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31-07-2007 Book Chapter1

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Microbiologically Influenced Corrosion in Military Environments

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Jason S. Lee, Richard I. Ray, Brenda J.

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14. ABSTRACTMICROBIOLOGICALLY INFLUENCED CORROSION (MIC) designates corrosion due to the presence and activities of microorganisms. Microorganisms can

accelerate rates of partial reactions in corrosion processes and/or shift the mechanism for corrosion proceses and/or shift the mechanism for corrosion (Ref I ). Most

laboratory and field MIC studies have focused on bacterial involvement: however, other signie-celled organisms, including fungi, can influence corrosion. This

article focuses on MIC of military assets and is divided into atmospheric, hydrocarbon and water immersed, and buried environments. Individual mechanisms for

MIC are dicused for specific examples. More general discussions of MIC are found in the articles "Microbiologically Influenced Corrosion" and Miccrobiologically

Influenced Corrosion Testing" in ASM Handbook, Volume 13A. 2003.

15. SUBJECT TERMS

microorganisms; metals; atmospheric corrosion; immersion

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Microbiologically Influenced Corrosionin Military EnvironmentsJason S. Lee, R. ichrd 1. Ray, and Brenda J. Little, Naval Research Laboratory, Stennis Space Center

M ICROBIOLQDGICALLY INFLUENCED to trace elements. Microorganisms can use many (radar. radio. flight instruments. wire strain

CORROSION (rN1IC) desionates corrosion due oreanic and inorganic materials as sources of gages. and helicopter rotors): hammocks: tape,

to the presence and activities of microorgtanisms. nutrients and energy (Ref 2). Organisms that thermal insulation: and building materials, Fungi

Microoreanisms can accelerate rates of partial require oxygen as the terminal electron acceptor cause corrosionl in atmospheric environments by:

reactions in comrosiot processcs and/or shift the in respiration are referred to as aerobes. Anaer- acid production. indirect dissolution of coatings.

mechanism for corrosion (Ref I ). Most labora- ohes urow in the abscnce of oxvcen and can use a or direct degradation of coatings. Direct deg~ra-

tory and field MvlC studies have focused on varietv of terminal electron acceptors. including dation is related to derivation of nutrients. Fungi

bacterial involvemeot: however, other sinele- sul fate, nitrate. Fe -' M'vn ". and others. Orean- assimilate oreainic material and produce organic

celled organismns. iticludinue (unui. can influence isins that can use oxv-en in addition to alternate acids includinue oxalic. lactic. formic. acetic. and

corrosion. This article focuIses on MIC of electron acceptors are known as tacultatise citric (Ref 4.

military assets ar-id ik divided into atmospheric . anaerohes. M*vicrobial nutrition and respiration Researchers isolated the folloivine- funual

hvdrocarhon anid water immersed, and buried are coupled and adapted ito ensironmental genera from polyurethane-coated 2024 alumni-

envionmets.Indlividual mechanism,, for MIC conditins Additionally. miicroorcani'ins liviil,,n uiihlcpe neirsee 1 etlt

are dIi scu ssed for- spcciftic exsamples. Mo re geni- itt co nsort ia Canl produce gosthconditions. hi, In skrmi.lii' ht'iicclo. Ph/imlo. stelnp/711i/tim:.

eral discussions r( f NII~C arc foutntd inl the artilcles nutrtie nts. anid elect roin acceptors not i\sai lale in UH mwiiwtiiixalIso known ats C/adoviniritlini.

M~ic robioloe1iealIs Infiluenced Corn isii it' and the hul1k env'i ronment.I' Penoi//jinu, and. Aurcihobsi'ditnn (Fit,. I e. Vecral

~Mieohiloeel l Utlueced Corrosion Test- _,encra. including .1ureo'ob.idhimni penwirated

in,,' iii .tSA Hwtit/his'k. Volume 1 3A. 200(3. the pol% urethane topcoat but not the chromate

Atmospheric Corrosion primer. The result w~as dishonding, of the topcoat

General Information about Because fungi are the most des iccait- resistiant

Microorganisms microoreanisnins and canl remaiti actis e doss n itoa1, (1o.60) (Ref 4). they are the inicroorteanismis a

Liquids katertis needed or all formis of life. anid most frequently involved in atmiospheric M0IC.

a\'ailIabt lit s' of xw'ater i niluences the di stri butiton \,lost futi c are aerobes arid arc tounid otiks in

andt oroxsil of miceroorganismns. Water avail- aerobic habitats. Funigi are notiphiolos~nticbt ic

abilits' can be expressed as water actis it\ I a,. organisms, having, a vegetative structure kinossit

with values raritsinu from 0) ito I. Microbial ats a hvphae. the outgrowsth of a Nin-ele imicro-

growth has been documeneted over a range ott scopic reproductiste cell or spore. n mass of'

wvate r act is'itites troin 01.00) to) 0).998. Micro- thbread like lihv.phae miake up a mivcc liuiin. \I\ celia

orunanisnis catn grow in thle tetmperatutre range inl are capable of al most i ndefIiniite .!ross.t h in the

wh~ich wsater exists as a liquid. appritximiatel\ 1) presenice of adequate moisture anid nutnients so

ito 1001 'C (32 to 212 Ft. INIicroor-aniisins canl that lu tic oftten reachI macroscopic dimiensions. .'.'

growv over at ratnge of It) pl-I units or mtore t Ref 21' Spores. the nonsegetatis e dormant stage. canl 7.0X ?

Mansy nierootr-anisins canl withstand hundred- surs ie long period,. of untasorable growth .

fold ortireater variations in pressure. The hig-hest conditions (droughit anid siarsation t. When

pressure founid in the ocean is slightly inhibibtorsy coniditioins for crowib are tasorable. Sporestogrsvh f any tnicroitrganins Hes mtl germlinate.

conlcentraitioins as loss as It) "M call itnhibit the Biodeterioration due to ('unci has beeti1 doco- t'-,'

oro\ýiss t ot some rnicroo roaiisniss. while ot hers incited for t he fol lost'm inconmtetallie miilita;rs'

mnay contit nute to g rnis at concenitrat ion s of' a assets: cell iilosecs ( paper. comuposit io n bioard.

millionfold or unreaier. NIOicrobhial species showv and wood). photographic lilili: pol\viii v

thou sandftold diferences in sucpihiltyo chlo ride fiIilns: oa di aphragmn coat i ti : ta

irradiafioi (Ref 3). coatitigs: paints: textiles (cottotn and %\o 01:ý sins\ I

Ni icroorunanistis also require ntie 1neits anid jackets: leather shoes: feat hers and doss nm natuiiral Fig1 nco t1-11hlopvfimiig

electro acceptors. All organisn requirt cr anid syntbet ic rheioptical inFg nrniiSii t1(111 r' uxni oi sts recreiinfts: ~ ,, honsxLTihii nidsn1

bon. iiirogeni. pltosph orus. anid soulfuir, ill alddit iOu mtec hanicalI. elect rontic. and electric equipmn ým'., lix Tv\%it).~ii iie ~lI t01

-212 / Coorrosion in Specific Environments

(Fig. 2), vvithfno corrosion of the base metal as spool flanges. Aspergillus niaier and Penicilliun and 17 bacteria) during storage and use. inde-long as the primer was intact. The biocidal sp. were isolated from wooden spool flanges pendent of climate or relative humidity. Theyproperties oftzinc chromate primer (Ref 6) were (Fig. 4). Fungal isolates could not grow on the identified the following species as those mostdocumented. N4one of the isolates in the study protective grease as the sole nutrient source. The frequently isolated from lubricating oils: Asper.detailed in Ref 5 degraded the polyurethane isolates grew on wood and produced copious gillus versicolor, Penicilljm chirsogelz, Peni-coating direcily as a sole source of nutrients: amounts of acids and CO,. In all cases, localized cillium verrucosum, Scopulriaopsis bres'caulis,however. All grew on hydraulic fluid that accu- corrosion was observed in areas where acidic Bacillus subtilis, and Bacillus pumilis. Micro-mulated on painted interiors during routine condensate dissolved the maintenance grease organisms isolated from one particular lubricantoperations. Glossy finish polyurethane was and exposed bare areas of carbon steel. could not always grow vigorously on others.colonized tmore rapidly than the same formula- Researchers (Ref 15) determined that 80% of Microbial growth in lubricants was accompaniedtion with a flat finish. Aged paint fouled more lubricants used for protecting materials were by changes in color, turbidity, acid number, andrapidly thain did new coatings. Laboratory tests contaminated with 38 biological agents (21 fungi viscosity. Acid number refers to the acid or basedemonstrated that in the presence of hydraulic

fluid, all of the isolates caused localized corro-sion of bare 2024 aluminum. It was demonstrated(Ref 5) that performance specification (MIL PRF85570) for cleaning painted aircraft interiors iseffective in removing fungal spores but does notkill fungal cells embedded in the paint. Fungalregrowth wLis observed within days of cleaning.

Numerous reports document fungal degrada-tion of coati ngs and. in some cases, corrosion ofthe underlying metal (Ref 7-9) in atmospheric ...exposures. It was reported (Ref 10) that shipcargo holds coated with chlorinated rubber andcarrying dry cereals and woods were severelycorroded within months. Heavy pitting andreduced thickness of the steel plate wereobserved. Corrosion products were populated (a) (b)with viable fungi. It was demonstrated (Ref I10) Fig. 2 A pice,,, disbonded pfik urethane p[int ,hoiwin rg growth of fungi. ,a Tip surtat v. hi, Lnderfie shfnv ig thatthat the tu n.ti derised nutrients fromn degradation fungi had peneirmad the (i il t'imof protective coatings in addition to the carco.Corrosion resulted from acidic metabolic by-products. Detenoration of the epoxy resin coat-ing of ship holds tilled with molasses. fatty oils.and other fluid cargoes was reported (Ref I I.Others t Ref 12) studied direct microbial detra- ,-dation of coatings. such as Buna-N (a polymerof acrylonitrile and hutadiene: polyurethane (a . - " .. . .carbamate polyniert: and a polysulfide. Theyfound that both bacteria and fungi could degradethese coatings. Pitting of the underlving metalcoincided with blisters and thc presence ofunicroorganisms. It was demonstrated (Ref 13)that tial func toningi of N1483 155-min hiwitzcr-hells stored in humid environments was directl\related to fungal degradation of the lbricating,,rease used to facilitate the screw Connect ionsihetween tile base and tire body of the shell.

Indirect dissolution of protecti•e greases byfunii was investigated (Ref 14. Protect i-ec.greases are used to provide corrosion protection (a)for seven-strand carbot steel cable used as wirerope and as highlincs. Each cable is made of sixstrands wrapped around a central core. Whencable is used as rope or highline. the cable iscoated with thick maintenance grease. threaded

irto) wiooden spo ol s (Fig. 3a--4:) and wrapped inbrown paper anrd black plastic. The maintenancegrease is applied to thie cable to provide corrosionprotectiir. Wire rope is stored on wooden spoollsfor weeks to months before being used. Itn aniinvestigation of localizcd corrosion 0o1 wire ropestored on woodJen spools. fungal growth wasobserved onr interiors of some wooden spools (b) (c)stored outdoors. Corrosion was most severe oir Fig. 3 Cirb(un wrt, e rop, e • , i irhirn 'te h tqihne 1eing u.dii to tranvs r equipm e'nt [ \\t4,n shi, at ,ea. hbiwraps of s, irc in direct contact witlr the woodenr 5t ' tr.iii( i steel in r, . i th n.intininii greisi. i t\ p', ii a,(wden ,,!a (1 used hi 'tee ,sre rope

Microbiologically Influenced Corrosion in Military Environments/ 213

composition of likricating oils and is also Sweden caused by sulfate-reducing bacteria Immersionreferred to as crosion number. Biocides. (SRB) was documented (Ref 19). Several

including 4-capro)1, have been evaluated as authors have documented the problem of MIC in Immersion environments are those in which

additives to prc7teo lubricants from mold for- aircraft fuel tanks. It was proposed (Ref 20, 21) the surface is boldly exposed to an aqueous

mation. BiocidL-!S have limited lifetimes and that microorganisms influenced corrosion of environment, in contrast to the previous exam-

limited effectivcne% (Ref 16). aluminum fuel tanks by: pies in which water was the limiting factor for

e Removing corrosion inhibitors. including microbial growth. The most important factor

phosphate and nitrate, from the medium controlling the distribution of microorganisms in

Metals Exposed to Hydrocarbon e Producing corrosive metabolites immersion environments is the availability of

Fuels e Establishing microcenters for galvanic activ- nutrients. For example. organic nutrients and

ity, including oxygen concentration cells bacteria are most abundant in the upper layers of

* Removing electrons directly from the surface oceans, and both decrease with depth (Ref 27).

One of the mist persistent corrosion problems of the metals Microbial biofilms develop on all surfaces in

throughout the rriilitatry is the result of microbialcottwihauusevrn ns(Rf2.contact with aqueous environments (Ref 28).

contamination rand decomposition of hydro- Several investigators reported a decrease in Chemical and electrochemical characteristics of

carbon fuels dur-inefuel transportation, storage, bulk fuel pH due to metabolites produced during the substratum influence biofilm formation rate

and use. Microbial interaction with hydrocarbon growth of fungi (Ref 21-25). One researcher and cell distribution during the first hours

fuels is limited to vater availability. Water is (Ref 24) demonstrated a correlation between of exposure. Electrolyte concentration. pH.

sparingly soluble in hydrocarbons. .Therefore. growth of Cladosporium (Honnoconis) and pH organic, and inorganic ions also affect microbial

microbial growth in hydrocarbons is con- at fuel/water interfaces and measured pH values settlement. Biofilms produce an environment at

centrated at oil/water interfaces, emulsified between 4.0 and 5.0 in the fuel. Fungal-influ- the biofilm-surface interface that is radically

water, and in separae water phases. The volume enced corrosion has been reported for carbon different from that of the bulk medium in terms

of water required for microbial growth in steel and aluminum alloys exposed to hydro- of pH. dissolved oxygen. and inorganic and

hydrocarbon fuels is extremely small. Because carbon fuels. Another investigator (Ref 22) organic species. In some cases, the presence of

water isaproductofthe microbial mineralization demonstrated metal ion binding by fungal localized microbial colonies can cause differ-

of organic substrates, it is possible for microbial mycelia. resulting in metal ion concentration ential aeration cells, metal concentrations cells.

mineralization o|f fueIl to 2eneratc a water phase cells on aluminum surfaces. It was reported (Ref and under-deposit corrosion. In addition. reac-

for further prol i teration. For example. Horyoi- 24) that corrosivity increased with contact time tions within biotilms can control corrosion rates

conis risitnte, the kerosene fungus. gre\ it' due to accumulation of metabolites under and mechanisms. Reactions are usually localized

80X mg water per liter of kerosene, and after (our microbial colonies attached to metal surfaces. and can include:

weeks* incubation, the concentration of water Others (Ref 251 demonstrated that the metabolic * Sulfide production

increased more than tenfold (Ref 17). products enhanced aqueous phase aggressive-Tile== fis stp iAiro ile :cid productionThe lirst step in microbial decomposition of ness even after the life cycle of Chuhmxno.\ritwn o Ammonia production

hsdrocarbons is an aerobic process that requires (Hor-moconi.) was completed. * Metal depositionmolecular oxvyen. Researchers (Ref 18) coin- Miolrobiologicallv influenced corrosion has * Metal oxidation/reduction

by bacteriatonreucipared degradation of hydrocarbons by bacteria been identified in engitnes. holding tanks. skegs. * Gas productionand funci. Bacteria showed decreasing abilities and oily waste tanks on surfice ships due toto degrade alkanes with increasing chain length. microorganisms growing in water contaminated Many of the problems of MIC of military

Filamentous funci did not exhibit a preference h\drocarbons. One study (Ref 26) determined assets exposed to aqueous environments are

for specific chain lengths. The first products that ship engine malfunction and corrosion were directly related to an operational mode that

of microbial oxidation of hdrocarbons are associated with MIC. The researchers identified includes periods of stacnation. Heat exchangers.alcohols. aldehydes, and aliphatic acids, both bacteria and funfi croing in engine fire protection systems. holdine tanks, and

An increase in the corrosi\ity of jet fuel iJP4( lubricants and attributed the problem to a Win- transfer lines are exposed to flow/no-flow

stored underground in unlined rock caerms in hination of mechanisms. including depletion of cycles. The following statements are applicable

protective additives, acid production, and sulfide for distilledldemineralized. fresh. estuanne. and

, production. Progressive changes in the for- marine waters. During stagnation. naturalls

.W imulations of lubricatitng oils hawe introduced occumng microorganisms form a biolilm. and

nitrogeti. phosphorus. and sulfur which provide aerobic microorcanisms use the dissolhed oxv-

required nutrients for microbial Lroth. The gen as tile tenminal electron acceptor. If the rate

" urrent trend to produce envirotnmentally benign of respiration is faster than the rate of oxygen

engine oils means that the resulting formulations diffusion through the biolilm. the metal/biotilnm.-speed interface becomes anaerobic. allowing anaerobic

a .re more readilv biodecraded. Slow-pe ma-Crine engines are at risk because they run for long bacteria to * produce corrosive metabolites.

periods of time at constant temperatures (37 to including acids and sullides. The amount of

55 C. or 99 to 131 'F) conducive to microbial sulfidc that can be produced within a biofilm

growth. Oil additives that encourace microbial depends on the sulfate concentration and the

growth include (Ref 26): numbers and activities of SRB. Seawater con-

tains approximately 2 g/L of sulfate and a

population of SRB whose numbers vary with

%ltal si.oaip,, e.g.. harium ,ulphunates nutrient concentration. Most sulfide films are

-, Ptiy;lkcn~l ,ucctnmlnldes not tenacious and are easily removed by turbu-ligh-imklcuilar-w.Ighi c ,ts~lic ciud, lence. Introduction of flowing oxygenated

MetalI didimhlo 'll V p ,11 e •

PN• morI nii.ilomane', svater causes oxidation and/or disruption of

Itindtcrcd phaienol, e.g.. 2.6 dathnerm but\ 1-4-mnehyl phenii surface deposits formed under stagnant condi-,Aromatic anu1| fll.nes-pien.\. 11i niphihii ~lmule iions.

4 in ute 11.111L Alk' I plhouphate, Copper alloys have a long history of suc-Fig. 4 ," , . c"i i w at•er I phpsphalci i.increr, phoph.l\s- ., ln I,n-!tt .u 1." cessful application in seawater piping system s

214 / Corrpsion in Specific Environments

due to their corrosion resistance. antifouling attack where chlorides penetrate the passive film corrosion potential and lowers the pH at theproperties, aind mechanical properties. The (Ref 39). Sulfides produced by SRB cause either surface.corrosion resistance of copper in seawater is a modification or breakdown of the oxide layer One of the most common forms of MIC attackattributable to the formation of a protective film and dealloying (Ref 40). Another report (Ref 41 in austenitic stainless steel is pitting at or adja-that is predom inantly cuprous oxide, irrespective indicated that predominantly nickel alloys were cent to welds. The following observations were

of alloy composition (Ref 29). Copper ions and susceptible to underdeposit corrosion and oxy- made for MIC in 304L (UNS S30403) and 316Lelectrons pass through the film. In seawater, gen concentration cells. Other studies (Ref 42. (UNS S31603) weldments (Ref 57): both auste-copper ions dissolve and precipitate as 43) demonstrated pitting and denickelfication of nite and delta ferrite phases may be susceptible:Cu,(OH)3CI (Ref 30). Copper seawater piping nickel-copper tubes exposed in Arabian Gulf and varying combinations of filler and basesystems are often exposed to polluted harbor seawater with deposits of SRB. materials failed, including matching, higher-,water containing sulfides. In the presence of Stainless Steels. The corrosion resistance of and lower-alloyed filler combinations. Micro-sulfides, copper ions migrate through the layer, stainless steel is due to the formation of a thin segregation of chromium and molybdenum withreact with sulfide, and produce a thick black passive chromium-iron oxide film. Crevice cor- chemically depleted regions increases suscept-scale. Failure of copper-nickel pipes in estuarine rosion is the most problematic issue affecting the ibility to localized attack.and seawaters can be associated with waterborne performance of stainless steels in seawater. Candidate materials for a double hull vesselsulfides that stimulate pitting and stress corro- Investigators (Ref 44) studied crevice corrosion designed with permanent water ballast. 3 16L.sion cracking (Ref 31-34). 90Cu-IONi suffered of stainless steel beneath dead barnacles and Nitronic 50 (UNS S20910). and AL6XNaccelerated corrosion attack in seawater con- proposed the following scenario: (N08367) were evaluated for potential MIC intaining 0.01 ppm sulfide after a one day exposure flowing and stagnant freshwater and seawater(Ref 35). Galvanic relationships between e Decomposition of the barnacle by aerobic (Ref 58). No pitting was observed in AL6XNnormally compatible copper piping and fitting bacteria, including Thiobacillus, reduces pH under any exposure condition after one year.alloys become incompatible after exposure to within the barnacle shell. Leaks were located at weld seams of Nitronic 50sulfide-containing seawater (Ref 33. 9 The acid penetrates the shell base and initiates and 316L stainless steels after 6 and 8 week

Sulfides produced within biofilms have the a corrosion cell between the crevice area and exposures to stagnant and flowing seawater. Asame effect as waterbome sulfides on copper the exposed SS substratum. failed vertical weld in 316 stainless steel after analloys. Alloying additions of nickel and iron into e Crevice corrosion initiates near the edge of 8 week exposure to stagnant natural seawater isthe highly defective p-type Cu 2O corrosion the shell base and propagates inward, shown in Fig. 5(a). Figure 5tb) is the corre-product film alters the structure (Ref 29) and sponding x-ray image indicating failure due toresults in a film that possesses low electronic and Crevice corrosion is exacerbated in ,sarml natural pitting. In all cases. large numbers of bacteriaionic conductivity. In an attempt to prevent sul- seawater where hiofilms form rapidly. Pit were associated with the corrosion productsfide-induced corrosion of copper-nickel piping. propagation under barnacles is assisted by poor (Fig. 5c). Residual material in pits was typical ofFeSO4 treatments were evaluated. Corrosion water circulation, removal of iron. A scanning vibrating electrodeof FeSO 4-treated pipes was compared with Several investigators (Ref 45-521 have docu- technique was used to demonstrate tbat thereuntreated pipes that had been cleaned according menttd the tendency for biofilms to cause a noble were no persistent anodic sites in atnogenousto military specifications (Ref 36). Batch FeSO4 shift, or an ennoblement, in open-circuit poten- welds or heat affected zones of these materialstreatments did not result in a persistent increase tial of passive alloys exposed in marine envi- exposed to sterile seawvater. The spatial andin surface-bound iron. The authors found that the ronments. Alloys tested include, but are not causal relationship between bacteria and pittingdissolved iron concentration in most harbor limited to: UNS $30400. S30403. S3 1600. in weldnments in 30*) series stainless steels is well

waters exceeded the amount of iron in the S31603. S31703. S31803. N08904. N08367. documented (Ref 59. 60).recommended batch FeSO , treatments. Ferrous S44660, S209 I1). S44735. N 10276. and R50250. Ethylene glycol/water and propxlene gl.col/sulfate (0.10 mg/L ferrous ion) treatments for The practical importance of ennoblement is water mixtures were evaluated as permanent90Cu-IONi and 70Cu-3)Ni alloys were eval- increased probability of localized corrosion as ballast waters for 316L double hull vesselsuated (Ref 37). Neither pretreatment before Eo,rr approaches the pitting potential (E,,,) for (Ref 60). The compounds are attractive as ballastsulfide exposure nor intermittent treatment dur- stainless steels vulnerable to crevice corrosion, liquids because they will have minimal impact ifing sulfide exposure significantly reduced sulfide especially types 304 (UNS S304(X) and 316 the outer hull is breached and the glycols arcattack on either alloy. However. continuous (UNS S3 1600). Intvestigators (Refs 53. 54) con- released to the environment. Both have lowtreatment eliminated the attack on both alloys eluded that bioilhns increased the propagation volatility and are miscible with water. In termsbecause the FeSO4 removed sullides from rate of crevice corrosion for UNS S31603. of corrosion protection. propylene glycol-basedsolution. S31725 and N08904 by I to 3 orders of magni- mixtures were shown to protect against pitting of

Nickel Alloys. Nickel 201. sometimes used tude. They attributed ennoblement to an increase 316L in concentrations of 50% or higher whenfor heat exchangers with distilled water, is vul- it kinetics of the cathodic reaction by the mixed with seawater (3.5% salinity). Slightlynerable to microbiologically produced acids biolilms. Others (Ref 55. 56) detmontstrated that higher concentrations (55%) of ethylene glycol-(Ref 38). The Ni-Cu alloys are used in seawater ennoblement of electrochemical potential in based mixtures were required under the sameunder conditions including high velocity ( pro- the presence of a biotihn could be reconciled conditions to prevent pitting. The compoundspeller shafts. propellers. pump impellers, pump without reference to modified oxygen reduction have little or no capacity to bind to particulatesshafts, and condensers), where resistance to mechanisms and without enhancement of and will be mobile in soils or sediments. Glycol-cavitation and impingement is required. Under cathodic processes. They concluded that the based mixtures were also shown to be bacterio-turbulent and erosive conditions, nickel-copper bioliltn does not dire•tlv affect oxygen reduction static at concentrations above 10%. Also. the lowalloys are superior to predominantly copper near the equilibrium potential and far fronm the octanol/water partition coefficient and measuredalloys because the protective surface filmn oxygen diffusion limiting current. They further bioconcentration factors in a few organismsremains intact. Nickel alloys are used exten- concluded that HO, and mantimese oxides did indicate low capacity for bioaccumulation.sively in highly aerated, high-velocity seawater not play a direct role in the oxygen reduction Carbon Steel. Unexpectedly rapid localizedapplications. The formation of tihe protective process at potentials > 3(X)mVsc5 z Instead. they corrosion of steel bulkheads and ship hull platingfilm on nickel is aided by the presence of' iron. demonstrated that anodic oxidation of organic of tankers in marine harbor environments wasaluminum, and silicon. However. under stagnant material in biolilms produced currents corre- documented (Ref 61 ). In each case, the localizedseawater conditions, nickel-copper alloys are sponding to passive currents or higher. Oxidation attack was found beneath macrofouling layers.susceptible to pitting and crevice corrosion of organic material affects tile value of the The biolilm at and around tile corrosion sites was

Microbiologically Influenced Corrosion in Military Environments/ 215

Pitareas

(b)

(a) (C)

Fig. 5 VicnrL 1 , %eII•'hl td"•tT' 'ilt, ii1 er I.l)ti),re to ,agnint naurMl e.awaltr for 8 t ,%v ,ks.ii \V Idm nt. 1) -r1-a ot jail ,d \ ,rti ,l %ehd. ov iao erl i a11 ,o( li aled Vtllh t orr(osi n

Iprltlut Is,.

populated with a rich consortium ofaerobic and water chemistry and microbial populations were densities up to I)W I(LA/cm2 did not remove

anaerobic nincroorganisms. and the SRB popu- measured as a function of time. Both were attached biolilms from stainless steel surfaces.

lation was elevated by several orders of magni- dynamic despite the stagnant conditions. Both natural marine and laboratory oultures

tude above that in the hiolilm remote to corrosion Catihodicall Protected Carbon Steel. In most changed the morphology of calcareous deposits

sites. Researchers (Ref 62) demonstrated a cases, carbon steel used in seawater is cath- formed under cathodic polarization at a current

cycle of sulfur oxidation and reduction causing odically protected or painted. It has been repor- density of 100 ltA.cm-.

aggressive corrosion of steel pilings in a harbor. ted that cathodic protection retards microbial In one study (Ref 69), cathodic potentials to

At low tide, the fouling laer %;as thoroughls growth because of the alkaline pH generated at - 1000 mV SCE caused a decrease in pH and an

aerated and thiobacilli produced oxidized sulfur the surface. It was demonstrated (Ref 64) that a increase of SRB on carbon steel. At potentials

species. High tide produced anaerobtc conditions potential of - 1. 10 V SCE markedly decreased more negative than - I(XX) mV SCE. the pH

within the touling layers and reduction ofsulfur settlement of Balantus cyprids on painted steel became more alkaline and SRB numbers

compounds. surfaces, but it had no effect on settlement. sand- decreased. A study of the influence of SRB in

Natural seawater has also been evaluated as a tube building. reproduction, or lanai release marine sediments usine electrochemical irn-

ballast fluid in unpainted 10)20 carbon -,feel hal- of other species. Biofouling in seawater was pedance spectroscopy to monitor corrosion and

last tanks. and deoxygenation has been proposed retarded using pulsed cathodic polarization of lipid analysis as biological markers. comple

as a method to reduce corrosion. However. it was steel (Ref 65). mented by chemical and microbiological analy-

determined tRef 63) that corToston of 1020 Numerous investigators have demonstrated a sis. showed that -880) mV SCE encouraged the

carbon steel coupons in natural seawater over a relationship between marine fouling and calcar- growth of hIydrogenase-positive bacteria in the

six month period was more aggresive under eous deposits on cathodically protected surfaces sediment surrounding the metal and facilitated

stagnant anaerobic conditions than stagnant (Ref 66-68): however, their interrelationships the growth of other SRB species (Ref 70).

aerobic conditions as measured by weight loss are not understood. Microbiological data for Because the enumeration technique strongly

and instantaneous corrosion rate (polarization calthodically polarized surfaces are often con- influences the number of cells one is able toresistance) (Fig. 6). Under oxygenated condi- fusing and impossible to compare because of count. and because the number of cells cannot be

tions, a two-tiered oxide layer formed (Fig. 7a). differing experimental conditions (laboratory equated to cellular activity. including sulfate

The outer oxide laver was reddish-brown vs. hield) and techniques used to evaluate reduction. some investigators have attempted to

and contained numerous filamentous bacteria constituents within the biotilm. Differences in measure cellular activity directly on cathodically

(Fig. 7b). The inner oxide was extremely organic content of seawater that produced dif- protected surfaces. One investigator (Ref 71)

adherent and resistant to acid cleaning. Under ferences itl current density. electrochemistry. cathoidically protected 50D mild steel (BS 4360)

anaerobic conditions. a nontenacious sulfur-rich calcareous deposits. and biolilm formation have coupons exposed in the estuarine waters of

corrosion product with enmeshed bacteria been reported (Ref 66). Aberdeen Harbor using an imposed potential of

formned on carbon steel surfaces (Fig. 7c. d). The influence of a preexisting biotilm on the -950 tnV Cu :CuSO4 and sacrificial anodes.

In anaerobic exposures. corrosion was inure torillation of calcareous deposits under cathodic Activities within biolilms were determined

aggressive on horizontally oriented coupons protection in natural seawater was studied using a radiorespironletric method-a technique

compared with vertically oriented coupons. Bulk (Ref 67). It was shown that applied current for studying microbial respiration using

116 / Corrosior' in Specific Environments

0,035 radiolabeled substrates or electron acceptors.Biofilms developed on all substrata-both

Anaerobic R1 --- Aerobic R1 -unprotected and cathodically protected surfaces.0r 2r-- R2 - R2 ob 0-R The activities of aerobic and anaerobic bacteria,

.R3 -1111 R3 --&- including SRB. were significantly greater on

0R43 R4--6--3 unprotected coupons. Furthermore. sulfide, a

-. 0.025 metabolic fingerprint of SRB activity, could bedetected only in biofilms on unprotected"coupons. These results show that a potential of

"C 0.02 -950 mV Cu: CuSO 4 does not prevent SRB

.0 from developing on cathodically protected sur-faces. The lower activity of SRB within biofilms

00,015 on cathodically protected coupons was not

, directly caused by any inhibitory effect of theC• cathodic potential. Instead. the greater activity of

C 0.01 SRB on unprotected coupons was the result ofproduction of an extensive corrosion film offer-

-0.005 , ing more favorable anaerobic conditions.The NACE Standard (Ref 72). which is

currently under revision, lists cathodic protectioncriteria for underground or submerged steel. cast

0 0 50. 100 10 200 250 3iron. alurninum, and copper structures. Micro-

0xposure, 50ys 1biologically influenced corrosion is cited as "oneExposure, days of several abnormal conditions which sometimes

Fig. 6 Instantaneous corrosion rates using polarization resistance (iR,) for carbon steel exposed in stagnant aerohlc or exist and where cathodic protection is ineffectivestagnant anaerobic natural seawater. Corrosion rates were higher for the anaerobic exposures ,solid linesl than or only partially effective.* It is important to

"oraerobicexposureibroken linesi. R1, R2, R3, and R4 retertothevertical locationoftheelectrode, with R I beingt losestto point out that in several studies tRef 6--8),

ýhe water surface and R4 located at the bottom of the experimental chamber. SRB were present on cathodicale y protected

steels, but accelerated corrosion w, as notreported.

Thermodynamic data with iron in a pH 7electrolyte saturated with hydrogen ,ultide wasstudied Reif 73). A potential of - 1024 mV SCEwas required to achieve cathodic protection. Itwas demonstrated Retf 74) that - 1024 mV wascapable of providing cathodic protection in thepresence of active SRB. The influence ofcathodic protection on the growth of SRB and oncorrosion of steel in marine sediments wasinvestigated (Ref 75). The investigators con-cluded that a cathodic potential of -880 mVSCE did not appear to be sufficient for protectionand that large amounts of cathodically producedhydrogen promoted the growth of SRB in the

,- sediments surrounding the samples. Laboratorytests were conducted iRef 76) in anaerobic.

(a) (b) arilicial sediments containing SRB. Resultsindicated that a polarization of - 1024 mV SCE.was adequate for corrosion protection. Cathodicprotection current density was between 4.5 and12 mA/lft. Another study (Ref 77) indicated that

a cathodic potential of - 1054 mV SCE loweredthe corrosion rate of steel by 82.7%, even though

protective potentials in the range -774 to1134 mV SCE did not inhibit growth of SRB.

It was concluded (Ref 78) that if anaerobic bac-terial activity is suspected. a cathodic polariza-tion shift of approximately 200 to 3M) mV SCEis required for carbon steel protection. Cathodicprotection was imposed on steel surfacesactively corroding in cultures of SRB (Ref 79).and it was concluded that cathodic protection in

(c) (d) the presence of SRB decreased corrosion by a

Fig.7 Carbon steel electridvs expospied ii aerobic id inaeroibic natural seater foir 290t dais. ai Aerobic. factor of 8 or 9.Fig. 7 Itt was shownrd (epse Ref 80)i:an aaroicn thate\ cathodical aly, a•Ae•l~t' I asshw (ef80 ha ctodcal

if)t Aeroblm. Scanning VIect ron microigraph of iron-osidev encrusted l(tteria enmesheid in t-orr-ison prtidut is. IR.

ti Anaerobii. (id -\naerobii(i, Scanning 'lehttrin mor rigr.iph of siufide-encruxtsd ori.anil.ni enmeshed in iorrosiion protected stainless steel surfaces in artificial

prodiiucts. scawater can become colonized by aerobic.

Microbiologically Influenced Corrosion in Military Environments/ 217

acid-producina Ncteria. Formation of calcar- areas. Many of these effects have recently been The sizing materials are highly susceptible to

eous deposits an! initial settlement of micro- reviewed (Ref 82). It was also demonstrated biodegradation of strength resulting from abra-

organisms rest-lted in decreased current density ,Ref 83) that marine bacteria are attracted sion between fibers and as a coupling agent to the

requirements to maintain a protection potential. to corrosion products at coating defects. The matrix. The sizing materials are highly suscep-

Subsequent colonization and pH changes desta- microorganisms responsible for damage to tible to biodegradation and can be expected to

bilized the calcareous deposits and dramatically coatings may or may not be involved in corrosion decompose in the presence of contaminating

increased the Current density required to main- initiation under the damaged coating. microorganisms (Ref 90).

tain the protectedpotential. Titanium and Titanium Alloys. There are no Researchers (Ref 91. 92) investigated fungal

Hydrogen crnibittlement of carbon steel is a case histories of MIC for titanium and its alloys, degradation of polyimides used as insulators in

form of corrosion involving the cathodic reac- One investigator (Ref 84) reviewed mechanisms electronic packaging. Growth of microorgan-

tion. Atomic hydrogen generated in the cathodic for MIC and titanium's corrosion behavior under isms on these polymers was found to result

reaction penetrates the steel resulting in the loss a broad range of conditions. He concluded that at in loss of their dielectric properties. They also

of ductility. A number of mechanisms have been temperatures below 100 'C (212 'F) titanium is studied biodeterioration of fiber-reinforced

postulated to account for the embrittlement not vulnerable to iron/sulfur-oxidizing bacteria, composites, graphite sheets, and graphite fibers

effect, which. )hNin combined with the presence SRB. acid-producing bacteria, differential used in composite materials. They observed

of local regions ofhigh stress, can result in severe aeration cells, chloride concentration cells. and fungal penetration into composite resin and

cracking (Ref 81). Hydrogen embrittlement is hydrogen embrittlement. In laboratory studies, graphite sheets and concluded that fungi caused

enhanced by the high levels of hydrogen gener- (Ref 85) corrosion of Grade 2 titanium (UNS substantial damage to composites under condi-

ated by SRB tinder certain conditions, as well as 850400) was not observed in the presence tions favorable to fungal growth. Investigators

that generated by overly aggressive cathodic of SRB or iron/sulfur-oxidizing bacteria at (Ref 93) demonstrated in the laboratory that

protection systems. If the levels of cathodic mesophilic (23 'C. or 73 'F) or thermophilic mixed cultures of marine bacteria could

protection are i ncreased too high to combat SRB (70 'C, or 158 'F) temperatures. Using the penetrate three conductive caulks (PRC 1764,

corrosion, there is a danger that hydrogen model in Ref 86, one would predict that titanium P18500, and P18505) used to secure antenna

embrittlement may be enhanced. The presence of would be immune to SRB-induced corrosion. foundations to ship superstructures.

H2S. which can be produced by SRB. is known to There are no standard free energy reaction data

retard formation of molecular hydrogen on the for the formation of a titanium sulfide. If one Burial Environmentsmetal surface and to enhance adsorption of assumes a hypothetical sulfide product to be

atomic hydrogen by the metal. Whenever alge titanium sulfide. the standard enthalpy of reac-

provide conditions for SRB. they may also tion is +587 U. WhIle standard free energies of Tapes and coatings for buried pipes and cables

enhance hydrogen embrittlement. reaction are not identical to standard enthalpies are susceptible to biodegradation and MIC (Ref

In summary, bacteria can settle on cath- of reaction, it is still unlikely that titanium t4. A recent study evaluated the potential forodically protected surfaces. Cathodic potentials will be converted to the sulfide under standard MIC of unexploded ordnances tUXO) buried in

to - 1*074 mV SCE do not prevent bioflih conditions of temperature and pressure. soil enviroments. Unexploded ordnances are

formation. It has been suggested that actual cell Aluminum alloys were evaluated (Ref 87) military munitions that have been prepared for

numbers may be related to polarization potential, for the impact of microorganisms on corrosion of action but remain unexploded and constitute a

dissolved organic carbon, or to the enumeration aircraft in bilge and toilet areas. The researchers potential hazard. The 1998 Defense Science

technique. Nurnibers of SRB may be increased isolated numerous microbiological species and Board estimated 1.4W8 indi\idual sites contained

or decreased depending on exposure conditions, were able to cause corrosion of 7075. which UXO i Ref 95 1. The munitions corrode at iarving

Carbon steel is considered protected when a is used in aircraft construction. However. the ,ite-Specific corrosion rates. In most subsurface

potential of -924 mV SCE is achieved. In authors could not relate their experiments to environments. microbial grow\%th is limited bv

many cases, the potential is further reduced actual aircraft. water. The likelihood that MIC w•ill take place is

to - 1024 mV SCE to protect the steel from Polymeric Composites. Microotr-anismsand directly related to water availability. Micro-

corrosion caused from the activity of SRB. The their products can be responsible for changes organisms concentrate at interfaces. including

decreased potential is not applied to prevent in physical. chemical, and electrochemical soil/surface interfaces. A survey detennined that

growth of SRB but is based on a theoretical level properties of polymeric materials. Reference S8 the microbial populations measured on the sur-

that will allow passivity of steel in a sulfide-rich demonstrated that under immersion conditions, face of UXO were sufficient to cause localized

environment produced by SRB. The main con- epoxy and nyhIon coatings on steel were breached corrosion and that the most likely mechanism

sequence of biotilin formation on protected by mixed cultures of marine bacteria, was microbial acid production. Microbiall)

surfaces appears to be an increase in the current In laboratory experiments (Ref 89). it was induced corrosion of carbon steel is independent

density necessary to polarize the metal to the demonstrated that epoxy resin and carbon fibers, ofpH over pH values 4.5 to 9.5. In this range. the

protected potential. The presence of large num- either individually or in Composite. were not corrosion products maintain a pH of 9.5 next to

bers of cells on cathodically protected surfaces degraded by sulfur/iron-oxidizing. 'hdrogen- the steel surface. regardless of the pH of the

does mean that in the event that cathodic producing, calcareous depositing. or SRB. solution. At. a pH of 4 or below. hydrogen evo-

protection is intermittent, discontinuous, or Bacteria colonized resins. fibers. and composites lution begins and corrosion increases rapidly.

discontinued. the corrosion attack due to the but did not cause damage. Sulfate-reducing Fungi and acid-producing bacteria can reduce

microorganisnis will be more aggressive, bacteria preferentially colonized vinyl ester the pH locally to values below 4.0. The localized

Coated Carboni Steel. Although coatings composites at the liber-resin interfaces. and corrosion mechanism of the steel fragments was

alone do not pre\ ent MIC, they delay the onset of hydrogen-producing bacteria appeared to disrupt in many cases pitting, with pits inside pits.

M IC and other corrosion reactions. Many types the fiber-vitsyl ester resin bonding with penetra- indicating multiple initiation sites, In other cases.

of polymeric coatings can be subject to biode- tion of the vinyl ester resin, tunneling was observed. Both types of localized

gradation. The attack is usually caused by acids It is standard practice to coat the surface of the corrosion are consistent with microbiological

or enzymes produced by bacteria or fungi. This filaments with a sizing chemical to provide a acid-induced corrosion.

often results in selectie attack on one or more better bonding with the resin matrix and to pre-

specific components of a coating system with vent abrasion between individual fibers during ACKNOWLEDGMENTconsequent increase in porosity and water or shipping and handling. This treatment permits

other ion transport through the coating and the optimal stress transmission between filaments. Preparation of this chapter was ftnded under

formation of blisters, breaches, and disbonded Fiber sizine chemicals arc starch-oil mixtures. Office of Naval Research Program Element

218 of Corro sion in Specific Environments

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