the Conduit A quarterly publication from

M&M Engineering Associates, Inc.

Vol. 15, No. 1 INSIDE THIS ISSUE:

Chemical Treatments for Closed
5
Loop Systems

PIN HOLE LEAKS IN TUBING Upcoming Events 9

Workshop—Fall Edition 10

By: Karen T. Fuentes, P.E.

Sr. Principal Engineer
Pinhole leaks in tubing occur frequently and for a variety
of reasons. Here are a few examples of conditions
leading to pin hole leaks in tubes.

Under Deposit Corrosion

As the name implies, under deposit corrosion results

when deposits are laid down on either the internal or
external surface of a water-touched tube. Once a
deposit is laid down on the tube surface the “chemistry”
of the environment under the deposit can become
significantly different to the general tube environment.
It is this concentrating effect under the deposit that
leads to pitting. The corrosion can be caused by a
number of chemical species including caustic (caustic
Figure 1. A small leak shown on the internal surface in
gouging), oxygen (oxygen pitting), and phosphate the tube wall (arrow).
(phosphate gouging or acid phosphate corrosion). In
water-containing piping and tubing in ambient or near
ambient temperatures, microbiological deposits can also
cause corrosion.

External deposits tend to collect in dead Tube wall

flow areas such as near baffle plates and

Internal
tube sheets. Internal deposits tend to
Deposit
collect on the bottom of horizontal
tubes, in the corners of the rifling of
internally rifled tubes, at the liquid line in tubes that are Figure 2. A cross section of tube shown in the area of
the leak.
only partially filled, in flow disruption areas such as
bends, or areas of high heat flux. (Continued on page 2)
 Case Study 1

A waste heat boiler was having repeated tube failures.

Examination showed that the tubes were failing due to
under deposit corrosion (Figure 1 and Figure 2),
specifically caustic gouging. There was broad smooth
corrosion with little undercutting underneath a heavy,
multi-layer deposit on the internal surface in localized
areas. The deposit contained a significant amount of
sodium. Normally, caustic is soluble and does not
concentrate to significant levels under a deposit without
the aid of high heat flux. At the hot spot, a fully
nucleate boiling condition is not achieved. Once the
Figure 3. A leak shown in the cold water line on the ex-
deposit forms and heat creates the concentrating ternal surface.
mechanism, if there is caustic in the boiler water, it can
create under deposit corrosion by caustic gouging.

Microbiologically Influence Corrosion (MIC)

MIC is caused by bacterial activity that attacks metal.

The bacteria either attacks the metal directly,
consuming certain constituents of the alloy (example –
iron utilizing bacteria), or they secrete acids which
attack the material. In either instance, only the material
directly under the colony is affected. In essence, MIC is
Internal Surface
a highly specialized form of under deposit corrosion
with the bacteria colony or biofilm acting as the Figure 4. A cross section shown in the area of the leak.
“deposit.”

Most metal alloys used in industrial applications are

susceptible to MIC, including copper, stainless steel, and
carbon steel. (It should be noted that copper alloys are
less susceptible to MIC as copper is a natural biocide.)
Under certain conditions, colonies of bacteria form on
the surface of the metal, typically in a circular pattern.
Some mechanical and chemical cleaning methods have
been developed to combat MIC, but the colonies can be
difficult to remove. Additionally, once removed, the
underlying pits become excellent sites for other types of
under deposit corrosion as material tends to become Internal Surface
“caught” in the pits.

Case Study 2 Figure 5. Deposits and lateral attack are characteristic

of MIC.
An office building was having repeated problems with
leaks in their potable cold water line. The water was (Continued on page 3)

supplied from a well, but was passed through a water

2
softener. The water was not chlorinated. The areas
experiencing the leaks were lines with low flow or
stagnant sections of the line. Examination showed that
the leaks were due to microbiologically influenced
corrosion (MIC) (Figure 3 through Figure 5).

Erosion

Erosion is the removal of material due to high velocity

flow that wears away the tube material. It can remove
significant amounts of material in relatively short
periods of time. Erosion typically forms “horseshoe”
shaped patterns with the most material removed near
the arc of the horseshoe. This is the area which
Figure 6. A leak shown in the externally finned tube.
typically penetrates the tube wall resulting in a small
leak. It is not until the tube is inspected internally that
the extent of the erosion damage is observed. When
erosion is assisted by corrosion, the mechanism is
referred to as erosion-corrosion.

Case Study 3

A service contractor added a scale removal chemical

(inhibited hydrochloric acid) to the cooling tower for
the purpose of cleaning the condenser tubes in a
centrifugal chiller, as well as the cooling tower and
interconnected piping. The scale removal chemical was
Figure 7. Horseshoe-shaped divots are characteristic of
allowed to remain circulating in the system overnight
erosion. In this example, corrosion also
instead of a few hours. Shortly after the scale removal, played a role.
the chiller experienced severely leaking condenser
atmosphere. As the last amounts of thermal energy are
tubes. The tubes were inspected using eddy current
extracted from the gases, they cool and reach their dew
inspection method that showed tube wall loss and a
points. The condensing water reacts with the
pressure test of the tubes showed a significant number
corrosives, such as sulfur, in the gas stream to produce
to tube leaks. Because of the extended period of
acids that corrode the tubing. Factors that affect the
exposure to the descaler, the inhibitor broke down and
acid dew point are: fuel type, amount of excess oxygen,
allowed erosion-corrosion of the tubes to occur (Figure
moisture level, tube surface temperature, air in-leakage,
6 and Figure 7).
and catalysts.1 Dew-point corrosion will cause general
Dew-point Corrosion wastage of the tube wall but is typically manifested as a
Dew-point corrosion refers to the corrosion that pinhole leak in the tube.
occurs on tubing exposed to gases containing corrosives
1
EPRI Technical Report: “Boiler and Heat Recovery Steam
that reach their dew points (the temperature at which
Generator Tube Failures, Theory and Practice,” Volume 2,
condensation of water entrained in the gases occurs). Water-Touched Tubes, No. 1023063, December 2011.
This is seen in tubing in systems such as economizers
(Continued on page 4)
and reheaters that are recovering energy from
combustion gases before they are released to the
3
 (Continued from page 3)
compounds. The peak corrosion rate occurs at about
260°F. Excess oxygen is also an important factor as the
higher the oxygen level in the combustion process, the
more SO2 will be converted to SO3. By controlling
excess oxygen to a maximum of 1 to 2%, it is possible
to avoid the the formation of fully oxidized sulfur
compounds and thereby reduce fouling and tube
corrosion.

Contact the Author:

Karen T. Fuentes, Sr. Principal Engineer
Figure 8. Image shows pin hole leaks in an economizer
tube.
(512) 407-3778
[email protected]

Now available online!

Boiler Tube Failure Handbook
The handbook presents examples of common failure
mechanisms in a variety of boilers including power boilers,
recovery boilers, and heat recovery steam generators
(HRSGs). Visual examination may help the equipment
operator decide whether further metallurgical examina-
tion and root cause analysis is warranted. The only sure
way to determine a failure mechanism and root cause is a
Figure 9. Image shows external wastage of tube in the
full metallurgical examination.
leak area (bracket) viewed from the internal
surface. Click to visit: http://mmengineering.com/boiler-tube
-failure-handbook/
Case Study 4

In Memoriam
A tube sample was removed for analysis after repeated
pinhole leaks were experienced in the economizer from
a coal burning, circulating fluidized bed boiler (Figure 8). Arthur H. Tuthill, prominent chemical engineer from
After sectioning the tube, wastage of the tube wall was Blacksburg, Virginia, died February 10, 2015, at the age
observed (Figure 9). Analysis of the external deposits of 95. He graduated from the University of
Virginia as a chemical engineer and earned his
identified primarily iron and oxygen (iron oxide), with master's degree in metallurgy from the Carnegie
some sulfur. A white layer of iron sulfate at the tube Institute of Technology. He worked in corrosion
engineering for Standard Oil, Valco Engineering, and
deposit interface is also typical of dew-point corrosion.
International Nickel, and as a corrosion consultant for
White deposits were observed in the leak area. Tuthill Associates. Art also worked with M&M
Engineering for many years. A prominent and special-
The first temperature at which sulfuric acid condenses ized corrosion engineer, he authored more than 100
depends on the partial pressures of SO3 and water technical papers and received numerous awards in his
vapor, and is usually around 250°F to 300°F. Coal firing field. His contributions to the fields of metallurgy and
corrosion will assist us for years to come; he will be
may have a slightly lower dew point range (250°F - 285° missed.
F) because much of the ash contains alkaline
4
 CHEMICAL TREATMENTS FOR
CLOSED LOOP SYSTEMS

By: David G. Daniels bacterial respiration are often acidic, and respiration
Sr. Principal Scientist also consumes oxygen causing the base of the biofilm to
be conducive to corrosion of the base metal. This fur-
ther encourages some types of bacteria as they use the
Closed loop cooling systems are integral to the HVAC
oxidized metal in their metabolism. This type of corro-
systems for offices, laboratories, production, and IT ser-
sion is so common that it has its own designation – mi-
vices. They are often in every occupied building, and
crobiologically influenced corrosion (MIC).
run above suspended ceilings over offices, laboratories,
and manufacturing areas, and through floors and con- It is very common for oxygen pitting and MIC to work
duits with other piping and electrical wiring. Leaks in together to corrode piping. Any area of piping that con-
these systems are more than just a nuisance or an in- tains crevices, such as the space between threaded fit-
creased maintenance cost; it can result in lost research, tings, is an excellent area for general oxygen pitting and
ruined or delayed products, inoperable computers, and microbiologically influenced corrosion (MIC). So
lost time for key personnel. threaded fittings are very common areas for leaks.

In a closed loop system, oxygen pitting is the most com- CLOSED LOOP CHEMICALTREATMENTS
mon type of corrosion. In order for oxygen pitting to Sodium Nitrite
occur, there must first be a deposit which covers a por- Sodium nitrite has been used for many years to prevent
tion of the metal surface, creating a differential between corrosion in a wide variety of closed loop systems. The
the oxygen content underneath the deposit and the ox- mechanism is somewhat interesting in that the nitrite
ygen content in the bulk water. The oxygen deficient molecule itself is an oxidizer and prevents corrosion by
area underneath the deposit becomes the anode, and causing a uniform layer of corrosion products on all car-
the area around the deposit that is exposed to the bulk bon steel surfaces. Since it is an active oxidizer, as long
as there is sufficient nitrite in the system, any area that
water becomes the cathode. This “big cathode, little
begins to create an anode will quickly be oxidized.
anode” configuration causes concentrated and accelerat-
ed pitting in a confined area producing pinhole leaks. However, if there is insufficient nitrite in the chilled wa-
There are two factors that can increase the rate of cor- ter loop, the nitrite corrosion inhibitor can actually ac-
rosion under the deposit. First is the concentration of celerate the rate of corrosion. The general guidelines
chlorides either in the bulk water or underneath the for nitrite-based treatments are for a minimum of 700
deposit. The chlorides accelerate the electron transfer ppm of nitrite.
from the base metal to the bulk water, greatly accelerat- Nitrite treatments traditionally also contain pH buffers
ing the corrosion rate. (caustic and sodium borate) to maintain an alkaline pH,
The second factor that can increase corrosion in a which is conducive to minimizing corrosion in carbon
closed loop system is microbiological. If bacteria are steel. If there is copper in the closed loop system, to-
allowed to propagate inside the closed loop system, lytriazole (TTA) is added to the treatment to maintain a
they can create a “living” deposit that consists primarily protective chemical layer on top of the exposed copper
of exo-polysaccharides and bacteria. The byproducts of metal surfaces.
(Continued on page 6)

5
Nitrite treatments have a concern in that the nitrite mol- Ironically, in closed loop systems that are very tight, dis-
ecule is the source of energy for certain types of bacte- solved oxygen levels can drop and thus minimize the ef-
ria. If the closed loop system becomes contaminated fectiveness of a molybdate treatment (which requires
with these bacteria, the nitrite level can decrease very dissolved oxygen to form a passive layer). Experts rec-
rapidly leading to corrosion. The nitrite will first be con- ommend a minimum of one ppm of dissolved oxygen in
verted to nitrate by nitrifying bacteria and then denitrify- molybdate-treated systems.
ing bacteria will convert nitrate to ammonia. Ammonia is
Silicates
very corrosive to copper.
Silicates were the first chemical corrosion protection
Furthermore, the bacteria generate biofilms which pre-
system used in water systems. Silicates are also classified
vent the nitrite treatment from accessing the area under
as anodic inhibitors similar to molybdate. However, the
the deposit. Adding more nitrite only further accelerates
protection mechanism consists more of the formation of
the reproduction of the bacteria making the problem
a filming layer of silicates on top of the carbon steel than
worse. Systems using nitrite should be regularly tested
an interaction directly with the ferrous metal. The sili-
for the presence of bacteria. In some systems, non-
cate layer forms slowly (weeks). Silicates can provide
oxidizing biocides such as glutaraldehyde or isothiazoline
corrosion protection for copper and other metals, as
are added to the treatment to prevent bacterial growth.
well as carbon steel.
Some closed loop systems have also used an oxidizing
biocide, chlorine dioxide, to eliminate bacterial contami- Silicates do not act as a nutrient for biological growth,
nation. which is an advantage they have over nitrites. Silica dep-
osition can occur if the system is over-treated, or in the
Sodium Molybdate
presence of high concentrations of calcium and magnesi-
Molybdate is generally classified as an anodic oxidizing um. The typical treatment level is between 50 and 100
inhibitor. Molybdate works in conjunction with the dis- ppm when used as a stand-alone treatment. Silicates may
solved oxygen in the water to form a protective ferric- also be used in conjunction with other treatments.
molybdate complex on the steel. Molybdate is also
Polymer Treatments
thought to create a negative surface charge on the outer
portion of the protective layer making it more impervi- Polymers have been used for many years to prevent scale
ous to aggressive chloride and sulfate. and corrosion product accumulations in cooling towers
and low pressure boilers. They are also now used in
Molybdate treatments cannot be used where there is a
closed loop systems. The polymer acts as a dispersant
significant hardness in the water (>500 ppm as CaCO3)
for any corrosion products or scale that might form, so it
(the presence of calcium and magnesium measured as
“prevents corrosion” by keeping the surface clean and
7500 ppm a CaCO3). Molybdate treatment levels can be
ensuring that any dissolved oxygen in the water attacks
anywhere between 200 – 800 ppm as molybdate depend-
all surfaces evenly. This produces a general, but overall
ing on the other constituents of the water such as sulfate
low level of corrosion. Current understanding of the
and chloride. Closed loop systems that use demineral-
mechanism is that polymers are a passive treatment—in
ized water makeup would tend to be on the lower end of
other words; they do not react with or cause any active
this range.
chemical change to the surface of the metal to create a
The world supply of molybdate tends to be concentrated passive layer (unlike nitrite and molybdate). Instead, it
in areas of historical political unrest. Therefore, over the presumes that if it can keep the surface clean, a uniform
years molybdate prices have varied dramatically, which oxide layer will form and pitting corrosion will be con-
can in turn make molybdate treatment competitive with trolled.
nitrite, or far more expensive.
In addition to the polymer, these treatments typically
6
contain pH buffers (caustic and borate) and may include
TTA for copper corrosion protection.

One of the advantages of this treatment is that it is

thought to be very environmentally benign. The polymer
in the treatment can be found in a number of consumer
products and has been used in the water treatment in-
dustry for many years.

Toxicity

As far as environmental toxicity, sodium nitrite has the

lowest LD50 (rat) of the treatments discussed here. In
order from most to least toxic they are:
Nitrite > Silicate > Molybdate > Polymer.

Table 1. Toxicity of Closed Loop

Cooling Water Treatments1

Primary Chemical LD50 (rat) (mg/

Constituent kg)
Nitrite 180
Silicate 800
Molybdate 4,233
Polymer >5000

CASE STUDY 1

A sporting facility located in a southern state had a natu- Figure 1. Typical corrosion of chilled water piping at the
ral grass field. The movable roof was open to the sun Case Study 1 facility.

during the day and closed in the afternoon, approximate-

ly three hours before game time. At that point, the mas- the expense of the molybdate during this time
sive air handling units were turned on to reduce the (molybdate prices had skyrocketed), the vendor chose to
temperature and humidity in the entire stadium to a reduce the amount of molybdate treatment to levels well
comfortable level before the game started. There were below what is considered normal. The system also had
over seven miles of chilled water piping in the stadium. some leakage which reduced the concentration and in-
creased treatment costs further.
After approximately twenty (20) leaks had occurred in
the chilled water loops, M&M Engineering was called in In addition to conventional oxygen pitting corrosion,
to assess the damage and make recommendations. there was a significant presence of sulfate reducing bac-
teria (SRB), which were contributing to the corrosion
We determined that there was significant oxygen pitting
rate.
throughout the carbon steel piping system that was re-
sponsible for the leaks (Figure 1). The investigation As a result of the corrosion, much of the 4-inch diame-
found that the chemical vendor had recommended a mo- ter or smaller steel piping of the chilled water system
lybdate-based chilled water treatment. However, due to had to be replaced by copper pipe, copper alloy fittings
and valves, and new insulation.
1
Rey S., Molybdate and Non-molybdate Options for Closed It is not only the corrosion of the piping that created
Systems—Part II, The Analyst.
(Continued on page 8)

7
 problems in the chilled water loop. Corrosion products
broke off and accumulated in narrow portions of the
system, behind valves, and plugged off heat exchangers
that affected the HVAC system. In this particular sys-
tem, the air handling units (AHUs) (Figure 2) contained
enough deposits to prevent proper operation. Remedi-
ation options included mechanical cleaning, chemical
cleaning, and complete replacement of the AHUs.

Figure 3. The replacement of piping was already under-

way when we arrived at the Case Study 1
facility.

heat exchangers were installed to carry chilled and hot

water to each room in the facility. The system was very
complex and included coils and reheater elements con-
trolled to ensure that the temperature and humidity in
the various offices, recovery areas, and operating rooms
were properly regulated. In this particular case, the fail-
Figure 2. Typical air handling unit (ACU) at the Case
Study 1 facility. ures occurred in the hot water loop.

Our investigation found that during construction, the

The pump seals are another area where corrosion de- hot water loops had been cleaned of construction de-
posits accumulated. The abrasive nature of the corro- bris and left filled with untreated water for testing. De-
sion products destroyed the seals causing additional loss lays resulted in the water remaining stagnant in the sys-
of seal and water, as well as leaking. tem for some time without any additional treatment or
Other less obvious problems were also found including monitoring. When it was finally put into service, the
higher than design energy costs associated with the in- chemical company had difficulty establishing and main-
creased resistance to flow, which the recirculating pump taining the passive nitrite chemistry. There were long
motors must overcome. periods where the nitrite level essentially dropped to
zero.
It should be emphasized that in this case, the corrosion
was the result of an inadequate water treatment; not Approximately a year later, the first leak appeared. This
the complete absence of it. Also, the corrosion oc- was quickly followed by 11 more leaks. Eventually, the
curred relatively quickly, but did not manifest itself until leak rate became so significant (inspection found 147
it progressed so far that significant amounts of the pip- heat exchangers that showed signs of leaking) (Figure 4)
ing and equipment had to be cleaned and/or replaced that the construction firm agreed to replace all 747 ex-
(Figure 3). changers. In this case, there was a complete lack of
treatment during the construction and subsequent com-
CASE STUDY 2
missioning phase. When treatment was eventually start-
A large hospital outpatient center had just been com- ed, corrosion already established in the system made it
pleted in a large metropolitan area. Over 700 HVAC (Continued on page 9)

8
 UPCOMING EVENTS

April 26-May 1, 2015

ASME Boiler Code Week
Colorado Springs, Colorado

June 2-4, 2015

35th Annual Electric Utility
Figure 4. Corrosion of an unprotected closed loop Chemistry Workshop
system after approximately one year.
Champaign, Illinois
very difficult to maintain. Corrosion products in the
system required frequent flushing to prevent damage to
the pumps and heat exchangers. The potential for even September 15-16, 2015
minor leaks to damage expensive equipment, offices, M&M Engineering Associates, Inc.
and sterile spaces such as operating rooms made the
4th Annual (Fall Edition)
wholesale replacement of all damaged equipment the
only acceptable option at a significant cost to the con- Preventing Failures in
tractor and disruption to the facility. Steam Generating
SUMMARY Equipment
As the two case studies above show, corrosion in Leander, Texas
closed loop systems can occur rapidly (one to two
years). Often the corrosion in the system goes unde-
tected until it is so widespread that large sections of October 13-15, 2015
piping have to be replaced. Once the corrosion mecha- EPRI International Conference
nisms have started, it is difficult to regain control and
remove corrosion products. Closed loop cooling sys-
of Corrosion Control
tems are meant to remain “closed,” with very little in Power Plants
makeup and no leaks or spills. Properly treated with San Diego, California
corrosion inhibitors and maintained, systems can oper-
ate for years with no appreciable leaking.
November 15-19, 2015
76th Annual International
Contact the Author:
Water Conference
David G. Daniels, Sr. Principal Scientist Orlando, Florida
(512) 407-3752
Visit our News & Events page for more details:
[email protected]
mmengineering.com/news-events/

9
 Preventing Failures in Steam
Generating Equipment

September 15-16, 2015 — Leander, Texas

M&M Engineering will host a Fall Edition of their 4th annual workshop for producers of
steam, be it used in power or process applications. The two day workshop focuses on the
issues most common in steam generating systems and is applicable to many industries
including: pulp and paper, refining, petro-chemical, and power generation.

Seating is limited - register TODAY!

Day 1 Day 2
 Equipment Associated with Steam Generation –  Introduction to Failure Analysis
A Primer  Failure Investigation Principles for Combustion
 Utility Feedwater Heaters and Damage Turbines
Mechanisms  Basic Steam Turbine Failures
 Water Touched Boiler Tube Damage  Condenser and Cooling Water Failures
Mechanisms
 Damage Mechanisms in Deaerators
 Steam Touched Boiler Tube Failure Mechanisms
 Water and Steam Chemistry-Influenced Failures
 Introduction to Nondestructive Testing & in the Steam Cycle
Inspection Contracting
 Discussion and Wrap Up
 High Energy Piping: Damage Mechanisms and
* (sessions are subject to change)
Corrections

The registration fee for this two day event is $750 (continental breakfast and lunch are included).
The registration deadline is August 14, 2015*. For details, and to register online, visit:
http://mmengineering.com/events/event/4th-annual-preventing-failures-steam-generating-equipment-workshop-fall-edition/
Or contact Lalena Kelly by phone or email for further information:
(512) 407-3775 or [email protected]

Event Location: 1815 S. Highway 183, Leander, Texas 78641

*Subject to a minimum number of attendees. Once registered, attendees should confirm workshop before making travel
arrangements.

10
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please contact: Address: ___________________________________________
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(512) 407-3752
[email protected]
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(512) 407-3777
[email protected]
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(512) 407-3778
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Leander, Texas 78641
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the Conduit

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Leander, Texas 78641

512.407.8598
800.421.9185
Fax: 512.407.3766
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