toxic gas.65 0.. are the main drivers for its use. require the strength of stainless steel.. Those designs that use stainless will last longer and be gentler to clothing. Unstabilized ferritic alloys..3 0.15 V .0 17. . ..00 1. which has led to the use of very highly alloyed ferritic stainless steel in their construction. one has to balance materials selection between cost (fortunately. but again any of the stainless steels with at least 16% Cr are adequate... .3 0.20 1. natural-gas-fired. The variability of the use environments leads to a huge spread in corrosion conditions and materials performance. and it is difficult to make a strong case for the functional value of stainless.0–18.35 0.50 0.40 1. Those.0 2.0 4.. whose low speed allows them to be constructed of lowstrength materials such as plastic or porcelaincoated steel... Laundry appliances have converted significantly to stainless. agitator-type washers. 301.. Washer tubs and drums are made of both ferritic and austenitic stainless.

242 / Stainless Steels for Design Engineers

the potentially serious consequences of failure, failure rates must be less than 10 – 4, while failure rates much less than 10 – 6 are impossible to verify and hard to justify. In any case, the competition is always between various stainless steels. Galvanized steel will not work. The issue is difficult enough for natural-gas-fired furnaces. Oil fired is a developing situation for which there is no good consensus. Wood burners and other unconventional furnaces (such as corn burners) present additional challenges, and answers are even less obvious. Water heaters are sometimes made of stainless steel. It is not uncommon for water to have a sufficient level of chlorides to lead to stress corrosion cracking if an austenitic stainless is used. Therefore, the recommended alloy for this application is UNS S44400. More recently, lean duplex alloys have been developed, such as 2101 and 2003, which can perform quite well without corrosion or stress corrosion cracking. More highly alloyed duplex alloys such as 2205 are more expensive but would work well.


1. M.J. Julio, M.L. Martin, and J.M. Baena, Cation Migration Tests in Metal Containers, Innovation Stainless Steel (Florence), Oct 1993, p 1.221–1.226 2. “Stainless Steel in Contact with Food,” Document Ugine, June 1996

3. “The Application of High Corrosion Resistance Stainless Steel YUS270 in Food Processing Facilities and Equipment,” Nippon Steel Technical Report 87, Jan 2003 4. J.T. Holah and R.H. Thorpe, Bacteria Retention on Cleaned Surfaces, J. Appl. Bacteriol., Vol 69, 1990, p 599–608 5. Agion Technologies,, accessed June 2008 6. Removal of Stains and Discolourations, Outokumpu,, accessed June 2008 7. “The Care and Cleaning of Stainless Steel,” Specialty Steel Industry of North America,, accessed June 2008 8. E.P. Kysinski et al., J. Food Processing, Vol 55, 1992, p 246–251 9. A.A. Mafu et al., J. Dairy Sci., Vol 73, 1990, p 3428–4332 10. P. Gelinas and J. Goulet, Can. J. Microbiol., Vol 29, 1983, p 1715–1730 11. R.A. Goyer, Toxicity of Metals, Properties and Selection: Nonferrous Alloys and Special-Purpose Materials, Vol 2, ASM Handbook, ASM International, 1990, p 1233– 1269 12. Allegheny Ludlum research, as presented in D.S. Bergstrom and C.A. Botti, AL 201HPTM (UNS S20100) Alloy: A HighPerformance, Lower-Nickel Alternative to 300 Series Alloys, Stainless Steel World, KCI Publishing, 2005

Stainless Steels for Design Engineers Michael F. McGuire, p 243-246 DOI: 10.1361/ssde2008p243

Copyright © 2008 ASM International® All rights reserved.


Marine Systems Applications
AS RECENTLY AS THE 1960s AND 1970s, handbooks on stainless steel were stating that “stainless steels are not stainless in seawater,” and “successful prolonged corrosion-free service of stainless steel in seawater requires sophisticated corrosion engineering, or enormous good fortune” (Ref 1). The advances in stainless steel made since then have thankfully made these statements obsolete. Not only have basic corrosion problems been solved, stress corrosion cracking also can be avoided. More impressively, this can be done with alloys with strengths much higher than those of the alloys, such as 316, that they replace and that have been only marginally successful in marine environments. The inertia in changing from the weaker, less-corrosion-resistant, more expensive austenitic stainless steels is large because of less availability of the newer, better alloys, and lack of familiarity with their benefits. Those who understand and use these newer duplex alloys will be rewarded. This chapter reviews the major marine applications of stainless steels, including desalination equipment, shipping containers, and heat exchangers that handle seawater. restricts their use to items of rather thin gauge, less than about 1.0 to 2.0 mm, depending on alloy. Thus, their use is limited to tubing. Superaustenitic alloys can be used at any thickness, although they are a costly material. The success story for stainless steel and seawater and therefore desalination is that of duplex stainless steel. With the same corrosion resistance as any super austenitic or superferritic alloy, it has nearly double the strength plus resistance to stress corrosion cracking. And while duplex stainless steel is not a cheap material, it does contain much less nickel than an equivalently corrosion resistant austenitic stainless steels, which is a major cost saving factor. Desalination technology is relatively new if one ignores the fact that distillation has been around for a very long time. Desalination in commercially viable quantities began with multistage flash technology in the 1950s. The underlying principle of this process is the evaporation of water vapor from salt water with the subsequent condensation of the salt-free water vapor. In the multi-stage flash (MSF) approach feedwater is heated and the pressure is lowered so that the water “flashes” into steam. A variation on this technology is multiple-effect distillation (MED), another low-temperature distillation process. The differences in all distillation-based systems reduce to the efficiency of the design in minimizing energy consumed per unit of pure water output. All distillation processes require heating of the input water and some process power. The other basic engineering approach to desalination is reverse osmosis (RO). The invention of polymer membranes that could separate the salt ions from the water made this technology possible. No thermal energy is required. The water is pumped at high pressure through these permeable membranes physically separating the

At one time not long ago stainless steel was thought to be an inadequate to marginal material for use in seawater. Its use in heated seawater was therefore all the more suspect. This was first changed with the development of superferritic and superaustenitic alloys. The superferritic alloys such as Seacure (UNS S44660) and 29-4C (UNS S44735) are quite resistant to seawater, even at high temperature. Their low toughness

244 / Stainless Steels for Design Engineers

salt from the water. The change in salt concentration across the membrane is a function of the pressure and the membrane itself. A second treatment may be used to improve water quality. The distillation methods require about 5 kWh/metric ton of water output, while the RO methods require twice that. The distillation methods require another 20 kWh of thermal energy from some source for feedwater heating, while the RO method requires none. Thus the ability to find energy from cogeneration or a source such as solar, etc may determine which process is preferred. Materials Selection for Desalination Materials used for distillation processes have evolved from use of type 316 (UNS S31600) stainless steel, first as lining and then as cladding. The superaustenitic alloys, the 6Mo variations, came next because they truly solved the corrosion problem, but at a price. Then, separately the duplex alloys were developed, with the first market the petroleum industry, whose demands and research made these alloys possible. It was not a stretch to see that high-strength alloys that could withstand seawater in offshore applications could do well on land as well. To give full credit, the pulp-and-paper industry was also beginning to employ duplex stainless steels

for their processes. Type 316 stainless steel has passed from consideration as a material for handling brackish water or seawater. In distillation systems, the rule of thumb is that 2205 alloy (UNS S32205), with its pitting resistance equivalent number (PREN) of 35, is sufficient for seawater up to 20 °C (70 °F); alloys 2507 (UNS S32750) or Zeron 100 (UNS S32760) should be used for seawater at elevated temperatures or high salinity. For the output of fresh water, lesser alloying is required. Stainless steel types 304 (UNS S30400), 316 (UNS S31600), 2101 (UNS S32101), 2003 (UNS S32003), or even 439 (UNS S43035) may be used depending on the combination of salinity and temperature of the output water. Besides their high corrosion resistance for lower total alloy cost, the duplex stainless steels have higher strength, which is a significant factor since distillation plants are large. The use of duplex allows wall thickness reductions that bring about larger savings than those based solely on their cost per unit weight. Figure 1 shows the difference among the candidate stainless steels in corrosion resistance (Ref 2). The viable materials for seawater are those that can withstand roughly 20,000 ppm Cl– level at the appropriate temperature. The strengths of the various candidate materials are given in Table 1. These are typical values.

Fig. 1

Corrosion resistance (pitting) as a function of salinity and temperature. 1. 304L (UNS S30403); 2. 316L (UNS S31603); 3. 2205 (UNS S32205); 4. 904L (UNS N08904); 5. 254SMO (UNS S31254). Source: Ref 2

Chapter 21: Marine Systems Applications / 245

Table 1

Typical analyses and properties of major marine alloys
Composition, % UNS Cr Mo N Ni PREN(a) Yield strength MPa ksi Tensile strength MPa ksi Elongation, %

2101 2003 2205 2507 304L 316L 317L 6XN 254SMO Zeron 100

S32101 S32003 S32205 S32750 S30403 S31603 S31703 N08367 S31254 S32760

21.5 20.5 22 25 18 16 18 21 20 25

0.3 1.5 3 4 0 2 3 6 6 3.5 (+0.75 W)

0.22 0.18 0.17 0.27 0.05 0.05 0.05 0.22 0.20 0.27

1.5 3 5 7 8 10 14 24 18 7

26 29 35 42 18 24 29 45 43 42

515 515 515 550 220 220 230 380 380 550

75 75 75 80 32 32 33 55 55 80

650 725 760 800 520 520 540 760 750 750

94 105 110 116 75 75 78 110 109 109

40 40 35 35 50 50 45 45 45 35

(a) PREN, pitting resistance equivalent number.

Refer to the appropriate design code for your particular application to find minimum properties. The reader is cautioned that duplex longitudinal properties are slightly lower than the transverse properties that testing requires. Pumps for seawater follow the same guidelines as piping, tanks, and all other components. Cast or wrought duplex are the alloys of choice.

The major uses of stainless steel in shipping are in bulk storage containment. Cargos range from food and beverages to chemicals and liquid natural gas (LNG). Practice in the past has been to use austenitic grades of stainless with cathodic protection when necessary to address inadequate corrosion resistance. However, since 2000 marine chemical tankers have become the largest consumer of duplex stainless steel. The reason for this is that cargo tanks ideally have the widest potential range of cargos possible. This range is defined by corrosion resistance. This factor alone is reason to choose duplex over austenitic alloys such as 316L (UNS S31603) or 317L (UNS S31703). An equally decisive factor is strength. With codes permitting the tank’s design to be based on yield strength, the use of duplex alloys—with strengths about double those of austenitic steels—permits significant weight reduction. This is a major economic factor for ship owners in that dead weight can be replaced by fee-paying cargo at the same operating cost. These incremental revenues, over the life of the vessel, are many times the original cost of the material. Based on the high value for strength in ship economics, it would seem that the higheststrength alloys, such as 2507 (UNS S32750),

may be justified based on strength alone; their exceptional corrosion resistance would be simply an excellent side benefit. Corrugated stainless bulkheads are positioned within the carbon steel hull. The stiff corrugated bulkheads are themselves structural strengtheners for the entire ship. The vertical corrugations also facilitate tank cleaning as internal stiffeners are eliminated. Cryogenic containers are still the bastion of austenitic stainless steels. As leaner austenitic alloys have become less expensive than 9% Ni alloy steel, a martensitic grade, they have become the material of choice. In this case, the 201 types are preferred to 304 because 201 has greater strength at the cryogenic operation temperature and is, of course, less expensive. The expanding market for LNG has made ocean transport increasingly important because large disparities in prices often are due to the difficulty in transporting it. The two best materials are UNS S20153 and S20400, which perform equally well. If higher strength is valuable to a design for cryogenic uses, then UNS S21904 (21-6-9 or Nitronic 40) could be used. This alloy has yield strengths of 460 MPa (65 ksi) at room temperature and 1200 MPa (175 ksi) at –196 °C (–320 °F). It is completely resistant to martensite formation. Other shipboard systems benefit equally from the use of duplex stainless steel. This extends to piping, hardware, propellers, shafts, etc.

Heat Exchangers
Coolers for captive water systems such as for power plants often need to resist corrosion by brackish water or seawater. To the extent that these are thin-wall tubing, ferritic alloys such as

246 / Stainless Steels for Design Engineers

Seacure (UNS S44660) or 29-4C (UNS S44735) have been used quite successfully. If thicker tubes are required, then the equivalent duplex or austenitic alloys can be used. This would include types 2003 (UNS S32003), 2205 (UNS S32205), or 2507 (UNS S32750) duplex stainless steels, depending on salinity and temperature; for austenitics, the 6Mo alloys such as 254SMO (UNS S31254) and AL6XN (UNS N08367) may be used. The duplex alloys have the advantage of lower cost. Both are resistant to stress corro-

sion cracking to very high temperature and salinity.


1. Peckner and I. Bernstein, Stainless Steel Handbook, McGraw-Hill, 1966, p 37-1 2. Stainless Steel for Desalination Processes, Feb 2006, Outokumpu, www.outokumpu. com, accessed June 2008

Stainless Steels for Design Engineers Michael F. McGuire, p 247-255 DOI: 10.1361/ssde2008p247

Copyright © 2008 ASM International® All rights reserved.


Petroleum Industry Applications
THE PETROLEUM INDUSTRY has had to deal with increasingly hostile environments in its search for new supplies of oil. And that petroleum, when found, often contains harmful ingredients. The result is increasing demand for steels with greater strength and corrosion resistance. Martensitic and duplex stainless steels have provided the corrosion resistance and strength to deal with higher levels of hydrogen sulfide, carbon dioxide, chlorides, and acidity. This chapter reviews the selection of stainless steels for petroleum applications, including oil country tubular goods (OCTGs), line pipe, offshore platforms, and refinery equipment. ginnings. Demand for steel for drill pipe, casing, and tubing has led to many developments, such as the technology for producing highquality seamless and welded pipe and tubing. Pipeline needs have fueled the market for highstrength, low-alloy plate. Offshore production in often-hostile environments has presented severe material challenges. And, as the light sweet crude that was easily found and produced on land is exhausted, future supplies of hydrocarbons are increasingly likely to contain sulfides, carbon dioxide, and saltwater in sufficient amounts to make corrosion a top priority in selecting materials. For reference in this chapter, Tables 1 through 5 list the relevant alloys for petroleum industry applications. Many, but not all, of these alloys are listed in the National Association of Corrosion Engineers (NACE) MR0175, Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment; the tables in this chapter also include some newer alloys not in the NACE document.
Table 2 Martensitic stainless steels for petroleum industry applications
UNS Common name Hardness, HRC, max(a)

The petroleum industry has driven large segments of the steel industry since both their beTable 1 Ferritic stainless steels for petroleum industry applications
UNS Common name

S40500 S40900 S43000 S43035 S43400 S43600 S44200 S44400 S44500 S44600 S44626 S44627 S44635 S44660 S44700 S44735 S44800 S46800

405 409 430 439 434 436 442 444 (18-2) … 446 26-1 Ti, E-Brite 26-1 Cb 26-4-4, Monit Seacure, SC-1 29-4 29-4C 29-4-2 468

J91150 J91151 J91540 K90941 S14125 S41000 S41426 S41427 S42000 S42400 S42500

CA15 CA15M CA6 NM 9Cr 1Mo S/W 13Cr 410 13CRS … 420 F6NM 15Cr JFE KL-12G JFE KNHP12Cr Nippon NT-CRS Nippon NT-CRSS 420M L80 13 Cr

... ... ... ... 28 22 ... 29 22 23 22 ... ... ... ... ... ...

Note: See Appendix 1 for alloy compositions. Source: Adapted from NACE MR0175, “Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment”

Note: See Appendix 1 for alloy compositions. (a) As specified in NACE MR0175. Source: Adapted from NACE MR0175, “Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment”

31 . cathodic protection.. 33 32 33 . which is extremely corrosive to carbon and alloy steel. This cannot be achieved with a martensitic structure.248 / Stainless Steels for Design Engineers Table 3 Precipitation hardening stainless steels for petroleum industry applications UNS Common name Hardness. pitting resistance equivalent number.. Source: Adapted from NACE MR0175. . HRC. after which further alloying is necessary. Each situation must be evaluated regarding which is the optimal solution. as shown in Fig. 2 (Ref 2) indicates. (a) As specified in NACE MR0175. The chapters on martensitic and precipitation hardening stainless steels discuss this in detail. 35 . J93345 J93370 J93380 J93404 S31200 S31260 S31500 S31803 S32001 S32003 S32101 S32205 S32304 S32404 S32520 S32550 S32750 S32760 S32803 S32900 S32906 S32950 S32977 S39274 Escoloy CD4MCu Z100 958 44LN DP3 3RE60 2205 (old) 19D 2003 2101 2205 (new) 2304 U50 52N+ 255 2507 Zeron 100 2803Mo 329 2906 7-Mo Plus AF 918 DP3W 31-47 30-34 38-46 39-47 30-36 34-43 27-31 30-36 20-24 27-31 25-29 34-38 23-27 27-32 37-48 32-44 38-44 40-46 33-41 26-35 36-45 32-43 39-46 39-47 Note: See Appendix 1 for alloy compositions. Nickel is necessary to prevent σ-ferrite formation. . These additions must be made in a very balanced way if a tough. . as Fig... hydrogen uptake ensues. Duplex alloys and austenitic alloys become susceptible at higher temperatures and do not . then the stress corrosion cracking (SCC) cannot be initiated. 3 (Ref 2). molybdenum. The effects of copper and nickel are also very significant. . and nickel can lower the corrosion rate of steel by a factor of 10.. Molybdenum is the most powerful alloying addition to magnify the benefit of chromium. sometimes the wetness is from saltwater. If hydrogen sulfide is present. Note: See Appendix 1 for alloy compositions. max(a) Table 4 Duplex stainless steels for petroleum industry applications UNS Common name PREN(a) S13800 S15500 S15700 S17400 S17700 S35000 S35500 S45000 S45500 S46500 S66286 13-8 PH 15-5 PH 15-7 PH 17-4 PH 17-7 PH AM-350 AM-355 Custom 450 Custom 455 Custom 465 A-286 Custom 465 (275) Custom 475 . “Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment” Combating Corrosion in Alloys for Petroleum Applications Alloying steel with chromium. Source: Adapted from NACE MR0175. (a) PREN. They have high annealed strength and can also be cold worked to higher strength levels. the selection process can become more difficult. or more corrosion-resistant materials are the main responses.. coatings. Figure 1 shows the influence of chromium alone... Being stainless does not by itself provide immunity. If the localized corrosion can be prevented.. What is the answer to the corrosion problem? Inhibitors.. Martensitic steels of all types have a maximum in susceptibility to SCC via hydrogen embrittlement near room temperature. They also represent an ongoing cost rather than a one-time cost.. which produces a 100-fold reduction in corrosion of steel in seawater and carbon dioxide (Ref 1). Only keeping hardness below wellestablished levels can render a martensitic alloy immune.. which would counteract the benefit of the chromium. As if this is not a sufficient material problem. This corrosion problem is compounded by the accelerating influence of high temperature in deeper formations. The first three responses are not always practical. The martensitic stainless steels used for these applications are resistant to carbon dioxideenhanced corrosion up to partial pressures of 100 atm... If localized corrosion occurs. copper.000. Molybdenum alloying expands the pH and chloride range from which an alloy can be free of the pitting corrosion that initiates SCC. but the duplex alloys have the corrosion resistance and strength to work in this regime. fully martensitic structure is to be maintained. and delayed failure follows. however.. which further aggravates corrosivity. Highstrength martensitic steels are susceptible to brittle delayed failure in the presence of hydrogen sulfide. which reduces toughness.. “Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment” The modern dilemma that makes stainless necessary is the addition presence of wet carbon dioxide. Carbon must be kept low to avoid the formation of chromium carbides during tempering.

... S30100 S30153 S30200 S30215 S30300 S30400 S30403 S30409 S30415 S30453 S30500 S30800 S30815 S30900 S31000 S31008 S31254 S31266 S31600 S31603 S31609 S31635 S31700 S31703 S31725 S31726 S31753 S32100 S32109 S32200 S32654 S33000 S33400 S34565 S34700 S34709 S35125 S35315 301 301LN 302 302B 303 304 304L 304H 153MA 304LN 305 308 253MA 309 310 310S 254SMO B66 316 316L 316H 316Ti 317 317L 317LM 317LMN 317LN 321 321H NIC 25 654SMO 330 334 4565 347 347H 332Mo 353MA Cronifer 2328 . Note: See Appendix 1 for alloy compositions.... 46 59 . 60 (C °140 °F).... . . . test duration...... ... stress corrosion cracking.... ... ..1 MPa. .. .. ... .5 m/s. .... . 39 54 38 . ...Chapter 22: Petroleum Industry Applications / 249 Table 5 UNS Austenitic stainless steels for petroleum industry applications Common name PREN(a) UNS Common name PREN(a) J92500 J92600 J92602 J92701 J92710 J92800 J93000 J93254 J93402 J94652 N06022 N08007 N08020 N08020 N08024 N08026 N08028 N08031 N08320 N08366 N08367 N08700 N08800 N08925 N08926 N08932 N80904 S20100 S20153 S20200 S20400 S20430 S20500 S20910 S21800 S21900 S21904 S24000 CF-3 CF-8 CF-20 CF-16F CF-8C CF-3M CF-12M CG-8M CK3MCuN CH-20 CN-3MN AL 22 CN-7M 20Cb-3 AL 20 20Mo-4 20Mo-6 Sanicro 28 Nicrofer 3127 hMo 20Mod AL-6X AL-6XN JS-700 332 25-6Mo Cronifer 1925 hMo URSB-8 904L 201 201LN 202 Nitronic 30 (204L) 204 205 Nitronic 50 Nitronic 60 Nitronic 40(219) 21-6-9 LC Nitronic 33 ... . 0.... Source: Ref 2 .. ...... 2 Influence of copper and nickel on the corrosion rate of martensitic stainless alloys used for oil country tubular goods... 25 .. CO2 partial pressure.. .. . 54 .. “Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment” Fig... . ... . .. . .. .... .. .. . 64 . ..... .... (a) PREN. .. pitting resistance equivalent number. 800 mL/cm2. 46 47 49 39 . specific volume.. .. .. Source: Ref 1 Fig. .. ........ . .. . 2........ . Test conditions: synthetic sea water. ... .. . . .. 150 h. Source: Adapted from NACE MR0175....... . . SSC. 49 36 ..... 28 28 38 ....... test temperature.. ..... ... .. ..... flow velocity.. . 1 Influence of chromium on the corrosion rate of steel in environments experienced by oil country tubular goods.... .

which enhances hydrogen uptake. duplex alloys are required. are optimized for the conditions of each well. The reader is encouraged to refer to the latest version of this document for further details. has nearly the least corrosion resistance of all stainless steels. The terms 13Cr. which have been defined by NACE. The variety of strengths and sizes are standardized by the American Petroleum Institute. torsion. so that the maximum hardness for a given material must be strictly adhered to when hydrogen sulfide is present. Any producer’s alloys must comply with this diagram’s regions. 22Cr. Source: Ref 2 exhibit the same increasing susceptibility with strength. The 22Cr and 25Cr alloys are duplex grades. with the 22CR alloys such as UNS S32205 used at temperatures up to 200 °C (390 °F) and the 25CR alloys such as UNS S32507 at temperatures up to 250 °C (480 °F). alloying must also. The former are used in the quenched and tempered condition. 3 Influence of molybdenum on susceptibility to stress corrosion cracking in solutions containing (a) 3. Oil Country Tubular Goods Oil country tubular goods (OCTG) include the drill pipe. Nickel-base alloys are required at hydrogen sulfide levels above 1 atm partial pressure. and tubing and associated hardware used to construct oil and gas wells. casing. This alloy. Molybdenum at 1% increases resistance to general corrosion in a sodium chloride/ hydrogen sulfide/carbon dioxide environment by about tenfold. . As temperatures and hydrogen sulfide partial pressures increase.250 / Stainless Steels for Design Engineers The NACE recommendations of suitable materials are defined by MR0175. and 25Cr are commonly used in the industry even though this greatly oversimplifies the alloying. Drill pipe is in tension. when hydrogen sulfide. the martensitic alloys should no longer be used. which is a straight-chromium martensitic often used for cutlery. while the duplex alloys are used as annealed or cold worked. Figure 4 shows this progression with the alloy recommendations of Sumitomo. To achieve higher corrosion resistance molybdenum is added. Casing is put in place to stabilize the well walls. while far better (about 100 times) than alloy steel in corrosion resistance. At higher levels of carbon dioxide and hydrogen sulfide. Table 6 summarizes these recommendations. So. Another 1% increases it another Fig. and high strength-to-weight materials are needed. and the duplex alloys are preferred. The 13Cr alloys are a family of martensitic stainless steels. Casing hangs from the wellhead under its own weight for distances from hundreds of meters to 7000 or 8000 m and must withstand very high collapse as well as burst pressures. while tubing is placed within the casing to carry oil and gas to the surface. levels exceed about 10–2 atm. Drill pipe is used to twist the drill bit and convey drilling fluids to the point of contact and flush away debris. and therefore performance. and compression alternately throughout its life. Martensitic alloys. The requirements behind this diagram are generic. The use of the highest strengths has always been limited by hydrogen embrittlement accelerated by hydrogen sulfide. commonly called “13Cr. the exact sequence of size and strength pipe for each level of the well. Well strings. Each of these components sees significant stresses. options that exist. until at 1 atm of hydrogen sulfide nickel base alloys are required. Stainless steels are required above a certain carbon dioxide level for all levels of hydrogen sulfide.5% NaCl and (b) 0% NaCl.” are the first step up from alloy steels. The 13Cr grades began as simply variations on 420.

Martensitic alloys are susceptible to SCC by a hydrogen embrittlement mechanism. Thus. If the hydrogen sulfide level exceeds 0. 4 Alloy suitability as a function of H2S and CO2 partial pressure. This susceptibility is strongly temperature dependent. nickel must be added to counter the ferrite stabilizing effect. unfortunately. which in turn eliminates the initiation point of SCC. which cannot transform to martensite and would therefore reduce mechanical properties.03 atm. for example. The nickel does help lower the general corrosion rate. Hydrogen sulfide may be contained in the petroleum. or it may come from sulfate-reducing bacteria. then 22Cr alloys should be used rather than 13Cr because of this risk. introduced by flooding. The 2% level of molybdenum also greatly reduces pitting. Simply adding molybdenum would cause the alloy to have excessive δ-ferrite. These alloys are otherwise almost identical to precipitation hardening martensitic stainless steels without the precipitating phase. The 22Cr and 25Cr alloys have significantly higher resistance to chlorides and wet hydrogen . Source: Ref 1 tenfold.Chapter 22: Petroleum Industry Applications / 251 Fig. This can cause a sulfide-free system to become sulfide rich after the fact and make initial materials choice wrong after the fact. Carbon and nitrogen in these alloys are kept at low concentrations. It decreases with temperature from a maximum at ambient to none at around 100 °C (210 °F). but necessarily increasing the cost.

and nitrogen levels of the 22Cr and 25 Cr alloys (see the chapters on corrosion in this book)... 410 .. There was one instance of very high-strength tubing cracking after cathodic contact with carbon steel casing. 450 A286 Austenitic A-2 Duplex Superaustenitic.5 4... ... hydrogen sulfide. that these alloys will see their first service as line pipe. .. .. ..... .5 3. 3.. ... . .. . salinity.. .. the case for stainless line pipe is easily made. . ..... .. 450 MPa (65 ksi).. .... (a) PREN. .. the duplex alloys have very fine grain size and a roughly 50/50 mixture of ferrite and austenite. .... 10 10 10 . 90.. .. ... . where they will not need to be cold worked to higher strength levels to be widely used... .. temperatures. . This evaluation is made based on the carbon dioxide..... 600 MPa (87 ksi). 35 . .... .. .. 15-5 15-7 17-4 . See Appendix 1 for alloy compositions.5 3.. molybdenum.... Besides the inherently greater corrosion resistance that derives from the chromium... . .... .. .. It is likely. .. The recent development of lean duplex alloys has not yet made its way into OCTGs...... . HRC Cl–...4 100 10 10 10 10 10 10 10 10 10 1 100 ..000 5.. The more common alloys are UNS S32654 and N08367. water... . and so forth. This was after removal from the well and after handling damage had occurred.. This acts as a crack arrestor should one phase be susceptible to cracking while the other is not. 6. For corrosion resistance above that furnished by superduplex materials such as the 25Cr alloys.. ...5 3...... min H2S. .. .. . There have been no reported downhole failures of annealed or cold-worked duplex alloys...5 3.. The more advanced of them contain high levels of nitro- gen... ..5 3.. These alloys achieve a tenfold increase in hydrogen sulfide resistance and very elevated SCC resistance.. 3.. 700 310 100 22 22 23 100 HRB 94 HRB .... . . .... 33 32 33 . The normal basis for ....... .. kPa Hardness. .5 3... .5 ..... ... mg/L J91150 J91151 J91540 J93254 J95370 N08926 S15500 S15700 S17400 S20910 S41000 S41425 S41426 S41427 S41429 S41500 S42000 S42400 S42500 S45000 S66286 CA15 CA15M CA6NM . . .. flow conditions. . super austenitic alloys fill a gap before nickel base alloys are needed. 22 28 27 29 27 23 22 23 22 31 35 22 ..... Line Pipe and Flow Lines With the awesome cost of corrosion. .... ...700 . . however.5 ..... .. 3...... .... ... .. . 3. type 3b .... Whether to use stainless depends on vulnerability of carbon steel. <40 >40 <45 (Ni+2Mo) >30 >40 . ºC (ºF) pH.. so for most downhole applications they will require cold working... are lower than those of the martensitic alloys. .... ....... 150 (300) 121 (250) . 5.. .252 / Stainless Steels for Design Engineers Table 6 Restrictions in use recommended by NACE MR0175 for selected stainless steels used for petroleum industry applications UNS Common name PREN(a) Temperature.. 700 700 3. .....000 .. ...5 3. Source: Adapted from NACE MR0175. ... 10 20 . . .. .. . .. . .000 Notes: See NACE MR0175 for further use and processing restrictions. type 3a Superaustenitic... pressures. ..... 65 (150) ... 232 (450) 232 (450) ..... 121 (250) 149 (300) 171 (340) 3. ..4 . pitting resistance equivalent number. ... ... “Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment” sulfide and can resist SCC at ten times higher concentrations than the 13Cr alloys. . .. ...5 .000 5. These alloys offer an inherent alloy savings over the 13Cr grades in nickel and molybdenum content while offering better corrosion and SCC resistance..000 60.. Their strength levels in the annealed condition. F6NM 420 .... The affected microstructure was found to be high (70%) in ferrite (Ref 3). These are the so-called 6Mo grades...5 . ....... 66 (150) . .

The use of inhibitors is subject to the risk of velocity limitations. Then. Nitrogen not only enhances corrosion resistance. carry communications. which has led to the use of duplex stainless steel because of its strength and resistance to corrosion and SCC. The main ingredients required in a duplex for strength and corrosion resistance are chromium and nitrogen. but again the lean duplexes offer possibilities to do so. These alloys are being promoted on their lower susceptibility to σ formation during welding. and if welding thermal cycles cannot be controlled that may be an issue. Line pipe differs from downhole in having strength requirements more in line with that of annealed duplex alloys. Superduplexes. Alloys S32001 and S32101 are well formulated for medium and high levels of corrosion resistance required for wet carbon dioxide. but also suppresses the formation of undesirable and embrittling intermetallic phases that might otherwise form at welding temperatures. mechanical damage. Coatings can be damaged by numerous occurrences in acidity. The modern alloys have high (greater than 0. hydrogen sulfide. or to line carbon steel with a protective coating. Duplex pipelines have been in service in the North Sea since the 1970s. and trace chlorides. The emergence in the early 2000s of lean duplex alloys provided strength and more corrosion resistance with lower nickel levels. the need to improve costs led in the 1990s to the use of martensitic alloys with high levels of nickel and molybdenum. or fluctuations in temperature or pressure. which is another reason why the lean duplex alloys are so attractive. This can be achieved by stabilizing the alloy with small amounts of titanium. not to mention cost. wells are located undersea. but for martensitic alloys. For subsea use. Cathodic protection is costly and complex. giving them a cost advantage during periods of high nickel cost. but superduplex seems to have become a pervasive choice because it is superbly reliable. These requirements gave birth to modern duplex alloys. This is not an overwhelming challenge for duplex alloys. When resistance to seawater is the main concern. de Waard of Shell (Ref 3). It would appear that under current conditions that alloy 2101 (UNS 32101) has a cost/performance edge over the martensitic competition and should for the long term. very long service lives can be safely extrapolated. Nevertheless. whereas resistance to crevice corrosion requires a PREN of at least 40. The main precaution for duplex alloys is maintaining a nominally 50/50 mixture of ferrite and austenite with no embrittling intermetallic phases. Such a critical item as an umbilical may seem like a poor application on which to economize. both relatively inexpensive alloying elements. more alloys have emerged. Since the development of the first widely accepted duplex alloys.Chapter 22: Petroleum Industry Applications / 253 these calculations follows that published by C. It is standard practice to control and monitor these wells via bundled umbilical tubing. temperature limitations. The competing technology when corrosion dangers arise is the use of corrosion inhibitors. the rule of thumb is that a pitting resistance equivalent number (PREN) of 35 or greater is required. The main attribute required by line pipe that is not as important in OCTGs is weldability. and even introduce chemical to the well. Use of a stainless corrosion-resistant alloy can have well-defined and controlled costs and performance over the life of an installation. and simply of the inhibitor working appropriately. . 25Cr duplexes are used without cathodic protection. Umbilical Tubing and Risers Increasingly. it requires a very low interstitial level so that the martensite is self-tempering and ductile in the as-welded condition. 22Cr duplex generally requires cathodic protection because of the risk of crevice corrosion. cathodic protection. which at the time were lower cost. By zinc coating lean duplexes such as alloy 19D (UNS S32001) and 2101 (UNS S32101). which helps to preserve austenite levels after welding and suppress intermetallic formation. This has made the superduplex UNS S32750 the standard.14%) nitrogen. such as UNS S32750. have become accepted alloys. control and adjust pressure. The depth of wellheads can increase collapse pressures to levels beyond the capability of thermoplastics. minimization of time above 350 °C (660 °F) is important. It also keeps the desirable austenite/ferrite ratios in weld metal. The tubing can provide hydraulic and electrical power. starting with UNS S31803 and evolving to UNS S32205 as the value of higher nitrogen became understood. This tendency increases with chromium and molybdenum content.

As we discussed. Converting natural gas to a cryogenic liquid presents a material problem.) diameter. MEA. ammonia. Liquefied Natural Gas Vessels Liquefied natural gas (LNG) is becoming an increasingly important commodity as the value of stranded gas makes it economically desirable to convert it to a transportable state. chlorides (a) PTA. The extreme ductility of 201LN compared to martensitic steel gives it a decided advantage in terms of rupture resistance. The traditional material. 316L 20Cb3 316L 321. Almost any structure is a candidate for stainless topside processing: piping. mixer Effluent piping Hot sections General Reactor internals Heat exchangers Trays Cyclones. has become expensive compared to the lower-nickel austenitic stainless steels. stainless steel wins the cost battle between these alloy systems. which otherwise can result in concentration cells and consequent pitting. 2205 … Depending on crude corrosivity Depending on chloride level Depending on crude corrosivity … … … Low pH excursions possible … Long exposure at high temperature … HCl catalyst regeneration … Condensers may need 6Mo … … Depending on temperature.254 / Stainless Steels for Design Engineers Risers are now produced in coiled tubing of over 100 mm (4 in. DEA Sulfuric acid Dilute sulfuric acid H2S. Except in rare cases. which 9% Ni steel is not. 409. which have no transition temperature and strengthen with decreasing temperature. condenser tubing Contactor. Seawater systems often employ 22Cr duplex with cathodic protection or unprotected 25Cr duplex. 2205. crude oil itself is sometimes a very corrosive fluid. H2S H2S. fittings. 347 410S. the corrosion environment is severe. 2507 410S. trays. pumps. chlorides Sulfuric acid. easier to weld and fabricate. 20Cb3. Table 7 Process Refinery Equipment Corrosion resistance is a major factor in the choice of materials in refinery operations. chlorides Preheaters. 2205 409 AL-6XN. Both titanium and stainless alloy UNS S32750 are equal candidates for this service. PTA(a) High-temperature strength needed HCl residue High temperature Amine plant Sulfuric acid alkylation Hydrotreating Catalytic re-forming Fluid catalytic cracking Hydrogen plant Hydrocracking Sour water stripping Sulfides. Source: Ref 4 . ammonium bisulfide. which is a major design and political concern with this potentially explosive commodity. polythionic acid. 347. distillation tower Towers Condensers Coke drums Compressor coolers. and of course is stainless. water. risk of chlorides Severity depends on presence of sulfuric acid Coker Gas plants SCA. reboiler tubes Trays Reboilers. so that very economical long lengths are feasible. 410 405. filters. heat exchangers Heat exchangers Stripper 405.000 in steel in the subsea jacket. 316 S44735. A savings of 1 ton in weight topside can save over $100. 321. depending on availability and current alloy prices. 2205. vapor lines Tubing. and the penalty for excess weight is also high. 304 304 2205 410 304 304 409. Alloy 201LN is cheaper. 410. flanges. ammonia Ammonia. 9% Ni martensitic steel. but in refining the by-products. Vessels to contain it must have strength and toughness at temperatures below –150 °C (–240 °F). Platforms Platforms present a special case in which the costs of maintenance are high. Hardware of any type and construction materials benefit from being stainless. 316L 304L. This leads to a rapid payback for the use of materials that are sufficiently resistant to corrosion such that corrosion loss allowance can be eliminated. A wise preventive action is to paint stainless that is covered by insulation or similar material. etc. Cl–. 6Mo 304. Stainless steels used in various refinery processes Corrosive agents Applications Alloys Notes Crude distillation Vacuum fractionalization Sulfur-containing acids (SCAs) SCA. such as 201LN (UNS S20153).

Sumitomo Products for the Oil and Gas Industries. www. C. Corrosion Resistance of Stainless Steels. H. which are prone to grain boundary chromium depletion by sensitization. sulfuric acid. Table 7 lists some major refinery processes and the materials used in them (Ref 4). Marcel Dekker. January 1997 3. polythionic acids. The aggressive chemical agents that refinery materials must withstand include wet hydrogen sulfide and carbon dioxide.” Nippon Steel Technical Report 72. and instead use low-carbon grades and stabilized grades. Most of these situations are discussed elsewhere in this book in detail. 1995 .jp. Lotz. and alkalines as well as simple oxidation. National Association of Corrosion Engineers. de Waard and U. accessed June 2008 2. Sometimes. REFERENCES 1. Dillon. “Development of High Chromium Stainless Line Pipe.. The remedies are to prevent the inadvertent formation of PTA and to avoid using These acids usually form accidentally when sulfide corrosion products react with moisture and air. Asahi et al. and materials respond to it much as they do to the Strauss test.” Paper 69.Chapter 22: Petroleum Industry Applications / 255 chemicals used in refining and the temperatures used may further aggravate that corrosivity. The attack is intergranular. presented at Corrosion/93. napthenic acids. 1993 4. chlorides. “Prediction of CO2 Corrosion of Carbon Steel. temperatures of use are such that embrittling or sensitizing phase transformations may occur.P. One that is quite specific to refinery applications is polythionic acid (PTA) attack. C.

Stainless Steels for Design Engineers Michael F. McGuire, p 257-263 DOI: 10.1361/ssde2008p257

Copyright © 2008 ASM International® All rights reserved.


Chemical and Process Industry Applications
ENGINEERS IN THE PROCESS industries must have materials that can contain a huge variety of chemical species at many temperatures, pressures, and flow rates. This is applied corrosion engineering combined with physics and structural design. It is obvious that this task depends on the availability of corrosion data, more than can be presented here. This chapter covers what data are necessary and how they can be found.

Single- and Dual-Environment Systems
Under ideal conditions, a material may need to resist one single major corrosion threat. If the most potentially damaging species can be clearly identified, then candidate materials can be found by searching published data. These data are available freely online from Web sites (such as Ref 1 and 2) or for a charge from sources such as the National Association of Corrosion Engineers (NACE; Ref 3) and ASM International (Ref 4). It is difficult for any published data to keep up with the latest developments. The testing alone of new materials can take a long time, and then it must wait for publication. All materials are not covered, especially when a manufacturer publishes data on proprietary alloys and excludes competitive materials. That having been said, any improvements over standard alloys will first be reported by the developers of the alloy, and they will logically tout its strongest points. For this reason, dialogue with the primary steel producers is encouraged. No one has more exposure to the latest trends in applications. A single-environment system is typically one in which the aggressive chemical species is the only consideration. This is normally the case for piping, tanks, or reaction vessels holding the species or materials immersed in the aggressive species. A dual-environment system is typically encountered in heat exchangers, but it must also be extended to single-environment systems in which the exposure of the nonreactant side of the material to the ambient environment cannot be neglected, as in the case of marine ambient environments.

The need to work with hostile chemicals begins with the manufacture of those chemicals. It was in the production of nitric acid that stainless had its first industrial application. These are industries with purely need-driven material challenges. New processes are constantly in development, and they present new environments in which materials must perform. The choices are highly pragmatic. In an industrial environment, the costs of a poorly performing material can be well known by its effect on downtime, maintenance, liability, etc. The essential knowledge is which materials will work. The selection of materials for the chemical and power industries is first a study of corrosion resistance, including resistance to stress corrosion cracking (SCC). Strength plays a secondary role but can be an important cost factor. These considerations may occur at very high or very low temperatures, in which case corrosion resistance may become oxidation resistance and strength may mean creep strength.

258 / Stainless Steels for Design Engineers

The challenges that must be met are primarily ensuring adequate corrosion resistance and secondarily having acceptable mechanical properties. The corrosion issues run the full gamut of potential forms of corrosion: • General corrosion • Pitting corrosion and crevice corrosion • Intergranular corrosion • Stress corrosion cracking • Erosion corrosion In addition to these forms of corrosion associated with liquids, there are considerations of gas phase attack, which may be oxidation, sulfidation, or attack by other gases. Mechanical design considerations are normally limited to static stress allowances. Previously, handbooks dealt very lightly with this topic because all the normally recommended steels had similar strength. The proliferation of duplex stainless steels has changed that. Now, high-strength alloys of high corrosion resistance and SCC resistance are available and are making traditionally chosen stainless steels less than optimal.

Fig. 1

Isocorrosion chart for sulfuric acid. Source: Ref 1

Corrosion Types
A designer wants to deal with general corrosion. Its rate can be predicted, and thickness can be chosen to allow for its occurrence. Corrosion data for general corrosion are normally presented in isocorrosion charts. These present the temperatures and concentrations for a given environment at which various materials will exhibit the same corrosion rate. This rate is most often 0.1 mm/yr, an amount that can be thought of as a tolerable level for many uses. Figure 1 shows an isocorrosion chart for stainless steels in sulfuric acid (Ref 1). The data are clear when presented in this fashion. It can further be appreciated that in general reducing alloy performance to a mathematical formula, such as the pitting resistance equivalent number (PREN) equation, would not be reasonable since the relative performance of alloys changes considerably with concentration. Thus, the design engineer must rely on experimentally developed data. Since these data are available both online and in print, no attempt will be made to reproduce them fully here. Examples are given in Tables 1 and 2 (Ref 1). Such tables are very useful, although the presentation is not visually compact. The inclusion

of carbon steel and titanium gives a valuable frame of reference for the engineer. If the forms of localized corrosion discussed next can be avoided, the corrosion tables are sufficient to guide the designer to a reasonable selection of candidate materials for any process in which the chemical species involved have been identified. If the data have not been developed for a certain environment, then the tables give a first approximation of which materials may be resistant from examination of similar environments, and a final decision can only be reasonably made though direct corrosion testing of candidate materials. Refer to the chapters on corrosion for a more thorough discussion of uniform corrosion. Pitting and Crevice Corrosion Stainless steel is unique among metals and alloys in that it derives its corrosion resistance from constituent alloying elements working together to form a thin passive layer that, when intact, is highly resistant to corrosion. The strength of the passive layer in resisting attack by halide ions, which are the most disruptive ions to the layer, is proportional principally to the chromium, nitrogen, and molybdenum contents of the alloy. This relationship follows the formula:
PREN = %Cr + 3.3%Mo + 30%N (Eq 1)

This formula is one of the commonly used versions, none of which is universally correct. Both tungsten and carbon can increase pitting resistance, while sulfur diminishes it. This is discussed in the corrosion section of this book.

Chapter 23: Chemical and Process Industry Applications / 259

The important consideration is that this formula assumes that the key alloying elements are homogeneously distributed in solution. This will only be true if correct thermomechanical processing occurs because, thermodynamically, these alloys are not used in an equilibrium condition. Were they to attain equilibrium, say by overheating, alloy segregation by precipitation could occur, causing localized loss of corrosion
Table 1 Corrosion table for sulfuric acid (H2SO4)
0.1 100 = BP 0.5 20 0.5 50 0.5 100 = BP 1 20 1 50

resistance, which is what causes pitting. Chromium is very reactive: Its affinity for oxygen makes the passive film strong. Pitting has nearly always been associated with manganese sulfide inclusions, and although there is still debate over the precise mechanism, it appears that chromium depletion at the metal-inclusion interface is to blame. Eliminating inclusions by eliminating either manganese or sulfur improves

Concentration, % Temperature, °C

1 70

1 85

1 100 = BP

2 20

2 50

2 60

3 20

3 35

3 50

Carbon steel 13% Cr steel 18-2 (UNS S44400) 3R12 (UNS S30400) 3R60 (UNS S31600) 18-13-3 17-14-4 2RK65 (UNS N08904) Sanicro 28 (UNS N08028) 254SMO (UNS S31254) 654 SMO (UNS S32654) SAF 2304 (UNS S32304) SAF 2205 (UNS S31803) SAF 2507 (UNS S32750) Titanium
Concentration, % Temperature, °C

2 2 2 2 1 1 1 0 ... ... ... 1 ... ... 1
3 85

2 2 0 0 0 0 0 0 0 0 0 0 0 0 0
3 100 = BP

2 2 2 1 0 0 0 0 0 0 0 0 0 0 0
5 20 5 35

2 2 2 2 1 1 1 1 0 ... ... ... 1 ... 1
5 60

2 2 0 0 0 0 0 0 0 0 0 0 0 0 0
5 75

2 2 2 1 0 0 0 0 0 0 0 0 0 0 0
5 85

2 2 2 1 0 0 0 0 0 0 0 0 0 0 1

2 2 2 2 1 1 0 0 0 0 0 0 0 0 1
5 101 = BP 10 20

2 2 2 2 1 1 1 1 0 1 0 1 ... 0 1
10 50

2 2 0 0 0 0 0 0 0 0 0 0 0 0 0
10 60

2 2 2 1 0 0 0 0 0 0 0 0 0 0 0
10 80

2 2 2 1 0 0 0 0 0 0 0 0 0 0 1

2 2 0 0 0 0 0 0 0 0 0 0 0 0 0
10 102 = BP

2 2 2 1 0 0 0 0 0 0 0 0 0 0 0
20 20

2 2 2 1 0 0 0 0 0 0 0 0 0 0 1
20 40

Carbon steel 13% Cr steel 18-2 (UNS S44400) 3R12 (UNS S30400) 3R60 (UNS S31600) 18-13-3 17-14-4 2RK65 (UNS N08904) Sanicro 28 (UNS N08028) 254SMO (UNS S31254) 654 SMO (UNS S32654) SAF 2304 (UNS S32304) SAF 2205 (UNS S31803) SAF 2507 (UNS S32750) Titanium

2 2 2 2 1 1 1 0 ... ... 0 ... ... ... 1

2 2 2 2 2 2 2 1 1 1 0 1 1 1 2

2 2 2 1 0 0 0 0 0 0 0 0 0 0 0

2 2 2 1 0 0 0 0 0 0 0 0 0 0 1

2 2 2 2 1 0 0 0 0 0 0 0 0 0 1

2 2 2 2 1 1 1 0 0 0 0 0 0 0 2

2 2 2 2 2 2 2 1 0 1 0 0 0 ... 2

2 2 2 2 2 2 2 2 2 2 2 2 2 ... 2

2 2 2 2 0 0 0 0 0 0 ... 0 0 0 1

2 2 2 2 1 1 0 0 0 0 ... 0 0 0 2

2 2 2 2 1 1 1 0 0 0 0 0 0 0 2

2 2 2 2 2 2 2 1 0 0 0 2 1 0 2

2 2 2 2 2 2 2 2 2 2 ... 2 2 2 2

2 2 2 2 0 0 0 0 0 0 0 1 0 0 2

2 2 2 2 1 1 1 0 0 0 0 2 0 0 2

Notes: 0, corrosion rate of less than 0.1 mm/yr. The material is corrosion proof. 1, corrosion rate of 0.1–1.0 mm/yr. The material is not corrosion proof but useful in certain cases. 2, corrosion rate of more than 1.0 mm/yr. Serious corrosion. The material is not usable. BP, boiling solution. Source: Adapted from Ref 1

260 / Stainless Steels for Design Engineers

Table 1

20 50 20 60 20 80 20 100 30 20 30 40 30 60 30 80 40 20 40 40 40 60 40 90 50 20 50 40 50 70

Concentration, % Temperature, °C

Carbon steel 13% Cr steel 18-2 (UNS S44400) 3R12 (UNS S30400) 3R60 (UNS S31600) 18-13-3 17-14-4 2RK65 (UNS N08904) Sanicro 28 (UNS N08028) 254SMO (UNS S31254) 654 SMO (UNS S32654) SAF 2304 (UNS S32304) SAF 2205 (UNS S31803) SAF 2507 (UNS S32750) Titanium
Concentration, % Temperature, °C

2 2 2 2 1 1 1 0 0 0 0 2 0 0 2
60 20

2 2 2 2 2 1 1 0 0 0 0 2 1 0 2
60 40

... ... ... ... ... ... ... 1 ... ... 0 2 2 1 2
60 70

2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
70 20

2 2 2 2 1 1 1 0 0 0 ... 2 0 ... 2
70 40

2 2 2 2 2 1 1 0 0 0 ... 2 1 0 2
70 70

2 2 2 2 2 2 2 1 1 1 ... 2 2 1 2
80 20

... ... ... ... ... ... ... ... ... 2 ... 2 2 2 2
80 40

2 2 2 2 2 2 2 0 0 ... 0 2 2 0 2
80 60

2 2 2 2 2 2 2 0 0 1 0 2 2 1 2
85 20

2 2 2 2 2 2 2 1 1 ... 0 2 2 2 2
85 30

2 2 2 2 2 2 2 2 2 ... ... 2 2 2 2
85 40

2 2 2 2 2 2 2 0 0 0 0 2 2 1 2
85 50

2 2 2 2 2 2 2 0 0 1 0 2 2 1 2
90 20

2 2 2 2 2 2 2 2 1 ... ... 2 2 2 2
90 30

Carbon steel 13% Cr steel 18-2 (UNS S44400) 3R12 (UNS S30400) 3R60 (UNS S31600) 18-13-3 17-14-4 2RK65 (UNS N08904) Sanicro 28 (UNS N08028) 254SMO (UNS S31254) 654 SMO (UNS S32654) SAF 2304 (UNS S32304) SAF 2205 (UNS S31803) SAF 2507 (UNS S32750) Titanium
Concentration, % Temperature, °C

2 2 2 2 2 2 2 0 0 0 0 2 2 ... 2
90 40

2 2 2 2 2 2 2 1 0 1 1 ... 2 ... 2
90 70

2 2 2 2 2 2 2 1 1 ... ... ... 2 ... 2
94 20

2 2 2 2 2 2 2 0 0 0 0 ... 1 ... 2
94 30

2 2 2 2 2 2 2 1 0 1 1 ... ... 2 2
94 40

2 2 2 2 2 2 2 1 1 ... ... ... ... 2 2
94 50

2 2 2 2 1 1 1 0 ... 0 ... ... 2 ... 2
96 20

2 2 2 2 2 2 2 1 1 1 ... ... 2 2 2
96 30

2 2 2 2 2 2 2 2 1 2 ... ... 2 2 2
96 40

0 1 1 1 1 1 1 0 0 0 ... 1 1 1 2
96 50

1 1 1 1 1 1 1 0 0 ... ... 1 ... 1 2
98 30

2 2 1 1 1 1 1 1 0 ... ... ... ... ... 2

2 2 2 2 2 2 2 1 0 ... ... ... ... ... 2
98 40

0 0 0 0 0 0 0 0 0 1 1 ... 1 0 2
98 50

1 1 1 0 0 1 1 0 0 ... ... 1 1 0 2
98 80

Carbon steel 13% Cr steel 18-2 (UNS S44400) 3R12 (UNS S30400) 3R60 (UNS S31600) 18-13-3 17-14-4 2RK65 (UNS N08904) Sanicro 28 (UNS N08028)

2 2 2 2 1 1 1 1 0

2 2 2 2 2 2 2 2 1

0 0 0 0 0 0 0 0 0

2 1 0 0 0 0 0 0 0

2 2 2 1 0 1 1 1 0

2 2 2 1 1 1 1 1 0

0 0 0 0 0 0 0 0 0

1 1 0 0 0 0 0 0 0

2 2 1 0 0 1 1 1 0

2 2 2 1 1 1 1 1 1

1 1 0 0 0 0 0 0 0

1 1 1 0 0 0 0 1 0

2 2 2 2 0 1 1 1 0

2 2 2 2 2 2 2 2 1

Notes: 0, corrosion rate of less than 0.1 mm/yr. The material is corrosion proof. 1, corrosion rate of 0.1–1.0 mm/yr. The material is not corrosion proof but useful in certain cases. 2, corrosion rate of more than 1.0 mm/yr. Serious corrosion. The material is not usable. BP, boiling solution. Source: Adapted from Ref 1

Chapter 23: Chemical and Process Industry Applications / 261

Table 1

90 40 90 70 94 20 94 30 94 40 94 50 96 20 96 30 96 40 96 50 98 30 98 40 98 50 98 80

Concentration, % Temperature, °C

254SMO (UNS S31254) 654 SMO (UNS S32654) SAF 2304 (UNS S32304) SAF 2205 (UNS S31803) SAF 2507 (UNS S32750) Titanium

1 2 1 1 0 2

... 2 ... ... ... 2

... ... ... 0 0 2

... ... ... ... 0 2

... ... ... ... 0 2

... 2 ... ... 1 2

1 0 1 0 0 2

... 1 ... 0 0 2

... ... ... 1 0 2

... 2 0 ... 1 2

... ... ... 0 0 2

... ... ... 0 0 2

0 1 0 1 0 2

2 1 1 1 1 2

Notes: 0, corrosion rate of less than 0.1 mm/yr. The material is corrosion proof. 1, corrosion rate of 0.1–1.0 mm/yr. The material is not corrosion proof but useful in certain cases. 2, corrosion rate of more than 1.0 mm/yr. Serious corrosion. The material is not usable. BP, boiling solution. Source: Adapted from Ref 1

Table 2 Corrosion table for fuming sulfuric acid (oleum), H2SO4 + SO3
Conc. H2SO4, % Conc. SO3, % Temperature, °C 100 7 60 100 11 60 100 11 100 100 60 20 100 60 70 100 60 80

Carbon steel 13% Cr steel 18-2 (UNS S44400) 3R12 (UNS S30400) 3R60 (UNS S31600) 18-13-3 17-14-4 2RK65 (UNS N08904) Sanicro 28 (UNS N08028) 254SMO (UNS S31254) 654 SMO (UNS S32654) SAF 2304 (UNS S32304) SAF 2205 (UNS S31803) SAF 2507 (UNS S32750) Titanium

0 0 0 0 0 0 0 0 ... ... ... ... ... ... 2

0 0 0 0 0 0 0 0 ... ... ... ... ... ... 2

2 2 ... 1 0 ... ... ... ... ... ... ... ... ... 2

... ... ... 0 0 ... 0 0 ... ... ... ... ... ... 2

... ... ... 0 0 0 0 0 ... ... ... ... ... ... 2

... 2 ... 0 0 ... ... ... ... ... ... ... ... ... 2

When a crevice is permitted to exist, it mimics the pH-altering action found within pits in which transport restriction leads to a buildup of metal and hydrogen ions and oxygen depletion. All alloys undergo crevice corrosion under less-aggressive conditions than those required to induce pitting, so care must be taken to avoid crevices. Intergranular Corrosion Intergranular corrosion is a problem that can be avoided entirely by correct alloy selection and proper thermal processing. The principle cause of grain boundary attack is alloy depletion at the grain boundaries. The most familiar form of this problem occurs when austenitic alloys having carbon levels above 0.03% are welded. The region near the weld where temperatures reach 600 to 900 °C (1100 to 1650 °F) may have carbon migrate to and along grain boundaries, the fast diffusion paths, where it combines with less-mobile chromium atoms and precipitates as chromium carbide. This lowers the chromium level in solution, resulting in poor corrosion resistance only at the grain boundaries. This is easily prevented by selecting alloys with low carbon levels. Duplex alloys, curiously, undergo chromium carbide precipitation under the same conditions but do not undergo significant chromium depletion because the neighboring ferrite grains, in which chromium diffuses more rapidly, contribute chromium, mitigating the depletion. Precipitation segregation of all types, not just by carbides, must be guarded against. Sigma phase, nitrides, secondary austenite, and others can cause local breakdown of corrosion resistance if alloys are heated to a dangerous temperature for sufficient time. It is important to learn these potential

Notes: 0, corrosion rate of less than 0.1 mm/yr. The material is corrosion proof. 1, corrosion rate of 0.1–1.0 mm/yr. The material is not corrosion proof but useful in certain cases. 2, corrosion rate of more than 1.0 mm/yr. Serious corrosion. The material is not usable. Conc., concentration. Source: Adapted from Ref 1

the potential at which passive film breakdown occurs. This is especially important for welds, which, if not annealed, can have maximum deleterious segregation by both inclusions and solidification segregation. All austenitic and duplex stainless alloys have best corrosion resistance when quenched from the solution annealing temperature. The precipitation hardening, martensitic, and ferritic alloys are more complicated but are less relevant to this topic. If information on them is needed, they are discussed in detail in their respective chapters.

262 / Stainless Steels for Design Engineers

vulnerabilities by reviewing the metallurgy of any alloy selected for service.

Stress Corrosion Cracking
The theory of SCC is still under debate. The reader will find the arguments confusing as the debate generates more heat than light. We will skip the theory; it can be found in the corrosion chapters. SCC, like excessive general corrosion or pitting, is avoided by referring to published test data from the corrosion tables. If a material must be used where a risk of SCC occurs, then stress levels must be managed to stay below the threshold stress for SCC. Figure 2 shows how various alloys resist SCC as a function of chloride concentration and temperature, the two most important aggravating factors. Material comparisons are made difficult because tests are normally run at a given fraction of a material’s yield strength. Thus, the data in Fig. 2 (Ref 1) must be interpreted. Higher-strength duplex alloys, while having better SCC performance than austenitics of equal corrosion resistance (e.g., 316 vs. 2304), have much better SCC resistance. Furthermore, the stress at which failure will occur is much higher since the yield strength at which the testing takes place is about twice as high for duplex alloys. SCC also exhibits a threshold stress below which failure does not occur. This is about 60% of tensile strength for duplex and about 30% for

austenitics. Designing within this limit is sensible practice. And, if alloy selection uses a rule of avoiding situations in which pitting can occur, SCC will also be avoided even if stress excursions occur since in general pitting is a necessary precondition for SCC.

Flow velocities can reach levels at which erosion becomes problematic, especially if hard particles are suspended in a fluid. Assuming that the material has sufficient corrosion resistance to survive well in the static environment, the best performance under erosive conditions is obtained by materials with higher surface hardness. Accordingly, the duplex perform better than austenitic alloys of the same corrosion resistance level.

Specific Environments
The list of specific environments against which stainless steels are sufficiently resistant to select for use in the chemical process industries is too long to provide here. Some of the most important specific corrosives, such as nitric, sulfuric, phosphoric, hydrochloric, and organic acids and others, are covered in the chapter on corrosion. The main caution to the designer is to make sure that the source material from which design guidance is sought is current. Many otherwise excellent handbooks are somewhat obsolete in that they do not include the very importance duplex stainless steel family or only include the oldest alloys in the group, such as 2205 (UNS S32205). Many new alloys now exist that range in corrosion performance from that of 316 to that of the 6Mo-plus-N austenitics. These alloys are usable in all gauges, have high strength and toughness, resist SCC, and can achieve the corrosion resistance levels of any ferritic or austenitic alloy. They can also provide significant savings in alloy cost at the same corrosion level because they have lower nickel levels.

Fig. 2

Stress corrosion cracking (SCC) resistance in neutral chloride solutions containing 8 ppm oxygen. Testing time, 1000 h. Applied stress equal to proof strength at testing temperature


1. Sandvik Materials Technology, www.smt., accessed June 2008

Schweitzer. Anderson and B. 2004 \aq2\ 4. 5th ed. P. accessed June 2008 3.outokumpu.B. ASM International.Chapter 23: Chemical and Process Industry Applications / 263 2. NACE 37755. Corrosion Resistance Handbook of Corrosion Data.. 1995 . www. Outokumpu Corrosion Handbook for Stainless Steels. Craig. D. 2nd ed. National Association of Corrosion Engineers.D.

in which this process is carried out have been sequentially carbon steel. At prices between the highs and lows of the first decade of the 2000s. 316L can survive. duplex stainless steels first went into production in kraft digesters. principally those of nickel and molybdenum. which enables paper of high strength. Over the years the materials used for the vessels. In the kraft process. In the previous sulfite process.Stainless Steels for Design Engineers Michael F. 1). p 265-267 DOI: 10. the advances in materials in the pulp-and-paper industry have been a model of rapid technology transfer and innovation. it is safe to say that future pulp-and-paper projects will be essentially the Paper-Making Processes The kraft (German for “strong”) process was introduced in 1937. In this environment.0 to 4. but it . So. and near immunity to stress corrosion cracking. McGuire. the lignin-connecting wood fibers are dissolved under conditions of elevated temperature and pressure in acidic conditions of pH 2. and stainless steel clad onto carbon steel. The harsh chemicals used in this industry called for better materials than the normal austenitic stainless steels without the expense of the 6Mo CHAPTER 24 Pulp-and-Paper Industry Applications Summary THE PULP-AND-PAPER INDUSTRY has seen more benefits from developments in stainless steel than any other industry. duplex costs have been roughly onethird less than that of an equivalent corrosionresisting austenitic stainless. This leaves a long fiber. replacing the sulfite process. Introduction The proximity of the Scandinavian paper industry to that region’s specialty steel industry has been symbiotic. essentially large vertical tanks. acidresistant brick vessels were used. As a result of the strong interaction between engineers having wellspecified needs for improved materials and metallurgists capable of providing them. are constructed of 2205 (UNS S32205) as a rule (see Fig.0. The digestion is typically carried out at 150 and 180 °C (300 and 360 °C) and 10 to 12 bar. Pricing changes mainly with alloying element costs. The pH of the sulfate is around 2. www. This need has been met through the use of the duplex alloys.1361/ssde2008p265 Copyright © 2008 ASM International® All rights reserved. called digesters. exclusive domain of duplex stainless steels because of their lower cost per unit of corrosion resistance. a discussion of the materials selection for the pulp-and-paper industry has changed from a fairly complicated analysis of which austenitic steel to use while guarding against stress corrosion cracking and pitting corrosion and when to use clad materials for cost savings.0. to a fairly simple discussion of which duplex stainless steel is most economical for a given piece of equipment. Since this revolution occurred in the 1990s before the latest surge in nickel prices. Beginning in 1988. hence the name kraft. high strength.0 to 4.asminternational. the digesters. stainless steel. and there has been no turning back in the replacement of austenitic stainless steels by duplex. which have become the new standard. such as in bleaching. Now. This factored in with strength nearly double that of the equivalent austenitic make them an overwhelmingly superior choice for pulp-and-paper equivalent except if very special corrosion requirements differ from the norm.

2304. The subsequent stage is blow tanks in which the pulp suspension is injected at high velocity. unlike either duplex or austenitic stainless steel. 0. Further downstream. and this can be done by chlorine bleaches or ozone/peroxide bleaches. but also offered freedom from stress corrosion cracking as well as materials savings because of their higher strength. This stage also sees erosion potential from hard particles. while the alloy level is beneficial against corrosion. environments change greatly. the materials selection criteria remain the same. Bleaching can be accomplished without chlorine in the so-called TCF. totally chlorine free. In the more unusual case of digesters using the sulfite process. The reduction in wall thickness allowed by the higher-strength duplex depends on the engineering code required. The hardness of the duplex helps mitigate erosion. 2205 is the alloy of choice here.005 mm/yr versus 0. it was found again that duplex performed better in that they were sufficiently corrosion resistant. The bleaching of the pulp is important for many types of paper. The American Society of Mechanical Engineers (ASME) code requirement is based on tensile strength and permits only a 24% reduction in wall thickness. The chlorine bleaching now must generally be done in closed systems. such as sand. but now they can be replaced by duplex alloys such as 2507 (UNS S32750). 1 The first kraft digester fabricated from alloy 2205. Alloys such as 316 are adequate for this environment. containers and process equipment benefit equally from duplex down to the handrails and walkways. Duplex stainless has become the clear choice. Subsequently. so the introduction of the use of 2101 (UNS S32101) or 2304 (UNS S32304) is a logical cost-saving move without strength or corrosion compromises. which again save cost by virtue of their higher strength. which results in a buildup of chloride levels to a point at which corrosion levels are unacceptable unless very highly alloyed materials are used. while the total kjeldahl nitrogen (TKN) code. The 2205 is twice as resistant to corrosion. highly alloyed austenitic alloys were used. This reduces the corrosivity of the environment as the ozone and hydrogen peroxide used in the process are relatively harmless to stainless steel. This has rendered the previous choice of carbon steel untenable. but 2003 (UNS S32003) would suffice. but the optimal materials remain duplex for various reasons. The optimum solution is a lean duplex such as 2101. the materials selected would be the same. molybdenum is not an essential alloying element. As one proceeds downstream in the process. would allow a 46% reduction. In the nonchloride environment. washing and screening. The environment is a mixture of alkaline liquid. This oxygen process dates from the 1970s. has seen increasingly severe environments as closed systems required for pollution control have become more common. At first. but lean duplex.011 mm/yr (Ref 1). The next step. while the vapor phase can contain organic acids. Courtesy of Outokumpu requires maintenance and has a finite life. This large a difference in strength levels required by codes is unfortunate and reflects an orientation to materials in which the yield/ tensile ratio is closer to unity. or 2003. in the pulp. The 6Mo grades have been successful. process. based on yield strength. offer cost reductions through their greater strength. In plants that use recycled paper and mechanical wood chip processing. The delignification of the pulp comes next. This wholesale use of duplex can make plants nearly maintenance . 2101 or 2304.266 / Stainless Steels for Design Engineers Fig.

Corrosion: Environments and Industries. Duplex America 2000 Conference. KCI Publishing. H. 2006. Vol 13C.Chapter 24: Pulp-and-Paper Industry Applications / 267 free from a corrosion point of view. 2000 2. Dykstra et al. Houston. REFERENCES 1. Tuomi et al. A.. ASM Handbook. Corrosion in the Pulp and Paper Industry. Additional detail about corrosion challenges and the use of stainless steels in the pulp-andpaper industry can be found in Ref 2. p 762–802 . a dramatic change in an industry in which the thousand-fold greater corrosion rates of carbon steel presented operators with endless equipment downtime problems. ASM International.

asminternational.1361/ssde2008p269 Copyright © 2008 ASM International® All rights reserved. p 269-278 DOI: 10. APPENDIX 1 Compositions .Stainless Steels for Design Engineers Michael F. McGuire.

75–2.15 0.0–19..060 0..045 0.040 0.0–12. . 0. ..0–18.06 0.15–0.5 7. ..0–10..20 0....18 0.3 .0 17.15 0.030 0.00 1.0 3.030 0..0–20. . .0–19.030 0.0 15.00 1.0–20. .030 0..10–0..0 0.60 optional 0.00 1.0–8.0 17..0 11.08 0. ..0 17.5–3.0–20.16–0.50 Al 0.0 17..15–0. 2. .0 (continued) .. .0 5. ..0–20.00 1. .. .5 8..16 0.12 0.00–4... . 0.0 18..0–10.15 0.08 0.25–0.. .015 0.0–15.045 0... .00–2...5–10.5 8..03 0.0 2.0 9.00 1.40 0.30–1...0 8.5 19.0–10. 0.0–10.00 1...8 2... .045 0.5–9.0 22..0–10.Table A1..08 0.0–22.045 0. . .03–0.00 1..20–0.. . . . ..0–10.0–15.0–1.00 0.20–0...030 0.0 17.0 .2–4.0–6..030 0.0–7....0 14.0–19..0 . ... .... Cu 1..5 17.030 0....0 17.0 7.0 7.04 0.75 3..0 12. .0 0.5 ...060 0.0–10..5 2.04 .5–2.0 8.0 8...0 2.08 0.25–0. 0.0 16.5–5..0 2. Notes: All compositions include Fe as balance.0–10.60 optional 0.0 18. .08–0..0–10...045 0..10 0..0–9..0 .20 . .20 0.25 .00 3.5 12.5 4.25 .0 18.40 .5–5.00 1.0–10. .....0 15.030 0.0 6.030 0..045 0.5 8..0 7. . ...030 0.0 14.15 0. ..75 5.0–18. ...0–20....0 2...08 0..30 0..0 7.045 0..0 2. .12 0. . 2.0 2.00 1....15 min 0...0 17...045 0.040 0. .0–18.0–18..0 16. (a) Unified Number System.06 min 0..... . ..00–3. .00 1.08 0.. Single values are maximum values unless otherwise noted.0 7.0–3 0. ..25 0.030 0. .0–15.0–18.50 16.030 0.. 0..5 8. .00 1.030 .0 6. ..15–0.15 min .30 0...0 5.0 8.0 2.75 1. 0...5 19.15 0.0 16..0 2.15 0.00 1..0 18..12 0.5 5.0–18. .030 0. % Cr Ni Mn Mo P S Other Other Si Composition of austenitic stainless steels Name Designation(a) C N 270 / Stainless Steels for Design Engineers S20100 S20103 S20153 S20161 S20200 S20300 S20500 S20400 S24100 S24300 S21900 S21904 S20910 S21800 S21400 S21460 1.030 0.5–4.5–7.0–16. .....40 0. .00 3.045 ...5 5. .0–24.040 0. .0 4..75 1. .5–18...50 0.0 7.0–10. .25–3.0 2.10–0.06 0. .0–24..0 17. .14–0.0–3.. 0.. .5 14.25 3.045 0..25 0.0–19.0 17...08 0.. . 2.00–1.5 3...40 0..15 0.20–0.0–6..0–6.0 0..0–6.0 16.030 0.0–21..5–18.045 0.15 0.015 0..00 1. ..030 0.5–7..0 12..045 0.060 0..040 0..35 0.0 18.0 17.030 Nb 0.40 0. ...0 16..0 Al ..5–16.5–13..0 1.5–3.16–0. ...0–12.0 5..030 0...5–7...030 0.0–18. .. ...5 8.08 0. ..75–1.0 ..0 19.0–19. Se 0..32–0.0–21. 0. 0.5–5.045 0.5 1...40 0. V 0.00 1.0–15.16 0..08 Ce .15 0..0 1.....75 0.05–0.045 0.0 2.8–1.00 1. .00 1.. .. ..15 0..08 0..5 4...0 10.0 9.5 11..0–6.5 8..0 2....1 Composition.0 .0–10.0 .0 14.24 0.. ..00 1.045 5.... . .0–15.0–10.0–14..5 8.. . 201 201L 201LN Gall-Tough 202 230 EZ 205 Nitronic 30 Nitronic 32 Nitronic 33 Nitronic 40 (219) 21-6-9 LC Nitronic 50 Nitronic 60 Tenelon Cryogenic Tenelon Esshete1250 216 216L 301 301LN 302 302Cu 302B 303 303Se 303 Plus X 304 304L 304H 304N 304HN 304LN 304BI 153MA 305 Cronifer 1815 RA 85 H 308 253MA 309 309S S21500 S21600 S21603 S30100 S30153 S30200 S30430 S30215 S30300 S30223 S30310 S30400 S30403 S30409 S30451 S30452 S30453 S30424 S30415 S30500 S30600 S30615 S30800 S30815 S30900 S30908 0.18–0.0–16...4–2. 0.0 10.08 0.5–9.0–18. 0..030 0. 0.03 0.030 0. Nb 0.5–14..40 0. Cu 0..030 0.12–0.... .0 .5–13..0–20...0–6. .08 0. .75 0. .0–18.060 0.0 8.75–4.20 1. . ..0 2. .0 17.0 11..10 0.060 0...35 0.5 17.2 .5–9..00 1. .5–7. V 0. UNS numbers are S or N followed by 5 digits..5 3.00 1.10 0.03 0.5–16.0 8.00 1. .045 .5–22.03 0.5–7.5–22.08–0..00 1.... .3 .0 2.0–10. . B 1.25 0.. Cu 3.0–19.10 0.0–19.018 0.045 0.. . 1.50 0. . ..045 0.030 .75 5.045 0.0 2.20 Ce 0.00 1.0 22...5 2..040 0..25 ..0 4. . ..045 0. .045 0.5 .060 0...0–17..030 .. .... . .0 0. .0 8.5 5.00 1..00 2.0 0.0–19..0 10..0–20.0 16.040 0.0–19.5–19...0–9. . .03 0.15–0.5–7.0 2.. 1..8 2.04–0.1–0.00 0. . .0–9..030 0.10 .0–11.0 2.10–0...18 . 0.0 20.0 16..060 0.0–19... 0..25–0. .0–4. 0. ...0–19.030 0..5 13...50 0..060 0.25 0.00 1..0 17.50–4.08 .0–3.0 17. . 14.0–10.0–19..0 18.00 1..03 0. . .030 0.0 18.030 0..60 optional .10 0.5 20. . ...75 0.040 0..... .0–8.20 ...5 16....5–23.060 0..045 0. 0.030 0.25 min 0. ..0 5.0–6.0 18.9–21...04–0..12–0.1–0..

10–0..0–26.0–5.. . .5 1.00 1.0–14.60 Nb 0.04–0.0 17.0–36. Nb 10xC to 1.030 ..00 1.09–0.015 0.045 0.0 24.0 1.0 2..0 34.030 .00 1.0 2. ...0 19..08 0.. 0. Nb 10xC to 1.10 330 332 332Mo* 334 347 S33000 N08800 S35125 S33400 S34700 0. .0 10. 1.045 0.0–20.11 ...03 0... 348 S34800 0.015 0..0–18.0 2.0–19.0 31.030 0.. 0.0 3.0 2..030 0.00 1.2 to 1. .0 9. 2..08 0. .0–22.0 24. ..030 0.03 0..0 2.0 1.045 0.0–20.. ...10 22. .030 0.0–21. 0. .0–18.030 0.0–18. to 0... .0 2. 353MA S35315 0.0 16.25 0.03 0..0 24. .5 13..045 0. 0.045 .0–3. .5 2.00 1..0 18.0 Ti 0.0–37.10 0.22 0..0 2.0–16..0 10. . .0 19. 0...0 .10 0.6 . . ..0 20... .10 0..045 0.0–14.20 0.0–26..04–0. . ..030 0.70 .03 0... .0 3..0–21.030 0.005 ..0–22..40 Co 0. ..0 19.03–0.08 0.0 24....04–0. 1. .75 1.0–18.10 0. .0 22.0 (continued) 17.10 .010 0.00 0.00 0...0 2.5–1.10–0.0 10.0 2.0–22..75–2.030 0..20 0.0–1.04–0.. . 370 384 S37000 S38400 0..0 2..50 1.0 2.15–0.03 0.0 17. 0..0–15.08 0.030 0.0–15. to 1.. 9.0 2.. ..030 0.08 0.10 0.0 16..1 (continued) Composition. Nb 10xC to 1.5 .030 0. to 0.25 0.0 18... 0.15–0.040 0.00 1.045 .045 0.. . ..045 321H S32109 0..040 0.0 2.40–0. .10 0. ..045 0.....045 0. 1.03–0.0–12. .. . .0–14..030 0.0 11.0–19.0 ..16 0...5–17.0 13.0–3.020 0.00 1..0–20..10.0–26..0–26..0–15.5 1. Ti 0...4828 S31000 S31008 S31009 S31040 S31041 S31042 S31050 DIN 1..0 10... .0–22.0–3.00 0. .5 9. . to 1. . .0 24.00 0.0–22.00 1.0 2.0–22.0–3.0–14. S30909 S30940 S30941 DIN 1...0 12.25–0.0–24.0 2.0–20.10 Nb+Ta 10xC .50 1.10 0.. ..0 19. .0 2.030 0. ..0 17..0 23..10 .10 .0 24.12–0. .0 12.6–1.0–26.0 2..00 1.0 19.. Ti 5x(C+N) ..0 19.60 Al 0.0 .0 2.0 2.4841 S31400 S31600 S31609 S31620 S31603 S31653 S31651 S31635 S31700 S31703 S31753 S31725 S31726 S32100 0.0 2.6–2. .0 1.15–0.0–22.0 10. .04–0. . 0.16 0.045 0.5 1.0–15.10 0. .0 19...0 18.00 0.35 2.. .0 22... .045 0.00 1.50–2.00 1.08 0.030 0.10–0. .045 0.10 Ce 0.2 to 1..0–17.0 20. ..0 16..0 14.70 Ti . .15–0.030 0.0–3.0 16.0 2.0 0.045 0. .0 10.0–26..08 0. ..10 .0–24.045 0..0 2...0 2..Table A1.0 2.00 1..030 0..0 ... 0.045 0..60 ... 0..045 0.0 12.. ..10 . ..00 1. .045 0. . ..0–4.045 0..0–21.08 ..00 0.00 1.10 .10 0. .030 0.08 0.0 19.045 0.0 16..75–1.10 Nb+Ta 0xC Co 0.. .0–19..00 1.00 1..0 2.10 0..0 2. .....6 24... .00 1.0 2.08 .045 0...5–2.0 16.0–13.0 30.0–20.5–14.0 2.15–0.03 0... % Cr Ni Mn Mo Si P Other S Other Name Designation(a) C N 309H 309Cb 309HCb 309Si 310 310S 310H 310Cb 310HCb 310HCbN 310MoLN 310Si 314 316 316H 316F 316L 316LN 316N 316Ti 317 317L 317LN 317LM 317LMN 321 17.0–26.00 0. . to 1. . ..0 .0–23...0–5..0–13..5 17.50–2.0 2.030 0.0 2...0 17.045 0.0–23.0–22.0 2.045 0.. .0–3.00 1.0 9..0 1..0–4.0–4.0 2.0 19....10 0.030 0..0–19. .10 0. ..0–14. UNS numbers are S or N followed by 5 digits.040 0.. Ti 0.08 0.0–26. .030 .0–14.030 max P .75 1.5–17. (a) Unified Number System. ..0 18.5–16. .0 1.0–26.05 0...10 Nb+Ta 8xC . Single values are maximum values unless otherwise noted.04–0. .0–19.05 Nb+Ta 10xC Co 0.10–0.70 Ti 4x(C+N) .10 . Nb 10xC to 1.0 12.08 0.0 2.35 0.08 ... ..5–23..10 .60 Nb+Ta 10xC . .0 11.0 24.030 0..0 2.0 19. 0.0 17. ..60 Al 0.00 1..50–3. 0.9 34..0 9. ..08 0..045 0..00 1...00 1. ..0 17.0–19...20 0.0–35.00 1.0 16. ..0–12..04–0.0 10.08 0.0–26.. Nb 10xC to 1.0 24.. 348H S34809 0.02 0.. 347H S34709 0.0–13.10–0.15 0...045 0..0–13.0 9.0 2..045 0.10 0..0–14.65–2.0–18.0–20. Appendix 1: Compositions / 271 Notes: All compositions include Fe as balance.03 0..0 4.10 min 0.11 .18 .0 11.0–13.0–18. 5xC to 0.030 0.0 4.5 15.. . 2....030 0.08 ..0–3.0 2.. .030 0..030 0. .04–0..030 0..50 1.030 0.0–18.75 1.0 18.0–24...0 11.030 .0–16..10 0. .0 3.0–35.0–19.5 19.

00 0.0–25.80 1.0 Cu 0.. 0.50 1..040 0. .18–0..5 Co.5–3.0 20... 0.15–0.5 4..75–1.. .0 24. .5–30.0–26.030 P 0. .40 0..0 1.0 balance 24.0–6.1 (continued) Composition.0-3...0 26. . .0 ..035 0.. ...0–29.0 5.0–23.0–28..0 2.045 0.0–8. Ti 0.0 22....045 ... ... .50 0..0 20..69–0....0..0 6.030 0.25 0.5 1..5–1..0–22.15–0.0 2. .0–37.0 21..38 ...025 0.03 0.0 2.0 12.0 23.0 20..30 0..02 0.0 24.20–0.0–4.5 Cu 1..... 0..05–0. .0–22.5 23.0 32.1–0.0–9.. UNS numbers are S or N followed by 5 digits.0–27.5–3.0–22.00 0.50–0.0–1.0 18.00 1.0–2.0–22. 0.0–3..0–21.015 0.0035 0..035 0. ....38 0. .0 .0 22. Notes: All compositions include Fe as balance.75 2.0 27.0 4.0 . 0.0 19. . .0–18.040 P 8xC to 0.15–0.50–2. S33228 S25045 S35135 S63008 S63012 S63017 S63018 S63198 N08020 N08024 N08026 N08028 N08366 N08367 N08700 N80904 S31254 S34565 S32654 N08020 0.60 Nb Cu 3. W 1.5–3. .50 0.. 0. .0–7..45–0.35–0.8 .0–23. 0..5–5.25–21..0–4.50 16.25 AL 22 Cronifer 1925 hMo Cronifer 2328 Nicrofer 3127HMo URSB-8 B66 NIC 25 CN-7M N08320 N08932 S31266 S32200 N08007 20Mod 0.0 1. .0 25.5 2.48–0.0 Cu 0.0–4..02 0. . .0 20.10 Nb 0.55 ..4–1. 0.03 1..0 24.0–10..0 7. N06022 N08926 0.25 Al 0.....0 Cu 3.0–21.0 20..0 19..0–22.5 4..50 20.28–0.0–1.0–4. . 0.08 0.25 0.50 1..0 4.50 0..030 0.030 . 4.0 6.0 6.50 1.5 2.0–28..0 21.5 1.0–7. 2..04–0..75 2.25 0...0–3.030 0.5–25.0–26....0–26..75 0.0–7.035 ..07 0.030 0.0–24.. . .030 .050 0.0 Cu 0.9–32.0 32.0 19. N08031 0.00 Nb+Ta W 2.0–37.0–6..10 Ce Ti 0.0 2.35 Ti 8xC to 1..0 3...0 1.03 0.00 1..5 0.5–1. ..7 3.5–3.0 .6 Cu 3. % Cr Ni Mo Si P Mn S Other Other 272 / Stainless Steels for Design Engineers Name Designation(a) C N AC66 Incoloy 803 Incoloy 864 21-4N 21-2N 21-12N 23-8N 19-9DL 20Cb-3 20Mo-4 20Mo-6 Sanicro 28 AL-6X AL-6XN JS-700 904L 254SMO 4565 654SMO AL 20 20.15–0.5–3.0 8.3–5.0 4.045 .0 7.0–24.35 V 0.18–0.035 0.10 0. ..9–9. .5–6.15–0.5 23.5–12.5 5.08 0.7 .0–11..0–23.25–4.08 0.. .0–4.25 0.0 19. 0.0–26..5 24.80 1.02 0....03 0..75–1.5–25..25 .0 Cu 0..25 0.70–1. ..5 6.5 1.15–0.5 Nb 1...03–0.40 1.0–26. . 0.030 0.030 ...5 Cu ..0–23..045 0.40–0. ..3–0.0–4.0 2.0–28.030 0.02 0. ..0 19. ..36 0..0–26...0–7..0 3.0 21.5-3.0 0.5 1.0 2.030 0.60 .0 2.010 ..0 22.0–7.0 22.07 0.0 24.0 19.00 1.00 Nb Nb 0..28–0.030 0.5 .030 0.0 26. ..0–24.5 1. .... 0.50–20..030 0.0 2. 1..5–25.0 .....0 0.. ..0 23.5 19..75 10.0–25.015 .005 .5 Cu 2. 0.0 19. ..0 33. 0. 0.4 Cu 1.0 0..07 26.015 0.0 2.6–1.0 32.015 0...02 0. ..0 2.50 1.0–1..25 0.035 0.90 0.0–26.0–6.0–38. 0..0 26..0–28.0 1.0 2.60 0.0 23. 0...03 0.0 31. 8xC to 1.05 0.06–0.4 Cu .0 0. .Table A1.0 29. 2. .5 2.. .0 6...0–5.0–25.50–18..25–0.04 0.0–40.50 23.0–21.0–5.0 5.28–0.0–3..030 0.04 0.35 8xC Nb . Single values are maximum values unless otherwise noted.5 2.045 0.0 Cu .60 Al .0–27.60 Ti 0. .0 17.0 .0 1. .. .5–1.0 35..58 0..60 0.015 0.03 0.02 0.0 0.5 7..0–2..00 1.0–28.5–14.0–21.0 0.045 0.5 25.0–7. . .0–38.0–3.0–23.4-0..15-0.50 0. (a) Unified Number System.0 Cu 0.030 0..0–22..0–38.15–0.28–0.0 1.0–33..0 8..0 0.0 Cu ..6–1.0 30.22 0. ..

.0 16...040 .0 1. 0..15 AL 0....45 ... . .. 0.. ..060 0. .0 0.50 0..20+4x(C+N) to 1.35 . . .0 10..00 1.0 0.75 0.03 0..03 .00 0.0 Al 1. .12 0. ...Table A1. ..75 409Cb S40940 0. SE 0.50 1....00 0. .00 1.50 0.30 Al 0.040 0..03 0.00 1.00 Mn 1.. 0... 0.5–11.00 1..03 0. Single values are maximum values unless otherwise noted . 0. 6x(C+N) to 0. ...040 0. (continued) 0......020 0... .. ...5–11. .5 439 S43035 0.30 0. .......0 .35 .07 0. 10...... 18.010 0.0–19.025 .. . . % Ni 0.2 Composition.03 0. ..35 0..0 16...60 . Ti+Nb:0....0–18.00 .00 0.00 1..020 .0 .04 16. . 13..030 0.030 10.060 0. . ..030 0.10 .. 0..060 0. .30 0.05 0.040 .01 0..0 1.....0 16.00 1. .....7 11. AL 1.. .20+4x(C+N) to 0. Al 0.30 .. . . 0..75 1..10 0..35 Ti .030 1..030 .0–18.00 1.. .. .7 10..0–16..040 . ..20+ 4x(C+N) to 1..00 0...0–13. .....40 0.17 . .. ..0 18 Cr–Cb AK alloy typical 0. 0.00 1.2 AL 3....5 12.10 0...15 Composition of ferrite stainless steels UNS Name 405 400 409 designation S40500 AK alloy S40900 C 0.030 0. . .01 17.08 .. .00 . .2 0. 1..25 Al ...025 . .030 0.5–11.04 17.00 Nb ..015 10.. 0.00 1..... .12 0.. ..10 0..0–19.50 0..040 . ...75 6x(C+N)to 0. ..25 1..25 0.030 0.00 1.. ..040 0..00 1.25 0.00 1.50 0..75 Nb ..00 0.045 Other Al 0..030 . 1..50 0..70 0...5–11. ....08 N ...040 0.08 0..5 8x(C+N) to 0.015 12.75 409 ultraform AK alloy S40930 466 0...035 0. ...5 0. .... ..0 0..5–11.5–11...00 1.030 0.. ..02 0..0 Alfa I 0...5–14.... . ATI. ..0–19..0 .00 P 0....5–1..50 1. Si 1....020 10...5–11.12 . ....0 430Se 430Ti S43023 S43036 0.20+4x(C+N) to 1..12 0.10–0.. .7 10.... 14. 0. 0. . ..05 0.75 .. ... ..15–0..035 .. AK 439 HP alloys 439 ultraform S46800 468 0.0 AL 4.040 1.0 439LT S43932 0. . . 1.5 429 430 430F S40975 AK alloy typical AK alloy typical ATI alloy typical ATI alloy typical Outukumpu typical S42900 S43000 S43020 0.60 . 0.7 409Ni 11 Cr–Cb 0.75 409 409 S40910 S40920 0. 1. 1....25 1.15 .0 0.030 ..030 0.50 Mo ..... ..030 0.020 0. . 13..... . . Appendix 1: Compositions / 273 Notes: All compositions include Fe as balance.030 .......0–20. 1..02 0.. 0.0 4724 0...00 1..150 min 0. .45 1.40 . 0..0 Alfa II 0.8+ 8x(C+N) Ti+Nb 10xC to 0. ........ 0.. .00 1..75 Ti+Nb 0. .50 8x(C+N) 0..040 .55 .. 13.045 S 0.. 12 SR 0.00 1. ..06 .00 1. ..040 0.00 1. . .20 .0–18..... 0...03 17.03 0. Cr 11..03 0. . 18.. 0.

5 0..0 .. 0.030 . 446 23.80 .4 .. .25 . (continued) Composition of ferrite stainless steels UNS Name 18SR C 0...0–18. 1. .. .. 0... ..01 0.0 17.5–26.12 0..030 .50 S44600 0...2 Cu 0.0–18. 444..7 1.30 Mo .0 0.... .70 9xC 0. ATI alloy typical Outukumpu 4762 typical 453 ATI alloy typical E-Brite. % Cr Ti 0. 29-4C S44735 0.030 .20 0.5 0...2 0....5–19. YUS 190-EM 20.8 17. . . .03 ..3 22.0 3. P .75 0. .020 0.20+ 4x(C+N) to 0.030 Ti+Nb:0.5 1.80 .. .00 0.025 ...030 . 28..3 .030 ....030 0....7 1.... Mn 0.00 2.6 .3–1.040 0....5–3. Single values are maximum values unless otherwise noted..00 0. .040 0.75–1...030 1.. ...3 1.020 0.25 Si .20 0. ...0 0....040 .0 0.0 0..040 0..3 0..0 0.0–27.7 Al 1.0 . 0.1–0..25 0.01 .040 1. 274 / Stainless Steels for Design Engineers 441..6 . . .08 .0 .0–23.5 0. ..0 1..... S44100 0....030 17.. 1... 0... .015 . 0...025 0.40 0. .0 0.0 0.0 0.0 16..5–4.60 Al 0.25 ... . 0..20+ 4x(C+N) to 0. Notes: All compositions include Fe as balance.. 26-1 S44627 0..0 24.. 0. ..20+ 4x(C+N) to 0. .040 0.0 1. 0. 434 436 designation AK alloy typical Outukumpu typical S43400 S43600 0.0 1..... S ...5–4. Ni 0. 1. .. 4509...00 0..0–30.. 10x(C+N) .50 0.5 1. .015 N . 0.5 0.035 0.25 0.5 Cu+Ni . .. .5–18.Table A1. .6 0.75 0.0 1. 0.5–4..025 0. 0....80 Ti+Nb:0.20 . Al 1. 0.5 1.5–0.. . ..00 0... ..025 0.01 .. .10 REM 0.2 Composition. 1. 0.. ..3 1.0 1.. 430J1L 442 436S 18.0 25...040 0..12 .20 .25 ..40 0..00 3.0–27...035 433 0.030 Ti+Nb:0. Other Al 1.0 0..040 0.4 1.. 4742 0.015 Monit S44635 0.3 16.5 24.30 18.75–1... 17.5 ..08 ..040 0. 8x(C+N) min ...... Sea–cure S44660 25. . Nb ...20+ 4x(C+N) to 0...5–3.035 1..75–1...25 1..5 0.80 Ti+Nb:0..75–1.0–27.02 .4 . .30 S44200 ATI alloy typical S44400 0.25 3. . . Nb+Ta 5xC:0. .

5 Cu .0–14.00 ..0 V 5...18 max 0...00 1.00 1. . . .25 W .040 0....3 . ..5 10.00 1.040 0.040 0.95–1.5 V 9.. . . . Se 0.50 1..95 0. .55 0.0–18. 1.75 0.. ..15 1..040 0.00 0.20 0...5–1.7 12.00 1.00–2.5 12. 0.0 12......030 0.5 11... .. .50–1.0–14.010 .5 12.5 Cu 1. Mo 0.. ..0–18.0 13.. Appendix 1: Compositions / 275 Notes: All compositions include Fe as balance. .00 0.15 max 0. .05 1. .25–2..15 2.0 16. .00 1.0–3.2 V . ... .05 1.0 V 420F 420FSe 422 424 425 425 mod Trinamet HP13Cr-1 HP13Cr-2 NT-CRS NT-CRSS KL-12Cr KL-HP 12Cr 431 440A 440B 440C 440F 440FSe BG-42 ATS-34 14-4 CrMo 154 CM CPM S30V CPM S60V CPM S90V designation S40300 S41000 S41003 S41008 S41040 S41003 S41400 S41425 S41500 S41600 S41623 S41800 S42000 DIN 1.0 16. .010 0.50 1.00 ...... ..00 0.02 0. .00 1.. . Se 0.00 0...15 0. JFE nominal JFE nominal Nippon nominal Nippon nominal JFE nominal JFE nominal S43100 S44002 S44003 S44004 S44020 S44023 Nominal PM Nominal PM Nominal PM Nominal PM Nominal PM Nominal PM Nominal PM 0. .0 5. .95–1..00 1.00 1.50 N .00 3. ... .15 max 0. ..75 ... .50 1... 1.0 12..60 1.0 14.45 . 1...030 0.00 1. 0. ..45 2. Single values are maximum values unless otherwise noted ..040 0.0 15...0 12..00 0.0 13.030 0.50–5...35 0.5 0...3 . Composition of martensitic stainless steels UNS Name 403 410 410S 410 410Cb 412 414 414 mod 415 416 416Se 418 420 4116 C 0.00 1..0 13...0 13.030 0.15 min 0.0 0.040 0... 0.. . .5–13. Ni .040 0..0 12....00 .75 0..00 0..00 .040 0. .15 min 1..0–15.03 0.25 1.. 1.030 max 0.. ..00 1.15 min 0... .50 4.. .040 0.. .0 16.6 1. 1. .00 1.01 0.00 1.15 max 0.20 0.50 1.0 16.08 0...06 max 0.030 0.00 1..05 1.5 1.040 0.0–14. .06 0.25 0.5–13... ....5–13.Table A1..5–14.0–17. .50–1.00 0.... 1.5 11. . .05 max 0.0 14.50 1.45 0...00 .040 S 0. . ...030 0.00 1.040 0.. . 0..50 . 1.040 0..30 max 0.50 .50–3.0 ..45 1.8 2. 4...05–0.0 4.20–0...... CU 2... % Cr 11.00 1..040 . ... .0–14. ..12 ... .5 5...5–13. .35 0.. .4 0.. ..30 ...50 1.5 1.. ....35 0....5–12.3 11. 1..25 0. .....15 0.5 14.0–14..06 0....0 .20 max 0. .0 11.60–0.25 .. ... .. . Cu 0.030 0.3 0.. 1...030 .15 min 0..00 1... ..00 1. 1... .. . .5 Cu 0..0–14. Si 0.040 0..0 14.. . .. 0.0 3.00 .030 0.00 1. 1.. 0.00 0.00 1.00 .00 1..20 1. 0. .00 1.0–18.4116 nominal S42020 S42023 S42200 S42400 S42500 . Mn 1.50 1.00 1.75 0...15–0.03 0..0 17.00 1.60 0... Other .....00 1.25 1..005 0... 0.0–16.030 0.. .040 0.05 0. ..0 12.0 11.20 .25 1..15 min 0..0 ...030 0..60 1..5 12.060 ..30–0..0–7....0 14..060 0.50–4.0 12.. ..00 1.3 0. . .3 0.50–1..040 0. Se 0.015 0.0–14. . ......3 0.0–13.. ...15 min W 2...040 0....0 12....0–18.3 Composition. ..030 0..30 .00 1. .00 1.0 14... .. . 4.80–2...5–13.. .40 . .030 . Nb 0..60 0..25–2....025 0.95–1.30–0..00 0..15 max 0..00 1..20 0..5 11.040 0. .. 0. .00 1...0–18..5–12.45 2..0 1...030 0...00 0. . .0 16.30 0.0–14....25 1.... ... 1.030 0..060 . .50 ... P 0.060 0... . . .0 12. ..5 10.... .01 0....20 0.75–1..030 0..030 0.025 0.08–0..5 .. ....0 14.. .010 0.040 0..00 0...040 0..5 11..10–0.060 0.20 ..75 0.. .4 5.00 0.. .15 max 0. .50 1.00 1.. .040 0.030 0. .040 0.75–0..00 1.50–0..... .040 0.60 1... 0. ...040 0.50 .0 1.0–14.00 1.00 1..

030 0.75–1.0–27.5 3.5–7. 0..09 0..8 0.03 0.50–1.08 0.10–0. .0–1.030 0...2 6.0 2.08 .025 . .03 0.30 0.10 .50 1. 2.0 26.9 3..0 0.0 1. Ti 0.0–2.50–1.8 1.2 Cu 3.5 0.5–2.00 0.0–23.0 1.0 1.5–6.008 0.5 1.25–13.35 0.0–22.5 . V 0.0 5.5 12.8–1.45 Al 0.20–0. .5–8.04 0.08 0. .. 2.25 0.0 24.50 0..5–8.07–0.5–3.0 1.25 0. . .75–1. Ti 0.0 2.0–3..03 0.040 0..5 Al 0.0–26. 0.5–3..0 1.010 ..0 24.0–2. 1.5 14.03 0.05–0.0 18. 3.0 14.5–2.0–6.. % Cr Ni Mn Mo Si P S Other Other Composition of selected precipitation–hardenable stainless steels Name Designation C N Stainless W 17-4 PH 15-5 PH 13-8 PH Custom 450 Custom 455 11.8 3..030 0.0 0.0 1.5 3.015–0.03 0.010 0.21 .030 0.040 0.03 0.8 .020 0.0 1.5–8.0 14.30 0..030 0.5 3.0–26.0 19.0 Cu 2.10–0.5 2. .70 4.0–4.0 0.75 1. .8 0.75 Cu 1.0–3.0 2.0 21.5 19.0 6.5–2.07–0.05–0.25 2.20 0..040 0.030 Al 0.. (a) Nominal value Table A1..0 2.0–5.020 0.0 3.. .5 0. .5–1.2–2.03 0.20 0..0 1.030 0.0–30.030 0.. 15.20 0....10 1.5.00 0.040 0.0 1.030 0.5 1.040 0.0–12.30 0.40 0.8–1..10 0.5 0.11 0..0 24.5–7.030 0...5–3..15–0. .1–0.0 0..5–21. .75 1.020 0.030 0.5–3.25 0.5–1.5 2.80 Co 8.30–0.0 4..030 0.040 0..0 16.0 28.0 0.0 0.0 5.3 276 / Stainless Steels for Design Engineers Notes: All compositions include Fe as balance.0–8.25 0.13 .040 0.5 .2 Notes: All compositions include Fe as balance.030 0.. .00 0.0 10. .5–2.0 0.0 6.0 1.5 Al 0.2–2.03 0.4 Composition..0 13.90–1.0–27.5–11.14–0..8 0.5 6.5 .20–0..8–7.0–5. .0 115.0 1.1–0.0 2. ..0 ..0 1..0 4.20–0. 1..50–1.015 0.2 1.5–3.0–26.. 0.0 0.030 0..0 24.5 1..035 0.03 0..50 .03 0.9–2.0 24..25 4.05 0. Ti 1.5 1..00 0...0–5.5 .050 Co 14 .0 15.0–5..0–26.25 14.030 0.0–23.0 1.0–18.015 0.Table A1.05 0..040 0.01 0.0–8.25–1.0 2.0–29.040 0. ..10 2.0–17.030 0.13 0.0 4...50 16.020 0.– 21.4 Ti 1..02 0.24–0.0 1.8 1.0–16.23–0. .04 0..0 0.0 11.0 1.0–16.. Ferrium S53(a) .0–7.0 0.00 1.5 .5 .0–1..00 1.0 7.0 0...0–5.4–2.010 0.5–8.0 24..5–4.5 4.010 0.010 W 1. Single values are maximum values unless otherwise noted.00 0.5 0.35–1.20–0.05–0.10–. Cu 1.5–5.5–17.5–5. Single values are maximum values unless otherwise noted .03 0.0–5.25 2.0 1... Al 1.0–28.030 0.15–0. 0. 0.08–0.0 0.45 Nb 0..20 0.25 7..5 3.5 7.030 0.0 5.030 0.5–5.4–2.8 0.5 0.040 0.35 0.0–8...0–7.0–2.040 0.9–3.35 Nb 8XC Nb +Ta 0..0–5.020 0.32 0.0 2.0 5.0 5..0 0.09 0.07–0.30 0.030 10.75–1.040 S17600 S17400 S15500 S13800 S45000 S45500 0.35 B 0.0–3.0–4.50 0.5 Composition.75 1.0–15.0 3.75 4.0 1...14–0.0–8..0 1.33 23.010 0.4–1.030 0.0 2.0 2.. % Cr Ni Mo Mn Si Composition of selected duplex stainless steels P S Cu W Name Designation C N 329 44LN DP3 3RE60 2205 (old) 19 D 2003 2101 2205 2304 Uranus 52N+ 255 2507 Zeron 100 2906 7-Mo Plus DP3W AF 918 2.0–26.2 1.10–0.5–23.5–9.040 0.0–9.0 0.4 Nb .1–0.8 1.50 1..20 0.25–5..035 0.0 S32900 S31200 S31260 S31500 S31830 S32001 S32003 S32101 S32205 S32304 S32520 S32550 S32750 S32760 S32906 S32950 S39274 S39277 0.0 6.8 1..0 3.0–17.040 0.5–3.00 0.25 1.0 22.0–19.010 0.50 1.5 2.0 1.030 0.0–26...0–5.030 0..0 1.15 0.5 5.040 0.030 0.50 6.0 1.17 0.50 10.5–7.0 6.0–6.035 0.25 2.5 Custom 465 Custom 475 17-7 PH 15-7 PH AM-350 AM-355 A-286 S46500 S17600 S17700 S15700 S35000 S35500 S66286 0.5–16.6 1.0 21.5 24...0–12.001–0.25 0.0–16...14–0.020 0. .5–6.0–26.5 1..5–3.040 0..03 0.045 0.5–5..08–1.07 0.75 1.75 6.6 0..030 0.020 0.030 0.05 . 0.5 1. 0.6 0.00 1.0 0.0 .35 V 0.0 24. .75–11.030 0. ..00 1.0 2.. .07 0. Al 0.0 0.03 0.5–21.5 0. . .

.5–14.0 8...0 Cu 2...04 0. ...50 4.0 3.04 0.03 0.75–2..0–15..04 0.15–0.03 0..04 0. Single values are maximum values unless otherwise noted.5–4.04 0.00 1.10–0.20 0.04 0.0 1.50(b) 0.0 10.00 1.. ..22–0.04 0.0 18..0 8..0–27. J92701 J92602 J93790 J93000 J93001 J93400 J93401 J93402 J94653 J94202 J94652 J94651 0...12 0.50 1.03 0.04 0.10 0.04 0..5–14.0–26.0 (continued) 1..20 .00 1.04 0.04 0...0 9.5–12.0 20.20 1. .08 0.0 3..5 2. 2.00 2. 2. 0. .0 9..50 1.18 ..8 3..10 0.04 0..0 8.0 .4 0.0 1.00 2.20–0.10–0.2 Nb ..00 1.10 0. .00 1.04 0...20–0.5 11.0–30.00 1.0–21. ..0–26.50 1. .04 0..0–6..0 16.50 1.9–3..25 Cu 1.5–23.3 V .2–0...0 12. ...30 0. .05 0.00 2.5–14.0 11.24 .06 0.5–26.50(b) . Nb 8XC min .0–3.00 1.04–0.2–0.00 1.0 20.25 Cu 2.0–4.04 0.0–12. .04 0.04 0.0–12.17 0..28 0.08–0.50 1. 312 304L 316L 316LN 304 347 316 304H 316H 316H Nitronic™60 316 303 302 Nitronic™50 317 308 309S 309H 309 254SMO™ 310 904L AL–6XN® J91150 J91151 J91153 J91154 J91803 J92613 J91650 J91540 J91422 J92180 J92110 J92205 J93373 J93380 J93370 J93372 J93371 J93404 J93345 J93423 J92500 J92800 J92700 J92600 J92710 J92900 J92590 J92901 J92971 J92972 .33 0.04 0.0–26.0 22.0 18. .0–21.07 0. 2507 (S32750) .0 13..50 1. .5–3....0 4. .0 15.50 1. .2 Cu.0 26..0 8..0 4..07 0..0–21.04 0.5–6..04 0.0–21.00 1.7 24.5 .50 1.04 0.0–21.00 1... .0 1.50 1. ..04 0.00 2.5 15.0–7.0 18. (10xC)–1.0–27.0 4..04 0.04 0.0 11...5–14.0–12.7 14.2–0..25 4..04 0.35 .04 0.0 8.04 0..00 0.04 0.7 6.10 1..442 446 .0 .. .20 2.... .04 0. . 0.. .50 2. 0.00 0.04 0. .5–4.. . .1–0.0 1.5 24. 1.30 .20 0..5–13.65 1.75–6.5 2.00 1...0 2.0 12.0–21..50 2.04 0.00 1. 6. 0.9 Cu 0.0 1.50 2.0 2.24 11..04 0.0 19.5–3..30 0.00 1...5–14...0–13.04 .04 0. 2.04 0.04–0..0–11.04 0. 0.2–0.30 0.. 2..0–12.10–0.0–23.00 0. 2. .0 ..0 17. ..04 0.50 1.04 0.00 2.5 0.2–0.. .0 Cu 1.50 1.50 1.0–6.35Nb Cu 1.5 23...5 18.7–6. 4..04 0..0–18.30 .15 0.03 0.00 0.5 5. .. Se 0.00 1.00 1..03 0...08 0.18–0.5 .0–13.0 18. ..04 0. ..04–0.50 3.00 1..00 2...0–27.0–3.04 0.0 18. .75–3.04 0..0–26..0 12.00 1.00 1.6 Composition.9–1.. ..4–1.0–21.03 Appendix 1: Compositions / 277 Notes: All compositions include Fe as balance.0–21.04 0. 0.5 21.. .0 22. .0. (b) Mo is not an intentional addition.025 0..0–11.50 1.00 1..20–0.04 0.0–3.15–1. .50 0..75–2.75–2.04 0.0 .0–12..50 2..0 8.5–1.05 0..04 0.35Nb 2. 420 420F 431. .00 1... .50 1.0 1.04 0.0 17.0 18. 0. (a) The wrought equivalent composition is not the same as the cast.25 0.5 24.06 0..04 0...0–21.0–12.04 0. . S41500 422 17–4PH 15–5PH 2205 (S32205) 255 (S32550) (S32760) .50 1.0–12..50 7.0 0. ..50 1. 0.6 4.0–8.0–21..0 11.6–6.04 0.00 2..10–0..0 20.00 1.0–22.0 24.0 22.0–9. ... .08 0..10 0.0 11.04 0.25 .25 1.08 0..04 0.0 1.0–15.00 1.. .03 0..5–19.0–11.0 17.70 0.04 0.0 23.1–0.75–3...04 0. .5–1.04 0.04 0.25 .40 .0–15. .5–17.0 8.04 0.04 0..0–7.5–1.Table A1.50 1.04 0.5 .25 0..04 0. W 0.08 0.0 .0 1..04 0..50 1.5 6. ..04 0.5 9.00 1.04 0.0 3.0 1.5 4.00 2.04 0..0 18.3 Nb.3V 2.0–11.20 0.0 17.0–30.0 9.00 1.10–0..04 0..04 0.. .0–9. 0.03 0.04 0.5 19. .0 1. 0.04 0.0–22..5–26.0–3.12 0. .0–22.0–21.75–2.2 Cu. 0.0 18...04 0.08 0.04 0.75–2.04 0.03 0.50 1.0–16.40 0.50 1.20–0..04 0.0 9.00 1.04 0..0 24.0–3.0 6. .5–8.18–0..0 8.04 0.5–5..5 24.. 0...0–15.. Cu 0.04 0.0–26. .0 9.5–5.6–4..5–3.0–22.. 0.5–1.04 0.. % C Ni Mo S Other N Cr Mn Si P Composition (continued) of Alloy Casting Institute (ACI) heat– and corrosion–resisting casting alloys Name Wrought equivalent(a) UNS designation Corrosion–resisting alloys .0 18.04 0.. 0.0–21.4–1.04 0..0–5.16 0..04 0..04 0.9–1.00 2.06 0.50 1..04 0.00 1..00 1.0–18.0 6.10 0.0–4.0–26. .5 4.04 0....5–3.. .30 0.0 23.04 0..00 2.00 1. CA-15 CA-15M CA-40 CA-40F CB-30 CC-50 CA-6N CA-6NM CA-28MWV CB-7Cu-1 CB-7Cu-2 CD-3MN CD-3MCuN CD-3MWCuN CD-4MCu CD-4MCuN CD-6MN CE-3MN CE-8MN CE-30 CF-3 CF-3M CF-3MN CF-8 CF-8C CF-8M CF-10 CF-10M CF-10MC CF-10SMnN CF-12M CF-16F CF-20 CG-6MMN CG-8M CG-12 CH-8 CH-10 CH-20 CK-3MCuN CK-20 CN-3M CN-3MN 410 .0–13..50 1.04 0..25 W..50 1..0 22.00 0. 0.70 1.0 11.5 26.0–8.30 0....0–11.15 0.06 0..0–23.0 10..00 1. .00 2.0–12.0 0. .0 20. ..5–1...50 1.5–25.04 0.40 S .0 9. .25 1.04 0.0–27.5–20.04 0.

35 0....0–22..0 2.35–0.1–1..5–3.5(b) 0.5–2..04 0.04 0..0 2..04 0...5(b) 0..0–27.. .5–30.. ..5 2.05–0.0 1..5(b) 0.0 2...0–20. . J82090 J92605 J93005 J93403 J92603 J93505 J94003 J94224 J94203 J94204 N08604 J94213 N08705 ...0 2.0 31. CN-7M CN-7MS CT-15C Heat resisting alloys HA HC HD HE HF HH HI HK HK-30 HK-40 HL HN HP HP-50WZ HT HT-30 HU HW HX 504 446 327 312 302B 309 .04 0.. .04 0.0 2..04 0. ... ..20–0.20–0.5(b) 0.5(b) 0. . 330 .0 2...04 0. .5(b) 0.......35–0.04 0.0 0.5(b) 0..5(b) 0...04 0. . .. .. .0–17..2 0. .0 2.. .. 4 max 4–7 8–11 9–12 11–14 14–18 18–22 19.0 2..0–22.35–0.0 2.04 0...04 0.0 2...0 2.0 27. (a) The wrought equivalent composition is not the same as the cast...0–4..15–1..9–1.04 0. 0....07 0.0–34. .5 2. ..50 0.04 0. .. .50 0.04 0.50 3..25–0.50 0. .20–0..40 0.0 23..0–37..04 0.0 18–22 23–27 33–37 33–37 33–37 33. .04 0.0 2.04 0.20–0.60 0.0 2.0 18.04 0.50 0. .04 Cu 3.5(b) 0.04 0..04 0.. .0 Cu 1.0 2.75 0..75 0.50 0.04 0...0 1.04 0.. .5(b) 0. .5–1..50 0.0 2.0 28–32 19–23 24–28 24–28 13–17 13.035 0..0 2.0 2....0 2.35–0.. % C N Cr Ni Mn Mo Si P S (continued) Other Name Wrought equivalent(a) UNS designation 278 / Stainless Steels for Design Engineers 320 ..6 Composition. .04 0.0 .. Zr 0.50–1.0 2.2 .50 0. N08605 N08603 N08005 N08006 N06050 0.35 0..0 2. . .0 Nb 0.0 2.60 0....5(b) 0. 8–10 26–30 26–30 26–30 19–23 24–28 26–30 24–38 23.5 0.0–6.50 0..04 0..035 0.75 0. .04 0.. .Table A1.5(b) 0..0 2.04 N08007 J94650 N08151 0. Single values are maximum values unless otherwise noted.5 2. (b) Mo is not an intentional addition.0 17–21 10–14 15–19 .0–25....50 1..0 2..0–21.45 0.0 2. ...07 0..04 0....20 0. . . .04 0. 310 .04 0.0 2.35–0. .0–22.55 0.5 2.04 0..5 .0 2.0 2....25–0.5(b) 0..45–0..5(b) 0..35–0.0 19.5 2.5(b) 0.04 0. W 4.20–0..0.0 2... ....0–27.5 2..5 2.35–0.04 0.0 19. . .20–0.04 0.5(b) 0..04 0. .75 Notes: All compositions include Fe as balance. . . . .04 0.0 22.04 0.04 0.5(b) 0.15 19. .04 0.04 0. ..0 2.65 1.5 0.20–0..5(b) 0. .04 0. .0 ..0–3. 1.0 37–41 58–62 64–68 1.04 0..75 0.

72 0.1 Physical properties of major stainless steel engineering alloys Density. McGuire.70 7.3 16.63 0.80 0.8 25.5 13.6 16.5 14. p 279-280 DOI: 10. J/kg·°K Electrical resistivity.9 17.8 7.2 11.2 25.60 0.5 502 500 500 500 500 480 500 460 474 477 460 460 477 460 500 510 500 500 0.5 13.74 0.6 16.95 8.1361/ssde2008p279 Copyright © 2008 ASM International® All rights reserved. W/M·°K Specific heat.00 7. 10–6 × K–1 Thermal conductivity.6 12.0 16.asminternational.90 7.Stainless Steels for Design Engineers Michael F.65 7. Ω·mm2/m UNS 201 301 304 304L 305 316L 321 904L AL6-XN© 409 430 439 468 410 2101 2003 2205 2507 S20100 S30100 S30400 S30403 S30400 S31603 S32100 N08904 N08367 S40920 S43000 S43035 S46800 S41000 S32101 S32003 S32205 S32750 7.72 0..80 0.9 24.3 10.3 14.6 16.6 16.5 16.3 15. www.3 16.90 8.5 10.5 13.89 0.5 10.60 0. GPa Coefficient of thermal exp.0 17.76 7.3 13.95 0.80 .03 7.0 23.60 0.3 10.6 APPENDIX 2 Physical and Mechanical Properties of Select Alloys Table A2.80 0.70 7.76 7.72 7.86 8.2 10.56 0.67 0.6 15.8 207 193 200 200 200 200 193 190 200 200 200 200 200 200 200 210 200 200 16. kg/dm3 Modulus of elasticity.06 7.72 0.3 16.6 16.73 0.72 0.92 7.3 16.8 7.5 16.90 7.0 24.

. % Hardness 201 201F 301 301 tensile 301 301 301 301 301 sink 304 304 304 304 304 304 304 304L 304L 304LT 304DD 304EDD 305 305 316L 316L 321 321 904L 904L AL6-XN© AL6-XN© 409 409 430 430 439 439 468 468 29-4C 29-4C 410 410 2101 Annealed 2B Annealed 2D 1 hard /4 1 3 S20100 S20100 S30100 S30100 S30100 S30100 S30100 S30100 S30100 S30400 S30400 S30400 S30400 S30400 S30400 S30400 S30403 S30403 S30403 S30400 S30400 S30500 S30500 S31603 S31603 S32100 S32100 N08904 N08904 N08367 N08367 S40920 S40920 S43000 S43000 S43035 S43035 S46800 S46800 S44735 S44735 S41000 S41000 S32101 260 min 330 205 min 320 580 815 1000 1160 270 205 min 335 265 305 325 315 705 170 min 255 255 270 260 170 min 245 170 min 310 205 min 285 220 min 270 310 min 365 170 min 260 205 min 345 205 min 315 205 min 205 415 min 550 205 min 320 530 min 550 min 700 515 min 850 900 1150 1270 1380 690 515 min 640 625 635 650 640 890 485 min 590 600 610 600 485 min 560 485 min 595 515 min 570 490 min 605 690 min 745 380 min 440 450 min 515 415 min 455 415 min 415 550 min 650 450 min 515 700 min 40 min 51 40 min 49 32 23 17 12 57 40 min 51 55 52 51 53 23 40 min 53 51 55 56 40 min 52 40 min 51 40 min 49 35 min 50 30 min 47 20 min 31 20 min 27 22 min 32 22 min 32 18 min 20 20 min 28 30 min 100 Rb max 89 Rb 95 Rb max 88 Rb 25 Rb 35 Rc 40 Rc 42 Rc 82 Rb 92 Rb max 86 Rb 81 Rb 85 Rb 85 Rb 85 Rb 29 Rc 92 Rb max 80 Rb 81 Rb 82 Rb 78 Rb 88 Rb max 73 Rb 95 Rb max 82 Rb 95 Rb max 78 Rb 90 Rb max 79 Rb 100 Rb max 88 Rb 88 Rb max 60 Rb 89 Rb max 67 Rb 89 Rb max 76 Rb 90 Rb max 76 Rb 25 Rc max 20 Rc 96 Rb max 81 Rb .. and pickled. 2BA is cold rolled.. annealed.5% reduction). /2 hard /4 hard Full hard 2D Annealed Hot rolled 2D 2B #4 polish 2BA 1 /4 hard Annealed 2D 2D 2D 2D Annealed 2D Annealed 2B Annealed 2B Annealed 2B Annealed 2B Annealed 2D Annealed 2B Annealed 2D Annealed 2D Annealed 2D Annealed 2B Annealed (a) Finish conditions: 2D is cold rolled. MPa Elongation.280 / Stainless Steels for Design Engineers Table A2. MPa Tensile strength. and temper passed.2 Name Typical minimum mechanical properties of representative stainless steel engineering alloys Condition UNS Yield strength. bright annealed. 2B is 2D with an added temper mill pass (approximately 0.

the CALPHAD methodology provides a theoretical framework on which extrapolations can be made to predict the phase equilibria for higher-order. cemented carbides. and zirconium alloys. Thermo-Calc can also be used to investigate meta-stable equilibria-type problems.Stainless Steels for Design Engineers Michael F. the weaker the nonideal interaction What Is Thermo-Calc? Thermo-Calc (Ref 1) is a powerful.1361/ssde2008p281 Copyright © 2008 ASM International® All rights reserved. nickel superalloys. . Although the databases are based primarily on the critical assessments of binary. manually removing certain selected phases from the system and thus restricting the formation of such phases). a number of diagrams have been plotted and attributed to a software package called Thermo-Calc. Thermo-Calc minimizes the total Gibbs energy of the system with respect to various constraints such as temperature. By suspending certain phases (i. was used in conjunction with Thermo-Calc for all the calculations made during the preparation of this book. pressure. there are databases for steels and iron-based The thermodynamic database for steels (Ref 3). and some higher-order systems. The version of the database used for these calculations contains data for 20 elements and 85 phases. Thermo-Calc is used in conjunction with thermodynamic databases containing polynomial functions that describe the Gibbs energies of the different phases according to certain models that take into consideration nonideal chemical interactions in solution phases. www. multicomponent systems (the higher the order of the system. Different databases are available for different broad classifications of materials. systems. and chemical composition and thus predicts the most stable energy state (or equilibrium state) that can form. or applications. Further information on the different databases available can be found at the Thermo-Calc Web site: www. McGuire. Also provided are instructions for accessing a demonstration version of the software. ternary. explain what it is. magnesium. which describes mathematically the thermodynamics of a system through a representation of the Gibbs energies of the different crystalline phases relevant to that system and defined by the chemical composition of the system. ironbased slags. as developed by Thermo-Calc Software AB. flexible software package available from Thermo-Calc Software AB for performing various kinds of thermodynamic and phase diagram calculations for multicomponent systems. p 281-283 DOI: 10.thermocalc. The software is based on the so-called CALPHAD (CALculation of PHAse Diagrams) method (Ref 2). which are then assembled into self-consistent APPENDIX 3 Introduction to Thermo-Calc and Instructions for Accessing Free Demonstration Version WITHIN THE MAIN BODY of this textbook. and more. and what are its uses.e. The purpose of this appendix is to give a brief introduction to Thermo-Calc. ternary. For example.asminternational. These databases are based on the critical evaluation of thermodynamic and phase equilibria data for binary. aluminum. titanium. and some quaternary systems. nuclear materials.

Examples of each of these kinds of diagrams are given in the main body of the text. as illustrated by some of the examples in the main body of this book). Step: The amount of one state variable parameter (or condition) can be changed. etc. while the other conditions remain fixed. pressure. phase transformations. and various thermodynamic properties. solidus. multiphase systems as illustrated in this book) • Molar volume. For example. Phase transformation temperatures can be predicted based on the actual chemistry (not nominal chemistry). Thermo-Calc can thus be applied to a number of practical problems related to metallurgy.e. pressure. and solvus temperatures. • Thermochemical data such as enthalpies. Thermo-Calc can therefore be used in conjunction with such databases to make predictions for multicomponent systems and alloys of industrial relevance as illustrated by some of the examples given in the main body of this book. density. composition. While many types of calculations can be made using Thermo-Calc. and thermal expansion • Scheil-Gulliver (nonequilibrium) solidification simulations Thermo-Calc is not restricted just to modeling the alloy. in-service performance. These calculations can be validated against real alloy data if this information is available but is not based on (or adjusted to fit) such higher-order alloy data. and pressure and then predict what phases an alloy might form at a given temperature when exposed to such a carbon potential. be used to perform calculations for most applications involving phase equilibria. ternary. temperature. 3. for example. heat capacity. processing. 15 elements are not uncommon. phase diagrams. the software typically is used to predict: • Stable and meta-stable phase equilibria for binary. and higher-order systems (calculations for alloy compositions with 6. 4. one can vary the composition of one of the components/elements and calculate how the phase amounts change for a fixed temperature or predict how the solidus or liquidus would change with varying alloy composition. Complex systems representing processing. Scheil: Thermo-Calc includes a ScheilGulliver model for nonequilibrium solidification and a modified Scheil model that considers partial equilibrium for components that are selected by the user. 10. • Amounts of phases (mass. Isothermal sections are the result of varying the amounts of two of the components for a fixed temperature. Four specific types of calculation can be performed using Thermo-Calc. Higher order in this sense means more than four elements (i. Alternatively. one would “step in” temperature. and by commercial industry. larger than a quaternary system). Map: Two axis variables (such as temperature. to see how the different phases and their amounts and compositions would vary with temperature for a given alloy. and composition and also the chemical compositions of the phases formed • Phase transformation temperatures such as liquidus. volume and mole fractions) formed (phase balance) as a function of temperature.. Single-Point Equilibria: The temperature. can also be considered. meta-stable equilibria. and activities • Driving forces for precipitation • Phase diagrams (isothermal and isoplethal sections for multicomponent. Isoplethal sections are generated by varying temperature and composition of one of the components. although the range of problems to which these can be applied is broader: 1. or activity of the components) are changed at the same time. another application is to calculate the carbon potential of multicomponent gas phase systems as a function of composition. The software can . as summarized by: • Alloy Design: Modification of alloy chemistries to improve properties or reduce costs using calculations to guide which compositions may be most suitable before preparing them for testing Applications of Thermo-Calc Thermo-Calc is used around the world within academia. 2. composition/activity of a component (or the amount of a phase) are fixed and the stable or meta-stable equilibrium for the specified conditions is calculated. For example. in government research laboratories.282 / Stainless Steels for Design Engineers parameters become). pressure. as well as critical assessments and data evaluations for multicomponent systems.

Appendix 3: Introduction to Thermo-Calc / 283 • Heat Treatment: Prediction of formation of problematic phases prior to thermal processing • Casting: Calculation of liquidus and solidus temperatures. A list of published articles citing Thermo-Calc is available at www.. Version 5. P. The demo version will run for approximately 1 month on a single computer. Höglund. All fields in the registration form should be completed before continuing to the download page. 1998 3. TCFE5—TCS Steel/Fe-Alloys Database. Vol 26. REFERENCES 1. L. and Thermo-Calc for Windows. Helander. and linking to their support. On installation of the It should be noted that the demo versions are limited to using just three elements (whereas in the full product the current upper limit is 40 elements) and are supplied with only certain small databases that are for demonstration purposes and the evaluation of the software only.thermocalc. How to Obtain a Free Demonstration Version of Thermo-Calc Thermo-Calc is available in two formats: Thermo-Calc Classic. additional documentation. Thermo-Calc Software AB. Andersson. 1. CALPHAD (Calculation of Phase Diagrams): A Comprehensive Guide. T. Thermo-Calc and DICTRA.F.0. Technical support for the demo versions of the software is limited. it can be downloaded again (i. p 273– . com. A link to register and download the demonstration version of the software can be accessed via a link on the Thermo-Calc web site at www. Elsevier. where further instructions regarding installation of the software will be provided. www. including a Users Guide/Examples manual in the form of PDF files will also be installed.e. Pergamon Materials Series.thermocalc. If you wish to run the software after the demo license has expired. The demo versions are free to use. obtaining a new demo license). 2002. Demo versions are available for both of these versions of the software. Miodownik. Sundman. and installation on a network system is not supported. which has an easyto-learn graphical user interface but only operates in the Microsoft Windows environment.thermocalc. Saunders and A. Shi.thermocalc. Computational Tools for Materials Science. Calphad. and B. calculation of thermodynamic properties of the alloy for input into casting modeling codes • Welding and Joining: Prediction of the phases formed at the joining of two dissimilar materials or the interaction with filler material • Quality Control: Investigation of properties and phase balance within designated compositional tolerances More examples are available in the literature (search on key terms Thermo-Calc or CALPHAD). N. 2002 2.O. 2007.P. which has a command line interface and can be run under a number of different operating systems (including Microsoft Windows and Linux/Unix). but problems related to installation or general inquiries can be addressed by visiting www. subject to the terms outlined in the Thermo-Calc Software End User License Agreement.

29–30 martensitic precipitation-hardening stainless steels. 196. 102(F) acids. 116(F) iron-chromium phase. corrosion in. sensitization. 213(F) considerations. 219 surface. 174 ferritic stainless steels. 47–48 alloying elements alloys. 94 duplex alloys. 70(F) alpha prime formation kinetics for duplex alloys. influencing corrosion. 33(F) isocorrosion curves for. 69–72 most widely used. 72 austenitic stainless family. 240 American Petroleum Institute (API). 40. 52–53 aeration cells. 1 aluminum oxide. 1 austenitic alloys. 175 stainless long products. aluminum or carbon steel. 234(T) oxidation resistance. and bases. 7–8. 71(F) body-centered cubic (bcc) phase. 277(T). S and O. 147. 282 Index A acetic acid corrosion rates for various alloys of. 199 aluminum inclusions and pitting. 1 families in perspective. 69. surface. All rights reserved. 53 adsorption-induced plasticity. 102 isocorrosion curves in. 157(T) influence on uniform corrosion. 33 (F) influence on thermodynamic activity of C. 157(T) metal migration into acetic solution from. differential. 147 alloy design avoiding unwanted phases. 36(F) isocorrosion performances of various alloys. 94. 138(F) American Iron and Steel Institute (AISI). 255 Alloy Casting Institute (ACI) composition of. 120. 217–219 aging treatments. 96(F) influence of. 120–121 Lankford ratio. Stainless Steels for Design Engineers (#05231G) www. 79. N.and corrosion-resisting casting alloys. 64–65 aluminum alloys. 266 anisotropy deep drawing. 51. sulfuric acid with chlorides. 149 influence on corrosion rate in contaminated sulfuric acid. formation on hardness. S and O. 135 American Society for Testing and Materials (ASTM). 130. 179 annealing austenitic stainless steels. 98(F) alteration. 191 aluminum-titanium-nitride (AlTiN). 238–239 American Society of Mechanical Engineers (ASME). 55 aesthetic finishes Chrysler Building in New York City. 226. 141(T) martensitic stainless steels. precipitation hardening stainless steels. heat. 34(F) alloy systems alloying elements. 197(F). 41 influence on thermodynamic activity of C. 168. 198 . formation with aging. 278(T) naming system. in sulfuric acid. 131(T) alloy oxidation. refinery applications. 73 transition temperature change with. 31–36 adsorption-induced brittleness. 217–219 flatness. 92–94 Thermo-Calc software. 93. 8 martensite. N. content on corrosion rate in hydrochloric acid. 38–39 aerobic bacteria. 228 protective layer formation. 35(F) isocorrosion curves for. plus formic acid. 5(F). 103(F) duplex alloys. 66 alloys influence of. possible. 170 aggressive chemical agents. 234(T) migration into acetic solution from stainless.asminternational.Copyright © 2008 ASM International®. 162–164 bright. 51. 1 Schaeffler–Delong stainless steels constitution diagram. 191 aluminum/titanium precipitates. 1 influence on alloy families. behaviors.

169 austenitic-ferritic “C” alloys. 221 rolled-on stainless steel finishes. 216(F) fabrication and joining. 157 automotive industry. 239 . 138–139 interstitial elements. 216(F) maintenance. 36–37 atomic rearrangements. 218(F) stainless steel selection expert system. 239(T) architecture and construction aesthetic considerations. 40 production process. 216(F) roof. in hydrochloric acid. 170–171 ferritic stainless steels. 229 carburization. 5 γ-austenite in precipitation hardening alloys. 6. 6 face-centered cubic (fcc). 145 austenitic stainless steels alloy families. 73–74 mechanical properties. 79–83 high-temperature mechanical properties. 145–146 mechanical properties. 203 isocorrosion curves for. processing and economy. 82 composition of. 239–240 kitchen. 216(F) ecological considerations. 6 austenite conditioning. 221 fabrication considerations. 82(T) compositions of commonly used lean. 75(F) intermetallic phases. 4 first commercial use. 220–221 maintenance schedule. 143 sulfur and oxygen. 155 atmospheres. 217(F) graphic depicting low release of metal ions from 304 and 316 stainless steels. 166 precipitation hardening steels. 43 martensitic stainless steels. 69–72 annealing. 221 fire resistance. 162–164 automotive structural components. design and maintenance. 152–154 precipitation hardening stainless steel. 217 cleaning methods for uncoated stainless steel. 9 diffusion rates. 9 carbon and nitrogen. 6 phase in duplex alloy at room temperature. 20–21. 271(T) composition of high-temperature. 7 semiaustenitic precipitation-hardenable stainless steel. 5 carbide precipitation. 180 face-centered cubic (fcc). 154 inclusions in steel. 215 argon oxygen decarburization (AOD) adoption. 184 control of nitrogen in refining by. 221–222 flatness. 82 heat exchangers. 270(T). 34(F) kitchen appliances. 146(F) composition. 82–83 impact strength variation with temperature. 246 high-temperature alloys. 5(F). 222 corrosion resistance. 219(F) ranking common stainless steels by pitting resistance equivalent number (PREN). 215. 165–166 long-term. 220(T) concrete reinforcing bar. 91 Schaeffler–Delong constitution diagram. 217–219 average chloride concentration in rainwater in United States. 145(T) corrosion resistance. 170 austenitic precipitation-hardenable stainless steels cold work and aging. 151–152 austenitic “H” alloys high temperature HE–HP. 222 environment. 237–240 laundry. 7 metastable state. 216(F) surface finish aesthetics. 217(F) balancing corrosion resistance. 218(F) salt exposure. 213–214 design considerations. 84–89 corrosive environments. 174 family. 202(F) secondary type. 66–67 atmospheric corrosion uniform corrosion. 6 lattice expansions. 219 grades recommended by expert system. 222(F) local weather pattern. 176 ductility. 82. 86(T) corrosion resistance ratings. 23 appliances facades. 44(F) drawability. 92 ferrite. 225 cleanliness. 177 duplex stainless steels. 12 polarization. 109 foundry practice. 6(F) lean alloy of martensite and. 2 attraction.286 / Index annealing (continued) deep drawing. oxidation. 72(T) compositions of corrosion-resistant. 70 alloy adjustment. 139 anode electrochemical reactions. 87(T) corrosion-resistant alloys. 217–219 surface finish and corrosion resistance. 88–89 critical pitting temperature (CPT). 214–215 balancing service environment. 70(F) Schaeffler diagram. 216(F) special finishes. of welds. interatomic. 43. 214(T) repair. 71(F) forming limit diagram of carbon steel and. 241 stainless steels commonly used for. 2 austenite alloying elements. 176(F) halogens.

235 bleaching. 231(T) stainless steel body. martensitic stainless steels. 226 alloys for major elements of automotive exhaust systems. 211 bright annealing. 131. 226 flexible pipe. 151 carbide. 231(F) Butler–Volmer equation. 132(F). 236(F) bases. 228 center pipe. 161–162 stabilization. 110 ferritic material. 163 metal migration into acetic solution from. 151–152 corrosion resisting. 69 welding characteristics. 231. 183 nitrogen and. 232 resilience and toughness of carbon and stainless steels for automobiles. 89 tensile properties of carbon steel vs. 188–189. 46–47 soaking. 53(F) surface finish. 72–78 machinability. 229(T) SCC (stress corrosion cracking). 228 fuel tanks. 227(T). 231(F) car manufacturers. 55–56 biological neutrality. 227(T). 201–204 welding parameters. 225 bus bodies. 229(T) trucks. for automotive components. 161–164 water vapor. 234(T) nitriding. precipitation kinetics. 225 exhaust manifold and high-temperature. 198 brightening stainless steels. 184 iron and tool. 4 brazing. 225–228 ferritic stainless. 20–21 C calcium effect on machinability of 303. duplex steels and transformation steel. 196 buffing. 164 biocorrosion. 156 Bauschinger effect. 231 B bacteria influencing corrosion. 227(T). 228 rail transport. 151–152 precipitation hardening. 174 metals. 229–231 tailpipe. 230 catalytic converter. 245 SCC performance. 78. carbon steel. 266 body-centered cubic (bcc) phase carbon and alloy steels. 249(T) pitting resistance equivalent number (PREN). 227(T) automotive emission standards. 185 grain sizes. 166–167 automotive and transportation alloy selection for exhaust systems. 82–83 mechanical properties after cold work and annealing. 228 decorative to highly engineered applications in automobiles. 147 duplex alloys. 189(F) inclusions and pitting. 158 “C” alloys austenitic–ferritic alloys. 185 carbon and. 185 bus life-cycle cost calculation for stainless vs. 79–81 petroleum industry applications. 182 nickel and. 182 coolants minimizing. 81–82 weaknesses. 7(F) . carbon steel for bus. 191 copper and. 74–76. 197 built-up edge (BUE) austenitic stainless grades. 4. 183(T) martensite and austenite. 82(T) sensitization. 31–36 basic oxygen furnace (BOF). 149. 82 oxidation resistance. 185 machining setup recommendations. 162(T) resilience and toughness of carbon steel vs. 231 life-cycle cost calculation for stainless vs. 230. 55 bacterial retention. 184 precipitation hardening stainless steels. corrosion in acids and. 121 ferrite. 232(F) muffler. 151 mechanical properties of corrosion resisting cast. 227 exhaust systems. 85 precipitation of carbides and nitrides. pulp. 228 tensile properties of carbon and stainless steels for automobiles. 43. 76–78 recommended thermal processing temperatures.Index / 287 lean alloys. 227(T). for automotive components. 230(F) structural components. 78 stainless steel in shipping. 231(T) microcar frame. 49–50 secondary phases in. 207(T) austenitizing. food contact. 41 calcium-fluoride based slag electroslag remelting (ESR). 1 change to face-centered cubic (fcc). 228 front pipe. 127(F) ferrite. 227(T). 229(T) thermal processing. 227(T). 73–74 mechanical properties. 183 ferritic stainless steels. 150(T) metallurgy of. 229(T) stress-strain curves for 301 variants vs. 262 stress-strain curve for single crystals of stable. food contact materials. 2 boron additions to ferritic stainless steels.

217(F) chloride-containing solutions. 234(T) resilience and toughness of. 82 carburizing. 147 austenitic-ferritic alloys. 72 austenitic stainless steels. 115 carbon dioxide. 77(F) ferrite. 79–80 protective layer formation. HD alloys. 228 depletion from austenite near grain boundaries. vs. 119(F) chemical agents. 261–262 isocorrosion chart for sulfuric acid. N. 151–152 austenitic HE–HP alloys. 257. 229(T) carburization. 148(T) chromium-nickel alloys. stainless steel for automotive components. content. 147 precipitation hardening. 85–86 chromium-oxygen system volatility vs. 227(T). 9 tooling. 258–262 erosion. 258–259. 41 oxidation resistance. 50 center pipe of exhaust systems. 182–184 chi intermetallic phase.288 / Index carbides duplex alloys. 283 casting alloys Alloy Casting Institute (ACI). 76–78 stainless steel. 135(F) metal migration into acetic solution from. 154 catalytic converter. 20–21. 76(F) carbon steel activities and activity coefficients of elements in. 23 caustic solutions.and dual-environment systems. 30(F) ion release from stainless steel grades. N. aggressive against stainless steel. 5 ferrite. 9 precipitation kinetics. 152–154 molten metal transfer. food contact. 6 machinability of stainless steels. 201 carbon diffusion. 152(T) metallurgy of “C” alloys. 262 stress corrosion cracking (SCC). 42. 85 chlorinated oils or waxes. 260(T). 257–258 specific corrosives. 147. 1 austenitic alloys. 65 Charpy V toughness high-temperature austenitic alloys. 151 ferritic HA. 149. 199 casting stainless steel processing. 154 high-temperature mechanical properties of “H” alloys. 12 mass transfer limitations. 76–78 precipitation rates by. at room temperature. 182–183 precipitation of carbides. 149(T) compositions of cast stainless corrosion resisting alloys. 153 naming system. 65 cathode effect of. 158–159 Thermo-Calc software. 40(T) body-centered cubic (bcc) phase. 7(F) chip breaking. 248 carbon solubility. 150(T) welding. 187(F) chloride concentration in rainwater. 3 ferritic stainless alloys with low. 157(T) influence on thermodynamic activity of C. 1 austenite. in austenite. 261(T) corrosion types. 261 single. 128(F) welding of austenitic stainless steels. 255 chemical and process industry. 258 intergranular corrosion. 110 inclusions and pitting. See also corrosion types corrosion table for fuming sulfuric acid. temperature and oxygen pressure. 228 cerium inclusions and pitting. 119(F) titanium-stabilized alloy. 50–51 chloride ion. 227(T). 262 chemical neutrality. 64(F) corrosion resistance. 148(T) duplex alloys. 228 catastrophic oxidation. medium and high. 151–152 metallurgy of “H” alloys. 1 corrosion rates of stainless vs. S and O. 156 variation of martensite hardness with. 229(T) tensile properties of. 3–4 influence of alloying elements on thermodynamic activity of. 151 room temperature mechanical properties of corrosion resisting stainless. 157(T) influence on uniform corrosion. 152–154 chromium alloys. 153(T) influence of alloying elements. 233–235 chemistry. 240 precipitation. 76(F) steel content. stainless steel for automotive components. 94 flatware. 43 influence on thermodynamic activity of C. 29 interstitial atoms of.. polarization. 262 forms of corrosion. 258(F) pitting and crevice corrosion. 29. austenitic stainless. 148(T) composition of cast heat-resistant stainless and nickel base alloys. S and O. 24(F) electrochemical reactions. 152 foundry practice. wet. 259(T). 149 mechanical properties of heat-resistant stainless. vs. 179(T) chromium alloying element. HC. 222(F) . 191 carbon alloying element. machinability of stainless steels. 261(T) corrosion table for sulfuric acid. 24 polarization. 157(T) influence on uniform corrosion. 83(F) niobium-stabilized alloy.

222 constitution diagram Schaeffler–Delong stainless steels. 261 pitting resistance equivalent number (PREN). 260(T). 183 copper sulfate. 70(F) Schaeffler diagram. carbon steel. 31(F). 237 flatware and cutlery. 32(F) corrosion combating. 145–146 balancing. 203(F) construction. 215(F) corrosion resistance architecture. 274(T) martensitic PH stainless steels. 235–236 machinability of stainless steels. 109. 143(T) tool and cutlery martensitic stainless steels. 244(F) martensitic PH stainless steels. processing and economy. See also sulfuric acid plus copper sulfate corrosion of stainless steel and titanium in. See architecture and construction contamination. surface roughness. cast stainless. 234(T) oxidation resistance. 237–238 coatings cookware. 233 composition Alloy Casting Institute (ACI) heat. 228 paralinear oxidation from evaporation of chromium superoxide. 186 thermodynamics of oxidation. 248. 257. 214–215 duplex alloys. 258–259. 257–258 stress corrosion cracking (SCC). 254–255 stainless steel in shipping. 204 ferritic stainless steels. 235 continuous slab casting. 111(T). 124(T). 261(T) tendency. 265–267 rail transport applications. 258 single. 220(T) cleanliness food contact materials. 196 commercial use applications. 140(T) martensitic stainless steels. 191 copper acid resistance. 37(F) influence of alloying element on. 99–106. 244–245 pulp-and-paper industry. 202(F) Welding Research Council’s 1992. 237 coolants. 21–22 mixed potential theory and polarization diagrams. 80(F). 271(T) duplex alloys commercially available. 121–122 function of salinity and temperature. 245 sulfur hurting. 213–214 austenitic precipitation-hardenable (PH) stainless steel. 71 machinability of stainless steels. 261–262 isocorrosion chart for sulfuric acid. 215 . 276(T) ferrite stainless steels. 182 migration into acetic solution from stainless. 235–236 uncoated stainless steel. 11 erosion. 184 coastal climates. 97 (T) duplex stainless steels. 112(T). 188 surface finish and. 148(T) chromium-nickel alloys. 273(T). plus sulfuric acid. 64(F) Pourbaix diagram. 135(F) stainless vs. 275(T) PH stainless steels. 241 stainless steel. 213 highly polished surface. 259(T). 195(T) stainless steel. 179–180 cold work. aluminum or carbon steel. 191 cold heading. 21 migration and ionic diffusion. 71. 145(T) austenitic stainless steels. 23(F) vs. 22–23 passivation. 197(F). 276(T) semiaustenitic PH stainless steel.Index / 289 machinability of stainless steels. 15–16 types. 5(F). 23–25 Tafel regime: electrode-kinetics control. in contaminated sulfuric acid. 110. 237–240 laundry appliances. 278(T) austenitic precipitation-hardenable (PH) stainless steel. 262 intergranular. 20–21 introduction. 258(F) pitting and crevice. 240–241 food contact. 21 corrosion rate alloys in simulated evaporator liquid. 33(F) stainless oil country tubular goods. 125(T). 237 tooling. 213(F) cleaning passivation. 232 ratings of austenitic stainless steels. 17(F) sulfide formation. 250 definition. 277(T). 196.and dual-environment systems. 63. 64(F) chromium alloys. 270(T). 148(T) Chrysler Building architecture using stainless steel.and corrosionresisting casting alloys. 87(T) semiaustenitic PH stainless steel. 79. 144 stainless steel for refinery equipment. in alloys for petroleum industry. 252–253 corrosion kinetics Butler–Volmer equation. 194–196 cleaning methods stainless steels. 19–20 mass transfer control. 141–142 material selection for desalination. 237–242 cookware. 135(F) Tafel slope. 258–262 corrosion cost. 57–59 volatile nature of Cr2O3. 75 coloring of stainless steels. 241–242 kitchen appliances. 134(T) concrete reinforcing bar. 158 cookware. 195–196 recommended methods. 233–237 heating and water heating. 262 table for sulfuric acid.

266 demand for steel. 177 texture. 177–178 intermediate annealing. 30(F) dissimilar metals and differential aeration cells. 254–255 creep rupture strength. 38–39 environmental variables. 16–17 standard half-cell reduction potentials vs. 240–241 martensitic stainless steels. 243 reverse osmosis (RO). 46–48 hydrochloric acid. 247 desalination materials selection for. 83(F) crevice corrosion austenitic stainless steels. 104(F). 35 sulfuric acid. 45–46 critical current density. 175(T) schematic. 83. 55–56 chromium influence. 29. 278(T) compositions of cast stainless. 105(F) dissimilar metals and differential aeration cells. normal hydrogen electrode. 174(F) strain rate. 46–48 sodium chloride/carbon dioxide environment. 27–37 corrosive environments austenitic stainless steels. 32(F) uniform. 261 critical. 34. 29–30 nickel. 103. 45 preventing. 84–89 “C” alloys. 88–89 platforms. 14(T) corrosion types atmospheric. 150(T) corrosion theory corrosion tendency. 105(F) stainless steels for unwelded and welded material. 148(T) duplex alloys. 174–179 geometry. 30 nitric acid. 43–45 preventing crevice.290 / Index corrosion resisting alloys austenitic stainless steels. 174 tooling. 45–46 SCC (stress corrosion cracking). 86(T) composition of Alloy Casting Institute (ACI). 29. 173. 49. 39 development precipitation–hardening stainless steels. pitting resistance equivalent number (PREN). 44(F) critical crevice temperature (CCT) and CPT. 174 forming stainless steel. 55 corrosion in acids and bases. 104(F) cryogenic containers. 230 pitting corrosion. 30(F) critical pitting temperature (CPT) austenitic steels. 137–138 welding. 91 mechanical properties of stainless. 23(F) cutlery flatware and. 258–259. 30 organic acids. 43. 31(F). 151–152 composition of. 160 delignification of pulp. 35(F) nitrogen. 105(F) duplex alloys. 244–245 multi-stage flash (MSF). 37–38 material variables. 33–34. 245 current density. 176. 45(F) critical crevice temperature (CCT) and critical pitting temperature (CPT). 48–49 crack propagation. 217 designers car manufacturers. 51–54 sensitization. 36(F) pitting. 29. 133–134 D deep drawing anisotropy. 241(T) cutting tools. balance. 12 galvanic vs. 38–39 duplex alloys. 48–54 SCC mechanisms. 254 refinery equipment. 36(F) phosphoric acid. 29 corrosion fatigue. 30(F) localized. 178–179 defects. 15–16 electrochemical reactions. 103–104 geometry. 215. 105(F) critical current density. 85. 49–50 molybdenum role. 50–51 environmental variables influencing uniform corrosion. electrochemical cells. 35. temperature with alloy content. 11–12 Faraday’s law. 14 Nernst equation. 31–33 sulfuric acid plus copper sulfate. 45–46 critical crevice temperature (CCT). 174–175 hydroforming. 38–39. 177 materials composition. 39–45 pitting resistance. 211–212 . 34–35. 54–55 influence of alloying elements. 133–134. 243–244 design. 84(F) creep strength. 36–37 biocorrosion and microbiologically induced. 52(F) crevice. 28–29 grain boundary. austenitic stainless steels. 48–55 crack initiation. 240 stainless steels commonly used for. 87 corrosion type. 214. 149. 243–244 technology. 12–14 Pourbaix diagrams. 85(F). 31–36 corrosion with fatigue or fraction. 277(T). 30 strong bases. 29–31. 44(F) vs. 35(F) hydrogen embrittlement.

austenite vs. 258. laundry appliances. 207(T) wrought 2205 duplex microstructure.. 102. 92(F) formation kinetics. 279(T) environment. 230(F) structure and alloy design. 102 annealing.Index / 291 differential aeration cells active alloys. 75(F) iron-nickel diagrams. stainless steel selection expert system. 6 digesters first kraft from alloy 2205. 170 sodium hydroxide. 280(T) physical properties of major stainless steel. 93–94 petroleum industry applications. polarization. 170(T) SCC (stress corrosion cracking). 56 schematic. 179(T) dual-environment system. 245 strength. 196 electroslag remelting (ESR). 73–74 equilibrium. 11–12 potential. 101–102 photomicrographs. 19 erosion. 248(T) phosphoric acid. 94–98 nitric acid. cold-rolled stainless. 103(F) partitioning of elements. 12 diffusion atomic rearrangements. 50–51 uniform corrosion. 276(T) compositions. 99(F) pulp-and-paper industry. 217(F) stainless steel selection. 155–156 equivalent weight (EW). 100 thermal processing. 194 electromotive force. 2 ionic transport. 236–237 dissimilar metals. 14 electrolytic pickling. 91(F) E earing deep drawing. 43 PREN influencing fatigue. 100–101 impact strength. 38–39 microfouling. 178 measuring tendency. 262 expert system recommended stainless steel grades. argon oxygen decarburization (AOD). 91–92 corrosion resistance. 265. 266(F) pulp-and-paper industry. austenite. 38–39 dissociated ammonia. 101 stainless steel for line pipe. 222 electrochemical cell closed circuit. and duplex with temperature. 101 organic acids. 14(F) electrolyte resistance. 178 fastest-growing stainless steel family. 170–171 umbilical tubing and risers. 180 hydrochloric acid. 47 soaking. 253–254 variations of ferrite. 28–29 epsilon martensite. 97–98 impact strength variation with temperature. 19 electrochemical reactions. 7–8. 151 crevice corrosion. 38 electrochemical corrosion. 253 stainless steel in shipping. 104–106 sensitization. 98(F) welding characteristics. 95(F) pitting corrosion. 98. 11–12 electrode-kinetics control Tafel regime. 99–106 corrosion-resistant “C” alloys. 186 machining setup recommendations. 216(F) . 216(F) exposure to salt. stainless steel selection expert system. 216(F) environmental variables stress corrosion cracking. 257 duplex alloys acetic acid. 49. 151 engineering alloys minimum mechanical properties of stainless steel. corrosion. 21 electrodes. 198–199 dissolution equation. 157–158 embrittlement. 8 high-temperature. 183(T) mechanical properties. 13 electropolishing. 97(T) concept. stainless steels. 170–171 composition of selected. 204–205 welding parameters. 91–92 fatigue. 92–94 sulfuric acid. forming stainless. 103–104 deep drawing.. 99 heat exchangers. 246 hot forming. 266–267 recommended annealing and stress–relieving temperatures. 37 term. 96 stress corrosion cracking (SCC) performance. 265 disinfection. 20–21 electrolysis cell. 102–103 pitting resistance equivalent number (PREN). 262 stress-strain curves for 301 variants vs. 178 ecological considerations. 241 dry film. 98 Fe-Cr-Ni phase diagrams. 96(F) formic acid. 20(F) differential aeration corrosion cell. galvanic vs. See also hydrogen embrittlement (HE) alpha prime. 21–22 diffusion rates. ferrite. 27 dryers. 93(F) machinability. 103(F) forming and machining. 22 electrolytic cells. 114 σ phase at higher temperatures.

174 carbon diffusion rate in. 47 soaking. 113–116 metal migration into acetic solution from. 273 (T). 227(T). 118–120 stress corrosion cracking (SCC). 98. 91 Schaeffler–Delong constitution diagram. 75(F) intermetallic phases. austenitic stainless steel. 115 toughness. 43 recommended annealing temperatures. 117(F) annealing. 121 hot rolling. 234(T) qualifications. 176 (F) groups of low. 174–179 deep drawing materials composition. 178 ferritics. 12. 120–121 time-temperature-transformation (TTT) curve for 430. 115. 111(T). 121–122 deep drawing. 165–166 automotive exhaust systems. 110. 210 food contact bacterial retention by material and cleaning time. 5 austenitic materials. of stainless steel. 4–5 ferritic “H” alloys. surface aesthetic. 237 flatware and cutlery. 113 texture and anisotropy. 226 body-centered cubic (bcc). 173–179 forces for hot working. 4 mechanical properties. 116. 3(F) phase in duplex alloy at room temperature. 176(F) hot. 35 corrosion rates for various alloys of acetic plus formic acid. suitability in forming stainless steel. 179(T) ferrite carbon and nitrogen. 202(F) stabilization with titanium. 117(F). 55 duplex alloys. 252–253 flux cored wire (FCW) welding. 235 chemical neutrality. 116 forming limit diagrams. 233–235 cookware. 4 thermal conductivity and thermal expansion. 178 flat.. 2 Faraday’s law. 99(F) fatty oils and blends. 1 austenite. 116(F). 99 duplex stainless steel. 241(T) surface disinfection. 6 δ-ferrite in precipitation hardening alloys. 21 fatigue corrosion. 205–206 welding parameters. 152 ferritic stainless steels alpha prime formation. 240–241 heating and water heating. 176(F) forming limit diagrams for stainless steel categories. 5 fingerprints. 219 flatware. stainless steel. 89 corrosion in. 241–242 kitchen appliances. 221 facades of appliances. 113(F). medium and high chromium. 233–237 stainless steels commonly used for appliances. 240–241 flexible pipe. 236–237 formability. 174(F) duplex alloys. 239 lowest cost and simplest stainless. 118–119 welding characteristics. 49 stress relieving. 239(T) stainless steels commonly used for cutlery. 274 (T) corrosion and oxidation resistance. 4 molybdenum. 180 . 165 stabilization. 178 embrittling phenomenon. 115 composition. 237–240 material cleanliness. 5(F). 228 flow lines. 173. cleaning methods for uncoated stainless. 127(F) metals. 239–240 face-centered cubic (fcc) phase aluminum alloys. rolled stainless steel. 112(T). 165(T) sensitization. 236(F) biological neutrality. 180(F) forming limit diagram of carbon steel vs. 138–139 hydrogen and boron. 109–110 machinability. 120 formic acid austenitic stainless steels. 103(F) duplex alloys. 4 phase diagram of iron chromium. 175–176 forming technology deep drawing. 245–246 high-temperature properties. 113 heat exchangers. 235–236 metal migration into acetic solution. 120. 234(T) petroleum industry applications. 70(F) Schaeffler diagram. 175(T) deep drawing schematic. 159 impact strength variation with temperature. ferritic stainless steel. 185 machining setup recommendations. 166 superferritics. 115(F) titanium and niobium. 109. 36(F) forming limit diagram (FLD). 183 (T) mechanical behavior. 102 isocorrosion curves in. 116–117 metallurgy. 207(T) ferromagnetism. 115 chromium. 220(T) fire resistance. 118 titanium for carbide and nitride formation.292 / Index F fabrication. 174 change to body-centered cubic (bcc). 114(F) kitchen appliances. 221–222 flatness. 3–4 carbon diffusion rate. 116 iron-chromium phase diagrams. 109. 247(T) pitting resistance equivalent number (PREN). 3 diffusion rates in austenite vs.

33–34 G Gallionella. 205 laser welding. 57. cleaning methods for uncoated stainless. coloring stainless steels. 210 martensitic stainless steels. 197(T) Guinier–Preston (GP) zones. 14(F) vs. 157 high-frequency induction welding. 8 boron additions to ferritics. stainless steels in. 159 hot strip tandem mills. 197 . 114 high-temperature properties. 175(F) optimized 409 for forming vs. 13–14 vs. 133. 168–170 heavy-duty emulsions. cleaning method. 232 hot ductility defects. 152(T) metallurgy. 179(T) heavy metals. 174–175 pitting corrosion. 179(T) grinding. HC. 152 high-temperature mechanical properties of. 228 fuel tanks. 82(T) intermetallic phases of austenitic stainless steel.Index / 293 hydroforming. 209(F) process. 176. of martensite. 55 galvanic cell electrochemical reaction. 211 high-speed tool steels. 152–154 corrosion resisting. 7 heat exchangers. 58(F) grade selection. 178 stainless long products. 147 ferritic HA. 201 duplex stainless steels. 159 hydrochloric acid austenitic stainless steels. 204 ferritic stainless steels. 12–13 oxidation. 45 deep drawing. 81–82 high-temperature embrittlement. 220(T) heat treatment. 82 martensitic stainless steels. 163 martensitic stainless steels and toughness. 121 hopper cars. normal 409. 149(T) “H” alloys. 245–246 heat-resistant alloys composition of Alloy Casting Institute (ACI). 6 austenite. 82–83. 231 fuming sulfuric acid. 79–81 water vapor. 159–160 hot Steckel mills. 77(F) ferrite-austenite. 190–191 high-temperature alloys austenitic stainless steel. 131. 84(F) oxidation resistance of austenitic. 138 H half-cell reactions reduction potentials. 177(F) orange peel. 134(F) mechanical properties of austenitic. Lankford ratio. suitability in forming stainless steel. 2 friction stir welding. 184 graphite. 177–178 hydrogen embrittlement. 77(F) corrosion. 76–77. 14(T) “H” alloys austenitic HE–HP alloys. 116–117 heat-affected zone (HAZ) austenitic stainless steel. 283 heat treatment and conditioning. 160 hot forming. 152–154 mechanical properties of cast stainless. 38 schematic. 88. 196 heat tinting. 207 chromium carbide formation in. 210 gas tungsten arc welding (GTAW) joint design. 212 front pipe. 46–48 defects in stainless steel. normal hydrogen electrode. corrosion resistance. 220(T) grain boundaries austenite. 152–154 halogens. 152(T) heat tint. 278(T) compositions. 214–215 graffiti. 179–180 stainless steel. coarse polishing. electrolytic cells. 180 hot mill defects. alloys in automotive exhaust systems. processing and economy. 206 secondary austenite. 9. ferritic stainless steels. 261(T) furnace. 173 stretch forming. 154 free energy. elimination. 14 gas metal arc welding (GMAW) joint design. 89(F) corrosion in. 177 limiting drawing ratio (LDR) vs. 8 grain size austenitic stainless steel annealing. phases. 227(T). 160 hot rolling. 209(F) process. 160 depletion of chromium from austenite near. 178 tooling. 109. 241–242 grit sizes. 179(T) surface finish. 121 carbide precipitation. 82 hardening austenitic stainless steels. casting alloys. 174 suitability of lubricants for use in. 178–179 foundary practice. 153(T) mechanical properties of heat-resistant. 39 Gibbs free energy electrochemical reactions. HD. Thermo-Calc software. 75 ferritic stainless steels. 208–210 geometry crevice corrosion. 132(F) material structure.

238(F) facades. 130(F) phase diagrams with varying chromium. 39–40. 101(F) hydrofluoric acid. electroslag remelting. 8–9 International Nickel Company (INCO) process. 159 initiation pitting. 6(F) laundry appliances. 241 laves. 175 lanthanum. 208. 51. 203 ferritic stainless steels. 265–267 pulp-and-paper industry. alpha prime formation. 182 migration into acetic solution from stainless. 35(F) isocorrosion curves for austenitic stainless steels in. 121–122 mechanisms. 2 intermetallic phases austenitic stainless steel. 96(F) kitchen appliances austenitic stainless steel. 100–101 influence of alloy content on corrosion rate in. 36. 158 limiting current electrode reaction kinetics. high-frequency. 52–54 hydrogen ion reduction. 97–98. aluminum or carbon steel. 16(F) pseudo-binary-phase diagram for. 21–22 iron body. precipitation kinetics. 204 variation with temperature for stainless steels. 21 increasing mass transfer. 15(F). 73–74 lime content. 72(T) martensite and austenite. 114(F). 178 Lankford ratio anisotropy measure. 130(F) iron dissolution. 186–188 induction welding. 48. 234(T) penetration rates. 252–253 liquefied natural gas (LNG) vessels. 3(F) phase diagram from Thermocalc. 55 crack growth. 37–38 . elements from stainless to foods. 237–240 interior or working parts. 202 kraft process paper-making. 222(F) machinability of stainless steels. protective layer. 239–240 ferritic stainless grades.and face-centered cubic transformations. 175 line pipe martensitic stainless. 188–190 pitting corrosion. earing tendency. 175 limiting drawing ratio as function of. 72–78 compositions of austenitic. 239 coastal conditions. 134–135 stainless steel application. 158. 9 leaching. 48–49 interatomic attraction. 210 lattice expansions. 120. 20(F) iron reduction. 10 sulfur. thermodynamics. selenium. 34(F) isocorrosion curves for stainless steels in. 113(F) L Lankford r. 3 ion release from stainless steel grades. 196 interstitial elements. 94. 198–199 hydrogen embrittlement (HE) corrosion fatigue. 15(F). 209(F) K kinetics.294 / Index hydrochloric acid (continued) duplex alloys. 43 stress corrosion cracking. 19(T) Pourbaix diagram. bright annealing. 265 I impact strength duplex alloys. 187(F) lead. and sulfur. 2 electrochemical corrosion. 239 knife-line attack. 116 stainless steel. 186–190 stainless steel. 186 lean alloys austenitic. 283 joint design. 65 laser welding. 239 food contact. 75(F) inclusion-related defects. 160 inclusions chip breaking at sulfides. 195 phase diagrams with varying carbon. stainless steel machinability. 82. 6 ionic current. tellurium. 186 oxides. 34(F) isocorrosion performance of duplex. 23. 19 ferrite. 28(F) J JFI Steel. 234 lead. 221 Thermo-Calc software. 28(F) hypochlorite bleaches. 193–194 hydroforming. 135(T) joining stainless steel. 211 ingot method. 54–55 stress corrosion cracking. oil country tubular goods and line pipe alloys. 177–178 hydrogen/argon atmosphere. 254 localized corrosion. 49 ferritic stainless steels. 40–43 role in machining stainless steels. 11–12 ionic diffusion. 41(F) iron-chromium phase diagram. 24(F) limiting drawing ratio. 7(F) laves phase. 238 exposure of stainless samples to North Carolina beach.

179(T) lubrication. 190–191 maintenance balancing service. 190–191 introduction. S and O. 215. 186 manganese sulfides inclusions. 127–128. design and. 159 influence of alloying elements. 185 carbides. 184 sulfur.Index / 295 lubricants oxides. 126–127 forms. 140(F) precipitation hardening stainless steels. 220–221 stainless steel selection expert system. 126 expanding austenite stability range with nickel. 134–135 passivation. 183(T) structure. 182–183 chromium. 183 nickel. 182–185 precipitation hardening. 185 material’s machinability. 131(F) flatware and cutlery. material’s. 70(F) Schaeffler diagram. precipitation hardening (PH) alloys. 245 typical analyses and properties of marine alloys. 186 titanium. 123. 188 x-ray examination. 139(T) microstructures of. 189–190 suitability in forming stainless steel. 182 cleanliness. 183 niobium. 183(T) martensite formation. 181(F) molybdenum. 183 cross-section size. 186 machinability of stainless steel families. and austenite. 128(F) martensitic alloys “C” alloys. 123 distinction from other alloys. 191 coolants. 243–245 heat exchangers. 133. PH alloys. 166 applications. 1 austenite. 185–186 process. 139–142 martensitic stainless steels annealing. N. 127. 128(F) high-temperature use. 186–188 super stainless steels. 181–182 iron. 245–246 materials for desalination. 124(T). 185 duplex. PH alloys. PH alloys. 9 composition range. 141–142 mechanical properties of. 126(F) reversion of. 75(F) Schaeffler–Delong constitution diagram. 189(F) Marangoni effect. 99 ferritic. 188–190 physical and mechanical properties. 216(F) manganese alloying element. 244(F) desalination. 186–190 selenium inclusions. 186 duplex alloys. 5(F). 134(T) corrosion rates of stainless oil country tubular goods (OCTG) alloys. 184 oxide inclusions. 41 stress risers. 207 marine systems corrosion resistance vs. 217 stainless steel. 185–186 manganese. 166–167 composition. 185 machining setup recommendations. 7 varying hardness with carbon content. 149. 191 carbon. 133–135 austenitizing. 183 sulfur inclusions. 131(T) iron-chromium phase diagrams. 130–131 . 195 petroleum industry applications. 6(F) lean alloy of. 135(F) corrosion resistance. 7–8. 130(F) machinability. 157(T) machinability of stainless steels. 244–245 shipping. 184 role of chemistry. 182–184 role of inclusions. 191 copper. 140(T) corrosion resistance of. 73–74 lattice expansions. 130. 5 inclusions and pitting. 7 formation. 240–241 hardness variation with carbon content. 126–127 OCTG and line pipe. salinity and temperature. 183 sulfide formation. 186 setup recommendations for turning wrought stainless steels. 182 lead inclusions. 181(F) machining stainless steels austenitic. 41 influence on thermodynamic activity of C. 151 composition of. 186 tellurium inclusions. 245(T) martensite carbon and nitrogen. 185 high-speed tool steels. 183 martensitic. 134(F) hot rolling. formed by cold work. 184 nitrogen. 202(F) tempering. 125(T) composition of. 73–74 platelets from surface. 275(T) compositions of tool and cutlery. 184 tooling and coolants. 247(T) phase structure. 197–198 M machinability. 184 coatings.

235 microstructures. 252(T) natural gas. martensitic precipitation-hardening stainless steels. 206–208 material structure. 7 austenitic precipitation-hardenable (PH) stainless steel. 250. N. 72 carbide precipitation. 182–185 marine alloys. in food contact. 129(F) recommended annealing. of “H” alloys. 179(T) ferrite. of stainless steel engineering alloys. 280(T) semiaustenitic PH stainless steel. 228 protective layer formation. 41 mixed potential theory. 196. 175(T) duplex alloys. 144(T) stainless steels. 24–25 material selection. 243 N naming system. 21–22 mineral resin. 227(T). 29–30 influencing critical pitting temperature in welded vs. 142 restrictions in use recommendations for stainless steels. 20 thermodynamics of electrochemical reactions. 2 metastable pitting. 57. 167–168 tempering. 247 diagram showing alloy suitability. 251(F) regulating high-strength alloys. unwelded austenitic grade. 155–157 metal dusting. of austenitic stainless steels. vessels for liquefied. 67 metal flow directions. 228 disulfide. 21 mass transport. 254 Nernst equation open circuit potential. 158 molybdenum alloying element. 123 soaking. 64–65 muffler. 22–23 mold powder. 1 austenite. 113–116 ferritic stainless. 49–50 uniform corrosion. 152–154 introduction. 236(F) mischmetal. 51–54 melting production process. ionic transport. 167 tempering and toughness. 133–134 toughness by austenite grain size and phosphorus. 10 mechanisms pitting corrosion. 147 National Association of Corrosion Engineers (NACE) alloy listing. 133(F) thermal processing. automotive exhaust systems. 8 martensitic PH stainless steels. 184 material variables stress corrosion cracking (SCC). 24(F) mass transfer control. 50(F) influence on thermodynamic activity of C. 1–2 metal oxides parabolic rate constants for growth. 207(T) mass transfer. 47 smallest stainless steel category. 82–83. 140(F) migration. 197(F). 166–168 tool and cutlery alloys. 166(T) sensitization. 74–76 machinability of stainless steels. 94–98 ferrite. 226. 12–14 neutrality biological. oxidation. 57 with oxide scale. 151–152 ferrite stainless steels. 29–31 mechanical behavior. 9 corrosion resistance. 39–40 precipitation-hardening. in food contact. Alloy Casting Institute (ACI). and tempering temperatures. 131–133. 138 stress corrosion cracking (SCC). 166 strain energy. 153(T) lean austenitic alloys.296 / Index martensitic stainless steels (continued) photomicrographs. 132. 132(F) welding characteristics. 233–235 New York City’s Chrysler Building. 61(F) metastable condition. 152(T) high-temperature. 59(F) standard Gibbs free energy of. 150(T) deep-drawing stainless steels. 213(F) nickel alloying element. 208(F) machinability of stainless steels. 55–56 microcar frame. 139(T) minimum. 116–117 mechanical properties austenite. 23. 1 austenitic alloys. continuous casting. 157(T) influence on uniform corrosion. 245(T) martensite. 127(F) stress relieving. 222(F) metallurgy “C” alloys. 40 microbiologically induced corrosion. S and O. temperature. 58(F) metals oxidation. formation vs. 226 “H” alloys. 228 multistage flash (MSF). 126(F). 183 oxidation resistance. 208(F) metal ions release. welding. 4 heat-resistant cast stainless alloys. bacterial retention. 145 corrosion resisting cast stainless alloys. 232(F) microorganisms. 5 . 235 chemical. food contact. 231. 84(F) high-temperature. ferritic stainless steels. austenitizing. 149. 4 influence on resistance to stress corrosion cracking. 206 welding parameters.

5 austenitic alloys. aluminum. 222(F) machinability of stainless steels. 249(F) influence of copper and nickel on corrosion rate of martensitic alloys. S and O. 64–65 electrochemical nature of. 30 influencing oxidation of iron-chromium alloys. 71. rates. 22 oil and grease marks. base alloys. 149(T) niobium carbide former. 60 under less-oxidizing atmospheres. 80(F) influence on thermodynamic activity of C. from evaporation of chromium superoxide. 60–61 influence of nickel on. 9–10 nitriding austenitic stainless steel and. 79. 30 interstitial atoms of. 196 parameters for. 64(F) quasi-steady-state approximation of moving boundary problem of internal. 50(F) nickel base alloys. 60(T) parabolic rate constants for growth of oxides. 57–60 transient. 35(F) pickling oxide scale. 12 schematic predicting thermal stresses. exposure of stainless steel. 249(F) martensitic stainless. 82 surface alteration. 134(F) machinability of stainless steels. 109. 13 orange peel. 118–119 Nippon Steel. 61–63 metal dusting. aluminum or carbon steel. in austenite. 101 isocorrosion curve for. 226 stabilization of ferritic stainless steels. 35(F) corrosion in. 67(F) thermodynamics of. 79–81 ferritic stainless steels. coloring stainless steel. 72 austenitic stainless steels. S and O. 14(T) standard hydrogen electrode. 94 stainless steel. 63. 64(F) Wagner’s theory. 250–252 oleum. and molybdenum. 60(T) effect of rare earth additions. 71–72 high-temperature martensitic stainless. 78 creep resistance. 61–63 oxidation resistance austenitic stainless steels. 33 open circuit potential. oil country tubular goods and line pipe alloys.” 219 oil country tubular goods (OCTG) influence of chromium on corrosion rate of steel. 80(F) oxide film coloring stainless steels. 6 machinability of stainless steels. 135(T) nitric acid austenitic stainless steels. 183 migration into acetic solution from stainless. 184 replacing titanium. 253 nondestructive evaluation (NDE). 199 nitrogen austenite. 134–135 stainless steels in petroleum industry. 9 corrosion rates for stainless steels and. 65 effect of silicon. 65(F) spalling and cracking of scale. 34 duplex alloys. of iron-chromium alloys. 67 metal with oxide scale. 14 North Carolina. 66–67 volatile nature of Cr2O3. 63–65 standard Gibbs free energy of formation of metal oxides vs. 20 oxidation effect of chromium. 57–59. 205 role in sensitization. 133. N. 72 carbide precipitation. 157(T) influence on uniform corrosion. 80(F) iron-chromium-oxygen phase diagram.Index / 297 austenitic alloys. 211 Ohm’s law. 80(F) ion release from stainless steel grades. cleaning methods. 89 corrosion in. 178 organic acids austenitic stainless steels. 36(F) overpotentials. 121–122 isooxidation curves. N. 196(T) . 234(T) resistance to stress corrosion cracking. 59(F) paralinear. 59(F) kinetics and. 58(F) temperature dependence of metal dusting of iron. 220(T) “oil-canning. 88 corrosion behavior of high-silicon alloys in concentrated.. 77–78 stainless steel for line pipe. 79. 47 stabilization. 61(F) oxidation-resisting grades of stainless steel. 35 duplex alloys. 86 delay in carbide precipitation by. 238(F) O Occupational Safety and Health Administration (OSHA). 193–194 nitrides duplex alloys. temperature. 211 normal hydrogen electrode (NHE) half-cell reduction potential vs. 3–4 influence of alloying elements on thermodynamic activity of. 157(T) influence on thermodynamic activity of C. 66(F) reaction at anode. 102 isocorrosion curves in. 157(T) influence on uniform corrosion. 184 solubility in austenite. 29. 78(F) ferrite.

193–194 uniform corrosion. 131. 130–131 phosphoric acid austenitic stainless steels. 193–194 removal of oxide scale. 27 penetration equation. 250–252 platforms. 130(F) iron-chromium-oxygen. with duplex alloys. 247(T) molybdenum influence on SCC susceptibility. in 303 matrix. 40(T) austenitic stainless steels. scale. 251(F) austenitic stainless steels for. 73(F). N. 127–128. 266 partitioning elements. 157(T) influence on uniform corrosion. 232 passivation effect on polarization diagrams. 1 ferrite. 248 umbilical tubing and risers. 279(T) stainless steels. 93–94 passenger trains. cleaning method for uncoated stainless. 252–253 liquefied natural gas (LNG) vessels. 190(F) inclusions. 254 martensitic stainless steels for. 196 isocorrosion curves in. 3–5 free energy. 188–190 metal with. 2 Fe-Cr-Ni. 2 intermetallic. 193–194 stabilization of austenitic alloy. 252(T) stainless steels for refinery processes. 249(F) demand for steel. 40. 85. 250 copper and nickel influencing corrosion rate of martensitic stainless alloys for OCTG. 210 oxygen austenite impurity. 248(T) presence of wet carbon dioxide. 265 process equipment. 1. 34–35 duplex alloys. for iron and sulfur. 249(F) combating corrosion in applications. 114(F). 15–16 phase diagrams computer models. 266 digestion. 1 inclusions and pitting. 93(F) pseudo-binary-. 25. 28 pigmented pastes. 220(T) paper-making processes bleaching pulp. 15(F). 113(F). H2S and CO2 partial pressure. 61(F) pickling to remove. 127. 250(F) National Association of Corrosion Engineers (NACE). 248. 19 penetration rates. 249(T) chromium influence on corrosion rate in environments by oil country tubular goods (OCTG). 248.298 / Index oxides effect calcium on machinability of 303. of stainless steel. 41–42 influence of alloying elements on thermodynamic activity of. 189(F) elongated. 253–254 pH. 102(F) phosphorus ferrite impurity. 248. 252(T) OCTG. 36(F) minimum temperatures for wet. 10 inclusions and pitting. 6 ferrite impurity. 41 machinability of stainless steel. S and O. 27 passivity. 3(F). 190(F) x-ray examination showing Ugima. 63 pitting activities and activity coefficients in liquid steels. 247. 156 oxygen gas reduction. 23 transpassive regime. 195–196 stainless steel. 19(T) petroleum industry alloy suitability vs. 58. 254(T) stress corrosion cracking (SCC). 101–102 electropolishing solution. 88 corrosion type. 261 . 29 steel content. 3 impurity. 8–9 structure of martensitic stainless steels. 24 passive behavior. and manganese sulfides. 59 (F) iron-nickel. 92(F) iron-chromium. 248 refinery equipment. 23–25 removing surface contamination. 254–255 restrictions in stainless steel use recommended by NACE. layer. 132(F) photomicrographs duplex alloys. 266–267 washing and screening. 39–40. 247 duplex stainless steels for. 179(T) Pilling–Bedworth ratio (PBR). 10 pickling oxide layer removal. 250. 188–189. 248(T) ferritic stainless steels for. 265–266 kraft process. 88 corrosion in. 28(F) oxygen pressure. 94. 156–157 martensitic stainless steels and toughness. 25 theory. 189(F) oxyfuel gas welding (OFW). 247(T) line pipe and flow lines. 25. 129(F) physical properties major stainless steel engineering alloys. 95(F) martensitic stainless steels. 157(T) influence on thermodynamic activity of C. 258–259. 254 precipitation-hardening stainless steels for. 3 impurity. 41 (F) phases alloy systems. 78 Ugima. 189(F) un-deformed. 64(F) P paint. corrosion tendency.

pitting resistance equivalent number (PREN). 138 stainless steels. 254 polarization anode. 37.Index / 299 critical. 195 petroleum industry applications. 52 Porsche. 159–160 hot Steckel mills. 16(F) powder metallurgy. 17(F) construction of. 45–46 production processes basic oxygen furnace (BOF). 142. 88–89 Pourbaix diagrams chromium. 137 stress corrosion cracking (SCC). 139 austenitic. test temperature. 103. 137 annealed condition. 103. temperatures. 255 porosity. 43. 44(F) geometry. 168–170 mechanical properties of martensitic PH alloys. 43–45. 22–23 passivation. 85(F) duplex alloys.. 43. 248(T) phases in stainless steel. 41(F) resistance. 103. 76–78 possible aluminum/titanium. 145(T) composition of martensitic. 143(F) properties of A-286 vs. 40(F) pit initiation. 142–144 specialized family. 25(F) mixed potential theory and. 24(F) polishing grit sizes for target surface roughness. 104(F) duplex alloys. 23. 169(T) semiaustenitic. 85 corrosion. 214 ranking stainless steels by PREN. 40 polarization diagrams effect of cathode polarization. 144(T) mechanism of PH. 159 precipitated phases Guinier–Preston zones. 185–186 machining setup recommendations. 138–139 processing routes for S15700. curve. 141. 197–198 polycarbonate. 104(F) pitting resistance equivalent number (PREN) austenitic alloys. 158–159 defects. 8(T) precipitation carbides. 24(F) effect of mass transport. 205 potassium hydroxide. 140(T) compositions of semiaustenitic. NaCl concentration. 142 thermal processing. 39(F) passive anode. 146(F) composition. 236(F) polythionate. 138 microstructures. 219(F) platforms. 138(F) presence of δ-ferrite and γ-austenite. pH. 145. 230 postweld stress relief. 140(F) passivation. 141–142 corrosion resistance of semiaustenitic. 78. 170 cast PH alloys. 214 pitting corrosion CPT (critical pitting temperature) vs. 41 passive anode polarization curve. crevice corrosion. 144–146 austenitic alloys. 157–158 hot rolling. 98. 138(F) precipitation-hardening stainless steels advantage over martensitic. 144 development. 24–25. 157(T) melting and refining. 258 critical pitting temperature vs. 206 welding parameters. bacterial retention. 40 mischmetal. 39–40 pseudo-binary-phase diagram for iron and sulfur. 159 impurities. 30(F) overpotentials. 50 polythionic acid. 139(T) mechanical properties of semiaustenitic. 276(T) composition of austenitic. 23 influence on uniform corrosion. 207(T) precipitation kinetics. 92. auto components. 137–138 influence of alloying elements. 156 casting. resistance. 22(F) schematic of passive anode polarization curve. 42(F) metastable. 102–103 varying pitting potential with temperature. 159 hot strip tandem mills. 103. 7(F) prevention. 40–43 influence of sulfur level on. 43–45 “weakest link” phenomenon. 155–157 . 10 possible aluminum/titanium precipitates. 160 electroslag remelting (ESR). 23–25 schematic. 168–170 welding characteristics. 102 ferritic alloys. 9 carbides and nitrides. 214(T) umbilical tubing and risers. 143(T) corrosion resistance of martensitic. 16–17 iron. 151 cold work influence on aging of A–286. 29. 141(T) machinability. 105(F) CPT vs. 145(F) recommended annealing and stress-relieving temperatures for martensitic grades of. 20 passivating alloys. 105(F) CPT vs. 156–157 influence of alloying elements on thermodynamics. stainless steel. 43 influence on duplex alloy fatigue strength. 183(T) martensitic. 99(F) pitting corrosion. 253 Pittsburgh Convention Center. 39 inclusions. 139–142 martensitic grades. 197(T) surface finishing. 40(F) stainless steel in chloride-containing solution. 23 cathode.

265–267 pulsed arc transfer. 28(F) iron and oxygen gas reductions vs. See also chemical and process industry aggressive chemical species. 243–245 secondary austenite. 258 Q quality control. 211 salinity. 157–158 vacuum induction melting (VIM). See also marine systems desalination. 79. 48 service. ferritics. 178 rolled finishes applications. 61(F) spalling and cracking of. 147 corrosion of high. 198 roping. 28(F) reference electrode. 228 protective layer formation. 70(F) Schaeffler diagram. 49 pulp-and-paper industry duplex stainless steels. 233 flatware and cutlery. due to chromium-rich precipitates. cleansing action of. 65 reduction. 142. 43–45 resistance welding. 15(F). 155 thermodynamics. 254–255 refining production process. 242 resistance Ohm’s law. 1 content in cast alloys. pH. 241 water heaters. and maintenance. 202 martensitic steels. 210 S Saab. 115 heat treatment vs. 210 shielding gas welding austenitic stainless steel.300 / Index production processes (continued) remelting. 265. 198–199 benefits. 220(T) . pH. 8–9 precipitation kinetics. 202–203 seawater. cleaning method for uncoated stainless. 210 sigma intermetallic phase. N. ferritics. 35(F) inclusions and pitting. 237 domestic goods. 178 rust staining. 215. 82(T) selenium. 217 shielded metal arc welding (SMAW) joint design. 47 ferritic stainless steels. 245 short-circuiting transfer. 283 R rain. 41 influence on thermodynamic activity of C. design. 143(T) corrosion resistance. 220 rainwater. 142 compositions. 7(F) silicon alloying element. 241. 265 paper-making processes. 64–65 single-environment system. 157 vacuum oxygen decarburization (VOC). 156 vacuum arc remelting (VAR). 209(F) process. 143(F) sensitization austenitic. 7 secondary phases. 240–241 heating. 46–47 duplex steels. 63–65 Schaeffler–Delong constitution diagram. current density. 71. 237–240 laundry appliances. 144(T) processing by T route. 217(F) rare earth metals inclusions and pitting. 47–48 ferritic. 230 safety. auto components. 47 schematic of. 216(F) sanitation. 143(F) stainless steel. 12 reduction potential iron and hydrogen ion reductions vs. 22 pitting. 47 effect of alloying. Thermo-Calc software. rates of metals vs. 266–267 kraft process. 22(T) reverse osmosis. 144 mechanical properties. 142. 243–244 ridging. time. 41 protective layer formation. 226. stainless steel selection expert system.austenitic steels in nitric acid. 5(F). 157–158 semiaustenitic precipitation-hardenable stainless steel. 157(T) oxidation resistance. 46(F) intergranular corrosion. 210–211 resistivity. 15(F). 207(T) shipping. average chloride concentration. 9 knife-line attack. corrosion resistance vs. 221 residential applications cookware. 244(F) salt exposure. 203–204 welding parameters for various stainless steels. welding. 186 semiaustenitic precipitation-hardenable stainless steels austenite-stabilizing elements. cleaning stainless steels. 48. 195 scale metal with oxide. 155–157 repair. 13–14 refinery equipment. 34. 36. S and O. 241–242 kitchen appliances. 156 propagation crack. 52(F) stress corrosion cracking (SCC).. 46(F) welding.

91. 50–51 ferritic stainless steels. 101(F) corrosion rates of duplex alloys with contaminated environment. 25 penetration rates. 276(T) composition of ferrite. 60(T) passivation. 105–106 austenitic stainless steels. 58(F) standard hydrogen electrode. 210 stability expanding austenite. 155–157 minimum mechanical properties of. 10 ranking by pitting resistance equivalent number (PREN). 73–74 stainless long products cold heading. 258 crack initiation. 131(F) lean alloy of martensite and austenite. 4 ferritic stainless steel. 195 disinfecting stainless. 127(F) strain rate. 280 (T) nitrides. 179(T) sodium chloride/carbon dioxide environment. 186–190 isocorrosion curves for. 276(T) concrete reinforcing bar. deep drawing. 14 Steckel mills. 101(F) duplex alloys. 52(F) debating mechanisms. 161–162 duplex stainless steels. 211 solution treatment. 170 ferritic stainless steels. 10 precipitation kinetics in 316.Index / 301 slabs. 220(T) composition of austenitic. 50(F) martensitic precipitation-hardening (PH) stainless steels. 49 crack propagation rates of metals vs. 214(T) refinery processes. martensitic stainless steels. 229(T) Schaeffler–Delong constitution diagram. 222 corrosion rates of. cleaning method for uncoated stainless. 2. 236(F) carbides. 183 (T) melting and refining. 180 stainless steel alloys austenite. 137 Sphaerotilus. 214(T) ranking common. 5 (F) selection expert system. 141. 87–88 corrosion form. 179–180 hot forming. 2 welding parameters. 149 categories for oxidation resistance. 159–160 inclusions. 270 (T). 185–186 machining setup recommendations. 135(F) corrosion table for. 121 influence of molybdenum on resistance. 254(T) remelting. precipitation-hardening stainless steels. 229(T) thermodynamics. 216(F) tensile properties of carbon steel vs. 57. 126(F). 19(T) physical properties of major. 157–158 resilience and toughness of carbon steel vs. 179 (T) machinability. 55 spots. 7 (F) properties. 142 . 271 (T) composition of duplex. 220(T) standard Gibbs free energy. 59–60 classifications by sulfur content. 177 stress corrosion cracking (SCC) advantages of duplex alloys. 173. 274(T) composition of martensitic. with nickel. 104–106 environmental variables. 158–159 casting alloys. 54(F) duplex alloys. vs. 32(F) lubricants for forming. 147. 51 soaking austenitic stainless steels. 147 strain energy. precipitation-hardening stainless steels. 105 dilation of austenite due to hydrogen in solution. 3–5 stainless steels. rolled. 101 sodium hypochlorite cleaning stainless steels. carbon steel. 174–179 defects in. 275(T) composition of precipitation-hardenable (PH). for automotive components. in sulfuric acid plus copper sulfate. 53. 158 slip dissolution. for automotive components. 31(F) deep drawing. 236–237 software package. engineering alloys. 48–49 crack propagation. 207(T) stains. See also casting alloys activities and activity coefficients of elements in. 173–179 hot rolling. hot–rolled bands. 165 martensitic stainless steels. 9–10 oxidation-resisting grades. engineering alloys. 73–74 stabilization ferrite. hot. 118–120 ferritic steels for exhaust systems. in sulfuric acid plus copper sulfate. 168–170 specialization. 187–188 cleaning methods for uncoated. 160 flat. 220(T) spray transfer. 78 stacking fault. 30 sodium hydroxide austenitic stainless steels. current density. 166 soap-fat pastes. cleaning method for uncoated stainless. Thermo-Calc. 35–36 corrosion rates of duplex alloys. 279 (T) precipitated phases. 109. 5–7 ferrite. 159 Steel Founder’s Society of America. 115. 9 casting. 40(T) bacterial retention by material and cleaning time. 273(T). 10. 88–89 corrosion in. 226 lean austenitic alloys. 8 (T) precipitation-hardening process. 281–283 soldering. by PREN.

215 deep drawing. 158–159 strip tandem mills. 100 electropolishing solution. 31–33 corrosion table. 209(F) process. 130–131 submerged arc welding (SAW) joint design. 23(F) tailpipe. 88(F) isocorrosion chart for. 218 (F) surface alteration. 190(F) effect on stainless machinability. for various alloys. S and O. 198–199 rolled-on finishes. 1. 196–199 austenitic stainless steels. 194–196 coloring. 158 sulfate process. 10 inclusions in stainless steel. 49–50 mechanisms. 50(F) water heaters. 193–194 T Tafel slope. 261(T) corrosion table for fuming. 248 resistance. 193 parameters for oxide film coloring of stainless. automotive exhaust systems. with oxygen and chloride content for 304 stainless. 48(F) stress relief annealing (SRA). 178–179 function of surface treatments. 51–54 petroleum industry.302 / Index stress corrosion cracking (continued) material variables. 51. 196(T) passivation. 174 strip casters. 159 strong bases austenitic stainless steels. with chlorides. 41(F) stainless steel machinability. 197–198 recommended cleaning methods. 193–194 polished finishes. 35–36 structure duplex alloys. 228 tellurium. stress corrosion cracking. 259(T). 88 corrosion in. 179(T) superaustenitic stainless steels. 193–196 introduction. 167–168 stress risers. 53(F) susceptibility of martensitic stainless steels. 89 bright annealing. 40. 210 submerged entry nozzle. pulp-and-paper. of martensitic stainless steels. 3 impurity. 261(T) duplex alloys. 188(F) ferrite impurity. 33 pickling oxide scale. 258(F) isocorrosion curves for various alloys in. 41 influence of alloying elements on thermodynamic activity of. 187 stabilization of austenitic alloy. 186 surface finishing aesthetics. 48 stress relieving austenitic stainless steels. 215(F) surface treatments brightening. 127–128. 193–194 sulfuric acid plus copper sulfate corrosion table for stainless steels and titanium in. 186–188 sulfuric acid austenitic stainless steels. 113 super stainless steels. 198 brightening. 242 zones of susceptibility. 187. 32(F) sulfurized or sulfochlorinated oils. 257. 123 susceptibility to. 164 ferritic stainless steel. 33(F) isocorrosion. 195–196 pickling. 78 sulfite process. 51(F) theory. 164 superferritics. 157(T) influence on thermodynamic activity of C. 227(T). 53 stretch forming. 188 stress sorption. 193–194 rolled finishes. 186–187 size and shape and machinability. with nickel content. 217–219 aesthetic surface finishes. 196 cleaning. 36 sulfides inclusions. 184 phase. 265 sulfur austenite impurity. 199 surface roughness. 262 threshold stress for. 183 metal flow directions in weld pool with and without. 157(T) machinability of stainless steels. 92–94 machinability of stainless steels. 32(F) oleum. 195(T) removal of oxide scale. 88(F) varying resistance to. 196 cleaning. 156 inclusions and pitting. 196 and corrosion resistance. 194–196 coloring. 262(F) stress-strain curve for single crystals of austenitic steel with and without hydrogen. 186 . 196 passivation. 42(F) pseudo-binary-phase diagram for iron and. 100(F) isocorrosion rates for various stainless steels. 196 influence of alloying element on corrosion rate in contaminated. 31(F) isocorrosion curves for stainless steel and titanium in. N. 33(F) isocorrosion curves for various alloys in. 208(F) pitting resistance of unannealed welds. 88–89 corrosion in. 34(F) isocorrosion curves of duplex grades. 6 comparing machinability. 260(T). 166 martensitic stainless steels. 195–196 removal of oxide scale.

75–76 duplex alloys. 165–166 martensitic stainless steels. S and O. 205 ferrite. 208–210 tuyeres. 104(F) tempering influencing martensitic stainless hardness. 47 stabilization of ferritic stainless steels. 165.Index / 303 temperature chromium-oxygen system volatility. 115 carbide former. S and O. 282 applications. 184 possible aluminum/titanium precipitates. 133–134 toughness austenitic stainless steels. 43. 131. 202 duplex alloys. oxygen injection. 166–168 precipitation-hardening stainless steels. 120–121 thermal conductivity duplex alloys. 191 tooling carbides. 281–282 step. 4. 78 corrosion table for. 93. 157(T) isocorrosion curves for. 94. 205 inclusions and pitting. See automotive and transportation trucks. 191 titanium carbonitride (TiCN). 165–166. 113(F) map. 4–5 thermal cutting. 161–162. 282 software package. 117. 167 tensile properties austenitic precipitation-hardenable stainless steel. 44(F) impact strength variation with. 162–164. 156 ferritic alloy stabilization. 176 high-speed tool steels. 282 single-point equilibria. 132. 75 tensile strength equation. 138(F) role in sensitization. 57–60 stainless steel. 118(F). predicting. 190 materials in deep drawing.. 167–168 tempering. 131–133. 283 heat treatment. 191 costs in deep drawing. 24 transportation. 132(F) trains. 2 thiosulfate. 32(F) isocorrosion curves in phosphoric acid. 93(F) standard Gibbs free energy of metal oxide formation vs. 2 quality control. for duplex alloys. activity of C. 174 ferritic stainless steels. 65(F) Thermo-Calc alloy design. 27 transpassive regime. 161–164 austenitizing. 232 transient oxidation. 58(F) variation of pitting potential with. 41 influence on thermodynamic activity of C. 156 influence of alloying elements on. 166. 166–167 duplex stainless steels. 283 Scheil–Gulliver model. 190–191 lubricants. 156 . N. 189. 97–98. in sulfuric acid plus copper sulfate. 4–5 thermal processing annealing. 118–119 high-temperature austenitic alloys. 60 transpassive dissolution. 191 coolants. N. 283 iron-chromium phase diagram. 170–171 ferritic stainless steels. 75(F) partitioning ratio varying with. 64. 168–170 soaking. in sulfuric acid plus copper sulfate. 244(F) critical crevice corrosion. 134–135 tungsten carbides for flatware. 45(F) critical pitting. 178–179 tools. for stainless steels. 204 ferritic stainless steels. 191 coatings. 283 thermodynamics argon oxygen decarburization (AOD). 133(F) martensite. 96(F) unstabilized 430-type alloy. 166. 164. 170–171 austenitic stainless steels. 282–283 casting. 74 texture deep drawing. 118–119 stabilization of ferritic steels. 83(F) martensitic stainless steels. N.. (CPT). 115(F) titanium carbide and nitride formation. 31(F) deoxidizer in chromium–iron alloys. 167 thermal stresses. 231 tubular goods. 145(F) austenitic stainless steels. and O. 191 titanium nitride (TiN). 282 phase determination program. 64(F) corrosion resistance vs. 157(T) oxidation. 170 stress relieving. 240 influence on thermodynamic activity of C. martensitic stainless steels. S. 283 free demonstration version. with alloy content. 211 thermal expansion austenitic stainless steels. 50 time-temperature-transformation (TTT) diagram high-alloy stainless steel. 157(T) tungsten inert gas (TIG). 226 titanium-aluminum-nitride (TiAlN). 7 martensitic stainless steels. 205 ferrite. 36(F) machinability of stainless steels. 282 welding and joining.

28–29 material variables. 210 thermal cutting. 248 Y yield strength austenitic precipitation-hardenable stainless steel. 216(F) weldability. 61–63 washer tubs and drums. 210 martenistic stainless steels. 201–206 duplex stainless steels. auto components. 29–31 stainless steel. 157–158 vacuum induction melting (VIM). 210 parameters for various stainless steels. 38 water marking. 65 . 74 high-temperature austenitic alloys. 190(F) machinability by sulfur levels with and without. 211–212 precipitation-hardening (PH) stainless steels. 190(F) x-ray showing. 211 Schaeffler diagram. 210 gas metal arc welding (GMAW). 202(F) sensitization. 203(F) welds influence of sulfur on pitting resistance of unannealed. 211 Thermo-Calc software. 208–210 high-frequency induction. 201–204 cast stainless alloys. 42(F) long-term annealing.304 / Index U Ugima oxide coating cutting tool and lubricant. 241 water heaters. 206 material selection and performance. 211 oxyfuel gas welding (OFW). 253 welding austenitic stainless steels. 208. 154 characteristics of stainless steels. 208 V vacuum arc remelting (VAR). chloride concentration in rainwater. 156 vanadium carbides for flatware. cleaning method for uncoated stainless. 84(F) yttrium. 204(F) Welding Research Council. 43 wet carbon dioxide. constitution diagram. 217(F) unmixed zone. 241. 240 high-temperature martensitic stainless. 133. 206–208 metal flow directions in weld pool. 212 nondestructive evaluation (NDE). 210–211 safety. 179(T) weather pattern. 157 vacuum oxygen decarburization (VOD) cleanliness. 48 shielded metal arc welding (SMAW). 211–212 resistance. 27–28 United States. See also corrosion types environmental variables influencing. 220(T) water vapor. 83. 211 joint design. 253–254 uniform corrosion. 208–211 recent developments. 208–210 Welding Research Council’s 1992 constitution diagram. 203(F) weld shielding gas composition and crevice corrosion resistance. 205–206 flux cored wire (FCW). 210 soldering and brazing. 189(F) umbilical tubing and risers. 230 W Wagner’s theory. 210 gas tungsten arc welding (GTAW). 209(F) laser. 81–82 wax-base pastes. 184 refining process. 206 processes. 179(T) wax or soap plus borax. stainless steel selection expert system. 204–205 ferritic stainless steels. 207(T) practices. 211 submerged arc welding (SAW). 242 waterline corrosion. 145(F) equation. 189–190 comparing 304L chips with and without. 134(F) Volvo. 208(F) new developments. 283 tungsten inert gas (TIG).

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