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CHAPTER 16

Surface Finishing
Summary
SURFACE TREATMENTS are extremely important to the end user, and they are totally within the end users control and specication. They include the proper cleaning of stainless, the various means of descaling after thermal treatment, and the choice and application of surface nishes. The cost ramications 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 reective 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 nishing is usually very important for stainless steel. The underlying economic justication for using stainless steel is that it does not corrode if properly specied 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 nish 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, uxes, 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 signicant amount of corrosion resistance. An oxide scale is quite different from a passive lm. Scales deplete chromium; passive lms 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), hydrouoric (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

194 / Stainless Steels for Design Engineers

used as a preliminary pickling because of its aggressive, and less-controllable, action. Pickling involves both scale dissolution and metal dissolution. Thus, pickling can be considered a deliberately imposed corrosion process. The scale formed during hot rolling may be an embedded scale with a minimal chromiumdepleted layer beneath the scale. 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. Nearly all the action of pickling derives from undercutting of the oxide scale and dissolution of the chromium-depleted layer. It is also vital that this layer be removed as it diminishes the corrosion resistance of the surface. Simply removing the scale mechanically may be insufficient if only the oxide is removed and the compromised (depleted) metal surface is left. Metal removal rates are proportional to the chromium level. Thus, sensitized material will undergo grain boundary attack if pickled. All stainless has slightly greater oxidation in the grain boundaries when it is oxidized, and this leads to ditching of the grain boundaries during pickling, resulting in the matte appearance of a pickled surface, as seen on two-dimensional at-rolled material. Typical concentrations for H2SO4 pickling are 8 to 15% by weight. Bath temperatures are generally 150 F (65 C). The rate of pickling decreases rapidly as iron builds up in the bath, and the bath must be replaced for efficient pickling. The attack of H2SO4 on the base metal can be severe, and undissolved constituents can remain on the surface as smut. This smut must be physically removed or dissolved by subsequent HF/HNO3 pickling. The HF/HNO3 pickling is carried out between 120 and 140 F (50 and 60 C). Higher temperatures cause excessive HF evaporation and can also lead to visible emission of nitrogen oxides. The NO2 (nitrogen dioxide) produced during the reduction of the HNO3 (oxidation of the metal) is visibly brown-red. The rate of NO2 formation increases at higher temperatures. HNO3 concentrations are normally from 10 to 25%. HF concentrations can vary from 1% for light scales to 8% for maximum aggressiveness and difficult-to-pickle alloys. The HF provides: a complexing agent for iron and chromium destabilization of the passive lm stabilization of the redox potential

The HNO3 provides: a source of H+ ions stabilization of the passive lm 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. It has been shown that the HNO3 can be eliminated and replaced by hydrogen peroxide (H2O2). This is the proprietary, patented UG3P process developed by Ugine (Ref 1) or Henckels CleanOx process. Electrolytic pickling is commonly used in the production of cold-rolled stainless. This process uses alternating positive and negative polarization in baths using sulfates or nitrates. The H+ ions are produced by the polarization instead of by an acid, so neutral solutions can be used. The low solubility of trivalent chromium (Cr+3), typically found in oxide scale, makes such scale hard to remove. Use of strong acids and complexing agents is required to get pickling to occur at an economically acceptable rate. Hexavalent chromium (Cr+6) is much more readily soluble in aqueous solutions, for example, oxidizing treatments such as Kolene,* a molten mixture of nitrate salt and hydroxide, or electrolytic conversion treatments such as electrolytic sodium sulfate. Both treatments convert the trivalent chromium to hexavalent form, allowing for easy scale dissolution. Their use may, however, lead to environmental problems as hexavalent chromium compounds are toxic and heavily regulated. Pickling may be assisted by prior treatment of the scale in molten 85% sodium hydroxide (NaOH), 14% sodium nitrate, and 1% sodium chloride bath. 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, making it more easily removed by subsequent pickling. Cleaning Stainless steel is very resistant to chemicals of many kinds, permitting it to be cleaned by many aggressive agents. Because contamination is on the surface of stainless rather than in the surface as is the case with many materials, simply using the cleaning agent appropriate for
* Kolene is a registered trademark of Kolene Corporation.

Chapter 16: Surface Finishing / 195

the contaminant will permit very thorough cleaning of the stainless surface. The stainless surface will not be harmed by cleaning as long as strong halides, iron utensils, and abrasives that alter the surface nish are avoided. Table 1 summarizes some cleaning recommendations based on the contaminant to be cleaned. The greatest controversy regarding cleaning stainless steels involves the use of sodium hypochlorite. Many highly qualied experts atly disapprove of its use because it can easily leave a residue of chloride on the stainless surface, leading to localized corrosion. But, in reality, health considerations make this position untenable. Sanitation concerns in the food service industry take precedence over this prohibition. In fact, every stainless steel, as explained in the Corrosion and Oxidation section of this Volume, is resistant to some level of chloride concentration at a given temperature and pH. Thus, short-term, room temperature use of hypochlorite bleaches will generally not harm most types of stainless steel if well rinsed after application. Field experience has shown that stainless steels with less than 16% chromium can be harmed by hypochlorite bleaches. Damage occurs mainly on abrasively polished surfaces in alloys with 16% chromium, such as 430, but does not occur on roll-nished or bright-annealed surfaces. Stainless steels with slightly higher chromium and nitrogen, such as 201, 301, and 304, are not attacked unless concentrated chloride solutions are permitted to stay on the surface, particularly in crevices. The recommendation not to use abrasives does not include soft abrasives such as calcium
Table 1
Contaminant

carbonate or brush material that is sufficiently soft not to mar the stainless surface. The user is encouraged to test whether a product meets this requirement by testing it on a small, preferably unexposed, area. Blasting the surface with carbon dioxide pellets is a rapidly growing process for removing paint and other adherent, soft coatings and deposits without damaging the surface of stainless steel. These cleaning recommendations apply to industrial, architectural, and domestic uses of stainless. For special levels of cleanliness required for medical, pharmaceutical, or semiconductor applications, refer to the chapters dealing with those applications. Passivation is a very commonly used surface treatment to remove surface contamination, notably iron, and to form a passive lm. The lm forms of its own accord when a clean surface encounters moist air, but lm formation can be accelerated by controlling the environment. The surface to be passivated should rst be cleaned by one of the methods discussed. This allows uniform passivation and avoids contamination of the passivating solution, especially by chlorides, which can cause a rapid attack. Those stainless steels with more than about 17% chromium can be pickled in 20% HNO3 at 50 to 60 C (140 F). Precipitation-hardenable (PH), martensitic, and straight chromium grades with less than 17% chromium should have 2.2 g/L sodium dichromate added to that solution to avoid attack. The free-machining grades are the most easily attacked of all types. 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, oil

Soap, detergent, or dilute ammonia Detergent and warm water or a hydrocarbon solvent Hydrocarbon solvent

More severe stains, discolorations, and rust stains Hard water scale, mortar Oxides, heat tint

Nonscratching creams or polishes

1015% phosphoric acid, sulfamic acidcontaining, or oxalic-containing cleansers If severe, treat by pickling; Scotchbrite, stainless scouring pad, or nonscratching cream or polish Alkaline, trisodium phosphate, or hydrocarbon solvent

Use a soft cloth or sponge, clean water; dry with forced air or a dry cloth. Wax and oil polishes minimize ngerprinting. Glass cleaner is appropriate for mirror nishes. Alkaline cleaners may also be used in severe cases but may require cleaning the entire surface to maintain visual uniformity. Do not use HCl-containing products. Hypochlorite bleaches must be well rinsed to avoid pitting. Neutralize with ammonia, rinse, and dry. Do not use HCl-containing products. If abrasives must be used, they should blend with existing surface nish in size and direction. Follow manufacturers directions

Paint

196 / Stainless Steels for Design Engineers

nitric/dichromate passivation is performed. This should be followed by a rinse, another 30-min NaOH treatment, and a nal rinse. In recent years, citric acid has become a popular replacement for HNO3 because it avoids the problem of toxic nitrates and hexavalent chromium. When citric acid is used, a 10% solution is applied for the same time and temperature as with HNO3. The use of NaOH before and after is still recommended for lowchromium and free-machining alloys. Refer to ASTM documents A 967-01, A 380-99, B 91200, as well as Federal Specication QQ-P-35. Brightening Stainless steels can be brightened by chemical or electrolytic action, which selectively dissolves the surface in such a way that it becomes microscopically smoother. Electropolishing is the most effective means of accomplishing this. It causes the surface roughness to decrease by approximately one-half in Ra (the arithmetical average of surface peaks and valleys as measured over a straight line). Electropolishing, like pickling, also selectively removes any exposed chromium-depleted regions, 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. The reectivity of the surface is a function of the preelectropolished surface. The most commonly used electropolishing solution is 40% H2SO4 and 45% phosphoric acid (H3PO4), balance water, used at 90 C (194 F) with a current density of between 1.0 and 3.0 amp/m2. Other baths using perchloric acid are technically good but carry the risk of explosion. Coloring Stainless steel passive lms are so thin that they are quite invisible. Oxide lms are thicker and through optical interference can cause different colors. The lms are formed thermally in a process known as heat tint. The color depends on oxide lm thickness, which is a function of the time at a given temperature, well metal composition, and oxygen partial pressure. 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). Reproducibility is sometimes a problem.

Electrochemical methods permit more uniform and reproducible color and tougher lms. The most prominent is the International Nickel Company (INCO) process. In this two-step process, the steel is rst immersed in a mixture of one part chromic acid, two parts H2SO4, and one part water at 30 C (85 F). This is followed by an electrochemical treatment with the same bath or with H3PO4 substituted for H2SO4. The colors produced are correlated to thickness and treatment parameters (Ref 2) as shown in Table 2. Rocha-Fila et al. conrmed that these coloring treatments did not degrade the pitting corrosion resistance since their formation mechanism more closely resembles passive lm formation than oxidation.

Aesthetic Surface Finishes


When steel is used in other than the asannealed and pickled state, it is often for aesthetic rather than functional reasons. The major exception to this is temper-rolled strip, which has a bright surface from cold rolling, but whose normal use is strictly functional. The hotrolled or cold-rolled annealed and pickled surface nish is nonuniformly dull and unattractive to most observers. When stainless steel rst appeared on the market, a highly polished surface was the paragon, as showcased on the Chrysler Building in New York City (Fig. 1). This surface nish was very expensive to produce since it had to be done by polishing and buffing. Soon, the more economical abrasive polishing became the standard, and it had the benet of removing the many cosmetic defects that then were common to the manufacture of stainless. 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.
Table 2 Parameters for oxide lm coloring of stainless steel
Heat treatment time Color Oxide lm thickness, 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

Chapter 16: Surface Finishing / 197

Stainless steel surface nishing is governed by: High strength and high work-hardening rate require more power for metal removal. High surface hardness inuences which abrasive will be effective. Low thermal conductivity can cause excessive temperatures during processing and distortion. Oxidation (heat tinting) that occurs over about 250 C (480 F) Residual stress due to surface working, especially in austenitic alloys Grinding is a relatively coarse procedure with usefulness that is largely conned to defect removal. Polishing for aesthetic purposes is generally done with abrasive coated belts and is done to both coils and sheets. There are no official roughness values for the various surface nishes. ASTM merely describes the nish by a grit with which it is typically made. Table 3 shows the varying surface roughnesses that are typical of polished stainless. Neither the producer nor the customer is protected by a clear specication as of this writing. Thus, the producer is encouraged to publish standards, and the customer should specify minimum and maximum Ra values for his purpose. 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. The difference can be more than 10 in. (0.25 m) in Ra, is quite visually apparent, and will make adjacent pieces of stainless from the same coil look different. This may be objectionable for certain products, especially appliances and architectural panels. Polish appearance varies also with the presence or absence of lubricant. Lubrication during polishing (i.e., wet polishing) gives sharper cuts and less heat tint from frictional heating, resulting in more surface brightness. Polish appearance also depends on the length of the grit line caused by an individual particle of abrasive. The length of the grit line varies with the speed of the material as it passes the rotating abrasive belt,
Table 3 Polished nish designations based on grit sizes to achieve target surface roughnesses
Finish number Grit number Ra max, m Ra max, in.

Fig. 1

View of the Chrysler Building in New York. iStockphoto.com/stevenallen

Mirror nishes could be achieved with cold rolling followed by bright annealing. This has not entirely replaced sheet buffing to obtain mirror nishes, but sheet buffing has been relegated to those few applications where a high degree of perfection is demanded. The main methods of producing aesthetic surface nishes on stainless steel are abrasive nishes and rolled nishes. The latter are superior in uniformity and corrosion resistance, but the polished nishes are still more common. Polished Finishes Polishing is carried out with coarse- to medium-sized abrasives that are bonded to a exible backing. This is distinct from grinding, in which abrasives are bonded rigidly to each other on a rigid backing. Buffing is done by very ne abrasives, which are loose and do their work by being forced along the surface by a soft material. The standard rule is that materials used in nishing must not permit iron or iron oxide particles to come in contact with the stainless surface or passivation layer.

3 4 7 8

60120 120180 240320 500

1.0 0.75 0.30 0.15

40 30 8 4

198 / Stainless Steels for Design Engineers

and the rotational speed and diameter of the backup roll for the abrasive belt. This combination of variables, while seemingly controllable, usually varies enough so that no two polished sheets look identical to the trained eye. This variability also causes problems in eld repair. Repair of a polished surface damaged, for example, by welding or scratching is quite challenging. A perfect match and blend to the surrounding original surface is an art, and no practitioner of that art can accomplish it perfectly. If the repaired area is small, then it can be acceptable, if not undetectable, but for large areas, repolishing of the entire surface is often the best remedy. A solution to the problem of matching polished surfaces is to use very long grit lines for nishes of the same roughness. By eliminating the variable of grit length, only correct pressure and grit size are required to achieve good visual matching. This can be done with a belt sander. These nishes are called hairline in Japan and grainline and other names in the United States. Lack of uniformity, difficulty of repair, and a decrease in corrosion resistance are the chief drawbacks of polished nishes. Bright Annealing Aesthetic nishes that do not depend on abrasion are derived from bright annealing. Bright annealing is annealing in a very low oxygen atmosphere, either dissociated ammonia* or hydrogen/argon. This process was originally developed as a means of producing bright ferritic trim for automobiles. That use has largely passed out of favor, but the process itself is intrinsically superior to annealing in air because no oxide is formed only to be later removed, usually at signicant expense. Because the original product was strip, many older bright-annealing facilities are narrower than normal sheet width. The wider, more modern lines are high speed and wide enough to produce bright sheet. Bright-annealed sheet will only be as bright and awless as the cold-rolled sheet that is annealed. Therefore, a quality product, generally as mirror-like as possible, must be produced with great care. The better producers have proprietary methods of prior pickling, annealing,
* At one time, dissociated ammonia referred to a 3:1 (mole ratio) mixture of hydrogen and nitrogen produced by the catalytic decomposition of anhydrous ammonia. Today, this composition is prepared by mixing gases. For many stainless steels, the 3:1 H2:N2 can be varied without difficulty.

and rolling by which the surface is made awless and very smooth. Final brightening occurs with temper passing after 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 nishes, which can take on any appearance and can be engraved onto a temper mill roll. All polished nishes can be duplicated as rolled nishes. But, in addition, many other designs such as replicating fabric or leather, geometric designs, or matte nishes can also be made. The pattern on the roll is impressed into the stainless surface, and elastic attening of the roll and the stainless cause about 50% less Ra on the stainless than on the roll. This effect increases with the yield strength of the stainless being processed. The benets of rolled nishes are: They can be made identically from coil to coil since roll engraving is quite precise. They retain the enhanced corrosion resistance of bright-annealed material. They are less expensive to produce, so the nal product is generally priced lower than polished material. In theory, such nishes can be made from airannealed material, but nishes applied by roll to two-dimensional surfaces that have been dulled by pickling are somewhat gray and indistinct. If the pickling is kept mild enough to retain surface brightness, then it is possible insufficient prickling has occurred to remove the chromiumdepleted layer caused by the air anneal. Some of the nishes produced by rolling are shown in the architectural chapter (see Chapter 18). These nishes can be applied to all the normal sheet alloys, including the lean duplex alloys. This has permitted rolled nishes to be used on UNS 32003 for building exteriors in Doha, Qatar, where corrosive conditions require a PREN (percentage chromium equivalent) of 25. The most critical applications from a surface perfection point of view use rolled nishes rather than abrasively nished number 4 polishes. These nishes also permit type 430 stainless steel to be used successfully in restaurant applications without corrosion issues where polished type 430 material previously had corroded. There are also instances for which polished UNS S31600 was corroding in coastal

Chapter 16: Surface Finishing / 199

architectural applications in the United States. When the abrasively polished surface was replaced with rolled nish UNS S30400 (Koolline), there was no further corrosion. Because alloying is such a high component of cost in stainless, it makes sense to employ rolled nishes whenever possible. However, it must be noted that when manual polishing is used to repair scratches or other damage in rolled nish material, its corrosion resistance may be reduced. Surface Alteration In carbon steels, surface chemistry can be changed to affect certain properties. Carburizing and nitriding are examples of such processes. Simply using these processes on stainless cannot be done because these elements combine too strongly with chromium as carbides or nitrides, dramatically reducing the corrosion resistance. There have been modications to carburizing and nitriding that permit austenitic stainless steels to have very high carbon levels implanted to a thin surface layer. 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.% carbon in supersaturation can be achieved without carbide formation. The properties of this layer are phenomenal; the hardness is 1000 Vickers 25 compared to 200 for the base alloy (Ref 3). In addition, the corrosion resistance increases signicantly. Only by such supersaturation with carbon could it be determined that carbon, like nitrogen, is a powerful antipitting alloying element when kept in solid solution. These processes are at the very initial stages of commercial use.
REFERENCES

1. Stainless Steels, Les Editions de Physiques, 1989 2. C. Rocha-Filo et al., J. Braz. Chem. Soc., Vol. 15 (No. 4), 2004, p 472480 3. Y. Cao, F. Ernst, and G. Michal, Acta Mater., Vol 51, 2003, p 41714181

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