CHAPTER 16

Surface Finishing
Summary
SURFACE TREATMENTS are extremely important to the end user, and they are totally within the end user’s control and specification. They include the proper cleaning of stainless, the various means of descaling after thermal treatment, and the choice and application of surface finishes. The cost ramifications of improper or suboptimal surface treatments are immense because of the possibility of them compromising corrosion performance, which is a characteristic for which the end user pays dearly. Beyond such considerations, one can also create surfaces on the stainless that enhance its beauty and performance. The surface can be made reflective or matte, ground or mechanically patterned, coated, painted, plated, or oxidized. It can be treated chemically or electrolytically. The surface can be altered on an atomic basis, sometimes producing profoundly different mechanical and corrosion-resistant properties. All of these are discussed in this chapter.

Function of Surface Treatments
Removal of Oxide Scale

Introduction
Surface finishing is usually very important for stainless steel. The underlying economic justification for using stainless steel is that it does not corrode if properly specified for the environment it faces. Thus, its surface appearance remains normally intact throughout its life. This appearance should therefore be aesthetically pleasing, even in an industrial setting, and the surface finish should not detract from its performance. 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. Even so, there are surface treatments required for stainless steel intended for such uses. The stainless surface must be freed of: • Oxides resulting from annealing, joining, or hot forming • Accumulated ambient foreign material • Applied process materials, such as forming lubricants, fluxes, etc • Contamination from other materials, especially iron.

Oxide scales form on stainless steel during annealing, hot-forming, and joining operations. 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, so the surface of the steel under the oxide is chromium depleted and therefore has lost possibly a significant amount of corrosion resistance. An oxide scale is quite different from a passive film. Scales deplete chromium; passive films enrich the surface in chromium by selective loss of iron. Oxide scales are arguably best removed by pickling. Pickling is the chemical dissolution of the oxide scale. The acids commonly used are nitric (HNO3), hydrofluoric (HF), and sulfuric (H2SO4). HCL, which is commonly used to pickle carbon steel, is not recommended for stainless because it locally attacks (i.e., pits) the surface. HNO3 is an oxidizing acid that by itself does not pickle stainless. It is used in combination with HF to modulate the attack by the strongly reducing action of the HF. This combination allows good control of pickling rates by varying the ratio of the two acids. H2SO4 is used alone. It is often

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

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

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

• Oxidation (heat tinting) that occurs over about 250 °C (480 °F) • Residual stress due to surface working.25 μm) in Ra. ©iStockphoto. and will make adjacent pieces of stainless from the same coil look different. especially appliances and architectural panels. The length of the grit line varies with the speed of the material as it passes the rotating abrasive belt. This may be objectionable for certain products. • High surface hardness influences which abrasive will be effective. The main methods of producing aesthetic surface finishes on stainless steel are abrasive finishes and rolled finishes.to medium-sized abrasives that are bonded to a flexible backing. The difference can be more than 10 μin. is quite visually apparent. Table 3 Polished finish designations based on grit sizes to achieve target surface roughnesses Finish number Grit number Ra max. which are loose and do their work by being forced along the surface by a soft material.com/stevenallen Mirror finishes could be achieved with cold rolling followed by bright annealing. There are no official roughness values for the various surface finishes. Neither the producer nor the customer is protected by a clear specification as of this writing. Table 3 shows the varying surface roughnesses that are typical of polished stainless. 1 View of the Chrysler Building in New York. Polishing for aesthetic purposes is generally done with abrasive coated belts and is done to both coils and sheets. The latter are superior in uniformity and corrosion resistance. wet polishing) gives sharper cuts and less heat tint from frictional heating.75 0. (0.15 40 30 8 4 . 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. but the polished finishes are still more common.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. Lubrication during polishing (i.e. This has not entirely replaced sheet buffing to obtain mirror finishes. Thus. but sheet buffing has been relegated to those few applications where a high degree of perfection is demanded. 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. resulting in more surface brightness.0 0. Fig. 3 4 7 8 60–120 120–180 240–320 500 1. Polish appearance also depends on the length of the grit line caused by an individual particle of abrasive. Buffing is done by very fine abrasives. • Low thermal conductivity can cause excessive temperatures during processing and distortion.30 0. µm Ra max. the producer is encouraged to publish standards. and the customer should specify minimum and maximum Ra values for his purpose. ASTM merely describes the finish by a grit with which it is typically made.. µin. 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. Polish appearance varies also with the presence or absence of lubricant. This is distinct from grinding. Polished Finishes Polishing is carried out with coarse.

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

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

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