Microbiological Influenced Corrosion (MIC) of Welded 316L

Stainless Steel Pipes

Mario Arenas, Png! P"#!
$o%a & Ca'bridge, (ntario Canada
Abstract) Grade 316 austenitic stainless steels are normally considered corrosion resistant in low-chloride
natural fresh waters. However, cases of premature corrosion failures in such environment have been observed
in welded 316 stainless steel pipes. This paper present the results of a failure analysis performed on a welded
316L stainless pipe which failed after four months of operation in a water treatment plant. uch rapid material
deterioration was ascribed to microbiolo!ical induced or influenced corrosion "#$%&. The term #$% is used to
describe a type of corrosion resultin! from the presence and activities of microor!anisms within biofilms. #ost of
the corrosion dama!e was found at the weld and weld toe areas. The intermittent operation of the plant allowed
the formation of biofilms, under which differential aeration concentration cells and pittin! corrosion sites
developed. The pittin! attac' resulted in wall throu!h holes which caused lea's in a number of stainless steel
pipes. (ased on the results of the analysis, it was su!!ested that iron reducin! bacteria "$)(& was associated
with the corrosion dama!e. *n insi!ht into the corrosion mechanism induced by $)( is discussed at the end.
1! I*+,(#-C+I(*
#icrobiolo!ically influenced corrosion "#$%&, also
'nown as biolo!ical corrosion, is the deterioration of
metals as a result of the metabolic activity of
microor!anisms. %ases of #$% have been reported in
carbon steels, stainless steels, aluminum alloys and
copper alloys in waters and soils with pH +,- and
temperatures ran!in! from 1.
o
%,/.
o
%
"1&
.

The bacteria causin! corrosion can be classified as
aerobic "re0uires o1y!en to become active& or
anaerobic "o1y!en is to1ic to the bacteria&. 2or
instance, sulphate reducin! bacteria "3(& is
anaerobic while iron o1idi4in! bacteria "$)(& and
man!anese o1idi4in! bacteria are aerobic. #$% is
associated with a variety of corrosion mechanisms
such as pittin!, crevice corrosion, selective
dealloyin!, under-deposit corrosion, and stress
corrosion crac'in!.
The present wor' illustrates a case where #$%
caused the failure of stainless steel pipes in a water
treatment plant. The plant was desi!ned to treat 15-.
m
3
6day of water ta'en from a la'e for the purpose of
municipal supply. *fter some time in service, periodic
water analysis revealed an elevated concentration of
trihalomethanes "TH#&. 7espite various ad8ustments
within the operatin! procedures, the concentration of
TH# remained at a level e1ceedin! the ma1imum
allowable limit. $n order to remediate the problem, a
consultin! company was retained to present
alternatives. (ased on the recommendations, the
plant was up!raded with the addition of serpentine
pipin! and was converted from chlorination to 9: and
chloroamination process. The up!raded plant was
approved to produce 13++ lt6min of ma1imum flow
rate. However, the current demand for treated water
was on avera!e 36. lt6min, appro1imately 5;< of the
water treatment plant desi!ned capacity. Hence, the
operation of the plant was intermittent accordin! to
the demands for treated water. *ppro1imately four
months after the up!rade, lea's were detected in
various pipes especially near chemical in8ection
points.
* representative in-situ photo!raph of a lea'ed pipe is
depicted in 2i!ure 1. 3esidues with a brown reddish
coloration lea'ed from the pipe.

.igure 1= >hoto!raph of a lea'ed pipe.
Arenas (1 of 9)
/! 0AMI*A+I(*
/!1 1isual and SM2#S $a'ination
* selected pipe that lea'ed was sectioned and then
visually inspected "2i!ure 5&. The pipe measured 6
inches in diameter and was made from chedule 1.
316L stainless steel "T>316L&.
.igure /) >hoto!raph of the pipe used for the failure
analysis.
$nitial e1amination of the outside surface revealed that
the lea' occurred at a circumferential weld in an area
with visible deposits "2i!ure 3&.
.igure 3) >hoto!raph illustratin! the lea' location "arrow&.
The pipe was sectioned in half and the inner surface
inspected "2i!ure +&. $n the nei!hbourhood of the
lea', a layer of deposits with colorations ran!in! from
red brownish to dar' brown was observed as
corrosion products "2i!ure /&. $t appeared that the
deposits ad8acent to the lea' were removed after the
failure.
.igure 3) $nner surface of the pipe at the lea' location.
.igure 4= Layer of corrosion deposits formed around the
lea' location.
%loser views of the lea' location revealed the
presence of holes alon! and near the weld toe
"2i!ure 6&. The lar!est hole developed at the weld
and measured appro1imately 3 mm lon! and 5 mm
wide. This was found to be a wall throu!h hole.
*nother hole e1tended from the weld toe into the
base metal and a third hole was observed at the weld
toe. *n area with a red-oran!e coloration was noted
in the vicinity of the lea' location, which su!!ested
the presence of corrosion products rich in iron "?3&.
The inner surface in the pro1imity of the pitted area
e1hibited an etched appearance indicative of
superficial corrosion attac' of the base metal "2i!ure
6 bottom&.
Arenas (2 of 9)
Leak
Leak
weld
Area with red-
orange coloration
Figure 13
.igure 6) tereomicroscope ima!es of the holes developed
on the inner surface of the pipe.
@1amination of the lea' area at a hi!her ma!nification
was achieved usin! the scannin! electron microscope
"@#&. >rior to the @# analysis, the sample was
briefly cleaned with ethanol and dried with warm air.
@# ima!es of the holes that formed at the weld toe
are shown in 2i!ure ;. 3ound penetrations observed
alon! the perimeter of the holes were believed to be
associated with corrosion pits. Li'ely, small pits !rew
and coalesced into lar!er cavities. The corrosion
attac' pro!ressed alon! the weld toe "2i!ure A&,
where multiple pits were observed at a hi!her
ma!nification "2i!ure -&.
.igure 5) @# ima!es of the holes at the weld toe.
.igure 6) @# ima!e of the corrosion attac' alon! the weld
toe.
.igure 7) @# ima!e of pits alon! the weld toe.
)bservation of the inside of a pit located alon! the
weld toe revealed a dendritic morpholo!y, as shown
in 2i!ure 1.. This is typically associated with a
microbiolo!ical corrosion mechanism which induced
the preferential attac' of one phase of the
Arenas (3 of 9)
weld
microstructure leavin! a Bs'eletonC after the corrosion
attac'.
.igure 18) 7endritic s'eleton left inside a pit after the
corrosion attac'.
@7 analysis was used to obtain compositional
information from the corroded areas. *n @7 scan
from the ed!e of the lar!est hole on the inner surface
"2i!ure 11& revealed the presence of iron, chromium
and o1y!en as the main elements alon! with minor
amounts of nic'el, man!anese, aluminum, calcium,
silicon and chlorine "It is not possible to differentiate
sulphur and molybdenum because the peaks of both
elements overlap&. The lar!e concentration of o1y!en
was indicative of the presence of iron o1ides as
corrosion products. *nother important findin! was the
si!nificant presence of chlorine which is an element
associated with pittin! in stainless steels. %hlorine
li'ely came from the decomposition of the
hypochlorite added for the water treatment and from
the water itself.
@lement #n 2e %r ) i %a
wt< 3.-1 +;.+6 15.-- -.36 5.13 5.;.
@lement % %l Di "#o
&
*l #!
wt< ;.6; 1.AA /..; 1.-. +.51 ..;3
.igure 11) @7 scan and composition from the ed!e of the
lar!est hole on the inner surface.
@7 analysis of the layer of residues observed near
the lea' on the inner surface is shown in 2i!ure 15.
The @7 scan showed lar!e pea's of iron, chromium
and o1y!en which confirmed that the residues were
primarily composed of iron o1ides.
@lement %r Di "#o
&
#n )
wt< 1/.15 3.1/ 1.1; 1.// 6.11
Arenas (4 of 9)
.igure 1/) @7 scan and composition from the layer with
corrosion products.
.
/!/ Metallograp"ic Anal9sis
#etallo!raphic e1amination was conducted on a
cross section cut from a selected pitted area "3efer to
2i!ure 6 top&. The section was analy4ed in the as-
polished and etched condition. The microstructural
features were e1posed usin! 1.< o1alic acid
electrolytically applied.
* mosaic ima!e of the section in the etched condition
is shown in 2i!ure 13. This micro!raph revealed the
presence of lar!e pits with a pear-li'e shape, typical
of #$% "2i!ure 1+&. The pits were primarily developed
at the weldE however, they also e1tended into the
base metal. $ma!es in the as-polished condition
revealed that the pittin! was associated with
tunnellin! and subsurface attac' "2i!ures 1/ and 16&,
thereby confirmin! that the pittin! was induced by
microbiolo!ical activity.
.igure 13) #osaic ima!e of the cross section illustratin!
corrosion pits at the weld.
.igure 13) )ptical ima!e of a lar!e pit with pear-li'e shape.
.igure 14) )ptical ima!e in the as-polished condition
showin! pit tunnellin!.
.igure 16) ubsurface attac' at the weld toe.
The !eneral microstructure of the stainless steel
consisted of ferrite strin!ers in a matri1 of twinned
austenite !rains "2i!ure 1;&. Do carbide precipitation
was observed. The heat affected 4one was narrow
and the !eneral weld microstructure e1hibited a
dendritic columnar structure typical of welds "2i!ure
1;&.
Arenas (5 of 9)
@lement %l i 2e %a % *l
wt< ..// ..61 6;..A 1.5A 5.;5 ..66
weld
weld
Base metal
OD surface
OD surface
.igure 15) #icrostructure of the base metal and the weld.
To better observe the presence of the ferrite phase in
the weld, an etchant solution of +.< Da)H was used
and a ferrite count analysis was performed. The weld
microstructure consisted of an interdendritic ferrite
networ' "dar'& in an austenite matri1 "2i!ure 1A&. 2or
the ferrite count, a total of 1. fields were analy4ed.
The mean ferrite percenta!e in the weld was
estimated as ;<, which was considered to be within
the acceptable ran!e. Do evidence of si!ma phase
was observed. The weld microstructure at a pitted
area is shown in 2i!ure 1-. The sinuous profile of the
pit ed!e was consistent with the selective corrosion of
the austenite phase.
.igure 16) )ptical microscope showin! the weld
microstructure etched with +.< Da)H.
.igure 17) )ptical microscope of the weld microstructure
at a pitted location.
/!3 Micro"ardness testing
#icrohardness testin! of the base metal, heat
affected 4one and the weld was performed to identify
differences. The microhardness measurements were
performed usin! an indentation load of 3.. !rams.
3esults are presented in Table 1. The microhardness
of the heat affected 4one and weld was A6 H3( while
that of the base metal was A1 H3(. The hardness of
the heat affected 4one was not si!nificantly hi!her
than that of the base metal. The hardness values
obtained were consistent with the annealed condition
of the alloy.
+able 1) #icrohardness results.
/!3 C"e'ical Anal9sis
>ortions of the base metal and the weld were cut for
chemical analysis. 3esults are listed in Table 5. The
composition of the sample conformed to the nominal
composition specified for !rade 316L stainless steel
"9D 316.3& per *T# *315-.-. The weld was of
similar composition as the base metal.
+able /) %hemical *nalysis "wt<&.
Element Base
Metal
Weld Compositi
on
!"
"31#$3
Arenas (6 of 9)
"am
ple
nit
s
Microhard
ness
A%erag
e
Base
metal
HV 0.3
162, 154,
153
156
HRB 82, 81, 81 81
HA
HV0.3
165, 168,
16!
16!
HRB 85, 86, 86 86
"el#
HV0.3
161, 1!5,
166
16!
HRB 84, 88, 85 86
&it
Base metal
weld
$ar%on 0.01 0.02 0.035 ma&
'an(anese 0.89 0.96 2.00 ma&
)*l+,*r -0.01 0.01 0.030 ma&
).l./on 0.62 0.68 1.00 ma&
0,os+,or*s 0.03 0.02 0.045 ma&
1./kel 10.0 11.1 10.0214.0
$,rom.*m 16.3 1!.6 16.0218.0
$o++er 0.24 0.19 2
1.tro(en 0.01 0.01 0.1 ma&
'ol3%#en*m 2.08 2.20 2.0023.00
* water sample was collected from the water
treatment plant and analy4ed for selected anions and
metal ions. The analysis was performed usin! ion
chromato!raphy and the results are presented in
Table 3. The pH was measured at ;./ and the level of
chlorides appeared to be typical for fresh water.
+able 3) %hemical *nalysis of the water "m!6lt&.
3! #ISC-SSI(*
The analysis of the selected pipe has shown that the
failure was due to pittin! corrosion induced by
microbiolo!ical activity. This was evidenced by a
number of observations !athered durin! the analysis.
The rapid failure of the pipe "after four months in
service& and the presence of perforations in other
pipes were indications that an a!!ressive and
accelerated corrosion process too' place, which was
not e1pected based on the temperature and chloride
operational levels. The rapid deterioration is
consistent with documented cases of #$% failures in
stainless steel pipes
"5&
. 2urthermore, the pear-li'e
morpholo!y of the pits with tunnellin! characteristics
Arenas (! of 9)
"u'stan
ce
Concentra
tion
An.ons
$,lor.#es 22
1.trates 14
1.tr.tes 14
'etal
.ons
$al/.*m 31
'a(nes.
*m
10
)o#.*m 15
+H !.5
Har#nes
s
($a$53)
120
formed below the surface was also consistent with
#$%. *nother evidence of #$% was the preferential
corrosion attac' of the austenite phase which left a
Bs'eletonC of dendritic ferrite inside the pits.
(ased on the reddish coloration of the corrosion
deposits observed around the pitted area, it was
determined that the bacteria causin! the corrosion
dama!e was iron o1idi4in! bacteria "$)(&. * positive
identification of the bacteria would have re0uired a
biolo!ical analysis which was beyond the scope of
this wor'. * practical !uide to determine the type of
bacteria producin! #$% in weldments of stainless
steel is !iven bellow
"3&
.
+able 3) #$% scenarios that may play a role in the corrosion of weldments in stainless steel.
The presence of iron o1idi4in! bacteria, such as
Gallionella, phaerotilus, Leptothri1, and %renothri1,
in fresh water has been reported in the literature
"+&
.
#ost $)( are microaerophilic, re0uirin! low
concentrations of o1y!en ")5& for !rowth
"/&
. $)(
o1idi4e iron from a soluble ferrous "2e5?& form to an
insoluble ferric "2e3?& form at6near neutral pH often
formin! dense deposits of 2e o1ides. This is
consistent with the red-oran!e coloration of the
deposits observed near the lea' location. The
dissolved ferrous iron comes from either the metal
surface or the incomin! water supply. The ferric iron
that the bacteria produces attracts chloride ions, as
e1plained below, and produces ferric chloride
deposits which are very a!!ressive towards stainless
steel.
The corrosion mechanism induced by $)( can be
considered as under deposit corrosion or formation of
a differential aeration cell
"6&
. * schematic of the
process is shown in 2i!ure 5.. 9nder sta!nant
conditions, $)( form dense deposits, e1cludin!
o1y!en from the area immediately under the deposit.
$n an o1y!enated environment, such as that
encountered in fresh water, the area deprived of
o1y!en becomes a relatively small anode compared
to the lar!e surroundin! o1y!enated cathode. #etal
at the anode dissolves, formin! metal cations that
under!o hydrolysis and decrease pH.
Arenas (8 of 9)
MIC by Mechanism Indicators
Manganese oxidizers Ennoblement of stainless
steel potential due to MnO2
Elevated manganese-
oxidizing organisms,
manganese, and possibly
chloride in deposits
SR primary Sulfides, SR facilitate
chloride attac! in anaerobic
systems
"ar!-colored corrosion
products, #ith iron sulfide,
chloride, and a high ratio of
$e%2&$e%'( near-neutral p)
SR secondary oxidation *itting stabilized by
thiosulfate formed by
oxidation of sulfides
+yclic anaerobic, aerobic
conditions( surface of
corrosion products in pit
oxidized red, orange,
or bro#n
,ron-oxidizing bacteria "ecrease of p) by oxidation
of $e%2 to $e%' in pits
Red&orange corrosion
products rich in $e%'( iron-
oxidizing organisms such as
-allionella( ph acidic
.igure /8. chematic of the #$% mechanism.
The e1tent of the pH decrease is determined by the
alloy composition
";&
. 9nder deposit attac' is
particularly a!!ressive on 3.. series stainless steels,
containin! 1;./ to 5.< %r. $n addition, chloride "%l-&
from the electrolyte mi!rates to the anode to maintain
char!e balance, formin! corrosive metal chlorides.
Therefore, a combination of factors involvin! the
differential aeration, a lar!e cathode6anode surface
area and the development of acidity and metallic
chlorides produced an e1tremely a!!ressive
environment which resulted in the rapid perforation of
the pipes.
The preferential attachment of the bacteria at the
weld and weld toe is not completely understood.
However, it has been proposed that the rou!h surface
te1ture of the weld in con8unction with the lar!er
proportion of austenite6ferrite !rain boundaries at the
weld facilitates the attachment of bacteria
"A&
.
$n the proposed failure scenario, an initial step was
the attachment of bacteria in preferred locations such
as the weld toe. )ver a period of time a biofilm was
formed which induced pittin! corrosion on the weld
metal. The pit acted as a microenvironment where a
number of electrochemical reactions too' place. The
main reactions are summari4ed below=
%athodic reaction in a neutral or sli!htly basic
environment=
)5 ? 5H5) ? +e
-
F +)H- "water o1idation&
*nodic reactions=
2e F2e
5?
? 5 e- and 2e
5?
F2e
3?
? e-
Hydrolysis= 2e
?5
? 165)5 ? /H5) G 5 2e")H&3 ? H
?
2ormation of 2e%l3= 2e?3 ? 3%l- G 2e%l3 "soluble&
The root cause of the lea's was considered to be the
intermittent nature of the plant operation, which
allowed the formation of biofilms on the metal surface.
>ossible spi'es in the levels of hypochlorite in8ected
into the system at the plant start-up sta!e mi!ht have
been also a contributin! factor. The hypochlorite could
have decomposed into chloride ions which
accelerated the pittin! process.
The condition of the stainless steel pipe was not
considered a factor associated with the failures. The
weld conformed to the chemistry of Type 316L
stainless steel and its microstructure did not e1hibit
!ross metallur!ical deficiencies. There was evidence
of minor weld heat tint in some pipes, which is 'nown
to facilitate the corrosion attac'. However, corrosion
was widespread and occurred even in pipes with no
evidence of heat tint, such as the one analy4ed in this
paper.
3! C(*CL-SI(* A*# ,C(MM*#A+I(*S
The analysis has concluded that the 316L stainless
steel pipes failed throu!h a microbiolo!ical induced
corrosion mechanism which created an a!!ressive
pittin! attac' at the weld and weld toe where bacteria
preferentially attached. $t was considered that the root
cause of the failure was the sta!nant conditions of the
flow which promoted the establishment and !rowth of
bacteria. The bacteria that caused the dama!e were
deemed to be iron o1idi4in! bacteria. There was no
indication that metallur!ical deficiencies in the weld or
base metal were the cause of the failures.
$n order to minimi4e future failures due to #$%, the
followin! measurements were recommended=
- The review of the desi!n capacity of the plant
to assure continuous flow of water as much as
possible avoidin! sta!nant conditions inside the
pipes.
- The establishment of a comprehensive biocide
mana!ement pro!ram after positive identification
of the bacteria causin! #$%.
.
,.,*CS
Arenas (9 of 9)
Cl:
1. . #a1wel, %. 7evine, 2. 3ooney, and $. par',
>aper .+;/5, %)33)$)65..+,D*%@, TH,
Houston, 9*. "5..+&.
5. I.3. ree'umari, I. Hirotani and J. Ii'uchi,
%onference paper at %)33)$)D 5..+,
#arch 5A - *pril 1, 5..+ , Dew )rleans, 9*.
3. T. 3. Kac', Biological Corrosion Failures, p.AA-,
*# #etals Hadboo' :olume 11. ASM
$nternacional. #etals >ar' L )hio.
+. 3. 3ay, K. Lee and (. Little, %onference paper at
%)33)$)D 5.1. #arch 1+ - 1A, 5.1., an
*ntonio TH, 5.1..
/. G.I. 7ruschel, 7. @merson, 3. ut'a, >.
uchec'i, G.M. Luther, Geochim. %osmochim.
*cta ;5, 33/AL33;. "5..A&.
6. K. T. (orenstein and >. (. Lindsay, Mater.
Performance 33, +3 "1--+&.
;. L. L. hreir, 3. * Karman, and G. T. (urstein,
eds., Corrosion Metal !"nvironment #eactions$
, pp. 16.-163, :ol. 1, 3rd ed., (utterworth-
Heinemann Ltd., London, 1--+.
A. I. 3. ree'umari, J. ato and J. Ii'uchi,
#aterials Transactions +6 Do.;, 1636-16+/
"5../&.
Arenas (10 of 9)
Arenas (11 of 9)