Y k Ai\-hn τ o ñ eÑ fv

EUROPEAN
COAL AND STEEL COMMUNITY

IVth CONGRESS

Working Party IV
Stress and strain
caused by chemical attack
- Practical studies —

Service conditions influencing the p itting corrosion of

stainless steel steam surfaces condenser tubes

by
Mr. N. A. LONG
Supervising Chemical Engineer
The Wallingford Steel Company
Wallingford (U.S.A.)

Commission
of the European
Communities
1968

XK1434T09ENC
SERVICE CONDITIONS INFLUENCING PITTING CORROSION OP
STAINLESS STEEL STEAM CONDENSER TUBES
 INTRODUCTION

The condensation of exhaust steam from the steam turbine-elec-

tric generator in a power plant is accomplished by the use of a large
shell-and-tube heat exchanger known as the surface condenser. Its func-
tions are to (l) create and maintain a vacuum by the condensation of steam
for more efficient generation of electricity and (2) recover the condensate
(condensed steam) for recycling back through the boiler tubes for future
use. These objectives are met by cooling water flowing through the tubes
and steam coming in contact with the outside of the tubes. The functions
of the condenser are directly affected by the performance of the condenser
tube material, which historically has been either copper or a copper-base
alloy.

Corrosion resistance is one of the main requirements of a con-

denser tube material. Although possessing excellent general corrosion
resistant properties, copper-base alloys are subject to several specific
forms of corrosion which have been, fully documented through the years
(Biblio. 1, 2 ) . As a result, the majority of design engineers and power
plant operators are generally well informed about the causes of and solu-
tions to the various forms of corrosion failures of non-ferrous condenser
tube alloys. However, today stainless steel is being used in place of
copper-base alloys for steam surface condenser tubes in the USA at an ever
increasing rate for reasons which have been noted elsewhere (Biblio. 3-71
9-11). Trouble-free service has been obtained with stainless steel con-
denser tubes in over 95% of the installations, but in some installations
unexpected and unforeseen tube failures have occurred due to pitting cor-
rosion on the cooling water side (Biblio. 7)· This attack has resulted
from deposits containing chlorides. The underlying cause of these cor-
rosion problems with stainless steel tubes appears to be similar in origin
to recently reported corrosion problems with admiralty tubes on the Ohio
River (Biblio. 12).

In other cases where pitting corrosion problems have occurred,

knowledge of the fundamental corrosion resistant properties of stainless
steels and awareness of a possible difference in behaviour between a
stainless steel and a copper-base alloy might have prevented the attack
from initiating in the first place. The latter is an important considera-
tion since operating procedures have been specifically developed to be
compatible with the use of copper-base alloys through years of experience.

Stainless steel tube failures resulting from the stagnation and

evaporation of salt water in seaboard condensers could have been avoided
if the operator had been aware of the consequences of high local chloride
concentrations on stainless steel surfaces. Other failures resulting from
prolonged and unnoticed fouling would.not have occurred if the tubes had
been given a cursory inspection during service so that a chlorination
practice or cleaning procedure could have been altered to suit stainless
steel. In another installation, field tests were conducted by persons
inexperienced with stainless steel, and the test results were evaluated
to standards developed for non-ferrous tubes. These circumstances led to
an erroneous conclusion and an adverse installation.

Although the performance of stainless steel has equalled or sur-

passed that of copper-base alloys in the vast majority of similar environ-
ments, responsible persons must recognize that a difference in behaviour,
not necessarily limited to a corrosion problem, is possible. For example,
a copper-base alloy may be experiencing such serious erosion that, although
the potential might exist in the water for calcium carbonate formation on
either condenser tube material, the continued loss of metal due to erosion
prevents the adhesion of the deposit. Stainless steel tubes are highly
resistant to erosion in these environments: as a result, a calcium car-
bonate scaling condition may develop and standard measures of scale con-
trol should be applied.

In the absence of prior operating experience with stainless steel

condenser tubes, good engineering and common sense dictate that the in-
stallation of stainless steel tubes should be given adequate surveillance
to detect and remedy unfavorable operating procedures or environmental
conditions.

The purpose of this paper will be to characterize the service

conditions and nature of the pitting corrosion which has occurred in stain-
less steel condenser tubes. It is the author's desire to provide this in-
formation as a reference for those concerned with the use of condenser
tubes and to further optimize the use of stainless steel.

Outline of Investigation

The following information is compiled from laboratory examina-

tions of 75 tubes from 2.5 electric utilities and a previously reported sur-
vey (Biblio. 7)· The examinations, which included affected and unaffected
tubes, entailed microscopic inspection of the tube surfaces, metallurgical
and chemical analyses of the tubes, and chemical analyses of the inside
surface deposits.

The data were reviewed and reduced to pertinent case histories

which depict the significant patterns of pitting corrosion that have emerged
for inland and seaboard locations. Typical service conditions related to
the case histories are presented along with the results of the laboratory
examinations of the affected tubes and a series of photographs which il-
lustrate the nature of the pitting.

The results of an isolated but important incident that occurred

at a seaboard location are also presented.
 Inland

The use of type 30^ stainless steel condenser tubes at inland

power plants represents approximately 85% of the total footage of stain-
less steel condenser tubing in service (Biblio. 9)· Type 316 stainless
steel has been used very infrequently at inland locations primarily be- '
cause type 30^, the less costly of the two alloys, has given excellent
performance. Chloride pitting corrosion is not expected to be a problem
with type 30^ because of the generally low chloride content of the cooling
waters. However, type 30^ is susceptible to pitting corrosion, and any
environmental conditions which favor the breakdown of passivity such as
high local chloride concentrations and deposits can lead to pitting cor-
rosion. At inland locations the environment, which is essentially under
a minimum amount of control, has resulted in tube losses due to pitting
corrosion in less than 3% of the inland installations.

The five known cases of inland tube failures due to pitting cor-
rosion are outlined in Table I. Case histories numbers 3 and k occurred
on the Ohio River, number 2 on a tributary of the Ohio River, number 5 on
Lake Erie, and number 1 on a man-made lake in the southwestern part of
the USA. The common feature of all five was that the pitting corrosion
resulted from patchy deposits of calcium carbonate plus chlorides. In two
case histories of unaffected tubes, examined but not reported herein, no
pitting corrosion was observed under a continuous deposit of calcium car-
bonate (Biblio. 13, 1*0.

Except for case history number 2, the inside surface of the

stainless steel tubes were covered with a predominantly black, mucklike
deposit. (Figure 1) Faint and almost indiscernible x-ray diffraction pat-
terns of this deposit made identification difficult, but the deposit was
eventually determined to be a hydrous oxide of manganese (Biblio. l6).
X-ray and wet chemical analyses established other consistent components
in the black deposit as organic matter, a hydrous oxide of iron (ferric)
and, to a lesser degree, calcium carbonate. Table II lists the percentage
composition of the major components of the deposit on an averaged basis
along with the chemical and metallurgical analyses of the affected tubes.

When the black deposit was removed by wiping, the presence of

patchy and tightly adherent deposits on the tube surface, subsequently
identified as carbonates plus chlorides, was revealed. (Figure 2) The
inside surface appearance shown in Figure 2 was also characteristic of
case history number 2, which did not have an over-lay of the black mangan-
ese deposit. Although the average analysis of the deposit in that case
history showed no appreciable manganese content, there were some local,
isolated black patches high in manganese that had the same visual appear-
ance as the manganese deposits previously described.
 When the patchy carbonate deposits were removed by reaction with
dilute nitric acid, the presence of pitting corrosion which had occurred
underneath the carbonate deposits was partly revealed. (Figure 3) The
pitting is revealed in greater detail in Figure k after the corrosion pro-
duct has been removed. Note that the physical appearance of the pitting
is typical for that form of corrosion when it has occurred under deposits
on stainless steel surfaces. Some undercutting was evident within each
pit, the degree varying for each pit in different locations. No quantita-
tive determination of chlorides was attempted, but their presence was
established in each deposit over a pit by x-ray fluorescence analysis and
the silver nitrate test. (Table II)

Examination of the affected tubes showed no chemical or metal-

lurgical abnormalities.(Table II) Even the earliest investigations in-
dicated that the pitting corrosion was the result of the external environ-
ment and not some irregularity in the stainless steel tube material. Since
affected and unaffected tubes were also basically similar in composition
and microstructure, this early conclusion has been reaffirmed. For an in-
direct measure of the aggressiveness of these local conditions on the tube
surface, note that even type I36, an alloy which is more resistant to pit-
ting than type 30^, also suffered pitting corrosion.

Seaboard

The use of type 3l6 stainless steel condenser tubes at coastal

power plants represents the remainder or 15% of the total footage of
stainless steel condenser tubing in use (Biblio. 9)· Although type 3l6
is more resistant to pitting corrosion than type 30^, type 3l6 is by no
means completely immune to this form of corrosion. This fact, coupled
with the greater quantity of chlorides present in coastal waters, explains
why the percentage of coastal installations which have experienced tube
losses due to pitting corrosion is higher than the percentage for inland
installations (approximately 10$ versus less than 3%)· Although the use
of type 316 in coastal waters may be relatively more hazardous than the
use of type 30^ in inland waters, the controlled use of type 316 by one
coastal utility was the only practical solution to severe corrosion prob-
lems with copper-base alloys (Biblio. l8, 19)·

The pitting corrosion problems due to obvious reasons, such as

those stemming from the stagnation and concentration of salt water and
lodged debris, will not be dealt with in the following discussion.

There were two cases of tube failures at seaboard locations

where the inside surface appearance of the tubes was identical. Some
environmental factors (i.e., the presence of a marine fouling problem)
were also similar. Case history number 1 occurred on the Atlantic coast
and number 2 on the Gulf coast of the USA (Table III).
 In each case the pitting corrosion was associated with a visually
identical deposit. The color of the deposit was mostly brown-black with
a purple overtone, although some tubes from both locations did exhibit the
extremes of the three colors. Figure 5 illustrates the typical appearance
of the deposit and a corrosion pit.

The pitting corrosion at these two coastal installations were

also characterized by a rust colored mound around and sometimes over the
pit. (Figure 6) Subsequent chemical analyses showed that this nodule was
composed of the corrosion products of the pit and, therefore, was the re-
sult and not the cause of the attack. Incipient pitting, faintly visible
to the left of the rust spot in Figure 5·, was normally in the middle of a
dark colored circular deposit found to be similar in chemical composition
to the overall deposit but more concentrated. This increased thickness
made the circular shape appear darker, A cross-sectional examination of
the shape of the pits showed that they were always deeply undercut - the
hallmark of the chloride pit in stainless steels. Chemical spot testing
of the corrosion products confirmed the presence of chlorides.

Again, identification of the overall deposit by X-ray diffraction

was difficult but the seaboard deposit was also determined to be a hydrous
oxide of manganese (Biblio. 1*0. The coastal deposits were, therefore,
chemically similar to the inland deposits! The other consistent components
of the coastal deposits were also similar: namely, organic matter and a
hydrous oxide of iron (ferric). The deposits formed at the two coastal
installations were much thinner than those formed at the inland locations.
This physical difference between the coastal and inland deposits explained
the color differences between the brackish and fresh water deposits. In
fact, the purple hue of the coastal deposits was finally attributed to re-
flected light interference by the "thinness" of the deposit and to varia-
tions in composition, and not to, as originally suspected, some chemical
compound such as a permanganate. The chemical analyses of the deposits
plus the chemical and metallurgical analyses of the affected tubes for case
histories 1 and 2 (Table III) are listed in Table IV.

Laboratory examinations of these affected tubes and unaffected

tubes from other seaboard locations again showed that there were no es-
sential differences in tube material. As at the inland locations, the
corrosion was the result of the environment and not the tube material.

Other than these two cases and the obvious cases of pitting cor-
rosion referred to previously, other instances of pitting corrosion at
seaboard locations can be grouped together because of the isolated nature
of the tube losses. In most cases the circumstances leading to pitting
corrosion were obscure primarily because of the very isolated nature of
the problem. As in all the other cases, the pitting corrosion was the re-
sult of high local chloride concentrations either alone or in conjunction
with other deposits. Laboratory investigations again showed that there,
were no reasons to suspect that the tube material was responsible for the
corrosion. More importantly, these investigations indicated that pitting
corrosion could have been prevented if a high degree of cleanliness was
maintained on the inside tube surface.

Case history number 3 outlined in Table III is a dramatic example

of the effect of cleanliness in pitting corrosion. More complete details
surrounding this case history are available (Biblio. 8 ) . For the intended
illustration the following information is pertinent.
 Figure 7 is representative of the inside surfaces of a small
group of tubes in the second pass of a two-pass condenser equipped with a
continuous condenser tube cleaning system. Due to a peculiar flow pattern
which was corrected later, this group of tubes in the second pass was not
cleaned. Note the resultant deposit and pitting corrosion. (Figure 7)
The results of the analyces of the tube and deposit are listed under case
hie tory number 3 in Table IV.

Figure 8 illustrates the inside surface of a tube from the first

pass of the same condenser. Note the high degree of surface cleanliness
and absence of pitting in the top tube section. (Figure 8) Also note the
salt deposits and associated incipient pitting in the bottom tube section
in the same photograph. The latter condition was not representative of
the tubes in the first pass. Normal practice at this station is to flush
the tubes with fresh water whenever the circulating pumps are stopped for
any extended time period. Evidently, this particular tube was either mis-
sed or inadequately flushed.

The amount of the deposit in the tube from the first pass was
almost immeasurable, but the deposits in the first and second passes were
found to be chemically identical. The tubes from either pass were found
to be identical in composition and microstructure.

General observations

There was a great deal of emphasis places on the "manganese at-

tack" of condenser tubes when these particular corrosion problems first
occurred. The results of case history number 2 in Table I (pitting due
to local carbonate patches identical in appearance to case histories 1, 3i
k and 5 but with no manganese deposit) detracted a great deal from the
role which manganese appeared to play in the cause of the corrosion. Even
less importance was attached to the role of manganese when, during an
evaluation of a stainless steel tube had been in service for 1 3/^ years,
the absence of pitting in the presence of a manganese deposit was observed
(Biblio. 15)· Similar observations about manganese deposits and the cor-
rosion of admiralty tubes have been noted (Biblio. 12). Manganese deposits
in stainless steel condenser tubes may act as initiating causes of the
corrosion problem, but the manganese itself does not appear to electro-
chemically participate in the pitting mechanism. A simulated brackish
water containing potassium permanganate did pit a type 316 stainless steel
condenser tube in an accelerated laboratory test (Biblio. 17)· However,
the formation of permanganate by the oxidation of manganous manganese in
cooling waters is unlikely. Air or the addition of chlorine normally re-
sults in the formation of a precipitate of manganese dioxide (Biblio. 20).

The high carbon content of the manganese deposits (Tables II and

IV) strongly indicates that the deposits were formed by manganese-removing
organisms and not by chlorination. The experiences of two inland utilities
are relevant in this matter. One utility never chlorinated and a manganese
deposit formed. The other utility discovered that they were able to re-
duce the amount of the manganese deposit by increased chlorination. Their
water analyses showed more manganese coming out of than going into the
condenser during chlorination. These results are in agreement with what
happened at the two seaboard locations where manganese deposits formed.
There the more frequent use of chlorination required to control marine
fouling resulted in a thinner deposit of manganese.

One distinguishing feature of all the locations at which a

manganese deposit formed was that the cooling water was wholly or partially
from an impounded source. Manganese is almost certain to appear in the
water due to biological activity whenever a stream is impounded (Biblio.
20). Therefore, the manganese deposits appear to be organic in origin and
formation. The sometimes sudden appearance of these deposits and the sus-
pected importance of chlorination, the most ommonly used method of con-
trolling organic fouling, could be explained by the bacteriological nature
of the deposits.

The effectiveness of chlorination as a bacetericide is known to

be dependent on the production of a free chlorine residual in the cooling
water. To be of any significant value, the free chlorine residual must
first be obtained in and then maintained throughout the circulating water
system (Biblio. 21). The fulfillment of the first requirement is hampered
by the uncertainty of the determination of the free chlorine residual in
many cooling waters. Only the total chlorine residuals are listed in
Tables I and III because these were the only residuals considered reliable
by the power plant personnel. Their observations have noted variations
in the amount of the manganese deposit between condensers in the same power
plant due to the point of application of the chlorine. In one power plant
the condenser which had the chlorine injected at the pump suction had no
manganese deposit while the condenser which had the chlorine injected at
the cooling water intake had a manganese deposit. The longer contact time
in the water intake tunnel probably reduced the effective chlorine residual
at the condenser. _ Since both chlorination schedules were identical, this
incident illustrates the importance of the second requirement (maintaining
chlorine residual throughout system). There are other aspects of chlorina-
tion, such as frequency and duration, which are also known to be related
to its effectiveness as a bactericide; however, a complete discussion of
the subject is beyond the scope of this paper.

Chlorination is commonly used as a chemical method to maintain

condenser cleanliness during service. Two automatic or continuous mech-
anical methods are available to clean condenser tubes during service
(Biblio. 19, 22). They are known in the USA as the Amertap and American
M.A.N. systems, but both methods were originally used in Europe. Other
conventional chemical and mechanical methods can be used to clean tubes
during outages.

Clean tubes result in improved heat transfer and resistance to

pitting corrosion for stainless steel tubes. The degree of cleanliness
required for efficient heat transfer can be measured by the turbine back
pressure (condenser vacuum). Case history number 2 in Table III was in-
cluded in this paper to illustrate (l) the effect of tube cleanliness on
pitting and (2) the degree of cleanliness which was associated with the
presence and absence of pitting. In many of the affected tubes examined
in the laboratory, conditions at the tube inlet would prevent deposit for-
mation for distances up to six feet from the inlet end in some cases. No
pitting occurred in the deposit free area but as the deposit buildup in-
creased toward the outlet end of the tube, the frequency and intensity of
the pitting also increased. The average rise in temperature of the cooling
water might have contributed to this pitting pattern, but the following
 observations suggested that this temperature factor was probably minor.
In many instances the pitting was confined to the middle of the tube; in
those cases where pitting progressed toward the end of the tube, condi-
tions at the tube outlet sometimes prevented or minimized deposit forma-
tion for distances up to one foot from the outlet end, and no pitting oc-
curred in this clean area. As in many other uses of stainless steels, ex-
cellent corrosion resistance can be achieved by maintaining a clean sur-
face. Cleaning will prevent the formation of nonuniform deposits which
can cause pitting due to local electrochemical cells resulting from con-
centration differences. The mechanism of the formation of pitting is the
subject of much investigation, but the development of pitting follows
established electrochemical principles (Biblio. 23, 2.k) .

There has been considerable interest and speculation about the

environmental factors which led to the local conditions responsible for
the pitting at the inland and seaboard locations. A corrosion mechanism
will be proposed for each location.

Pitting at the inland locations occurred under local deposits

of calcium carbonate containing chlorides. The pits were saucer shaped
and only slightly undercut. This is a characteristic appearance for pit-
ting which has occurred under deposits in the presence of chlorides as a
result of an oxygen concentration cell.

An increase in the temperature of certain cooling waters can

cause a calcium carbonate deposit to form due to the thermal decomposition
of calcium bicarbonate. At all of the inland locations listed in Table I,
the Langelier Index for calcium carbonate saturation was positive at the
same given time (Biblio. 23)· Therefore, local high temperatures could
have caused the formation of the local calcium carbonate deposits.

Condenser tube deposits are poor conductors of heat, and gener-

ally non-uniform in distribution and composition. The resultant non-uni-
formity of the resistance to heat transfer will cause variations in local
temperatures. The manganese deposits at the inland locations could have
either caused or aggravated a non-uniform flow of heat which resulted in
locally higher temperatures.

At the one inland location that did not have a manganese deposit
there were reports of low cooling water velocities which could have caused
local overheating. The tube examined in the laboratory from this location
had local carbonate patches only in the top half of the tube. The bottom
half was free of carbonate patches and essentially clean except for some
sand which had settled out in the exact bottom of the tube. This appear-
ance was not representative of all the tubes, but the condition was in-
dicative of an insufficient volume of cooling water.

Locally, higher temperatures, therefore, caused by insufficient

coolant or nonuniform deposits, can be suspected as the cause of the local
carbonate deposits and the resultant pitting at the inland location.

The cause of the pitting at the seaboard location was not readily
apparent, but incipient pitting was observed to be associated with local
patches of the manganese deposit which were thicker than the bulk of the
deposit. The appearance of the pits was unmistakable; they were the typ-
ical severely undercut chloride pit. The nonuniformity of the deposit can
be suspected as giving rise to local chloride differences. High local
chloride concentrations are possible because of the greater availability
of chlorides in these waters.

10
 There is every reason to suspect that the temperature factor
described for the inland location is an important factor at the seaboard
locations as well. Temperature differences could lead to oxygen concentra-
tion differences in addition to the chloride concentration differences.
These accelerating factors must be suspected when the relative rapid rate
of attack which occurred at these seaboard locations is considered.

11
 BIBLIOGRAPHY

(1) G.G. Page, "Some Operating Conditions Influencing Attack of Non-

ferrous Tubular Condenser and Heat-exchange Equipment,"
First International Congress on Metallic Corrosion, London:
Butterworth & Company (Publishers) Ltd., 1962, pp. 613-618.
(2) D.A. Sudrabin and A.H. Tuthill., "Why Copper-Nickel Alloys for
Desalination",
Metals Engineering Quarterly, vol. 7. Ρ· 1^ (196?) August.
(5) J.R. Maurer, "Basic Considerations in the Use of Stainless Steels
in Modern Condenser Design",
Paper presented at the International Nickel Power Conference,
Estes Park, Colorado, August 1, I96I.
(4) J.R. Maurer, "Design and Application of Stainless Steel Utility
Surface Condensers",
Paper presented at the International Nickel Power Conference,
Wrightsville Beach, North Carolina, May 5i 196^.
(5) J.R. Maurer, "Use of Stainless Steel Condenser Tubes Growing at
Increasing Rate" ,
Power Engineering, vol. 68, pp. 59-60 (196^) November.
(6) R.H. Marks, "Stainless Steel Materials Gain for Condenser Tube
Service" ,
Power, vol. IO9, pp. 9^-95 (1965) October.

(7) N.A. Long, "Recent Operating Experiences with Stainless Steel

Condenser Tubes" ,
Proceedings of the American Power Conference, vol. 28, pp. 798-807
(1966).
(8) Ibid. , p. 804.

(9) J.R. Maurer, "The Use of Stainless Steel Tubing in Condenser and
Related Power Plant Equipment",
Paper presented at the Southeastern Electric Exchange, Atlanta,
Georgia, October 13,1966.

(lO) N.A. Long, "Have You Considered Stainless Steel Condenser Tubes?"
Paper presented at the Second Joint Meeting of the Institute Mexicana
De Ingenieros Químicos and the American Institute of Chemical
Engineers, Air Separation and Ammonia Plant Safety Symposium, Mexico
City, Mexico, September 25, 1967·

13
(il) F.L. LaQue and M.A. Cordovi, "Experiences with Stainless Steel Surface
Condensers in the USA",
Paper presented at the International Nickel Power Conference,
Lausanne-Ouchy, Switzerland, October 13, 1967·
(12) E.B. Morris, "An Unusual Condenser Tube Corrosion Problem on the
Ober River",
ASME Paper 67-PWR-l.
(13) N.A. Long, Wallingford Steel Co., Wallingford, Connecticut,
unpublished report, May 3i 1965·
(14) Ibid., March 8, I966.

(15) Ibid., August 26, I965.

(16) N.M. Rice, Wallingford Steel Co., Wallingford^ Connecticut,

private communication, 196*t.
(17) N.A. Long and N.M. Rice, Wallingford Steel Company, Wallingford,
Connecticut, unpublished report,-November k, I96A·.

(ΐθ) D.W. Hoskinson and C K . Kuester, "Operating Experiences with Stainless

Steel Condenser Tubes in Central Stations",
ASME Paper 64-WA/CT-l.
(19) C K . Kuester and C E . Lynch "Amertap at English Station",
ASME Paper 66-WA/CT-l.

(20) A.E. Griffin, "Significance and Removal of Manganese in Water Supplies"

Journal Amercian Water Works Association, vol. 52, pp. 1326-3^ (i960)
October.
(21) S.A. Cole, "Control of Slime and Marine Fouling",
ASME Paper 55-S-48.

(22) F.G. Jensen, "First Year of Operation with the M.A.N. Condenser
Tube Cleaning System",
ASME Paper 66-WA/CT-2.

(25) H.H. Uhlig, Corrosion Handbook, New York: John Wiley & Sons, Inc.,
19^8, pp. I65-I73.
(24) Ja.M. Kolotyrkin, "Pitting Corrosion of Metals"
Second International Congress on Metallic Corrosion, NACE, 1963i
pp. 23-32.
(25) W.F. Langelier, "The Analytical Control of Anti-Corrosion Water-
Treatment" ,
Journal American Water Works Association, vol. 28, p. I5OO (1936)
October.

14
 Table I - Service Conditions of Stainless Steel Condenser Tubes at Inland Locations

Case history number 1 2 3 4 5

Tube material 304 304 316 304 304

Gauge, BWG 20 22 22 22 20

Service time 8 mos. l8 mos. 2 yrs. 6 yrs. 7 yrs.

Tube location Air Impingement Impingement Impingement Air

removal & air removal removal

Water source Lake River River River Lake

pH 8.5 7Λ 7.2 7-5 7.5
ppm chloride, CI 1490 240 45 27 25
ppm total dissolved
solids ND 750 200 262
ppm calcium, Ca 185 225 60 35 40
M.O. alk. as
ppm CaCO 328 100 38 133 70
velocity, fps 7 7 7 7 7

Chlorination
2/wk summer
frequency 2/wk summer Daily 3/day l/wk winter 2 wk/summer
ppm total residual 1 1/2 1 1/2 1/2
duration 5 mins. 1/2 hr. 20 mins. 1/2 hr. 2 hrs.

Cleaning NO MECHANICAL CLEANING

ui
M

Table II - Chemical Analyses of Tube and I.D. Deposits at Inland Locations

Case history number 1 2 3 4 5

Tube check analyses 304 304 316 304 304

% chromium, Cr 18.41 I8.O9 17.40 18.73 19.44
Yo nickel, Ni 9.46 10.20 12.65 8.83 10.08
% molybdenum, Mo 0.19 O.29 2.38 0.13 0.29
carbon, C 0.050 0.066 O.O7I 0.054 O.050

Tube microstructure Welded &

Weliftd Cold DrawnfcAnnealed Annealed

I.D. deposit analyses

% manganese dioxide hydrate, MnO_,K 0 31.0 nil 40.0 40.6 22.0
% calcium carbonate, CaCO., IO.5 64.0 1.1 3-7 5.5
% carbon, C I2.7 7-9 7-6 4.7 12.4
% iron oxide hydrate, Fe-O^.H-O 6.2 24.4 7-3 51.0 11.8
% silicon dioxide, SiO_ 2.0 2.5 31.0 nil 43.9

presence of chlorides confirmed Positive in all cases

 Table III - Service Conditions of Stainless Steel Condenser Tubes at Seaboard Locations

Case history number 1 2 3

Tube material 316 316 316
Gauge, BWG 20 22 20

Tube location Impingement & air removal All All

Water source Tidal river Bay Tidal river

pH 7.6 8.1 6.7
ppm chloride, CI 9,000 20,500 9,000
ppm total dissolved solids 15,450 38,000 14,000
ppm calcium, Ca 140 ND 250
M.O. alk. as ppm CaCOj 45 HO 120
ppm hydrogen sulfide, H2S 0.4
velocity, fps 7.5 7.5 6.5
Chlorination
frequency 12/day 6/day Before outages
ppm total residual 1/4 1 ND
duration 2 hrs. 1/2 hr. Shot feed
Cleaning None None Amertap
Service time 3 mos. 5 mos. 1 yr.
ë

Table IV - Chemical Analyses of Tubes and I. D. Deposits at Seaboard Locations

Case history number 1 2 3

Tube check analyses 316 3I6 316
io chromium, Cr 17.44 17.60 17.59
i nickel, Ni 13.62 I3.32 13.23
Ì> molybdenum, Mo 2.79 2.85 2.82
i carb on, C O.059 O.O54 O.O63
Tube microstructure Welded, Cold Drawn & Annealed

I.D. deposit analyses

io manganese dioxide hydrate, Μηθ2· Ξ2Ο 66.4 79.4
io calcium sulfate dihydrate, CaS0^.2H20 0.2 3.0 29.7
io carbon, C 1.8 11.7 5.8
io iron oxide hydrate, Fe20j.H20 3I.8 3.7 0.1
io sulfur, S 60.8
io chloride, Cl 0.1 0.1 1.5
-»
Figure 1; Black manganese deposit from an inland
location (Case No. 1, Table I) (1.25 x)

Figure 2: Carbonate patches containing chlorides

under a black manganese deposit (Case No. 2,
Table I)(1.25 x)

19
Figure 3'· Outline of pit under a carbonate patch
shown in Figure 2 after treatment with
dilute nitric acid (12.5 x)

Figure 4: Detail of pit shown in Figure 3 after

removing corrosion product (12.5 x)

21
Figure 5- Brown-black manganese deposit from a sea-
board location (Case No. 2, Table III)
(1.25 x)

Figure 6: Corrosion product nodule over pit

(Case No. 1, Table III) (3.75 x)

23
Figure 7 : Inside surface of a tube from the second
pass-not cleaned (Case No. 3» Table III)
(1.25 χ)

Figure 8: Inside surface of a tube from the first

pass-as cleaned (Case No. 3, Table III)
(1.25 x)

25
 S u m m a r y

Stainless steels are subject to pitting under certain local con-

ditions which can exist at the metal surface-environment interface. Fac-
tors in the metal and environment play an important role in determining
whether pitting will occur. The absence and presence of pitting in stain-
less steel tubes of similar chemical composition and metallurgical struc-,
ture indicate that these metal factors are relatively unimportant. However,
pitting corrosion in stainless steel steam surface condenser tubes was
found to be significantly influenced by the local environmental conditions
on the inside tube surface.

The corrosion mechanism appears to be initiated by non-uniform

deposits that form in the presence of chloride as the result of certain
environmental conditions. Non-uniform deposits are suspected as the causes
of concentration and temperature differences which result in local electro-
chemical cells that lead to pitting. An effective method of corrosion con-
trol, therefore, would be to prevent the formation of non-uniform deposits
by chemical and mechanical cleaning methods.

The most common troublesone deposit found in stainless steel con-

denser tubes is a hydrated manganese oxide apparently produced by bacteri-
ological action. Chlorination should be an effective chemical method for
controlling the formation of this deposit, but no effective treatment pro-
cedure has been established. Manganese deposits are most apt to form a
cooling water source that has been impounded. Pitting corrosion is not ex-
pected to occur from a water of very low hardness and chloride content.

The use of stainless steel surface condenser tubes continues to

expand in the USA because stainless steel tubes fulfill the basic condenser
tube alloy requirements - good overall heat transfer and excellent resist-
ance. Corrosion problems have been limited to a small percentage of instal-
lations where pitting has occurred in the cooling water side due to non-
uniform deposits. Cleaning offers a practical solution to the corrosion
problem, and improved heat transfer and reliability in any installation.

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PUBLICATIONS DEPARTMENT OF THE EUROPEAN COMMUNITIES
14349/5/68/1