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Materials Selection

In The CPI
TABLE 1. MATERIAL
An overview of the many factors to be considered SELECTION CHECKLIST
when selecting materials of construction n Chemical environment
n Impurities
n Microbiologically influenced
corrosion (MIC)
James J. Briem n Corrosion inhibitors

S
electing a material of construc- n Corrosion accelerators
Briem Engineering tion for process equipment in the n Chemical reaction inhibition
chemical process industries (CPI) n Acidity
is normally not difficult. The material n Aeration
IN BRIEF selection is often based on past industrial n Velocity [corrosion erosion and
RESOURCES experience. With few exceptions, past ex- flow-accelerated corrosion (FAC) ]
perience is by far the best way to choose n Temperature
CORROSIVE
an acceptable material of construction. n Downtime corrosion
ENVIRONMENT
However, when past experience cannot n Heat transfer
VELOCITY be used as a guide, material selection can n Internal pressure
be complex and difficult. Unfortunately the n Vacuum loading
TEMPERATURE n Residual stresses
complexity of the problem is often not fully
CLEANING/SANITIZATION recognized. The individual making the ma- n Thermal stresses
OPERATIONS terial choice may fail to consider all of the n Cyclic stresses
factors involved. n Abnormal stresses
SURFACE FINISH/ n Safety and health factors
PASSIVATION
The objective of this article is to provide an
overview of the many factors that should be n Codes and Specifications
DOWNTIME CORROSION considered when selecting a metallic or non- n Product contamination
n Base material cost
MATERIAL PROPERTIES metallic material of construction. A checklist
n Ease of fabrication
is provided in Table 1. Some of the many fac-
SAFETY n Finish appearance
tors are obvious; others are not so obvious.
n Desired life
COST Neglect of the not-so-obvious factors could n Reliability
result in costly equipment failures. n Availability
AUSTENITIC STAINLESS This article elaborates briefly on corrosion
STEELS n Vendor
considerations, stress loading and a number n Ease of repair
CONCLUDING of other factors that affect material selection. n Required maintenance
COMMENTS Initial and ongoing cost considerations are n Value of lost contents
also reviewed. n Value of downtime

Resources
Corrosion resistance is the first and most ob- Corrosive environment
vious factor to consider when selecting a ma- In a corrosive environment, the primary con-
terial of construction for process equipment. stituents and their concentration ranges are
The chemical environment provides the first usually known by the process or project en-
clues to selecting an acceptable material. gineer. Not so obvious, however, is the pres-
As mentioned, past industrial experience is ence of impurities. The classic example of a
the best way to address the corrosion issue. harmful impurity is the chloride ion, which,
Other resources include laboratory corrosion under certain conditions, is known to cause
tests, pilot-plant corrosion tests, published stress-corrosion-cracking (SCC; Figure 1)
corrosion charts, data published by the Na- and pitting of stainless steels. These insidi-
tional Assn. of Corrosion Engineers (NACE; ous forms of corrosion can occur at concen-
Houston; www.nace.org), manufacturers trations as low as a few parts per million.
data, textbooks, articles and materials con- An impurity that is commonly found in
sultants. Most of these sources are available water is bacteria. Bacteria cause a type of
on the Internet. corrosion known as microbiologically influ-
36 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JUNE 2015
FIGURE 1. This is a polished and etched metallurgical cross-section FIGURE 2. Microbiologically influenced corrosion (MIC) cannot be confirmed from
of a stainless-steel pipe viewed at 200x magnification. The branching, visual inspection. Carbuncles near a weld seam are a strong indication of MIC. Fresh,
transgranular cracks are characteristic of stress corrosion cracking wet carbuncles removed from a newly drained pipe can be cultured to confirm the
presence of microbes and identify species present

enced corrosion, or MIC for short (Figure selection. As a general statement, the
2). This is a form of corrosion in which lower the pH, the more aggressive the
the bacteria can eat through stainless- corrosion. A pH variation of a few points
steel tanks and piping in a few months. could make the difference between using
The bacteria primarily attack the retained, a relatively inexpensive material and a
ferritic, metallic grains in stainless weld- costly material of construction. For ex-
ments, although MIC can occur in the ample, a lower pH environment allows
base metal remote from weldments. The a lower chloride concentration to stress-
bacteria burrow caves (Figure 3). As ob- corrosion-crack stainless steels.
served with a scanning electron micro- The presence or absence of air (ox-
scope, the cave surface has the appear- ygen) may also affect the corrosion
ance of a honeycomb structure (Figure resistance of a material in a specific
4). Unfortunately, most commonly used environment. The presence of O2 or
metals are subject to MIC attack to vary- the occasional exposure to air may be
ing degrees. necessary to maintain the protective
The author’s company is currently in- oxide films on materials, such as stain-
vestigating MIC attack in a new process- less steel, which depend on a chrome-
ing plant at which the hydrostatic test oxide film for corrosion resistance. On
water was left in the stainless-steel piping the other hand, the presence of air may
system for several months after the hydro- destroy the corrosion resistance of a
static test. This stagnant water allowed material that is normally not corroded
bacteria to eat through several million dol- in a reducing, O2-free chemical environ-
lars’ worth of piping in a few months. ment. Boiler feedwater is a good exam-
Some minor constituents of a chemi- ple. A boiler can fail in six months if O2
cal environment can actually inhibit cor- is present in the boiler feedwater. The
rosion. One not too obvious example of same boiler could last six decades with
this is the inhibition of SCC of titanium in deoxygenated feedwater.
methanol. Titanium is subject to SCC in
anhydrous methanol at room tempera- Velocity
ture, but if water is present in concen- Velocity must be evaluated when select-
trations above 1%, the titanium will not ing a material of construction, particularly
stress-corrosion-crack. As another ex- when considering pumps, agitators, and
ample, low concentrations of sulfites pre- other equipment subjected to relatively
vent oxygen pitting in boilers. high fluid velocities. Velocity can mani-
An infrequent, but potentially costly fest itself in a corrosive environment as
mistake is to select a material of con- “corrosion-erosion” or flow-accelerated
struction that, if corroded, could inhibit a corrosion (FAC). Of concern here is the
process chemical reaction. Nickel, cop- fact that most published corrosion data
per and other metallic corrosion products are based on relatively stagnant corro-
have been known to kill a chemical re- sion conditions. Although there are a FIGURE 3. This magnified cross sec-
action that was essential to the chemical few exceptions, corrosion increases as tion of a weld in a stainless-steel pipe
reveals a cave structure that confirms
processing operation. velocity increases. An example is com- MIC. The cave structures typically
The acidity of a chemical environment mercial-grade ambient-temperature sul- occur at the boundary between a weld
may have a significant effect on material furic acid transport in carbon steel pipe. and the base metal

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JUNE 2015 37


FIGURE 4. The honeycomb struc-
ture observed on the surfaces
inside the cave confirms MIC. This
is a scanning electron microscopic
view at 1,800x magnification

At a velocity below 3 ft/s, the acid can be steam and cleaning agents can corrode
safely handled using carbon-steel pipe. processing equipment even though the
At higher velocities, the protective iron- basic production environment is non-
sulfate layer is stripped away from the corrosive. When designing for a specific
pipe wall and corrosive failure occurs in operating environment, don’t neglect the
a short time. cleaning operation.
One notable exception to the above
is microbiologically influenced corrosion. Surface finish/passivation
Bacteria like stagnant water. Flowing Surface finish is an important consider-
water inhibits MIC. ation particularly when dealing with stain-
less steels used in the pharmaceutical
Temperature and food-processing industries. The sur-
The basic effect of temperature on the face finish must comply with U.S. Food
corrosiveness of an environment is well and Drug Administration (FDA; Washing-
known by most process and project en- ton, D.C.; www.fda.gov) requirements to
gineers. As a rough estimate, the corro- minimize the possibility of any bacterial
sion rate doubles for every 10°C increase growth on surfaces.
in temperature. This is essentially true up Another important finish consideration
to the boiling point. If the operation is at for stainless steel is the issue of surface
a temperature above the dew point, in a passivation. Process engineers are famil-
gaseous state, the corrosion rate is es- iar with the passivation of stainless steel
sentially nil. with an oxidizing acid, such as nitric or
The above statements explain why citric acid. The passivation treatment pro-
condensing a corrosive gas results in cor- duces a passive protection chrome-oxide
rosive attack that would not occur if the film on stainless steels. This chrome-
operation is kept above the dew-point oxide film is responsible for the overall
temperature. corrosion resistance of the commonly
The effect of temperature must be used austenitic stainless steels, such as
carefully assessed for each environment. 304 and 316. There is some controversy
Many material failures occur because the over the necessity for using a passiva-
temperature evaluated was the mass tion treatment, either initially or at intervals
temperature of the corrosive material in a while the equipment is operating. It is this
vessel, not the higher inside-surface tem- author’s opinion that the main reason for
perature of a steam-jacketed vessel. passivation is not necessarily to form the
protective chrome-oxide film but rather to
Cleaning/sanitizing operations thoroughly clean the surface of any de-
Consideration should be given to the posits on the surface that could initiate
procedure and frequency with which pitting corrosion of the stainless steel.
the process equipment will be cleaned Normally, stainless steel will self-passivate
and sanitized. It is not unusual for the with intermittent exposure to the oxygen
cleaning operation to corrode process- in the atmosphere. If there is no intermit-
ing equipment. Periodic cleaning with tent exposure of the stainless-steel sur-
38 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JUNE 2015
FIGURE 5. This sprinkler system pipe
sat too long without flushing or oxygen
scavenger maintenance. Premature
failure was caused by grooving corro-
sion of the longitudinal pipe welds

face to oxygen, then intermittent passi- of a vacuum should be considered. Be


vation treatments may be necessary to cautious of potential vacuum loading re-
maintain the passive chrome oxide film sulting from steam collapse in storage
on the stainless-steel surface. If this pas- tanks. Vents frozen shut by ice or cor-
sive film is not maintained, the stainless rosion product have caused many tank
steel becomes active and has a corro- failures when cold weather conditions
sion resistance approximating that of caused steam to condense inside the
carbon steel. vessel, creating a vacuum.
Both metallic and non-metallic equip-
Downtime corrosion ment may contain residual stresses that
Corrosion that occurs when a piece are usually produced during equipment
of equipment is not operational can be fabrication. Forming, welding and ma-
more severe than corrosion that occurs chining metals may result in significant
when the equipment is online. Equip- residual-tensile stresses approaching the
ment that operates in a gaseous environ- yield strength of the metal. These residual
ment at moderate temperatures above stresses are often the primary cause of
the dew point will suffer more corrosion SCC. Residual stresses may contribute
at lower temperatures than when online to corrosion fatigue failures.
at an elevated temperature. An example Thermal stresses are another consid-
of this is a boiler economizer operating in eration that should not be neglected for
fluegas containing SO2. process equipment operating at non-
In a recent project, a boiler firing a bio- ambient temperatures. Thermal stress
fuel gas with high-sulfur content failed in occurs in a monolithic material that op-
less than a year due to frequent shut- erates at different temperatures in differ-
downs. A large fire-suppression sprin- ent locations. Thermal stresses are also
kler system sat stagnant and failed due important when combining different ma-
to grooving corrosion (see Figures 5, 6 terials with different coefficients of ther-
and 7). mal expansion. Consider a plastic-lined
vessel where the thermal expansion of
Material properties the plastic can be an order of magnitude
The next group of factors affecting ma- higher than the substrate steel.
terials selection includes mechanical and Cyclic stress is often overlooked or
physical material considerations. underestimated. Cyclic stresses cause
On occasion, the thermal conductivity fatigue failure. Fatigue is the failure of a
of a material may determine its accept- material under cyclic loading at a stress
ability for process equipment, the most level well below the published tensile
obvious example being heat exchangers. strength of the material. As a very rough
Low thermal conductivity may be desir- estimate, fatigue strength is only about
able for certain equipment. For example, half the tensile strength of the material. In
an un-insulated fiberglass-reinforced a corrosive environment, cyclic stresses
plastic tank may be more economical can result in “corrosion fatigue,” a stress-
than an insulated carbon-steel tank. related material failure that can occur at a
Evaluation of internal pressure is ad- stress below the normal fatigue strength
dressed by standards, such as the ASME of the material.
Boiler & Pressure Vessel Code and the Most published fatigue data are for
ASME Piping Codes, and needs no elab- fatigue strength in an air environment.
oration here. When corrosives are present, the fatigue
The intended or unintended presence strength is even lower and if failure oc-

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JUNE 2015 39


FIGURE 6. Stagnant water inside the sprinkler pipe caused grooving corrosion FIGURE 7. This metallurgical cross section of a sprinkler system pipe reveals
of the longitudinal weld seam grooving corrosion of the longitudinal weld seam. The grooving corrosion is
caused by the weld seam being anodic (corroding) relative to the rest of the
pipe wall, which is cathodic

curs, the failure mechanism is defined as normal and reasonable first step in evalu-
corrosion fatigue. ating initial cost is an assessment of basic
Abnormal stress loads must be con- material cost. Consider the ease of fab-
sidered. Examples include pump vibra- rication. Are the materials easily formed,
tion loads, loads resulting from agitator cut, bonded, drilled or welded? Is heat
mountings, and, of course, the impact of treatment required?
an errant fork truck. Finish and appearance will impact cost.
Polished stainless steel may be neces-
Safety sary for equipment used in the food and
Today’s increased concern for safety and pharmaceutical industries. Sprayed foam
health has had its impact on materials of insulation is less expensive and less at-
construction. In the area of safety, it’s eas- tractive than lagged, block insulation.
ier to comply with an OSHA (Occupational The life expectancy and desired reliability
Safety and Health Assn.; Washington of the equipment may impact initial cost.
D.C.; www.osha.gov) guard-rail require- As an example of the result of the trade-
ment on a metal tank than on a plastic offs between initial cost and lifecycle cost,
tank. Asbestos is no longer an acceptable consider the bulk storage of commercial-
material of construction. In the food and grade sulfuric acid. The standard practice
pharmaceutical industries, the material is to construct a new carbon-steel above-
selection is often limited to a material that ground storage tank to API 650 standards
is virtually impervious to chemical attack. using a 1/8 to 1/4 in. corrosion allowance.
Another factor to consider is the degree The steel may be specified as copperized
of hazard to humans and the environment to slow sulfuric acid attack. During the life
that could result from the accidental re- of the tank, periodic thickness surveys are
lease of hazardous materials contained in performed to monitor thinning of the shell.
a vessel or pipe should failure occur. Toward the end of the tank’s life, capacity
The government, industry and individual may be reduced because of thinning of
companies have codes, standards and the lower plate courses. In this case, the
specifications that will often impact or even best solution is a low initial cost with care-
determine the selection of a construction ful monitoring of vessel condition.
material. These codes, standards and Material availability and the choice of a
specifications must be considered when vendor will affect cost. Selecting a relatively
selecting materials of construction. exotic material that is fabricated by only a
few vendors could significantly increase
Cost the cost and extend the delivery time of
Naturally, in selecting a material of con- the equipment. This could impact overall
struction, the objective is to find a mate- project costs if the lack of availability de-
rial that will result in a long safe service lays startup because of extended delivery
life at a reasonable cost. In assessing the times. Consider also the qualifications of a
economics of a material, both initial cost vendor. A sound, basic material poorly fab-
and lifecycle cost should be evaluated. A ricated seldom performs well.
40 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JUNE 2015
Unfortunately it is not uncommon to more critical than operational stress.
neglect consideration of ongoing cost The corrosive environment primarily re-
factors when selecting a material of con- sponsible for SCC of stainless steels is
struction. Ease of repair, required main- chlorides. The primary variables that ef-
tenance and availability of spare parts fect stress corrosion are stress, chloride
should be considered. concentration, acidity and temperature.
The value and potential danger of the Each of these factors has a limit below
material stored in a tank may impact mate- which SCC will not occur regardless of
rial selection. Some consideration should the other factors. For examples, if the
be given to process downtime should a stress level is low enough then SCC will
material fail. These three factors may af- not occur regardless of the chloride con-
fect the degree of conservatism used in centration, the alloy or the temperature.
selecting a material of construction. Although there are exceptions, SCC rarely
occurs at a temperature below 160°F. If
Austenitic stainless steels one of the listed variables is kept below
Austenitic stainless steels, such as 304 a threshold limit, the equipment will never
and 316 stainless steel, are the most fail from stress corrosion cracking.
commonly used metals in the CPI. As When assessing chloride concentrations
such, austenitic stainless steels deserve it is important to note that what may be
some special attention here, not only stated as being only a few parts per million
because of their extensive use, but also chlorides is not necessarily representative
because austenitic stainless steels are of chloride concentration on the stainless
subject to some unusual forms of cor- surface. Often the processing equipment
rosive attack. is operating in a situation where the chlo-
Austenitic stainless steels are subject rides are concentrated. For example, in
to general corrosion, pitting corrosion, a heat exchanger, the heat may actually
SCC and MIC. Of these, general corro- drive off the water and leave the chlorides
sion, where the surface corrodes rela- such that the chlorides will salt-out to a
tively evenly, is perhaps the most under- concentration of half a percent, which is
stood. With general corrosion, the rate above the threshold limit for SCC.
of corrosion normally slows with time
since the corrosive agent must diffuse Concluding comments
through the rust layer before it can at- The purpose of this article is to make pro-
tack the stainless steel surface. Pitting cess and project engineers more cogni-
corrosion of stainless steel normally oc- zant of the many factors involved in prop-
curs in chloride environments. With pit- erly selecting a material of construction.
ting corrosion, the rate of attack actually If all of the factors reviewed in this article
increases with time because the pit acts are carefully evaluated, the process engi-
to concentrate the corrosive agents and neer is well on the way to selecting the op-
the pit forms a localized galvanic corro- timum material of construction. I mention
sion cell. Both factors increase the rate this not because you need to consider
of pitting corrosive attack. them all for every application but to show
MIC has been discussed above. The you that there is a lot more to selecting
rate of attack can be very aggressive. an acceptable material than looking at a
MIC is capable of causing stainless steels published corrosion chart. n
to fail in a matter of months. Although Edited by Gerald Ondrey
most bacteria are killed by sanitizing the
equipment, at a temperature of about Author
180°F, the caves where the bacteria live James J. Briem, P.E. is the founder of
still remain. Reintroducing the corrodant Briem Engineering (4134 Rider Trail
North, Saint Louis, Missouri 63045;
allows the bacteria to reoccupy homes Phone: 314-298-3773; Email: jimb@
(caves) and the MIC continues. MIC is a briemeng.com), which is a materials
tough problem to deal with. testing and engineering firm established
As noted previously, stainless steels are in 1983. At Briem Engineering, Briem
supervises engineers and technicians
subject to SCC. The two prime factors involved in materials’ investigations and
that cause SCC are stress and, as the tests including: nondestructive testing
name implies, a corrosive environment. and inspection, corrosion evaluation, material selection, fail-
ure analysis, stress testing and mechanical testing. Prior to
The stress that is normally responsible founding Briem Engineering, he was an engineering supervi-
for SCC is residual stress, such as found sor at Mallinckrodt Chemical Inc. and Proctor & Gamble Co.
in the heat-affected zone of a weld or re- He holds a metallurgical engineering degree from Rensselaer
Polytechnic Institute (Troy, N.Y.). He is a member of NACE,
sulting from a forming operation. These ASM, ASTM and ASME. He is a licensed professional engi-
residual stresses are usually significantly neer in Missouri and Ohio.

CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM JUNE 2015 41