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14 viewsASM Localised Corrosion
ASM Localised Corrosion
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Rashid GuliyevCopyright
© © All Rights Reserved
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/ 19
Localized Corrosion
Chairman: Stephen C. Dexter, College of Marine Studies, University of Delaware
THE FORMS OF CORROSION deseribed in
this article—filiform, crevice, piting, and biolog
ical corrosion—all have the common feature thal
the corrosion damage produced is localized rat
frthan spread uniformly aver the exposed met
Surface. This maker these forms of aflack more
Giticult to deal with than those. producing” a
generalized attack (see the article "General Cor
fosion” ja this Volume). Instead of dealing vith
lov, relatively uniform loss of metal thickness,
the engineer ie naw faced with high rates of metal
penetration at specific sites (or localized deterio
Fron under a coating system in the case of
filiform corrosion), while the remainder of the
metal (or coating) g0es largely unaffected. The
attack can also be harder to detect Because much
of the damage may be subsurface, with only a
Small opening visible 10 the eye at the metal
Surface Moreover, these forms of attack. are
economically important and dangerous because
they’ can leat to premature falure of a structure
by rapid pencteation with file overall weight
The purpose of this article is 10 provide the
engineer with enough information to identity which
Tym of corrasion ts taking place on an existing
Sinictre oF which form of corrosion is likely 10
‘occur on @ new structure. Trerelore, most of this
lanl is devoted to ilustrating the appearance of
these localize forms of corrosion and to describing
the classes of metals and alloys susceptible to them
lund the environmental condoms under which they
‘secur. Some information s also given on the mect-
tunisms othe attack and measures that aa be used
to prevent it, More information on these later (wo
topes ean be found in the refeserces piven in this
faricle ay Well a6 the Sections "Specific Alloy
Systems” and “Fundamentals of Corrosion’ it
this Volume
Filiform Corrosion
(Christopher Hahin
Materials Protection Associates
Filiform corrosion occurs on metalic surfaces
coated with a thin organic Hin thats typically 0.1
nin (4 mis thik, ‘Te patter of stack is charac
terized by the appearance of in filaments emana
ing from one or more sources in semirandom dire:
tions The source of inition is usally a defect or
technical scratch in the coating. The filaments
fe fine tunnels composed of corrosion proucts
tunderneuth the bulged and cracked “voatig.
Filiforms are visible at an arm's length a small
‘blemishes. Upon closer examination, they appear
as fine striations shaped like tentacles or cobweb
Tike traces (Fig, 1). A form has an active head,
and a flanenious tail Fig. 2). close-up of the
hheadtall interface is shown in Fi. 8
iif corrosion iv often mistaken as having
biological origins because ofits wormalike appeat
ance: Firm eorronion routinely oceurs on coat
fed steel cans, sliminum fol lasinsted packging,
Painted aluminum, and other lacquered metalic
ems placed in areas subjected to high hurmidity.
Flitorm corrosion has been observed on masy
‘orginiclly coated metals and alloys, inching
eels, tin-plated steel, shumiaum, and magne:
Sum. The stseeptiblty of 2 metal to Mliform
‘corrosion can be determined BY placing several
‘coated and scratched panels in a salt fog chamber
fs described in ASTM D 2803 (Ref 1). If suseep-
tible, filiform laments will gradually grow out
perpendicularly from the scratch. Many of these
laments wil fler orient ihemvselves in the roll
lng direction of the panel
Fig.
Filiform attack oceurs when the relative bu
icity is typically between 68 to 9% for most
‘cases. The Towest reported relative humidity was
58% for nitrocellulose lacquer on steel, and even
lower relative humidities were reported for alt=
‘minum in very corrosive environments (Ret 2),
‘The average width ofa filament varies between
0,08 to 3 mm (2 to 120-mils) Filament wicth
‘depends on the coating, the ambient relative
humidity, und the corrosive environment. Type
cal flgaent height 48 spout 20 um (0 mi). The
Fitament growth rate can also vary widely, with
rates observed a fow ss 0.0! mndl (0-4 tld)
fan up to maxim rate of 85 md 38 mls
1). The depth of tte inthe form tonnels can
be as deep a8 15 jim (0.6 mill. The Mid in the
leading hen of filiform i typically acidic, with
pel trom Lo 4, In all cases, oxyeen or air and
Wwhler were needed ta sistain for cortsion,
“This indicates that filiform corrosion i a specta!=
fed gitferential aeration cell (see the “Glossary
fof Terms” in this Volume for a deoition of
tilferential aeration cell
1 Alscsuered oe! con I exibing form creson shonin Both large ond imal floes peal
‘knted inthe ling Erosion of the steel hee. Wahoo hi 10% maguaton oy bg ercop,
tho ftorme Tock the te sions or minuto tentacles a
Filiform Corrosion
of Coated Stools
Characteristics of Coated Steels. Stcl und
tin-psted steel are routinely coated to provide
resislanee to atmospheric corrosion, isolate
foodstuffs from their containers, and to provide
an adherent surface for ink and paint. Transp
nt organic coatings can also be lightly dtd
‘with various dyes to impart a brass. rome, or
bluish cast to amprove the appearance of the
steel. Tin plating on steel is very thin? the
toner of 1.5 jam (0,06 mil} thicken iss porous
barrier (sce the article "Corrosion of Tin and Tin
Alloys" this Volume}. In some environments,
tin is often cathodic to steel. in aggressive env
ronments, tn plate provides litle eoeresion pro
{ection fr the sce] subseate, The corrosion rate
of steel is fairly slow in alkaline environments,
but increases markedly in acidic environments
‘when the pHs ess tha, Steely sujet fo ping
in concentrated chloride eavironnients, Tin is
amphoteric Gt comrades in alkaline und acidic me
{Gu}. ba it isnot rapily attacked in certain deaer
ed acide, However tee! and tin ure huh realy
{rded by aerated acs. Such condition of lo
PH, aeration, and bigh chloride concentrations are
fle found to exist in The active heads of for
corrosion eels in see
"To preven! general rusting, many coatings are
applied to stel fo shield i from moist or hurnid
fehvironments. Fiifarm corrosion his hem be
served on steels coated with lacquers, vacaish,
polyurethane, boiled linseed ol. and various
ky uted, awl epoxy rains, The coatings ar
applied by spraying. by direct contact with rubs
ber nalls, by dipping. oF by electrostatic metho.
Cured aad dried coatings ate uneven in thick-
ress, with numerous hills and valleys. Lacquers
an contain entrapped solvents if they are insu
ficiently cured
In peneral, organic coatings are flexible, and
they tend to soften at ight
12 Filorm carosin on PYC-conted aluminum fl.) Advacing bee ond erxked tal ation of fl
‘lamin sozng ut of he porove ara section ofa ffocm call SEM. 690™. Til region of form cal Tal oppor indecem due fo era obacon
w
ings cam separate from the steel subsirate be
‘cause of physical abrasion, The ease of separa:
lion depends on how well the surface wa pre
Dred before it was coated. Organic coatings can
be semipermeable 10 water and can have numer
us flaws caused by Improper application of the
‘oats. poor curing, or solvent entrapment
Coted ariles may sista Soave minor mech
ical abrasions’ during their curing or storage
Coatings often crack when bistered by corrosion
product expansio
fon. Coutigs, therefore, have mans” pot
defect sources at which filiform corrosion can
hegin. Heads of filiform cells will continue to
remain active & long as the coating keeps ex
pnding and crackingand if moistare and oxygen
re available.
Conditions Leading to Filiform Attack.
Filiform corrosion generally occurs in coated
Steels when the relative bumality is exween 6010
98% ina temperature range of 3010 38 °C 70 to
95°F). The surrounding atmosphere must contain
air oF onyagen, Atk usally begins at cuts,
knicks. pores, or other disruptions in the costing
Carbon dionide ean also stimulate Bliferm corr.
sion by dissolving in water to create carbonic
cid Ifthe eondensing almospheres contain con:
Centiations of chlorides, sulfates, sulfides, or
Sarbon dioxide, the bkelihood of liform coro
‘ion is substantially increased because these con
siluents help to seidiy the fliform head, The
fate of advancing growth generally inereases with
[reater condensed salt concentration und higher
ity inthe head. Fiform corrosion has been
‘observed on steels coated with varios hequers
land other siowerdrying resins. Table 1 lists
hform grovith rates for steel ut 230 25°C (7440
77°F). the physical dimensions of laments. and
the active unge of relative humidity for aiferent
coating systems
‘General Appearance. fiform cells on cout
fed steels consht ofan active head, which s Bk,
blue-grecn, or grayish in color and a brownish
Localized Corrosion / 105
a
mel SEM. 90%. (b) The glans ceronon pret of
13 Slotup ofthe edarcing fad shown fo
J 3 Fig ie, Mite erchs ean be seen othe
node! inerfoce af @ Bllerm corazon call Thom
‘Gackt ere enry points fr water andar to prove @
{ource of hydrooy ions ond a ecco. Itermedne
‘roson products rej Begining term inthe oad,
‘ond they undergo tro reaction to erm an exponded
i. The tal regions 9 progressive reaction zone tat
‘iimotely forms spent corrxon produc. Bebwen the
Faad and porous end, sts gredoaly rod wi wale
nd onygen en ore slowly wanspeted in he dreon of
‘he tel form final corsion pres SE. 760°"
rusty flament-shaped tail, Filament growth tends
{obe more random when the ste! surface has no
burnished texture or pronounced rolling dee
tion. Typical Hlament growth rates are about 02
10-4 mil (& 1a 16 Mid), with an average 106 / Forms of Corrosion
lament width of 0.2 mam «® nis). Filament
heights vary with the type of coating and. the
corraive environment, A moist environment of
Oe relative humieity is Iypicaly needed 1 r00
temperate 10 initiate Worm attack, Warmer
temperatures generally exacerbate the situation
The solion inthe advancing hea of form i
usually acidic, with moistare and oxen entering
primarily through the long tail. The typical ach
In the ifr head is pH 1 10 4. Anions such a
chloride, sulle, or sulfate way enter the head rom
‘corrosive atmosphere or by direct deposition on
the surface und combine with the condensed water
‘vapor that perclates thrash the eracked coating.
Atmospheric corosives may be supplemented by
‘continual aching of solvents or unveacted const
tents of the costing that combine wth water: The
head is filed with ferous ions and the tail with
ferric hydroxides and hydrated iron oxides, de
pending on the lonstudinal postin in the tail and
the age ofthe filaments, The dvancing head of one
Slament is defected or hated when it contacts tail
‘of another fliform, because a ifr ails gene
ally alkine and filled with spent corrosion prod:
lets. The head Iiterlly tunnels though the sub
strate, separating the coating from the steel und
bulging fon! by expansion of eorrsion products oF
by hydrogen gas evolution ithe head is very acide
(Ref 3. The omsant forwatd motion oF a lament
wil e2ase if the tal is rot continually aerated snd
Supplied with water vapor condensate
‘Mechanism of Fiiform Attack. Coated
steele have numerous defects on thelr surfaces
Uohere air and water vapor condensate can pene
trate throogh to the steel substrate. If the con-
densing stmosphere contains significant concen
trations of alls, the condensate is more
slectroyticaly conductive, and iron can more
Feadhily dissolve mto solution, The activity ofthe
heads initiated when ts oxygen concentration of
DH is considerably les than inthe a. Dissolved
Sait nthe head sobion can further decrease the
Solubility of oxygen, High salt concentrations can
flso lead! to firther acidification of the fiform
bead. In contrast, the tail is Bete uerated und
receives s greater amount of freshly condensed
water Vapor. Voltage messirements beiveen the
head nd al epions normally indicate a potential
diterence of 0.1 10.0.2 V. The head advances as
iron goes into solution: this undercuts the bond
between the coating and the Stel substrate
‘The mechanism of coating expansion inthe
head region #8 not Yet fully understoad. Corea:
sion product exparsion and the undercutting of
the coatngistel interface in the head aze major
eoninbutors to flament head bulging (Ret
Head and tail solution chemistry and temperoture
alse ullect the film streagh of the coating and is
boning to the steel substrate. The head is a
noving pool of acidic electrolyte. The tuling tal
‘a progressive zone of corresion products and
reactanis that ve gradually being converted to
Spent corosion products, The ead of the tal Is
there corrosion prodvets have been completely
reacted and fully expanded. The alkainty ofthe
tal region also stimulates coating eracking and
chonuing by softening and weakening the paint
Alm,
the filiform ead solution is particularly
‘acigio (ptt 1 10 2, blistering can occur because of
Hydrogen evolution asa cathodic reaction:
Me
‘The head or tal may bulge or blister consider
ably. the bulged coating ruptures completely, 4
2H! + 20
‘ew initiation site js ereated, and this permits the
formation of ew Aiament Beis,
‘The size of filaent is apparently governed
by the original detect size andthe Beaty ofthe
fm, The texture of the rolled surface and the
‘nature ofthe coating also shape te geometry and
the spread rate of fliform atack. The ferrous ions
formed in te head are transported toward the
and further oxidized in the fst section ofthe tal
Dy forming fersic hydroxide
‘Water and oxygen can caicr the cll at cracks
in the coating in he tail ron or atthe head!
intetface. Water is citer consumed by the head
clecirlvie or ean be involved in cathodic rex
tions. Flyroxyl ions are provide By the oxygen
reduction reaction, which tes place inthe lal
ae
Fes fet Fer 1 40,
ho-Fet
~ ow
0, + 280 + &
‘There isa general transport of iron ions toward
theta egion, where they combine with hydroxyl
fans to form ferric hyeroxides inthe tal, Toward
the end of the lal, ferric hydroxide decomposes
to ferric oxide and water. Other iron hydrates
may alsa form, Beaune the corrosion products
of iron expand considerably, the coating bulges
for splits. Ax the coating Farther racks er spits
tore oxygen snd water can ener the tal ner
"imulating the corrosion reactions. In some brit.
tle coatings, the head may be very smal, and
racks may form rapidly. A. general diagram
llaetating the mechanism of filiform cosroston in
Jeon and steel is shown in Fig. a)
Mila ot
\
Cracked or
porous en
FeIOW, 466,04 + 1,0
|
Fet 430M ~Fe(OHl, FSIOM,= FEO, + 0440
Aout f ANON, 8,0, 1 40
v
Arar 40,1 HHO 30-308 / 2AIOH,- ADs » 24,0
WO eth A 6 208 - ao,
1
fond predomi
‘var, gion,
20H Mat = 20H = Maori,
Diagrams ofthe filiorm corrosion cal in te (a) chunu (0), ond mogpesum c). Corrosion products
4 ee Ieelad: For corruon to deren
S"seraion al en by
M®™ = ne) is balanced by the
Localized Corrosion / 113
“wo vews of deep pt nc type 316 soils ste ene hed defo expose a CaCl soon
Courony oF NW. Sac, Aled Corporation
‘eathoile reaction on the adjacent surface (Os +
2H.0 + de> 40H). The increased concentra
tion of M?™ within the pit results inthe migration
Df chloride ons (C1) to maintain neutrality. The
Imetal chlorige formed, MCI. is hydrolyzed by
‘water to the hydroxide and free acid (M'CI. +
HO MOH H°CL }. "The generation of this
nucid lowers the pH values at the bottom ofthe pit
(pH approximately 1.5 to 1.0), while the pt of
the bulk soltion remains neutral
‘Most of the research facuses on understanding
the factors thit_control pit initiation. Varios
theories have been. proposed that attempt 10
texplin the pitting phenonienon (Ref 35) These
Include kinetic theories. which explain the bresk> 114/ Forms of Corrosion
Fig. 21
ft of omparatreon iting reac
ig. 22 oreo seven clloys 24h test n 7
vgn. Panata Here taey #8 ee
down of passivity in terms of the competitive
absorption between chloride ions awl oxy ged,
tnd thermodynamic theories, which consider the
pitting potential as that potential at which the
‘hoc iwi in equilibria withthe oxide fl.
Occurrence and Testing
Piuiny corrosion occurs in, most commonly
used metals and alloys. Iron buried in the so
forrades with the Formation of shallow pits, but
Stainless stcels immersed in senwater character
intially corrode with the formation of deep pits
‘Aluminum tends to pit in waters vontaiing C1
(for example, at stagnant areas}. and aluminum
brasses are subject to pitting attack in polluted
waters,
In environments containing appreciable con
centrations of CI” or Br, most sinless mate
als dor example, iron-base. nikel-base, cobalt
base, and titanium alloys) tend to corrode at
specific reas and tend to form deep pits. Figure
20 shows deep pits that formed ina type 316
Stainless nee! centrifuge head from a calcium
chloride (CaCl) solution. Lons such as thiosulfate
{8.05 } may also induce pitting of stainless steels
Tavthe absence of passivity. sich as in deserated
alkali metal blondes and nonoxidiving metal
‘hlorides (or example, stannous chloride, Sn,
Ross of a 24h at on fv erent lay in7 volt MSO, + vale
He 9G Fach, + 196 Gly woluton ot 28°C (77°F)
Fig. 23
titel temparatre above wich iting i cared for fur fe
‘lye, 22 ja in 7 vale WSO, 3 volts HEI 186 FeCl, +
ACL taliion. ly 4: Ne16Cr-16Me. dily'C-22: N22 T9MO-IW,Remetng
Soy compotion: are given toe.
or nickel chloride NiCl), pitting does not aceur,
‘slthough genera, oF uniorm. corrosion may Be
fnpreciabe in such environments,
The selection of materials for resistance to
pilling corrosion in specific industrial services is
better made when based on field testing and
actual service performance. However, such et
fifcal information is often generated unde ill
‘fined environmental conditions and is deper-
ent on many uncontrollable factors that do not
allow n precise comparson among the potential
‘Gundidate alloys or aetals. Accvleraied fahorate
Fy tests might he useful in this respect. Such tests
include the classic immersion tests freely coe.
foding conditions} and the sdvanced electrochen-
‘sal techniques
‘he immersion tess are very practical in pro-
viding decisive, direct comparison among vars
tiloys, and these tests correlate very well with
Service experience. Figure 11 clearly distinguish=
es the improve! pitting resistance of alloys G
(NE20Fe CHEMO), 625 UN-2CHIMO) and
C-776 (NEIGCT-I6MO-4W) from that oF alloy 825
(Ni30Fe-21Cr-3Mo) and ype M5 staloless stee
Aso. immersion tests allow emphasis on the
effet of temperature on pitting resistance (Fix.
12) and allow establishment ofthe rial iting
iemperature, thts, the temperature above which
pitting occurs in a specific envionment (Fig. 23),
‘The higher the crieal pitting temperature is for
‘example > 120 °C, or 80°F, for alloy €22), the
ore resistant the alley isto pitting corrosion.
“The electrochemical lechnigues used to inves-
tigate piling corrosion include the simple moni
toring of corrosion potential snd its Muctuation
ith time due to piting attack. potentiostaic
festa, potentiodymamc texts (al relatively slow
sean rates of few millivolts per minute), rapid
scan potentiodynamic techoigUes. potemiostaic
induction time studies. potentiosatic serateh
techniques, glvanostatic polarization techniques
{or anodis putting tests, constant potential tech
bigues (or polenlistatic point-t- pot methods)
Lind eysie polarization [or anodic hysteresis Toop
techniques). Reliable, comparative data can he
encrated with the electrochemical testing tech
iques lo assess the effects of potential. temper
{ture, pH, chloride ion concentration, heat treat
tment, and alloying elements [Ref 36). The
potentiostatic polarration method is judged the
most practical in generating data relevant 10
sot service performance (Ref 36, 37). More
Aletaled information on testing ard evaluation of
pitting cormosion can be found in the articles
SyLaboratory Testing” and “Evaluation of Biting
Corrosion’ in this Volume,
Prevention of
Pitting Corrosion
Iypical approaches to alleviating of minnie
ing pitting corrosion find their rots in te follow:
ing major principles:
1 Reduce the aggressivity of the environment—
for example, chloride ios concentration. tem
perature, acct, and oxidizing agents
se Upamace the materials of construction —for ex.
anple. rédition of molybuenunvtungsten
‘overaioying of welds, and lining with high
alloy
© Modify the design ofthe systom—for example
erovices,circulate/stie to eliminate stag-
ms. and easove proper drainage
based on the concept of ertical
potential 10 induce piltiig corrosion,
