How important is passivation for SS?

Keeping stainless steels stainless

By Carl R. Loper Jr. May 4, 2004

Stainless steels are inherently resistant to surface attack in mildly corrosive environments. However, when corrosion does occur, it can result in the formation of pits on the surface or within crevices of the part. Why does this situation develop, and what can be done to prevent catastrophic failure? Ca ses of Corrosion
Stainless steel's corrosion resistance is due to a thin, chromium-rich, transparent oxide film on the surface 1. This protective film develops when more than 10.5 percent of chromium is present in the alloy and when the as or li!uid environment the stainless steel is exposed to provides oxy en to its surface. "nder these conditions, the surface is passive, or resistant to corrosion. #ailure to develop and maintain this passive film renders the surface active, or possessin corrosion resistance similar to conventional steel's or cast iron's. $t is essential that the entire surface %e in a passive condition. $f small re ions of the surface are active, they will %e readily attac&ed in a corrosive environment. This condition can %e measured usin electrochemical techni!ues as a potential of 0.'( volt %etween those active re ions and the ad)acent passive re ions. This condition will accelerate the rate of metal dissolution into the surroundin electrolyte.

!"at #s $assivation?
*assivation is the process of formin a protective oxide film on stainless steel. +owever, some confusion still exists a%out the definition of passivation and what really causes a passive film to form on the surface of stainless steel. ,n one hand, -ST. -/(0-00 notes that 1*assivation is a process %y which a stainless steel will spontaneously form a chemically inactive surface when exposed to air or other oxy en-containin environments. $t was at one time considered that an oxidi2in treatment was necessary to esta%lish this passive film, %ut it is now accepted that this film will form spontaneously in an oxy en-containin environment providin that the surface has %een thorou hly cleaned or descaled.1 ,n the other hand, -ST. -/(0-00 also notes that 1*assivation is removal of exo enous or free iron or iron compounds from the surface of a stainless steel %y chemical dissolution, most typically %y a treatment with an acid solution that will remove the surface contamination %ut will not si nificantly affect the stainless steel itself. "nless otherwise specified, it is this definition of passivation that is ta&en as the meanin of a specified re!uirement for passivation.1 Thus, passivation may refer to the chemical removal of free iron or iron compounds from the surface, or it may refer to the spontaneous development of a chemically inactive surface 3protective oxide film4 on the stainless steel. 5hile it is essential that surface contamination %e removed completely, it is the latter interpretation of passivation that relates to esta%lishin the corrosion resistance of stainless steels. ,nce the surface is cleaned and the %ul& composition of the stainless steel is exposed to air or an oxy en-containin chemical environment, the passive film forms immediately.

Creating t"e $assive %ilm

*assivation typically is accomplished either throu h an appropriate %ri ht annealin of the stainless steel or %y su%)ectin the surface to an appropriate chemical treatment. $n %oth procedures the surface is cleaned of contaminants and the metal surface is su%se!uently oxidi2ed. &rig"t 'nnealing. Bri ht annealin entails heatin the stainless steel to a suita%ly hi h temperature 3usually more than 1,000 de rees #, or 1,060 de rees 74 in a reducin atmosphere such as dry hydro en as. ,r anic contaminants are volatili2ed and most metal oxides 3includin those of iron, nic&el, and chromium4 will %e reduced, resultin in a clean, oxide-free surface. The stainless steel then is rapidly cooled 3throu h the temperature ran e of 1,800 and (00 de rees #, or ('0 and 695 de rees 74 to inhi%it car%ide precipitation, and then at lower temperatures exposed to air, where the protective oxide film forms spontaneously.

C"emi(al )reatment. Typical chemical treatment involves exposin the stainless steel surface to an oxidi2in acid solution in which the si nificant varia%les are time, temperature, and concentration. .any com%inations of these varia%les can %e used, %ut two of the most common are: 1. 90 percent nitric acid at '0 to 190 de rees # 390 to 50 de rees 74 for 90 to 190 minutes. -cid concentrations up to 50 percent can %e used, and the solution and residual effluent must %e monitored closely. 5hile very effective as a passivator, this solution may have environmental ramifications. 9. 6 to 10 percent citric acid plus 0.5 to 9.0 percent ;<T- 3ethylene-diamine-tetraacetic acid4 at 1'0 de rees # 3'' de rees 74 for one to 10 hours. ;<T- is a chelatin a ent that &eeps iron in solution over a wide p+ ran e. This solution has hi h reactivity with free iron, is less sensitive to exposure time, is far less corrosive to other materials, is less costly, and is considered environmentally friendly when used properly.

Meas ring $assivation

*assivation results in the formation of an oxide film havin a hi her chromium-to-iron ratio than the underlyin stainless steel %ecause of the preferential oxidation of chromium and the preferential dissolution of iron. Best performance is achieved with a 7r-#e ratio of the surface oxide of more than 1.5. -ST. -/(0-00 sets forth several techni!ues to determine the presence of free iron 3a measure of ade!uate passivation4 on the surface of stainless steel. The most commonly used of these is the copper sulfate test, in which a sulfuric acid-copper sulfate solution is swa%%ed on the surface for six minutes. The presence of any free iron 3inade!uate passivation4 is indicated %y the deposition of copper on the surface where free iron is present. This test may %e readily conducted on stainless steel sheet, tu%e, pipe, and fittin s, as well as on welds and heat-affected 2ones 3+-=4. $t should %e stressed that the protective oxide film formed durin effective passivation of the stainless steel is transparent and not o%serva%le to the na&ed eye. Stainless steel owes its corrosion resistance to its ready

#i ure 1 This interior view of a weld made on /06@ exhi%its the formation of heat tint on the weld and +-= caused %y the presence of oxy en durin or%ital weldin . oxidation to form this protective film> however, stainless steel's exposure to an oxidi2in environment at hi her temperatures 3or to a more hi hly oxidi2in environment at a iven temperature4 will result in the formation of an oxide 3heat tint4 of increasin thic&ness, ran in in color from a li ht straw to a dar& %lac&. The thic&er this heat tint oxide is, the reater the pro%a%ility that corrosion will occur %eneath the oxide film. -5S's <1(.9-00 ?uide to 5eld <iscoloration @evels on $nside of -ustenitic Stainless Steel Tu%es standard depicts tints developed on welds and +-=s caused %y variations in weldin parameters. $t is li&ely that the dar&er, thic&er oxide tints are the result of the formation of an oxide with hi her iron and ma nesium content> that is, reduced chromium content. $reserving t"e $assive %ilm

*reservation of the passive film re!uires the presence of oxy en in the environment to which the stainless steel is exposed. $n many instances of passivation failure, or corrosion attac&, the inte rity of the passive oxide film is compromised %y the concentration of halide ions, for example, chlorine, which chemically attac&s the oxide film. ;xtreme chloride concentrations may develop %ecause of evaporation in systems that are not properly drained, which ne ates the corrosion protection expected of stainless steels.

Re* (e* Corrosion Resistan(e

-n example of reduced corrosion resistance is shown in %ig re +. $n the interior of an or%itally welded section of /06@, the inner surface of the weld %ead, and the ad)acent +-=, are covered with a varicolored oxide film, or

#i ure 9 -fter removal of the heat tint oxide, evidence of in-service pittin in the +-= is apparent. heat tint. The color of this film is a function of the film thic&ness that developed at various distances from the weld. 5hen the section was placed in service, a corrosive environment preferentially attac&ed the stainless steel surface under the heat tint. ;vidence of in-service pittin in the heat tint in the +-= may %e seen in %ig re 2. This heat tint must %e removed %efore the part is placed in service for optimum performance. @i ht oxides can %e removed with %ri ht annealin when possi%le> li ht tints and iron contamination may %e cleaned with citric acid solutions> dar&er tints may re!uire cleanin with various pic&lin pastes> while heavier, dar&er oxide films will re!uire pic&lin solutions. #a%ricators, desi ners, and users of stainless steel components must understand the factors involved in successful passivation, identify the conditions under which that protective oxide film may %e compromised, and use techni!ues that expose inade!uate passivation. Carl R. Loper r., !h."., !.#., is a retired professor of materials science and en$ineerin$ at the %niversity of Wisconsin&'adison and ad(unct professor in the 'aterials "epartment at the %niversity of Wisconsin& 'ilwaukee. He can be reached at )*+&,-+&,.*/, fa0 )*+&,-+&,.12, loper,engr.wis(.e* . 3he author would like to thank 'onty 4. 5u0haus of '5 Services 6nc. and "avid 78"onnell and Carl 5ettermann of Rath 'anufacturin$ Company 6nc. for their assistance with this article. Aote 1. This film is a%out 10 atoms, or /5 an stroms, thic& 30.000/5 microns, or 1.6x10 -' inches4.