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Stainless Steels for Design Engineers (#05231G)

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STAINLESS STEELS FOR DESIGN ENGINEERS

MICHAEL MCGUIRE

ASM International® Materials Park, Ohio 44073-0002 www.asminternational.org

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 www.asminternational.org Printed in the United States of America

Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

METALLURGY

Chapter 1

Metallurgy........................................................................................................1
CORROSION AND OXIDATION

Chapter 2 Chapter 3 Chapter 4 Chapter 5

Corrosion Theory............................................................................................11 Corrosion Kinetics..........................................................................................19 Corrosion Types..............................................................................................27 Oxidation.......................................................................................................57
STAINLESS STEEL ALLOYS

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

PROCESSING

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
APPLICATIONS

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
APPENDIXES

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

iv

Preface
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 Eng-tips.com who have contributed much collective knowledge and perspective to this book.

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The large amount of the alloying elements makes the deviation from the behavior of pure iron greater. Stainless steel is an exceptional alloy system in that it is not a dilute solution. 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. A given structure. in addition to the impurities sulfur. phases coexisting simultaneously. McGuire. 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. such as carbon. and silicon. 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. 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 result of the large number of alloying elements in relatively high concentrations is that stainless steel can have many stable phases concurrently. Carbon and alloy steels. Aluminum alloys share the face-centered cubic (fcc) structure of pure aluminum. subsequent processing or service conditions may alter the carefully established phase structure. are relatively dilute solutions of several elements in the parent matrix. just as a gas or liquid is a phase. alloy steels. www. The producer of stainless steel controls the chemical composition and thermomechanical processing. Therefore. The large number of alloying elements makes possible a larger range of possible phases or basic crystal structures. The three basic phases of stainless steels are ferrite. molybdenum. there can be a number of . In almost every case.Stainless Steels for Design Engineers Michael F. and martensite. In contrast. silicon. chromium. so that when the processor or end user receives the product it is usually in the correct condition. stainless steels contain no less than about 11% chromium alone. stainless steels are chemically complex. The total amount* of these alloying elements seldom exceeds 5%. Introduction Most widely used alloy systems. Most stainless alloys have manganese. manganese. as discussed in this chapter.org CHAPTER 1 Metallurgy Summary COMPARED TO ALLOY STEELS. Alloy steels may contain several percent of alloying elements. there are more detailed treatments of the alloys made of these phases and their properties. and aluminum alloys. carbon. such as carbon steels. is what is meant by a phase. and nickel in thermodynamically meaningful amounts as well as large concentrations of nickel and/or molybdenum.asminternational. austenite. p 1-10 DOI: 10.1361/ssde2008p001 Copyright © 2008 ASM International® All rights reserved. In subsequent chapters on types of stainless steel. consequently. nickel. the calculations that predict which phases will exist are more difficult. and aluminum. focuses on phases normally encountered in stainless steels and their characteristics. are principally of the magnetic body-centered cubic (bcc) phase or a slightly distorted version of it. which can have a certain range of compositions. The same is true for most aluminum alloys. However. niobium. with very few exceptions. In solid metals. oxygen. Alloy steels typically contain very small amounts of titanium. and phosphorus.

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

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

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

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

3 Lattice expansions due to carbon. they provide useful information about the compositional effects on phase development in nonequilibrium situations. quite probably because of chromium depletion occurring during and as a result of inclusion growth. and those with less than about 30% chromium plus nickel will form martensite if deformed sufficiently. usually chrome/ manganese silicates and sulfides. 4. Of these. produces the same effect but to a lesser degree. Those with carbon above 0. But in the annealed state. and only ferrite. If present in sufficient amounts. The nickel equivalent (vertical axis) summarizes how nitrogen. and it forms a low-strength film with a low melting temperature. only nitrogen is considered a beneficial alloying element. It both strengthens and improves the pitting corrosion resistance of austenite.02% would eventually break down into austenite plus carbides. but they can reach phenomenal hardness of over Rc 70. Source: Ref 2 . When an alloy solidifies as austenite. The low diffusion rates restrict such colossally supersaturated zones to thin surface layers. The sulfur and oxygen then precipitate during cooling or subsequent hot working as isolated inclusions. This permits carbon and nitrogen to exist in very high degrees of supersaturation if introduced below this temperature. Austenite is not embrittled by hydrogen to the extent ferrite or martensite is. Interstitial elements are much more soluble in austenite than in ferrite.6 / Stainless Steels for Design Engineers form. 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. permitting lower levels of nickel to be used in austenitic alloys. as is done by various proprietary processes. sulfur and oxygen precipitate as primary inclusions before or during solidification. Fig. Thus. The work hardening of austenite is increased by nitrogen. as seen in Fig. and other elements combine to create a nickel-like effect. 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. carbon. The diffusion rates in austenite are quite low compared to ferrite. 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. Both carbon and nitrogen stabilize the austenite phase. 3) (Ref 2). In most common stainless steels. This causes poor hot workability and hot cracking of welds. for example. The austenite structure does not discourage the formation of intermetallic compounds such as sigma. Sigma is almost never seen in commercial 316 alloys. the retained austenite in alloy steels. but hydrogen does raise its flow stress and hardness while lowering its work-hardening rate. causing it to expand about 1% linearly per 1 wt% of solute (Fig. Sulfur and oxygen are considered impurities because they form inclusions. hydrogen. The horizontal axis does the same for chromium and those elements that have a similar effect. A third interstitial solute. Interstitial atoms of carbon and nitrogen distort the fcc lattice. so even interstitial elements cannot move quickly enough to precipitate below about 400 °C (750 °F). sulfur immediately segregates to the grain boundaries because of its low solubility in austenite. but it does. and martensite will be present. The difference of three orders of magnitude for carbide formation reflects the difference between the diffusion of carbon and that of substitutional elements. In most austenitic stainless alloys. The formation of sigma in ferrite is about 100 times faster than in austenite. The interface between these inclusions and the matrix is the locus of corrosion pit initiation. Before the AOD was developed and carbon levels in stainless steels were higher. austenite is normally present in the metastable state. make their formation very sluggish. fortunately. This produces solid solution hardening of the austenite. austenitic stainless steels were sometimes stabilized by titanium or niobium to counter the effects of carbon. austenite.

It is essentially ferrite that has been formed with a supersaturation of carbon. There are two forms of martensite. The complexities of tempering require its discussion in detail to be found in Chapter 3. The as-formed martensite to the degree it has significant carbon content is hard and requires tempering to give it adequate toughness.” It is worth noting. it forms at cryogenic temperatures or by cold working. epsilon. This transformation can occur spontaneously on cooling or isothermally with externally applied deformation. the hardness of the martensite increases dramatically with interstitial content because of the huge strain interstitial elements impose on the bcc lattice. It is also. nonmagnetic.1 to 0. austenitic alloys are more ductile. It is nonmagnetic. 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. 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. “Austenitic Stainless Steels. The physical properties of austenite compared to ferrite include lower thermal and electrical conductivity and greater thermal expansion. 4 Precipitation kinetics in 316 stainless steel.2% carbon. In the 650 to 800 °C (1200 to 1470 °F) range. Thus. the ε. of course. γ2. have high work-hardening rates.” gives a more thorough and quantitative treatment of the mechanical properties of austenite. Thus. The tempering reaction is the precipitation of carbon in the form of carbides with the concurrent loss of internal strain in the martensite lattice. The lowest alloy level is that of the basic 12% chromium steels with 0. 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. and therefore have higher tensile strengths. a range that can be encountered in the heat-affected zone (HAZ) at γ/δ boundaries during welding. At this temperature. This secondary austenite is called type 3 and is also poor in chromium. Secondary austenite can also coform with sigma as γ/δ grain boundaries are depleted of chromium.Chapter 1: Metallurgy / 7 The mechanical properties of austenite are quite different from those of ferrite. In duplex stainless steels. alpha prime. This gives martensite a fairly narrow composition range. around a maximum of 2000 MPa (290 ksi). This so-called secondary austenite. γ2. another type forms. “Martensitic Stainless Steels. As in carbon steel. Source: Ref 3 . thus losing some corrosion-fighting chromium. making it quite hard. and the α' . The resulting structure is very fine and highly faulted. it has the same composition as the ferrite from which it forms and is called type 1. Fig. is somewhat enriched in nickel over the ferrite from which it forms but poorer in nitrogen than the primary austenite. Chapter 3. which are primarily the leaner austenitic alloys. giving it poorer corrosion resistance. Austenite can be cold worked to extremely high strengths. a secondary austenite. has a hexagonal close-packed (hcp) structure. Epsilon is formed in steels with low stacking fault energy. can form from ferrite below 650 °C (1200 °F). It appears in martensitic alloys of the precipitation-hardening type. distorting it into tetragonality. 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. however. type 2. The most highly alloyed martensites are found in the precipitation-hardening grades.

8 c = 4.28 a = 2.8 / Stainless Steels for Design Engineers and is very difficult to identify microscopically. 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. nickel. on the order of hours. 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. (b) bcc.72 a = 8.g. The a' martensite is the familiar magnetic variety known in alloy steels that forms both by quenching and by deformation.Ti) Fe. Sigma is a brittle tetragonal phase richer in chromium and molybdenum than either the ferrite or austenite matrix around it. which enhances substitutional diffusion. Before its true nature was understood. alpha prime is an ordered ironchromium phase (i. which makes their precipitation slower than that of carbides. body-centered cubic.391 a = 10. The mechanical properties of stainless martensite are parallel to those of alloy steels.B)6 (FeCr)21Mo3C. Ni. Table 1 lists data on the more common precipitates found in stainless steel. Cr. This phase forms at chromium contents as low as 15%. Intermetallic phases form by diffusion of substitutional alloying elements.68 a = 10. sites on two intersecting superlattices).2 NbC NbN TiC TiN CrNbN Cr16Fe5Mo2C (e.. originally called 885 °F embrittlement. manganese. This is sometimes confused with temper embrittlement.33 a = 4.59 a = 8. Deformation. between 300 and 525 °C (570 and 980 °F). 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. The high quantity of alloying elements in stainless give an extreme depth of hardening.80 c = 4. This makes alloys like 310H.24 a = 3. rather than random.e. but examination of the iron-chromium phase diagram shows that it is archetypically an equiatomic iron chromium compound. at which the phase dissolves. The principal intermetallic phases are described next. chromium or molybdenum.037 c = 7. Intermetallic Phases The number of phases that can coexist in an alloy is proportional to the number of alloying elements in the alloy.13–4.4 a = 4.807–8. chromium. its presence was known through its causing the phenomenon called 475 embrittlement. They can render the bulk alloy brittle when they form along grain boundaries. leading to subsequent sigma formation..57–10. A Composition NbC NbN TiC TiN Z-phase M23C6 fcc(a) fcc fcc fcc Tetragonal fcc a = 4. It is not surprising that stainless steel with iron. causing localized lower corrosion resistance. iron and chromium atoms occupy specific. 347 versus 304).68 a = 10. It is strongly promoted by silicon and suppressed by nitrogen. Mo Fe2Mo. Sigma. This structure is quite brittle.40 a = 4.54 a = 4. and often molybdenum.878 a = 11.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. M5SiC Cr2N CrN Ni3(Al.73 c = 7. It forms at relatively low temperatures. Fe2Nb Fe36Cr12Mo10 Ni16Nb6Si7. silicon. Ni16Ti6Si7 M23(C. Not to be confused with martensite. titanium.18 a = 3. but they can form in a matter of minutes in alloy-rich grades.62–11.47 a = 4. In unstabilized alloys the prior precipitation of carbides destabilizes austenite. essentially 25Cr-20Ni. Intermetallic phases are normally hard and brittle. especially prone to sigma formation. The physical properties are very close to those of ferrite of the same composition. Alpha Prime. so there is no concern with ancillary phases such as bainite. so it will not occur inadvertently during thermal processing such as welding or annealing. but fortunately it takes a relatively long time to form.g. Stabilized alloy grades show more rapid sigma formation than unstabilized alloy grades (e.57–10. face-centered cubic. Sigma forms much more rapidly from ferrite than from austenite because of the 100-fold . accelerates their formation. Its composition is sometimes given as (CrMo)35 (FeNi)65.) Cr23(C. which occurs in the same temperature range but is caused by phosphide precipitation on prior austenite grain boundaries of martensite. Fe3Nb3C. and niobium should have numerous ancillary phases.

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

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

OHϪ. galvanic versus electrochemical cells. Volume 13A (Ref 5). electrons have been transferred from the metallic phase. charge is transferred across interfaces of species of different chemistry. 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 4 describes the various forms of corrosion and how they are related to alloy metallurgy. This chapter aims first to provide an introduction to the fundamentals of electrochemical theory as it pertains to corrosion. where they participate in the reaction: O 2 + 2H 2 O + 4 e − → 4 OH − (Eq 3) Inside the water-based solution. and Pourbaix diagrams. thereby constituting a so-called ionic current. Consider. The cell is made up of four parts: the two electrodes where the charge transfer Reactions 2 and 3 take place . the Nernst equation. 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 examples provided relate these fundamentals to the corrosion resistance of stainless steels. iron to O2 + H2O. or any others) migrate. Thermodynamics are presented in light of electrochemical potentials as opposed to purely chemical ones. Topics covered include an overview of electrochemical reactions.asminternational. 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. Ref 1 is recommended.Stainless Steels for Design Engineers Michael F. For an in-depth study of electrochemical kinetics and electroanalytical methods. Chapter 5 focuses on oxidation. Uhlig and Revie (Ref 3). McGuire. For a broader study of corrosion. 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. for example. Electrochemical Reactions In electrochemical reactions.1361/ssde2008p011 Copyright © 2008 ASM International® All rights reserved. Chapter 3 introduces the formal terms needed to describe electrode reaction kinetics. H+.org CHAPTER 2 Corrosion Theory Summary THIS CHAPTER INTRODUCES THE fundamentals of electrochemical theory as it pertains to corrosion. the reader is referred to texts by Jones (Ref 2). and a gas phase O2(g). Second. Faraday’s law. chemistry. p 11-18 DOI: 10. a metallic phase (iron). and Fontana (Ref 4) and to ASM Handbook. www. and structure. Figure 1(a) shows the arrangement of an experimental setup in which Reaction 1 could proceed. ions (Fe2+. On the left.

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

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

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

however. NHE Fig. which.059(14 − pH ) = 1. Hydrogen reduction is another possible cathode reaction in water: 2+ = 0. NHE) 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.447 − 0. Eq 12 can be written by assuming unit activity for water and unit activity coefficient for OH−: EO 2 / OH – ing to Eq 13. cathode.624 V (vs. is determined by evaluating Erxn. NHE) (Eq 16) Figure 4(a) shows a schematic plot of the two reduction potentials (Eq 15 and 16) versus pH. that the locations of anode(s) and cathode(s) on the iron surface cannot be identified with ease. At room temperature (298 K). whether a system consisting of anode. then there is thermodynamically a possibility for corrosion. the iron dissolution Reaction 2 will have a reduction potential accord- RT PH2 ln 2 nF aH + (Eq 18) = 0 − 0. The rate of corrosion. assuming a Fe2+ activity of 10−6 (this is an arbitrary value but is usually taken to represent a low ion concentration).401 + 0. .227 − 0. If this is positive. and using Table 1. for example. Similarly. and electrolyte can react thermodynamically.0295 log(aFe 2+) = –0. pOH = –log COH− and pH + pOH = 14. 1 atm oxygen partial pressure. Because a spontaneous reaction requires Erxn to be positive.059 pH V vs. which is in most cases determined by corrosion kinetics. 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). is discussed in Chapter 3.401 + 0. that is. becomes at room temperature (using Table 1 for the standard potential): EFe 2+ /Fe = −0.059 pH V (vs. 4 Reduction potential versus pH for iron and (a) oxygen gas reduction and (b) hydrogen ion reduction .059 pOH = 0. Consider. a case of iron in aerated water. This is indicated by the region shaded in gray in Fig. if the only pertinent reactions were Eq 2 and 3. It should be noted.Chapter 2: Corrosion Theory / 15 Corrosion Tendency The tendency to corrode. 4(a). Figure 1 (with electrode Reactions 2 and 3) can be viewed as an idealized equivalent cell for this situation. the following definition of pH has been used: pH = –log CH+.

447 + 0. Source: Ref 7 . In Fig. When comparing these two figures. pH = 1. the regions where iron is stable are denoted as immunity (corresponding to immunity from corrosion). − Fe(OH)2 = HFeO 2 +H + . 5a). several electrochemical and chemical reactions need to be considered when constructing these types of diagrams. EFe 2+ /Fe = −0. In the case of iron. whereas oxygen gas is able to corrode iron in the entire pH range.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. 4(a) and (b). The following pH-independent electrochemical reactions need to be considered. and they will result in horizontal lines (Fig.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. they are evaluated from the equilibrium constants): Fe 2 + + 2 H 2 O = Fe(OH )2 + 2 H + . pH = 14. 5 Pourbaix diagram for iron. (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. Each reaction is represented by a line. it is noteworthy that hydrogen ions are able to cause corrosion only under relatively low pH conditions. (b) Actual complete diagram. Fig. 5a).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.65 − 0. pH = 6. 5a): Fe 2+ + 2 e− → Fe.810 − 0.5 log aFe 2 + Since these are independent of potential. they will appear as vertical lines (see lines 19a to 19c in Fig.30 + log aHFeO− 2 ( ) (Eq 19b) Fe 3+ + 3H 2 O = Fe(OH)3 +3H + . 3 ( ) (Eq 20a) ) EFe(OH) / HFeO2– = −0.0295 log aFe 2+ HFeO 2− + H 2 O = Fe ( OH 3 + 2e− . In reality.

Uhlig and R. Electrochemical Methods: Fundamentals and Applications. but from the Pourbaix diagram it can be seen that changes in ion activity do not have dramatic effects on the boundaries. The ionic activity was previously arbitrarily set at 10–6. Corrosion and Corrosion Control: An Introduction to Corrosion Science and Engineering. Fontana. Unfortunately.0591 pH For the pH-dependent reactions (chemical and electrochemical). Revie. 3rd ed. Source: Ref 8 = 0.R. 2 EHFeO. it prevents further corrosion. Figure 6 shows the Pourbaix diagram for chromium (Ref 8). Bard and L. for example. EFe(OH) 3 /Fe(OH)2 Fig..J.A. REFERENCES 1.0886 pH 2 + 0. Wiley. On the other hand. While chromium oxidizes even more readily than iron. EFe(OH) 3 / Fe 2+ ) = 1. Iron or carbon steel alloys are therefore not particularly corrosion resistant in water solutions. Finally. Prentice Hall.495 − 0.0470 − 0. if the reduction potential of the assumed cathode reaction were to lie in point B. This is the basic design principle behind iron-chromium-based stainless steels. Jones. Principles and Prevention of Corrosion.H. If this point were to be.0295 log aHFeO– 2 ( ) (Eq 21b) Fe 2+ + 3H 2 O = Fe ( OH 3 + 3H + + e− . 1985 4.1773 pH − 0. 1986 . Wiley.057 − 0. it corrodes selectively due to its low reduction potential.0591 pH (Eq 21a) Fe + 2H 2 O = HFeO − + 3H + + 2e− . but this means that it also protects the iron alloy due to the properties of Cr2O3. Fe-OH corrosion products are generally not passivating. it forms Cr2O3 over a significantly large region that is of relevance to pH values in water solutions. A.271 − 0. this means that the reduction potential for this assumed cathode lies below any reduction potential of iron. Figure 5(b) shows the Pourbaix diagram for iron overlaid with the common cathode reactions in water. then the reduction potential for a possible cathode reaction would be placed on this diagram. 2nd ed.G./Fe = 0. Faulkner. if the reduction potential of the assumed cathode was at point C.Chapter 2: Corrosion Theory / 17 Fe + 2H 2 O = Fe ( OH 2 + 2H + + 2e− . In fact any Fe2+ ions present could plate as iron.. 3rd ed.. H. in A in Fig. 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. 5(a).0591 log aFe 2+ ( ) (Eq 21c) Fe(OH)2 + H 2 O = Fe(OH)3 + H + + e− . Since Cr2O3 is protective. 2001 2. Eq 15 and 18 (Ref 8). McGraw-Hill.W. 2nd ed. and hence under these conditions iron is immune (since Erxn is negative). M. If iron would be an anode and the tendency to corrode were to be evaluated. When chromium is added to iron as an alloying element.. 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. corrosion would occur. one can readily label the regions depending on what iron species increasing pH favors. Corrosion Engineering. then there is a tendency to dissolve iron to Fe2+ since Erxn is positive. D. EFe(OH) 2 / Fe ) = −0. These types of diagrams are called Pourbaix diagrams. 1996 3. resulting in Fe(OH)3. 6 (Eq 21d) Pourbaix diagram for chromium in water.

Atlas of Electrochemical Equilibria in Aqueous Solutions. Pourbaix. p. CASTI Publishing. ASM Handbook. 1991 7. D. Vol 13A.. 59 8.D. 71st ed. ASM International.18 / Stainless Steels for Design Engineers 5. Cramer and B.A. and Protection. Inc. Ed. 1996. Testing. Corrosion: Fundamentals. S. Bradford. 2nd ed. CRC Press. Handbook of Chemistry and Physics. 2nd ed...S. Jones... p 41 SELECTED REFERENCE • M. NACE. S.. Corrosion Control. 1974 . Covino Jr.A. 2001. Principles and Prevention of Corrosion. Prentice Hall. 2003 6.

6 7.50 25. i/A is often replaced by j. MFe and ␳Fe are molar mass and density of iron. As stated. or thickness reduction r.12 25.485* A* ␳Fe).41 0. ni. 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.Ni/2 Fe/2. valence.22 23.1361/ssde2008p019 Copyright © 2008 ASM International® All rights reserved. the ratio of Mi /ni is computed as an equivalent weight (EW) according to: EW = 1 fi ni ∑M i (Eq 2) where fi.485 C per mole electrons. Fe/ O2/OH–. Practically. Source: Ref 1 .39 (a) Equivalent weight. this can be readily converted to lost mass m. the amount of corroded (dissolved) iron is determined by the current i.41 0.) per year.97 27.9 7.13 24.Cr/3.87 7. 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. This chapter deals with corrosion kinetics.42 0. g/cm3 EW(a) Penetration rate.9 7. therefore.62 25. the rate at which corrosion reactions occur is the most important consideration.485).Stainless Steels for Design Engineers Michael F.41 0. mpy Fe 304 321 309 316 430 446 20Cb3 Fe/2 Fe/2. or mpy. The magnitude of this current will determine the rate or iron dissolution according to Faraday’s law.0 7.98 0. It is often the thickness loss (referred to as penetration per unit time) that is useful. resulting in iron dissolution and consumption of oxygen gas according to the net reaction. which was introduced in Chapter 2: nNF = it.485). which in the case of iron becomes r = MFe* i* t/(2* 95. p 19-25 DOI: 10.Ni/2 Fe/2. and Mi are the weight fraction. Because n = 2 and F = 95. that is. 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.Mo/3.46 0. which is defined as current density and has the units amperes/square meters. which in the case of iron loss becomes m = N* MFe = MFe* i * t/(2* 95.41 0. In practice.Cu/1 7.Cr/3 Fe/2. If the thermodynamic conditions favor electrochemical corrosion of iron. the moles of dissolved iron are given as a function of time as N = i* t/(2* 95. respectively. then a net corrosion current i will flow. Here.asminternational. which allows us to understand the rates of corrosion. and molar mass of element i.41 0.Cr/3.001 in. Erxn = EO / OH – EFe / Fe is positive.30 24. www.Cr/3.Mo/3 Fe/2.Cr/3. McGuire.Cr/3 Fe/2.9 8.Cr/3.Ni/2.Ni/2 Fe/2. respectively.7 7.92 25.org CHAPTER 3 Corrosion Kinetics Summary CORROSION INVOLVES chemical reactions with equilibrium that is known through thermodynamics. In the case of alloys. Fe2+/Fe. 2Fe (S) + O2 + – 2H2O → 2Fe2+ + 4OH .

If the magnitudes of cathode and anode polarization are large. 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 . and the electrode states are then defined as being polarized. 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. they can vary over many orders of magnitude depending on the surface chemistry and structure and on electrode reaction.i terms are the exchange current densities and represent the equally large cathode and anode currents at equilibrium (zero overpotential) at the electrodes. (2) ion conduction. Ref 2 is recommended): CO (0. (b) conduction of ions in the electrolyte. the overpotential is negative. the overpotential reduces the activation energy for the electrode Reactions 3 and 4.20 / 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. a net current passes through it). and (c) conduction of electrons from the anode to the cathode.e. the cathode and anode potentials deviate from the half-cell potentials. such as Reaction 3. at the anode the overpotential is positive. 1. for the cathode. When a cell is not under open circuit (i. Similarly. 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. Kinetic steps: (1) electrode reactions. 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. These involve: (a) electrode reactions at the cathode and anode. ηc = Ecathode – EO2 / OH and for the anode. which results in electrons that are favored to be removed from the solution and transferred into the electrode. 1 the corrosion potential. The α-terms are fractions that define the amount to which the . ηa = Eanode – EFe 2 + Fe.c 2 Ac C O* RT ⎟ ⎝ ⎠ 2 The Butler-Volmer Equation For the case study 2Fe (S) + O2 + 2H2O → 2Fe2+ + 4OH–. In the case of a reduction reaction at a cathode. as such. The exchange current densities are a measure of the electrocatalytic ability of the surface to promote/demote the electrode charge transfer reactions. t ) ⎛ αnF ηc ⎞ ic exp ⎜ − = j 0 . which are defined by the deviation from the equilibrium half-cell potentials.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. The other two kinetic processes are discussed briefly in this chapter. thus producing a net anodic current ia. and driving an electrode toward a lower potential drives electrons from the electrode into the solution.. resulting in a net cathodic current ic at this electrode. Effectively. (3) electron conduction Fig. The polarization is quantified as overpotentials ␩. as would be expected in a galvanic cell. that is.

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

respectively. to close the circuit.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 .. Consider.. that is: 0 Ecathode = EH − + /H 2 RT PH2 ln 2 + ηc nF aH + j0 .000 Fig. 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 .000 10.0295 log aFe 2+ + ηa = −0.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). a steel corroding under deaerated conditions.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. 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 . 2. Assume that the pH is such that a passive layer does not form (see the discussion of Pourbaix diagrams in Chapter 2). 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. The cathode and anode reactions. Kirchoff’s law can be used to design a so-called polarization diagram. in a water solution.624 + β a log jcorr j0 . the electrolyte resistance can be computed as: ⎛ F2A ⎞ Relectrolyte = L / ⎜ ∑ zi 2Ci Di ⎠ ⎟ ⎝ RT (Eq 18) Now.a (Eq 22) (Eq 17) Using Ohm’s law (R = U/i). 2 Schematic polarization diagram . Strictly speaking. = 0 − 0. are: 2 H + + 2 e− → H 2 (Eq 19) (Eq 23) Eanode = −0.a (Eq 24) ( ) A polarization diagram is now constructed by plotting the anode and cathode potentials versus log jcorr. the potentials of anode and cathode when current is flowing are in each case the equilibrium potential plus overpotential.447 − 0. as shown in Fig.c jcorr The resistivities of some test solutions are shown in Table 2. as a case study.000 3.

The building up is actually a selective dissolution of iron. 3 Corrosion rate and the effect of (a) Tafel slope and (b) exchange current density . the corrosion current resulting from the cell depends on the equilibrium half-cell potentials (Ecathode and Eanode). At some high enough Fig. which causes a greater remaining surface concentration of chromium and other alloying elements. the cathode polarization deviates from the Tafel behavior as a result of the effect of the mass transfer (hydrogen ion supply). On the other hand. This protection by chromium requires a threshold level of 11 to 12% chromium. this term can be neglected. Passivation Theory. a passive layer constituted of adsorbed molecules or thin oxide/hydroxide layers decreases the corrosion current. A schematic polarization diagram is shown in Fig. The polarization diagram for a passive alloy is quite different from those discussed for active alloys. In general. which simply equals icorr * Relectrolyte (the electrolyte resistance is evaluated from Eq 18). the potential-decade current relation drops to lower currents. Researchers (Ref 3) have reported that the constituents of the passive film are alpha Cr2O3 and Cr(OH)3nH2O. In the case of stainless steels.. The overall mixed potential of the surface would be at a corrosion potential Ecorr. the range of pH and other conditions under which this would occur has been increased thanks to the chromium content. It is noteworthy that the cell shown in Fig. this results in an increased corrosion current up to a point. A schematic of a typical polarization curve is shown in Fig. etc. Figure 3 shows schematically how decreasing any of the Tafel slopes and increasing an exchange current density increases the corrosion rate. Figure 4 shows the effect of increased mass transfer. In an active (nonpassive) alloy. which would result in an increase in the limiting current.e. with a Tafel slope. 3. When a passive alloy is anodically polarized. the Tafel slopes (βc and βa).c and jo. Once the passive layer is formed and offers protection against further dissolution. in many cases. that is. In effect. 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. the exchange current densities (jo. 1 does not have a macroscopic anode and cathode. 5. In Chapter 2. Different microscopic regions on the surface are assumed to act as cathodes and anodes. The effect of the electrolyte resistance has been ignored. This happens at potentials beyond the passivation potential Epp. however. The grain size may decrease with increasing chromium content. as the passive layer is building up). The structure is reported to be a nanocrystalline spinel. epitaxial to the surface. defined in Fig. it was identified through the Pourbaix diagrams that there were conditions under which an alloy could be passive. and in the lack of more detailed knowledge.Chapter 3: Corrosion Kinetics / 23 the potential drop across the electrolyte needs to be included. corrosion current is where the two polarization curves intersect. Effect on Polarization Diagrams.a).. it initially behaves like an active alloy (i. and any limiting current density (jl). dependent on the limiting current in Eq 23. the cathode and anode areas are assumed to be equal. 2. which readily forms a Cr2O3 scale.

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

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

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

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

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

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

Because the influence of alloying element varies with environment. Stainless steels require more than a minimum amount of alloying to resist sulfuric acid. 0. Corrosion rate legend: 0. it cannot be assumed that this relationship is true for other environments. 1.com/applications/documents/start.” a lookup table in which the corrosion rate of many stain- less steels in a great number of environments can be obtained.” refer mostly to corrosion in these aqueous solutions.asp (Ref 8). while it is useful and necessary to have these experimental data. Free sites tend to promote proprietary alloys. in which the slow thinning rate of the chosen alloy can be determined through the mixed potential theory and polarization diagrams. The corrosion rate of the various stainless steels in the myriad possible environments has been measured in probably all practical cases. > 1. Many of the isocorrosion charts in this book are reprinted from this source. Source: Ref 8.1 mm/yr (corrosion resistant). see source for interpretation of data. The influence of alloying element is by no means the same in all environments. Sulfuric Acid. In the case of stainless steels. it is also helpful to understand the peculiarities of some of the major alloy-environment pairings. the alloy chemistry is chosen such that the passive-active behavior favors corrosion in the passive regime. http://www. as these charts suggest. This information is available to guide the designer in selecting appropriate steels for various environments. which contains a “Steel Professional Tool. None is more accessible than the Web site of Outukumpu. 5 Corrosion table for stainless steels and titanium in sulfuric acid plus copper sulfate.0 mm/yr (material not recommended). Figure 5 shows an example of one such table. These tables are supplemented by isocorrosion diagrams such as that shown in Fig. “Corrosion Kinetics. although other empirical relationships exist or can be generated. Straight 16% chromium grades such as 430 fare poorly. we need to discuss some of the more commonly encountered severe environments. and it is highly recommended that it be used. These data can be obtained from a number of sources. < 0.outokumpu. such as the National Association of Corrosion Engineers (NACE) and ASM Handbook volumes. So. Courtesy of Outukumpu Stainless Unfortunately. These diagrams show constant corrosion behavior under varying environmental conditions such as temperature and solution composition. The serious engineer will consult multiple sources and unbiased sources before making alloy decisions. Corrosion in Acids and Bases The examples discussed in Chapter 3.Chapter 4: Corrosion Types / 31 Fig. 2. 6.1–1 mm/yr (useful in certain circumstances). while the nickel-containing .

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

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

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

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

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

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

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

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

. 0..01 1.. 0. .5 . which most authorities (Ref 18) have concluded are associated in some way with pit initiation.022 0.93 0.93 . These spikes measure local dissolution.. 8 1..046 0. After removal of the carbon.. 1. making them more soluble.3 1.. Inclusions in stainless steel are typically oxides and sulfides. The question of what causes the initial dissolution that causes both stable and metastable pits focuses on inclusions. As potential increases.0 0..01 0.97 .4 0..345 0.01 0.02 1. . . while others continue to grow as stable pits.053 0.. The bottom line is that oxygen and sulfur are generally removed by silicon/manganese deoxidation. stable or not... The potential at which stable pitting occurs is the pitting potential.15 0. Figure 21 depicts a polarization curve for stainless steel in a chloride-containing solution. they will affect subsequent events.. 0.1 0.45 0.21 .17 . This lowers the activity of oxygen and sulfur. 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).. which is in keeping with the reduction in dissolution of the matrix that these alloying elements confer.. 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. but that this process occurs in both the liquid and solid states. depend on variables not of the inclusion chemistry but of the matrix composition.24 0.05 1.372 0.. 1.. %i Metal Al C Mn P S Si Ti H N O Cr Ni Carbon steel. Different researchers assume dissolution of the inclusion..85 ...0 0.. 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 . 0.006 0.45 1.3 1. while others assume dissolution of the matrix.06 0.97 17..05 0. .32 0. metastable pitting events are not noted. .. possibly indicating that the root causes are more metallurgical than electrochemical. It also alters the efficiency of deoxidizing elements.. 1600 °C Stainless steel...025 0.007 0... as measured by current transients. Pitting events. Some such sites complete their dissolution and repassivate. 3...45 0.40 / Stainless Steels for Design Engineers of debate.. The dissolution during metastable pitting is located at the matrix-inclusion interface.. while metastable pitting can occur at much lower potentials.. cause the generation of iron ions and local pH reduction. 0..47 . To the extent these remain concentrated in a small volume.. 0.0 .05 .66 0. notably molybdenum and nitrogen levels (Ref 17). 21 Schematic of a passive anode polarization curve Inclusions.0 . Aluminum is a powerful deoxidant in carbon steel but is less effective in stainless.05 9..... small spikes in corrosion current occur. The reactions in stainless steel differ thermodynamically from those in carbon steel because of the presence of high chromium concentrations. which if left in solution would later precipitate as low-meltingpoint iron compounds that would make the steel fragile and unworkable at high temperatures.49 0. 1600 °C %i fi ai %i fi ai .. as Table 1 indicates (Ref 19). and the potential at which pitting occurs is the beginning of the transpassive regime. In the absence of inclusions. The dissolution parameters.. Pitting occurs in the zone in which passivity is expected. . 18 0.45 1.. the subsequent objective is to remove or render less harmful the dissolved oxygen and sulfur.02 0. . Fig. Their effect on sulfur is similar to that on oxygen.0 8.6 . . while titanium becomes a stronger deoxidizer in stainless. . called metastable pitting.05 0. .. .0 0..

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

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

sulfur. 22 indicates that the precipitation of sulfides that cause chromium depletion occurs in delta ferrite on freezing when sulfur exceeds 0. Pitting has been extensively correlated with environment and compositional variables. if . Certain other types of inclusions/precipitates are less harmful in this regard. which have a strong affinity for chromium and a solubility that decreases strongly with temperature. However.007% and in austenite when sulfur exceeds 0. which then provided a crevice capable of sustaining stable pitting. 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). then stable pitting would ensue. 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. These hypotheses deal with how a passive film on a homogeneous surface could break down.000 and 680. Faster cooling favors austenitic solidification. since it is clear that the surface is not homogeneous.3 % Mo + 16 % N (Eq 11) These equations are useful. respectively. Examination of the decreasing solubility of sulfur in stainless in Fig. which unfortunately have abundant inclusions and chemical inhomogeneities capable of locally diminishing the integrity of the passive film. and their correlation is shown in Fig. 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. Metastable pitting is diminished by the presence of these elements. The low chromium around inclusions is a sufficient condition for the local dissolution measured as metastable pitting. which. which have two phases. The initiation of pitting is also affected by stress and inclusion orientation (Ref 25).3 % Mo (Eq 10) For duplex alloys. Titanium. approaching that of the wrought alloy. their precipitation will result in some degree of chromium depletion around the precipitation site because chromium diffuses too slowly to be replenished.3 % Mo + 30 % N (Eq 9) For ferritic alloys. which hold no nitrogen in solution: PREN = % Cr + 3. if approximate. and nitrogen. This fundamentally is due to the high ratios of the diffusivities of oxygen and sulfur to chromium. Pitting Resistance. carbon. to cause the same phenomenon. are present in steel. also forms sulfides and oxides more strongly than manganese and therefore does so at higher temperatures. for instance. Oxygen behaves in a parallel manner and is usually present in sufficient quantities.01% in manganese/silicon deoxidized steels. about 0. 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. these mechanisms presuppose a stainless steel surface that is homogeneously passive and try to explain the observed inhomogeneous behavior of the passive film. which are about 10.Chapter 4: Corrosion Types / 43 can also be altered by freezing rate. Whenever fast-diffusing elements such as oxygen. these hypotheses are not necessary to explain the behavior of everyday stainless steels. especially with regard to the passive film. There have been numerous proposed mechanisms for the breakdown of a passive film in chloride-containing media. and if the depletion zone shape and size are favorable. 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. these have been summarized in other publications (Ref 23). which is often added to form carbides and nitrides. This will be relevant to later discussions of stress corrosion cracking (SCC). neither of which matches the bulk composition: PREN = % Cr + 3. 25 (Ref 26) They do not include tungsten.003%. The most well-known and useful correlations are between the PREN and the critical pitting temperature (CPT) and by extension to the pitting potential. Rare earths also behave the same way. For austenitic alloys: PREN = % Cr + 3. The influence of stress was to cause cracking at otherwise unfavorably shaped inclusions.

which are beneficial against uniform corrosion and which slow the growth of pits by this same action. do not contribute to increasing the resistance to the onset of pitting. assist repassivation. so welded alloys have different CPTs for the same PREN (Fig. if modified to 0. The latter.5% NaCl solution of the ASTM G 150. has half the effectiveness of molybdenum. especially during prolonged testing. FeCl3 testing benefits from the fact that the solution creates a reproducible positive potential. It should also be noted that the critical PREN values vary with crystallographic structure. These equations are all-other-thingsbeing-equal equations and are useful for gross alloy behavior predictions. and nitrogen. Source: Ref 26 Fig. there are significant problems in actually conducting good tests. Nitrogen seems to act by concentrating at the passive film-alloy interface rather than by buffering the solution by ammonia formation. these elements are not found in solution because of their affinity for oxygen. but it also has some problems—most notably the potential for dilution of the test solution.1N NaCl. In most practical cases. While pitting is of great theoretical and practical interest. Research on very pure sputtered films of iron-chromium alloys have demonstrated that both titanium and niobium in solution diminish active dissolution. 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. The most commonly used test media are the unacidified 10% FeCl3. which seldom varies enough to have a visible effect but has been shown when in colossal supersaturation to have a factor of about 10. there is a standard test by which the CPT is measured. They neglect carbon. which is used in the ASTM G 48 practice B. It also does not include the negative influence of elements such as sulfur. microstructure. Pitting in a given medium capable of causing pitting does not occur below a temperature that is characteristic of the medium and the material. etc. sulfur. 26 Differential variation of critical pitting temperature of several stainless steel alloys for unwelded wrought and welded material.44 / Stainless Steels for Design Engineers Fig. carbon. with the myriad exceptions of stress state. This is another manifestation of pitting initiated by the local stability of the passive film. and improve pitting resistance (Ref 29). and the 3. 25 Variation of critical pitting temperature with pitting resistance equivalent number (PREN) of austenitic steels in water plus 6% FeCle. with which they form compounds. another interstitial that it resembles in solution thermodynamically (Ref 27). the . which is primarily a function of local chromium content. not unlike nitrogen. Molybdenum and nickel thus seem to bolster local chromium content in the passive film. It is noteworthy that the elements copper and nickel. While the PREN approximates the pitting resistance of an alloy. 26) (Ref 13). surface finish. the equations cannot deal with inhomogeneity issues. which has been proposed (Ref 36). Likewise. Ferritic alloys require somewhat lower PREN values to exhibit similar pitting resistance as austenitic alloys of somewhat higher PREN. Monitoring of the electrochemical potential during the test is considered mandatory by most researchers. allows the ECPT. Source: Ref 13 present.

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

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

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

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

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

It is mitigated by material variables such as cold work and by alloying elements that increase austenite stability. as shown in Fig. Chloride containing environments are the main ones that induce SCC. impurity. 31 Influence of molybdenum on resistance to stress corrosion cracking (SCC) in austenitic steels Fig. 32.50 / Stainless Steels for Design Engineers SCC. Many publications cite nickel as beneficial in enhancing resistance to SCC. assuming. if pitting can be delayed indefinitely. of course. However. Environmental Variables. if metastable or stable pitting is occurring. All other things being equal. 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. Resistance to general corrosion is proportional to nickel content. 31 (Ref 31). which are probably the greater cause of resistance to SCC. temperature. and the temperature is sufficient. The minimum in the curve corresponds to the nickel level at which the structure is entirely austenitic. But. Water can cause Fig. This is simply the delay of initiation. but ferritics and duplex alloys are less prone to SCC. also increases the threshold stress for SCC. such as chromium and molybdenum. its role seems mainly to be as an austenite stabilizer and as a retarder of active corrosion. which we already know helps prevent pitting and crevice corrosion. then SCC will proceed. However. alloying elements that delay or prevent localized corrosion do the same to delay SCC. 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. more harmful localized corrosion. then SCC can also. 304 has been reported to have no meaningful threshold stress for SCC in hot caustic solutions. is not occurring. while higher levels promote austenite stability and correspond to alloys having more alloying elements. often referring to the data from Fig. but least stably so. the threshold stress has been reached. Certain combinations of concentrations. and dissolved oxygen can cause SCC as well as other undesirable corrosive attack. Molybdenum. such as that due to intergranular chromium depletion. 32 Variation of resistance to stress corrosion cracking with nickel (and other) content and structure . Hot caustic solutions are aggressive against stainless steels. Lower nickel levels produce better immunity through the duplex structure.

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

altering dislocation mobility. HE is implicit in all these models. or causing lattice decohesion. It has been proposed and supported by calculations that hydrogen lowers the energy required or vacancy formation. but none is specific enough to have been tested by critical experiments to prove or disprove it. The lowest energy . 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. 34 Crack propagation rates of various metals plotted versus current density. 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. This has led to speculation that porosity is a weakening mechanism responsible for SCC (Ref 35).52 / Stainless Steels for Design Engineers Fig. It has been demonstrated that hydrogen is absorbed into the material at the crack tip. The main question is whether it causes damage by creating porosity. It has been observed that where SCC occurs there is a large concentration of vacancies.

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

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

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. The bacteria that are known to influence corrosion can be sorted as aerobic bacteria that lie in aerated water and anaerobic bacteria. failure will occur at a lower N under the corrosive environment. such as ozone. 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. Among the anaerobic bacteria that are known to [16] (Ref 40) affect stainless steels can be counted: Desulfibrio and Desulfotomaculum. macroscopic so-called tubercules form that can cause crevice-type shelters where differential aeration and pit initiation can occur. chlorine. corrosion fatigue causes brittle failure under a combined environment of corrosion and a tensile stress component. . which must be viewed as a combination of SCC and fatigue. High-frequency loading gives less time for corrosive attack and brings crack propagation rates down closer to those in air. it tends to be a problem for the medium-alloyed steels such as 304 and 316. an obvious pit corrosion site may not be necessary because of the combined action of cyclic stresses and the environment. Some materials show a combination of both. So. This is called biocorrosion or MIC. Examples are the iron-oxidizing Gallionella and Sphaerotilus. 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. 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+). In some materials. or peroxide. which are used in these environments. The stress. Both of these are so-called sulfate-reducing bacteria (SRB). while the last two seem to indicate an SCC–type behavior. 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). The importance of the environmental interaction is reflected in the sensitivity to frequency of stress application. 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. Due to this. Countering MIC with biocides can cause problems in manganese-containing waters. for example. and the collaborative effect of corrosion and fatigue is that corrosion accelerates the plastic deformation that accompanies the evolution of extrusions and intrusions. can cause manganese to be oxidized to manganese dioxide. The cracks are transgranular. especially since the observed susceptibility to HE is proportional hardness. is cyclic and in a test of stress versus number of cycles (S vs. 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). microbiologically induced corrosion. The same uncertainties that cloud our understanding of SCC necessarily disguise the precise mechanism of corrosion fatigue. Biocorrosion is most commonly encountered in ambient aqueous environments. Oxidizing biocides. however. which are the environments in which most microorganisms have evolved to thrive. However. The first case seems to be merely fatigue assisted by corrosion. Corrosion Fatigue Just like SCC. crack propagation rates are elevated above those in air at all stress levels. In corrosion fatigue. N). which provide enhanced hydrogen solubility where it can aggravate the applied crack opening with a wedge effect from hydrogen dilation. especially the dislocations within the plastic zone at the crack tip. while in others a threshold stress intensity must be reached before an acceleration is noted. Biocorrosion and Microbiologically Induced Corrosion There are many cases for which biological organisms contribute to initiating or enhancing rates of corrosion.

p 533–540 18. Vol 51. http://www. Michal.M. R. Soc. Vol 148 (No. and this turbulence can cause flow erosion in copper materials. making use of stainless steels more attractive.O. Laycock and R.. Grekula et al. Sci. Tobler and S. Hoelzel et al. Y. 2004. Eng.1/qx/productCategory. Ernst. JFE Technical Report 7. Met. Hydrogen Effects on Materials Behavior. J. Sci. Vol 415. Suutala and M. Proc. Newman. Lothongkum et al. J. http://www. Dexter. M. A. A. 1993. Williams. B. Met. P01488.T.. D.J.C. Vol 48. p 94–99 12. J.P. Feb 2001. Parkins. Dec 2001. Y. Hahhinen. Microbiologically Influenced Corrosion. H. Sieradski and R. Corrosion: Fundamentals. Stinner.J.E.. 1981.Kurkela. REFERENCES 1. Z. p 1980 3. Wiley. Electrochem Soc. Kimura et al. http://www. Feb 2002. Sedricks. 2003.P. Ryan. KCI. The development of microbiological consortia allow anaerobes to flourish under biofilms that form in an aerated environment. Corros.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.E.J. Houston. K.outokumpu. Institute of Metals. Vol 133. Proc. Electrochem. 1979. S. Corrosion: Metal/Environment Interaction. A. 1985. Stainless Steels. M. Alkire.J. macrofouling organisms are important. p 195–200 30.C. Scr.. A. p 201–210 37.alleghenyludlum. Soc. Vol 13A. High Cr Stainless OCTG with High Strength and Superior Corrosion Resistance. Stainless Steel World. Parks. Mater.W. Vol 32A.C...F. Kawasaki Technical Report 31. TMS. Science. E. Electrochem. 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.O. Fujimoto . S.. F. And. Brewer. p 352 10.C. R. Spiedel. Institute of Materials. 1994 15. Nippon Steel Tech. Baroux et al. Ryan et al. et al. 1996 20. Metals Institute. Metals Institute. 1988. Vol 14. Sci. Corrosion of Stainless Steels.Suter. Trans. 2001. p 1030–1041 16..alleghenyludlum. Webb. Newman. B. 2003. and Protection.com/pages/ products/xq/asp/T. 2004.C.. Bohni. June 2001. http://www. Szlarska-Smialowska.alleghenyludlum. Fritz.S. p 5 34. Vol 47 (No. p 255–261 39. B.D. 2003. Stainless ‘84. Hakkarainen.G. Vol 384. 40. 1999. Audouard. Grubb. Newness-Butterworths. p 1489–1494 38. Testing. F. Electrochem. 1979. p 398–413 .com/applications/ documents/start. Truman. S. ASM Handbooks. 2006. 1968. Corrosion. and T. H. p 93–103 40. Vol 28. L. p 770–777 22.N. p 284–294 2. Kobyashi. S. Critical Factors in Localized Corrosion. G. Sci. p 4171. J. html 7. Report 90. p 1771 17. and G.pdf 13. Stainless Steel ‘84. p 240–247 25. 1993 24. p 569 23. Cao.. Trans. London..com/ludlum/ Documents/AL-6XN_sourcebook. 1997. Corrosion. Vol 1. Pitting Corrosion of Metals. H. Electrochem Soc. TMS. Tahtinen. p 1097–1117 6.. Hydrogen Effects on Materials Behavior. Bohni. Also. A. Critical Factors in Localized Corrosion. p 137–153 29. Vol 32A.. J. Soc. They create crevices and sites where microfouling can start early. 1976. These represent a differential aeration cell that acts just like a severe crevice. Vol 5.P. Les Editions de physique. 2003. Stainless Steels ‘87.. J. and H.com/ludlum/ Documents/al610_611. Acta Mater. July 2004. p 115 4. 1993. and R. Newman. Sci. 1986. Adv. and C. p 779 32. 2001 31. Turkdogan. p 332 36. W. A. Proc. 28. Mater. 1984. At the same time. 5). Nature.. Mimura et al. H. Tagashi et al. Vol 39. M. Corros. Vol 150. NACE. Hanninen et al..Virtanen. E. N. 2003. Nagumo et al. Lee. V. Technol. Vol 161. p 247–252 27.pdf 14. Metal. 2005.asp 9. they are sources of turbulence in flowing systems. Corros. Pound.J. p 268 11. Fundamentals of Steelmaking. p 1519 21. p 158 33. 5). M. B174–B185 26.. 1986 19. Trans. N.. Spiedel. Stainless Steels Les Editions de physique. TX.... M. Br. T. Gadgil.. Jan 2006 8. p 583–594 5. p 143–148 35. Vol 12A. H.Virtanen.G. Corros. J.. M. K. Kim and H.P. 1985. Met. 2003.

than those of the base alloy iron (FeO. etc. and Fe2O3) or the major ternary element nickel (NiO).Stainless Steels for Design Engineers Michael F. for which temperatures are high enough to form mixed oxides or spinels. Fe3O4. For a thorough study of oxidation. 1 that the major alloying element in stainless steels. a lower temperature T.5 yX 2 ( g) → MX y (Eq 1) Due to the high temperatures involved. soften. copper. and to a great extent. In Eq 1. The electronegative gaseous oxidant X could be sulfur. as do metal and oxygen ion mobilities in the different oxide phases. This is partly due to its ability to retain strength at higher temperatures at which many otherwise useful alloying systems. the free energy G is decreased by a lower nobility of the metal (or a higher activity a of a metallic alloying element). The Effect of Chromium. is negative. hydrogen would be added as a product in Eq 1. chromium. plays an important role as a heat-resisting material. these reactions are generally rapid and thus are a concern for high-temperature applications such as components for power generation.5 y ⎟ ⎜ a P ⎝ M X2 ⎟ ⎠ (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. referred to Ref 1 to 3). and even titanium. but the discussion here mainly is limited to oxidation by oxygen or water vapor (in the latter case. a reaction will be possible when the net free energy In the case of alloy oxidation. Corrosion Theory. such as aluminum. and there might be degrees of solubilities of oxides in one another. The standard Gibbs free energy ΔG0 is often presented in Richardson-Jeffes (Gibbs free energy-temperature) diagrams such as the one shown in Fig. Birks.1361/ssde2008p057 Copyright © 2008 ASM International® All rights reserved. chlorine. Thermodynamics of Oxidation As discussed in Chapter 2. 1 (Ref 4). and a higher partial pressure P of the oxidizing gas according to: ⎛ aMeX ⎞ y ΔG = ΔG 0 + RT ln ⎜ 0. the chromium content determines the oxidation behavior of stainless steels. Meier. It is evident from Fig. the activities of the oxide species also need to be considered. Kinetics of their growth is complex because metal solute diffusion in the metal phases varies. Stainless steel retains strength and has excellent oxidation resistance from room temperature to nearly 1000 °C. McGuire. www. The oxidation of multicomponent alloys is a complex process from both thermodynamic and kinetic points of view. Cr2O3. p 57-68 DOI: 10. forms a thermodynamically significantly more stable oxide. at which other economical alternatives are lacking. often considered mainly as a corrosion-resisting material. and Pettit distinguished between two basic types of behavior: (a) a noble matrix .asminternational. A range of oxides may form with various degrees of thermodynamic stabilities and stoichiometries (including complex ones with different cations).org CHAPTER 5 Oxidation Summary STAINLESS STEEL..

that the matrix iron is nonnoble and so are many of the solutes (chromium. an element for which the free energy defined by Eq 2 is negative is nonnoble. manganese. in which oxidation takes place under significantly oxidizing conditions. The concept of nobility is decided by the thermodynamic conditions of Eq 2. silicon. aluminum.5O4 (with a solid solubility with Fe3O4) and FeCr2O4 form. then gradually Fe3O4 and Fe2O3 would form toward the gas as oxygen potential increases. that is. and that the spinels Fe1. molybdenum.58 / Stainless Steels for Design Engineers Fig. such as air. where FeO would form next to the metal. Isolated pockets of spinel may form within the FeO layer. etc. A high-temperature Fe-Cr-O phase diagram is shown in Fig. The progressive change in oxidation behavior as chromium is added to iron has been described in the literature (Ref 1). In such a situation. It can be seen here that Fe2O3 and Cr2O3 are soluble in each other. If chromium . We first discuss the more common case (b). The oxidation of iron proceeds predominantly due to the rapid ionic diffusion of Fe2+ cations on the FeO layer. At lower chromium contents and above a minimum temperature. 1 Standard Gibbs free energy of formation of some metal oxides as a function of temperature.5Cr1. 2. Source: Ref 4 metal with less-noble alloying elements and (b) both matrix element and alloying elements are nonnoble.). an iron-chromium alloy would behave as pure iron. it can be seen from Fig. 1. which leads to growth of this layer.

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

18 0. 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. 4b) as a result of a very small degree of deviation from stoichiometry in the cation lattice.15 0..35 12 17..20 + 4X(C + N) to 0.75 11. 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 ⎞ ⎤ 2 DCr 3+ = ⎡ − ⎣VCr 3+ ⎦ γΛ υ ⋅ exp ⎜ ⎝ RT ⎟ ⎠ ⎛ ΔH m ⎞ ⎤ − =⎡ ⎣VCr 3+ ⎦ ⋅ cons tan t ⋅ exp ⎜ ⎠ ⎝ RT ⎟ (Eq 5) .20 .7 Al 1. 0.25 .... . these initial oxides are typically Fe-Cr-Ni-Mn mixed oxides.0 9..8 2 2 1 S43935 S44600 S30215 S30415 S38150 S30900 S31000 6X(C + N) to 1. The case will be determined by the equilibrium defect structure of the oxide. .0–19. the electric charge can be carried by either n-type (electrons) or ptype (electron holes) electronic defects..0–22... . For stainless steels.0 .0–12. 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.... and electron lead.. Single values are maximum.. .5 .60 / Stainless Steels for Design Engineers Table 1 UNS Oxidation-resisting grades of stainless steel in common use Composition. This is called transient oxidation... 4b. 0. that is.3 0.7 1. the partial pressure of oxygen at the scale-metal interface falls until only the most reactive element present in high concentration can be oxidized.04–0.5–11.75 .25 0. .0–27. 1.0 18 17. 0.2 ...25 . ..04 . which depends on temperature and oxygen partial pressure. and the chromium is oxidized at the metal-scale interface.0–22. whereas if chromium ion mobility dominates..015 0.05–0.0–19.0 1 0. 0.3 18 23.0 0.25 ... the oxidizing gas is reduced at the gas-scale interface. . . 0.0–19.25 .0 20. In stainless steels.0 ..35 0...12–0.. 0. 1 .. 1.0 Al .. .. 2.0 24.14–0.. As these oxides thicken. .08 0. as shown in Fig.015 0... Note: All compositions include Fe as balance..0 12.08 0. scale-gas surface.... 1 ..01 0. . at high oxygen potentials. 10.0 ....0–24. forming mixed oxides having composition similar to the base alloy. If oxygen ion mobility dominates... ..75 0. 0.07 0.... .3 0..2 Al ...3 .015 0.8 0. .06 0.. 1.3 1 0.0 18.55 . . chromium cations are the predominantly mobile defects (Fig.0–26. 0. In principle....0–15.45 0. then the scale would continue to grow at the oxide-metal interface.. this means that a layer of Cr2O3 is eventually established in contact with the alloy..25 ..5 0.04 Ce . either or both metal or oxygen ions can migrate. leading to metal deficiency...02 0. the oxide will grow at the 3/ 4 ''' 2 4 ⎡VCr ⎤ 3 ⎡ ''' ⎤ ⎣ ⎦ p = K 2 pO2 → ⎣VCr ⎦ = K1 K 2 Po2 (Eq 4) The electron holes that form as charge-compensating defects serve as the “electron lead” in the electrochemical cell in Fig. Cr2-5O3.0–10. The Cr2O3 scale serves as both electrolyte. 0.. The defect can be described as an interaction with oxygen..4–2..0 10. . The contribution of chromia grain boundary diffusion is large and probably dominates the process at temperatures of interest.2 0...0–3.10 0.5 2 0... ...6 8. .0 19.6 . 4(a). In the case of Cr2O3. Similarly... through which electronic defects are transported..02 0.0–2. % 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 0.10 1. unless otherwise specific (a) Indicates typical analysis made them the standard alloys for automotive exhaust systems. 1.2 0.. 0...04 Ce 0.0 17.0 22.... through which ions are transported.. 0. 1 0..0–10.

As a case study.457 C. F is Faraday’s constant (96.e. Consider a general case. The case is for mobile cations e BCr 3+ = 3FDCr 3+ RT (Eq 6) where zi is the ion charge. scales are relatively thick compared to range of space charge effects).05). as shown in Fig. resulting in a low degree of nonstoichiometry in Cr2–δO3 compared to Fe1–δO (where δ can be as large as 0. let us assume that the mobile ion defect is cations due to metal vacancies in the scale. (c) nonstoichiometry is small and uniform throughout the scale (i.457 C/gram equivalent).. 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) . (a) A protective scale that prevents gas access. This treatment follows the derivation in Ref 1. and (d) double-layer where zi is the ion charge. F is Faraday’s constant (96. (b) electrode reactions are rapid enough to be in equilibrium at the interface and surface.eq–1).Chapter 5: Oxidation / 61 Fig. effects are ignored (i.. 3. 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. It was first described in terms of oxide defect structure and resulting transport properties by Wagner (Ref 6). 4 Metal with oxide scale. and the theory is explained in most of the monographs on oxidation. Compared to wustite (FeO). the equilibrium constant of Eq 4 is quite low.e. (b) Schematic of electrochemical oxidation through a protective oxide scale that serves as electrolyte and electron lead. and φ is the electric field (V). defects are in thermal equilibrium throughout the scale). such as Chapter 3 in Ref 3 and Chapter 4 in Ref 1.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. The molar flux J (moles/m. 4 under the assumptions that (a) the scale is compact and adherent.

the potential gradient is eliminated. then two fluxes are present: Jc = − κc F zc 2 2 assumed. 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 mobile particles are a single type of metal cations (e.62 / Stainless Steels for Design Engineers Now. Therefore. μM = μ′′M) to the scale-metal interface (x = X. 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. keeping in mind that conductivities and metal chemical potential may vary within the scale. c By combining Eq 18 and 19 and inserting Eq 16 for the flux. 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. and the following equation results: Jc = − 2 2 zc F (κ c + κ e If the mobility and thus partial conductivity of electrons is significantly higher than that of the ions (a reasonable assumption). Eq 15 needs to be integrated after variable separation.. M κκ 1 Jc = − 2 2 ∫ c e dμ M κ zc F x μ ' c + κ e M Since from diffusion theory we know that Dc = BcRT. and inserting this in Eq 9. a linear drop across X. the anode reaction is in equilibrium. If quasi steady state is .g. 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. μM = μ′′M) one obtains. Cr3+) and electrons. 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. It was assumed at the onset of this analysis that the deviation from stoichiometry is small and constant throughout the scale. 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. 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. and the chemical potential gradients can be replaced by the metal (M) potential gradient. Integrating from the gas-scale surface (x = 0.

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

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

this SiO2 layer seems to promote oxide spalling. but if its volatilization is inhibited by low atmosphere circulation. 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. the SiO2 layer is formed. an internal Cr2O3 layer forms and thickens. however. they might form so-called oxide pegs at the interface (Ref 16). but some hypotheses have been suggested. Silicon additions of 1. . due to the low oxygen potential needed to form Al2O3. 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). Molybdenum normally forms MoO2 oxide. and this causes an enrichment of silicon at the oxide-metal interface. Molybdenum is suggested to strain the lattice due to its larger size and consequently increase the rate of bulk diffusion of elements (Ref 11). Alumina is among the most stable and defect-free oxides. internal oxidation may result below the metal-scale interface in alloys in which formation of a continuous alumina scale film does not occur. especially in cyclic service. and yttrium additions are known to improve oxidation resistance of high temperature nickel. In consequence. there is little problem. even though they have significant metallurgical and mechanical drawbacks. the aluminum-bearing alloys provide the greatest oxidation resistance attainable in engineering alloys. the surface aluminum-oxide layer flakes off.Chapter 5: Oxidation / 65 tox Oxide tm Metal tox Oxide Fig. The effect on the growth kinetics could be because the reactive element ions collect at grain boundaries and block fast path diffusion. stabilizing Cr2O3 scales at lower chromium levels. 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. which can enhance the rate of initial Cr2O3 formation. the aluminum content is not sufficient to force alumina scale formation at the scale-metal interface. liquid MoO3 can accumulate and dissolve the protective Cr2O3 scale. (2) As sufficient silicon is enriched. 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. Cerium. Rare earth additions have been suggested to have a multitude of beneficial effects. but this can oxidize further to form the low-melting and volatile MoO3. Molybdenum is usually considered detrimental for oxidation resistance. Furthermore. lanthanum. The improved adherence could be because these elements getter tramp elements such as sulfur and suppress void formation at the interface. 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. giving it an extremely low diffusion rate. Also. Also. 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 explanation for any of this does not seem clear. Effect of Rare Earth Additions. 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. Eventually. and preventing spalling of the oxide scale during thermal cycling. Aluminum forms a very stable thin outer layer of Al2O3 that initially reduces the oxidation rate.and iron-based alloys (Ref 6). If. increasing adhesion.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. such as reducing the growth kinetics of Cr2O3 scales. If the MoO3 evaporates. if sufficient aluminum is present to maintain the protective alumina scale. leading to catastrophic oxidation. 7 stresses Schematic of a cross section of oxidized sample indicating dimensions in Eq 29 for predicting thermal strategic material.

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. In this case. 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.) does. molybdenum. assume a binary system A-B of “noble” iron and “reactive” chromium. and separating variables results in: XdX = S NO DO O υN B dt = S NO 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. The flux of oxygen inward into the metal is then the cause of increased mass. in principle. Assuming a quasi-steady-state situation as shown in Fig. etc. 8 Quasi-steady-state approximation of the moving boundary problem of internal oxidation. 9 . were mentioned. Beyond X. However. silicon. 9. the oxygen concentration is negligibly low compared to the surface composition. Counterdiffusion of B is assumed to be negligible Fig. the oxide of the reactive element can. which is in equilibrium with the gas phase. the accumulated mass due to oxygen addition: o 3 0 NB υX N Cr 2 X m= = Vm Vm (Eq 31) Differentiating Eq 31 with time. it is not. therefore. all the chromium is assumed to be oxidized. during annealing for microstructural control. The molar volume Vm is used to obtain the flux in units of moles per square meter. steels are exposed to furnace gases at high temperatures that have relatively low oxygen or steam contents. depending on the concentration of the reactive element and atmosphere. Assume for a start that the DO >> DCr. case b is perhaps the most relevant. At the distance X. For simplicity. (a) a noble matrix metal with less-noble alloying elements and (b) both matrix element and alloying elements are nonnoble. equating to Eq 3. Both cases are shown schematically in Fig. 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. Fig. 8. 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. and most of the discussion has been devoted to this. (a) Adsorption of oxygen leading to internal oxidation and (b) external oxidation as the B element migrates. Within the layer 0 < x < 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. that is the atmosphere does not cause iron (or nickel) to oxidize but chromium (and aluminum. for which case a will apply. and thus while oxygen diffuses into the alloy. When designing against oxidizing environments.

when the volume fraction of BOυ versus volume metal in the internally oxidized zone reaches a critical value g*. p 455 8. Effect of Oxide Grain Structure on the High Temperature Oxidation of Cr. London 3. let us see what causes this to transition into an external scale. C. this will decrease the inward flux of oxygen. Richardson and J. molybdenum. New York 2. The Effect of Reactive Element on Self-Diffusion in Cr2O3.. Pettit. and F.Chapter 5: Oxidation / 67 This expression predicts a parabolic dependence of X with time.A. (b) decreasing decrease with (a) increasing NB S.H.S. Cambridge University Press. N.E. nitrogen atmosphere. the remaining material can be rapidly nitrided by the residual.D.. silicon. oxidation and carburization may occur simultaneously and at a higher rate than exhibited in pure oxidation.H.. p 455 6. Now. Park.E. tion morphology if the ratio (NB B O O Gradually. Vol 40B. 1988. niobium.I. p 459–472 9. Birks. Metal dusting is often characterized by the generation of large. just as Eq 3 did for the external oxidation. edited by M. Rothman. 10 Temperature dependence of metal dusting of iron. Combust. Z. Plenum Press.E. smooth pits that look as if metal had been scooped from the surface. which manifests itself as the breakup of bulk metal to metal powder. Source: Ref 18 trogen absorption. Sproule. G. p 103–107 7. Wagner and K. refer to Appendix B in Ref 1. Chem. New York. During oxidation in air. etc. p 119–137 . If D NO O Cr was not negligible. Oxid. Vol 9. 1938. Grünewald.. Oxidation of Metals. Phys. Jeffes. the condition called metal dusting may occur. AIME. Ebbinghaus. Metal Dusting. King. Introduction to the High-Temperature Oxidation of Metals. F. and (c) decreasing D . This occurs at temperatures at which the carbide is most stable (Fig. but if the oxygen is depleted before all surfaces are oxidized. 1938. Chem. PA. is clear that the rate of penetration of the internal oxidation front will 0. C. 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. 1965 4. 1998. K. S. Z. Elsevier Applied Science. and thus the transition to external may occur at a lower solute 0) concentration than what is predicted by (CCr Eq 34. Peterson.L. The underlying phenomenon is the formation of metal carbides. there would be a gradual change in oxida0D )/(N SD ). Wagner and K.. Dayananda. 1975. Rothman. Oxide films inhibit ni- 1. specifically.. 2006. essentially pure. and W. D. Vol 93. W. B. It was assumed in the derivation of Eq 33 that counterdiffusion of chromium does not occur. Kofstad. Norman L. there is a transition from internal to external oxidation. 2nd ed. Hauffe. Warrendale. Met. Under reducing conditions. P. Grünewald.B. Vol 40B.J. may be present). Caplan and G. J. based on that at some point. if large surface area is present under conditions of restricted air supply. J. Iron Steel Inst. Vol 160. and S.I. Wagner developed a model (Ref 16). High Temperature Corrosion. REFERENCES (Eq 34) If more than one reactive elements were present (such as is the case in stainless steels in which aluminum. N. this happens when: ⎡ πg* S DOVM ⎤ N >⎢ NO ⎥ DBVOx ⎦ ⎣ 2ν 0 B 1/ 2 Fig. oxygen can be depleted to the point that oxidation essentially ceases. 10). Oxidation of Metals and Associated Mass Transport. 1948. in products of combustion atmospheres. Peterson Memorial Symposium. p 261 5. When considering Eq 33. For a more rigorous derivation (without assuming quasi steady state).H. Under even more reducing conditions. King. Meier. 1993. Phys. Flame.

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

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

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CHAPTER 6

Austenitic Stainless Steels
Summary
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.

Introduction
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

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

The solubility is given by (Ref 12): log (C ppm ) = 7771 − 6272 T (°K ) (Eq 7) Fig. chromium carbides. 8 The precipitation rates for Cr23C6 as a function of carbon content . supersaturation is reached below about 850 °C. Carbon is normally considered as an undesirable impurity in austenitic stainless steel. surpassing the 9% nickel martensitic steels in cost. Source: Ref 13 The equilibrium diagram for carbon in a basic 18%Cr10%Ni alloy is shown in Fig. At a carbon level of 0. 8. and. corrosion resistance. 7. While it stabilizes the austenite structure. which is found in most 304. depleting the grain boundaries of chromium in solution. carbon diffuses to and combines with chromium essentially in situ. very little carbon is soluble in austenite. and diffusion rates are sufficient for carbon and chromium to segregate into precipitates.06%.4% at solidification but decreases greatly with decreasing temperature. grain boundary diffusion is much more rapid than bulk diffusion. Fig. of course. form whenever carbon reaches levels of supersatura- tion in austenite. Precipitation of Carbides and Nitrides.03% of L grades is mostly in a supersaturated solution. At these temperatures. At room temperature. Because of this affinity. even the 0. And.76 / Stainless Steels for Design Engineers material. it has a great thermodynamic affinity for chromium. and grain boundaries provide excellent nucleation sites. 7 Carbon solubility in 18–10 austenitic stainless. because carbon diffuses several orders of magnitude more rapidly than chromium. while diffusion decreases exponentially. supersaturation increases exponentially. The absence of carbides in austenitic stainless is due to the slow diffusion of carbon and the even slower diffusion of chromium in austenite. M23C6. This results in precipitation rates that vary with temperature and carbon level as shown in Fig. Below this temperature. The solubility of carbon in austenite is over 0. toughness. so precipitation occurs along grain boundaries.

This is very evident for carbides.Chapter 6: Austenitic Stainless Steels / 77 Fig. oxides. where diffusion is enhanced by increased defect density. Other precipitation processes that give rise to chromium depletion are α and χ and the solidstate precipitation of oxides. chromium depletion occurs (Ref 15). but also true for oxides. especially in the interior of grains. Source: Ref 16 Fig. Alloying elements can have a major influence on carbide precipitation by their influence on the solubility of carbon in austenite. Nitrogen is much more soluble than carbon and does not give rise to sensitization phenomena as does carbon even though Cr2N can be a . Nitrogen is especially useful in this regard (Fig. as does cold work. 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. Chromium and nitrogen increase the solubility of carbon and thus retard and diminish precipitation. nitrides. 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. because it is lower in chromium. primary carbides. 11). Underneath chromium-rich oxide scales is a layer depleted in chromium and lower in corrosion resistance. This is why not only scale from welding must be removed. 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. 10 Variation of carbide precipitation locus with time. and sulfides. Figure 10 shows how the locus of precipitation changes with time and temperature. 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. and sulfides are not per se harmful to corrosion resistance. if the same compounds form and grow in the solid state. Molybdenum and nickel accelerate the precipitation by diminishing the solubility of carbon. Thus. Increasing austenite grain size accelerates precipitation. This zone. also has very unstable austenite and is quite prone to martensite formation. but also the underlying chromium-depleted zone. 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. 9 Depletion of chromium from the austenite near grain boundaries due to chromium carbide precipitation. But.

Thus. so its precipitation seldom has the possibility of occurring. 12 Variation of hardness with depth and therefore carbon content in colossal supersaturation For titanium carbide and niobium carbide. It would be a mistake to ignore the titanium-consuming capacity of oxygen and sulfur unless they have been minimized by refining. new processes have been developed to supersaturate carbon in austenite below the temperatures at which it has sufficient mobility to form carbides. kinetic considerations may result in that not occurring. is actually beneficial to corrosion resistance in solid solution. Manganese and chromium increase the solubility of nitrogen in austenite. which can be done quite readily. it was found that adding more powerful carbide formers than chromium could preclude the precipitation of chromium carbides. Stabilization. The solubility is over 0. Recently. 11 Delay in carbide precipitation induced by nitrogen level. after accounting for the oxygen and sulfur. or that niobium exceed eight times. This socalled colossally supersaturated austenite results in very high hardness (Fig. carbon can be free to form Cr23C6 if it is reheated to temperatures above 500 °C. any additions made to form carbides must be sufficient to account for the prior formation of these compounds. although this is not observed at normal concentrations. Nitrogen also competes with carbon for available titanium or niobium. 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. 12) and corrosion resistance over limited depths. Source: Ref 17 stable phase when the solubility limit is exceeded. however. If quenched from this state. for successful gettering of all carbon. like nitrogen. for which solubility is much lower. however. Carbon has always been considered totally undesirable from a corrosion point of view because of its tendency to form chromium carbides. we can see that carbon.55 − (Eq 10) Oxides and sulfides are more energetically favorable than are carbides and nitrides of these metals. . Even if sufficient titanium or niobium is present to combine with all carbon. They form carbides with solubility that follows the following equation type: log [ M] [ X] = + A − H RT (Eq 8) Fig.97 − 6780 T 9350 T (Eq 9) log [ Nb] [C] = 4. This requires in rough terms that titanium exceed four times the carbon plus nitrogen. the respective solubilities are: log [Ti ] [C] = 2. Titanium and niobium are the most useful elements in this regard. Thus.78 / Stainless Steels for Design Engineers Fig.15% in austenite. there must be sufficient titanium or niobium to combine stoichiometrically with all these species present. dissociate carbides. High temperatures.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. such as encountered in welding. Before carbon was easily lowered to harmless levels. From this. but it does become an issue in ferritic stainless steels in this regard.

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

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

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

15 . .6 1.03 0.5 1.60 ...04 17.07 0.50 2.57–10.. times can be as short as several hours. such as 310.) (FeCr)21Mo3 C. As a rule of thumb..2 11.8 1.5 19.24 a = 3. . c = 4.4828 S30815 S31008 S35315 S33000 S35125 0. High-Temperature Mechanical Properties.. Intermetallic Phases.07 0.6 25.05 Ce ...04 0.2 NbC NbN TiC TiN CrNbN Cr16Fe5 Mo2C (e.0 1. .33 a = 4..Ni. (b) body-centered cubic .15 0.7 1.15 0.. 1.. (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 = 4.391 a = 10.54 a = 4. 0..50 1. stress rupture.5 0. Fe2Nb Fe36Cr12 Mo10 Ni16Nb6 Si7.05 0.1 10.40 a = 4. .1 9. long-term properties such as creep. maximum service temperatures should be reduced by 50 to 100 °C in the presence of steam.. and while σ will have little detrimental effect on short-term properties at these temperatures. The resistance of a material to creep is generally measured by the creep rupture strength. .8 1. just a few percent intermetallic phase can cause toughness to decrease by an order of magnitude.5 .8 17.037..0 24. c = 7.. so alloys such as 153MA are less prone to it. Sigma formation is retarded by nitrogen..5 23. The most relevant is σ.8 0. Halogens can attack oxide scales and cause their degradation or volatilization. i.05 0. face-centered cubic. c = 7. Fe3Nb3C.08 0. 2.1 2.0 18. formation times are relatively long.. It can contain as little as four iron to one chromium or molybdenum in a tetragonal structure.... which is the stress that causes Notable high-temperature austenitic alloys Designation C N Cr Ni Mo Mn Si Other Max temp.8 21.2 35. Above about 500 °C. then some σ is a foregone conclusion.17 0. ..80. on the order of 100 h or more.878 a = 11. Austenitic alloys have no advantage over ferritic in this regard.0 35. . 0. 0. apart from austenite and ferrite.6 1.8 0.. ..0 34.. Silicon and aluminum are detrimental..0 Al.. followed by some loss of corrosion resistance..6 Ti 0.08 0.07 0.8 18.72 a = 8. then their toughness will be seriously reduced by the brittle σ.. 0..Cr. Transition elements may combine to form intermetallic phases in which the formula can vary from B4A to A4B..47 a = 4..28 a = 8.6 1. .0 19. Other relevant phases are χ and Laves. σ is an even greater concern as these are prone to its formation and can inadvertently form some during processing. .0 21.68 a = 10.06 0. 0.1 8.82 / Stainless Steels for Design Engineers (OH)2 species.5 12. 600 to 1000 °C service. In richer alloys.Mo Fe2Mo. For alloys..90 0. as is molybdenum.8 18. which will form first at triple points and then throughout grain boundaries.807–8.. °C 302B 304H 321H 153MA 309S 309Si 253MA 310S 353MA 330 332Mo S30215 S30409 S32109 S30415 S30909 DIN 1.73.1 9.0 8. If such alloys are intended for use near room temperature.4 1.50 0. Table 2 Alloy In lean austenitic alloys used in high-temperature.. Because of this morphology. The greatest risk from these phases is the loss of room temperature toughness..40 Nb 950 820 820 1000 1040 1040 1100 1090 1200+ 1200 1200 Table 3 Precipitate Secondary phases in austenitic stainless steel Structure Parameter. M5SiC Fe.08 0.03 0.05 Ce . Ni16Ti6 Si7 (a) fcc. it can exist in many conventional austenitic alloys.. yield strength is less appropriate than creep strength in assessing the adequacy of an austenitic stainless steel for structural purposes.08 0.06 0.5 0.3 0. and especially rupture ductility are degraded by σ. Lower chromium and higher nickel are beneficial. Thus.7 1. If the temperature at which the alloy is to be used is one in this temperature range.e. 0.62–11.40 . Table 3 lists the most common secondary phases encountered in austenitic stainless steels.05 Ce . .08 0.05 0..g.. 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.

Nitrogen is the better addition in this regard. such as carbon and nitrogen. the creep deformation strength. Thus. Cold work and precipitates tend to be ineffective strengtheners at temperatures that produce solution annealing and precipitate coarsening (overaging).000 h.Chapter 6: Austenitic Stainless Steels / 83 rupture after 10. however. Substitutional elements have limited effect.000 or 100.000 or 100.000 h. 19 Charpy V toughness after 200 hr aging Fig. the stress that results in a strain of 1% after 10. If deformation is a greater concern. can be used as a basis for design.000-h creep strength . that is. 20 Relative 100. Figures 19 to 22 compare mechanical properties of the major high-temperature austenitic alloys (Ref 25). plus it has the collateral benefit of strongly retarding intermetallic phase precipitation. Fig. but interstitial solid solution elements. are quite useful. solid solution hardening is preferred.

In normal atmospheric conditions. 22 High-temperature. thus giving the common perception that they are superior in corrosion resistance.84 / Stainless Steels for Design Engineers Fig. short-time yield strength Corrosion-Resistant Austenitic Alloys Stainless steels are almost always chosen at least in part for their corrosion resistance. That is the key aspect of the more modern austenitic stainless steels that have come into use in the last two decades. Austenitic alloys require higher levels than this to stabilize the austenitic structure at room temperature. alloys with more than 10.5% chromium do not rust. .000-h creep rupture strength Fig. The main advantage austenitic alloys have is their ability to utilize the powerful and inexpensive alloying element nitrogen. 21 100.

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

02 0..06 0. 0.2 Cu 0.2 6.24 16.1 2.4 19. The corrosion-resistant austenitic stainless steel grades range from 316 to the various highmolybdenum. These alloys were also very difficult to process. . .8 1. Table 5 lists the performance of the various popular corrosion-resistant austenitic stainless steels...02 0.03 0. the most notable of which are listed in Table 4 with their typical analyses.7 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.4 18.50 0.45 0.5 20.4 0. The chapter on corrosion deals with this topic in more depth. Further experimentation showed that molybdenum was not beneficial under highly oxidizing conditions.4 0.2 6.4 18. Then. First.06 0.5% molybdenum. 317.2 Cu .4 . which gives them a critical pitting temperature around 100 °C.4 Cu 0.5 10.0 20. The passive layer is extremely thin compared to oxide layers..3 Nb . Its formation does not cause chromium depletion beneath it. Copper was beneficial against sulfuric acid.06 0.4 6. This limited chromium and molybdenum levels to a total of about 30%.0 24. This was exploited in the alloys UNS S34565 and S32654.1 3..5 0. and the current density required to form the film is correspondingly reduced.86 / Stainless Steels for Design Engineers a homogeneous passive film.. but more importantly..3 Cu 0.5 0.01 0. as oxide layers do.7 1. 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. 317 was the most significant corrosion-resistant alloy..5 0.. This was found to increase PREN by another five units.7 24.1 4.02 0.5 7. Early grades were based on alloying with chromium and molybdenum with sufficient nickel added to preserve the austenitic structure. .. It is on the order of 1 to 10 nm thick. . The PRENs of these alloys are over 50. 0.22 0. Table 4 Alloy The discovery that nitrogen was beneficial against corrosion permitted a breakthrough in alloy development by the 1980s.0 25. Research into the thermodynamics of nitrogen in austenite showed that manganese increased the solubility of nitrogen appreciably. With PRENs of around 40.5 21..4 16.06 0.0 25.4 . and the class of alloys known collectively as the 6%Mo alloys was commercialized.. . also suppressed σ formation to times that permitted thicker sections to be welded without embrittlement.0 3. Nitrogen was increased to around 0.0 18.02 0. .8 Cu ..02 0.20% from nominal levels of 0.. more chromium and molybdenum were added. and 904 without the high levels of nickel and molybdenum that render these alloys so expensive... 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.. . .7 1.. the film is thinner.7 1. at least in part because they rapidly formed brittle grain boundary σ-phases in as little as several minutes at some temperatures.5 12.8 1.02 0. but that silicon was helpful under such conditions.02 0. which is an impossible goal in reality.01 0.5 19. 0..0 18.8 10.40 . This permitted even higher levels of total alloying to be achieved.5 0. Alloy development came in stages.7 1. Allegheny’s AL-6X™ is representative of this group.20 0.. high-nitrogen alloys commercialized in the last ten years.02 0.3 0. .. This left a great deal wanting in corrosion resistance. essentially a 301 in alloy cost.0 22. which contain 3 to 6% manganese and about 0. 1. .5 0.0 24.. As the alloy content of chromium and molybdenum increase.5 13. 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. The same case could be made for a 317-equivalent alloy in corrosion resistance with less than 7% nickel and 0...5 Cu 0.3 2.1 4.1 4.. . 0.8 6...05%. Each of these elements facilitates the formation of the passive film and reduces the corrosion rate in the active state..03 0...0 0.50% nitrogen..5 0.1 4. these alloys were resistant to seawater at ambient but not at elevated temperatures..02 0.0 24.

The key is to choose an alloy that is resistant under the conditions of use. Conditions that are below the threshold for pitting can cause crevice corrosion. abundant replacements like manganese and nitrogen are available.Chapter 6: Austenitic Stainless Steels / 87 alloy development. or both. is lower than the CPT. • Anodic or cathodic polarization may prevent SCC under conditions at which it would otherwise be expected. which. 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. All stainless steels suffer from SCC under some set of conditions of environment and material thermomechanical history. and then proceeds in a discontinuous manner. . much of the literature has focused on arguing a case rather than clarifying the phenomenon. • SCC is preceded by localized corrosive attack. but also exists in caustic environments. The threshold stress varies with alloy and thermomechanical history. Austenitic stainless steels are not alone in their susceptibility to SCC. then designing its Table 5 Corrosion resistance ratings of various austenitic stainless steels. The relation to crevices would thus seem to be that surfaces contain numerous flaws with respect to corrosion resistance. The most dangerous situation is one in which the expectation of pitting is marginal. The critical temperature for crevice corrosion is also measured in 6% FeCl3 (ASTM G-48 B or D). GTAW a wrought alloy also lowers the CPT to about the level of the CCT. As a rule of thumb. The mechanism of SCC has been a subject of intense academic controversy for many years. • SCC is aggravated by increased chloride concentration and acidity. or it may cause SCC in environments in which it would not otherwise occur. • Alloying or treatments that delay localized attack or stabilize austenite can delay SCC up to the point of virtual immunity. It is the lowest temperature at which crevice corrosion occurs. It is almost entirely lacking in plastic deformation with little. There is no justification for the use of scarce and expensive resources such as nickel and molybdenum when cheap. This temperature. which has an incubation time. if any. • Stress must exceed a threshold for a given set of conditions for SCC to occur. the CCT (critical crevice temperature). To a first approximation. the environment to initiate SCC must be sufficiently severe to cause localized corrosive attack. SCC occurs when there is both a tensile stress of a sufficient magnitude and a sufficiently aggressive environment. The same environments that cause pitting corrosion also cause crevice corrosion. 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. • Fracture may be transgranular. can in a crevice dissolve and alter the environment sufficiently that the new harsher environment can generally destabilize the passive film and proceed autocatalytically. while not capable of sustaining pitting. 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. this means using an alloy that will not pit under the conditions of use. pitting resistance equivalent number. Stress corrosion cracking is the bane of austenitic stainless steels. Because of this. intergranular. metal loss. 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–]. the future use of 316 and 317 should be numbered. 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.

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

Thus. which can initiate pitting. M. 1993. p 3 4. Les Ulis. which remove chromium-depleted sites. Rosenberg and C. mirror-type polished finishes do not degrade corrosion resistance. “Press Formability of Stainless Steels. Oxide formation depletes surface chromium. “Physical Metallurgical Developments in Stainless Steel. Powder injection-molded stainless components often have porosity that is generally spherical. Stand.R. The 120 grit #3 finish often seen on stainless reduces pitting resistance by as much as the equivalent of 5 PREN. Surface Finish. High-chromium ferritic stainless steels are also very good choices. 1993. They become hazardous when they contain chloride ions. Design Guidelines for Selection and Use of Stainless Steel. Les Editions de Physique. Aciers Inoxidables. S. p 98 3. p 40 14. p 565 9. p 410 15. Paris.Chapter 6: Austenitic Stainless Steels / 89 Fig. p 579 11. and residual stress have been cited as possible 1. 1993. Marshall. 1993. Paris. Constitution Diagram for Stainless Steel Weld Metal.T. Treatments that enhance surface concentrations of beneficial elements or remove detrimental constituents can greatly alter performance. “A Diffusion Model for the Influence of Oxygen and Sulfur on the NonEquilibrium Distribution of Chromium in . Paris. Schaeffler. Prog. Les Ulis. Very fine abrasive polishing causes little residual stress and has very minimal crevice creation. A 1000fold increase in weight loss in the ASTM G 48 B test has been seen by a superficial loss of 6% chromium. REFERENCES chromium duplex can be used to 150 °C. Q. The mechanism for this has not been clearly established..J. K. Nat. Vol 48. Les Ulis. F. Aciers Inoxidables. 2002. The increase in attack rate from this depletion is huge. Vol 77. Les Editions de Physique. Les Ulis. Aciers Inoxidables. A Modified Phases Diagram for Stainless Steel Weld Metals.1998. Elsevier. Pickering. P. Mechanical Properties of Austenitic and Duplex Stainless Steels. exposure of MnS inclusions. p 564 8.. A. equal to a reduction in chromium content of 5%. Chin. Aciers Inoxidables. Les Editions de Physique. or when they dissociate strongly. but they do not enhance corrosion resistance as does electropolished mirror finishes.-J. the microcrevices abrasion produces. All of these factors are operative and can act in unison. above which temperature nickel base alloys are required. p 680–688 2. refer to the various corrosion tables. Phys. Bar. especially coarse abrasion. Innovation in Stainless Steels ‘93 (Firenze). 1984 10. Dai et al. Nov 1949.. p 596–600.217 12. J Res. 1993. This is equivalent to the depletion seen in sensitization. Studies have shown chromium depletion of a maximum of 6% extending 10 μ before reaching bulk chromium levels.B. Prog. When exposed to the surface. 26 Resistance to hydrochloric acid. that is. Source: Ref 28 contributing causes. Austenitic Stainless Steels. has a major detrimental effect. p 2.” paper presented at Stainless steels ‘77 5. SSINA. as are other stainless steels. doi:10. Met. Aciers Inoxidables.” paper presented at Stainless Steel ‘84. H. Les Editions de Physique. Microstructure and Mechanical Properties. Rolled finishes are much preferred. Paris. Because of the large number of organic compounds that may be considered.L. p 566 13. Irish. 1993. Met. Les Editions de Physique. such as with formic acid. McGuire. at high temperatures.-X. Vol 11. Blom..1088/1009-1963/11/6/315 7.. Organic acids are generally less aggressive against stainless than are mineral acids since they are less dissociated in solution. Delong. Nordberg. so strong pickling or electropolishing of the descaled surface is especially important. Vol 56. Paris. Feb 1960. Goteborg 6. The corrosion resistance of austenitic stainless steels is quite dependent on surface condition. W. Likewise. 1952. surface abrasion. Les Ulis. such pores act as crevices and lower the pitting potential also.

. Paris. Les Editions de Physique. p 568 Aciers Inoxidables. ASM. p 1–15 25.com W. Vol 41. www. Allegheny Technologies. Les Editions de Physique. Austenitic Stainless Steel Welds and Slabs. A Super-Austenitic Stainless Steel for Tubing and Piping Applications.” paper presented at Proceedings MS&T ‘04.F. Paris. “AL6-XN® Alloy” . 17. N. High Temperature Stainless Steels. www. Les Ulis. NACE. Nippon Steel Technical Report 90.90 / Stainless Steels for Design Engineers 16. p 362 Aciers Inoxidables.com 28. July 2004 27. 1961. 1993. Grubb. ASM. p 448 Aciers Inoxidables. ASM. Trans. ACOM Files.com 26. High Temperature Stainless Steels. Les Editions de Physique.outukumpu. 19. 1993. 22. Les Ulis. p 1213–1219 23.. Trans. J. 1993. paper 04291 presented at Corrosion 2004. Accelerated Oxidation of Metals at High Temperature. 18. Vol 44. 2004. p 453 Aciers Inoxidables. Grant. 20. Leslie. Mechanism of Rapid Oxidation at High Temperature. 1993. p 454 www. 1958. Vol 54. Vinckier.outukumpu. ACOM Files. Okamoto et al. p 128–137 24. J. Les Ulis. 1961. 21.outukumpu.C. Stickler and A. Les Ulis. Trans. Paris. Les Editions de Physique. J.2004 R. Paris.

1 Wrought 2205 duplex microstructure .asminternational. such as 2304. Their low nickel content makes them more economical than austenitic alloys of the same level of corrosion resistance. Their limitations lie in their lack of cryogenic toughness and their inability to withstand temperatures much above 300 °C without forming embrittling phases. p 91-107 DOI: 10. they are exceptional materials. But between –100 and 300 °C Fig. so they are considered as highly corrosion-resistant alloys but not high-temperature alloys because of embrittling phases. Discovered in the 1920s. 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. They possess excellent strength. They are called duplex because at room temperature they consist of two phases. they languished in a suboptimized and underutilized state until recently. www. They also display exceptional resistance to stress corrosion cracking (SCC) and corrosion fatigue. 1. as seen in Fig. The mixture of ferrite and austenite in their structure gives them higher strength than either phase by itself. correspond to 316L in corrosion resistance but have double the yield strength. ferrite and austenite. while the higher alloy grades like 2507 compete with the 6% molybdenum superaustenitics in corrosion resistance while still possessing much greater strength. and corrosion resistance. toughness. McGuire. Duplex alloys have at least 20% chromium. They should largely replace alloys such as 316L and317L in the future.1361/ssde2008p091 Copyright © 2008 ASM International® All rights reserved. This Introduction Duplex stainless steels are the newest and fastest-growing alloy group in the stainless steel family.org CHAPTER 7 Duplex Stainless Steels Summary THE NEWEST FAMILY of stainless steels is the duplex alloys. The leaner grades.Stainless Steels for Design Engineers Michael F. especially when their greater strength can be utilized to reduce the amount of material required.

This lowers the activity of chromium and thereby effectively attracts more chromium to the austenite phase than would otherwise be present. The salient points are that the typical successful alloys nearly bisect the two-phase field for austenite and ferrite. The pitting resistance of the austenite increases signifi- Fig. First. Second. it would preferentially partition to the ferrite. and each phase would have equal corrosion resistance despite having different compositions. the control of nitrogen in the refining by the argon oxygen decarburization (AOD) process allowed the control nitrogen content up to the solubility limit. This stabilizes the austenite. Additions of nitrogen concentrate nearly entirely in the austenite. further exacerbating the differential between the two phases. the absence of a continuous austenite phase provides relief from SCC by having any propagation of cracks in austenite arrested by the ferrite phase. in the ferrite matrix. It is also obvious that the composition of the austenite and the ferrite must be quite different. Ferrite contains a great deal more chromium than austenite. both related to nitrogen.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. It took a long time for that to be accomplished. At this point. The shaded area results from nitrogen additions . especially with nitrogen. Why this was so important can be seen by studying the structure of these alloys. its pitting corrosion resistance contribution from chromium is much greater than the resistance of the austenite because in duplex grades: PREN = %Cr + 3. This is where nitrogen saves the day. the alloys developed over the first 50 years of development became obsolete. hence. Figure 2 shows a simple Fe-Cr-Ni constitutional diagram (Ref 1). 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. In addition.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. The austenite would be islands If one were to add molybdenum to increase pitting resistance. 2 The Fe-Cr-Ni phase diagrams. The optimization of the alloy system had to wait for two events. keeping the ratio of ferrite to austenite more nearly constant with temperature.

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

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

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

It owes its strengthening primarily to: • Solid solution hardening by nickel. chromium. 9 Sigma formation kinetics at various alloy levels Rp 0. d is the lamellar spacing.02))d −1/ 2 Rp1.15 − 0. below 0.g. The influence of nitrogen is interesting in that at lower levels (e. copper.02 +2( Mn + Cr ) + 14 Mo + 10 Cu + (6.2 = 120 + 210 N + 0.02) +14 Mo + 1.54δ)δ + (7 + 35( N + 0.5δ + 8d −1/ 2 (Eq 4) (Eq 2) (Eq 3) Fig.96 / Stainless Steels for Design Engineers Fig. and results are in megapascals. 8 Kinetics of ( formation The strength of the duplex grades is driven by the strength of the continuous ferrite phase. 10 Delay in ( precipitation in lean duplex 2003 where δ is the ferrite content in percent.1% nitrogen) austenite is the weaker phase. molybdenum.2 + 40 ± 9 Rm = 470 + 600( 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.0 = Rp0.. but additional ni- .

35–1.5–7.5–3. 0.0 2. trogen strengthens the austenite so that above 0.0 0.0–2.8–7.5–6.040 0.0 0... no highertemperature properties are shown.0 2.5 2. 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 . As would be expected.030 0.0 1.40 0. ..0 0.30 0.03 0.10–0.0 24.5 1.0 5..5–5.8 1.08–0.0 21. .0– 6..30 0.8–1..2–2..03 0.5 2.2–0.020 0.03 0. 0.5 ..5–3.20–0.5 1.5 2.030 0.0 3. with the austenite taking on a (110) [223] texture and the ferrite (100) [011] to (211) [011] (Ref 2).05–0.040 0..0–19.05–0.. the austenite becomes the stronger phase.0 24.5 . such as α′ and σ. The most deleterious effect on toughness comes from the precipitation of intermetallic phases...0–3.030 0.0–26..03 0.0 19.030 0.040 0..03 0.0–26.0–22..70 4..0–23.5 1. . .... Duplex alloy low-temperature toughness is intermediate to that of ferritic and austenitic alloys.5 3.8 0. .030 0.020 0.75 1.25 2.5–5.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. .5–2.6 1.0–6. Toughness is a significant consideration when using duplex alloys to replace the extremely tough austenitic alloys.5 19.0 1.2 1.0–5.0–30. 40 40 40 .0 21..20–0.5–2.05–0.2 Table 2 Grade Duplex mechanical properties Name Rp0.03 0.6 0.2–0.040 0.0–26.2–2. 0.0 1.0 1.0–4.5–3...1–0.0 4. the dependence of these properties on temperature is significant since flow in body-centered cubic (bcc) structures is thermally activated.035 0.0 1.0–28.8 0.0 24....20 0.5–3.030 0.8 .0–8.5 1.20 0.0 0.010 0.5–2..0 1.025 .0 28.0 5.0 1.2 Rm A5 HB RC Charpy-V –40 °C.10–0. Because the ferrite phase controls mechanical properties.5 24.030 0.5–8.0 0. 302 310 270 293 31 31 31 30 25 32 32 31 28 32 32 . Because use of these alloys above 300 °C is not recommended.0 24. ..32 0.0–8.8–1.0 0.8 .035 0.. it should be noted that the duplex alloys can have excellent toughness levels.25–5.. ..0 .0 1. The two phases are elongated parallel to the major strain axis of working such as from hot or cold rolling...0 2.03 0.0 4.0–23.10 0.2–2.020 1.5–1.5–3.0 24.15–0. ...0 21.1–0..5–21. 0..0 1. 40 .05–0.8 3.0 0.0 2.03 0.020 0.0–8. .0 0.030 0.1–0.0 .03 0. Since they have a ductile-to-brittle transition.. 0.0 24. .5–3.5 1. they also are not well suited to cryogenic use.0–26.14–0.0 1.0–2.020 0. 32 .0–26.040 0.0 1.0–26. .0 1.17 0.035 0.0 6.030 0.03 0.9 3..5–8.0 6.030 0. As working increases. .. 0.20–0.0 2.9–3.0 0.0 24...030 0.5 0.0 18.0–5..0 2.. .35 0.2 6. .5 3.5–3.24–0.040 0.0–3.0 6.0 26.0 2.030 0..35 0.5 4. .75 1.20–0. 0.0–5. such as 100 J at –100 °C in the solution-annealed condition. 0.0–4.030 0..0–29.0–8. toughness improves with decreasing grain size and deteriorates with cold work.010 0..20 0..14–0.0 2.2% nitrogen.5–1.03 0.0–5.5 3.20 0. Figure 11 shows the variation of yield and tensile strengths of various grades along with that of austenite and ferrite of similar composition.8 1.0 22.03 0..0 1.040 0..30 0.04 0. .030 0..0–26.5–23.8 .03 0...030 0.08 0...8 1. ..0–27.4–2.030 0.30–0. which cause a sharp decrease .0 1. 0.5 1. ..020 0. 40 .030 0.5–21.6 0..30 0.0–6. Impact Strength..20 0..33 23.0 3. .04 0.5 3....8 . This having been said.23–0.25 0.0 2..0 5.5–6.25 0.0 5.040 0.0 0.. the microstructure and properties become increasingly anisotropic.14–0.

Fig. The combined effect of cold work and α′ can be seen in Fig. While this is intuitively reasonable. 12. 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. as was shown in Fig. austenite. strength and corrosion resistance). its fatigue limit in a given environment approaches that in air. so the net useful strength under cyclic loading is much greater than that of equivalent-PREN austenitic alloys. 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). 11 Variation of ferrite. 11. and duplex with temperature. 12 Increase in transition temperature with α′ formation with aging for (a) annealed 2705 and (b) coldworked 2205. Source: Ref 4 . it is not diminished because the duplex reward the user with a higher level of yield strength and fatigue strength in air. Fatigue.98 / Stainless Steels for Design Engineers Fig. 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. Figure 13 shows that ratio for various alloys plotted versus their PREN. 2003. Source: Ref 4 in toughness level and a concurrent increase in transition temperature. As an alloy’s resistance to corrosive attack increases. indicating simply that corrosion plays an increasingly small role in fatigue crack propagation as corrosion resistance increases.e.. Lean alloys such as 2001.

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

While this contamination is deadly to 316 and 317. In real-life situations. Source: Ref 6 . Sulfuric Acid. 16 Isocorrosion (0. 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. Source: Ref 5 Fig. it has only a minor effect on the copper-alloyed duplexes (Fig.5%) and S32760 (0. more highly alloyed duplex grades. including sulfuric acid. the Fig. Historically stainless steels have had their poorest performance when confronted by hydrochloric acid. sulfuric acid can be contaminated with chlorides.5%) gives them much better performance than the otherwise similar S32750. phosphoric acid.1 mm isocorrosion curves. Here again. Source: Ref 5 Fig. 16). 15 The 0.1 mm/yr) performances of several austenitic and duplex alloys. 14 The 0.100 / Stainless Steels for Design Engineers the ferrite.1 mm isocorrosion curves. Figure 14 shows the behavior of S32304 compared to 304 and 316 in sulfuric acid. hydrochloric acid. and organic acids. sodium hydroxide. General Corrosion The duplex alloys offer important advantages in performance over the austenitic grades in a number of significant aggressive media. The use of copper as an alloying element in S32550 (1. This performance extends to situations in which the aggressiveness of these media is enhanced by contamination. This approach is common to all more recently developed alloys starting with the revision of 2205 from UNS S31803 to S32205. mainly toughness. which has primarily higher nitrogen. Hydrochloric Acid. such as seen in flue gas desulfurization. Figure 15 shows additional.

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

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. In formic acid.5 × %W) + 16%N (Eq 7) .3(%Mo + 0. Alloys such as S32205 perform well. the most aggressive organic acid. If one has the actual analysis of each phase. as seen in Fig. contaminants again can render it so. Duplex alloys perform particularly well in organic acids and have an excellent record in industrial plants.102 / Stainless Steels for Design Engineers Fig. 22. while in mixtures contaminated with halides its performance ranks very closely to expensive nickel-based superalloys such as N06625 and N06455. The ferrite phase has the relationship common to ferritic grades: PREN + %Cr + 3. outperforming even titanium (see Fig. In acetic acid. and nitrogen levels. then the proper relationship to use is Eq 2. 21). 21 Isocorrosion (0. the superiority of duplex alloys is quite evident. S32750 is resistant at all concentrations almost to the boiling point.127 mm/yr. Source: Ref 9 In combinations of acetic and formic acid. S32750 shows virtual immunity. Tungsten has half the value of molybdenum and is frequently included: PREN = %Cr + 3.1 mm/yr) performances of various alloys. Even the lower alloyed S32205 can offer an order of magnitude improvement over S31703 in hot contaminated acetic acid. 20 Minimum temperatures for wet phosphoric acid (WPA) with an isocorrosion rate of 0. Halides are particularly common and aggressive contaminants. Organic Acids. Source: Ref 9 steel. Performance again improves with increasing chromium. Figure 20 shows the substantial improvement in performance of the duplex alloys over 316L when contaminants are present. These relationships are incomplete in that they only address the major alloying elements. PREN. molybdenum. 304L handles lower temperatures and concentrations. Pitting Corrosion The different analysis of the two main phases in duplex alloys means that each has its own pitting resistance equivalent number. while the austenite obeys the more familiar: PREN + %Cr + 3.3%Mo (Eq 5) Fig.

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

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

Like pitting. The temperature at which SCC occurs at the fastest rate increases with nickel content. SCE. H2S also accelerates failure in chloride environments (Fig. 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. Source: Ref 5 Fig. 27 Critical crevice temperature (CCT) and critical pitting temperature (CPT). if not solved. through which cracks must propagate (Ref 16). saturated calomel electrode. In ferrite. whose initiation mechanism has not been identified. This is also characteristic of ferritic and martensitic materials and mirrors their hydrogen embrittlement behavior. which seems to avoid the hydrogentrapping dislocation types that seem to be associated with hydrogen failures. 29) than austenitic alloys. The arrival of duplex stainless steels has to a very large degree ameliorated. So. This is in spite of their higher yield strength. while we cannot state the mechanism for SCC. 30). and cold work accelerates failure and lowers threshold stress values. Source: Ref 14 Fig.Chapter 7: Duplex Stainless Steels / 105 Fig. SCC is unfortunately poorly understood. 26 Critical pitting temperature (CPT) as a function of NaCl concentration. while in austenite susceptibility appears to begin around 50 °C and increase monotonically with temperature. The duplex alloys in this regard are governed in their behavior by their ferrite matrix. 25 Variation of critical pitting temperature (CPT) with pH. 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. The major environmental factors that affect SCC are chloride concentration and temperature. Source: Ref 15 occurs at temperatures and in environments where stainless would be a perfect material if only it did not stress corrosion crack. Other ferritic and martensitic alloys display pronounced susceptibility to these failures modes when their hardness . But the duplex alloys have good strength mainly through fine grain size and solid solution hardening. SCC has both its initiation and propagation mechanisms still open to debate. Ferritic stainless steels are known for their resistance to SCC in the annealed condition. again giving these alloys more usable strength. we can map out the conditions under which duplex alloys are susceptible to SCC. that problem. While duplex alloys behave in many regards like ferritic alloys in their SCC or hydrogen embrittlement response. SCC susceptibility is a maximum below 100 °C. The duplex alloys show a higher threshold stress for SCC as a percentage of their yield strength (Fig.

Source: Ref 5 exceeds Rc 22. Source: Ref 17 Fig. 28 Stress corrosion cracking (SCC) in neutral aerated NaCl. Testing duration 1000 hr. 29 Constant load stress corrosion cracking (SCC) tests in aerated MgCl2 at 150 °C.106 / Stainless Steels for Design Engineers Fig. Thus. . it is very important to understand duplex SCC behavior as a separate study and not interpret it in terms of austenitic or martensitic SCC. Source: Ref 5 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. 30 Suggested chloride and pH limits for cold-worked duplex alloys. The duplex alloys have annealed hardness over Rc 30 without being in danger.

Bernhardsson. Conf. 1991. p 2. B. Vol 1. J. NACE. R. Drugli et al.. Les Editions de Physique.P. Beaune. 1993. Les Editions de Physique. 1991. Glasgow. Vol 412. Hutton.217–2. p 168–175 17. R. Stainless Steel ’87. Lacombe. p 770 13.N. Houston. AIM. Abington Publishing. Duplex Stainless Steels. Stainless Steel ’93. 1994. p 511–519 8. p 1237 7. Nordberg H. Williams. Tsuge. E. R. p 45 9. Walden et al.-M..M. Corrosion Handbook for Stainless Steels. Les Editions de Physique. AIM. Innovation of Stainless Steel. B. Duplex Stainless Steels ’91. Duplex Stainless Steels ’86. Seki. Nichols J. Werkstoffe und Korrosion. Proc. 1990 15. 12th International Corrosion Congress. Vol 1. Bernhardsson. and G. B. Gunn.. The Hague. 1991. 2003 2. Nederlands Instituut voor Lasteckniek. Las Vegas. Duplex Stainless Steels ’91. S.. TWI. 1986. April 1992. Nature. and D.47 11. McPhail. C. 1997. 1988. J. Stainless Steel Europe. p 3. D. Duplex Stainless Steels ’94. MS&T Conf. S.F. T. H. The Institute of Metals. paper KIV . NACE. p 126–135 14. Francis. 1994. p 3–48 5. H. Kudo. Paper 164 presented at Corrosion ’90. Beranger. Charles. p 137–150 6. Chater. NACE. M. Roscoe et al.V. 2004. 1994 10. Avesta Sheffield. P. M. p 831–846 12. and A. Florence. Audouard. Proc. Why Stainless Steel Corrodes.Chapter 7: Duplex Stainless Steels / 107 REFERENCES 1. Las Vegas. Ryan.. p 28 3. Vol 42. Beaune. Vol 3. McGuire. Paper 270 presented at Corrosion ’90. Stainless Steels. 1990 16.229 4. Florence. J. Baroux. Horn.

The older. and they are limited at low temperatures by brittleness and at high temperatures by softness. Stabilization does not preclude excessive grain growth in the fusion or heat-affected zone (HAZ) of welds. In October 1967. provided their strength is adequate. 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. which requires a lengthy subcritical anneal to avoid martensite and to evenly distribute chromium after all carbides have stably formed. This makes them excellent for high-temperature applications with thermal cycles. 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). and less-expensive high-carbon ferrochromium could be used instead of expensive low-carbon versions. This makes their welds brittle. and 446 and the more modern stabilized alloys led by 409 and 439.” Early in the 20th century. Thus. This process is called stabilization. carbon combines with chromium.and oxidationresisting alloys in existence. unstabilized grades are not always fully ferritic. To be used. Even as they have grown in use more than any other type of stainless. to develop the fully ferritic structure. The mechanical properties of ferritic stainless steels appear similar to austenitics strengthwise. they contain simply enough chromium to overcome their inherent level of carbon impurity and hit the 11% chromium in solution required for “stainlessness. p 109-122 DOI: 10. So much extra chromium was required because during annealing. they could still economically displace the popular but expensive 304 for many routine applications.10% to around 0. 436.org CHAPTER 8 Ferritic Stainless Steels Summary THE FERRITIC STAINLESS STEELS are the lowest-cost highly corrosion. which can render them brittle.1361/ssde2008p109 Copyright © 2008 ASM International® All rights reserved. the first commercial use of argon oxygen decarburization (AOD) changed the world for ferritic stainless steel. McGuire.04%. which transforms to martensite if quenched. reduced the carbon plus nitrogen levels sufficiently that their effect could be nearly negated by small additions of titanium or niobium. This process. They are useful mainly as light-gauge sheet since their toughness drops off rapidly for heavier sections.Stainless Steels for Design Engineers Michael F. 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. The level of carbon plus nitrogen was lowered from around 0. but they lack the ductility of austenitics. they are normally in the annealed condition. It was not until carbon and nitrogen levels were brought down to AOD levels that it became truly practical for ferritic alloys. In their minimal form. which combine strongly with carbon and nitrogen and effectively remove them from solution. lowestcost stainless steels. 434. there exist two types of ferritics: the early high-carbon types such as 430. 430 came into being. The newer stabilized alloys behave as if they are interstitial free.asminternational. and the attainable levels of carbon removal required 16% chromium for this to occur. rendering it useless as a corrosion fighter. and the . Their carbon levels cause them to form some high-temperature austenite. technology was documented long before AOD was invented (Ref 1). www. Introduction Ferritic stainless steels are simplest.

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

. 10.5–1 0.3 .03 10. 11....6 .35 12 SR 0. .45 .5 12.45 6x(C + N) to 0.. 1 ..03 .03 10...8 + 8x(C+N) Ti + Nb 10xC to 0. 0...03 0.. .. .35 1 0. 14.3 .5 439 439LT S43035 S43932 0..25 0.0–16.15 min 0...015 11. ... 0... 1 0. .. 0... ...03 ...20 + 4x(C+N) to 1..5 0.03 0..04 0. .7 409Ni S40975 0.. .04 0. 0.75 Ti+Nb 0..3 0....0–18.04 0...7 11 Cr-Cb 0.06 0. ...2 .02 6x(C + N) to 0.10 0... 1 0. .7 1 1 1..0–18. .04 0. ..03 ...45 0. 1 .04 .3 .07 0...04 16.6 . 17. 0.02 0. .04 0..02 8x(C + N) to 0.3 Chapter 8: Ferritic Stainless Steels / 111 4742 AK alloy typical AK alloy typical Outukumpu typical 0..0 430Ti S43036 0..02 . .35 0.5 0......12 0...7 1 0...0 16...25 1.04 0.5 0..3 0..15 Se 0. 1 . 13..06 0. 0........ 10..015 12 Alfa I 0.0 18 Cr-Cb 0........08 .03 10. 0.03 .015 ......12 . 0.... 0..... .25 .75 409 ultraform AK alloy 0..... .5–11.0 430Se S43023 0....4 .2 0.. 0..75 1 1 1 0.0–18.. .5–11.035 0.. 18 1.. .. 1 1 1 1 0.75 0.. 0.75 ..08 .2 Al 3 Al 4 Al 1 Al .20 + 4x(C+N) to 1.. . 1 1 ..10 0.4 ... 1. . ..45 1 1 1 .03 17. ..04 .... 1 . ..... 18.... . ..0–19.. .... 18 18SR 0.... 0. 13 4724 0.. . 0...04 0.. .01 0..5–11. AK alloys S46800 0. .5 0. ...... .. 0... . 0. (continued) 0.Table 1 Cr Ni Mn Si Mo P S Other Ti Nb Ferritic stainless compositions 0.0–20. 1 ..5–14.08 ...025 ..0 409 S40900 0.02 10.. .. .04 0..025 .01 8x(C + N) 0.5 ... .75 10.5 1 0.20 + 4x(C + N) to 1. 0.02 0. .... . . 0. ..06 0.001 0..10 0.75 Nb 0.5 0. ...7 466 409Cb S40930 S40940 0. 0.05 0...... . . .. 0. ..15 Al ..03 0....5–11. . 16.04 0.03 0....0 16.12 0.03 ..0 17. 1 1 1 ...17 .15–0.35 Ti + Nb: 0.06 . 0.12 .....02 .25 Al Alloy Designation C N 405 400 S40500 AK alloy 0...03 0.5 0.1 0.5–11. 13 Alfa II 0. . .08 0.03 0.75 .... . .25 .04 0.3 0...10–0.30 Al 0....5 429 430 430F AK alloy typical AK alloy typical ATI alloy typical ATI alloy typical Outukumpu typical S42900 S43000 S43020 0.5 0.55 ..5–11.04 0...5–11...05 .0–19 439 HP 439 ultraform 468 ATI..04 ....04 0.. 1 1 . . ....01 0.0–19.. . ...75 409 S40910 0.03 0.. . 0. 0. . .20 + 4x(C+N) to 0. 0.. 1.035 0. .. .15 Al ..... 1.25 ..25 1 1 1 0.02 0. . ...50 1 .01 0. .03 0........5 0....03 0. .. 0.7 Al 1 Al .. .03 .....03 0.. .7 409 S40920 0.02 0.01 17..0–13..

...5–4.0–30 0.5–26.0–27.04 0.6 0.5 1 0....03 0. .25 .75 1 1. 430J1L 0.2 0. 0.0–30 23..75–1. .5 0. YUS 190-EM 0. .025 0. .......5 Al 0.. . 4509..025 0.01 .... S44627 0.20 + 4x(C + N) to 0... .04 0.03 0.04 0. .02 0..... 26-1 3..0–18.. Nb + Ta 5xC 0.0 28.. .. . .25 0.2 1 0.02 0...0 25.. S44200 ATI alloy typical S44400 0. 0.3–1. .4 .5 1..03 .. 1 1 1 1 1 1 0..001 .25 0.04 0..035 17..01 .80 Ti + Nb: 0.3 8x(C + N) min Ti + Nb: 0...035 0.5–0. 0.5 0...02 0.3 0.3 .7 1.015 18.03 1 0.04 0. 24 453 ATI alloy typical Outukumpu typical ATI alloy typical 0.02 0.60 Al 0. .. 0.75–1.5 3... 0.. .0–27. 112 / Stainless Steels for Design Engineers 442 436S 444.0 26...Table 1 Cr Mo P S Ti Ni Mn Si Nb Ferritic stainless compositions (continued) Other Alloy Designation C N 434 436 441. . 0.025 0. .75–1.025 0.1 REM 0.....5 .5–4.0–23...5–19. Ti + Nb: 0...08 . 22 E-Brite...2 Cu 0.0–27.5–18.02 0.. 20 10x(C + N) ..03 0...80 1 1 1 0. . .04 0..75–1.. .0 .015 25..04 0.5 0.12 0.0 17...12 0.4 ...25 . .25 . .. . 0.80 ...5–3..03 0.20 + 4x(C + N) to 0.04 0..01 0..20 Monit Sea-cure 29-4C 446 CC-50 S44635 S44660 S44735 S44600 Cast alloy 0.. 0.4 0.25 0..3 . .20 + 4x(C + N) to 0..2 0. 0. 0..6 0... . .015 . S43400 S43600 S44100 0.3 0. .5–4.0–18..5–3....6 4 1 1 1 1.5 ..03 0.. .3 0.035 .1-0. . 16.... 1.80 Ti + Nb: 0.5 2..03 0.. .0 16.5 0..5 3. .4 0..75 1 0..5 . 24. .02 0. .04 0..2 0. . 4762 0.8 17. .03 .20 + 4x(C + N) to 0. 9xC 0...001 .5 Cu + Ni .03 ..7 .. ..5 433 0...04 . 1.... .4 .

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

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

K. 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. The thermodynamic driving force for carbide and nitride formation is given by (Ti )(C) = −7700 + 2. precluding chromium carbide precipitation. it is not practical to quench alloys quickly enough to prevent carbide precipitation as is possible in austenitics (detailed in the Chapter 6. carbon cannot be kept in supersaturation even by the most rapid quenching. 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. carbideSource: Ref 3 . TiC forms. removing them from solution. TiCS forms in the solid state if sulfur is present. Sensitization occurs at higher levels of carbon by prolonged heating at 600 to 850 °C. such as 321. The solubility of carbon in ferrite is vastly lower than it is in austenite. the heat treatments to avoid sensitization are essentially reversed.” 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. 4 430 time-temperature-transformation (TTT) curve.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. if not. so that the removal of carbon from solution is preceded by the removal of oxygen. But. Carbon in austenite can be retained in supersaturation for extended periods of time. and sulfur in that order. 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. Stabilization causes nonchromium carbides to form at high temperatures. 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.08% (Ref 3). but does not exist in low interstitial ferritic alloys. 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. Figure 4 shows the time-temperaturetransformation (TTT) curve for an unstabilized 430-type alloy with carbon plus nitrogen of 0.75 T −15790 + 5. The rate of diffusion of carbon in ferrite is around 100 times greater than that of carbon in austenite. The latter effect was real in early austenitic alloys.. This is why austenitic L grades do not sensitize even though they are slightly supersaturated. greater than about four times the carbon plus nitrogen). 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. In ferritics. 1. 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. which have much greater diffusion rates than austenitic alloys. nitrogen. Because of these factors. 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. In practice. “Austenitic Stainless Steels”). since carbon mobility is quite high. leading to knife-line corrosion attack after welding. 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. depending on concentrations. Fig.e.Chapter 8: Ferritic Stainless Steels / 115 are “stabilized.

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

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

This is probably due to titanium’s ability to eliminate sulfur and oxygen from solution. but without proper heat treatment even alloys of this purity can incur debilitating loss of toughness due to carbide and nitride precipitates (Ref 9). Toughness improves for niobium-stabilized alloys up through full stabilization and then begins to decline. their corrosion resistance is improved (Figs.118 / Stainless Steels for Design Engineers Fig. This is a result of excess stabilizing alloy acting as a solid solution hardener and therefore a toughness reducer. but titanium-stabilized alloys have a lower rate of corrosion than niobium-stabilized alloys. This toughness reduction is more pronounced with titanium. 10 Corrosion of niobium-stabilized 29% Cr plus 4% Mo alloys in ASTM A 763 Y test. Combined carbon plus nitrogen levels below 100 ppm are necessary to avoid both sensitization and embrittlement. The upshot of this understanding was the introduction of dual stabilization. so stabilization is the correct engineering answer. The distinguishing of α' from those related to interstitials and their stabilizers (Ref 10) permitted stabilizing elements to be optimized. It was not known until about 1980 just what the mechanisms of embrittlement were in the ferritic stainless steels. however. 11 and 12) (Ref 11). These levels are not economically attainable for commercial alloys. 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. The same study recommended that dual stabilization follow the following formula: .7 × C + 6. Maximum improvement in corrosion resistance levels off once full stabilization is reached. which is a stronger solid solution hardener (Figs. Source: Ref 11 Fig. Titanium combines with carbon and nitrogen stoichiometrically by: Ti = 4 × C + 3. 9 and 10) (Ref 11). 9 Corrosion of titanium-stabilized 29% Cr plus 4% Mo alloys in ASTM A 763 Y test. through which both weld and base metal toughness and corrosion resistance are optimized.4 × N (Eq 7) Fig. Source: Ref 11 Niobium requires a greater weight percentage: Nb = 7.6 × N (Eq 8) As titanium and niobium are added to alloys. Excess amounts of the stabilizing elements have negligible effect. Stabilization is generally considered as the simple gettering of carbon and nitrogen by a suitable carbide and nitride former.

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

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

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

Trans. E. Webb. Vol 113. 1973. Grubb. Vol 44. 2003 4.M. ASTM. if not eliminated. and P. 5–12 7.” paper presented at 1984 ASM Int’l Conference on New Developments in Stainless Steel Technology. Grubb and R. K. Vol 412. Bohni.J. 1980 11. E. reduced to very low levels (Ref 18). J. REFERENCES 1. p 27 13. at which point corrosion in seawater is. Williams. Wright. Vol 148 (No. 5). Shibata. p 5–9.80 Vsce. as opposed to austenitics. p 126–143 2. p 483 3. R. Met. Farrar. A. D. McPhail. 2001. Sept 1979. J. Les Editions de Physiques. J. 1977.. Ryan. Alloying. Newell. Trans AIME. Ohmura.122 / Stainless Steels for Design Engineers this susceptibility is a maximum near room temperature and declines with increasing temperature. J. El-Kashif. Abo et al. “Hydrogen Embrittlement of Superferritic Stainless Steels. Koseki. 2002. Electrochem. p 1247–1255 10.W. Vol 4. Grubb. Suter. Wright. H. K. “Use of Cathodic Protection With Superferritic Stainless Steels in Seawater. 1991 12. Why Stainless Steel Corrodes.D. ASM. Trans. and D. J. 1934. Stainless Steel ‘77 9. The 885 °C (475 °C) Embrittlement of Ferritic Stainless Steels. Stainless Steel ‘77. H. p 1568–1575 14. The Role of C and N in the Brittle Fracture of Fe-26Cr. Pit Initiation in I M NaCl With and Without Mechanical Stress. McGraw Hill. and R. Stainless Steels. April 1947. p 770 17. Grubb and J.” Special Publication 706. Beckett and R. Metall. Chiba. Grubb. Chater.. 1998.. which see their maximum susceptibility above room temperature. H. Conf. New Orleans. Handbook of Stainless Steels. B174 16. Asakura.” paper presented at Corrosion 84. Paxton. Met. “Micromechanisms of Brittle Fracture in TitaniumStabilized Stainless Steels. Les Editions de Physique. Franks. Nature. p 251–260 6. September 1984 18. F. T. p 213 8. Sato. Stainless Steels. M. H. Prog. p 617–626 5. ISIJ. Detroit. Int. J. 2004. and K. M. Hutton. April 1984 . Stainless Steel. Maurer. Fujita. Oct 1996 15.A. Streicher. Stabilization of High-Chromium Ferritic Stainless Steels. T. Alkire.. Nippon Technical Report 71. Proc. Grobner. Vol 10A. Yamamoto.. N. B. High Chromium Irons. E. 1992. Peckner and Bernstein. and A. P. Soc. This limits these alloys’ ability to employ cathodic protection safely to –0. ISIJ Int. R.

they fill an important niche as a strong. Ferrite can appear in the as-cast structure and be formed during austenitizing or tempering. All the usual concerns inherent in any martensitic alloys are still present. 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. 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 0.1361/ssde2008p123 Copyright © 2008 ASM International® All rights reserved. In addition they are always susceptible to stress corrosion cracking (SCC) when their hardness exceeds about Rc 22.0% carbon. hard. There is no aspect of martensitic steels that does not apply directly to stainless martensitic steels. but their special hardening mechanism of precipitation within a martensitic matrix causes them to be categorized separately somewhat arbitrarily. Chromium strongly promotes the formation of ferrite.Stainless Steels for Design Engineers Michael F. and niobium are also added at times for specific purposes explained in this chapter. etc.org CHAPTER 9 Martensitic Stainless Steels Summary THE SMALLEST CATEGORY of stainless steels in usage volume is the martensitic stainless steels. hardness. These limitations combine to make their excellent properties usable in only mild environments compared to other stainless steels. The additional concerns one must have with stainless martensite relate mainly to those that are due to the strong ferritizing influence of chromium. This was the first commercial use of stainless steel and cutlery with the same basic analysis is still sold today.25% carbon. retained austenite.” The designers and engineers already familiar with martensitic carbon and alloy steels will find nothing confusing about martensitic stainless steels. The useful alloys of martensitic stainless steel contain from roughly 11 to 18% chromium and up to 1. 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. 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. and tough alloy of fairly good corrosion resistance and as a strong. tungsten. www. Their high strength and hardness for their relatively low cost ensure their place as a very useful engineering material. stable. Nearly all the precipitation-hardening stainless steels are used in the martensitic state. p 123-135 DOI: 10. Martensitic stainless steels are the most marginally corrosion resistant of all the stainless alloys. vanadium.asminternational. Relatively small amounts of nickel. The distinction between martensitic stainless steels and some other stainless alloy families is sometimes vague. Even so. Much of the carbon in them detracts from the effective chromium content by forming chromium carbides. The presence of ferrite in a martensitic structure is detrimental to strength. . By this conventional logic. McGuire. molybdenum. and toughness. which restricts the temperature and composition ranges over which it is possible to obtain a fully austenitic structure from which to form martensite. The requirement that they be fully austenitizable limits the amount of corrosion-resisting chromium and molybdenum they can contain. Table 1 lists the most significant of the martensitic stainless steel alloys. “Corrosion Types. high-temperature alloy. temper embrittlement.

..014 12.5 11.50-3.5 11.....0 12.... .52 0. 0..45 1.80-2. .5 .06-0..5 1 .. N 0...5 10...0-13. .512.03 1 1 1 1..6 0.55 0.03 0.5 12. ..20 1. .. .....20 0.65 0.50-1. .. .5 11. 2. 0..0 12. .03 0.03 .15 max 0....15 min Se 0.30-0.08 410Cb S41040 Wrought 0.0-14.45 0.5-14.0-14.15 max 0. .03 0..7 0.512.025 0..05 415 416 416Se S41500 S41600 S41623 Wrought Wrought Wrought 0.5 12..15 min 0.0 14.... ... 0.03 . 1...5 0..5 11. .0 13.. .50-1.5 11.0-14.30V .... ....50-0.6 ....... Alloy UNS Form C 403 410 410S S40300 S41000 S41003 Wrought Wrought Wrought 0.30-0.. ..15-0..03 410 S41008 Wrought 0..30 0.5 1 .06 max 0...20-0.513.18 max 412 S41003 Wrought 0... 0.30-0. .. .50-1.. (continued) .513....12 N .03 0. .5 1 1. .15 min 0.60 1 1 1 .03 .6 1 1 0..75-1.15 min 0... . . 1.25 W ..50-4.00 1.025 . . ..50-1..03 0..15 max 0..07 3..0-14. 1.03 0.5-13.05 max 0. 0...25 1.0 12..15-0. 0. .25 1.03 0. .0 14.5 Cu HP13Cr-2 Wrought 0.6 0.20 0.00 -3...5-13.00 3.80-1...05-0.030 max N .15 min Se 2...03 ...45 0.5 .5-13. 1.15 V .. 0..01 0... .25-2.00-2.08-0. Wrought .015 11.30 Cu .15 max .4 .. .20 .25 0..... ..06 0.0 12..03 0...0 11.030 max 124 / Stainless Steels for Design Engineers 414 414 mod S41400 S41425 Wrought Wrought 0.... 1. .50 W .0-14. ..0 -14 13 13 12.00 1 1 1 0.06 0.. . 1.30 Nb 0.5 0.0 0.5-1.. . 1..00 -3 1 2 1.0-14.00 0. 0...03 0.5 10.. .0 12....25 1 0.5 1 . Wrought 12. .03 0.5 1 0.. 5 4.50 4.50 1. 1 1 1 1 0.... 420F 420FSe 422 424 425 425mod Trinamet S41800 Wrought S42000 Wrought DIN Wrought 1. 4 418 420 4116 0..005 0..040 N NT-CRS JFE Nominal JFE Nominal Nippon Nominal Wrought 0. .00 ....30 max HP13Cr-1 Wrought 0.03 0. ..25 0.50-5.15 max 0.. 0.75-1.0-14. 1 1 0..... .50 .....15 min 0.0-16.6 0.Table 1 Mn S Si Cr Mo Ni Other Other Compositions (wt%) of martensitic stainless steels 0...70 0.15-0.5 ..70 0. 0. .25 0...00 Cu .4116 Nominal S42020 Wrought S42023 Wrought S42200 Wrought S42400 Wrought Wrought S42500 .75 0.

03 0.. 12..02 2 . . ...3 0..20 1.25 0..45 .5 0.. . . .4 1 0..2 Chapter 9: Martensitic Stainless Steels / 125 J91150 J91151 J91153 J91154 J91650 J91540 J91422 Cast Cast Cast Cast Cast Cast Cast 0...5 1 0. .5 1.. . ...... ..020-0.8 1. . .40-1.02 0.04 0. .5 0...4 Wrought 0... ...04 0.65 1. 1 1 1 1 0.01 Wrought Wrought Wrought Wrought Wrought Wrought Wrought Wrought Wrought 0..20-0..06 max 0....25 ...50 0.5 V 9.5 1 1 1 17 13 11.95-1. 0.5-14.3 15.Table 1 (continued) Compositions (wt%) of martensitic stainless steels Mn S Si Cr Mo Ni Other Other Alloy UNS Form C NT-CRSS .90-1...0 16.15 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. 2.50-14.95-1..50 . 1 1 1 1 1 1 0..... 4... ... ..75-0.5 0.20-0.25 W 0..0 14.010 N . .03 ..... 0...... .....35 0.03 0.0 16...3 14 14 4 2 0..4 0....5 Cu 0. .25-2.. .06 max 0..5-14.0 11...50 0.0-18.75 .15 min Se 1...40-0. . . ..03 0.10-0. 0.15-1.03 .00 0.. .... .5 Cu ...05 1.. .40 0.75 0.05 Nominal Nominal Wrought PM 1.4 ... .0-17.50-4..00 11. 0.. .. 0.75 0. .5 1.00 0. 1 1 1 1 1... 0. .0 16...20-0.15 1.....90-1. ...35 0..20 max 0.95 0. ..5 14 14 .0-18. ..50 11...0 V .2 V .40 0. . ...0-18.75 0..75 0.5 0. ..0-18.015 N 0.. .15 max 0.0 16.5 0.. . .5-14..0 10. 12 2 5.01 Nippon Nominal JFE Nominal JFE Nominal S43100 S44002 S44003 S44004 S44020 S44023 Nominal Nominal Nominal Wrought 0.. . ..03 0.040 0.0-18. . 1.20 0..6 4 4 4 .010 N 0.20-0.95-1.00 0.05 1.....04 0.15 max 0... 1 1 1 1 1 3... .50-1..0 11. .60 0. .0 11. .. .60-0..00-12..25 1.....20 0.50-1...5-14...0 16. 0..03 0.0 V 5.75 0.45 Nominal PM 2. .. .30 V KL-12Cr Wrought 0.3 2 5.28 ...00 .. 11 .. .50-12.

Not understanding these alloys can lead to unexpected consequences in mechanical properties or corrosion performance. Further. 2 (Ref 2). The ferritic alloys often have compositions that allow them to be partially martensitic under some conditions. The formation of martensite is essentially mechanical (i. There is regularity to the relationship between the parent austenite and the martensite. Greninger and Troiano determined that the close-packed planes of the austenite {111} varied from the {011} of the martensite by only 0.e. involves a great deal of strain energy that must be taken into account. Martensite Formation Martensite as a phenomenon deserves a brief review. via deformation. about 4%. 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). but they customarily are not and will not be in this work.126 / Stainless Steels for Design Engineers tungsten should also be considered precipitationhardening alloys.. 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. and this can be macroscopically visible as in Fig. The austenite may be supersaturated with carbon or nitrogen. 1. This is shown diagrammatically in Fig.2°. This free-energy differential increases with decreasing temperature. Martensite forms essentially independent of time and the fraction transformed depends only Fig. which accompanies the transformation. The shear and volume expansion. not diffusion). the martensite start temperature Ms. The sum of many such dislocations is shear. but that is not necessary for the transformation. 1 Martensite platelets emerging from the surface. 2 The martensite reaction ab contrasted to the nucleation and growth-type transformation of austenite to ferrite. on temperature. At a certain temperature. Martensite forms as result of the diffusionless transformation of austenite. The composition of the martensite is identical to that of the parent austenite. These relationships define the habit plane that constitutes the austenite martensite boundary. ac . the direction of the <101 bar> of the austenite was only 2. 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. 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. The driving force for the transformation is simply the much lower free energy of the ferrite phase over the austenite phase. Source: Ref 2 Fig. 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.7° from the <1 bar 11 bar> of the martensite. 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.

but above about 0. Indeed. some residual austenite is commonly found between lathes of martensite. above which some δ-ferrite tends to be stable at all temperatures below the melting point. These interstices are considerably smaller in the bcc structure even though it is expanded from the fcc. and Fig.86 A.05%) levels austenite is stable up to about 12% chromium. Figure 7(a) shows that at low-carbon (0.5% chromium to qualify as stainless and even more for better corrosion resistance. the carbon diffuses from these inter- stitial sites and forms various carbides. the untransformed austenite is hindered from transforming by the compression it receives from the already-formed martensite. as shown in Fig. leaving the parent martensite less strained. 4 Strain energy of martensite dependence on carbon content. 3 Change in size of the octahedral interstitial site with the change from face-centered cubic (fcc) to bodycentered cubic (bcc).86 by 3. • It should be fully austenitic at some temperature. 3 (Ref 3). Fig. metastable austenite can readily be transformed to martensite by deformation. the body-centered cubic (bcc) phase becomes preferable energetically. The distortion is accommodated by accommodation from site to site at low carbon levels. • The temperature at which austenite forms on heating should be sufficiently high to permit tempering above the temper embrittlement range. These criteria are somewhat challenging. softer.56 A to 2. 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. and tougher. The amount of distortion is proportional to the amount of carbon in the interstices of the structure. Source: Ref 2 . but this temperature is too low for diffusion transformation. The octahedral sites change from 2.Chapter 9: Martensitic Stainless Steels / 127 This energy differential between ferrite and martensite is stored in the high-strain energy matrix. Source: Ref 2 Fig. 7b) (Ref 3). The carbon is in a state of supersaturation in the as-formed martensite. Thus. but its solubility is lower. 5 (Ref 4) shows how hardness varies with carbon content. Nitrogen behaves similarly to carbon in both austenite and martensite. also raise hardness. Figure 4 shows that the large strain energy in martensite varies with the carbon content. However. and it is less significant as an alloying element accordingly. At the Ms temperature. Applied strains affect the transformation. A stainless martensitic alloy should have the following characteristics: • It must have at least 10. Phase Structure Figure 6(a) to (h) shows a series of photomicrographs of various martensitic alloys (Ref 5). Increasing carbon slightly expands the chromium level at which full austenitization can occur (Fig. When the martensite is tempered.86 by 2. Hydrogen and boron. as interstitials.018% carbon this can no longer be accommodated and a tetragonal distortion occurs (Ref 3).

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

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

°C α+γ 1200 Temperature.6 0. 8 (a) Iron-chromium phase diagram at 12% chromium. chromium and molybdenum. It can be seen that the elements that promote austenite.8 0. with the exception of cobalt. which are ferritizers. %C 1000 800 α + carbide 600 0 0.130 / Stainless Steels for Design Engineers Fig. 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.2 0. 7 Iron-chromium phase diagrams at two low-carbon levels 1800 1800 1600 Liquid 1600 L+α σ α+γ Liquid Temperature. (b) iron-chromium diagram at 17% chromium chromium levels and temperatures at which austenite is stable as is shown in Fig.5 0. °C 1400 γ 1400 γ γ + carbide 1200 1000 γ + carbide 800 α + carbide 600 0 0.9 1.1 0. all depress the Ms temperature.6 0.0 Mass. The coordinated increase in these elements lowers the Ms to such a degree that the .0 Mass.9 1.8 0.4 0. Table 2 quantifies the influences of the various possible alloying elements on the key properties of martensitic stainless steels. %C Fig.1 0.7 0.3 0.7 0. are increased. so must austenitizers such as nickel. This is because as the main corrosion fighters.2 0.4 0.3 0. 9 (Ref 3).5 0.

but more importantly it influences subsequent toughness. those above 0. quenching. 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. so achieving low phosphorus levels depends mainly on restrictions on raw materials for melting.Chapter 9: Martensitic Stainless Steels / 131 alloys become stably austenitic before much higher corrosion resistance is obtained. Obviously. and mechanical properties. should be heated gradually through stage heating to avoid cracking due to thermal stresses.10% per hour. Phosphorus precipitates at prior austenite grain boundaries during tempering with a maximum effect at 475 °C. Since carbon solubility varies strongly with temperature at austenitizing temperatures (Fig. Austenitizing temperature also determines austenite grain size.. This is the infamous temper embrittlement. This limits the use of nickel while encouraging the use of elements like molybdenum. Thermal Processing The main concerns with processing martensitic stainless steels are austenitizing. 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. This loss increases with base carbon level and austenitizing temperature. an example of which is shown in Fig. this would limit one’s ability to temper at a high enough temperature to achieve desired toughness. The carbon potential of the furnace atmosphere must be controlled to avoid potentially serious problems. and annealing. The higher-carbon grades. Carbon or nitrogen pickup could also occur if the atmosphere was rich in these elements.. Soaking at 800 °C until uniform temperature is achieved minimizes this risk. 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 . Another concern during austenitizing is superficial carbon loss. if transforming martensite to austenite during tempering caused subsequent untempered martensite or other undesirable phases. 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. Refining phosphorus from any chromiumcontaining steel is quite challenging thermodynamically. Ms. 7a and b). The ability to temper without austenite reversion is an important trait.20% carbon. Because this is difficult or costly. resulting in much lower surface hardness. If hydrogen atmospheres are used the Influence of alloying elements on ferrite. grain size control is the main tool for controlling temper embrittlement. Heating in air to 1050 °C can cause surface carbon to decrease by approximately 0. Ms. Fig. 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. 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 . 6(e). This affects Ms. tempering/stress relieving.

the previously mentioned phosphorus segregation to prior austenitic grain boundaries occurs. Stress relief without delay would be mandatory. and. 10 Influence of austenite grain size and phosphorus level on toughness danger of embrittlement after quenching must be recognized. which we understand as stress relieving. If the material contains retained austenite. μm Fig. Separately at the 475 °C range. Air hardening is generally sufficient. This effect begins to disappear above 550 °C. there is a slight growth in the number of fine cementite particles and a corresponding decrease in the amount of carbon in solid solution. °C +40 P: 0. carbide precipitation and coarsening. a true precipitation-hardening effect. Avoiding quench cracking and excessive warpage is almost always a greater concern than depth of hardening so air quenching is standard. and tungstenalloyed grades will resist softening during tempering because of the strength of the secondary hardening they undergo due to precipitation . a further precipitation of M2X and M7C3 as well as the transformation of M3C into M7C3 can result in a secondary hardening. it may decompose to ferrite and carbide with a negative effect on toughness.035% P: 0. At 400 °C. This results in a slight decrease in hardness.003-0.132 / Stainless Steels for Design Engineers +120 [ ] +80 [ ] P: 0. and tungsten. The result is a pronounced softening and toughening. Because the quenching and the transformation it causes are inevitably accompanied by residual stresses in a brittle material. the M2X carbide can become the more stable species and be responsible for the secondary hardening. 11 (Ref 6). The microstructural changes at these temperatures are the above-mentioned loss of carbon from solid solution. Heating as-quenched material to between 150 and 400 °C produces stress relieving. vanadium. The high chromium content of these alloys renders them very deep hardening. Pickling should never be done on asquenched material because this could easily result in hydrogen uptake and delayed cracking by hydrogen embrittlement. The hardening reduction with stress relief and tempering for a 12% Cr alloy is shown in Fig. Higher-carbon grades should not even be allowed below room temperature before stress relief. Besides the normal flow on a microscopic scale.047% P: 0. At 500 °C. In the presence of strong carbide-forming alloying elements such as molybdenum. coarser M23C6 and M7C3 begin to grow at grain boundaries. Oil quenching which is faster may be slowed by heating the oil. vanadium. Thus true tempering is conducted above this temperature. of course. stress relieving should be immediate to avoid cracking.004% [ ] 0 [ ] [ ] −40 [ ] −80 5 10 20 50 100 200 Austenite grain size. The molybdenum.021% Transition temperature. This is accompanied by a pronounced softening. stress relief.

The nominal analyses of some prominent grades are shown in Table 3. Nickel seems to amplify this action by its influence on diminishing the solubility of carbon in the matrix. The addition of vanadium and niobium. The basic 12 % Cr martensitic alloy has been the basis of alloying improvements that were done to produce better high-temperature performance. 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.and corrosion-resistant alloys exist. While 420 is the common alloy and is quite serviceable. 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. 12 (Ref 3). further alloying with molybdenum for corrosion resistance and vanadium for hardness of the carbide phase has led to improvements. A high-profile use of martensitic stainless steels is in cutlery. Thus. Hunting knives. which measures the ability to withstand chipping in use. both of which form much more stable carbides than chromium. the tempering of the higher-alloy martensitic stainless steels can truly be considered a precipitation-hardening reaction. 440C was the maximum step up from 420. These alloys are used at very high hardness levels. The higher-carbon. Powder metal techniques . Electroslag remelting (ESR) or vacuum induction melting-vacuum arc remelting (VIM-VAR) provides the cleanliness required. which can be introduced into the matrix in conventional production.Chapter 9: Martensitic Stainless Steels / 133 500 Initial hardness 450 300°C 400 350°C 400°C 300°C 350°C 450°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. sport knives. however. as shown in Fig. Applications High-Temperature Use. 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. This has produced limitations in the amount of highly wear-resistant constituents such as vanadium carbide (hardness Rc 75). much more wear. so cleanliness is very important to toughness. and chefs’ cutting tools are highly valued items and contain some of the most sophisticated martensitic stainless alloys. Tool and Cutlery Alloys. The martensitic alloys have a tendency toward centerline segregation during solidification as well as toward the formation of primary carbides. 11 Influence of tempering on hardness hardening of carbides and nitrides. At one time.

000 tons per year of this product (Ref 7).1V) 4 (0.45 ..0 14..0 14...5 16. .4 1 . 0.... it shows excellent resistance to SCC at high strength levels. 0.... Table 4 lists several such alloys by JFE: the first two can be made to meet L80 specifications and produced as seamless. .15 2.. .. . The addition of nickel and molybdenum yields full austenite and martensite transformation and improves corrosion resistance. .. Low carbon and nitrogen levels give good toughness without tempering and minimize the loss of chromium to carbides.03 0.35 0...000 16 Rupture life.45 2.5 14 14 14 14 17 13 . .0 V ..0-14.. ..05 1.. h Fig..05 1. 9% V.1Nb) 3 10 30 100 300 1000 3000 10..0-18. This has led to the use of low-carbon martensitic stainless steels.2C-10.. 1 1 .2C-10.....1Nb) 3 (0. .2C-10. 4.2C-10.134 / Stainless Steels for Design Engineers 4 50 2 45 40 Applied stress. The third alloy is a near match for the precipitation-hardening stainless Custom 450 (UNS S45000) (Ref 8). ..75 0. Use of stainless can eliminate for corrosion inhibitors in H2S and CO2 environments.... .... 1 1 0.3 0.03 . . ..3 .. Like other precipitation-hardenable steels..... are not subject to the same limitations as continuous casters and have alloys the production of alloys with high volume content of VC.... ..1V-0.4 0.0 V 5.. . .. ...60-0..5 0.. . One such alloy is Crucible CPM 90V with 14% Cr.. 0.. .. .3% C. ... .. ..15 min 0.. maintaining it in solution for corrosion resistance.. ..... 1.. 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 1.03 .2 1 . 0.95-1.5 0.. ..75 4 4 4 4 2 0... 1% Mo.. ... This alloy has equal or better toughness and corrosion resistance as 440C but has ten times the wear resistance at the same macrohardness....5Cr) 2 (0.3 0. Figures 13 and 14 show the improvements in corrosion resistance . and 2.. ..5Cr-0. 12..2 V .. kg/mm2 35 3 30 1 25 20 1 (0.15 1.. ..4116 Nominal S44002 S44004 Nominal Nominal Nominal Nominal Nominal Nominal Nominal Wrought Wrought Wrought Wrought Wrought Wrought Wrought Wrought PM PM PM 0.5Cr-0.5 V 9.. 0.5Cr-0.. JFE reports production of over 100..4 . ... . .15 V ...0-18. The need for corrosion resistance in oil production tubulars has grown as the quality of petroleum deposits has become less optimal.20 1...75 0. Oil Country Tubular Good and Line Pipe.65 0.. 1 . . 0.05 1.0 16. ..

....5 Cu 0. .. ASM Handbook Desk Edition..org/mgo/ 6. 7)... Deshimaru et al.html 3. 13 13 12.. . p 59 2.. Marburger. p 481 4. will cause a great increase in their use.01 0. . M.. Jan 2006. .. D. This does not diminish their importance.. Koistinen.. .. Carbon steels are limited in sour envi- 1.7 12. ISIJ International 1960. Transportation and Storage of Energy. JFE Technical Report (No.” Acta Met.E. K. The stainless can resist this failure mode at higher strengths.. .015 N 0. 1. “High CR Stainless OCTG with High Strength and Superior Corrosion Resistance. Vol 7. Kimura et al... 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). p 28–9 5. 13 Corrosion rates of stainless versus carbon steel ronments to about Rc 22 to avoid SCC by the hydrogen embrittlement mechanism. .. “A General Equation Prescribing the Extent of the Austenite/Martensite Transformation in Pure Iron. .. 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. 1959. 2).03 0...45 2 .5 Cu . ... .ac.. 1993.R. then the strength improvement. These are corrosion resistant and yet meet X70 and X80 class specifications.02 0.. Lower carbon levels permit the use of field welds without tempering so that similar alloys can be used for line pipe. coupled with the orders of magnitude improvement in corrosion resistance. March 2004 p 55–67 8.8 2.45 0. http://www.. p 386–405 7. .. JISI. Vol 195.010 N Fig.J.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. 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.. p 7–13 .5 5. ... Aciers Inoxidables. Paris..01 0.5 . The improvements in martensitic steels for these applications are hardly more than a thorough revisiting of the developments of the 1950s and 1960s. . “Steels for Production.025 0.4 5.. 1985. ...msm.cam.. http://products. S.3 11 12 1 2 1. . Irvine et al.040 N 0.” JFE Technical Report (No..uk/phase-trans/ 2002/martensite. Les Editions de Physique les Ulis. REFERENCES Fig...asminternational.. R. 2 4 5 4.5 Cu 1. .025 0.. Bletton.45 1.010 N 0.. 0. These alloys are the last two in Table 2.4 2 ..

But. with Stainless W (UNS S17600) by U. The workhorse alloys are the martensitic PH grades. This precipitation hardening can also be made to occur in a fully austenitic matrix. although not with the flatness expected from non-PH stainless. The border between the more highly alloyed martensitic stainless steels. The PH grades were developed at the beginning of World War II. In no case is corrosion resistance better than that of normal 304 found in PH stainless steels. The later-developed grades are distinguished from the first by their more uniform. elemental copper. Some authors have astutely treated them as a single group. we treat them separately because they are traditionally considered as separate alloys. www. If cost is a greater concern than corrosion resistance or toughness. 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. 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. or even phosphides.Stainless Steels for Design Engineers Michael F. Primarily used as forgings. Steel generally acknowledged as the first.S. If enhanced strength and very high corrosion resistance are required. then martensitic stainless steels should be considered for applications where strength and hardness over that of annealed ferritic and austenitic stainless is required. and this also provides a commercial PH alloy. and other hot-worked forms. bar. McGuire. and wire and are designed for applications that require extensive forming before hardening. they can be fabricated in a relatively soft state and then hardened with very little dimensional change. which undergo secondary hardening during tempering. In addition.1361/ssde2008p137 Copyright © 2008 ASM International® All rights reserved. nitrides. and the PH alloys is indeed vague. The semiaustenitic alloys are more amenable to production as sheet. p 137-146 DOI: 10. and therefore tougher. they can also be obtained in cold-rolled sheet and strip. Here. or when the higher thermal expansive coefficient of an austenitic material is desired. which are used in many forms. 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. the martensitic PH grades are by far the more common. when a nonmagnetic material is required. 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. strip.asminternational. then the designer should look to duplex stainless steels for the optimal material.org 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. microstructure through the elimination of residual δ-ferrite and retained . This martensite can then be further hardened by the coherent precipitation of intermetallic compounds.

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

fully martensitic at room temperature. even though the matrix is untempered martensite. The complexity of PH steels comes from the processing involved in producing the martensitic structure in which the precipitation will occur.. their unusual combination of high strength plus ductility and toughness in the fully hardened state.. low-carbon (less than 0. 17–7 PH and 17-4 PH. 18 .. if not at room temperature. The inaccuracy of the diagram for more complex systems was overcome. MPa Tensile.g. it is subjected to an aging treatment designated by the aging temperature in Fahrenheit (e. cryogenic treatment. to predict equilibrium phase composition. 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. It is this work hardening that gives the PH alloys. contained up to 10% δ-ferrite stringers. This is accomplished by adding elements that lower the martensite start temperature. a precipitation reaction can still be made to occur by the same type of aging treatment without martensite ever forming. 40 20 70 25 70 60 180 8 25 13 28 . such as ThermoCalc. 48 40 49 48 54 48 54 . molybdenum. to predict the phase composition of alloys that have been homogenized by hot working. Table 1 shows the more significant of these alloys compared on a strength basis. and nickel.. 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 . H-950). Their martensite is a relatively soft. at least at a reasonably attainable subzero temperature..50 12 14 23 10 14 11 13 5 13 14–16 42 41 41 34 47 42 . Table 2 shows Mechanical properties of martensitic precipitation-hardenable alloys UNS Condition Yield. The most advanced PH alloys are martensitic PH grades by Cartech. which caused poor through-thickness toughness. Martensitic Precipitation-Hardenable Stainless Steels The martensitic PH alloys are.Chapter 10: Precipitation-Hardening Stainless Steels / 139 austenite that provides the work-hardening ability in many of these PH alloys.. A second major group of PH grades is the semiaustenitic. Last. This is confusingly called the annealed condition. This would be expected from the Schaeffler-Delong diagram. or condition A. These aging temperatures range from 950 °F (510 °C) to 1150 °F (620 °C). but this is asking too much of the Schaeffler-Delong diagram. if the austenite is made very stable by further alloying additions. such as more chromium. and it has the possibility of superior corrosion resistance because of higher chromium content. and alloys were designed that had minimal δ-ferrite and still transformed entirely to martensite. The austenitic PH strength is better above 750 °F. as stated..05%) martensite as opposed to the higher carbon found in the martensitic stainless steels.. This was done first by trial and error and more recently by using thermodynamic computer models. 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. The early alloys of this type. These steels are supplied in the fully martensitic condition with hardness in the low Rc 30s.. After the material is fabricated.. 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) .. This is balanced by the need to use either cold work. which was developed for welds.. The austenite is more formable than martensite. especially the semiaustenitic ones. 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. The most straightforward alloys are the martensitic.. . Custom 465 and 475. also called the martensitic PH alloys. MPa Elongation. or a destabilizing anneal to cause the matrix to become martensitic before its precipitation aging treatment. % HRC Toughness. These grades in the normally furnished condition A are fully austenitic.

1 0. ...... . 1 2 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 .3 8. .1 17 16 15 13 15 12 12 12 11 10 6... .4 0. The main advancement metallurgically in these alloys from the top. . 0. (c) 17-7 PH displaying ferrite stringers in a martensite matrix..2 0 ..3 V 14 Co Typical microstructures of precipitation-hardenable (PH) stainless steels: (a) 15-5PH as-quenched martensite. P 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.2 3.....2 0..3 0...3 0.... .5 0..2 ..0 Co 1W 0... Figure 2 shows a series of photomicrographs of PH alloys....3 Nb . 0. .. .2 Nb 8. 2 their nominal compositions.. and earliest.2 0...5 2.... (b) 13-8 PH solution treated and aged displaying fine martensite. 1.. 1.. . 0.3 0.6 0.1 ..3 Nb 0.6 0..6 0.8 . 2 0...5 .3 0.. 1. .3 4..5 6 8.5 . Alloy designers found that to .3 4.5 11 11 8 5.. .1 0.. .4 0.. . 3..2 0. ...1 0 0 0 0 0 0 0 0 0. .1 0.... .3 . 1 .6 0.2 0.. ... .5 0. 1 1 5 2 0. (d) 17-7 PH showing residual ferrite stringers and inclusions Fig.. ..2 0.

the higher levels of austenite reduce subsequent mechanical properties after aging. The alloying characteristics of these grades are: • Low carbon. corrosion resistance is compromised. The precipitation hardening mechanism is the precipitation of Mo2C. But. To minimize δ-ferrite requires reducing chromium or molybdenum. Rapid quenching of these alloys is not required. The martensite carries no nitrogen in solution. and full transformation to martensite does not occur. which also reduces corrosion resistance. As a result. But.” 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. Its composition superficially seems deficient in chromium to provide “stainlessness. They are air hardenable. to increase the temperature at which austenite forms. Custom 465 and 475.Chapter 10: Precipitation-Hardening Stainless Steels / 141 reduce δ-ferrite they also tend to stabilize austenite. Last. When this happens. the cooling of these alloys must be completed expeditiously through the final stages of martensite formation with minimal delay. which also happens to reduce the temperature at which martensite forms. MS. 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. It has been established that this hardening mechanism optimizes resistance to stress corrosion cracking (SCC) for a given strength level. so this is viewed as an acceptable compromise. one of the recent alloys designed by computer-assisted thermodynamic calculations. from a utility point of view. nitrogen. Thus. as alloy strength increases. 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. the remaining austenite tends to stabilize. but air melting and argon oxygen decarburization (AOD) refining are quite adequate. The newest alloy is Ferrium S53. these alloys are designed to have maximum mechanical properties with adequate corrosion resistance. barely qualify as stainless with around 11% chromium. so the resistance to pitting is given by: PREN = %Cr + 3. 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 . 4340. 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. no chromium is rendered ineffective by the formation of Cr23C6 since carbon is either held low or stabilized by titanium or niobium. The alloys with the greatest strength potential. 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.3%Mo (Eq 1) In the martensitic PH alloys. It was designed to replace 300M. silicon. The martensitic PH stainless steels obey the same rules as other stainless steels with regard to corrosion resistance. the higher levels of molybdenum reduce the tendency to form secondary austenite during aging. During delays after the start of martensite transformation has occurred. microstructural cleanliness is essential. As with any alloy used at such high strength levels. Corrosion Resistance.

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

4 17 15 17 16 7.Chapter 10: Precipitation-Hardening Stainless Steels / 143 Fig.1 0.. In 17-7 and 15-7.3 4.1 0.8 1 1 .9 0..1 secondary hardening from the tempering of martensite rather than the classic precipitation hardening via precipitation of intermetallic compounds. it is the precipitation of .5 0.. which relies on manipulating the amount of carbon in solution.8 2.1 4. 0 0 0. aluminum rather than titanium is the precipitating agent because titanium would preferentially deplete the alloy of carbon and nitrogen..2 2. 2..1 0.4 0. In AM350 and AM355.3 0.1 7.. .1 0.1 0.5 0. 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 0.3 . precluding the action of the conditioning heat treatment.8 0.3 0.

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

. The mechanical properties can be greatly enhanced by cold working prior to aging. 4 A-286 properties as a function of test temperature.6 0. so aging treatments are typically 16 h.5 26 1. and Fig. 0. 4 shows some typical properties as a function of temperature for a standard 980 °C solution treatment followed by a 720 °C.3 .. effectively ending further development of austenitic PH alloys. Thus. compared to nickel-base PH alloys. unaged condition • High toughness at all temperatures and strength levels • Excellent creep and stress rupture properties • Excellent oxidation. It has slightly .7 Fig. Diffusion. The lower cost of the A-286 alloy.3 3 0.. The toughness of the austenitic matrix is abundant and quite temperature insensitive. The hardening mechanism of A-286 is the precipitation of Ni3 (aluminum.15 . Source: Ref 5 potential to be used to near 700 °C without fear of overaging.05 0. the nickel.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 0.5 0.. The corrosion resistance of A-286 is comparable to that of 304 and 316. is slower in austenite. as is shown in Fig.and cobalt-based superalloys. titanium).04 1. which has the following advantages: • High ductility and therefore high formability in the soft. even at the higher temperatures.5 1. austenitic PH stainless represents a way to strengthen the austenite matrix.15 1. 2. makes it attractive for a variety of aerospace and nonaerospace uses. 5. corrosion. 16 h aging.5 15 14 25. and SCC resistance This alloy is rightly considered an ironbased superalloy and is the root of the group that succeeds it in properties. These last alloys can attain greater strength and creep resistance than A-286. Table 6 gives the typical composition of A-286. Charpy V-notch values of over 60 J are typical from –200 to 800 °C.

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

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

5 0.75–3.00 2.00 2.5–26.5–3.50 1.50 1.0 18.30 0.5 24.0–13.5 0.00 2.00 1.05 N max 2.5–3.04–0.75–2.0–12.0 1.0 12. 0.0 8.0 20.5 19.00 2.6 0.22–0.00 1. 0.5 Cu.0–6.0–21.0 18.2–0.50 2.08 0.0–12.70 1.00–6.5 24.25 N 4.0–12.3 V.0 18.40 0.30 N 3.00 1.0 10.08 0.0–21.35 Nb. 0.10 0.25 N 1.0–12.12 0.50 1.10 0.0 9.00 1.0 1.0–20.15–1.03 0.9–1.5 4.04–0. 0.00 1.0–25.0 4.08 0.0 1.04 0.00 2.03 0.6–4.0–5.0–26.5–3.0–27.50 3.5 5.50 7.50 1.15 0.0 0.20 0.0 9.00 1.5–1.00 2.35 Se 0.20 2.0–9.0 22.0 W.10–0.10–0.50 18.5–30.15–1.2–0.00 1.0 8.0 17.0 2.7 1.30 0.50–1.03 0.04–0.16 0.07 0.24 N 3. 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-30 431.0 11.50 3.5–1.0–26.0 11.10 1.0 9.0–3.75–2.0–15.0 18.3 V 2.0–11.00 1.50 2.30 N 2.50 2.00 1.0 26.03 1.0 22.00 1.0 9.0 1.0–22.5–20.0 22.00 1.10–0.03 0.0 0.00 1.3 Nb.0 16. 0.0 9.0–4.50 1.00 0.5 max 1.2–0.0–7.0 12.50 0.00 1.0–11.08–0.0–30.0 8.0 2.00 2.0–3.0 17.0–4.00 1.0 18.0–8.10 0.50 1.07 1.25 1.25 Cu 1.07 0.20 1.0–13.50 2.00 1.00 1.50 1.2 Cu.5–23.00 1.20–0.50 1.0–7.0–4.50 1.0–21.0–12.0–21.0–18.0–3.20 0.0–13.0–26.5–12.0 8.0–11.00 21.0 4. 0.5–14.00 11.50 1.0 19.50 4.0 6.15–0.00 1.0 0.00 2.0 13.25 2.5–8.0–21.1–0.0 22.0 23.0–21.50 1.75–3.5–1.5 CD-3MN CD-3MCuN 2205 (S32205) 255 (S32550) J92205 J93373 J93380 0.08 0.0–21.0 18.5–4.50 0.00 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 11.28 0.50 0.0–12.00 0.25 2.0 20.5 0.20–0.05–0.025 0.0–30.5–14.50–4.0 8.0–21.0 18.4 0.442 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 0.00 1.50 1.5 15.5–5.0 8.33 N 3.0 18. 0.50 1.5–14.50–1.148 / Stainless Steels for Design Engineers Table 1 Compositions of cast stainless corrosion resisting alloys Composition(a).5–19.25 W.0 1.0 0.2–0.0 22.2–0.0 Cu 0.0 0.5–25.0–12.0 11.0–26.00 1.0 2.00 2.5 6.0 Cu.04 0.0-27.9–1.0-22.0 8.0 Cu 1.50 1.15 0.20–0.5–3. 0.0–8.50 2. 0.0–15.07 0. Source: Ref 1 .25 2.0 17.50 1.0–23.0 6.06 0.4–1.00–9.0 24.0–22.7 24.0 4.5 4.0 12.00 1.0–34.50 1.00 2.0 (10xC)–1.6–6.0 8.40 Ss 0.75–2.5 1.5 24. 0.0 20.0–21.00 0.00 0.0 Cu.12 0.00 24.10–0.20 0.24 N 4.0 2.0–21.8 1.70 1.0 4.25 17-4PH (AISI 630) J92180 CB-7Cu-2 15-5 PH (XM-12) J92110 0.0-26.00 1.06 0.18 N 0.75–6.03 0.05 N max 2.08 0.0 9. 0.50 1.5–3.2 Nb 0.15 1.4–1.0–23.00 1.0–11.00 1.5 11.0–18.65 1.0–11.5–1.0 17.0 3.5–1.40 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 0.35 Nb. 0.0–21.03 0.00 1.0–27.0 max Cu.0–22.50 1.5–13.2–0.06 1.0–15.0 18.18–0.0 10.50 1.50 0.03 0.30 N 1.75–2.00 1.0 19.5–2.06 0.0–3.0–12.0–3.20 N Nb 2.2 Cu.9–3.03 0.30 0.0 6.0 11.00 2.0 0.0 20.25 Cu.5–6. 0.5 23.5–14.50 1.0 23.10 0.9 Cu.0 27.0 18.10 0.50 1.00 14.50 1.0 2.50 0.10–0.0 31.0–3.50 1.08 0.0 9.00 1.50 1.0–15.50 1.0 15.75–2.5–17.7 6.7–6.1–0.0–26.0–16.0–22.50 1.30 N 2.0 3.18–0.5 Nb (a) Balance Fe for all compositions.5 26.5–26.5–14.00 1.0–27.0–21.0–21.0 19.5–5.

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

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 309 310

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

330

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

Alloy

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
Alloy

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

Alloy

Temp

HA HC HD HE HF HH TYPE 1 HH TYPE 2 HI HK HL HN HP HPNb(a) HPNbTi(a) HT HU HW HX

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

4.4

2.0

6.3 0.9

50 18.7

8.0 1.6 8.5 2.6 12.0 2.8 15 5.2

0.9

1.7

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

2.1

... ... 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.
REFERENCES

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, www.iso.org, ISO 13583-2 3. Steel Founders Society of America, online documents: http://www.sfsa.org/sfsa/pubs/ index.html
SELECTED REFERENCE

• http://www.sfsa.org

than does carbon. Melting and Refining The arc furnace is nearly universally used for the first step in the production of stainless steel. www. The end user should. The necessary chromium is added as ferrochromium. widespread engineering materials they are today. chromium. reacts more strongly with the purifying agent. Since the charge materials for stainless steel are typically carbon steel and stainless steel scrap. is thermodynamically very difficult in stainless steel because the essential element. Casting. whose carbon levels range from 0. and powerful hot rolling mills has led to stainless steels of much higher quality produced at lower cost. such as molybdenum and nickel.1361/ssde2008p155 Copyright © 2008 ASM International® All rights reserved. McGuire. and it is seldom beneficial for the end user to specify processing paths. this flexibility allows scrap of all types to be used. was a lengthy process that necessarily involved high chromium losses to the slag as carbon was removed. The advent of AOD. p 155-160 DOI: 10. The carbon content of the heat of steel is roughly 1. which are relatively scarce and expensive commodities. 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. These production methods have undergone a major evolution over the last 50 years and are mainly responsible for stainless steels becoming the practical. Ironically. The fundamental difference is that the basic decarburization step. casting. done in an arc furnace. austenitic alloys.org CHAPTER 12 Melting. which is common to all steel making. be knowledgeable and require the producer to document the process and the producer’s control of it. early stainless steel making. This process was not only very expensive.10%.07% in normal The equilibrium for this reaction is: Ln (K ) = −ΔG 4575T (Eq 2) . and Hot Processing Summary THE PRIMARY PRODUCTION PROCESSES of melting. It is not normal. Union Carbide engineers perfected a method. the previously mentioned AOD process. In the 1960s. Traditional carbon and alloy steel-making methods are not suitable for stainless steels.5% when it is melted and ready to charge into the separate refining vessel. the carbon levels that could be achieved were not much below 0.Stainless Steels for Design Engineers Michael F. whose cost is inversely related to its carbon content. The vast majority of stainless steel is made by arc furnace melting followed by argon oxygen decarburization (AOD) refining and continuous casting.010% in stabilized ferritic alloys to about 0. however. impossible to produce. It is this carbon whose removal is the primary focus of refining. the low processing cost of stainless steel has spurred demand and made some of its ingredients. continuous casting.asminternational. Thus. ladle metallurgy. and hot processing are invisible to the end user. of removing nearly all the carbon from molten stainless steel without significant loss of chromium. The arc furnace is quite flexible in the types of charge materials it can accept. oxygen. even more costly.5 to 2. forcing the cost of many alloys to spike even higher than in earlier years. making most of today’s stainless steels.

sulfur can be readily removed by contact with a basic slag. is often deliberately kept at moderate levels (0.020% or less in ferritic alloys. and welding methods. This is done at a temperature consistent with economic refractory life. stagnant. Phosphorus is an impurity for which no practical removal technology exists in stainless steel. 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. These trade-offs. The injection is done through tubes called tuyeres in the bottom of the barrelshaped vessel. This could be further reduced by aluminum. and CO (Ref 1): Log = %Cr 13. argon or nitrogen. machinability can be improved by calcium additions that produce malleable oxides to replace the deleterious sulfides (see Chapter 15).008 to 0. Titanium.030% in austenitic alloys and 0. although a harmful impurity from a corrosion standpoint. The injection and the reaction cause extremely thorough mixing. should be viewed with skepticism by end users. This is the vacuum oxygen decarburization (VOD) process. Titanium is believed to reduce hot working defects. The choice of which inert gas to use. This mixing not only allows the CO-producing reaction to reach equilibrium. which would never happen in the flat. producing measurable calcium content in the metal. which evolves from the melt. other impurities can be removed from the molten stainless. but also the mixing of the slag and metal also permits desulfurization. which are beneficial to processors. chromium. can be used when required. In both processes. about 0. By increasing the ratio of argon to oxygen in the injected gas as the refining proceeds. on the other hand. 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. Besides carbon and oxygen. 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. such as calcium and magnesium. which are . The thermodynamic activity of aluminum is considerably reduced in iron as chromium levels increase. oxygen to argon/nitrogen.925 log p CO T %C (Eq 3) Thus. Stabilized stainless steels require low carbon and nitrogen levels.156 / Stainless Steels for Design Engineers where K is the equilibrium constant. For example. The ending ratio can be as low as 1 to 9. and G is the Gibbs free energy. Thus. Once the steel has been deoxidized. is the injection of oxygen and argon into the bath to keep the partial pressure of CO (pCO) very low. though. A typical starting ratio is 3 to 1 oxygen to argon/nitrogen by volume.001% in the AOD. The excellent mixing of the slag and metal in the AOD permits this to be done efficiently. whose product integrity is compromised. The key to the AOD process.76 − 0. is enhanced as a deoxidizer in chromium-iron alloys. strong deoxidation with aluminum or titanium can reduce small amounts of calcium from the CaO in the slag. More active deoxidants. Sulfur can be reduced to less than 0. so the more expensive argon must be used. arc furnace bath. but aluminum-based inclusions are generally undesirable.15%+) for machinability (see Chapter 15). Sulfur. increasing the temperature works to increase the elimination of carbon as CO. 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.015%) for tungsten inert gas (TIG) welding penetration (see Chapter 17) and at high levels (0. Any known process to remove it first removes chromium. Also note that even if no intentional addition of metallic calcium is made. The silicon plus the manganese in the steel combine to reduce the oxygen content of the steel to around 100 ppm. is based on cost and final nitrogen content desired. such as laser welding. The VOD process can achieve slightly lower carbon levels but does not achieve cleaner steel as some believe. can be used in many cases to eliminate the need for the weld penetration enhancement of sulfur while increasing welding speeds. for instance.800 =− + 8. and this excellent purity level is commercially furnished without additional price premium. Working through the thermodynamics yields the relationship that summarizes the important relationship among carbon. It is possible to use a vacuum system to keep the partial pressure of CO low when refining with injected oxygen. the carbon is selectively oxidized without concurrent chromium oxidation. it exists in almost all stainless steel at levels close to its normal specification limit. so its role as a deoxidizer is less valuable in stainless steels.

20 . Use of VIM is generally limited to high-value. Heavy metals are eliminated by high-temperature AOD blowing. The refining treatments used for carbon steel and stainless steel are very similar. sulfur.. Using this technique.14 . its presence is tolerated since it has no differential effect over the range in which it is found. Casting. The tapped molten steel generally has excess heat from the highly exothermic refining process.006 –. It should be noted that chromium. Consequently. Alloy adjustment can be done in the AOD or preferably in a treatment-and-transfer ladle. high-purity. but there are subtle differences because of the difference in the thermodynamics of dilute solutions like carbon steel and highly alloyed. and oxygen in stainless steels is significant.01 –. nitrogen.003 . This technique is very effective for the finetuning of reactive elements such as titanium. Remelting Some stainless steels and related alloys are remelted to refine composition or ingot structure. the material to be remelted is cast into a cylindrical electrode and placed inside a cylindrical water-cooled vacuum chamber.01 –. This is a nearly slag-free process. Limited decarburization is possible via injection of oxides such as Fe3O4 or SiO2 to create CO evolution inside the vessel. –.13 . There are two principal remelt processes: vacuum arc remelting (VAR) and electroslag remelting (ESR).07 –.6 –. or low-tonnage melts. The deleterious effects of phosphorus on corrosion are not avoided unless much lower levels are achieved. This can be done very precisely by wire feeding of alloying elements through the slag into the heat.0 .13 .06 . Table 1 shows the factors by which additions of various elements to stainless steel (j) alter the thermodynamic activity of other alloying elements (i).01 .03 –.04 –.01 –.. Equation 4 is used to calculate the activity of elements in steel.11 –.27 –.05 –.01 0. which solidifies in a bottom-up fashion. and the purified drops collect to form a molten pool on top of the starter plate.11 0.005 –.Chapter 12: Melting.01 –. nondilute solutions like stainless steel. and the molten drops fall through the intervening vacuum. Care must be taken not to reintroduce such impurities after refining.05 –. nitrogen. In VAR. 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. which is a risk when using damp or contaminated scrap for coolant. Melt purity is largely controlled by the purity of the starting material.01 .08 .39 . The activity coefficient γ varies with the concentration of alloying element x by: RT lnγ i = RT lnγ i0 + on interstitial solubility. very low carbon levels (less than 50 ppm) are achievable commercially. –.45 –..02 –. has a powerful effect Table 1 Influence of alloying elements on the thermodynamic activity of carbon..04 –. and oxygen J i Al C Cr Mn Mo N Ni O S Si Ti W O N S 0 .06 –. which is always present in nondilute quantities.02 –. This allows the composition to be measured and adjusted before it must be cast. A high-current direct current (dc) arc is established between the electrode and a starter plate at the bottom of the chamber.03 . which can be stirred by argon bubbling via porous plugs. 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. and little refining is possible.03 –.02 –.01 .13 .34 . The shallowness of the molten pool produces a refined grain j =1.53 –. This oxygen precipitates as oxides in the solid state..05 . VAR parameters are adjusted to maintain a shallow pool.01 –.. and Hot Processing / 157 made from a higher percentage of low-phosphorus carbon steel scrap. The end of the electrode is melted. Volatile constituents escape from the molten drops. as is hydrogen. and use of AOD master melt stock for VIM remelting is common.001 .01 . The higher solubility of carbon. Vacuum induction melting (VIM) is another method of melting stainless steels.05 .0 .003 .

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

In powder metallurgy.) can struggle to attain 4.01 in. the low diffusion rates in austenite slow recrystallization so that the steel does not always soften between stands in tandem mills. and lower reductions must be taken than for alloy steels. which if not countered by roll bending or roll shifting schemes can lead to significant variation in thickness across the sheet.). powder technology is also used to produce massive components. Another method of shortcutting the casting/ ingot step has been perfected: the powder metallurgy approach. embedded scale that must be removed from the surface before further processing in most cases.5-mm (0. not to have to be duplicated among many stands. Then. 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.5 mm (0. 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. typically a fourhigh reversing rougher rolls slabs to about 3-cm (1. Chapter 9 on martensitic alloys discusses these materials.2-in. Ferritic stainless steels are extremely easy to hot roll since they have a soft. avoiding most of the costly machining steps. In either case. the refined molten metal is atomized by gas or liquid and made to freeze into small particles. which permits energy-saving hot charging of slabs. such as roll shifting. the transfer band is rolled to final gauge on a separate reversing four-high finishing mill with coil boxes to preserve temperature. In hot Steckel mills. are quite homogeneous. it seems unlikely that strip casting will soon become a major factor even if it is perfected technically. Coil boxes (on reversing mills) address this problem to a degree by permitting the semirolled coil to equalize in temperature. In both cases. For example. Traditional powder metallurgy production methods are used to make small near-net shape components. Some alloys can be cold rolled in the “black band” state at a cost of coarser surface finish and greater rolling mill roll wear. 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. as much as 0. or roll bending. although rolling stainless on hot tandem mills used primarily for carbon steel can be an excellent production method.06 in. Hot Rolling Hot rolling remains an essential process for the vast majority of stainless steel used.25 mm (0. the hot-rolled band must then be annealed and pickled since the as-rolled hot-rolled band . 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 increases mill loads.) thickness for 316 stainless. 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. Furthermore. This permits the melt shop and caster to be adjacent to the hot mill. roll crossing. 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.18-in. having been quenched extremely rapidly. This is the same justification for using Sendzimir mills to cold roll stainless. singlephase structure at hot rolling temperatures. The high separating forces on the hot rolling mill stands also cause greater roll deflection and compression. Hot rolling characteristics of stainless steels vary greatly. Austenitic stainless steels have high strength at hot rolling temperatures. 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.Chapter 12: Melting. 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. the logic applies more to austenitic alloys than to the easily rolled ferritic stainless alloys. and Hot Processing / 159 number of such machines in pilot or limited production. They have not had sufficient commercial or technical success to have become a factor in the industry. The microstructure during hot rolling is the crucial factor. These particles. the hot-rolled band carries a heavy. Powerful hot strip tandem mills that routinely roll carbon steel to 1. If normal cold rolling or use as hot-rolled coil is foreseen. Casting.) thick. Hot Steckel mills have become the favored method of hot rolling stainless steel because their throughput better matches stainless steel melt shop production outputs. More impressively.

1977. 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. This poor hot ductility manifests itself as “slivers. and cold rolling processes. REFERENCE 1. etc. The latter alloys reject sulfur and oxygen during solidification and slab reheating to the grain boundaries. as well as slab surface working in the caster pinch rolls. D. a skid mark from a slab-heating furnace will remain through the hot rolling. They arise from many causes and are manifest prima- rily as edge cracks and slivers. Hot ductility defects are more subtle.M. Thus. poor mechanical properties. digs. These tendencies are fought by low oxygen and sulfur levels and minimal slab-reheating temperatures and times. This is true of all hot mill scratches. But. Rolling stainless requires a different mindset than rolling carbon steel. residual cold work and hardness variations. 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. Edge cracks are simply a lack of ductility at the colder strip edge.160 / Stainless Steels for Design Engineers has poor corrosion resistance. The most inherently challenging alloys for hot working are the duplex alloys and the alloys that solidify in the fully austenitic state. 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). Bernstein. annealing. McGraw-Hill. Inclusion-related defects are all essentially avoidable by using state-of-the-art technology. and many factors can affect the size of that window depending on alloy type. They do have repercussions on delivery. which argues against the benefits of rolling stainless on a mill built and primarily used for carbon steel. These are seldom seen by the end user because they are removed when they are not prevented. where they form very weak films. Peckner and I.” which can require grinding of the entire hot band surface. which facilitates diffusion of sulfur and oxygen to the grain boundaries and also encourages very large grains. Stainless hot ductility often has a narrow temperature window. gouges. 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. The former has a mixed-phase structure. Defects Stainless steel hot-rolled bands can contain many types of defects. and the phases can exhibit mechanical incompatibility at certain temperatures. Handbook of Stainless Steels. Sometimes. p 3–13 . as well as a heavy oxide layer.

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

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

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

then using stabilized or low-carbon grades is indicated. the metal matrix becomes significantly depleted of chromium (Ref 4). so that residual stresses may be relieved by creep. and even alloys like 317. One hour at 900 °C (1650 °F) reduces residual stress by about 85%. . can be eliminated by stress relieving at around 350 °C (660 °F) for 2 h. stainless surfaces should be scrupulously clean before annealing. which while done commonly. Newer alloys have higher nitrogen contents to suppress formation of sigma and other deleterious inter- metallic phases. Vacuum or inert gas is preferable to hydrogen for alloys containing stable oxide formers such as aluminum or titanium or for alloys containing boron. which renders this stabilizing unnecessary. where the postanneal pickling attacks the different oxide more strongly. Sigma forms initially because solidification segregation causes local enrichment of sigma-promoting elements. Stabilizing anneals are sometimes conducted on stabilized alloys such as 321 and 347. Austenitic stainless steels heated in air. A second anneal at lower temperature. They are commonly stress relieved at temperatures slightly below the annealing temperature. More stringent levels may be required if mirror finishes are desired. If vacuum is used. and annealing times should be generous. If forced air or water quenching are impractical or if section size prohibits rapid cooling. about 900 °C (1650 °F). Cool down must be rapid as oxidation potential increases as temperature decreases. of course. This requires aggressive pickling. Current preferred practice for these alloys is to maintain carbon and nitrogen below 0. Lower temperatures require exponentially longer times for the same stress relief. which arises from the easy mobility of dislocations. so it must not only be redissolved. which provides the thermal energy for dislocation interactions to lock into place. or inert gas atmospheres may be used. This Bauschinger effect. then is done to permit the carbon to combine with the stabilizing element rather than leaving it available to form chromium carbides. This produces a sharp yield point without premature nonproportional elastic deformation. Cold-worked austenitic stainless steels have a markedly diminished proportional limit. If this is not done. hydrogen. with times doubling for each 100 °C (180 °F) decrement as decreasing diffusion rates. may not be practical for many stainless users. This latter sigma forms at grain boundaries and will cause embrittlement and reduced corrosion resistance. Carbonaceous materials left on the surface are even more objectionable because they can cause carburization and subsequent loss of corrosion resistance.3 Pa). which can cause etched spots on the surface. not only must any oxide be removed. chromium. which can cause distortion or lead to stress corrosion cracking in service. form oxide scales. This is useful when carbon levels are sufficiently high that significant dissociation of carbides occurs at annealing temperatures. it should be less than 2 × 10–3 torr (0. Beneath this oxide.164 / Stainless Steels for Design Engineers Atmospheres for annealing are important. Last. If an inert gas or hydrogen is used. the higher ends of the annealing ranges are recommended. so must the chromium-depleted layer. such as molybdenum. but also the alloy must be homogenized to remove the residual concentration gradients from the sigma. Even hard water deposits can cause differential oxide growth. The chromium-depleted zone.03% for corrosionresistant service. and the use of lowernitrogen alloys should be reexamined and questioned if specified. Superaustenitic stainless steels. present a special problem because these alloys have significant sigma-forming tendencies. It can also form from slow cooling of slabs or hot bands. are encountered. vacuum.and molybdenum-depleted regions will still exist. particularly in compression. So. Alloys used for high-temperature service benefit from the creep-resisting contributions of higher carbon levels. The dew point must be –40 °C (–40 °F) or lower. For this reason. Stress Relieving Austenitic stainless steel weldments often contain residual stresses. To avoid oxide scale formation.). Use of high-chromium andmolybdenum alloys without enhanced nitrogen is no longer recommended. often more than 5% lower in chromium and to a depth of as much as 10 µ (395 µin. Austenitic alloys that are subject to sensitization must be cooled rapidly enough from annealing temperatures to avoid carbide precipitation during cooling. does pickle rapidly precisely because it does have less chromium. however. which govern creep. the key consideration is moisture content. and sigma will re-form much more rapidly during subsequent exposure to high temperatures.

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

The nickel-bearing alloys have such high hardenability that annealing in the critical range cannot produce softening by any practical cooling rate. Martensitic alloys are put into the annealed condition for processing before they are quenched and tempered for their final use. Lowtemperature heat treatment runs the risk of α' formation and is best avoided. such as the 440 group.B. The principles of heat treatment of the two alloy categories are the same. Other additions like vanadium. The traditional martensitic stainless steels are iron/chromium/carbon alloys. nickel. If other constituents. Austenitizing Table 3 lists the austenitizing and tempering ranges for martensitic stainless steels. Forging and hot working should always be followed by annealing to avoid stress cracking due to the deep hardening of these alloys. exist during the austenitizing heat treatment before quenching. in fact. This is a characteristic of the so-called super 12Cr alloys. the more economic subcritical anneal is the predominant annealing heat treatment. high range. full subcritical annealing is required. they will not transform to martensite. low range. o C (oF) Austenitizing. and/or molybdenum and low carbon. 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) .166 / Stainless Steels for Design Engineers Stress relieving is rarely a concern for any type of ferritic stainless. alloys have been developed for petroleum applications that contain high copper. then only subcritical annealing is feasible.C F. simpler to heat treat because their low carbon and nitrogen levels alleviate the need to temper. C>0.403 Ni/Mo. Thus. and subcritical annealing of these alloys becomes a slow. Martensitic Stainless Steels The martensitic stainless steels resemble the unstabilized ferritic stainless steels described. Only austenite transforms to martensite. The martensitic stainless steels form essentially 100% austenite on heating and have very high hardenability. 425. oC (oF) Tempering.20 440A. Temperatures for this are listed in Table 3. The more highly alloyed newer alloys are.20. so their ability to be softened by annealing is limited. so subcritical annealing is always recommended for these alloys. Full austenitizing is crucial to producing a microstructure that is fully martensitic. Stabilized grades have no need for postweld heat treatment. and if they are. and tungsten promote secondary hardening and tempering resistance. that Table 3 Alloy martensite cannot be avoided by furnace cooling from austenitic temperatures. Soaking Hot working should be carried out in the austenitic range. which directly determines strength and corrosion Recommended annealing. as in the nickel-containing grades. 416. But. o C (oF) Full anneal. C<0. 410. 415. austenitizing. Fig. More recently. Annealing Martensitic stainless steels can be annealed by subcritical anneal and sometimes by full anneal depending on alloy level. 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. 9.20. 414. o C (oF) Tempering. C<0. molybdenum. If the alloy level is such. and tempering temperatures for martensitic alloys Subcritical anneal. have enough carbon that the austenitizing temperature determines how much carbon is put into solution. Nickel reduces the temperature at which austenite is stable as shown in Chapter 9. such as δ ferrite or carbides. sometimes with a small amount of nickel and/or molybdenum. 431. Unstabilized grades should not be welded. even for nickel-free alloys the hardenability is so great that annealing by slow cooling is quite difficult. Some alloys. The carbon in solution in the austenite will become the carbon level in the martensite. oC (oF) Straight Cr. difficult process.

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

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

. air cool to RT for 30 min Cold reduce 955 °C (1750 °F) 10 min... 730–760 °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. . The higher the temperature of the conditioning. room temperature. oil/water quench 900 °C 120 min.. .. 180 min at –75 °C 930 °C for 90 min. 760 °C (1400 °F). air cool.... oil/water quench 900 °C 120 min. 930 °C for 90 min. air cool 1065 °C for 30 min. chill to –75 °C for 8 h .. . air cool 930 °C for 90 min... The heat treatment scheme just described would be condition A-1400. RT. oil or air cool below 15 °C 1035 °C 30 min. air cool 1065 °C for 30 min. water quench 980 °C for 1 h. air cool.. This material. . air cool –75 °C 8 h –75 °C 8 h .. air cool 1065 °C for 30 min.. 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. . 180 min at –75 °C 930 °C for 90 min. 730 °C 16 h 730 °C 16 h. air cool... air cool. xxx °F for 180 min 440–470 °C for 180 min 540–590 °C for 180 min .. The martensitic transformation finishes (Mf) near room temperature. .. water quench 830 °C for 1 h. . chill to –75 °C for 8 h 760 °C (1400 °F) 90 min... 760 °C (1400 °F).. oil/water quench PH... 450–540 °C 180 min . . oil or air cool below 15 °C 925 °C 15 min.. . the less carbon is precipitated and the lower the resulting Ms. oil/water quench 980 °C 120 min. Cold reduce 955 °C (1750 °F) 10 min. . 90 min. 15-7 A T C R THxxx CHxxx RHxxx 1065 °C for 30 min. ered sensitization. air cool 930 °C for 90 min. .. air cool 925 °C 1 h.. oil or air cool below 15 °C 1035 °C 30 min.... 275 475 A RHxxx Hxxx A Hxxx A Hxxx A Hxxx A Hxxx A Hxxx A Hxxx 925 °C 15 min. . air cool 1065 °C for 30 min. xxx °F for 4 h xxx °F for 4 h xxx °F for 4 h . –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. . oil or air cool below 15 °C 1035 °C 30 min. .. air cool. would be said to be condition T. water quench 1035 °C for 1 h. 730–760 °C 180 min . cool rapidly 925 °C 1 h.. after quenching to room temperature... oil/water quench 980 °C 120 min. precipitation-hardenable. 180 min at –75 °C 930 °C for 90 min. air cool. oil or air cool below 15 °C 1035 °C for 1 h. 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 ... 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). 730–760 °C 180 min 930 °C for 90 min. 180 min at –75 °C 930 °C for 90 min. water quench 830 °C for 1 h.. oil or air cool below 15 °C 925 °C 15 min.. xxx °F for 180 min ...... This process is called austenite conditioning. oil or air cool below 15 °C 1035 °C 30 min.. air cool 1065 °C for 30 min. The highest conditioning temperatures of 955 °C (1750 °F) cause a sufficiently .. 930 °C for 90 min. air cool 1065 °C for 30 min. air cool. air cool. cool rapidly 980 °C for 1 h. The carbide precipitation occurs at the interfaces of the small amount of residual ferrite these alloys have and also at grain boundaries.. air cool.

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

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

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

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

8 26. This diagram shows the locus of failure under varying strain states.91 1.92 1. then a material may be considered isotropic. true strain curve and is called n. the ratio of the diameter of a disc to that of the deepest cylinder into which it can be drawn. the ratio is about 1.49 1. the best-performing deepdrawing stainless steels are low interstitial ferritic steels with boron added. mm Conical cup value.Chapter 14: Forming / 175 bead contour. The measure of anisotropy is the Lankford ratio (Ref 2).2 compared to 2.9 12.5 Table 1 Steel and 2. such as cost and material performance in service must be factored in. Figure 2 shows the LDR as a function of the Lankford ratio. and the anisotropy. Figure 3 shows a comparison of the FLDs for austenitic stainless steel and carbon steel.01 2.94 0. the Lankford ratio equals the ratio of the lateral strain to the through-thickness strain during the tensile test of a sheet specimen.67 1.79 1.21 0. % Hardness HV Lankford value n value ro r45 r90 r ¯ Erichsen value.60 1. developed by Keeler and Backofen (Ref 5). R determines the average depth (that is.50 0.8 9.0 are more common. A number of stainless steels are compared in Table 1 (Ref 4). The ability to be deep drawn is measured by the limiting drawing ratio (LDR). the wall height) of the deepest draw possible.7 28. Indeed.24 0.9 26. The FLD tells Fig. lubrication. but values between 1.22 0. N/mm2 Elongation.44 1. are certainly reservoirs of knowledge of current practice. When this expression equals 1.8 64.5 9. die radii.07 1.83 1.7 8. the work hardening rate.) may be more important than material properties in determining whether the desired part can be made successfully. the material properties are the same for all crystallographic orientations. some tests are not good predictors of deep-drawing performance.0 for 304.77 0. The producing mills.90 1.5 37. The ferritic stainless steels in sheet form have LDRs of around 2. For austenitic steel.8 9. deep-drawn component. Optimizing the material/drawn component combination is far from simple. r45 is the strain ratio measured at 45° to the rolling direction (of the sheet metal-forming operation).5 26. The most widely used summary of a material’s formability is contained in its forming limit diagram (FLD). r0 is the strain ratio in the longitudinal direction.8 34. expressed as: r0 + 2r45 + r90 4 R= (Eq 1) where R is the average strain ratio. As the value increases from 1.21 0.11 l.0. it can be greater than 2.7 26. It shows that when comparing different types of materials. while for flat-rolled carbon steel and ferritic stainless steel.0 . while not necessarily exhaustive sources of information. Source: Ref 3 Deep-drawing materials comparison 0. End users are encouraged to deal directly with the producing mill early in the design stage of any new highproduction.2% proof stress.51 0. It should noted that the very ductile 304 fares no better than carbon steel because of the advantage of a beneficial anisotropy.63 1. etc. which is the instantaneous slope of the true stress.0 173 135 137 116 159 172 0.5 27. blank size.19 2. 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. 2 Limiting drawing ratio variations with Lankford ratio.12 2.83 1. N/mm1 Tensile strength. and r90 is the strain ratio in the transverse direction.8 34.03 9. The material properties that are important to formability are ductility. as measured by tensile test elongation. especially when other considerations.76 1.0. As a first approximation. which the ferrous bcc structure has.66 1.2 31.20 0.47 1. the drawability increases because the material tends to maintain a constant thickness while changing shape from a flat blank to a cup shape. that is.10 2.

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 comes with a cost penalty as the easiest way to improve formability is to increase the nickel level. compares to the already highly evolved 409. Another is to use the least-expensive alloy. Even such minor process changes as blank temperature variations due to ambient temperature can alter work-hardening rates enough to cause breakage problems. although replacing the expensive nickel with copper or manganese. HSF. the preferable alloys are the leaner austenitics. this can occur when designs push the . 3 Forming limit diagram of carbon steel compared to austenitic stainless steel.176 / Stainless Steels for Design Engineers Fig. The specific alloy composition is often finely tuned for a given part and tooling design. Certainly. high-strength ferritic. yet beneficially anisotropic. making them an optimal material for objects such as sinks. austenitic stainless steel. HAS. Figure 5 shows how the FLD of an enhanced 409 ferritic stainless steel. highstrength ferritic stainless steel. This has been accomplished by reducing the total interstitial content (i. This gives 201 and 301 the ability to redistribute deformation from thinning areas elsewhere and stretch extensively. These alloys form martensite more rapidly than do 304 and 305 during stretching. There has been much research to develop ferritic stainless alloys with improved formability. fully recrystallized. high-strength austenitic. Figure 4 shows generalized FLDs for austenitic. There are various drivers that cause this. carbon plus nitrogen) and by thermomechanical working to give a fine-grained. has been shown to be effective. Quite often. F. which is the precursor of failure. 201 and 301. Source: Ref 3 Forming limit diagrams for categories of stainless steels. high-strength austenitic stainless steel. Since tooling is costly. 409 Ultra Form. and duplex stainless steels. ferritic stainless steel. 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. These diagrams are generated by examining circle grids printed on material that is deformed to failure in various modes. maximum drawability is obtained by low work-hardening rates coupled with maximum elongation. The single most important value on the curve is the intersection of the curve with the major strain axis at zero minor strain. 4 Fig. as exemplified by 305 and high-nickel 304. Many austenitic components are made by stretched deep drawing. A. This can be used as an index of formability and is the elongation possible for plane strain conditions. ferritic. For austenitic stainless steel. FA(50). In some industries. and small deviati ons can dramatically increase breakage rates. designers push component design to the limit of a material’s ability to be formed. Martensite has a 4% greater volume than the austenite from which it forms and a much greater strength. In this case. microstructure. Deep drawing of components is seen as a way to obtain near-net shape. 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. There is much more variety within the families of stainless steel than within carbon steel. such as the household appliance industry. One is to eliminate extra operations or components by consolidating them into one more complex deep-drawn part. ferritic-austenitic stainless steel. it is necessarily a high-volume application.e. as in 204Cu.

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

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

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

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

or days. Maintaining tolerances: How long can the machining operation continue before adjustments are made? 10. From a more focused viewpoint. Machining. and long products all are frequently machined. Some of the variables can affect the appearance of the material. Rather than attempt to understand all aspects of machining. Fig. in itself. 1 The 5 M’s of machinability . 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. a better understanding of the metal itself is advantageous. or day? 4. hours. Consistency: Does the material machinability stay the same when bundles are changed? 2. Any change in one of these sectors can change the behavior or efficiency of a machining job. while others affect the performance of the piece. making machining an art as well as a science.asminternational. that is. Cycle time: How fast can a part be completed? 6. McGuire. methods. The incorporation of complex oxides has led to the development of materials that allow higher machining speeds and increased productivities. Tool life/wear: How long does the tool last in the machining operation? This could be minutes. www. it is helpful to consider a material’s machinability. plate. machine.1361/ssde2008p181 Copyright © 2008 ASM International® All rights reserved. shift. Productivity: How many parts were made in an hour. Optimum machinability is obtained when each of these sectors come together. Minimal operator intervention: Does the operator need to constantly adjust setup? Introduction Stainless steel forgings. In Fig. the machinability of a material is further described by: 1. Chip control: Are the chips manageable? 8. 3. shifts. material. Maximum cutting speed: How fast can the part be cut without affecting tool life? 9. Surface finish: How smooth or shiny is the part? 7. is a complex topic with many variables.Stainless Steels for Design Engineers Michael F. Cost per part: What is the cost of the final geometry? 5. Technology in the production of a more machinable stainless steel is advancing. a macroview shows how the machinability of a material is influenced by the interaction of humans. providing the best possible conditions for efficient machining. both of which are reducing machining costs and keeping shops competitive. castings. its ability to be machined and the factors that affect its ability to be machined. and management. p 181-191 DOI: 10. 1.org CHAPTER 15 Machining Summary MACHINING STAINLESS STEELS is a complex operation. Not only does a shop need the correct supporting equipment and supplies.

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

duplex 314.020 . thus creating hotter cutting conditions.007 0.150 0.015 0.020 . It is best known as a free-machining contributor that promotes better tool life and greater machining speeds..300 0.030 0. 0.015 0. M42(b) T15.300 0..020 CC-7 CC-6 CC-6 .030 M2. 436. M42(b) T15. and the wear on tools increases.020 0.. 502(c) 175-225 Annealed 0.007 0. CC-7 CC-6 CC-6 .015 0.007 0.040 0.300 155 125 100 80 145 115 90 70 95 75 60 65 50 40 0.020 0.. 2507 295-310 Annealed Martensitic and PH steels 403. 135-185 Annealed 302.. Source: Ref 1 (a) Caution: check horsepower requirements on heavier depths of cut. CC-3 CC-3 CC-2 . Nickel also increases elevated temperature mechanical properties. 500 425 325 . M33. 310S. M3 M2. 202.. (c) Free machining versions. CC-7 CC-6 CC-6 . material Brazed Indexable ipr AISI fpm ipr grade grade Material Condition Ferritic steels 405...300 0. 308. M3 M2. such as duplex and 200 series alloys. M3 M2. M3 M2.030 0.007 0. 309. 850 550 450 . 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. (b) Any premium high-speed steel (T15.007 0.015 0.007 0.015 0. 225-275 Cold drawn or 310.. Copper improves ductility and reduces the strain-hardening or work-hardening rate (with the exception of participation-hardening alloys. for which copper is used as the precipitant). 420..007 0.015 0.150 0.030 0. 316.007 0. M41–M47). 347. Sulfur reduces mechanical and corrosion properties and can be a cause of hot cracking in the resulfurized grades. M3 M2.015 0.020 0.. 301. 135-185 Annealed 430.007 0..020 0. Nickel increases the toughness and ductility of stainless and reduces the work hardening rate.. M3 M2. M3 M2.030 0. as.015 0.. M3 M2..020 . .. the amount of carbide increases.020 0.040 0. M3 T15. 429.015 0. 304. In high-manganese grades. M3 M2. Molybdenum increases the strength and elevated temperature mechanical properties. however. 0.015 0. Chips can be more difficult to break. 384.625 0.040 0. 385(c) 2205. Speed. ipr Speed.625 0...300 0. 321.. M3 M2. in.007 0.150 0. M3 M2.040 0. Nickel will have a tendency toward increased BUE..020 0. 305.015 0. manganese has the same relative effect as nickel when used in greater amounts. material Speed.015 0.625 0. M3 T15.030 0. 446(c) Austenitic and duplex steels 201.020 M2. 309S. This increase in hot hardness and strength means more energy will be needed to cut the material.007 0. 302B. fpm Coated Tool Tool Tool material Feed.007 0. 700 450 375 475 300 250 0. M3 M2. fpm Feed.030 0. CC-7 CC-6 CC-6 CC-7 CC-6 CC-6 PH.030 0.015 0.007 0. M42(b) T15.007 0.Chapter 15: Machining / 183 Table 1 Machining setup recommendations for turning wrought stainless steels Uncoated High-speed steel tool Hardness.. better tool life will generally result.007 0. 434. 442. CC-3 CC-3 CC-2 .020 0.007 0.015 0.040 0. 501. This causes chips to be more difficult to break. M42(b) T15. While the molybdenum helps in chip breakability. annealed 316L. 330.015 0.015 0. 409.015 0. Feed.020 0.150 0.. M42(b) T15. 425 350 275 .. in the 200 series stainless steels. M42(b) T15.150 0.015 0... 304L. 348. which increases the tendency of BUE and promotes better tool life.020 .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 . 0. the structure changes to martensitic.015 0.020 . 317..150 0. 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 .040 0. 410.625 150(235) 120(190) 95(150) 75(115) 95 75 60 45 80 65 50 40 0..020 0.007 0.300 0.040 0. 0.040 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.. for instance. 135-175 Annealed 422. precipitation-hardenable..007 0.040 0. M42(b) T15.040 0. Manganese is generally added to combine with sulfur to form manganese sulfide (MnS)..030 0.150 0.007 0.007 0. M42(b) T15.015 0. which acts as a self-lubricant and improves machinability.300 0. it will require more rigid setups and will reduce tool life. M3 M2.015 0. HB Depth of cut(a).007 0.625 0.020 0. 275-325 Quenched and tempered 375-425 Quenched and tempered 0.

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

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

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

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

steelmakers have known that injecting calcium into the melt converts refractory inclusions into soft. These manganese sulfide inclusions become exposed on the surface of the bar and become initiation sites for pitting corrosion. malleable. but the hole left behind by the sulfide becomes a collection site for contaminants.15%. 430FR. 347. sulfur is a major negative factor for corrosion resistance. Grades in this group include 316/316L. Further processing of these materials can induce cracking even further. corrosion resistance. 4 Effect of sulfur on stainless machinability. Source: Ref 2 on the sulfur additions. the higher the sulfur.188 / Stainless Steels for Design Engineers Fig. Since the 1900s. Outokumpu’s Prodec materials. among others.15% are considered resulfurized grades. It is well documented that sulfides negatively affect corrosion resistance and mechanical properties of stainless steels. The grades in the third group include 303. The beneficial effects of sulfur are undeniable. This has led steel producers to look at other inclusion systems for a viscoplastic inclusion without the negative effects of sulfur. and 430.35%. The second group has sulfur contents ranging from 0. since these films are low strength. With these stress risers in place.25 to 0. or mechanical properties are more important than machinability. Oxides The basic machinability-enhancing agent discussed thus far has been sulfur. any cold deformation can lead to cracking along the sulfide stringers. This group of stainless steels still holds corrosion resistance. 321. The benefits of sulfur to improve machinability outweigh the losses due to defective parts. This has led to the development of alternative methods of improving machinability. weldability. For these stainless steels. with some grades reaching 0. but the amount of sulfur is not the grading criterion. at least from the machinist’s viewpoint. Sandvik’s Sanmac materials. 430F. Despite these deficiencies. Sulfur increases the hot shortness of materials during hot-forming operations.4570. and the higher the strain produce a high probability for a crack to initiate. Sulfur hurts corrosion resistance by locally depleting chromium from the matrix to precipitate as a sulfide. 304/304L. The question of performance of the finished component is another issue. they may induce the formation of microcracks brought on by solidification shrinkage stresses. and mechanical properties as critical but has the advantage of increased machinability. 420F. The third group with sulfur levels у0. many duplex and super stainless grades. for the end user. Sulfides in stainless steels have a dark side. Sulfur levels are generally 0. the smaller the bar. which lead to reduced mechanical properties in notch-sensitive alloys. Manganese sulfides form stress risers within the material. the sulfides found in stainless steels are very effective in improving machinability. Product offerings include Ugitech’s Ugima and Ugima XL (Ugima 2) materials.010%. Grades in this group are 316LVM and other remelted stainless grades. leading to poor processing yields. where contact forces are very high.030%. complex oxides that act as freemachining agents with high-temperature lubricating capabilities. especially when sulfur levels exceed 0. Passivation of the components will help. Hot workability is also hurt by sulfides.010 to 0. especially in the transverse direction. A fourth group of grades can be included in this classification. This is where mills will rebalance chemistries and processing to enhance machinability beyond what the first three groups offer to create enhanced machining grades. especially in austenitics.45%. Figure 5 shows that small amounts of calcium can greatly increase tool life. sulfur content is limited to 0. Sulfur tends to form segregated films with low melting points during solidification. These calciumbased oxide formulations have been commer- . 1. and others. which concerns the end user. but the detrimental effect is equally evident. a susceptibility to longitudinal cracking can become an issue. 410. As the amount of sulfides increases in stainless steels. Other sulfide inclusions that form on the grain boundaries contribute to intergranular corrosion. And. and Carpenter’s Project 70+ materials. In the first group. As a general rule. The oxide inclusion chemistry is based on the CaO-Al2O3-SiO2 system. welding.

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

High-Speed Tool Steels. sharp cutting tools. the Ugima oxide is a discontinuity and will aid in chip breakage.4570 and is sold under the trade name 303 Ugima UX (4570 Ugima in Europe).025% sulfur level. VB30/0. Machining tests at Ugitech and many field experiences have shown increases in machining performance of 30% with the addition of 1. Courtesy of Ugitech . Fig. the contribution toward machinability flattens and possibly decreases.3. as seen in Fig. The vertical axis. However. As shown. Tooling and Coolants The machining of stainless steels can be much more complicated than for other materials.8% copper to a 303 stainless steel with the Ugima oxide. manganese sulfide eventually loses its lubricity. Data generated at Ugitech as well as data generated by other producers have shown that once sulfur content reaches 0.3 mm of tool wear in 30 min. which seems to contradict the experience of many machine shops. Ugitech has seen synergistic effects with copper additions as well.30%. the chip is shearing along complex oxide stringers. 8. represents 0. the combination of sulfur and the Ugima oxide extends the machinability range for sulfur levels beyond 0. helping the chip break. 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. and optimum lubrication type and amounts are very important. 9 Comparison of 304L chips with and without the Ugima oxide. As machining speeds increase. Machine and tool rigidity. Like sulfur. and the oxide acts as a high-temperature lubricant that will allow faster machining speeds without the need to use specialized tooling. machine power requirements.4 to 1. Tool lubrication is only one function the complex oxide performs. 8 Comparison of machinability of AISI 303 at different sulfur levels with and without the Ugima oxide. The cutting tools themselves are the main variable other than the Fig. Further additions of copper up to 4% have exhibited even better machining performance.190 / Stainless Steels for Design Engineers ing agent. The grade chemistry meets EN 1.30%. Figure 9 exhibits cross-sectional photomicrographs of 304L chips with a 0.

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

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

The rate of NO2 formation increases at higher temperatures. It has been shown that the HNO3 can be eliminated and replaced by hydrogen peroxide (H2O2). Because contamination is “on” the surface of stainless rather than “in” the surface as is the case with many materials. for example. Electrolytic pickling is commonly used in the production of cold-rolled stainless. Bath temperatures are generally 150 °F (65 °C). pickling can be considered a deliberately imposed corrosion process. Simply removing the scale mechanically may be insufficient if only the oxide is removed and the compromised (depleted) metal surface is left. HNO3 concentrations are normally from 10 to 25%. The NO2 (nitrogen dioxide) produced during the reduction of the HNO3 (oxidation of the metal) is visibly brown-red. lead to environmental problems as hexavalent chromium compounds are toxic and heavily regulated. simply using the cleaning agent appropriate for * Kolene is a registered trademark of Kolene Corporation. Both treatments convert the trivalent chromium to hexavalent form. however. and this leads to “ditching” of the grain boundaries during pickling. Pickling involves both scale dissolution and metal dissolution.” This smut must be physically removed or dissolved by subsequent HF/HNO3 pickling. This is the proprietary. as seen on two-dimensional flat-rolled material. or electrolytic conversion treatments such as electrolytic sodium sulfate. All stainless has slightly greater oxidation in the grain boundaries when it is oxidized. Their use may. allowing for easy scale dissolution. makes such scale hard to remove. The H+ ions are produced by the polarization instead of by an acid. HF concentrations can vary from 1% for light scales to 8% for maximum aggressiveness and difficult-to-pickle alloys.* a molten mixture of nitrate salt and hydroxide. typically found in oxide scale. and less-controllable. making it more easily removed by subsequent pickling. The attack of H2SO4 on the base metal can be severe. Higher temperatures cause excessive HF evaporation and can also lead to visible emission of nitrogen oxides. The rate of pickling decreases rapidly as iron builds up in the bath. 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. oxidizing treatments such as Kolene. 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. action.194 / Stainless Steels for Design Engineers used as a preliminary pickling because of its aggressive. so neutral solutions can be used. Typical concentrations for H2SO4 pickling are 8 to 15% by weight. 14% sodium nitrate. Cleaning Stainless steel is very resistant to chemicals of many kinds. . and undissolved constituents can remain on the surface as “smut. Thus. The low solubility of trivalent chromium (Cr+3). and 1% sodium chloride bath. Nearly all the action of pickling derives from undercutting of the oxide scale and dissolution of the chromium-depleted layer. Thus. Use of strong acids and complexing agents is required to get pickling to occur at an economically acceptable rate. 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. patented UG3P process developed by Ugine (Ref 1) or Henckel’s “CleanOx” process. It is also vital that this layer be removed as it diminishes the corrosion resistance of the surface. The HF/HNO3 pickling is carried out between 120 and 140 °F (50 and 60 °C). Hexavalent chromium (Cr+6) is much more readily soluble in aqueous solutions. resulting in the matte appearance of a pickled surface. sensitized material will undergo grain boundary attack if pickled. This process uses alternating positive and negative polarization in baths using sulfates or nitrates. and the bath must be replaced for efficient pickling. Pickling may be assisted by prior treatment of the scale in molten 85% sodium hydroxide (NaOH). permitting it to be cleaned by many aggressive agents. The scale formed during hot rolling may be an embedded scale with a minimal chromiumdepleted layer beneath the scale. Metal removal rates are proportional to the chromium level.

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

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

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

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

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

• There are thermodynamically metastable conditions due to the low diffusion rates in the face-centered cubic (fcc) matrix. 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. 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. • There is increased microsegregation in the fusion zone with increasing alloy content. • The possible formation of chromium carbides in the heat-affected zone (HAZ) can cause susceptibility to grain boundary corrosion (sensitization).asminternational. it is complex in theory and practice. Knowledge of each aspect is required for the process to be designed and executed properly. 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 older method of preventing sensitization is to stabilize the alloys with titanium. The welding process must. The main objective is to show how standard welding technology is correctly applied to stainless steels. which can localize the heating. or with niobium. It does not form refractory oxides that would diminish weld soundness.1361/ssde2008p201 Copyright © 2008 ASM International® All rights reserved. This chapter gives a basis for understanding the influence of alloy composition and metallurgy on the welding process.org CHAPTER 17 Welding NEARLY ALL WELDING of stainless steel is done by end users or processors. which must be protected. McGuire. less than 0. which is what makes it stainless. thus increasing the potential for residual stress and therefore hot cracking. resulting in reduced corrosion resistance unless this layer is removed. so that: 1. It stays in solution as a corrosion-resisting element. toughness.04%. • Surface oxidation during welding depletes chromium in all types of stainless steel from the underlying surface. corrosion resistance. of course. This chapter does not attempt to teach welding. must be protected from oxidation. which must be respected as a process that combines melting. for the intended service conditions. • The possible precipitation of intermetallic phases in the HAZ can lower toughness and corrosion resistance. 2. The foremost special consideration of welding stainless steel as opposed to carbon steel is that the chromium in stainless steel. This prevents rapid precipitation by reducing the supersaturation of carbon. The . as in type 321. etc. • Stainless steels contain readily oxidized chromium. and thermal processing. refining. 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. 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. www. Like thermal processing. This is foolproof only if carbon levels are low. as in 347.Stainless Steels for Design Engineers Michael F.

Another serious threat posed by thermal stresses is hot cracking. This diagram has an arbitrary cooling rate resembling that of tungsten inert gas (TIG. 1.06 in. The Schaeffler diagram has been improved by the Welding Research Council’s adoption of the modification shown in Fig. retain some ferrite at room temperature. zinc.202 / Stainless Steels for Design Engineers recombine successfully with titanium during cooling. This is avoided only in thin-gauge (>1. 0.03%) unstabilized alloys must be annealed after welding to redissolve chromium carbides if the cooling was sufficiently slow for the carbides to have formed.5 mm. if present. it strongly rejects sulfur to the intergranular areas. normally between 3 and 10%. When austenite freezes. Source: Ref 1 . such as phosphorus. as with laser welding. 1 The Schaeffler diagram. a useful empirical mapping of weld metal phase composition shown in Fig. which does not reject the sulfur. Fortunately. This is not harmful since the ferrite is richer in chromium and in molybdenum. most 321 and 347 are produced with carbon levels below 0. This weakness occurs when the steel solidifies in an austenitic mode.) material or when the HAZ is drastically reduced. Welds of less highly alloyed austenitics. This approach is highly effective but cannot be used for some highly alloyed grades with compositions that do not permit a ferritic solidification mode. and copper. which super- Fig. oxygen. In such alloys. forcing it to precipitate as sulfide inclusions within the grains. which are balanced to freeze in a ferritic mode. sulfur and other contaminants. permitting a thin zone of sensitization called knife-line attack. tends to make austenitic welds less ferritic and has the opposite effect in duplex alloys. 2. The high thermal expansion of austenitic stainless steel can cause high residual stress around welds. The higher carbon-stabilized alloys and the high-carbon (>0. The amount of ferrite expected can be measured by magnetic devices and estimated from the Schaeffler diagram. generally those with less than 20% chromium. Very rapid cooling. where it forms weak films.03%. must be excluded from the weld zone. This is solved by balancing the composition so that alloys solidify first as ferrite. 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. described in a separate section of this chapter) welds. 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. which may require annealing to eliminate. as in laser welding.

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

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

6 kJ/cm (Eq 3) The light gauges ensure sufficiently short times at high temperature that precipitation of . these alloys are only rarely seen with minimum section size of more than 3 mm (0. and these are not generally available commercially. • The grades more highly alloyed with chromium and molybdenum can form α' and σ. more slowly than can be done in welds.6 kJ/cm (Eq 2) and D = 75 × E – 350 above 6. the required titanium level is Ti > 0. However. The stabilized group should not be exposed to nitrogen. successful welding is simplified to making a sound. If for some reason they must be used and welded.Chapter 17: Welding / 205 Duplex stainless steels. which is very brittle. This issue concerns the HAZ. 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. which must dwell in σ-forming temperatures for some period of time. this can be achieved by limiting heat input to less than 6 kJ/cm. Ferritic stainless steels can be split into two groups for purposes of welding: the older semiferritic group and the more prevalent stabilized ferritic group. Thus. Unless they are cooled extremely slowly. rendering the alloys ferritic at all temperatures. 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. The stabilized ferritic stainless steels are commonly welded. This is discussed in detail in Chapter 8 on ferritic stainless steels. In the fusion zone. 434. The first group. While the technical remedy for this is simply annealing. 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. in which chromium is between 16 and 18% with carbon up to 0. excessively low heat inputs can result in fusion zones that are predominantly ferritic. 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.6 for up to 6.6 (Eq 1) In the HAZ. Because of the low toughness these alloys have in large cross sections. the austenite transforms to martensite. the relationship is: D = 206 × E – 585. At the other extreme. The salient metallurgical characteristics for welding of the two groups are: • Both groups offer good thermal conductivity and low thermal expansion. then the techniques for welding martensitic stainless steels should be employed. it is: D = 29.) and normally have sections less than 2 mm (0. The reason is that the welds are invariably partially martensitic and thus normally brittle. with a resultant loss of toughness and corrosion resistance. An empirical relationship between grain diameter D and heat input E (kJ/cm) has been reported (Ref 2). It is rare to see any welding more extensive than spot welding of unexposed surfaces with these alloys.20 + 4(C + N). which requires annealing to eliminate.08 + 8(C + N). These are empirical relationships that take into account that some titanium oxidizes before it can stabilize carbon and nitrogen. Niobium can replace some titanium.11 in. heat inputs that are too high lead to the formation of embrittling intermetallic phases. Only very specially controlled compositions of 430 can be welded successfully.08 in.6 × E – 50. • The semiferritic group will form martensite. For 409. which otherwise would cause the formation of the high-temperature austenite. In practice. The semiferritic alloys such as 430. Postweld stress relief is not needed for duplex weldments and indeed could be harmful because of the danger of embrittlement. • Both groups require protection from oxidation by shielding gases.). The levels of stabilizing elements required to prevent austenite formation and sensitization are well known and are reflected in the alloys’ chemistry specifications. can tolerate relatively high heat inputs since these factors determine the stress intensity that will be generated by thermal gradients. leading to embrittlement.08%. well-shielded weld without producing excessive grain growth in the HAZ. • The stabilized group can lose toughness via excessive grain growth. and 436 are seldom welded and often called unweldable. These alloys form appreciable amounts of austenite when heated above 800 °C (1470 °F). it is seldom economically viable. while the requirement for the higher chromium 439 is 0. is exemplified by the alloy 430.

crevices. The considerations in welding them are: • Shielding must be sufficient to prevent loss of oxidizable alloying elements such as titanium. Such alloys include duplex. It has been determined that there exists an optimum level of titanium around 0. • Filler metal must match the base metal if like properties are required. distortion may be encountered. Obviously. Table 1 summarizes the major metallurgically important parameters for the various types of stainless alloys. the major challenge they present is avoiding the potential cracking. such as 309L. For all normal uses of martensitic stainless steels. For low carbon levels. • Postweld heat treatment solution annealing must be adequate to homogenize weld solidification segregation. aluminum. The problem becomes more severe with increasing carbon level because the transformation takes place at lower temperatures in more brittle material. because these alloys are designed for extreme mechanical performance. chromium.30%. If mechanical requirements permit. Last.206 / Stainless Steels for Design Engineers intermetallic phases should not be a concern. or prominences. any heat treatment to achieve the properties of which these alloys are capable must be a final step. the desired approach is to start with a well-tempered or annealed material and then preheat and maintain high interpass temperatures. These alloys are easily welded and not prone to cracking or developing embrittling phases. those of low-alloy stabilized ferritic stainless steels with regard to cleanliness and shielding.10 to over 0. below 0. which ensures this minimum transition temperature (Ref 3). Material Selection and Performance Stainless alloys that are prone to precipitation of intermetallic phases require special prewelding consideration. Since this transformation cannot be avoided. Their carbon content ranges from 0. Especially in the superferritics. it is essential to preserve their correct chemistry by shielding with a fully inert gas mixture. and superaustenitic alloys. Martensitic stainless steels vary little in alloy content. Aside from the cracking consideration. Any amount of time for which these alloys have been exposed to temperatures at which inter- . The soft joint may deform to accommodate thermal strains and thus minimize weld cracking. 300 °C (570 °F). can be used. a final heat treatment is required to achieve the quenched and tempered properties for which these alloys are designed. Even with preheating. But. then austenitic filler. If mechanical properties equal to that of the base metal are not required in the weld. martensitic welding considerations are similar to. The impact properties of ferritic stainless steels are always a concern because their transition temperature can become elevated to ambient levels. 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. while very complex metallurgically. preheat can be omitted. ranging from 11 to 18% chromium with small amounts of nickel and molybdenum. are straightforward from a welding perspective. which is even more readily oxidized than chromium. dual stabilization with titanium and niobium as well as not having excessive heat input are the best way to ensure weld toughness. • The high aluminum or titanium contents of many PH alloys cause their welds to be “slaggy. preheating to 250 °C (480 °F) is advised and for higher carbon levels. precipitation-hardening (PH) stainless steels. Thus. of course. Because it is difficult to have low enough carbon plus nitrogen to stabilize at this titanium level. especially in superferritic alloys. Precipitation-Hardening Stainless Steels.10 and 0. • Austenitic PH grades are fully austenitic and subject to hot short cracking. which is most likely to occur in the HAZ from stresses caused by the austenite-to-martensite transformation on cooling.” and these slaggy welds have are irregular with objectionable recesses. Likewise.20% carbon. and. but less stringent than. 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. but between 0. superferritic. even though they can form. the use of austenitic (309L) weld filler metal should be considered. oxygen must be rigorously avoided because it will quickly deplete the essential titanium. Extraordinary surface cleaning at and near the weld will pay dividends in final quality.10%.10%.

... . 309L 420.... . 316Ti 321. Austenitic stainless steels that are intended for autogenous welding are often specified with elevated sulfur levels. 20–40 301. . Slow cool Anneal .a. 19-D 2205 25 Cr duplex 2507 superduplex Same as base alloy 20–40 Ar+2% O2. Unfortunately. 309L.. 316L 29-4C 2209 2209 25Cr-10Ni-4Mo-N 25Cr-10Ni-4Mo-N 20–40 20–40 6. which causes a decreased surface tension toward the hotter center of the pool.. 310 310 316L. 308L 308L 309.5 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 22. the pipe purchaser cannot know if the pipe has had a sufficient anneal... accurate knowledge of material history is vital.. use of lower nitrogen alloys would not be prudent engineering practice. . Full solution anneal 430..5%Ar+2.5%Ar+2. shooting the hottest metal to the bottom of the weld pool. This effect exploits the temperature-dependent surface concentration of sulfur in the weld pool.5 CO2 Ar+2% O2.. . 675.5%Ar+2. as shown in Fig. He+7.015%.. 308. 309L. Ar/3% CO2/2% H2 He+7. 309L 309 Mo L 410L.5%Ar+2.. None or full anneal no . . He+7.5 CO2 Ar+2% O2.5 CO2 Ar+2% O2... . n. 304 304L 309 310 316L. 4. He+7. 2101. . 100 oC . This decrease in corrosion resistance can only be eliminated by a long anneal. . 310 440. The effect on corrosion resistance is less desirable since the abundant MnS inclusions that result from the higher sulfur levels decrease pitting resistance. 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.. . Likewise. 308. 309L 439L.5%Ar+2. . 347 Superaustenitic 308. .a. n.5%Ar+2. Full solution anneal 410. causing the molten pool to flow toward the center on the surface and then flow downward.5 CO2 Argon/helium 250oC 250 oC 250 oC no 250 oC min 250 oC min .. 302. variations within specification of nitrogen content influence the time it takes intermetallic phases to form......5%Ar+2.. He+7. 2304. 308.... He+7.... .005 to 0.... . which is a good thing... This speeds welding and minimizes weld and HAZ width... 310 Same as base metal 20–40 20–40 20–40 20–40 Ar+2% O2. Once a welding procedure is qualified for an alloy with given nitrogen content. .0 5–25 5–25 5–25 5-25 Ar+2% O2.5 CO2 Ar+2% O2. 317L 347. 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.. n. 276 Same Same Same Same Same Same 16 PH grades Martensitic 410 420 440 Supermartensiic Ferritic 430 434 409 439 Superferritic 2003... This is done to improve weld penetration through the so-called Marangoni effect.5%Ar+2.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 .. 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..0 6.0 6. on the order of 0.. 308.. 50 oC . He+7... Thus. .a.5 CO2 Ar+2% O2. .

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

. 6 Joint designs.. .....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 ... Gas flows..5–3 1. It is helpful to incorporate a highfrequency circuit to aid in establishing the arc. mm (in. GTAW. ideally until temperatures cool to below oxidation temperatures... For manual GTAW using a filler wire.) Gap d. the shielding gas precludes the need for coatings. SMAW. SAW.. 55–65 60–70 60–70 60 55–65 60–70 80 10–15 10–15 10–15 ..... Thoriated electrodes containing 1.. must be adequate to prevent air infiltration by aspiration or turbulence before arc contact. usually 12 to 18 L/min.A. the wire should be fed continuously into the weld pool. . 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.. . submerged arc welding.. . technique. The weld pool exposes a great deal of surface area to the atmosphere in a very turbulent manner. If consumable electrodes are used. gas metal arc welding. 1–2 1–2 1–2 1–2 2–3 1–2 2–3 1–2 . .) Root K. Courtesy Ugine S.. The shielding gas must replicate the controlled gas mixtures used to refine stainless steel and establish the original composition. shielded metal arc welding Fig. 1–2 1–2 1–2 5 1–3 1–3 3–5 1–3 1–3 3–5 . mm (in... 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. gas tungsten arc welding.. Moving the tip of the wire in and out of the protection of the gas shield is especially .2% thoria are recommended because they have better emissive properties and provide better arc stability at higher currents. 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.Chapter 17: Welding / 209 Groove Process Thickness th. Intermittent wire addition can lead to creation of zones of essentially autogenous weld. . . .7 to 2.) 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. negating many of the benefits of filler metal addition..

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

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

Corrosion. 1993. Chiba. Int’l Conf on Stainless Steel. issues associated with solute redistribution are eliminated. 37. This makes welding of these alloys much more foolproof than with the early duplex alloys. etc. 1991.D. Welding of Stainless Steels. Kotecki. ISIJ 4. p 786 5.212 / Stainless Steels for Design Engineers the express purpose of use in the as-welded condition. REFERENCES 1. Les Editions de Physiques. Stainless Steels. Brazing. p 178 . A.. 1992. the lean duplex alloys have very delayed precipitation of intermetallic phases because of their higher nitrogen and lower chromium and molybdenum contents. The friction stir welding (FSW) process offers the promise of reliable solid-state joining. Washko and J. laserassisted GMA or GTA welding. S. Welding. so girth welds in the field are possible. The low carbon makes welds of this material that are tough and do not require tempering.F. The relatively low temperatures involved essentially eliminate generation of weld fume (see the discussion of safety). Vol 6. The dual-stabilized ferritic alloys have tougher welds than those stabilized with only titanium or niobium. Likewise. Other new welding processes. ASM Handbook. promise greater productivity. such as S31803. Feen. B. Sheet Metal Ind.J. 1. New developments in welding also have an impact on stainless steels. 1981. p 28–34 3. By avoiding melting and resolidification. Garner. 1983. Aziez and R. p 677–707 2. and Soldering. ASM International. Proc. such as multiple (GTA or GMA) torch welding. Grubb. D.

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

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

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

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

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

“Standard Test Method for Specular Gloss”). These are American Society for Testing and Materials (ASTM) designations for abrasively produced finishes. 3 has a surface roughness average (Ra) of 0.218 / Stainless Steels for Design Engineers Fig.4 to 0.4 in. and 8. 3. where the discovery of .8 µm (15 to 30 µin. (a) Rolled-in low-glare finish (InvariMatte). 8 finish. Courtesy of Outokumpu Special finishes for 304/304L and 316/316L stainless steels available from one manufacturer. (c) Rolled-in moderate-glare finish (InvariLux). 4. Finish No. Source: Ref 7. The greatest consistency of appearance comes from specifying a brand of rolled-on finish from a given manufacturer. Finish No. only the method of producing them. Finish No. 4 finish (InvariBlend). 7 The classic abrasively produced finishes are No.) in length. Specular gloss at 85° is typically 40 to 60 (per ASTM D 523. No. 3 calls for 80 to 100 grit abrasive. coil to coil. with grit lines typically 1 cm (0.). Source: Contrarian Metal Resources (Ref 8) Fig. 6 Various rolled-on stainless steel finishes. This is crucial in architecture. which are traditionally produced by abrading the surface with different grit size abrasives. There is considerable difference in appearance from sheet to sheet. 4 calls for 120 to 150 grit abrasive. 8 is a mirror finish obtained by final polishing with 800 grit abrasive. 3 and 4 are directional. Finishes No. and manufacturer to manufacturer. The standards for appearance do not exist within specifications. Any of the traditional finishes can be replicated by a rolled-on finish with greater uniformity. (b) Rolled-in no. with the possible exception of bright annealed having a difficult time matching the mirror quality of a No.

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

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

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

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

“Which Stainless Steel Should Be Specified for Exterior Applications?” International Molybdenum Association. Corrosion: Environments and In- 7. Atmospheric Corrosion.l-v.metalresources. Corrosion in Marine Atmospheres. European Confederation of Iron and Steel Industries. 2. 2005. org. John Wiley and Sons. Release of Chromium.metalresources..net.org.H. 10. accessed June 2008 The Nickel Institute. accessed June 2008 Care and Maintenance of Stainless Steels.info. www.com.euro-inox. 1985. accessed June 2008 D. accessed June 2008. Houska. p 42–60 Guide to Stainless Steel Finishes. Leda-Vannaclip. 3rd ed. 8.nickelinstitute. Nickel and Iron from Stainless Steel Exposed Under Atmospheric Conditions and the Environmental Interaction of These Metals. ASM Handbook. accessed June 2008 . org. Griffin. p 51 6. Euro Inox. p 3–12 3. 2006.Chapter 18: Architecture and Construction / 223 REFERENCES 1. Ed. ASM International. accessed June 2008 5. accessed June 2008 4. W. imoa. 9. Oct 2004. Berggren et al. dustries. www. accessed June 2008 Contrarian Metal Resources. Stainless Steel Selection Criteria.. 11. Contrarian Metal Resources. H. C. www. Bulletin of the National Dairy Federation 189. Guttman. Vol 13C. Ailor. www.au. www. www. Atmospheric and Weathering Factors in Corrosion Testing. www. R. org. The Nickel Institute.eurofer.nickelinstitute. net.B.. 1982. www.

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

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

Table 1 lists a number of the grades of stainless steel commonly used in exhaust systems and where they are used. dual-stabilized T439) 436S (T436S) 441 (DIN 1. T441) 433 (T443) 304/304L (UNS S30400. The alloys are listed in order of increasing severity of the requirements for each major system component. formability Flexible pipe 600–800 1110–1470 Catalytic converter shell 600–800 1110–1470 • • • • • • • High-temperature • strength. . • formability. T441) 433 (T443) Front pipe 600–800 1110–1470 High-temperature strength.4509) 304/304L/304H (UNS S30400. 18CrCb) 444 (UNS S44400. dual-stabilized T409) 409 ALMZ (aluminized 409) T439HP (UNS S43035. S30403) Tailpipe 100–400 210–750 Corrosion resistance. dual-stabilized 439) 18CrCb (DIN 1.4509) 436S (type 436S) 444 (UNS S44400. 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. formability • • • • • • • • • • • T439HP (UNS S43035. thermal fatigue strength.4509. thermal fatigue strength. thermal • fatigue strength. from inner and outer surface • • • • • • • • • • • • • • 409HP (UNS S40930.4509) 18CrCb (DIN 1. Risk of such damage is due to the intermittent use of vehicles.4509. from inner and outer surface • 409HP (UNS S40930. S30403) T321 (S32100) 316/316L (S31600/S31603) 316Ti (S31635) 332Mo (S35125) 625 (N06625) 409HP (UNS S40930. dual-stabilized T409) • 409 ALMZ (aluminized 409) Source: Adapted from Allegheny Technologies Inc. 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. salt • attack resistance. S30403. T441) 433 (T443) 409HP (UNS S40930. • oxidation resistance. dual-stabilized 439) 18CrCb (DIN 1. salt • attack resistance • High-temperature • strength. oxidation resistance. 18CrCb) Type 304/304L (UNS S30400. dual-stabilized T409) 409 ALMZ (aluminized 409) T439HP (UNS S43035. There are numerous alloying approaches for optimizing the ferritic stainless alTable 1 Component loys for spalling resistance.4509.4509. dual-stabilized 409) T439HP (UNS S43035. S30409) 321 (UNS S32100) 309S (UNS S30908) 310S (UNS S31008) 332Mo (S35125) 600 (N06600) 601 (N06601) 625 (N06625) 409 ALMZ (aluminized 409) T439HP (UNS S43035.4509. 18CrCb) 444 (UNS S44400. • formability • • • Oxidation resistance. which causes cyclic oxidation and the ensuing spalling of the oxide scale. the exhaust manifold must possess the greatest resistance to high-temperature oxidation damage. 18CrCb) 441 (DIN 1. dual-stabilized 439) 441 (DIN 1.4509) 18CrCb (DIN 1.4509) 18CrCb (DIN 1.Chapter 19: Automotive and Transportation Applications / 227 As the highest-temperature component of the exhaust system. All approaches involve raising chromium content but use different techniques to enhance the effect of chromium. common name (related designation) High-temperature strength. 18CrCb) 441 (DIN 1. oxidation resistance. dual-stabilized T439) 441 (DIN 1.

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

giving not only a very high work-hardening rate but extraordinary resistance to localized thinning. or its low-nickel counterpart 201.4 8.58 1. or aircraft aluminum alloys..e. 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.3 38. Across the board. The value of a material as an energy-absorbing structure (i.8 9. all of which are more expensive. then this characteristic makes 301. 201 and 301. those that most easily transform to martensite during deformation) is shown in Fig. but this characteristic would be insufficient in many cases without considering mechanical properties.9 17 18. it has become the standard material for seat belt anchors and hose clamps. J/m3 Toughness. MPa Uniform elongation. and TRIP steels (Ref 1). more varied applications for stainless in automotive engineering. the main distinguishing trait of stainless that qualifies it as the optimal material is its corrosion resistance. mm 0.2% proof strength.9 59. energy-absorbing components since austenitic stainless can be rivaled for such applications only by heat-treated alloy steel. safety. less durable. % Carbon steels TRIP 700 DP 750 DP 800 Austenitic stainless steels HyTens X HT 1000 Source: Ref 1 1.536 1.48 1.44 473 513 573 703 811 896 818 920 976 16. In this higher-strength condition.131 1.9 1. aluminum falls far short of austenitic stainless in energy absorption per unit weight.Chapter 19: Automotive and Transportation Applications / 229 Structural Components The driving forces of durability. dual-phase steels.e. or less formable.6 Table 3 Comparison of resilience and toughness of carbon steels and stainless steels for automobile structural components Type Resilience.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). one that enhances crash worthiness) is measured by the energy it can absorb per unit of mass. Austenitic stainless steels are the toughest and stiffest practical materials available to the automotive engineers. Even with its lower density. Indeed. and therefore fracture. j/m3 Carbon steels TRIP 700 DP 750 DP 800 Austenitic stainless steels HyTens X HyTens 1000 Source: Ref 1 0..32 105 101 74 0. titanium. When crash worthiness becomes a prime consideration. This allows it to transform at a known rate to martensite during deformation. its superior strength and toughness would qualify it for many automotive applications. 1. Table 2 Comparison of tensile properties of carbon steels and stainless steels for automobile structural components Type Thickness. MPa True stress at ultimate tensile strength. MPa Ultimate tensile strength.16 1. 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.996 1. % Total elongation. even if stainless steel were not corrosion resistant. 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.5 28. and weight reduction have spawned other. necking. an ideal material for structural.55 306 639 937 1068 1429 1377 52. The superiority of metastable stainless steels (i.726 364 269 .

but the initial cost of the bus was lower. which allowed strong.” as it were. Another manufacturer. if the entire system is stainless and the investment is avoided. the question of when doing so is a better engineering decision involves economic considerations. then the initial cost of a stainless body actually can be lower than one in coated carbon steel. engineered various components of austenitic stainless steel into its otherwise aluminum-intensive A6 series. The economic analysis is shown in Table 4 (Ref 2). The use of stainless steel in strategic components enables greater weight reduction than that which the vehicle would have in all aluminum. The design key was to use rectangular 304 stainless structural tubing. 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. .230 / Stainless Steels for Design Engineers Fig. Now. The incremental savings of eliminating coatings on individual body components is thus essentially nil. Audi. not only was the long-term cost of operating the bus lower. Volvo and Saab have designed austenitic stainless steel bumper systems that also serve to reduce overall vehicle weight. This swung the economic pendulum to stainless in a major way. and the virtual elimination of body maintenance. Now. coating and painting could be eliminated. 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). Large automotive companies generally have large fixed investments in painting and coating systems to protect entire bodies from corrosion. 2. and lower rear wishbones in its Carrera GT. While it is probably apparent to the reader that essentially any body component can be made in stainless and be made better in stainless. who began in the 1980s using 304 stainless steel in buses. Porsche uses austenitic stainless steel for front and rear side members. the accompanying savings in fuel consumption. stiff sections to be welded into space frames. This is the experience of Italian bus manufacturers. 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. internal push rods on front and rear axles. A stainless bus body is shown in Fig. Some components in which these virtues are most readily exploited are bumper systems (Ref 2). However. buses are 80% stainless. With essentially the entire body now in stainless. 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.

These considerations combine to make stainless the best material for many of their components. led in the United States by the state of California. while tanks may also be 316L for corrosion resistance when the transported material requires it.448 2. The engineering basis for this is the same as for buses: high strength. Structural members in trailers are typically 304.838 0 0 0 0 0 30.0 day U. $ 101 U. which reach maximum load at a volume limit rather than a weight maximum.0 years 1.897 57 0 4.00% 5.322 2. no coating costs.838 10.402 36. This weight reduction would directly translate into greater load-carrying capacity because the payload of liquid-carrying trailers is limited by total gross weight. lined carbon steel tanks are now largely obsolete. Their economy of operation is also a major attraction. have made manufacturers reexamine the suitability of polymeric fuel tanks.391 28. Trailers used for hauling foodstuffs or corrosive materials are now constructed almost entirely of stainless steel. These tanks contribute more to the required maximum 2 g/day of hydrocarbon emissions than is tolerable. Other Automotive Components Stringent emissions controls regulations. 2 Stainless steel bus bodies.185 30.76% 20. These vehicles are prized for their ability to be driven and parked in very small or congested locations.023 1. which would permit major weight reduction. Tank wrappers are often made of bright annealed and buffed 304.050 32. such as Volkswagen. Normal cargo-carrying trailers also use some stainless where corrosion is problematic. $/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. Trucks Over-the-road trailers are an excellent example of stainless steel being used for utilitarian purposes.Chapter 19: Automotive and Transportation Applications / 231 Microcars are now a familiar sight in Europe.582 4.00% 4.S. such as in doors and door frames.331 25. Figure 3 shows a stainless steel microcar frame. The ability to add a few thousand more pounds of payload would quickly pay back a small premium in material cost. have installed stainless steel fuel tanks in their vehicles (Ref 2). Weight reduction is less important in these trailers. so a Fig. and a product with long life and low maintenance costs.425 . 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. Manufacturers of trailers would be well advised to consider upgrading to duplex grades such as 2003 or 2205 or to cold-worked austenitic stainless.S. few manufacturers.

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

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

This film acts as a barrier to corrosion. is the spontaneous passive film.3 μg/g in cereals to 1. the 6Mo alloys. These sample steels were subjected to boiling solutions of oils.234 / Stainless Steels for Design Engineers Stainless steel contains many constituent elements.4 4. Were they to enter the food with which the stainless came in contact. These negligible levels of leaching simply indicate that foodstuffs are a benign chemical to stainless steel.71 0. which can have 15% salt.12 ≤ 0. which is so stable chemically.12 Source: Ref 1 .300 7. So. which would result in metal release.9 ≤ 0. releases less than 0.12 ≤ 0.3 8. both of which are permissible. The distinguishing characteristic of stainless.3 8.12 ≤ 0. Carbon steel releases iron at over 100 mg/cm3 in the same period. types 304. In food production. 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 0.6 4. alcohols.9 18. more extreme levels of acidity and salinity can be encountered. however.12 0.22 0.160 15. must withstand prolonged contact at 45 °C (115 °F).7 24.12 ≤ 0.22 ≤ 0. and 444. Choosing the proper grade of stainless. No increase was noted from the natu- rally occurring level of up to 0.1 ppm level (Ref 2).12 ≤ 0.12 ≤ 0. that had both industrial finishes (2B and BA) as well as freshly abraded and air-aged finishes. are projected to last 20 years before pitting.40 0. This having been said.12 ≤ 0.6 6. None caused the transfer of either chromium or nickel to exceed the statutory 0. and 3% acetic acid.12 0.58 12.000 0. 316 stainless pits in about 1 day. 439. This is significant because only pitting corrosion is likely to release metals ions into a food substance. and temperature.010 mg/cm3 of iron.87 0. while higher alloy grades. 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 2.42 5.22 0.1 μg/g in meat and fish.93 3.19 930 5.12 ≤ 0. Nevertheless. however.43 0.430 57. 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.0 7.2 17. as opposed to preparation for serving. water.31 ≤ 0.12 ≤ 0.9 31.62 7.12 ≤ 0.19 ≤ 0. of which their YUS 270 is one (equivalent to UNS S31254).28 0.3 3. 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. 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.12 0.19 ≤ 0.40 6.0 36. This is complemented by other studies showing that the transfer of ions from food contact vessel to food is diminishingly and negligibly small.700 62.19 ≤ 0. Stainless. salinity.7 2.900 112. Under such conditions. it is necessary to apply the correct assessment of the corrosivity of the foodstuff in question.19 ≤ 0. while guidelines exist for the minimum alloy content permissible for normal food contact. then stainless would be a poor food contact material. no alloy greater in pitting resistance than 304 is required in residential or commercial cooking food contact. if not optimal. is the responsibility of the design engineer. one must still verify the corrosion due to a particularly aggressive food ingredient.82 14. Nippon Steel reported (Ref 3) that materials used in the manufacture of soy sauce. such as those promulgated by the National Science Foundation (NSF).19 0.19 0.7 26. Tests have been conducted on stainless steels. Tests have been made of the rates at which metal ions can enter foodstuffs (Ref 1).40 0.12 ≤ 0.00 ≤ 0. Table 1 shows the vastly lower rates of metal ion release from stainless than from aluminum and carbon steel. Stainless therefore is effectively inert. based on pH. food contact materials.350 2.

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

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

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

coastal salinity is not a problem. practice of service centers not stocking 201 despite its being the most costeffective general-purpose stainless grade. and that this is a drawback to their wider adoption. and appearance to 304 and can be most easily interchanged without complications in manufacturing and field performance. 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. corrosion will occur unless 304 with a bright-annealed finish or a brushed finish rolled onto a bright-annealed 304 is used. It has been pointed out that there is an array of 201-type grades. This is normally the case for commercial equipment. if inexplicable.238 / Stainless Steels for Design Engineers are satisfactory under normal use. The corrosion on 430 would be considered excessive. which cannot be passed on to their customers. The extended nickel price elevation from 2004 onward has a good chance of changing that situation as end users rebel against surcharges. In the vast majority of ambient conditions. For Fig. In the high ambient salinity of coastal climates. Mechanically polished 304 stainless is inadequate for coastal environments. 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). Under these conditions. Figure 2 shows how different alloys withstand coastal conditions. 2 Stainless steel samples exposed on a North Carolina beach for 10 yr. Use of 201 versus 304 reduces surcharges by almost 50%. This applies to inland conditions or coastal conditions where interior environments are protected by air conditioning or adequate cleaning of the stainless is practiced. 201 is quite adequate. Smaller manufacturers are often precluded from these savings because of the general. welding. Designers seem to generally neglect the possibility that their equipment may be used in coastal climates. Source: Ref 12 . These are the same guidelines used for architectural applications. 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. and the use of 304 represents wasteful overengineering. which can be a much larger savings than the base price savings. 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 is usually a very important quality criterion for appliance manufacturers..025 16.. such as for beverages.5 28...00 1. .035 0. Rolled-on finishes are generally preferred.0 1. such as 430. and esthetics. Not a small reason for this is that this finish requires only a single temper pass to both flatten and provide the finish.0 0. stoves. 0. .0–30. The more commonly used alloys for appliances are listed in Table 2.15 0. and ice.0–14. but deep-drawn grades are more finely tuned to specific process paths and must be more tightly specified than general-purpose grades. This occurrence is strictly a thermodynamic phenomenon related primarily to the titanium and nitrogen levels.15 0.0 16. C N Cr Ni Mn Si Mo Ti/Nb 201 301 304 316 430 439 468 436 444.20 + 4 × (C + N). Interior or working parts of appliances. This is especially true of dispensing machines.0 0.0–18.5 5. and welding.0–10. Food preparation tables also fit into this category.50 0. to 0. Stainless steels commonly used for appliances Composition.00 1.0–19..00 1...025 0. YUS190 29-4C S20100 S30100 S30400 S31600 S43000 S43035 S46800 S43600 S44400 S44735 0. 0. . It is still preferable to use a dual-stabilized grade such as 468.9 18.5 2.20 + 4 × (C + N).75–2... There are important visual considerations in these applications..80 3. 0. however.0–18.08 0.5–19. These finishes also supply the added corrosion resistance that makes alloys such as 430 acceptable.. Use of dual stabilization permits keeping titanium levels to a minimum.00 2... meaning much lower breakage during press-forming operations.10 0.0–8.00 1.10 .025 0..0–18.00 1. .. There are important precautions. bending. In the case of dishwashers. microwaves. are generally made from austenitic stainless steel.5–4. from using ferritic grades.08 0...50 Ti + Nb: 0. 0.00 1.12 0.00 1.. These include refrigerators. This yields very consistent forming characteristics.00 1. which look the same on ferritics and austenitics... .75 ..50 .75 0.5–5.030 . which occur if significant TiN precipitation occurs before solidification in the original steel production.0 17. and they should be used whenever forming requirements permit. making it possible to avoid TiN-caused surface defects.07 0. Shelves and exhaust hoods also benefit from being made of stainless. is put side by side with an austenitic such as 201 or 304. % UNS No. This is difficult to achieve for 17% Cr alloys if stabilization is by titanium alone. of course. to 0. This can be solved by specifying rolled-on finishes. durability. Consistent. .0 1.00 1..5 Ti + Nb: 0. serving pans. Stainless interiors are often found in refrigerators and dishwashers. which should be minimized so that the product of titanium times nitrogen is less than 0.0 8.0 16.00 2.0-3. Rolled-on finishes also have very high visual consistency.70 1.0–20. to the degree they require high cleanability or contact food. If antimicrobial coating were to be used in food contact. chafing dishes..25 .0 18. This subtle difference can be magnified to objectionable levels when a mechanically polished ferritic stainless. .Chapter 20: Commercial and Residential Applications / 239 parts made by deep drawing.12 0.5 6.0 17.00 1. 1. ice cream.5–7. substitution is still very possible.20 + 4 × (C + N).. The greatest savings comes. Ti + Nb: 0.0025 when Table 2 Alloy concentrations are in weight percent..030 0..04 0. since most appliance components experience little more than cutting.10 . are also often made of stainless. to 0. Appliance facades are increasingly using stainless. to 0. The drivers here are cleanability.80 ... Mechanical polishing results in unacceptable corrosion resistance.0 1. Coatings are rarely used.0 16.0 3. 2.80 .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.0–18. drawers. Canisters. and the low work hardening rate of ferritics causes the mechanical polish to take on a different color shade. etc. 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.0–20.00 1.20 + 4 × (C + N). to 1.0–18. .. etc.0 16.00 1..0 0. forming requirements are often severe enough to require the use of austenitic stainless. which lends itself to the typical deepforming operations used in their manufacture... Nb + Ta: 5 × C. which is the majority of the time.5 10.

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

. .5 16.0 14.. but the coating is cracked by strains that the steel itself easily tolerates. 4. . one has to balance materials selection between cost (fortunately. This trend began in Europe with the development of high spin speed. ..75 4.40 1. such as 439 or 468.60–0.0 2. Laundry appliances have converted significantly to stainless..030 0. 0. 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. are the main drivers for its use.95–1. contain corrosion elements. . High-efficiency (90% or higher) furnaces can use low-temperature plastic pipe. These furnaces gain their extra efficiency by condensing water from combustion gas exhaust.. If components can be made by bending rather than stretching. 0...00 . 0. .0 14. 0. An additional benefit to stainless over porcelain is that stainless starts smooth and becomes even smoother with use.65 0. . . which has led to the use of very highly alloyed ferritic stainless steel in their construction.. .00 1. then the lowercost ferritics can be used..0 17. With the development of high-efficiency. and grade selection depends on forming and joining requirements. whose low speed allows them to be constructed of lowstrength materials such as plastic or porcelaincoated steel.0 . Dryers are less challenging....0 14. or 304..Chapter 20: Commercial and Residential Applications / 241 Table 3 Stainless steels commonly used for cutlery Composition. while porcelain becomes quite abrasive over time as wear opens voids with edges that can be quite sharp and cause significant damage to clothing. . and austenitics can be 201.00 ... which are necessary in horizontal axis machines to take water removal from 80% to 95%.. 29-4C alloy is nickel free) and probability of failure.... Those designs that use stainless will last longer and be gentler to clothing.. along with the implied quality of stainless. require the strength of stainless steel. The variability of the use environments leads to a huge spread in corrosion conditions and materials performance.0 4.75 0.00 1... These features have eroded the share enjoyed by vertical axis. stainless has come into domestic use as a heat exchanger material. Those. ..15 V .4116.. The stresses induced by the high spin speeds. ..0 16.0 13.15 1.3 0. The selection is based on forming requirements rather than corrosion or strength. 1..40 . but at least one used alloy 6XN (UNS N08367) alloy for formability.05 1. 1. Ferritics should be a 17% stabilized grade. but failed joints in them caused their recall after several fatalities were reported. Porcelain-coated carbon steel obviously can be strong.. 12.50 0.45 2.0 4.35 0.. . horizontal axis washing machines. but again any of the stainless steels with at least 16% Cr are adequate.0 0. .0 4..5 V 9. agitator-type washers. These washers use far less water and energy to achieve higher levels of cleaning with less damage to clothing.0 14. Unstabilized ferritic alloys. % 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..00 0. 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 0.0 V Many kitchen utensils are also made entirely or in part with stainless.0–18.4 0. so pitting corrosion must not be allowed... This condensate can. 301.0 . 1. . Some manufacturers have always used lower-alloyed stainless steels..030 ... Type 304 is the alloy most commonly used. 0. forced-air furnaces. Washer tubs and drums are made of both ferritic and austenitic stainless.. should never be used in welded applications..0–14... .0 14..3 0.... ... 0. The worst consequence of perforation by pitting could be the release into the home of toxic gas. .2 V ..05 1.. depending on incoming air.... Given the number of units produced and .5 0. .. . High-temperature plastics were tried... .. .20 1..0–18. Heating and Water Heating.030 . Alloy 29-4C (UNS S44735) was the original alloy used nearly universally in the United States..00 ..0 V 5.. such as 430.45 ..15 min 0.20 1...3 .. 1. and it is difficult to make a strong case for the functional value of stainless. natural-gas-fired. The proper handling of combustion products is an interesting problem in materials selection.15 2.. Alloy 29-4C was the original choice for most secondary heat exchangers.75 0. The intermediate efficiency furnaces (80 to 90%) require the use of corrosion-resistant vent pipe to prevent corrosion from condensation in the flue...5 14. .05 1.. In the end...

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.

REFERENCES

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, www.agion-tech.com, accessed June 2008 6. Removal of Stains and Discolourations, Outokumpu, www.outokumpu.com, accessed June 2008 7. “The Care and Cleaning of Stainless Steel,” Specialty Steel Industry of North America, www.ssina.com, 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. www.asminternational.org

CHAPTER 21

Marine Systems Applications
Summary
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

Desalination
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
Alloy

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.

Shipping
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.

REFERENCES

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. www.asminternational.org

CHAPTER 22

Petroleum Industry Applications
Summary
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)

Introduction
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”

. 2 (Ref 2) indicates. Each situation must be evaluated regarding which is the optimal solution. . The chapters on martensitic and precipitation hardening stainless steels discuss this in detail. 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. If localized corrosion occurs.. cathodic protection. Nickel is necessary to prevent σ-ferrite formation. as shown in Fig. They also represent an ongoing cost rather than a one-time cost. Figure 1 shows the influence of chromium alone. They have high annealed strength and can also be cold worked to higher strength levels. The effects of copper and nickel are also very significant. “Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment” Combating Corrosion in Alloys for Petroleum Applications Alloying steel with chromium. 35 . Source: Adapted from NACE MR0175. Carbon must be kept low to avoid the formation of chromium carbides during tempering. (a) As specified in NACE MR0175. Duplex alloys and austenitic alloys become susceptible at higher temperatures and do not ... As if this is not a sufficient material problem. fully martensitic structure is to be maintained. as Fig. after which further alloying is necessary... These additions must be made in a very balanced way if a tough. The first three responses are not always practical. pitting resistance equivalent number. Being stainless does not by itself provide immunity. however. HRC.. Molybdenum alloying expands the pH and chloride range from which an alloy can be free of the pitting corrosion that initiates SCC. then the stress corrosion cracking (SCC) cannot be initiated. “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. which reduces toughness. Martensitic steels of all types have a maximum in susceptibility to SCC via hydrogen embrittlement near room temperature.. which further aggravates corrosivity. 31 . but the duplex alloys have the corrosion resistance and strength to work in this regime. Note: See Appendix 1 for alloy compositions. The martensitic stainless steels used for these applications are resistant to carbon dioxideenhanced corrosion up to partial pressures of 100 atm. If the localized corrosion can be prevented. Only keeping hardness below wellestablished levels can render a martensitic alloy immune. . hydrogen uptake ensues.. which produces a 100-fold reduction in corrosion of steel in seawater and carbon dioxide (Ref 1).248 / Stainless Steels for Design Engineers Table 3 Precipitation hardening stainless steels for petroleum industry applications UNS Common name Hardness. This corrosion problem is compounded by the accelerating influence of high temperature in deeper formations. Molybdenum is the most powerful alloying addition to magnify the benefit of chromium. the selection process can become more difficult. What is the answer to the corrosion problem? Inhibitors.. (a) PREN.. . which is extremely corrosive to carbon and alloy steel. or more corrosion-resistant materials are the main responses. This cannot be achieved with a martensitic structure. Highstrength martensitic steels are susceptible to brittle delayed failure in the presence of hydrogen sulfide. and delayed failure follows.. 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 . . sometimes the wetness is from saltwater. coatings... and nickel can lower the corrosion rate of steel by a factor of 10. which would counteract the benefit of the chromium.000. molybdenum. 33 32 33 .. copper.. Source: Adapted from NACE MR0175. If hydrogen sulfide is present. 3 (Ref 2).

. .. 54 . 64 ...... ......... SSC.... .... . 60 (C °140 °F)..1 MPa.. .. .. Source: Ref 2 ........ stress corrosion cracking.... “Sulfide Stress Corrosion Cracking Resistant Metallic Materials for Oil Field Equipment” Fig. 49 36 . .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 ... . . specific volume.... . . ... ... ..... . 2. . .............. Test conditions: synthetic sea water.. 2 Influence of copper and nickel on the corrosion rate of martensitic stainless alloys used for oil country tubular goods. 46 59 .. pitting resistance equivalent number... Note: See Appendix 1 for alloy compositions. ... .... CO2 partial pressure. .. .. ..... 1 Influence of chromium on the corrosion rate of steel in environments experienced by oil country tubular goods...... 800 mL/cm2.. .. . .. .. . . 25 . . .. . . flow velocity.. . . ... . .... .. . . . Source: Adapted from NACE MR0175.. ... . Source: Ref 1 Fig. ....... . ..5 m/s. . 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 ... . 39 54 38 . test temperature.. (a) PREN..... 0....... 46 47 49 39 .. 28 28 38 .. test duration. . . ... 150 h...

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

It decreases with temperature from a maximum at ambient to none at around 100 °C (210 °F). then 22Cr alloys should be used rather than 13Cr because of this risk. If the hydrogen sulfide level exceeds 0.03 atm. but necessarily increasing the cost. Thus. Hydrogen sulfide may be contained in the petroleum. Carbon and nitrogen in these alloys are kept at low concentrations. unfortunately. This can cause a sulfide-free system to become sulfide rich after the fact and make initial materials choice wrong after the fact. 4 Alloy suitability as a function of H2S and CO2 partial pressure. Source: Ref 1 tenfold. The 2% level of molybdenum also greatly reduces pitting. These alloys are otherwise almost identical to precipitation hardening martensitic stainless steels without the precipitating phase. for example. The 22Cr and 25Cr alloys have significantly higher resistance to chlorides and wet hydrogen . This susceptibility is strongly temperature dependent. nickel must be added to counter the ferrite stabilizing effect. The nickel does help lower the general corrosion rate. Martensitic alloys are susceptible to SCC by a hydrogen embrittlement mechanism. or it may come from sulfate-reducing bacteria. introduced by flooding.Chapter 22: Petroleum Industry Applications / 251 Fig. which cannot transform to martensite and would therefore reduce mechanical properties. which in turn eliminates the initiation point of SCC. Simply adding molybdenum would cause the alloy to have excessive δ-ferrite.

5 ..... .. flow conditions. . .. .. 3.... .... 65 (150) . .. .000 5. There was one instance of very high-strength tubing cracking after cathodic contact with carbon steel casing...5 3.... . 700 310 100 22 22 23 100 HRB 94 HRB . . The affected microstructure was found to be high (70%) in ferrite (Ref 3)... .. . . .. 35 ... . .. The recent development of lean duplex alloys has not yet made its way into OCTGs.. 6....... 10 20 . . . “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.. The more common alloys are UNS S32654 and N08367.... . 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 . . .. . 700 700 3. . This acts as a crack arrestor should one phase be susceptible to cracking while the other is not....... . . 450 MPa (65 ksi). are lower than those of the martensitic alloys.. salinity.... These alloys achieve a tenfold increase in hydrogen sulfide resistance and very elevated SCC resistance.... . Source: Adapted from NACE MR0175....5 3... . . .. the case for stainless line pipe is easily made....... <40 >40 <45 (Ni+2Mo) >30 >40 .. .000 Notes: See NACE MR0175 for further use and processing restrictions......... . . hydrogen sulfide... .. . .. For corrosion resistance above that furnished by superduplex materials such as the 25Cr alloys. min H2S....5 .... This was after removal from the well and after handling damage had occurred.... . There have been no reported downhole failures of annealed or cold-worked duplex alloys.. ....... 10 10 10 .4 100 10 10 10 10 10 10 10 10 10 1 100 . HRC Cl–.... .5 3. so for most downhole applications they will require cold working. Their strength levels in the annealed condition..5 3.. ... This evaluation is made based on the carbon dioxide.... . and nitrogen levels of the 22Cr and 25 Cr alloys (see the chapters on corrosion in this book)...... . 121 (250) 149 (300) 171 (340) 3..000 5. F6NM 420 . 33 32 33 ... .. . . 3.5 . 450 A286 Austenitic A-2 Duplex Superaustenitic... It is likely.. . ºC (ºF) pH.000 .... ... 232 (450) 232 (450) ........ The normal basis for . Besides the inherently greater corrosion resistance that derives from the chromium.5 3. 90. (a) PREN... pitting resistance equivalent number...4 . . . that these alloys will see their first service as line pipe. These alloys offer an inherent alloy savings over the 13Cr grades in nickel and molybdenum content while offering better corrosion and SCC resistance. . water... 600 MPa (87 ksi). .. These are the so-called 6Mo grades.. The more advanced of them contain high levels of nitro- gen.. ... See Appendix 1 for alloy compositions.. temperatures. .5 3.. .. 66 (150) . ... . pressures..... .. 15-5 15-7 17-4 .700 ... . 3... .5 4.... .. . however.5 3.. . .... . 5.....000 60... Whether to use stainless depends on vulnerability of carbon steel. 3. 150 (300) 121 (250) .. . 22 28 27 29 27 23 22 23 22 31 35 22 .. Line Pipe and Flow Lines With the awesome cost of corrosion... ....5 . molybdenum. ...... super austenitic alloys fill a gap before nickel base alloys are needed. . type 3a Superaustenitic. .... .. where they will not need to be cold worked to higher strength levels to be widely used. kPa Hardness. ..... ... .... 410 .. . . . . and so forth. type 3b ...... .... the duplex alloys have very fine grain size and a roughly 50/50 mixture of ferrite and austenite.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..

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

vapor lines Tubing. depending on availability and current alloy prices. condenser tubing Contactor. 2205. filters. trays. 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. 410. 2507 410S. distillation tower Towers Condensers Coke drums Compressor coolers. 304 304 2205 410 304 304 409.254 / Stainless Steels for Design Engineers Risers are now produced in coiled tubing of over 100 mm (4 in. 347. Both titanium and stainless alloy UNS S32750 are equal candidates for this service. fittings. and the penalty for excess weight is also high. has become expensive compared to the lower-nickel austenitic stainless steels.000 in steel in the subsea jacket. chlorides Preheaters. 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. MEA. 2205. the corrosion environment is severe. 410 405. chlorides Sulfuric acid. A savings of 1 ton in weight topside can save over $100. 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. 316 S44735. which have no transition temperature and strengthen with decreasing temperature. 321. DEA Sulfuric acid Dilute sulfuric acid H2S. 347 410S. A wise preventive action is to paint stainless that is covered by insulation or similar material. H2S H2S. and of course is stainless. water. The traditional material. heat exchangers Heat exchangers Stripper 405. flanges. ammonia Ammonia. Platforms Platforms present a special case in which the costs of maintenance are high. Cl–. easier to weld and fabricate.) diameter. which otherwise can result in concentration cells and consequent pitting. ammonia. Table 7 Process Refinery Equipment Corrosion resistance is a major factor in the choice of materials in refinery operations. As we discussed. 6Mo 304. but in refining the by-products. chlorides (a) PTA. Almost any structure is a candidate for stainless topside processing: piping. which is a major design and political concern with this potentially explosive commodity. Converting natural gas to a cryogenic liquid presents a material problem. polythionic acid. 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. Hardware of any type and construction materials benefit from being stainless. Vessels to contain it must have strength and toughness at temperatures below –150 °C (–240 °F). 316L 20Cb3 316L 321. The extreme ductility of 201LN compared to martensitic steel gives it a decided advantage in terms of rupture resistance. pumps. stainless steel wins the cost battle between these alloy systems. Except in rare cases. 9% Ni martensitic steel. 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). crude oil itself is sometimes a very corrosive fluid. 316L 304L. 2205 409 AL-6XN. 409. which 9% Ni steel is not. ammonium bisulfide. mixer Effluent piping Hot sections General Reactor internals Heat exchangers Trays Cyclones. risk of chlorides Severity depends on presence of sulfuric acid Coker Gas plants SCA. etc. Alloy 201LN is cheaper. Seawater systems often employ 22Cr duplex with cathodic protection or unprotected 25Cr duplex. Source: Ref 4 . so that very economical long lengths are feasible. 20Cb3. reboiler tubes Trays Reboilers.

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

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

Copyright © 2008 ASM International® All rights reserved. www.asminternational.org

CHAPTER 23

Chemical and Process Industry Applications
Summary
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.

Introduction
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

(continued)
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

(continued)
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

(continued)
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

(continued)
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.

Erosion
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

REFERENCES

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

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

org 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. At prices between the highs and lows of the first decade of the 2000s. Beginning in 1988. essentially large vertical tanks. Since this revolution occurred in the 1990s before the latest surge in nickel prices. In this environment. which enables paper of high strength. This leaves a long fiber. exclusive domain of duplex stainless steels because of their lower cost per unit of corrosion resistance.0. The digestion is typically carried out at 150 and 180 °C (300 and 360 °C) and 10 to 12 bar. The pH of the sulfate is around 2. and stainless steel clad onto carbon steel. the lignin-connecting wood fibers are dissolved under conditions of elevated temperature and pressure in acidic conditions of pH 2. are constructed of 2205 (UNS S32205) as a rule (see Fig. hence the name kraft. but it .0 to 4. replacing the sulfite process. Pricing changes mainly with alloying element costs. principally those of nickel and molybdenum. high strength. 1). Introduction The proximity of the Scandinavian paper industry to that region’s specialty steel industry has been symbiotic. So. and near immunity to stress corrosion cracking. stainless steel. called digesters. in which this process is carried out have been sequentially 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 grades. This need has been met through the use of the duplex alloys.Stainless Steels for Design Engineers Michael F. and there has been no turning back in the replacement of austenitic stainless steels by duplex. Over the years the materials used for the vessels. Now. such as in bleaching. McGuire.0.asminternational. 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. the digesters.0 to 4. 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 the kraft process. www. As a result of the strong interaction between engineers having wellspecified needs for improved materials and metallurgists capable of providing them. p 265-267 DOI: 10. 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. In the previous sulfite process. which have become the new standard. the advances in materials in the pulp-and-paper industry have been a model of rapid technology transfer and innovation. acidresistant brick vessels were used. duplex stainless steels first went into production in kraft digesters. duplex costs have been roughly onethird less than that of an equivalent corrosionresisting austenitic stainless. 316L can survive.1361/ssde2008p265 Copyright © 2008 ASM International® All rights reserved. to a fairly simple discussion of which duplex stainless steel is most economical for a given piece of equipment.

the materials selected would be the same. Further downstream. highly alloyed austenitic alloys were used. Courtesy of Outokumpu requires maintenance and has a finite life. In the nonchloride environment. 2101 or 2304. 2205 is the alloy of choice here. molybdenum is not an essential alloying element. or 2003. totally chlorine free. in the pulp.266 / Stainless Steels for Design Engineers Fig. This reduces the corrosivity of the environment as the ozone and hydrogen peroxide used in the process are relatively harmless to stainless steel. such as sand. 1 The first kraft digester fabricated from alloy 2205. Duplex stainless has become the clear choice. but the optimal materials remain duplex for various reasons. This has rendered the previous choice of carbon steel untenable. Alloys such as 316 are adequate for this environment.005 mm/yr versus 0. based on yield strength. In the more unusual case of digesters using the sulfite process. has seen increasingly severe environments as closed systems required for pollution control have become more common. Subsequently. The delignification of the pulp comes next. This oxygen process dates from the 1970s. which again save cost by virtue of their higher strength. The subsequent stage is blow tanks in which the pulp suspension is injected at high velocity. and this can be done by chlorine bleaches or ozone/peroxide bleaches. environments change greatly. At first. This stage also sees erosion potential from hard particles. 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 vapor phase can contain organic acids. process. 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. containers and process equipment benefit equally from duplex down to the handrails and walkways. As one proceeds downstream in the process. unlike either duplex or austenitic stainless steel. The 2205 is twice as resistant to corrosion. The bleaching of the pulp is important for many types of paper. offer cost reductions through their greater strength. The reduction in wall thickness allowed by the higher-strength duplex depends on the engineering code required. but 2003 (UNS S32003) would suffice. The environment is a mixture of alkaline liquid. The American Society of Mechanical Engineers (ASME) code requirement is based on tensile strength and permits only a 24% reduction in wall thickness. washing and screening. but now they can be replaced by duplex alloys such as 2507 (UNS S32750). The 6Mo grades have been successful. In plants that use recycled paper and mechanical wood chip processing. The next step. but also offered freedom from stress corrosion cracking as well as materials savings because of their higher strength. 2304. it was found again that duplex performed better in that they were sufficiently corrosion resistant. would allow a 46% reduction.011 mm/yr (Ref 1). but lean duplex. The chlorine bleaching now must generally be done in closed systems. 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. while the total kjeldahl nitrogen (TKN) code. 0. the materials selection criteria remain the same. The hardness of the duplex helps mitigate erosion. The optimum solution is a lean duplex such as 2101. Bleaching can be accomplished without chlorine in the so-called TCF. while the alloy level is beneficial against corrosion. This wholesale use of duplex can make plants nearly maintenance .

A. Tuomi et al. REFERENCES 1. Duplex America 2000 Conference. Vol 13C.. Additional detail about corrosion challenges and the use of stainless steels in the pulp-andpaper industry can be found in Ref 2. 2006. ASM International. Corrosion in the Pulp and Paper Industry. 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. Corrosion: Environments and Industries. 2000 2. Houston. H.Chapter 24: Pulp-and-Paper Industry Applications / 267 free from a corrosion point of view. KCI Publishing. Dykstra et al. ASM Handbook.

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

0–10..030 0.06 min 0.0–9. 1..5 3.03 0...5 11.045 0. .0 1.040 0.030 0.. .08 0.040 0..0 17.0 18.030 .0 .030 0...0–15.08–0..045 5.0 8.0 17.0 3. % 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. .5–9..030 0. .0–12.5 19. ..5 7.0 16. ..00 0.. .00 1.5 5.5–2...14–0. .20 . Se 0.03 0.25–0. .0–11.40 0.0–18. Cu 1..040 0.50 16.045 0.0 5..00 1.5 17. .. 0. .. .0 0.0 2... Single values are maximum values unless otherwise noted.0 18.15 0.0 2.040 0..40 0. .10 0..0 8.030 0.030 0.045 0.0–18.40 0.15 0.50–4.08 0.1–0...045 0....0–19.030 0.030 0.8 2..5 8..0 5.0 5..08 ..0–20..0 17.08 0.00–3.12 0... .1–0..0 18.5 2....50 0.030 0..15 0..015 0.0–20.0 22..00 1..5 14. .030 0.0 20..5–9..5 17. 0. .0–15...03 0. .75 0.0–10. .20–0.40 .40 0. 1.. ..0 16..10 0. B 1..50 Al 0...0 2.9–21.03 0. ..0–16. ..75 1.5–5.0–20. 0. .10 0. . V 0..0 18. .0 17.25 0.00 0... 2....0–8.0–9.030 0..0 17.. . ..... ..08 0..0 7.045 0..0 10.0 6..00–2.Table A1. 0..0–19..030 0..00 1.0 8.0 0.25 ..00–4. .045 0.12–0..05–0.5–14.0 12.0 4..0–19.00 1.. .0 ..5–16.5–3.30–1..045 0. ..18 . ..0 17. 0.00 1...0 16. . .16–0.15–0. .00 1. .0 7.00 1..10 . .5–19.0 1.045 0...0 2..0 8..00 1.0–10..60 optional ..0 8.5 . 0.5 4..0 7..2 .75 1.15 0.5 5. .40 0. 0. .. 0...0–21..0 2.0–19.0 2.0–6..30 0.15–0.0–15.5–5.015 0.0 2..0 11.0–10.04–0. .15 0.25 min 0.0 16. ..5–7.32–0.00 1.5 16..8 2... .03 0.0–10.0–20.. Cu 3. .25 0..20–0..0–7. .030 0.040 0.0 18... ..0 14.060 0..40 0... .75 0.0 2...030 .16 0.5–10..5–18.0–10. .0–20.16–0..0–9.00 1...0–20..08–0. ...0–19.35 0..0–15.030 0.5–7. 2.50 0...00 1..0 18. .0 0..0–18..030 0. .0–19. .060 0..0 6.08 0..030 0..0 9.04 .03 0.60 optional 0.15 0.0 16.030 0..5–23.15 min 0..16 0... .5 12...5–3.08 0. .50 0. . ..5 20.5–7.0–4.0 16. ..0–10.0 17.0–19.24 0.0–19.5–22.5 8.045 0.0 Al . ..0–18.0 2. .18–0.045 0.0 18.030 0.045 0.030 0..15–0.045 0... .. .00 3..12 0.060 0...0–1.. .00 1.. .5 4...75–1..0–19.5 3.0 17.75 0.0 4.0 . 0. ..5–13.0–19. Notes: All compositions include Fe as balance. .00 1..10 0..25 0..5 8..06 0.08 0.4–2..10–0. .0 (continued) .20–0.. 0. ..0–6..0–10.0 15.0 18.045 0..5–16.00 1.0 16. 0.0 .0 12...060 0. .060 0.0–10..1 Composition.00 3.. 2.00 1.045 0. . . 14.08 Ce ..75–2.5–4..15–0..0–18...18 0.12–0.5–7.20 .. (a) Unified Number System...30 0.5 8.0 14.5 8.0–16. .0 15.08 0. .060 0.06 0..5–22.045 ..75 3..030 0.12 0. .0–18..75 5.0 2.60 optional 0. ..00 1...0–15.0–10. 0.25 ..030 0.25 . .0 2.. 0.0 19...0 .0 9.0 17.25 0.5 2.00 1.0–24. ..0–6.5 13.0 11.. . .15 0....5–18..030 0. . 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 0.060 0.. .0–19. .0 7.040 0.25–0.20 0.030 0.0–20..04 0.5 8.0 0.08 0..08 0..00 1.00 2.0 2..0 8... .0 8. .. V 0.0–6.0–6.. .5–13..045 0.03–0. . . . 0..... . Nb 0. .5 5...5–7..00 1...060 0.045 0.0 17.0–18.0–10.0–10..20 Ce 0..5 .0–17.5 1.....0–6..0–10..... .0 ..75–4..25 3. ... .0 17.0 . ... 0. .00 1.5–7.018 0.0–21.10–0.. Cu 0. .15 min .0–10.75 5.0–19.00 1.030 0..0 22.0 10.15 0.00–1.. .08 0..15 0.030 0...00 1.15 0.0–22. ..045 0.20 0.0–14.045 .0 0.045 0..0 5..5–5.0–8.25–3.00 1.5 19.0–10..10–0.0 7.0–3....0–6.040 0.0–18.0 17...0–12.0 14.0 2. .2–4...20 1.04–0.10 0...35 0.045 0.0–18.030 0..0 17.0–3.0 2.0 7. 0.5–9.0 2. UNS numbers are S or N followed by 5 digits..3 .....030 ..0–3 0..25–0.8–1...0 2.0 10.3 .5 8.0–24...060 0... .030 Nb 0.00 1. . .. ...

0–20.0–16.. .0 22...03 0.08 0.60 Al 0. . .0 18.10 .0 12.0 19.08 0....0–14.0 18.0 2.030 0.10 0..0 13.. Nb 10xC to 1... 347H S34709 0...0 9..15 0.030 0.0 11.00 1. .030 .. .0–21.70 .0–26...0–37.0–3..00 1..030 0. .0 19. .0–12.0–20.0 0.015 0.10 Nb+Ta 0xC Co 0. 2.045 0.045 0. 0.0–16..00 1.00 0.0–36.0 4. 353MA S35315 0.10–0.0–22.0–14.. .10 Nb+Ta 8xC .08 0.08 . ..0 17....045 0..0 10..030 0.045 . .0–13.0–14..045 0.00 0.045 0.0 16.0 9.045 0.0 2.10 0..5–17.5 2.00 1.0–18..0–22.10 Nb+Ta 10xC .0–3...0–18. ..10 .50 1..0 2... .0–35. 0.10 22. Nb 10xC to 1.75–1....0 2.0–13. 0..0 22.. ..20 0.6 24..0 2.5–14.0–26.0–19.03 0.5–16..0 11.0–15..0 24. ..0 10..00 1.0–18.0–14.08 0.045 321H S32109 0.0 18.0–23.0 19.0 2..045 0..0 2.045 0.045 0.60 Al 0.. 0.00 1..60 Nb+Ta 10xC .040 0..Table A1.0–24.0 10.05 0.015 0.0 2. . 0.030 max P .045 .10 min 0. .03 0.00 0... .5–2.030 0.0–20.030 0..08 0.0 3.. . ... . to 1.60 Nb 0.04–0. . ...0–3. . ..10–0.0–1. . .. 1.35 0.0–3. ...0–22. .0–18. 0.0–3.5–17.03–0..40 Co 0.0 30.0–26.030 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..15–0.. . .0 19..0–21.18 . .0 12.22 0..75 1.50–2..50 1...00 1... 348 S34800 0.0 20. .0 12. 5xC to 0. S30909 S30940 S30941 DIN 1.0 19.0–20.0–13.0–14.0 14.0 2.0–19..10 Ce 0.08 0. .0 19.0 16..0 1.0 2.0–21. Appendix 1: Compositions / 271 Notes: All compositions include Fe as balance...0 2..030 0. .10.0 16..0 34.04–0.0–4. .00 1. .0–13.0 .75 1.10 0.0–3.045 0.16 0.0 11.... .0 16.03–0..04–0..0–14.0 24.0 2.70 Ti 4x(C+N) ..00 1. . .030 0.04–0.0–22..04–0... Nb 10xC to 1.0–26.0 1.0 2.00 1.20 0..0 3. .0–19..0 24.0 24.0 2.2 to 1. .40–0.15–0...030 .0 2..0–4.045 0. 9.60 .0 2. ..2 to 1.030 .04–0. . 0..50–2.11 . . .00 1. 1....10 330 332 332Mo* 334 347 S33000 N08800 S35125 S33400 S34700 0.0 24.10 0..0–18.0 2. .. to 0.045 0..0 19.1 (continued) Composition.005 .0 17..0 2.5 .045 0.75 1.0 2.0 16..00 1.5 9.0 9.10 .030 0..08 .0 24.0 2.0–26.75–2.0–19.10 .0–35.15–0.030 0....0 2.. Single values are maximum values unless otherwise noted. .0 3.5 13.045 0..10 .030 0.0 24..0 17.10 ..030 0. .00 1... .00 1.. 0. .0 9..045 0.0–26.030 0..0 ..03 0.0–15.040 0.. . .0 2..0–24.045 0.0–26. .030 0..0–5..08 0.25–0.0 1.00 1...0 11.030 0.0 18.0 . Nb 10xC to 1.0 .0 2.045 0.0–24..0–19. 370 384 S37000 S38400 0.045 0...0 19.10 0. (a) Unified Number System..030 0. .0 (continued) 17.09–0.0–23.10 0.0–3..4828 S31000 S31008 S31009 S31040 S31041 S31042 S31050 DIN 1. 0.10 0.... 1. to 1.00 1.0 17.0 Ti 0.5 19.0 2..030 0.25 0.0–20..03 0. .045 0.5–23.00 1. .08 0. .00 1.00 1..20 0.0–20.. .35 2.010 0.12–0.5 17.0 20... .10 . .0 23.0 2.02 0.10 0.0 10. 0.030 0...030 0..0 2.08 0..0–4..5 1... .50–3. ..10 .08 ..0 19..15–0.0 16..00 1.10 0.00 0.0 12.0 2.030 0..0 17.. . Nb 10xC to 1. ..0–22.. .11 .0–15. .5 1..045 0.0 2.5–1.08 .030 0. Ti 5x(C+N) .0 2.00 0.0 24.0–5...6–1.04–0..0–22.6–2..0 .4841 S31400 S31600 S31609 S31620 S31603 S31653 S31651 S31635 S31700 S31703 S31753 S31725 S31726 S32100 0. .0 31..03 0.0–12. Ti 0..0–13.0–22.0–26..00 0......05 Nb+Ta 10xC Co 0.0 10. 0.10 0. ..0 2..70 Ti .10 0.10–0..0–26.0 10.9 34.25 0..030 0.0 1. to 1.50 1.0–18.0 2. . .0 2.030 ..15–0. ..... Ti 0..0 18.65–2. .10 0.030 0.6 .045 0.5 1.10 0.10 0.045 0.00 0.030 0.04–0.0 10..0 4..030 0.0–19..0 16..5 15. .08 0.00 1..0 2. .0 2..08 0.. UNS numbers are S or N followed by 5 digits..10–0.0 1.10–0.045 0. . to 0. . 0.045 0.. ...0 2. .040 0. ..03 0.0–18. .0–15.08 0.0 17.020 0..0–22.0 2. .0–14.0–17.16 0.. 2...00 1. .0–19. 348H S34809 0.0 19..0–26.

.60 Al . 0.0–25. ..0 20.0 22.030 0. .. 0.50 0.0 19.0 Cu 0. .035 .15–0.0–24..0 24.05 0..0–4.30 0.75 2.3–5.9–32.0 24..025 0.045 0.0 22.0–37.5–1.. 0..015 . ...03 0..48–0.0 6.045 .. .50 0.75 10.0 2.6–1.0–9....0–28..0 5.0.0 19.030 P 0.0 0. . .0–28.0–33.0 0.5 0..045 0. ..0–4.0–26....10 Nb 0.. .0 Cu 0...0 5. 0..04–0...02 0.0–4..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 0..0 2.0–25.5–12..0–26.1 (continued) Composition...15–0..030 0..0–22.0 20.0–7.40 1.. ..0–5..5–30.035 0. .0 0.0 4.0 25.10 Ce Ti 0..0 22.50–2.0 18.07 0.0 21...0 21...0035 0.0 0. .5–3..28–0.08 0..90 0.50 1..0 7.015 0.0–22...0 .Table A1. .35 V 0.03–0.0 2. 4.0 26.0 Cu 3.02 0.45–0..0 8. 0..0–7. (a) Unified Number System.50–18. .0 30.0 3.0 19.5–3.5 23..50 0..0–26.. W 1.0–7. .0–22.08 0.0 1. 2..0 0.0 33..7 . ...00 1. 0.5 1.6 Cu 3... 0. UNS numbers are S or N followed by 5 digits.5 Cu 1. . . 0.5–1.50–20. .0–23..02 0.0 26.80 1. .0–21.0 20.38 0.0 ..00 Nb Nb 0.8 .0–2.035 0.0 24.. ..0 1.5–25.5 Nb 1...25–4.0–26.50 0.. 0..4-0..00 1.02 0.030 0.58 0.0–22. 2.0–5.0 23.....06–0.55 .0–21.030 0.0 21.4 Cu 1. .. S33228 S25045 S35135 S63008 S63012 S63017 S63018 S63198 N08020 N08024 N08026 N08028 N08366 N08367 N08700 N80904 S31254 S34565 S32654 N08020 0.0–7.18–0.04 0.0–7... % 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..3–0.1–0.0–26.50 1.0 6. .60 0.0 Cu .015 0...50 16...9–9.0–38.0 balance 24.0 2.0 0.045 0.5–14.0 2.0–6.0 12..00 Nb+Ta W 2. Ti 0.25 0.0 2..5 25.0 1.5-3.5–25. .0–3.70–1.0–3.030 0..045 0.0–4.030 0.6–1. 0..15–0.0–23.0–2. .04 0.02 0.15-0.0-3.030 .0–24.. 0..0–10.0–26.0–22.0 32.. 0.5–3.28–0.0–23.5 1.50 23..030 .03 0.0 .5–3.28–0. ....0–38.40–0...60 0. . .015 0..0–3.. Notes: All compositions include Fe as balance.0 19...0 Cu 0.5 6.0–38.0 .030 0. .5 4.0–18.00 0.5 7.15–0. 8xC to 1.0–21.0 20.0–21..0 2.25 .040 0..10 0.0 29.5 2. ..5–6..0–4.0–23.0–23..15–0.0 31.. .0 22..0 2.60 ..0 7.35 8xC Nb .4 Cu .0 8.5 2.15–0.5 24.5 1.0 19.0 24. .0 Cu 0. 0.5 5.35–0.005 .0 35.5 Cu 2.0–28.. 0.0–27..35 Ti 8xC to 1.5 Co.02 0.5 1.0–6.5 2. 0.0 23.0 Cu 0.0–37.25 0. .0–29.0–25.25 Al 0.60 Nb Cu 3.045 .50 1....0 2. .03 0.7 3.5 2.. . .69–0....0 17..0 19.25 0.050 0.25 0.50 20.0–11.38 ...0 . 0.0 1.0 1. .030 0..03 0..0 32. ..0–24.030 .15–0..75–1.0 Cu .40 0.0–3.5 19.0–22. .0–1.00 1..0–28.08 0. N06022 N08926 0.5 23...4–1. .28–0. .07 26....5 1.25 0.030 0. .50–0.07 0.00 0..0–1.0–7.5–25.75 2..0–4.0 4. N08031 0.010 ..0–26.0 2. Single values are maximum values unless otherwise noted.0 20.18–0.25–21.0 3. 0..015 0.36 0.25–0.5 Cu .0–1.22 0.0–8.030 0.0 6..75 0..5 4.0 .75–1. .0 19.035 0..5 .03 0..0 4...030 0. .25 0.0–6...0–28..5–1..00 1.5–5.0 27. .035 0.20–0.5–3.0 32.50 1.05–0.030 0.0–27.60 Ti 0....0 23.0 26.0 2.03 1.. 1.040 P 8xC to 0..0 6..0 1. .0–40.80 1.

.75 409Cb S40940 0... Appendix 1: Compositions / 273 Notes: All compositions include Fe as balance...5–1..20+4x(C+N) to 0. .50 0.45 .030 ..03 .. 18.00 0.030 0. . .... ...0–19.7 11. 1.0 16...55 . Ti+Nb:0. 14. .07 0.. 0...75 1.0 1.040 .02 0. .. .060 0..35 Ti .. 0.0 439LT S43932 0....0 10....040 .7 10. ..030 0....... 1.50 0.5–11. .. .12 0.. ..50 0..030 0....5 0.00 1.0 18 Cr–Cb AK alloy typical 0.030 0.20 ..00 0. ..0 .0 Alfa II 0...5 429 430 430F S40975 AK alloy typical AK alloy typical ATI alloy typical ATI alloy typical Outukumpu typical S42900 S43000 S43020 0.040 .. . .0 AL 4..0 ..0–18.01 17.25 1.. .20+4x(C+N) to 1... 1.....040 .. ATI.15 Composition of ferrite stainless steels UNS Name 405 400 409 designation S40500 AK alloy S40900 C 0.40 ... ..0 Alfa I 0... ..10 0. .00 0..02 0...15–0.00 1.030 0. .00 1..0–18...030 .... ...04 16. .06 . .. ..05 0..50 Mo ...75 6x(C+N)to 0. 0...35 .00 1. 0...0 . 12 SR 0.. .50 8x(C+N) 0..015 10....030 . . .. 0.045 S 0... 0.35 0.12 0.... ..0 0.00 0.00 1.0 1.... 6x(C+N) to 0...00 .. 0..60 . 0.00 Nb .5–11....... 0.... .....00 1.010 0. . .2 AL 3. .040 0.. Al 0. .020 ...... .. . .10 0.00 Mn 1. .10 ... 0..030 1..60 ..030 . .. 1. 0....0–19.. . ... Si 1.75 Nb ....040 .0 0.00 P 0.5 12..03 0.7 10.00 1..00 1..50 1.20+4x(C+N) to 1.75 .5–11..03 0.0 4724 0. ..03 0... ..00 0.. 0.... 0.50 0.. . 1.035 0.040 0. AK 439 HP alloys 439 ultraform S46800 468 0.2 0.5–11.30 Al 0...5–11..08 N ..0 Al 1.. ..025 .12 0. 13.015 12.. 0.040 0.05 0.5–11...03 0. ...030 10..5–11. ...0–18.03 17. . .. ..08 .15 AL 0.Table A1.... ..03 0.00 . 0.70 0.020 0.0–16.01 0. .. .030 0. .25 1.35 .40 0.5 439 S43035 0.0 0.020 0..30 .00 1..... .00 1.2 Composition....10 0.0–19. Single values are maximum values unless otherwise noted ...00 1.. .5–14.0–20. 10. ..75 Ti+Nb 0. ..10–0.12 .040 0.045 Other Al 0.75 0. 0....035 .45 1..75 409 ultraform AK alloy S40930 466 0..5 8x(C+N) to 0. 13... ..150 min 0..75 409 409 S40910 S40920 0. . 13.50 1..0 0.030 0.17 .00 1.. % Ni 0.25 0.50 0.020 10. SE 0.. .30 0.04 17....00 1. .025 .. .7 409Ni 11 Cr–Cb 0.00 1. .040 1..00 1.030 0. . Cr 11. .25 Al .0 16.. 0. (continued) 0..25 0.08 0..8+ 8x(C+N) Ti+Nb 10xC to 0.30 0..00 1.. .. ..00 1. 18..040 0.15 . . 1..... AL 1..0–13.03 0.. .00 1...0 16...060 0. .. ...20+ 4x(C+N) to 1.060 0..0 430Se 430Ti S43023 S43036 0.

5 1.. 274 / Stainless Steels for Design Engineers 441..0–30. 446 23. .20 ...015 N . Single values are maximum values unless otherwise noted.0 3..80 Ti+Nb:0.....20+ 4x(C+N) to 0. .. 1.75–1.020 0..0–27.25 Si . % Cr Ti 0.5–0.0–23. 0.3 0. .25 3.025 0. 0.0 25...040 ...00 2...00 0... .20+ 4x(C+N) to 0..1–0..0 .. ATI alloy typical Outukumpu 4762 typical 453 ATI alloy typical E-Brite. 0.....3 16.5–4.2 Composition. .5–19.040 0..015 Monit S44635 0.5 0.80 Ti+Nb:0.0–18. 10x(C+N) . Sea–cure S44660 25. .7 Al 1.40 0. . 0.. . . .. .. Notes: All compositions include Fe as balance.. ..25 .0 0.030 17..6 0.040 0.12 0..75–1. .035 1. 0. 0...0–18..0 0.040 0.. 29-4C S44735 0.75–1...3 1. 0.0 1...5 1.3–1. . ..0 24.0 17. . ...025 .0 0..4 . ..75 0. 1..0 0.015 .8 17.5–3. 17.30 18. .5 Cu+Ni . .0 ..035 0. ..0 0. .0 1...00 0..5 0.0 16.0 0..0 0.030 1.20+ 4x(C+N) to 0..... . 434 436 designation AK alloy typical Outukumpu typical S43400 S43600 0.040 1..5 0. 0.5–3.2 Cu 0.20 0.02 .08 . .5 0.025 0...20 .. S44100 0.. 1.60 Al 0.. P .6 ..08 .....5 24....0 1.040 0...3 .....0–27.040 0..0–27. Other Al 1.030 .25 0...30 S44200 ATI alloy typical S44400 0. Nb . .. .50 S44600 0.01 ...0 0. Ni 0.30 Mo ..01 0.. ... .035 433 0.020 0.01 .0 1.70 9xC 0.2 0..030 .. 4742 0.75–1.3 1.. ...5 .5 0.20+ 4x(C+N) to 0.10 REM 0.50 0...03 .030 0.. .80 ..030 ... . 8x(C+N) min .. Al 1.. .25 1. 26-1 S44627 0..75 0. .030 .5–26..00 0.25 .030 Ti+Nb:0.6 . ..7 1..7 1... ... 444.5–4.12 . 0. ..40 0.. 0..25 0.025 0..80 .040 0..5–18. 0. 1. (continued) of ferrite stainless steels Composition UNS Name 18SR C 0.4 1.20 0.4 . 430J1L 442 436S 18..... Nb+Ta 5xC:0. 28.25 .0 0..0 1..3 22. S .030 .00 0....0 .030 Ti+Nb:0..00 3...5 1.Table A1. 0. 4509..040 0. YUS 190-EM 20.. 0. Mn 0...5–4.

.5–12..50 ... % Cr 11..75–1.. Se 0. ..25 .00 1. .0–18. ..50–5.. .3 .0–15. ..75 0.. .75 0. .015 0... 0.. .20 0.. 4. . ..00 1.15 max 0.50–0. . 0...0 .95 0..... 1..3 0.. Si 0.20 . ..5 Cu .. .....3 0..040 0.00 1. Mo 0.20–0..00 1.2 V .... 0.00 1.0–14.50 . Other ..0 13..5 14..50 1.10–0.0–14.. 0.4 5....0 14. .15 0.25 1..0 17. .. ..040 0. 1.5 V 9.45 0..30 max 0..0–18. ..50 1.00 1..030 0....... .20 0...... Composition of martensitic stainless steels UNS Name 403 410 410S 410 410Cb 412 414 414 mod 415 416 416Se 418 420 4116 C 0.030 0.0 14... 4.0–14.....60–0...0 14.05 1..040 0....Table A1.02 0.0 5....00 1.18 max 0..35 0.95–1.25 0.4116 nominal S42020 S42023 S42200 S42400 S42500 .15 max 0.. . .15 max 0.5–13.00 1.15 min 0.040 0. Single values are maximum values unless otherwise noted ..0 16.00 ..45 1.5 11.15 2.15 min 0..50 1.00 .040 0.50–4. ..00 0...05–0....0 1. .0 11.60 0...5 5...040 0. 1.030 .040 ..030 0. .00 1.5–13.50 1. .3 Composition... ..5 0.. .0 12. ..03 0.00 1...20 0. 1..040 0.060 0.. .00 1. .040 0..35 0...040 0. Cu 0.00 1. ...00 1.. . CU 2.00 1.0 16.50 ..50 4.060 0... .50–3..5 11.20 0. .25–2...030 0.00 1..30–0.30 . .. .0 .00 0. .0–18... .3 0.00 1.15 0.5 ..030 .5–14.3 0. .005 0. . 0.40 .00 0.040 0...040 0.030 0.. ..25 1.60 0. .5 10. . .. 1.. ..030 0.5 11. .040 0.60 1.040 0..5 11. .0 16..... . 1...50 . ..20 max 0..15 max 0.25 W .0 .00 1.0 12... 0.00 1..05 0.. .. .25–2.....00 1. .040 0..0–16..0–18.0–14..040 0.030 0.5–12.... .3 ..55 0.0 12.00 0.0–14. 1.00 1..... Se 0...5 Cu 0..15 1..00 0.01 0...08 0. .5 12.00 .01 0..00 1. .. ...00 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 1.040 0.00 0..3 11.30 0...0 13. .50–1.... .15 min 1.5–13. ..25 1... .5 Cu 1.00 0...45 2.. P 0.. . . .040 0...030 0. . .05 1.010 0.030 0..50 1.040 S 0.7 12.20 .75 0...00 1......... ...25 0..060 .030 0.0 12.. 1.0 4.0 11. ..5 1.00 .75 .25 1. .... ... Mn 1.....010 0..0–14.12 .040 0. .4 0.0 0.00 1.0 12.... .15–0... .00 1.. 1.05 max 0..03 0.. .0–14... 0. .0 16.0 13...75 0..0 13. . . Nb 0. . ... ..35 0.00 1.06 max 0.06 0.00 0.50 N .45 2..8 2.00 . .. ..060 0.. 1.040 0...15 min W 2. 1. ...15 min 0.040 0. .0–3. .060 .010 .30–0.0–7.5 12. .. .030 max 0..5–13..040 0.95–1. .0 12...00 1...50 1.20 1.0–17.50 1. .5 1..00 1. 0.00 0.030 0.0 V 5.50 1.30 . . Appendix 1: Compositions / 275 Notes: All compositions include Fe as balance.45 . 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..05 1.0 1.....040 0.030 0.... .0 16..50–1..030 0.. 1.00–2..030 0.. Ni .0–14.60 1.80–2...5 10.15 min 0.5–13.06 0...0 12.0 15.0 14...50–1.. .030 0.025 0.0 14..5–1.00 1...60 1. 0..75–0.0–13.025 0.00 1.00 0.0 14.08–0.0–18.00 0. Se 0.00 ..6 1...00 3.15 max 0....00 0. .. .00 . .5 12.95–1.. ..0 12..00 1.0 3..00 1. . .. .0–14...040 0. .00 1.00 1. 0. ..030 0..

0–16. Cu 1.030 0.040 0.35 V 0.5 Custom 465 Custom 475 17-7 PH 15-7 PH AM-350 AM-355 A-286 S46500 S17600 S17700 S15700 S35000 S35500 S66286 0.80 Co 8.10 1.030 0.0 15..0–5.5 1.4 Ti 1.010 0..9 3.03 0.030 0.2 1. .50–1.0 0.1–0.5 7.70 4.8 1.. .00 1..45 Nb 0.0 1..0 3. 0..08 0.0 2.02 0.5–2..0–5..030 0.05 .5 2.0 4.15 0.030 0.5 0..0–23.0 24.0 24.8 1.0 10.50 .0 21.0–4.5–3.8 3.40 0.35 0..030 0.8 1.020 0.5 5.0 13. . .5 0.0 S32900 S31200 S31260 S31500 S31830 S32001 S32003 S32101 S32205 S32304 S32520 S32550 S32750 S32760 S32906 S32950 S39274 S39277 0..25 0.0 2..0–5.040 0......75–1.5 3.020 0.50–1.5 6.8 0.0–26.040 0..0 1.03 0..5 ..03 0.5 0. .20–0.4 Nb . 0. .0–26.5 ..5–1.25 2.6 0.03 0.0 2.0 0..040 0.5 3.5–9.5 Al 0.030 0.50–1.5–8.07 0.13 .5–3..0–5.01 0.0 16.0 14.0 6.0 Cu 2.30 0.0 26..0 0..030 0.5–3.25 4. 2.0–30.03 0.07 0.25 14.5 1.30 0..8–1.040 0.5–7.9–3. . .0 11.2–2.... .5–6.. 1.75–1..0–5.0 2.5–21..Table A1. .030 0..5 3.75–1.0 0..0 1.040 0.90–1.0–23.5–6.75 Cu 1.04 0.0–3.0–5.040 0.35–1.040 0...0–18.030 0.. % 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 2.0–6.6 0..20 0.5–4.2 Notes: All compositions include Fe as balance..010 .5–3.0–26.5–7.0–2.0 1.5 .5–1.5–23.75 1.07–0.0 1.5 .. 0.25 0.25 2.03 0..0 1. 0.. .0 2.10–0.08–0. 0.03 0.0 0.0 2..025 ..0 0.0 2.04 0.5–2.75–11.25 0. .5 2.015–0.0 24.0 28.5 Composition. .040 S17600 S17400 S15500 S13800 S45000 S45500 0.0 0.0–2.0–7.6 1.0 0..4 Composition..2 Cu 3.50 6.5 0.030 0.08–1.030 0.0–8.0 1.03 0.0–5..07–0.0 1.30 0.0 1.020 0.040 0...0–26..0 1.030 10.0–26.030 0.0 0.0 3. 15.0 21..0 24.5–3.25–1...0 1.13 0. .2 6.10 2. (a) Nominal value Table A1.00 1..2–2.0–22.5 1.030 0.0–12.0 1.0 24..0 1.9–2.0 5.05–0... 0.00 1.. .0–16. Ti 0.010 0.75 1.0 2. .8–7.0–1.010 0.010 0.4–2.5–8.0 2.5–8.25 7.5 19.015 0.0 5.10 .0–28.0 1.25–5.0–8.0 19.5–21.00 0. V 0. .045 0.020 0.035 0. Al 0.8 .14–0.0 4.040 0.5 12.50 1.0–27.5 4.50 1..21 .5–3.008 0.030 0.0–3.040 0.0–4. .20–0..75 1.5.20 0.25–13.5–2.5–5.00 0.0–17.001–0.10 0.0 7.0 115.0 0.03 0.5 24. .0 0.8 0.0 6.0–5.00 0. Ferrium S53(a) .030 0.50 0.0 5.015 0.. Ti 0.4–2.08 0.0 3.– 21.25 0.0 0.00 0.75 6.09 0.5 .0–2.5–3. ..50 16.0 18.0 6.23–0.0 5.0–26.5–2.03 0.10–0.0–6..0–12.030 0.035 0.10–0.0–26. .0 6.00 1.2 1.05–0.0–15.35 0. 0.. Ti 1.5 1.030 0.5 1.0–29.50 0.030 0.035 0.050 Co 14 .5–11.030 0. Single values are maximum values unless otherwise noted.5–7.10–.0–3..11 0..3 276 / Stainless Steels for Design Engineers Notes: All compositions include Fe as balance.040 0. % 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 11.20–0.0 5.0–9..040 0...5 14.030 0.50 1.75 4.03 0.5 0..0–27.1–0.5 .0–1.0–8.0–16.05–0.8 0.5 1.5–5.040 0.30 0.07–0.0 4.25 0.20 0..030 Al 0.0 0.25 1.14–0.0 0.0–17.32 0..50 10. . Single values are maximum values unless otherwise noted .0 24.8 0.33 23.0–7.0 ..020 0..0 1..0–19.0 1.0 1..15–0..5–16.14–0.5 3.03 0.15–0.010 W 1.20 0.030 0.45 Al 0.040 0.0 0..030 0.05 0.0 .17 0..0 1.25 2.8 1..03 0.00 0.020 0..5 Al 0.08 .0 2...0 22.1–0.4–1. 3.09 0.5–5. 1.5 2.030 0.35 Nb 8XC Nb +Ta 0.5–5. .05 0..00 0.0 1.0 1.0 1.8–1.35 B 0.5 0. Al 1..010 0.20 0.24–0..020 0.30–0.0–8.20–0..5–8.5–17.0 0. 2. .75 1.0 24.0 14.030 0.

.5 26.04 0.22–0.5–25.00 2..00 1.5–3.. W 0..0 0.04 0.04 0.12 0.0–21.04 0..03 0. 2.08 0.03 0.0 1.0–12...05 0.50 1.06 0.8 3.0–21.00 1.5 24.. 0... .1–0.04 0. S41500 422 17–4PH 15–5PH 2205 (S32205) 255 (S32550) (S32760) .. .24 .6 Composition.0 4.0 1.5 9..0–21. ..5–3.0 12. .0 1...2 Cu.04 0.50 1.00 1..50 1. 2507 (S32750) .3 V ..5 11. 0.0–3..9 Cu 0.0–21.50 1..0 1.20 0.5–14.0 16.5 .50 1..0–21..0–15.75–3.00 2.0–8..0 1.50 7.04 0..0–27.03 0.04 0..04 0.. .0 .50 1.0–9..04 0.20–0.04–0.04 0.. 0. .0–12.04 0.04 0.5–8..0 8.0 20.0 20..5–1. .0 1..00 1. 0..0–11. .2 Nb . . 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 ..04 0.00 1...0 12.6–4.0 12.04 0.04 0.03 0.04 0.04 0..04 0...04–0..65 1..04 0.08 0..5–13.5–14.00 1.0 11.0–21.0–9.5 2.0–11.0 13. ..0 8..5–4.0 0. 2..5–26...04 ..50 2..0–3.50 1.3V 2...0 2.0–7.04 0.25 Cu 1..50(b) 0.0 17.25 4.00 0..0 20.0 .04 0.10–0.0–21.30 0.0 11. .0 8.15 0..04 0.. .50 1..70 0.5 23.50 1...0–11. 0.04 0..0–21..04 0.0–3.2–0.0 9.24 11.08–0..0–23.00 1.40 0.50 3.0 22.25 0..08 0.75–2.00 1. Single values are maximum values unless otherwise noted.0–26..0–4.00 1. ...7 14..5 ..08 0.0–13.04 0.5–3.15–0.. .10–0.0–22.04 0.10 0..9–3.0–21.04 0.50 1.30 0. 0. 0.2 Cu.0.00 1.0 17.00 1.0 4.4–1.0–22.0 18.70 1.. .25 ..0 9.50 1.04 0.06 0. 0.10 0.00 2.00 1.0–7.5–6. Cu 0.04 0.10–0..50 2.5–1.5–4..04 0.6–6.00 1..04 0.50 0... ..10–0.. .75–6.04 0.. 4.04 0...04 0.0–27.50 1.0–11..50 1.20 0.. .75–2..0 18.2–0.0 (continued) 1.0–18...0 18..75–2..04 0.18–0..5–5..0–12.5 19. .07 0.0 26. J92701 J92602 J93790 J93000 J93001 J93400 J93401 J93402 J94653 J94202 J94652 J94651 0.5 4.0–15.. ..7–6.04 0.00 1.00 2.0–21.00 2..04 0.0 3.0 4.04 0..0–30.75–2. 0.2–0. ..06 0. Nb 8XC min .00 1...50 2. ..0–12.0 17.0 17..0–3.0–21.0–8.5 6.03 0.5 2.04 0.0–18.03 0.75–2. .0 1.04 0.5 .04–0.7 6.18–0. ..0–26. . .00 2.04 0. .16 0..5–14.50(b) .0–30.00 1..25 W..9–1.04 0.04 0.04 0.00 2.04 0.03 0.18 .0 11...35 .0 22.04 0.00 2. 2.10 0. 0..04 0. .10 0.04 0.4–1..04 0..50 1.30 0. .04 0.00 1.0 15.35Nb 2.20–0..0 8. .0 1.75–3.5–12. 0.5 15.0 23.0 Cu 2.0–26.0 11.04 0..50 1.5–14.04 0...0 22.5 0.. ..10–0.0–13..30 0. 0.10 0.0 8.04 0.00 1.0 11..04 0.. .04 0..0 9.20 0.Table A1.50 1....20–0.5 4.0–3..00 1.3 Nb.50 1.0 20.04 0.0–12. . .5–3. .5–19.0–22. .5–23.0 18.. . . .4 0. .0 22.17 0.0–26.. .00 1..0 2.0–26.25 ..03 0.04 0. .04 0.00 1.35Nb Cu 1.0 .40 .5–1.00 1.04 0.0 Cu 1..6 4.00 2.04 0.. . .00 1. (10xC)–1. .04 0.5 24..04 0.0–12. .04 0. ...50 1.04 0.0 18.50 1...0 9.04 0..25 Cu 2.0–4.. 2.04 0.0 8. % C Ni Mo S Other N Cr Mn Si P Composition of Alloy Casting Institute (ACI) heat– and corrosion–resisting casting alloys (continued) Name Wrought equivalent(a) UNS designation Corrosion–resisting alloys .0–13.. .00 2.5 21.0 18.025 0.04 0.0 10.04 0. 0.20 1..5–17.04 0. (b) Mo is not an intentional addition.5 5..04 0.0 23.0 18..04 0..0–5.0 8.. 0. .5 24.0 1.0 1.03 Appendix 1: Compositions / 277 Notes: All compositions include Fe as balance. 2.28 0.0–12.50 1.5–1. Se 0.12 0.25 1..0 18.5 18.50 1.0 10.0–11.00 1.0–12.30 .1–0. 1.08 0. 420 420F 431.0 18.20–0.06 0...9–1.442 446 .07 0.0–26.5–1.0–22.00 1.0 9..0–6.04 0.20 2.04 0.0 3.50 1.0 ..00 0.04 0.. .04 0.50 2..04 0.0 6.7 24.0–16.04 0..2–0.. ..5–5.50 1.5–26..0 3.00 2. .04 0.. 6.00 1.0–27..5–14.15–1...50 4.00 1..25 0.30 0.0–6.00 1..0 9.0 6.40 S .0 24.05 0.00 1. .0–27.0–23.00 0. 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 . (a) The wrought equivalent composition is not the same as the cast...50 1.00 0.04 0.15 0.33 0.08 0...30 .0 19.04 0.20 .00 0.04 0.04 0.04 0..04 0. 0.2–0.04 0.25 1. .0–21.0 . .5–20.0 24.10 1..0–15.0–15...0 8...

...40 0.20–0.0 Nb 0..5(b) 0..5–30.. .0 27.04 0.04 0.04 0.04 0..5(b) 0.0 19.04 0..20–0.2 .. N08605 N08603 N08005 N08006 N06050 0. 8–10 26–30 26–30 26–30 19–23 24–28 26–30 24–38 23.9–1.04 N08007 J94650 N08151 0.04 0.0 2.04 Cu 3..0 2.2 0.04 0..0 28–32 19–23 24–28 24–28 13–17 13.04 0...0 2. 330 .55 0.75 0...04 0.0 1.60 0.5(b) 0.5(b) 0.50 0..0 2.5 0.0–3.0 2.25–0. . .0–20.5(b) 0.35–0. ..0 37–41 58–62 64–68 1. ..5(b) 0..04 0...0 2.75 0.....04 0.04 0.5(b) 0..04 0.07 0.04 0. .0–27..60 0.04 0....04 0..0 1.65 1. .0 ..35–0. . ... 0.0 2. . ..0 2. . .5–3.0–34. .20–0..04 0.0–22..04 0.04 0. ..04 0.04 0.04 0..1–1. .035 0....04 0..0 2.0 2.0–21.0 2.0 18...0–4.0 2.5 2.0 . 4 max 4–7 8–11 9–12 11–14 14–18 18–22 19..0 2..50 0.5(b) 0.5(b) 0.. Zr 0.. (b) Mo is not an intentional addition.04 0.6 Composition. .04 0..04 0.75 Notes: All compositions include Fe as balance.04 0.04 0... ..5 2.0–17.0 2..0–25.5 2.. J82090 J92605 J93005 J93403 J92603 J93505 J94003 J94224 J94203 J94204 N08604 J94213 N08705 .04 0...5(b) 0.35 0.35–0.04 0.5(b) 0.0 2.15 19...0 23.5(b) 0.04 0.0 2..035 0..07 0..0..20–0.. 1....35 0.5 2.50 0.0 2..5(b) 0...04 0.05–0.. .0 2.75 0.5(b) 0.. .50–1. .04 0.5 2..50 1..35–0.. (a) The wrought equivalent composition is not the same as the cast....5 .0 18–22 23–27 33–37 33–37 33–37 33... .0 2. . ..5(b) 0.0–37. % C N Cr Ni Mn Mo Si P S (continued) Other Name Wrought equivalent(a) UNS designation 278 / Stainless Steels for Design Engineers 320 ..20 0.0 2.04 0..45–0.0 2..04 0...5–1. .0 31..0 2. .0 2.75 0. ..35–0.20–0.5 2. . .04 0.20–0..Table A1.. .0–22.... .20–0. . . .45 0.5(b) 0.0 0.04 0.. Single values are maximum values unless otherwise noted.25–0..0–6.0 Cu 1.04 0.50 0.0 19...50 0.50 3.04 0..35–0. ..15–1.0 17–21 10–14 15–19 ..50 0. .04 0.50 0. 310 .0 2. .5(b) 0.0 22... . . 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 .0 2. . W 4...0–22. .. .. .5(b) 0.0 2...0 2.35–0.5 2.5–2. ..50 0.0–27.5 0.. ..0 2.0 2.

72 7.5 13.95 8. GPa Coefficient of thermal exp.65 7. p 279-280 DOI: 10.5 14.1 Physical properties of major stainless steel engineering alloys Density.90 7.5 16.1361/ssde2008p279 Copyright © 2008 ASM International® All rights reserved.70 7.06 7.03 7. J/kg·°K Electrical resistivity.95 0.6 16.80 0. kg/dm3 Modulus of elasticity.5 13.80 .70 7.6 16.60 0..8 207 193 200 200 200 200 193 190 200 200 200 200 200 200 200 210 200 200 16.72 0.6 12.90 8.72 0.76 7.3 14. 10–6 × K–1 Thermal conductivity.3 13.5 10.92 7.6 16.89 0.00 7.2 10.86 8.5 16.63 0.56 0. www. W/M·°K Specific heat.72 0.3 16.60 0.9 24.3 10.8 7.0 23.5 13.5 502 500 500 500 500 480 500 460 474 477 460 460 477 460 500 510 500 500 0.6 16.3 16.3 16.3 15.8 25.org APPENDIX 2 Physical and Mechanical Properties of Select Alloys Table A2.74 0.80 0.9 17.2 25.3 10.Stainless Steels for Design Engineers Michael F.73 0.2 11.80 0.0 16.asminternational.6 16.6 16.8 7.0 24.3 16.90 7. McGuire.72 0.76 7.5 10.6 15.67 0.60 0. 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 7.0 17.

bright annealed. annealed.280 / Stainless Steels for Design Engineers Table A2. and temper passed.2 Name Typical minimum mechanical properties of representative stainless steel engineering alloys Condition UNS Yield strength. MPa Elongation. 2BA is cold rolled. .. /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 Tensile strength. 2B is 2D with an added temper mill pass (approximately 0. % 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 .5% reduction). and pickled.

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

although the range of problems to which these can be applied is broader: 1. Step: The amount of one state variable parameter (or condition) can be changed. Isothermal sections are the result of varying the amounts of two of the components for a fixed temperature. processing. and higher-order systems (calculations for alloy compositions with 6. etc. pressure. larger than a quaternary system). Single-Point Equilibria: The temperature. pressure. • Thermochemical data such as enthalpies. 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. the software typically is used to predict: • Stable and meta-stable phase equilibria for binary. ternary. Alternatively. Thermo-Calc can thus be applied to a number of practical problems related to metallurgy. another application is to calculate the carbon potential of multicomponent gas phase systems as a function of composition. volume and mole fractions) formed (phase balance) as a function of temperature. 4.e. 2. pressure. can also be considered. and solvus temperatures. or activity of the components) are changed at the same time. Map: Two axis variables (such as temperature. Four specific types of calculation can be performed using Thermo-Calc. as illustrated by some of the examples in the main body of this book). and pressure and then predict what phases an alloy might form at a given temperature when exposed to such a carbon potential. Examples of each of these kinds of diagrams are given in the main body of the text. Complex systems representing processing. in government research laboratories. For example. 3. solidus. meta-stable equilibria. to see how the different phases and their amounts and compositions would vary with temperature for a given alloy. While many types of calculations can be made using Thermo-Calc. phase diagrams. phase transformations. density. in-service performance.282 / Stainless Steels for Design Engineers parameters become). 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. • Amounts of phases (mass. Phase transformation temperatures can be predicted based on the actual chemistry (not nominal chemistry). as well as critical assessments and data evaluations for multicomponent systems. temperature. 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. Higher order in this sense means more than four elements (i. while the other conditions remain fixed. heat capacity. and thermal expansion • Scheil-Gulliver (nonequilibrium) solidification simulations Thermo-Calc is not restricted just to modeling the alloy. 15 elements are not uncommon. The software can . and various thermodynamic properties. 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. for example. composition.. 10. 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. 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. For example. 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 composition and also the chemical compositions of the phases formed • Phase transformation temperatures such as liquidus. multiphase systems as illustrated in this book) • Molar volume. one would “step in” temperature. and by commercial industry. be used to perform calculations for most applications involving phase equilibria.

and Thermo-Calc for Windows. N. which has a command line interface and can be run under a number of different operating systems (including Microsoft Windows and Linux/Unix). P. L. Demo versions are available for both of these versions of the software. Computational Tools for Materials Science. If you wish to run the software after the demo license has expired.0. com. 1. The demo version will run for approximately 1 month on a single computer. additional documentation.e. TCFE5—TCS Steel/Fe-Alloys Database. Höglund. T.thermocalc. Pergamon Materials Series. 2002. obtaining a new demo license).O. REFERENCES 1. p 273–312. Miodownik. it can be downloaded again (i. 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). On installation of the software. where further instructions regarding installation of the software will be provided.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.P. but problems related to installation or general inquiries can be addressed by visiting www. www.. Saunders and A. Shi. Sundman.F. Elsevier. 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. How to Obtain a Free Demonstration Version of Thermo-Calc Thermo-Calc is available in two formats: Thermo-Calc Classic.thermocalc. which has an easyto-learn graphical user interface but only operates in the Microsoft Windows environment.com .com. 2002 2. Vol 26. CALPHAD (Calculation of Phase Diagrams): A Comprehensive Guide. Thermo-Calc Software AB.com and linking to their support. Andersson. subject to the terms outlined in the Thermo-Calc Software End User License Agreement. including a Users Guide/Examples manual in the form of PDF files will also be installed.thermocalc. 2007. and B. Helander. Version 5.thermocalc. Thermo-Calc and DICTRA. 1998 3. A list of published articles citing Thermo-Calc is available at www. All fields in the registration form should be completed before continuing to the download page. The demo versions are free to use. J. Calphad. 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. Technical support for the demo versions of the software is limited. and installation on a network system is not supported.

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

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

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

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

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

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

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

103(F) duplex alloys. 174(F) duplex alloys. 233–235 cookware. 115. 207(T) ferromagnetism. 115(F) titanium and niobium. 115 chromium. 173. 3(F) phase in duplex alloy at room temperature. 152 ferritic stainless steels alpha prime formation. 174–179 deep drawing materials composition. 240–241 heating and water heating. 221–222 flatness. 178 flat. 202(F) stabilization with titanium. 3–4 carbon diffusion rate. 4 phase diagram of iron chromium. 165–166 automotive exhaust systems. 210 food contact bacterial retention by material and cleaning time. 174 change to body-centered cubic (bcc). 70(F) Schaeffler diagram. 176(F) forming limit diagrams for stainless steel categories. 185 machining setup recommendations. 173–179 forces for hot working. 247(T) pitting resistance equivalent number (PREN). 112(T). 241–242 kitchen appliances. 35 corrosion rates for various alloys of acetic plus formic acid. 183 (T) mechanical behavior. 227(T). 113 texture and anisotropy. 43 recommended annealing temperatures. 121–122 deep drawing. 180(F) forming limit diagram of carbon steel vs. 234(T) qualifications. 221 facades of appliances. 205–206 welding parameters. 274 (T) corrosion and oxidation resistance. 4–5 ferritic “H” alloys. 235 chemical neutrality. 115 composition. surface aesthetic. 176 (F) groups of low. 175–176 forming technology deep drawing. 240–241 flexible pipe. 241(T) surface disinfection. 252–253 flux cored wire (FCW) welding.. 220(T) fire resistance. 166 superferritics. 245–246 high-temperature properties. 237–240 material cleanliness. 120–121 time-temperature-transformation (TTT) curve for 430. 4 molybdenum. 159 impact strength variation with temperature. 233–237 stainless steels commonly used for appliances. 120 formic acid austenitic stainless steels. 116. suitability in forming stainless steel. 236–237 formability. 55 duplex alloys. 239(T) stainless steels commonly used for cutlery. 113 heat exchangers. 116(F). 113–116 metal migration into acetic solution from. 99(F) fatty oils and blends. 127(F) metals. 237 flatware and cutlery. 115 toughness. 118–120 stress corrosion cracking (SCC). 165 stabilization. 138–139 hydrogen and boron. 236(F) biological neutrality. 176(F) hot. 110.292 / Index F fabrication. 102 isocorrosion curves in. 2 Faraday’s law. austenitic stainless steel. rolled stainless steel. 117(F). 116–117 metallurgy. 36(F) forming limit diagram (FLD). 178 ferritics. stainless steel. 109. medium and high chromium. 228 flow lines. 114(F) kitchen appliances. 273 (T). cleaning methods for uncoated stainless. 47 soaking. 5 fingerprints. 4 mechanical properties. 239–240 face-centered cubic (fcc) phase aluminum alloys. ferritic stainless steel. 21 fatigue corrosion. 99 duplex stainless steel. 49 stress relieving. 120. 116 iron-chromium phase diagrams. 174 carbon diffusion rate in. 175(T) deep drawing schematic. 109. 121 hot rolling. 234(T) petroleum industry applications. 75(F) intermetallic phases. 179(T) ferrite carbon and nitrogen. 178 embrittling phenomenon. 239 lowest cost and simplest stainless. 118 titanium for carbide and nitride formation. 5(F). 5 austenitic materials. 3 diffusion rates in austenite vs. 91 Schaeffler–Delong constitution diagram. 1 austenite. 109–110 machinability. 12. 118–119 welding characteristics. 89 corrosion in. 226 body-centered cubic (bcc). 113(F). 117(F) annealing. 219 flatware. 165(T) sensitization. 4 thermal conductivity and thermal expansion. 6 δ-ferrite in precipitation hardening alloys. 180 . 111(T). 116 forming limit diagrams. 98. of stainless steel. 235–236 metal migration into acetic solution.

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

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

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

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

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

layer. 254(T) stress corrosion cracking (SCC). 88 corrosion in. 58. 92(F) iron-chromium. 94. 29 steel content. 254 precipitation-hardening stainless steels for. 189(F) elongated. 179(T) Pilling–Bedworth ratio (PBR). 254–255 restrictions in stainless steel use recommended by NACE. 247. 193–194 stabilization of austenitic alloy. 93–94 passenger trains. 34–35 duplex alloys. 114(F). 248(T) presence of wet carbon dioxide. 265–266 kraft process. 2 intermetallic. 248. 247(T) line pipe and flow lines. 8–9 structure of martensitic stainless steels. 88 corrosion type.298 / Index oxides effect calcium on machinability of 303. 39–40. 247(T) molybdenum influence on SCC susceptibility. 28 pigmented pastes. 3 impurity. 127. 10 pickling oxide layer removal. 249(F) demand for steel. 250 copper and nickel influencing corrosion rate of martensitic stainless alloys for OCTG. 85. 248. 250. 249(F) combating corrosion in applications. 27 passivity. 193–194 removal of oxide scale. 266 digestion. 195–196 stainless steel. 15(F). 248 umbilical tubing and risers. S and O. 253–254 pH. 6 ferrite impurity. 41 (F) phases alloy systems. 101–102 electropolishing solution. 190(F) inclusions. 93(F) pseudo-binary-. 189(F) oxyfuel gas welding (OFW). 63 pitting activities and activity coefficients in liquid steels. of stainless steel. 220(T) paper-making processes bleaching pulp. for iron and sulfur. 27 penetration equation. 23–25 removing surface contamination. 59 (F) iron-nickel. 132(F) photomicrographs duplex alloys. 40. 25 theory. 265 process equipment. 1 ferrite. scale. 254 martensitic stainless steels for. 248 refinery equipment. 41 machinability of stainless steel. 3(F). 190(F) x-ray examination showing Ugima. H2S and CO2 partial pressure. 250–252 platforms. 28(F) oxygen pressure. 193–194 uniform corrosion. 19 penetration rates. 210 oxygen austenite impurity. 23 transpassive regime. 129(F) physical properties major stainless steel engineering alloys. 130–131 phosphoric acid austenitic stainless steels. 1. 247 duplex stainless steels for. 64(F) P paint. 73(F). 248(T) ferritic stainless steels for. 157(T) influence on thermodynamic activity of C. 196 isocorrosion curves in. 3–5 free energy. and manganese sulfides. 61(F) pickling to remove. 40(T) austenitic stainless steels. 279(T) stainless steels. 127–128. 266–267 washing and screening. 2 Fe-Cr-Ni. 1 inclusions and pitting. with duplex alloys. 248. 3 impurity. 252(T) stainless steels for refinery processes. 250(F) National Association of Corrosion Engineers (NACE). 252–253 liquefied natural gas (LNG) vessels. 36(F) minimum temperatures for wet. 232 passivation effect on polarization diagrams. 251(F) austenitic stainless steels for. 15–16 phase diagrams computer models. 131. 19(T) petroleum industry alloy suitability vs. cleaning method for uncoated stainless. 113(F). 41–42 influence of alloying elements on thermodynamic activity of. 249(T) chromium influence on corrosion rate in environments by oil country tubular goods (OCTG). 188–189. 25. 266 partitioning elements. corrosion tendency. 102(F) phosphorus ferrite impurity. 25. 24 passive behavior. 261 . 130(F) iron-chromium-oxygen. 95(F) martensitic stainless steels. 258–259. 156 oxygen gas reduction. 78 Ugima. 157(T) influence on uniform corrosion. 252(T) OCTG. 156–157 martensitic stainless steels and toughness. 10 inclusions and pitting. N. 189(F) un-deformed. 188–190 metal with. in 303 matrix.

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

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

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

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

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

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

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