Pr Materials Selection In The CPI An overview of the many factors to be considered when selecting materials of construction James J. Briem Briem Engineering IN BRIEF RESOURCES ‘CORROSIVE ENVIRONMENT: vELOoTY TEMPERATURE CLEANNG/GANTIZATION (OPERATIONS ‘SURFACE NSW PASSIVATION DDOWNTIVE CORROSION MATERIAL PROPERTIES SAFETY cost ‘AUSTENITIC STANLESS. STEERS ‘CCRGLUDING (COMMENTS electing a material of construc tion for process equipment in the ‘chemical process industries. (CP) is normally not difficult, The material ‘selection is often based on past industrial ‘experience. With few exceptions, past ox- perience is by far the best way to choose ‘an acceptable material of construction However, when past experiance cannot be used as a guide, material selection can be complex and difficul. Unfortunately the ‘complexity of the problem is often not fully recognized, The individual making the ma- terial choice may fail to consider all of the factors invalved, ‘The objective of this article is to provide an ‘overviow of the many factors that should be ‘considered when selecting a metalic or non- motalic material of construction. A checklist is provided in Table 1. Some of the many fac- {ors are obvious; others are nat so obvious Neglect of the not-so-obvious factors could result in costly equipment failures, This article elaborates briefly on corrosion ‘considerations, stress loading and a number of other factors that affect material selection Initial and ongoing cost considerations are also reviewed. Resources Corrosion resistance is the first and most ob- vious factor to consider when selecting ama- terial of construction for process equipment. The chemical environment provides the frst clues to selecting an acceptable material ‘As mentioned, past industrial experience is the best way to address the corrosion issue (Other resources include laboratory corrasion tests, pilot-plant corrosion tests, published ‘cortosion charts, data published by the Na~ lional Assn. of Gorrasion Engineers (NACE; Houston; www.nace.org), manufacturers data, textbooks, articles and materials con- sultants. Most of these sources are avaliable (on the Internet, (Chemical enone Impures Microbial intunced cae MC) Cares into Cares aocelertrs Chemie reacton inten ety deren ‘lot coasion reson and ‘ow accelerated carason FAO) | Teegeratre Dowie caosien Heat rater Ira presse Vacuum cing asta stresses “Therma sess yale sess ‘Aerormal sesses Safety nd ea acs aces ane Specitcatons Profit cortsmnaon Base materi cost fase o oration Fins appearance Des ie ality ratty Neier eof rar Facuired martrares Vl ott coniots Vale of downtime Corrosive environment Ina corrosive environment, the primary con- stituents and their concentration ranges are Usually known by the procass or project en= gineer. Not so obvious, however, is the pres- tence of impurities. The classic example of a harmful impurity is the chloride ion, which, Under certain conditions, is known to cause stross-corrosion-cracking (SCC; Figure 1) and pitting of stainless steels. Thess insidi- ‘us forms of corrosion can occur al concen- trations as low as a few parts per milion. ‘An impurity that is commonly found in waler is bacteria. Bacteria cause a type of corrosion known as microbiologically influ-FIORE. Tis enced corrosion, or MIC for short (Figure 2), This is a form of corrosion in which the bacteria can eat through stainless- steel tanks and piping in a few months. The bacteria primanly attack the retained, ferric, metalic grains in stainless weld ments, although MIG can occur in the base metal remote from weldments. The bacteria burrow caves (Figure 3). As ob- served with a scanning electron micro- scope, the cave surface has the appear- ance of a honeycomb structure (Figure 4). Unfortunately, most commonly used ‘metals are subject to MIC attack to vary- ing degrees, ‘The authors company is curently in- vestigating MIG attack in a new process- ing plant at which the hydrostatic test water was lettin the stainless-stee! piping system for several months afte the hydro static test. This stagnant water alowed bacteria to eat through several milion do lars’ worth of piping in a few months. ‘Some minor constituents of a chemi- cal environment can actualy inhibt cor- rosion. One not too obvious example of this is the inhibition of SCC of titanium in ‘methanol. Titanium is subject to SCC in anhydrous methanol at room tempera ture, but if water is present in concen- trations above 1%, the titanium wil not stress-corrasion-crack. As another 6x- ample, low concentrations of sulfites pre- vent oxygen pitting in boilers. ‘An infrequent, but potentialy costly mistake is to select a material of con- struction that, if corroded, couid inhibit a process chemical reaction. Nickel, cop- per and other metallic corrosion products have been known to kil a chemical re- action that was essential to the chemical processing operation. ‘The acidity of a chemical environment may have @ significant effect on material pals and etchod metalgical cross acon tastiest! pipe wed a 200» mapieaton, The renting, ‘rangranulr craks ar chores of ste carson erckng selection. As a general statement, the lower the pH, the more aggressive the Contosion. A pH variation ofa few points, Could make the diference between using a relatively inexpensive material and a coslly material of construction. For ex- ample, a lower pH environment allows a lower chiorde concentration to stress- ccorrosion-crack stains stots The presence or absence of air (ox ygen) may also affect the corrosion resistance of a material in a. specific enviroment. The presence of Op or the occasional exposure to air may be necessary to maintain the protective ‘oxide fms on materials, such as stain- tess steel, which depend on a chrome- oxide fim for corrosion resistance. On the other hand, the presence of air may destroy the corrasion resistance of a material that is normally not corroded in a reducing, Op-tree chemical environ ment, Boiler feedwater is a good exam ple. A baller can fallin six months it Op is present in the boiler feedwater. The ssame boller could last six decades with deoxy. Velocity Velocity must be evaluated when select- ing amaterialof construction, particularly ‘when considering pumps, agitators, and ‘other equipment subjected to relatively high fluid velocities. Velocity can mani- fest itself in a corrosive environment as *corrasion-erosion” or flow-accelerated corrosion (FAC). Of concern here is the fact that most published corrosion data are based on relatively stagnant corro- sion conditions. Although there are a few exceptions, corrosion increases as velocity increases. An example is com- mercial-grade ambient-lemperature sul- {uric acid transport in carbon steel pipe. FIGURE2, Niccbioialy ince caroson (MC) cannt be canfmed fom ‘aval epost, Carnes nears weld seam ar 2 tong inden of MC Fresh, \etcabunces removed an anew rained pipe can be cated to confi the presanee of mcrabes an dont specasproson FIGURE 3. This magi cross se ‘in ofa weld ina slalessste pe reveals a cve suture hat conms ‘MG. The cave stctres ical ‘ocr at the boundary betnoon a weld rd the base metal afiPr FGURE 4. Th honeyomb strc. {ee eserves on the suas. Ins he cave eons MC Tis Ia searing een meressoie view at 800 magnon Ata velocity below 3 ft/s, the acid can be salely handled using carbon-stee! pipe At higher velocities, the protective iron- sulfale layer is stripped away from the pipe wall and corrosive failure occurs in a shor time. One notable exception to the above is microbiologically influenced corrosion Bacteria ike stagnant water, Flowing water inhibits MIC. ‘Temperature The basic effect of temperature on the cortosiveness of an environment is well known by most process and project en- gineers. As a rough estimate, the corr: sion rate doubles for every 10°C increase in temperature. This is essentially tue up to the boling point. If the operation is at a temperature above the dew point, in a gaseous state, the corrosion rate is es- ssontially ri ‘The above statements explain why condensing a corrosive gas results in cor- rosive attack that would not occur if the operation is kept above the dew-point temperature. ‘The effect of temperature must be carefully assessed for each enviranment. Many material faiures occur because the temperature evaluated was the mass temperature of the corrosive materal in a vessel, not the higher inside-surface tem: erature of a steam-jacketed vessel Cleaning/sanitizing operations Consideration should be given to the procedure and frequency with which the process equipment will be cleaned and sanitized. It is not unusual for the cleaning operation to corrade process: ing equipment. Periodic cleaning with steam and cleaning agents can corrode processing equipment even though the basic production environment is non: corrosive. When designing for a specific operating environment, don’t neglect the leaning operation. Surface finish/passivation Surface finsh isan mportant consider- ation perticuarly when deaing with stain- less steels used in the pharmaceutical and fooc-provessing industries. The sur- face finish must comply with U.S. Food and Drug Administration (FDA: Washing- ton, D.C.; wwnwfda. gov) requirements to minimize the possibly of any bacteral growth on surfaces Another important finish consideration for stainless steel isthe issue of surface passivation, Process engineers are far iar with the passivation of stainless steel with an oxidizing acid, such as nitric or citi acid. The passivation treatment pro- duces a passive protection chrome-oxide fim on stainless. steels. This. chrome- oxide fim is responsible for the overall corrosion resistance of the commoniy Used austenitic stainless steels, such as 04 and 316. There is some controversy over the necessity for using a passiva tion treatment, either italy or at intervals while the equipment is operating. itis this author's opinion that the main reason for passivation is not necessary to form the protective chrome-oxide fm but rather to thoroughly clean the surface of any do- posis on the surface that could inate pitting cortsion of the stainless steel Normally, stainless steel wil slt-passivate with intermittent exposure to the oxygen in the atmosphere. If there is no intermit- tent exposure of the stainless-steel sur-face to oxygen, then intermittent passi- vation treatments may be necessary to maintain the passive chrome oxide fim on the stainless-steel surface, I this pas~ ve flm is not maintained, the stainless steel becomes active and has a corro- sion resistance approximating that of carbon steel Downtime corrosion Corrosion that occurs when a piece of equipment is not operational can be ‘more severe than corrasion that occurs when the equipment is online. Equip- ‘ment that operates in a gaseous environ- ment al moderate temperatures above the dew point will suffer more corrosion at lower temperatures than when online at an elevated temperature. An example Of this is a boiler economizer operating in fuegas containing SO. Ina recent project, a boiler fring a bio- fuel gas with high-sulfur content filed in less than a year due to frequent shut- owns. A large fire-suppression sprin- Kier system sat stagnant end failed due to grooving corrosion (see Figures 5, 6 and 7). Material properties ‘The next group of factors affecting ma- terials setection includes mechanical and physical material considerations. On occasion, the thermal conductivity of a material may detetmine its acoept- ability for process equipment, the most obvious example being heat exchangers, Low thermal conductivity may be desir- able for certain equipment. For example, an _un-insulated _fiberolass-reinforced plastic tank may be more economical than an insulated carbon-stee! tank, Evaluation of internal pressure is ad- dressed by standards, such as the ASME Boiler & Pressure Vessel Code and the ASME Piping Codes, and needs no elab- oration here. ‘The intended or unintended presence of a vacuum should be considered, Be ‘cautious of potential vacuum loading re- sulting from steam collapse in storage tanks. Vents ftozan shut by ice or cor- rosion product have caused many tank failures when cold weather conditions caused steam to condense inside the ‘vessel, creating a vacuum. Both metalic and non-metalic equip- ment may contain residual stresses that are usually produced during equipment fabrication. Forming, welding and ma- chining metals may result in significant residual-tensile stresses approaching the yield strength of the metal, These residual stresses are often the primary cause of ‘SCC, Residual stresses may contribute to corrosion fatigue fallures. ‘Thermal stresses are another consid- ‘ration that should not be neglected for process equipment operating at non- ambient temperatures. Thermal stress ‘occurs in a monolithic material that op- erates al different temperatures in difer- cent locations. Thermal stresses are also important when combining different ma- terials with different coefficients of ther- mal expansion. Consider a plastic-ined ‘vessel where the thermal expansion of the plastic can be an order of magnitude higher than the substrate steal Cyolic stress is offen overlooked or underestimated. Cyclic siresses cause fatigue failure, Faligue is the falure of a material under cyclic loading at a stress level well below the publshed tensie srength of the material. AS a very rough estimate, fatigue strength is only about haif the tensile strength of the material. In a corrosive environment, cyclic stresses ‘can result in “corrosion fatigue,” a stress- related matoral failure that can ocour at a stress below the normal fatigue strength of the materia Most published fatigue data are for fatigue strenath in. an air environment When corrosives are present, the fatigue strength is even lower and if failure oc- FIGURES. Tis sprinkler systom pipe ‘ato larg wiht shag or onypen ‘cavengat maintenance. Premature are was cased by grovingcaro- ‘Son of te longitu pipe weldsFAGURE.. Stora wate inside te spike pipe caused grooving crasion ofthe login wed seam [FIGURE 7. This metalrgcl css section o srk sytem pipe eveals ‘oovingcoosion ofthe longitudinal weld seam. The govig cortsin is ‘Caused bythe weld seam being aro credng rave tothe rest of he ‘pe wall which scathade cours, the failure mechanism is defined as corrosion fatigue. ‘Abnormal stress loads must be con: sidered. Examples include pump vibra tion loads, loads resulting from agtator mountings, and, of course, the impact of an errant fork truck, Safety Today’s increased concern for safety and health has had its impact on materials of construction. In the area of safety i's eas ierto comply with an OSHA (Occupational Safely and Health Agsn.; Washington D.C.; wwawosha.gov) quard-rall requie ment on a metal tank than on a piastic tank. Asbestosis no longer an acceptable ‘material of construction. In the food and hermaceutical industries, the material selection is often lrited to'a material that is vitually imperious to chemical attack. Another factor to consider isthe degree of hazard to humans and the environment that could resuit from the accidental re lease of hazardous materials contained in a vessel oF pipe should fallure occur. ‘The government, indusiry and individual companies have cades, standards and specifications that will often impact oreven determine the selection of a construction material. These codes, standards and specifications must be considered when selecting materials of construction Cost Naturally, in selecting material of con- struction, the objective is to find a mate- rial that wil result ina long safe service We at a reasonable cost. In assessing the ‘economics of a material, both initial cost ‘and lifecycle cost should be evaluated. A normal and reasonable first step in evalu- aling inital cost is an assessment of basic ‘material cost. Consider the ease of fab- rication. Are the materials easily formed, cut, bonded, dlled or welded? Is heat treatment required? Finish and appearance willimpact cost. Polshed stainless steel may be neces- sary for equipment used in the food and pharmacautical industries. Sprayed foam insulation is less expensive and less at- tractive than lagged, biock insulation. ‘The ife expectancy and desired reiabilty Of the equipment may impact initial cost. Asan example ofthe result ofthe trade. offs between initial cost and itecycle cost, consider the buk storage af commercial. grade sulfuric acid. The standard practice is to construct anew carbon-steel above- ground storage tank to AP| 650 standards Using a 1/8 to 1/4 in, corrosion allowance. ‘The steel may be specified as copperized to slow sulfur acid attack. During the Of the tank, periodic thickness surveys are performed to monitor thinning of the shell ‘Toward the end of the tank's lfe, capacity may be reduced because of thinning of the lower plate courses. In this case, the best solution is a low initial cost with care- {ul monitoring of vessel conaition. Material availabilty and the choice of a vendor wil affect cost. Selecting a relatively exotic material that is fabricated by only a few vendors could significantly increase the cost and extend the delivery time of the equioment. This could impact overall project costs if the lack of availabilty de- lays startup because of extended elvery times. Consider also the quaifications of a vendor. A sound, basic material pooty fab- ricated seldom performs wellUnfortunately it is not_ uncommon to neglect consideration of ongoing cost factors when selecting a material of con- struction, Ease of repair, required main tenance ‘and avalabilly’ of spare parts should be considered. ‘The value and potential danger of the ‘material storedina tankmay impactmate- rial selection. Some consideration should ‘be given to process downtime should a ‘material fal. These three factors may af- fect the degree of conservatism used in selecting a material of construction, Austenitic stainless steels Austenitic stainless steels, such as 304 and 816 stainless steel, are the most commonly used metals in the CPI. AS such, austenitic staniess steels deserve some special aitention here, not only because of their extensive use, but also because austeniic stainless steels are subject to some unusual forms of cor- rosie attack. Austenitic stainless steels are subject to general corrosion, piting corrosion, SCC and MIC. Of these, general coro sion, where the surface cortodes rela tively every, is perhaps the most under- stood. With general corrosion, the rete of corrosion normally slows with time since the corosive agent must difuse through the rust layer before it can at- tack the stainless stool surface. Piting Corrosion of stainless steel normally oc- urs in chloride environments. With pit ting corrosion, the rate of attack actually increases with time because the pit acts to concentrate the corrosive agents and the pit forms a localized galvanic corro- sion cel. Both factors increase the rate Of pitting corrosive attack IMIC has been discussed above. The rate of attack can be very aggressive. MICis capable of causing stainless steels, to ‘ail na matter of months. Although ‘most bacteria ae killed by sanitizing the equipment, at a temperature of about 80°F, the caves where the bacteria Ive sill remain. Reiniroducing the corrodant allows the bacteria to reoccupy homes (caves) and the MIC continues. MIC is a tough problem to deal with. ‘As noted previously stainless steels are subject to SCC. The two prime factors that cause SCC are stress and, as the name implies, a corrosive environment. The stress that is. normally responsible for SCC is residual stress, such as found in the heal-affected zone of a weld or re sulting from a forming operation. These residval stresses are Usually significantly more critical than operational stress. The corrosive environment pritnatily re- sponsible for SCC of stainless stools is chlorides. The primary variables that ef- fect stress corrosion are stress, chioride concentration, acidity and temperature. Each of these factors has a limit below which SCC will not occur regardless. of the other factors. For examples, it the ‘trees level is low enough then SCC will not occur regardless of the chloride con- centration, the alloy or the temperature, hough there are exceptions, SCC rarely ‘occurs at a temperature below 160°F. If ‘one of the listed variables is kept below a threshold imit, the equipment will never fail from stress coosion cracking. ‘When assessing chloride concentrations: itis important to note that what may be stated as being only a few parts per milion chiorices is not necessarily representative Of chloride concentration an the stainless surface. Often the processing equipment is operating in a situation where the chio- rides are concentrated. For example, in a heat exchanger, the heat may actually chive off the wale and leave the chlorides such that the chlorides will salt-out to a ‘concentration of haif a percent, wrich is above the threshold init for SCO. Concluding comments ‘The purpose of this article isto make pro- cess and project engineers more coghi: Zant of the many factors involved in prop certy selecting a material of construction. If all ofthe factors reviewed inthis article are carefully evaluated, the process engi- neers wellon the way to selecting the op- timum material of construction. I mention this not because you need to consider them al for every appbcation but to show you that there is a lot more to selecting an acceplable material than looking at a Published cortsion cher. . Edited by Geratt Ondray Author James rom, PE tho funder ct Bier Engrnring (4136 fi, Tal Non, Sam tous. Misoun 62045; Prone 314-298-3775, Era: be baereng.co, whe 8 ats leringand engraning meats In 10881 Bem Engen, Bre Spevses engines afd ectnicars bd eee es nur ordesrue Tey andiespacton, carson erate, aa sen tte anaes, sbose stg and ect test. Por 1 foun Be Ene, he es an engesing supa al neko! ene ne are Proce & Gable Co Hots ametalugelongraring ayo fom Ronee Peace st (roy MY} He 3 mentor ef NACE DSRK ASTI an ASME. He 8 ose posal 9 ner Mes ae Ohi aA