(ot/,o9toil f*l¡g

Environmentol Crocking-
Corrosion Fotigue
Richard P. Gangloff'

CoRRosIoN FATrcuE (cF) is an important but complex mode t,d gage length and specimen diameter, rcspcctively
of failure for high-performance structu¡al metals operating a't,b Basquin relationship material proper'ty pammeters
in deleterious en\,ironments. This view is based on the like- E'l,c Coffin-Manson relalionship material property para-
lihood of cyclically varying loads and chemical enüron- meteIs
ments in service, the need for predictable longJife number ofload cycles for specimen failutc by fatigue
component performance and lifc exte¡sion, the universal number of load cycles for fatigue crack initiation
susceptibiliry of pure metals and alloys to CF damage, and tmnsition fatigue life, or number of load c¡'cles
the time-dependent multivariable characte¡ of corosion where the magnitudes of the elastic and plastic axial
fatigue. For example, stress corrosion cracking (SCC) im- slrain ranges are equal
mune alloys are susceptible to CF. Corrosion fatigue has d¿ldN macroscopically averaged fatigue crack growth mte
aFtected nuclear po\\,er systems, steam and gas turbines, fatiguc crack length
aircraft, marinc stn¡ctu¡es, pipelines, and bridges; CF issues fatigue load c."-cle count
are ce¡tral to the behaüor of many aging systems [1-3]. Ar appljed slres\ intensitt fa.¡or range, ¡(.- - K ,
The objective of this chapter is to highlight moderD labo- A, t1t Paris Law material propert.v constants
ratory methods for characterizing the cor¡osion fatigue be- aKnr thrcshold stress intensitv range
haüor of metals in aqueous electrol¡es. The principles and R strcss ratio, r(-in/K,**
mechanisms of CF are summarized in the first section of p notch tip radius
this chapter, follorved by discussions of expeúmental meth- f Ioading frequency in cycles per s or Hz
ods in the second section. Specimen dcsign and loading, 1td|' time-po¡tion of the load c-vcle rvhere CF damage occurs
enüronment control, stmin and crack size measurement, Kraaa threshold stress intensity for monotonic load SCC
and computer automation are discussed. The emphasis üLldl velocit], o[ monotonic load SCC
throughout is on exemplary experimental methods and re- Ec free corosion potential
sults, as rvell as on CF data anahsis and interpretation. The E modulus of elasticity
third section of this chapter cices applications o[ CF data to Ar("¡ effectivc stress intensity ¡angc, K.,.. - (.1
ser-vice, the advantages and limitations of the experimental (.r strcss intensit!,value in a fatigue load c.vcle rvhcre
methods, and directions for research on CF experimenta- cmck-surface closure contacf is expe¡imentally i!-
tion. St rnbols and terms are defined in the Nomenclature. solved and operationallSr defined
This chapter, with extensive references, extends previous stress intensitv ¡?nge at a fixed crack lcngth, ao
rrcüervs of corosion fatigue test techniques [4,5]. This chap- ^(o
c constant in the equation \üth units of mm-l
ter rvas published originally in 1995, the following literature ü/dtr timc-based crack ^I(-contiol
gror.vth rate in fatigue, often appr-
in the BibliogEphy reflects new devclopmenrs in Corrosion oximated by (d¿ldN)(0
Fatigue. CF co¡'r¡sion fatigue
SCC stress conosion cmcking
No¡rrenclature HCF high-cycle fatigue
LCF low-cycle fatigue
applied engineering üue stress range in a fatigue FCP fátigue crack propagation
^(' load cycle, óm- - onir where o is load/initial cross- HEE h¡dr-ogen enüronment cmbrittlement
sectional a¡.ea H atomic hydrogcn
A€, fi-ue plastic axial strain mngc in a fatigue load cycle, HCP hcxagonal-closed-packcd
rpmax - €pmin LEFM linear e!astic fiacturc mechanics
Aer true total axial strain range in a fatigue load cycle, SN strcss range versus life
€¡-.. - E¡-;n CP cathodic polarization
€ lr'ue axial strain,ln (1/lo) cpm cycles per minute
€¿ true diamctral st¡ain, ln (d/do) Mode I applied load perpendicular to the cmck plane and
grorvth direction [ó-8]
lP.of.ssor and Chair, Depar(menr Mode II applied load parallel to the crack plane and the
ol Maleria¡s Scicncc and Engi-
neering, UniveNity ol Vireinia, Charlorlesli¡¡e, VA 22903. clack gro*th direction
2 CORROSION TESTS AND STANDARDS MANUAL

Mode I1I applied load palallel to the crack plane and hldrogen chcmically adsorüs on straincd-clean initiation sites
pcryendicdar to the gro\r4h direction or cmck surfaces as the result of electrochemical ¡'eduction of
v" Poisson's ratio for isotr-opic elastic deformation, hldrogen ions or rvater- (Adsorbed hydrogen is also produced
often taken as 0.33 by the reactions of H2, HrO, C2H2, or I-l2S molecules rvith
LVDT Lineal Variable Differential Transformer metal surfaces.) Hydrogen production follo\\'s mass tmnsport
EPD electricalpotentialdifference within the occluded crack (pit or creüce) solution, crack tip
dissolution, and h¡dr.olysis of cations for local acidiñcation;
and precedes hldrogen diffusion by latiice, interface, or dislo-
BASIC PRINCIPLES catio¡l processes in the initiation-vohlme or clack tip plastic
zone. Fatrgue damage is promoted by hydrogen-affected lat-
Fundamentals of Corrosion Fatigue tice bond decohesion, grain or dislocation ccll boundary
decohesion, enhanced localized plasticilv, or metal hydride
Delinition fomation (in materials such as HCP titaDium-based alloys).
Conosion fatigue is deñned as the sequential stages of Hydrogen-enhaaced CF cracking is either i[tergmnular or
metal damage that evolve rvith acct¡mulated load cycling, in transgmnular, with the latter iñ'olüng dislocation subso.l-rc'
an aggrcssive environment compared to inert or benign sur- turc, low index crystallographic planes, or interfaces.
ror.rndings, and resulting f¡on] the interaction of ireversible A second mechanism for CF is bascd o¡ damage b], pas-
cyclic plastic defolfnation \l,ith localized chemical or elcctro- sive film rupture and ransient anodic dissolution at a sur_
chemical reactions. Environment-enhanced fatigue is a mod- face initiation site or crack tip. This modcl was developed
ern tem; however, corosion fatigue is traditionally used with several necessary empirical elements to prcdict CF pro-
when emphasizing electr r¡chemical environments. Mech- pagation in carbon and stainless steels in high-tempemture
aoical fatigue cxperiments and anal¡'ses, detailed in recent pure tr¡ater [22,23], ard is sometimes applied to titanium
textbooks [6-8], providc the basis for understanding CF. and aluminum alloys in aqueous chloride solutions. Local-
ized platic straining, described by continuufir mechanics or
Stages of Corosion Fatigue dislocation plasticily, ruptures the protectivc ñlm. C¡ack
CF damagc accr¡mulates with increasiog load cycle count advance occurs by transient anodic dissolution of metal at
(N) and in four stages: (l) cyclic plastic deformation, (2) the breached film, and at a decrcasing rate rvhile the surface
microcmck initiation, (3) small crack grorvth ro linkup and repassivates pending rcpetition of this sequence. The in-
coalescence, and (4) macrocrack propagation. A cardinal crement of CF gro$.th depends Faradaically on the a¡odic
principle is to design a CF experiment to isolate and quanti- charge ([ansient current-time integial) passed per load
tativelv characterize one of these four stages. The methods cycle. Charge is governed by clean-repassivating surfacc
i¡ this chapter are organized as follorvs: (f ) smooth speci- reaction kinetics for the CF-sensitive alloy microstnrcture in
men life for high rycle fatiguc (HCF) described bt, A6 versus occluded cr:ack solution, and by the time between n¡ptures
NÍ d^ta, (2) smooth unia\ial or notched specimen life for given by local strain rate and film ductiliry- As with the hy-
low cvcle fat¡gue íLCF) describcd b\ Acp ver.sus \ or All drogcn mechanism, film rupture modeling is complex and
Vp vcEus N,, respcctivclv, and (3) [arjgue crack propagalion controversial; confirming data exisr 122,23), bu1 other rc-
(FCP) kinetics described by da/dN vercus rhe 6.acture search shows the model ro be untcnable for specific alloy/
mechanics AK. en\'ironment systems [24].
Several CF mechanisms were proposed based on inte¡?c-
Meclunisms
tions betrveen dislocations aDd environment-based processes
It is important to underctand damage mechanisms in at initiation sites or cmck tip surfaces. For example, in-situ
order to co¡'rectly inte¡p¡et and extEpolate laboratorv CF tmnsmission electron microscopy and dislocation rñodeling
data. Similar to SCC, rhe mechanism for CF mav involve show that adsorüed hydrogen localizes plastic defomation
h\drogen embri lcmenr; hlm rupture, djssolu;ion and in several pure metals and allo¡,s [25]. Second, reaction-
¡epassivation; enhanced localized p!asticitv; interactions of product films are not capable of extensive plastic deforma-
dislocations rvith surface dissolutior¡, 6lms or adsorbcd at- tion rclative to the under\¡ing mctal, and may cause CF
oms; and complex combinations of rhese processes [9-ló]. damage by one or more proccsses, \,iz: (l) i¡lterference u.ith
The contribution of each mechanism is co¡¡oversial and the rcversibility of slip, (2) localization of persistent slip
rlepends on metallurgical and cnüronmenr (thermal and bands, (3) reductio¡ of nea¡-surface plasticitv Ieading to re-
chcmical) variables. While providing significant insighr, duced or enhanced CF depending on rhe oácking mecha-
existing mechanism-based models are generally not capable nism, (4) localization of Dear-sur-face dislocation structure
of accl¡¡ately predictiDg CF behavior beyond the range of and voids, or (5) film-induccd cleav^ge U4,15,2ó-28). Ad-
labomrora data. so¡'bed caiions could similar!¡, affect farigue [29]. Finallv,
Hydrogen enüronmcnt embrittlement (HEE) is an impor- anodic dissoltr¡ion may eliminale neat.surface uork harde;-
tant mechanism for CF crack propagation in felritic and ing ald hcnce stimulare faligue damagc [30]. These mecha-
martensitic steels, as well as aluminum, titanium, and nisms have not been developed and tested quantitatively.
nicltel-bascd alloys exposed to gases and elecrrol).les within
ordcr r¡f 100"C of ambient tempemture U5-2l1. This hv_
polhesis is supporrcd bv exrensivc bul cir'cum"r¡ntial eü, Factors Controlling Corrosion Fatigue
dence, and is mosr readilv acceprcd lbr high-strcngrh alloys
Two consideEtions are central Lo understaDding the ef-
in strong hldrogcn-producing enüronments. In HEE atomic fects of mechanical, metallurgical, and chemical variables
 CHAPTER 2ó- ENVIRONMENTAL CMCK.NG 3

on CF- Thc infll¡ences of electrolyte composition, conductiv- to tlre mcthods developed for measuring purely mechanical
ity, pH, electrode potential, temperature, viscosiry, and bio- c)'clic stress-stmin data [8,37]. Whilc macroscopic constitu-
logical acúvily are govemed by the mass t¡anspoñ and tive properties may not be environment sensitir,e, slip local-
electrochemical reaction conditions within occluded pits, ization ca¡ be affected by electrochemical reactions [14,3J].
cr-evices, or cmcks, including the role of st¡ain io creating
reactive ctean surfaces [3,/,32]. Second, CF can be time- Meclnn ic al Drir ing Force s
dependcnt. Crack growth is ohen rate-limited by one or Considering smooth specimens, thc ranges of applied
more of the slow steps in the mass tmnsport and crack sur- stress or plastic strain control the fatigue or CF responses of
face reaction sequence; slow loading rates enhance CF metals for HCF and LCF conditions, respectively. For HCF,
dalr. ge L171. Increased cmck tip strain rate is deleterious smooth specimcn CF life increases with decreasing elastic
when the extent of per-cycle electrochemical r€action is sfess mnge, at cycles in excess of thc hansition fatigue life,
prorñoted f22-21).2 Nr, according to the Basquin equation
Variables that affect CF wer€ rel,ielved elsewhere [.15--17].
lmportant factors are cited herc to illustrate important CF Ld =o'r(Nt)1' (l)
test methods and to guide data interpretation.
and due to decreasing globally plastic stmin at cycles less
Mechanical Varíables than N¡, according to the Coffin-Manson equation for LCF
An important issue is the influence of an electrochemical (2)
environment on the cyclic deformation behavior of metals
ae, =ei(N¡)-'
U 1,33-351. As illustr¿ted by the data in Fig. I for a carbon- Alternatively, Eq l, divided by E to relate N,. to elastic
manganese steel in high-temperature water, enüronment strain range (^6/E), is added 1l] Eq 2 in order to relate NIto
does not tlpically affect the relationship between stresscs total applied strain range, the surn of the elastic and plastic
and st¡ains derived from the rñaximum tensile (or compres- stmin ranges.
sive) points of steady-state (saturation) hysteresis loops The material propeny parameteñ for HCF and LCF (ó, c,
[36]. Such loops should rclate to elastic and plastic defor- dt, and t'¡) depend on metallurgical, environmental, and
mation prior to substantial CF microcracking. CF data of lime variables. Data in Fig. 2 shorv that the HCF life of A1SI
the so¡'t shown in Fig. I arc produced by either stress or 4140 steel is dcgraded by aerated neut¡al NaCl solution,
total stmin controllcd uniaxial fatigue experimenrs, ide¡tical compa¡ed to similar fatigue lives for dry and moist air as
well as deaerated chloride [-]&J91. The data in Fig.3 shorv
1200 that distilled water and aqueous 3¿l¿ NaCl similarly degrade
4533-E Siool the LCF resistance of an unrecrystallized precipitation-
289"C hardened aluminum alloy [35]. The Basquin and Coffin-
^c 1mo
Marison relationships are generally obeyed for faligue in
-
= eoo clectrochemical enüronments; howevcr', multiple porver larv
segments may occur. Critically, the HCF endumnce limit or
1

o.^^^ {%)= {ad1965 o)* (^d§56)11

^rr
É
o 40o

tt> 2ñ Ten.€olnp. Slrán Rale (%/s)

O An
Open Symbols: 0.4¡0.4 A Pure Waler
Closed Symbolsi 0.004rc.4 o Fflfl Wat6.
0L
0.0 05 10 15
Tolrl Stratn Range, a€r (%)

FlG. l-The nil eflect o, env¡ronment on the cycllc stress-

strain response ol a CMn sl€el ¡n moist a¡r and pressurlzed
waler at 288"C [36¡. Data are represented as true stress-{rue
total straln range,

2Considering HEE, ir is impoñant (o consider the p.¡maÍv htóo-

gen sor.rrce when designing CF experimenls and in(erpre{ing ¡€-
sults. In addition ro occluded crack tip hydrogen produclion,
hydrogen can dittuse over Iong distances lrom ploduclion siles al
mildly strained bulk solution-exposed specjmen sur[aces (o the
propagating CF c¡ack tip. Bulk surlace hydroscn production is CvdBroi.iru
important for tel-I us alloys at long exposure times in acidic or'
H2S beadng solütions, and \\'ith cathodic polarization [21]. This FlG. 2-The déleter¡ous effect ol aerated aqueous chloride sol-
hydrogen source is less impoúant for aluminum and titanium ál- ution on the ¡lCF l¡lé of smooth specimens of tempered mart.
loys in electrolytes that forrn passne surlace tilms capable of block- ens¡tic AlSl 4140 steel. Symbols with horlzontal anows ¡ndicate
ing hvd¡ogen uptake. ihat CF failure has not occu ed after I 07 load qcles [38].
4 CORROSION IESIS AND STAND/ RDS MANUAL
ll2
10 Ar, Srres Inrensi\ nange lñt 'n
Al.Zn-Mg-0.01 Cu 910 ?ol0¡0Ó0s
t0'
Ti-óar-6v-25n l¡ ill Añ.€al,
+ Dry Air wR R"0.1 l.0.ur" to'
:; + Hao
-.G Nacl

<lL
-, ,o
l0'l
= o.82
l0

-0
.e r0

2Nr
'' I
FtG. 3-The deleterlous effect of aqueous chlo¡ide solutlon t e

on the LCF tife of a pre{ipitation harden€d alu¡ninum alloy [e5]' l'

o 0.6M ti¿cl(Du ' 6.4 -10 Hr
10 . 0.6r' NaCl roH , ó.'¡l - l Hr
o 0.6MNaCt + IC' (DH'1,0' l0 H¡
3 . 0.6Mr\3cl l flcl (pH. t.0 - l llr
threshold stress mnge can be eliminated b)' the aclion of the r05 ¿
- -Ambie¡l Air (Loftr Lrmit,
electrolytc, as illustrated in Fig 2. A common explanation
for this effect is pitti¡'¡g-based CF crack i¡itiation.
Rates of CF cmck propagation are uniquely defined by A(s¿r . 14 ¡oH , 6.¿, I H¡r

the linear elastic fi"acture mechanics stress intensity factor A(rcc . ll rPH ' 10, I t¡l|
, ó4. l0
range that combines the effects of applied load, cmck size, AKrcc ' 10.5 IDB Hzl

AKs.c - l0 r¡tl . l.o, l0 ¡rl l0ó

and geometry Í17,401. The similitude principle states that
fatigue and CF cracks groN at equal rates when subjected to
equa! values of [ó-8]. The d¿ldN versus AK telationship
may be complex;^K howcver, an effective approach is based o¡ ¡0
a poiver (or Paús) relationship of the foún [4/] 8 ¡0 20 l0 40 ó0 100 lr0
Ax, §tr¿rs tnl¿¡s¡ty na¡9¿, r¡r ' in.l/?
&tldN = A^K- (3)
FIG" /t-The eñect of soldion pH and loading frequency on CF
AK is limitcd to stress intensity changes above zero because crack propagat¡on ¡n an o¿/p litanium alloy exposed lo aque
compr.essive loads do not cause appreciable crack tip plastic ous chloride [4r1.
stmin and damage. The material properties (A and ,?) dc-
pend on environmental a¡d time variables. Fo¡ metals in
CF cmck formation in notched specimcns is most effec-
vacuum a¡d moist air, FCP is described by a single porver
law and an apparent threshold stress intensity range below
tively characterized by the notch-root plastic sfain range
rvhich d¡ldN tends to zero [42]. Mor.e complex cracking calculated by Neuber's method, elastic-plastic finite ele-
behavior is obse¡r,ed for CF, as illustrated for aqueous chlo ments, or fracture mcchanics approximation [7,8]. The lat-
ride solution-enhanced FCP in titanium (Fig.4) and ad- ter approach is illusÍated in Fig. ó, showing the results of
vanced aluminum'lithium-copper alloys (Fig. 5) [43,44). over 100 experiments rvith C-Mn and alloy steels in aqueous
Note the complex of dald.Ay' for FCP in chlo- chloride solution compared to moist air [E4ó--48]. The load
nol vacuüm or moist air. Environmental
ride solution, but ^¡(-dependence cycles to produce 1 mm of fatigue crack extension, mcas-
elfects on Paris regimc FCP have been chamcterized uied opticá[y, increase nith dccieasing AKlrfi, an estimatc
broadly; however, data on near-thrcshold CF (da/dN <10-6 of Dotch root AeP, for air and chloride solution.r At fixed
mm/cycle) are scarce [/ó,42]. Ni is reduccd b-v chloridc exposure at fiec corosion,
Crack closure can strongly affcct fatigue and CF [45]. This
^K/Jp, to fatigue in moist air. An endur¿nce limit is ob-
relative
phenomenon is based o¡ crack surface contaci duüng sewed for moist air, but not this CF case. Cathodic polariza-
unloading, critically at siress intensity levels above ze¡o and tion (CP) restores a polion of the moist air fatigue initiatioD/
applied-positive K-,. values. Crack rvake contact is caused early grorvth life, as discussed in an ensuing section.
by corrosion debris, plasticitl,, crack path roughness, or
phase tmnsformation products; each mechanism may be lnading Frequency (I;requetlcy Domaín Issues )-Slo'.v fre-
sensitive to aqueous cnüro¡mental reactions [ó]. To ac- quency CF experiments mav be necessar.¡ because of mass
count for closure, ddldN is correlated with an effective tlansport and elec¡rochemical reactio¡ ratc limitations or¡
stress inter¡sity range that is defined operationallJr as the
r¡r1:
differcnce between applied K,""* and thc I(, level rvhere sur- is calculared assuming a shary crack ol leng(h ánd geometry
face contact is resolved (see Data Analysis and Evaluation in equivalent to the not.h. This merhod is a reasonable alternative ro a
linile elemenr oI Neuber ana,vsis of notch srmin, bur only for
this chapter). c¡acklike notches oF the sort shown by the insefl in Fig. ó f71.
 CHAPTER 26- ENVIRONMENTAL CMCKING 5

l0 - 100
A333-6 sle€l (Higuchi)
AA2O9O TBT O EPPrn
LT.1/2. l Hz 0 2po.n
K-",- l? MPaJm ^o 0.ol wn

1o-4 A106-8 Sresr (ANL)

l a 0.Ol lpm
ro-1 a o.a ppm

!
10 - E
E
E Carbon Steel
10- 250-290.C
z 10 -
ro6 to'' 1o_'l 10- 1o' 10' 100
Strsln Rate (%/8)
lo-? FlG. 7-The effect ol strain rate on lor,!, cycle CF ¡n the GMn
UR Plate
steel/higtFtemperatue water system. The dissolved orygen
UR Sheet conlent of the pure water eñv¡ronment was vaÍeq as indi'
cated by the we¡ght-parts.per-milllon values in the legend [361.
10 '
1 5 l0
Frequency effecls on CF crack propagation have been
(MPaJrn)
^K chaEctcrized broadly and rnodcled bascd on the HEE and
Flá FTtre efiea of aqueous NaCl on lt|e CF crack film rupture mechanisms Uó-18,22-24). FCP mtes are
propagation response of un¡ecrystalllzed sheel l independent for alloys in r¡oist air, inef gases such as N2
and plate ot an advanced Al-Li-Cr.FZr alloy [44¡. or A,, or vacuum at lo\v to moderate temperatures. For CF,
there are th¡ee possible ftequency responses: (l) purely
timc-dependent, rvhere d¿ldN increases with decrcasing
damage, but are challenging becausc of prolongcd test time- frequency proportional to ( 1/ür, (2) cycle-time-dependent,
The generally deletcrious effect of decreasing / on smooth rvhere d¿ldN i4cr€ases with decreasing flequency propor-
specimen CF life is illustrated in Fig. 7 for an LCF case in- tional to (l/<¡rp with P on the order o1 O.S,-and 1¡) cicle-
!'oh'ing a C-Mn p¡essu¡c vessel steel, corroding freely in dependent, where daldN is cnvironmentally e¡lhanced but
high-temperatLlre watcr \üth varyi¡g dissolved oxygen levels frequency-independent. The parameter n gives the propor-
bet$,een 0.01 and 8 ppm. (The ftee corrosion potential for tion of the load-cycle time that produces CF damage, and is
these steel CF spccimens incrcases as the dissolved oxygen olte¡ taken as 2 for a svmmetrical cvcle, since enüron-
concentlation increases.) For fixed Aep, the ratio of N} for mental cmcking may not occur during uoloading [./ó]. An
faligue in ',vater to rhat lbr air, cach al 270'C, declines w¡¡h altemative model of the Íiequency effect considerli rhat
decreasing average total strain rate (proponional to fre,
quency) [36]. LCF lives are mte-independent for fatigue in
laboratorv air at low to modemte tempcratures wherc creep
is minimal. 7000-f6 Series Alumlnuñ Alloys (S-L)
¿.5.3.5% N.cl (pH 7), E"q,

E
: Q to"
E
E
z 10-

o 7075-T73,80.C
e 7475, PH 3, N¡2C,O.

o 7079,23% NaCl

Cycres to húratio¡ {r mm Crack)

FlG. 8-The varied efks of loading frequeñcy on CF crack
FlG. 6-The efiecr d chlor¡de on the CF crack formal¡on and propagatlon rate ¡n peak aged AA7g75,7017,7475, and lii,g
early (1mm) growth rqs¡stañce of notched steel specimens: exposed to aqueous cfiloride sola¡t¡on (free coroslon) at con-
sol¡d line fgr lour steels in NaCl, data po¡nts fo¡ seawater, ancl stant and R. The fatigt¡e crack is parallel to the plate roll-
dashed l¡ne for lour steels in NaCI [46-411. ^K ¡n the SCC sensitlve S-L orientation [50].
¡ng plane
6 CORROS/ON ?ESTS AND STANDARDS MANUAL

0.5 r€sponse is illustrated for AA7017 and M7475 (Fig. 8) in

0_005
seawater and acidified NaCl, respectively, and for two stecls
HSLA S1Oé in ¡eutral NaCl \vith cathodic polarization (Fig. 9), each at
fixed Á¡( and R U8,50,51).In both systems, p is 0.3 to 0.6.
.9 ,o'
E
Note (Fig. 9) thal cycle-rime-dependent daldN achicves a
plateau or saturation level at slorv frequencies belorv a criti-
cal value that depends on steel composition. The rhird case,
findependent CF, is illustrated for AA7075 in 80"C chloride
,.1 solution (Fig. 8) and for the t\\.o steels at high frequencies in
,/l
/.)-/' I
NaCl at 25'C (Fig. 9) [a9,5/]. This Ésponse (true corosion
3.5% NaCr,-1000rvs.¿ fatigue) is oftc¡ obseffed at lolv at high loading Ire-
lAr+ ^1(,
quencies, or for alloys that resist enüronmeDtal cracking. In
0.01
some cases CF da./dN increases with incrcasing F. This
I behavior is illustrated in Fig. 4 for a titaniuú alloy at low
r""o
;;;;;; A,K; in addition, note a crossover to time-dependent CF
above 20 MPafi and time-cyclc-dependent CF at inter-
FlG. g-The efiect ol load¡ng frequency on CF propagation ¡n
r¡ediate [43].
API-2H and A7l0 steels, at the 525 to 750 MPa yield strerigth
le\rel, exposed to aqueous i¡acl solution w¡th CP to -1000 Figure^i(l0 illustrates the minimal effect of loading fte-
mVSCE at constant and R [5] l.
quency on CF crack formation ald early growth for blunt
^K notchcd steel specime¡s in aqueous chloride solution at free
corrosion [4ó]. Thcse data are notable for the Ére combina-
electrochemical reactions occur throughout the entire load- tion of lorv f and high cyclic lives ( 175 days rvere required to
cycle [/7]. A single alloy/enüronment slr'stem can exhibit obtain 3 x 106 cycles at 12 cpm), and for the lack of a fre-
each drr/d-fv-f relationship, depending on A1(, f, and alloy quency effect on the cvcles required to produce I mm of CF
composition, as illustrated for aged 7000 series aluminum cracking. This result iridicates that one or more of the earlv
alloys (AA) (Fig. 8) and steels (Fig. 9) [,¡8,49 5,¡]. These
plots illustrate the two usual ways of presenting fiequency-
dependent CF daldN data, \\,ith the abscissa as either ]og o
or log (l/{).
The / range where d¿ldN is most circle-time -o- ^
dependcnt varics rvith mass transpon and reaction kinetics .-.--._
¡_ _
that are material-environment sensitivc. -f.-
Time-depcndent cracking is obscrved for high-strength l,¡0 11-6
SCC-prone alloys rvhen K.". in the fatigue c'ycle is above =
K¡5¡¡ and dalclr is rapid. This casc, illustrated in Fig. 8 for
AA7O79
eled by ^tf
< 1 Hz and for AA7075 ar F< 0.001 Hz, is mod-
linear superposition of SCC daldt and inert enü-
: I t.8

ronment d4ldN data f49,52,531. Cycle-time-dependent CF

(or cyclic stress corrosion cracking) involves substantial CF
at levcls that arc belorv (r... or rr,herc daldl is slo$,. This
^K
lo5 roe fi1
No b.r of Cx l.r ro fr urc

cycles lo c.aek l l'¡trotr,N

FIG. 1(FThe frequency independenc€ of CF llfe for blunt Nx¡ rc¡ ol C!.ls ¡o frillrr
notch specimens ol A5l7 steel, lreely corroding in aqueous
3.5% NaCl as a funct¡on ol notch root strain range [46]. (lnitia- FlG. fl-The effect of env¡ronrnent on tensile and tors¡o-
tion here ¡s in fact crack fo¡mation plus early growth to a nal high-cycle corrosion fatigue in the To7s/NaCl sotution
f -mm depth.) systern [54,
 CHAPTER 2ó- ENVIRONMENTAL CRACK|NG 7

stages of cF (cyclic pl¿stic defor'¡nation, pitting, crack nu- smooth-uniaxial fatigue specimens, r€spectively L47,591. CF
clcation, and small cr:rck grorvth) are frequency-insensitive, of polished specimens of 1020 and 4140 steels, exposed to
consistent wiih the /:independence of long crack CF at lorv NaCI during high-frcquenc!¡ r'otating bending, occurred only
AK for many allo¡* including steels in NaCl [,]ó,5/], Results if a critical anodic cu¡rent was exceeded [3&39]. In this
of the sol1 shorvn in Fig, 10 are limited and this behaüor study, CF was cssentially eliminated by solution deaeration
has not been modeled. rvhich reduced the srcel corrosion rate cuEent and free cor-
rosion potential (Fig. 2). Applied cathodic polarization simi-
Other Meclnnical Factors larly reduced CF of polished spccimens.
Applied load or stmin waveform, stress ratio, load spcc- Understanding the effect of applied polarization on CF
trum, and ovcrloads can CF [1ó,22,23,54-5ó]. This propagation requires a description of crack tip electrochem-
chapicr emphasizes uniaxial^fÍect
tensile loading of CF speci- istry, particularly local pH and potential, as aftecting rhe
mens because en\,ironmental effects on Iatigue under tor.- kinetics of passive film fomation, dissolution, hydrogen
sional or multiaxial loadiag have not been studied- An production, and hydrogen entr,y. Occluded cmck processes
exception is illuslated in Fig- I l, showing fatigue lifc data a¡e complex, as are the obserwcd dependencies of CF d¿ldl1
for smooth spccimens of AA?075 in moist air and aqueous on electrode potential. For example, CF crack glowth rates
NaCl [57]. Note the strong e¡vironmental degradation of Nt for steels in chloride incrcase with incrcasi¡g cathodic po-
fcrr uniaxial loading rcprcsented by ¡ormal stress range (^o), larization, rvith a modest minimum in daldN at about 200
but a rcduced effect for torsion aL a given applied shear mV active to the free corrosion potential [1ó,20]. Figure 13
stress ránge. Such results can be explained based o¡ thc illustratcs that thc ennironmental cnhancement of d¿ldN
deleterious role of triaxial tensile stresses, and the associ- increases with the total mte of H production at thc cmck
ated high hydrostatic (mean) tension, in CF propagation by tip, raised to the -/4 power, for C-Mn steel in NaCl (Ec =
HEE; this stress state is present for uniaxially loaded Mode -ó75 mvscE), polarized betu,een -750 and -1325 mVSCE
I crack, but not for torsional loading and Mode II or III [1óJ. Hvdrogen production was calculated f¡om a crack
cracks. Fatigue initiation may be similarl!, environment chemistry model [60]. For this system, solution deaemtion
enhanced for unia\ial tensile and torsional loading, explain- does not affect CF d¿ldN whe[ electrode potential is fixed
ing the modest reduction in Nt for torsion (Fig. I 1). potcntiostatically [ó1]. The oppositc effects of polarization
o¡ smoolh specimen CF life and crack propagation in steel
Electrochemical Variables can be reconciled. Dissolutiorl and pitting probably govern
enüronme¡t-cnhanced fatigue crack initiation LI 1,38,39):
Ebctrode Potential hydrogen plays a secondary role for the fast loading f.e-
Both anodic and cathodic polarization can affect CF, with quencies, near-thrcshold stress intensities, and uniaxial
different trends observcd for crack iniliation compared to stress states t)?ical ofsmooth specimen studies. Slow loading
propagation, and for steels comparcd to either aluminum o¡ frequencies and cmck tip hyd¡ostatic tension plomote crack
titaniúm alloys. For ferritic and martensitic steels in aque- growth by HEE. Here, impofant contúbutions to crack tip
ous chloride solution, high-cl,cle CF occurs at electrode po- hydrogen producrion are from cmck acidification near [Tee
te¡tials near free corTosion for aerated solt¡tion (Ec = -650 cor'rosion and water rcduction at cathodic potentials [,]ó,ó0].
mvscE), but is often reduced in severity or eliminated b¡' Cathodic polarization of aluminum and titanium alloys in
cathodic polarization to ncar -1000 mVSCE [58]. This be- chloride provides an interesting contrast to steels. Duquette
ha\.ior is illust¡¿ted in Figs. ó and 12 for notched and

E API-2H Steel 3% NaCl

t(]2 to3 l0'1 3 l\¡Pa\ñ B=0.1
^K=23
0.1 Hz I
z
a ln l% N¿cl, E = Ec ii
O rn l?¿ N¡Cr t = -1.0
ct
200 v scl: 5
= e 100
o
r50 f=3Hz
&

r00 5.0

Clacl Ip Hydrogen Produclion Barc (¡,/cm¿)

Fle l3--The effect ot electrode potential on relative CF crack

t05 t06 I07 to8 109
propagatlon rate ¡n the C-Mn steeuchlor¡de system, as por-
Nu,nbcr d Cyclos ro Fai urc trayed by the crack t¡p hydrogen production curent calcu-
lated tom a crack chemistry model. The equat¡on of the line
FIG. 12-The benef¡c¡al efiect o, cathodic potarization lrom regression analysls is: y = 2.39 + 0.22 )q whe.e y ¡s the
on h¡gh-cAcle CF crack ¡n¡tiat¡on ¡n a C-Mn stoel ¡n 1% NaCt normalized (dimensionless) crack grcvrth rate and x is crack
solution [591. t¡p hydrogen productlon rate ln A,/cm2 [ ,6].
8 CORROSION TESTS AND STANDARDS MANUAL

and others reporLed that the fatigue lives of smooth speci- aK¡ tsi-3/2
mcns of AA70?5 and Al-Mg-Li in NaCl sol!1tion wer-e ma\i- t 2 4 68¡0 20 40 60
mum at potentials mildly active of free colTosion: both
a5338, A508
anodic and highly cathodic polarization degraded corosion STÁGNAT¡T PIVR.288'C
fatigue life [15,57,58]. CF propagation occurs at the f¡ce o0t6? Hr
corrosion potential, is exacerbated by either anodic polari- o . O0l8 %S
zation or extreme catbodic polarization, and is arrestcd by ¡ 0.0t3 %s
modest cathodic polarization. This trend was demonstrated +, O00S rS
tor AA7o79, M7075 and AA2090 in NaCl and explained
based on HEE [19,ó2,ó31. At ncgati\.e potentials from ca-
thodic polarization, crack tip hydrogen production may be
rcdr,rced by the effect of alkaline occluded-cmck solution on
ASI¡E ¡I IIET
í980)
the overpotential and exchange current density for hydro- Rf 0.25
gen production on strain-bared surfaces, and hydrogen up-
takc may be blocked by crack su¡-face films.

Sulfur lon Content

Sulfur ions in electrolytes exacerbate CF crack propaga
tion in many alloy;. Various forms of sulfur are important
in sour oil or gas well and geothermal brine enüronments, 2 4 68t0 20
and are also ploduccd in unlikely ways. For example, the
I 40 60
AK, Ht¡ ñ-¡/2
daldN versus data in Fig. 14 shorv the CF behavior of
^K steel in sterilc 3.5,/¿ NaCl solution with
martensitic HY130 FlG. ls-The effect oI alloy ¡rpurity-sulfur content
CP, an environment that enhances cracking by t\vo- to on CF crack propagal¡on ¡n the GMn steeuhlgh-
eight-fold relative to moist air ar¡d more compared to FCP temperature pure waler system [221.

HY13O STEEL in vacuum. Note the strong eovironmenial effect caused by

a sulfate reducing bacteria (SRB; desulfrovibrio r.ulgaris)
cultured in Postgate C food-medium and with cathodic po-
larization [ó4]. Thesc, and similar data fot both biologically
actil€ a¡rd abiotic gaseous H2S saturated sterile chloride
solutions, are interpreted based on sulfide-stimulated HEE
I Postgate C
164,ó51. Bacteia metabolize the food-source and consume
hydrogen to produce sulñde ions and other sulfur species.
E iol These anions poison recombinant hydrogen desorption to
reduce H2 production and increase hydrogen entry into the
;t- metal at the crack tip, similar to the deleterious effect of
dissolved H2S.
.E
f In a second example, CF is promoted by increased impurity-
sulfur in ferritic steels subjected to low-fi'equency loading
,o (4, in pressurized purc water at 288oC (Fig. 15) 122,231. MnS
NaCr (-1000 mvscEl
(, inclusions, which intersect clack flank su¡'faces, dissolve to
enrich the occluded crack solution in sulfidc. These anions
o promote cmck advance by increasing the anodic charge that
o is passed per film rupture eventr or perhaps by the HEE
mechanism. This effect of steel sulfur content is severe for a
stagnant environment \\.ithin the autoclave, and is elimi-
0_r H2 nated by turbulent solution []ow rvhich reduces sulfide
R=0.1
(ar MotsT atR buildup within the cmck [óó].

11050 Other Chetnical Factors

STRESS ¡NTENSITY RANGE (MPa/n) Solution pH, ionic composition, conducti\¡ity, and tem-
perature can affect CF [11 17,22, 23,43,58].
FlG. f ¿t--CF crack propagaüon in HY'lg¡ stel ¡n aqueor.s
(sterile) chlorlde and active sulfatereduc¡ng bacterla envi- M e tallurgic al V ariable s
ronrE¡ú§, boh_úth CP to -l(m mVSCE, AK values Metallurgical factors ca¡ influence CF c¡'ack initiation
aborre 20 MPa Jm r€lr applied at R of Ol and f of 0.1 tq and growth. Prominent in this iegard are se¡sitizatiotr of
wh¡le AK < 20 [4P a vm riras applid at corstant túmx ol gmin boundaries in austenitic stainless steels [22,2J],
«l MP a v m and f of 1 or 5 Fl¿ Ttle dashéd llne repr€sents locally inte¡se slip in aluminum alloys from dislocatio¡
l¡leratu¡re data lor FCP ¡n the sleewacuum syslem [64], interactions rvith shearable precipitates [ó7], and metalloid
 CHAPTER 26- ENVTRONMENTAL CRACKING 9

impurities segregated to giain boundaries in stecls [ó8], CF HCF to notched cases. CF experiments follorv direcdy from
crack initiation often occurs at surface intersecting inclu- procedures for mechanical tests with bcnign enüronments;
sions that concentrate strain and may dissolve to produce a the latter are well-developed and standardized, while CF
locally aggressive e¡üronment [ó9]. CF crack propagation expeúments a¡e not. For example, ASTM Committee G-l
in the ferritic steel/aqueoLis chloride system is apparcntly has published 14 standards or practices for SCC experi-
not aifected by substantial changes in steel composition, ments (see Volume 03.02, Section 3 of the Annual Book of
microstnlcture, and yield strength [5/]. In another case, ASTM Sta¡dards), but none for corrosion fatigue.
aluminum allo¡, processing route, and the resulting degr-ee CF experiments arc hindered by several commor¡ factor.s.
oI recrystallization and gmin size, did nor substa.tialiy af- Aggressive environments are difficult to contain at a con-
fect aqueous enüronmental LCF life and FCP kinetics stanl condilion, and hinder precise measurements of
[35,44,701. Increasing copper content in precipitation- specimcn displacement, load, and crack size. CF is influ-
hardened Al-Zn-Mg alloys reduced the eDvironmental enced by many interactive mechanical, chemical, and
enhancement of da/dN, rvith the importance of the effect microstrl¡ctuÉl variables that must be factored into ex-
dcpending on aging condition [ó7]. perimental design. It is often nccessarl, to investigate slow,
rate deformation and cracking phenomena in a realistic
Relationship between CF and SCC time; experiments must be conducfed for one day to one
year or r¡ore. CF damage is localized at surface slip struc,
Corosion fatiguc is related to, but uniquely distinct from, ture and near the crack tip; high resolution observations are
SCC [7,/]. Purely time-dependent CF crack propagation in not generally available and behaüor must be interpreted
SCC-prone alloys is govemed by the integrated amount of from indirect measurements.
time-based caack extension per fatigue load cycle. In such
cases CF and SCC occur by the same mechanism and are
Smooth Specimen Ao-Life Meüod
affectcd by the same variables, as modeled by simple linear
for High Cycle CF
superposition L49,52,53). SCC is discussed elsewhere in this
manual. Gooerning Stand.arcls
Time-cycle- and cycle-dependenl CF are more complex, Experiments to characterize high cycle CF life according
involve unique mcchan¡sms, anJ occur al slress intensitics to the Basquin Law (Eq l) follow from ASTM standards for
rvhere SCC is insignificant. In these cases, the CF damagc metals in mojst air (see ASTM E 466, Practice for Conduct-
mechanism is unique for reasons traceable to cyclic load- ing Constanl Amplilude Fatigue Tests of Metallic Marerials;
ing, and including: (a) increased crack tip stÉin rate [22- and E 468, Practice for Presentation of Constant Amplitude
241, (b) resharpening of the blunted crack geometry during Fatigue Test Results for Metallic Materials). Such methods
unloading, panicularly at high (c) altered crack chemis- werÉ detailed for steels and aluminum alloys in aqueous
^K,evolution of persistent slip
try by convective mixing [72], (d) chloride solutions 138,39,57-59,ó9,79, 801. Tlpical data arc
band, slip step, and dislocation ccll structures into embry- presented in Figs. 2, I l, and 12.
onic damage, often at low Aep or lou, LK Í73,74), ar,d, (e)
mobile dislocation transport of hydr.ogen in the cráck tip Specimens and knding
process zone [18,50]. These additional factors must be con- High-cyclc CF specimens focus failure in a careftilly pre-
sidered when inter?¡€ting and modeling CF data [,/ó]. pared reduced-unifo¡m or mild-blend-radius gage section,
often of circular cross-section and with cnds for gripping in
Literature Sources for CF Data and Mechanisms the fatigue machine. T)?ical specimen designs are shown
elscwhere, including methods for lorr-damage gage machin-
In additior¡ to the examples prescnted in Figs. I through ing and polishing (sce ASTM E 466 and Ref 8/). HCF
15, extensive CF data have been published in seveml vol- specimens are loaded in uniaxial tension or bending (three-
nñes f l, 2, 9- I 2, 5 8,7 5-7 81. point, four-point, or cantilevered) rvith electromechanical,
scruoh¡draulic, or. Iotating wheel/mass machines, and grips
TESTING TECHNIQUES o[ various designs (see ASTM E 466 and Ref 81). Elastic
strainjng is load or displacement controlled; involves eithcr
Common Elements of a Corrosion negative, zero, or positive mean stress; and varies with time
Fatigr¡e Experiment sl-mmetrically in a sinusoidal or linear-mmp rvaveforrn.
Since CF is dominated by electrochemical su¡'face damage,
An experimert to characteúze the CF properties of a N¡ could decrease and variability may increase \üth increas-
metal involves cyclic straining of a pl.ecisely machined ing s!¡rfacc area that is stressed.
specimer¡ in an electroll,te. (Precorrosio¡ effects on fátigue High-cycle corrosion fatigue experimcnts are conductcd
are not considered.) Environment containmcnt about the for 105 to 109 cycles to failure, at a relatively high fre-
specimen must guarantee constaDt solution pürity and quency of 25 to 100 Hz to conserve time. (Nt of 106 cycles
composition. Specimen potential should be monitored, of- requires 5.5 h, u,hile 109 c-vcles rcquire 230 days of continu-
ten controlled potentiostatically, and not affected by gal- ous loading at 50 Hz.) Multiple, reliable, and inexpensjvc
vanic coupling to the grips or test machine. The mechanical rotating-bend machines are often dedicated to these
parameters that must be measured depend on the experi- experiments. Caution is r.equired rvhen extrapolating the
me¡t, be it HCF, LCF, LEFM-crack propagaLion or notched, results of relatively rapid frequency experiments, to lower /
and are paogfessivcly more difficult to monitor ñ!m the and/or the very tong life regime in excess of l0e cycles,
IO CORROS/ON 7ES7S AND STANDARDS MANUAL

Ent ironr rcnt al Cell D es i gn

The design of the enüronmental cell depends on electro-
lyte aod temperatr.u!. A tlpicat cell is illustrated in Fig. 16
for containing aqueous chloride solution at añbient tem-
pemture [79]. Glass. Plexiglas@, Teflon@, or other plastics
are adequate celt materials. The specimen is grippcd outside
of the test solution to preclude galvanic effects, and the cell
is sealed to the round or square/rectangular specimen with
O-rings arvay foom the high-stress gage section. Solt¡tion
can be circulated hom a large stoÉge volume and at a con-
stant flow ¡ate. The cell should include reference and
counter electrodes to enable specimen (working electrode)
polarization rvith siaodard pote¡tiostatic (or galvanostatic)
procedures [38,39,59,79). When fixing potential or current,
care should be taken to correctly ground or isolate the test
specimen, to uniformly polarize the gage surface, to account
for lR effects u'hen necessary, and lo isolate counter-
electrode reaction products. Provided that potential is con-
trolled, there is probably oo reason to control the oxygen
content of thc solution. Tempemture is maintained betwecn
subzero and boiling levels with a heater or cooling coil, a FIG- l6--Lrn¡ax¡ally loaded srnooth-gage specimen and
specimen thermocor.rple, contro! electronics, and a conden- environmental chamber for high.cycle CF experimenta-
sation appaÉtus. Cells for more complex environments t¡on wilh aqueous chlor¡de solutions at near ambient
are detaiied in ensuing subsectior¡s on E¡vironmental Cell temperatures fal.
Dcsign,
CF studies have not provided such information, often be-
Paranteter Measurement, Cotltrol, cause of time-intensive slow frequency exfrcriments a¡d tbe
and Cotnputer A ut ot11.ttio n man]¡ important variables. A sense of the variability in CF
The maximum and minimum applied loads (or, alter- data is porlrayed by the extensive HCF results collected for
nately, displacements) are measured with a load cell (or C-Mn and alloy steels in manne environments [58]. The
remotely attached extensometer'/L\aDT) and controlled distribution of HCF lives at a given stress range $,as ana-
during a HCF expcriment. Ao is calculaied f¡om standard lyzed based on Weibull statistics applied to a data base of
elastic solutions for bars under uniaxial tension, or beams 30 000 points for stecls in benign environmcnts [82]. While
subjected to bending. Elastic strain range is calculated f¡om instnrctivc, these statistical results are not necessarily rele-
and gage displacement is not twically measured. vant to high-cycle CF rvhere electrochemical reactions in-
^o/E troduce additional vaúability.
Crack Delection Futlrre work must address two areas to proüde the foun-
Total load cl,cles to failure are measured, but crack initia- dation fol. statistically based analyses of high-cycle CF (as
tion and growth are not monitored during an HCF experi- rvell as enüronmental LCF and FCP). For simple laboraton,
ment. IDfoÍnation on these siages of HCF is critical, but conditions, the Weibull analysis of mechanical HCF failurc
difficult to obtain. Methods for CF crack detection are probability [82] must be extended to include CF. Second,
discussed in the subsection on Small Crack CF Methods, variable load, temperature, and environment chemistry his-
tories are likely to be complcx in applications and signifi-
Data Analysis and Ettaluation cantly affect CF life. Such historv effects have not been
High-cycle CF data are presented in a logarithmic plot of studied. The scaling of Basquin relationship data to prcdict
stress range versus cycles to failure according to the Bas' the life of a strucnrre is qualitative and uncertain. Either the
quin Larv (Eq 1). Dara are also plotted as srress amplirude local st¡ain approach to CF crack formatio¡/early growth
(Ao/2) 't ersus reversals to failure (2N¡ for simple wave, lifc or the fracture mechanics analysis of CF propagation
forms). The Basquin Law is based on the initial applied proüde a better foundation for life plediction and failurr:
elastic srress mnge and does not consider the complicating analysis.
effect of a growing crack on Material property constants
o; á, and the endurancc limit^o.(or fatigue strength at a given Smooth Specimen Merhod
number of cycles) are environment-sensitive. The mechani- for Low.Cycle CF ^€,(N)
cal information that should be l-epoñed \ ¡ith HCF data is
sta¡dardized (see ASTM E 468), and electrochemical factors Goteming Standards
should be cited as discussed in this manual. Expeúmcnts to characterize low-cycle CF life according
Design and alloy development studies require mean as to the Coffin-Manson rclationship (Eq 2) follow f¡or¡
well as minimum (lower bor¡nd) Basquin relationships and an ASTM standard for LCF of metals in air, and a classic
statistics on the distribution of versus Nl data. This dis- ASTM manual on laboratory methods (see Ref 37
tribution depends on the fatigue^odamage mechanism. Most and ASTM E 606, Practicc for Strain-Controlled Fatieue
 CHAPTER 26- ENVIRONMENTAL CMCKING II
Testing). Lo\\-cycle CF experiments are detailed elsewhere l ala 5
- ,qI
133 36, 74,831, and r\pical data are prcsented in Figs. 3 and 7.

Specinrcns and Loading

Unilbrrn-gage or mild-radius (lrourglass) round specimens
are subjected to uniaxial tensile loading rvith rigid gripping
and a test machine that pnrüdes for either tensior)-
compression or tension-telsion snaio cycling. Square or
rcctangular specimens have also been successfully cm-
ployed. Specimen aligúnent is critical for this rigid gripping
systcm [8,1]. Total axial displacement is generally controlled, l. Wo.l,ñC .l..trod. 2. !uc¡r. .ñ.ñ!..
3 6rip¡
with regard to maximum and minimum limits as well as §. E¡tan.oñ.r.r 6 r.i!lo¡.! i.r.
time depcndence, while load is measured, often with a com- 7 o-.iit 6 R!l.r.nc. .r..rod. 9. iúb¡.r Dond¡ lO c.rni.. .r..ro¿.
putcr-automated servoelectric ol servohydraulic closed-loop
test machine. Such machines proüde a variety of stÉin-time
profiles. Loading frequencies are spically less than those
employed for HCF experiments because fuilure occurs in less
than lM cycles. Lorv cycle CF experinrents diffe¡ f¡'om the
HCF case in that gage displacement must be measured with
sufficient resolution to apply bctwee¡ 10r and lfr].
^sP
Env ironntental Cell D es ign
Cells for environment containment and control are i<len
tical tor LCF and HCF (see previous subsection rvith this
title), LCF cells are, ho\\,ever, more complicated becalrse of
the requircment to measurc specimen gage displacement, as aAJú\n.,h:eh.¡.BurFun¡r
illustrated in Fig. 17 [J3,3ó], For simple aqueous enürDn-
mcnts, diametral ol axial displacemcnt is measured by a
contacting (but galvanically insulated) extensometer, per-
haps cmplol.ing pointed glass o¡ ceramic añns extending
from a bodv located outside oI the solution. A hcrn, etically
sealed extensometer or LVDT can be submergcd in many
electrolytes over a range of tempeÉtures and pressures.
Alternately, the specimen can be gripped in a horizontally ¡3. o¡l'sphst dkrd¡d ¿rÉ.¡
'nd.!
mountcd test ñachine, and half-submerged in the electro-
l],te, \vith the exte¡someter contacting the d¡y side of the b
gage (Fig. 17a) [J3]. For both simple and aggressive envi-
FlG. l7--€ñvlrorünental chambers for low.cycle CF in: (a) an
ronments, grip displacement can be measurtd extemal to elecholyte at aÉ¡erú ternpemtut€ 1331, ar¡d (b) h¡gh-lentperature
the cell-contained solution, as shown in Fig. l7b for high- water [361.
temperature u¡ater in a pressurized autoclave [34,3ó]. It is
necessary to conduct LCF experiments in air (at tempera-
ture), with an extensometer mounted directly on the speci- stress a¡d stmin ¡angc calculations are not accu¡?te. E\peri-
mcn gage, to rclate grip displacement and specimen strain. ments are often terminated and failure is defined for a pcrcent
decline in Tota! shain mte, average plastic stmin rate, or
Pofa Éfer Measurenrcnl, Conlrol, ^o. of displacemcnt cycling should be maintained
the frequency
and C o í1p Lt te t Aut o t nat io n constant during 1]rc lo\uc,vcle corrosion fatigue cxpeúment.
Applied load and gage displacement are measured Personal computer programs are ar,ailable to control the
throughout an LCF experiment. Frorr¡ these data, it is pos- closed-loop test machine during an LCF expcriment and to
sible to calculate true and A€P, where axial plastic analyze load-displacement-time data.
strain mnge equals (^Er ^d,-^eT, For thc hourglass speci- Crack Detection, Data Analysis, and EvaluLtion
^o/Á). can bc measured at any
men, tñ.re total diametral strain
time, and converted to axial strain according to [37] Thcse procedures are ide¡tical for LCF and HCF, as dis
cussed in the preüous subsections, Crack Detection and
E=(o/E)(1,2v¿)-2ed (4) Data Analysis and Evaluation.

If or is mair¡tained constant by the test machine, Fracture Mechanics Methods

then ^Er increases
^s¿ and decreases until the hystercsis loop for Corrosion Fatigue Crack Propagation
^d at a constant^Ép
stabilizes form for a ryclically hardening mate-
rial, and üce-versa for a softening alloy [237]. The stabilized- Gotenting Standatds
Ioop value of axial is used in the Coffin-Manson Law to Experiments to char¿cterize CF cÉck propagation kinetics,
correlate N/, When^€p substantial crack glowth occurs, these in terms of LEFM Paris relationships (Eq 3) and near-AK1¡¡
12 CORROSION ?ES?S AND STANDARDS MANUAL

data, are guided by an ASTM standard for metals in air Displaceñenl transducer
(ASTM E 647, Test Mcthod for Measuremcnt of Fatigue
C¡?ck Growlh Rates), a compilation o{ laboratory experi-
ence \vi1h this standard [84], and a review of inert enüron-
ment FCP testing [85]. The ASTM standard contains an
appendir specific to CF crack growth in marine environ-
ments (ASTM E 647 and Ref86). Procedu¡es for CF in other
enüro¡ments are not standardized; horvever, methods have
evolved for specific technologies [2,4]. CF d¿ldN data are
presented in Figs.4,5, 8,9, and l3 to 15,

Specimens and loading

CF crack propagation data are obtained with a variety of
notched and precracked specimen geometries that are q'ell-
charactenzed in terms of stress iñtensity and compliance
functions [85,87]. The Mode I compact tension, single-edge
cmck, three- or four-point bend, altd center-cracked tension
specimens are used commonly, and are prepared based on
standardized procedures (ASTM E 647). Specimen in-plane
dimensions are selected to guamntee elastic deformatio¡)
with limited small-scale crack tip plasticity. Specimen
thickness, and the plane stress or plane st?in deformatio¡
state, is a variable. Closed-loop servohydraulic test ma-
chines are most effective lor CF propagation experiments,
ñith the control parameter being load. (Load-line displace-
ment or crack mouth opening displacemeñt cor¡trol are
somctimes used.) Such machines proüde a range of load or
displacement waveforms (sinusoidally time-dependent is
q¡pical) and frequencies (10-4 to 100 Hz arc tl?ical !alues).

Env i ro nn tent al C ell D es ign

Cells fo¡ CF crack propagation expenments are designed
to control solulion composition and specimen electrochem-
istrl analogous to HCF and LCF (sce previous subsections
with this title), while allowing for measurements of applied
load, crack opening displacement, and crack length. A vari-
ety of approaches is reüerued elseu,here, including electro- FlG. l8-+nv¡ronmental chambeE for CF in electrolytes
chemical details for seveml enüronments [4]. Two cells for where: (a) the CT spec¡men is loaded horizontally and dlpped
ambient temperature electrolytcs are shoi!,n in Fig- 18. If ¡nto solution [4], and (b) the CT crack is enclosed by a
the test machine and loading axis are mounted in a horjzon- clamped cell and polarized potent¡ostat¡cally. ln parl b load
tal plane (90' to the normal orientation), thcn the cornpact (Pld¡splacemed (^) data are recorded by computer and
tensio¡ crack tip can be dipped into solution r,vhich is ex- autographically for coÍrpliance measurement of crack length
posed to air without complex sealing (Fig, l8a). The alter- and lGr,
nate approach in Fig. 18b employs a vertical loading axis
\üth a segmentcd Plexiglas or Teflon cell, sealed to the faccs
of the compact tension specimen i!,ith O-rings and includ- remote containers and including high pressure and tem-
ing a short segment in thc notch mouth. Solution flolv is peÉture compensation capabilities. Procedurcs to eliminaie
through the notch, parallel to the cmck f¡ont. Small cells galvanic couples and to maintai¡ solution puritv arid com-
clamped to specimen surfaces (Fig, l8b) arc equally effec- position are identical to those cmplo.ved in HCF and LCF
live for center-through-cracked plate specimens. Specimens experime¡ts. Crack opening displacement is measured with
with sur{ace cracks ot single-edge cracks are effectively con- a remote or immerscd extensometer or L\¡DT- The cell must
tained in environmental cells that are large and sealed to not iüterfere with specimen loading or displacement. For
the round or flat ends inboard from the grippjng points example, in Fig. l8b, thc shaded midportion is a {lexible
188]. Compact tension and surface crack specimens have membrane designed so that cell clamping forces do not al-
been contained in pressurized metal autoclaves \vith elec- ter specimen compliancc. This is importanf for aco.rrate
trolytes or steam at elelated tempemture (Fig. l9) [89]. In measurements of ctack closu¡e.
this particutar stud¡r, a yoke rvas employed to simultane- Typically, metal-belloNs/gasket sealed HIGH VACUUM
ously tesi two spccimens in one autoclave and load ñame. chamberc are utilized for environmental fatigue experi-
Refere¡ce and counter electrodcs are readilv employed in ments in inert or deleterious gaseous en\,i¡ro[ments L4].
the various cells (e.g., Fig. l8b), perhaps with salt bridges to Such an apparatus is outside the scope of this review.
 CHAPTER 26- ENVIRONMENTAL CRACKING 13

due to this current distribution in the mctal, arc small (less

than 1 ñV) and probably unimportant. Nonetheless, pm-
de¡ce tlictates thal the influence of applied cuúent be
tested by employing an independent monitor of cmck
length in limited qualification and calibration experiments.
Third, the electrical potential signal olten increases \\¡ith
increasing load in the fatigue cycle becausc electrically con-
ductive crack surfaces are increasingly parted. Accordingly,
potential should be measured at maximum load, and errors
in crack length due to residual "crack surface-shorting con-
tact" should be corrected based on post-test crack length
measu¡ements [94]. Finally, solutio¡ flow or temperature
changes can upset the stability of the electrical potential
signal dtre to thermally-induced voltages and material resis-
tance changes-
GroundJoops betr,veen potentiostat and electrical poten-
tial crack monitoring electronics degrade the quality of
polarization as well as CF cmck length and gro\-,"th mte
measurements. A successful approach to this problem is
based on a specimen (rvorking electrode) that is grounded
commonly \üth the test machine, constant-ct¡üent polver
supply and EPD amplifier, coupled with a potentiostat that
uses a grounded working electrodc. In this case the speci-
mcn should not bc grounded virtually through an opera-
tional a¡nplifier. With this procedure, and the seveml-ohm
(or larger) altematc clrrent path through thc t]?ical load-
ing system and test machine, it is not necessar,.r to electri-
FlG, l$-Two compact tension spec¡mens mounted in a h¡gh cally isolate the CF specimen from the grips. As a test of
pressure,temperatule sia¡nle§s steel autoclave capable of goundJoop inteF"ity in CF, guarantee that specimcn elec-
contain¡ng water, steam, or acldified |üS bearing b.ine envi- t¡ochemical current does not change, at fixed electrode po-
ronments [489]. tential, upon revesing the polariry of thc cmck monitoring
current.
Giren the success of the direct-EPD method, with cu¡rent
Ctack l-e ngt lt M e axre n rcnt applied tbrough the bulk of the CF specimen, there is gen-
CF propagation experiments are unique in the need to erally no need to employ an indirect method based on a foil
monitor crack length, often over a long time. Much has been gage bonded to the specimen surface and solely carrying the
$ritten on two videly employed methods, dircct or altemat- applied currcnt. This latter method eliminates the effect of
ing current electrical poter¡tial difference and compliance applied current on cmck electrochemistry (if such an effect
(see ASTM E 647, andRets U,90,91), as r.vell as on less-tried exists); however, long-term creüce and galvanic co¡rosion
methods such as eddy current, acoustic wa!e, optical, or associated with the attacl¡ed foil may be important. CF
crack su¡'face marking [92]. Compliance and EPD are cmck grorvth in the midregion of a specimen is reasonably
broadly caliblated and well-suited fo. precision (f25 ¡rm or indicated by compliance or direct EPD, but not by the
better), Iong-teIm-slable monitoring of crack length in many surface-mounted foil gage method.
common fractu¡re mechanics specimens and aggressive CF
enüronments. Thcse methods can be computer-automated Pal,anxeter Measurenent, Cont rol,
for test machinc and stress intensity contrcl (sec follorving and C o111p Lú er Aut otl tat io n
subsection). The principles and instrumentation for each Applied load and crack length ñom electrical poteltial or
mcthod arc detailed elsewhere (ASTM E ó47 and Rcf 8-7). compliance are measured as a function of load cycles dur-
Scvei'al points are pertinent 1o CF. First, compliance al- ing a CF experiment. Aparl from simple constant load range
Io$§ monitoring of both crack length and crack closure (increasing loading, mode¡rr FCP and CF experimcnts
[9-3]. The advantage of the EPD method is simplicity; it is ^K)
are computer-automated io control the Al(-history, with the
not necessarJ to imme.se a displacement gage in the elec- mode seleciion based on thc goal of the work, be it mecha-
troiyte. (Thc compliance scheme illustrated in Fig. 18b nism- or application-based. Load js computer-vaded, in real
avoids this complication.) The EPD method is best-suited time and af ftequencies between 10-4 and 50 Hz, lo main-
for monitoring the g¡owth of surface fatigue cracks. Sec- tain the crack length dependence of stress intensity range
ond, therc is no eüdence that the I to 50 A dircct or alter- according to (ASTM E 647)
nating current used in the potential diffcrence method
affects CF kinetics. Prcsumably, the resistance to current AK=a,Ko q¡r¡61. - r.,, (5)
flow through the metal is orders of magr¡itude lower com-
pared to that oI the most conductive soluiions in an oc R-value is typically maintained constant as changes. A
cluded crack. Voltage differences along a crack surface, and ^(
programmed C of 0 yields a constant AK ex'periment, §,hich
14 CORROSION TESTS AND STANDA RDS MANUAL

is useful for establishing transient and steady state CF standardization [96]. CF daldN versus AK"¡ data, as well as
grouth mtcs for mechanistic rescarch. Negative C-values rrcsults obtained al high constant R (above about 0.7) or
proüde for a experiment for measuring near- high constant K.,. (see Fig. 5 and subsection, Programmed
^K-decreasing
CF. Positive C gives a experi¡¡ent that Strcss IntensitJ, Experimentation), are reasonably closure-free
^Krs data in a reasonable time
yields ^K-increasing
and confirms stress inten- and are an inirinsic property for a given material-
sity govemed cracking when used in conjunction with á environment system [ó2]. Closure-hee CF data are neces'
nega¡ive C experiment. Guidancc on those values of C that sary for basic studies of crack tip process zone damage
minimize the effect of prior load history is standardized mechanisms, while crack closure phenomena may be im-
(sec ASTM E ó47)-' portant to applications. As an example, corTosion fatigue
cracks in steels exposed to seawatcr at lorv R are arrested by
Data Analysis and. Evaluation cathodic polarization, because calcareous cor-rosion prod
Applied strcss intensity range and CF crack growth rate ucts precipitate within the growing crack and cause crack
arc calculated at regular crack Iength intervals, based on suface closure contact at K levels well above zero f20,97)-
standardized analytical procedures (ASTM E ó47). For con- A-K.ü is substantially less than both the applicd and the
tinuously increasing or decreasing experiments, da/dll is ^K
intrinsic AKrH. Rough intergranular CF crack surfaces, cou-
^.K difference (sccant) or
calculated by either a point-io-point pled with local Mode II displacements, may also promote
incr:emental polt'nomial method. For constant AK, daldN is crack clost¡re. Closure benefits may, however, be limited to
dete¡mined by linear regression of cyclic crack length data. simply loaded laboratory specimens. For example, compres-
The simple secant calculation amplifies daldv variability, sion elements of a complex load history can crush corosion
rvhile polynomial methods average the growth kinetics ovcr debris and crack surface roughness asperitics, and can thus
seven (typically) ¿ versus N points. Growth mte variations rcduce crack closure.
depend on the size of the crack groMh inter-val. It is par- As a second complication, crack tip str.ess, strain, and
ticularly challenging to establish physically meaningful stmin mte lvithin the proccss zone are more fundamental
variations from an average gro\lth rate law. than Ar( or and gove¡¡t CF crack groyth kinetics. It is
FCP variability was considered in conjunction with an in ^K.ff,
not presently possible to unambiguously calculate the st¡css
terlaboratory test program that measured daldN versus intensity dcpendence of these more fundamental parameters
^K
for a well-behaved high-strength steel in moist air [95]. For t16,22-24). Shoji and corvorkers argue that the time-
this best case and 14 laboratories, &¿/d¡r' variability frtm bascd mte of mechanical FCP (d¿ldry' in an inert environ-
replicate standardized experiments rvithin a single labora- meot is proportional to the rate of dislocation emission
tory equaled between lt3,/¿ ard x50o/o (i two rcsidual from thc cmck tip, or equivalently, to the crack tip strain
stándard deviations about the mean regression curve) at rate [98]. The value of daldr¡ for FCP in vacuum, or more
fixed Variability in CF experiments has not been ad- typicall]- moisi air, is therefore an indircct crack tip drjving
dressed^K.quantitatively; however, thc rcsults from the moist force parametcr for correlating CF daldN dau which arc
air FCP prog¡¿m provide a lorver bound. The increased also often stated lvith ¡€spect to a time-ratc. In this ap-
complexity and prolonged test times t,?ical of CF experi- proach, daldl¡ is the product of daldN and f. An example of
ments, as u,ell as the FCP behaüor of more complex alloys, this con'elation is shou.n in Fig. 20 which represents the
should lead to inc¡eased variability and uncertaintv. CF enhancement in d¿ldlv rclative to the air case for three
Two complications are notable for CF experimentation.
CF dald1v versus applicd data may be affectcd by a crack
closure mechanism that ^K depends on aqueous enüronment í 1E-04
ASTM A302-B Sieels At 243 C
exposure (see subsection, Mechanical Variables) [ó,45];
such CF g¡owth kinetics are defined as an extrinsic propcrlv
that may be test method-spccific. As a diagnostic, if CF E 1E.05
E
daldN dcpcnds strongly on /1, if the environmental ot
'r'-""---.
value is high and increases \^,ith decreasing loading^KrH fre-
quency, or if crack arrest occus during CF propagation at 9,¿.0"
constant applied then environment-sensitive crack clo- .1
^K,
sure should be suspected. A bilinear specimen compliance
tracc (o[ applied load vcrsLrs crack mouth or load line dis- .,91E-o7
placement) confirms the presence of crack closure. L]J
Closure is characterized and eliminatcd approximately for !
a given ü/dN bv reducing the applied AK to the dif- E re-o¿
o datA,0.2 < F < o.7
ference between K-o, and K.¡ rathcr than K.", ^¡<.fi,
and Kñi., Kc! .D
A HealB,B=0,333
is detemined by a global compliance method that is nearing E É Heatc,B-07
i: ,E-og a
re¡s
0A IE 07 1E-O6 1E¿5
I 1E,O9
1E-09 1E 1E-04
aDuring tatigue and CF crack propagalion, a südden larye decrease
Time-Based Ak Rale, mm/second
or incrcase in the maxiñum stress inrcnsily level of the load cvcle
produces a slfong reducrion in subsequenl gro\t,(h mtes, or so- FlG. 2G-TirE-based CF propagatlon rate tor several
called delay rctardation. These g¡o\¡lh rates are important, bul arc heats of A«12€ steel ln high-tempeJature water ver-
not stead)-s(a{e and not simply govemed according to Eq 3 [ó-8].
Mosl CF experiments are desigüed and conducred to avoid such
sus ¡r¡echanlcal da/dt for the sarne alloy ln molsi air
and at several R values [991.
 CHAPTER 26- ENVIRONMENTAL CRACKING 15

high-sulfur-content heats of a C-Mn stcel in elevated- and the magnilude of current transients depended on the
tcmpcrature water [99]. The speculation is that this rela- sign of the plastic stmin, and the repassivation characteús-
tionship between thc benign and CF time-based latcs of tics for this system varied with cycle count, demonstrating
cracking is followed independent of R, l, and loading the complexitl¡ of CF. This method was employcd to rank
^K, material-e¡vi¡on-
\\,avefofin, as demonstrated for severa! rhe susceptibilis of alloys to CF, based on the stability of
ment systems [98]. In FiC- 20 tlrcsc parameiers are varied surface passive films U0l1.
u,idcly: for example, /between l0-4 Hz and l0-1 IIz, and R
between 0.2 and 0.7, but a siogle CF crack g¡oüth law is S¡tall Crack CF Methods
observed. Based on the film mpture (and perhaps HEE) An impo¡1ant goal of CF experimentation and modeling is
mechanism, environmental d¿ld¡ should increase with in- to quantitatively couple smooth spccimcn and fracture me-
creasing crack tip strain rate L22-24), ancl henceTvith the chanics approaches to unde¡stand tbe total life of compo-
mechanical daldti: as suggested in Fig. 20, nents u,ith microscopic defects. Studies of the so-called
"small crack problem" have contributed in this regard [ó].
Specialized Corrosion Fatigue Experiments Small crack size can be a particularly important variable
that affects CF propagation rates 1102,1031. For example,
Several new CF experimental methods have evolved over CF cracks sized betwcen 100 and 1000 Lrm grew up to 1000
the past decade. fold faster than predicted compared to long crack compact
tension specimen daldN data at fixed for the case of a
Programoted Stress I ntensity ErpeiDrcntatiotl high-strength mafensitic stcel in NaCl ^,K,[,/04]. Such crack
Real-time computer-control of stress intensity during a geometry effccts are traced to differences in crack solution
CF experime¡t provides impoftant beneñts. For cxample, mass transport and crack surfacc electrochcmical reactions
CF experiments can be designed rvith a large negative C- that govern HEE and film rupture processes fló,102,1031.
value (Eq 5) to produce continuously decreasing at con- Both electrical potential and high magnification optical
stant applied K-n" and increasing R [ó2, /O0]. This^K
approach methods have bec¡ dcvcloped to monitor the formation and
minimizes the complicating effect of crack closure aod pro- gro*.th of CF cracks smaller than 500 }rm 1105,10ó1. Each
üdes near-AKrH data, albeit at high R. The CF results pre- method is capable of micron-level resolution. The electrical
sented in Fig- 5 were obtained based on this method [44]. potential approach monitors average short crack growth
Since both and R change during this tlpe of experiment, into the specimen bulk, while microscopic methods focus
the effects ^(
of these trvo mechanical paramcte)'s must be on su¡face crack interactions with spccific microstructuml
charactcrized and understood lvhen using the constant K-.. features including inclusions and corosion pits. The data
method in CF [ró]. Second, variables such as elect¡ode po- presented in Fig.2l ',vere obtained f¡om in situ monitoring
tential, solution composition, or fiequency are easily of AM024 in aqueous chloride solution with a long focal
changed as the crack grows at constant to probc subtle length (15 to 40 cm) and high magnification (500x with
^,K
growth mtc changes for basic research [ó/,ó4]. A constant I pm resolutio¡r) optjcal microscope interfaced rvith a ser-
segment can be conducted over a¡ interval of CF crack vohydraulic test machine and video system [,10ó]. Micro'
extc¡sion,
^1< then can be step-increased or decreased at sfructLlrally small CF cracks initiated at co¡stitücnt
^(
constant r<;ax [51,ó2,64). The data presented in Figs. 9, 13, particles aDd grew at mtes that were equal to values ob-
and 14 werc obtained with this method. tai¡red rvith the standard LEFM method discussed in the
subsection on Fracture Mechanics Methods. While the
Cyclic Strain- Induced D issolut ion
The cyclic-mechanical depassivation meihod involves
mcasuremenf of t¡ansient electrochemical current during Alloy 2024T3
cyclic plastic st¡aining of a smooth specimen in an electro- Oeaéraled NaCl C700 mVScE)
lyte at 6xed potential [J4, /0,/]. A three-electrode cell, cou- to_¡
pled with a fast-response potentiostat and tbe mechanical
LCF procedures described in the subsection on the Smooih
Specimen Mcthod, are cmployed in this regard. Data i¡- to'5
clude time-dependent applied plastic strain, stress, and an'
odic current density. The phase difference between the
mechanical and electrochemical parameters, the strain de-
pendence of the cl¡r'rent density during repeated repassiva
tion rcpair of ruptured suface films, the anodic charge
passed per fatigue cycle, and the char€e accumldation with
increasing cycles and time are interpeted to probe CF dam- 10'7
age mechanisms. For example, peak anodic current density 110
and the cycle-cr,rmulative charge increased with increasing §ress ¡ñlen§¡ly taclor range (Mp. m
'r2)
strain rate for LCF of a ferritic stainless steel in NaCl, con-
sistent with the fil¡n rupture model [3,1]. (This current re- FlG. 2l--CF propagallon rate versus lor micrGstruc-
flects metal oxidation to produce cations in solution and in ^K lo deaerated
turally small cfticks in AA2O24 exposed
formation of the passive film, or, collectively, metal re- aqueous chloride at f¡xed potential. CYack growth was
moval.) Additionally, the time dependence of repassi\ation monitored by in situ optlcal microscopy [106'1.
1ó CORROSION TESTS AND STANDARDS MANUAL

chcmically small crack effect is not observed for the system

h Fie. 2l L1061, data of this tlT)e are impo¡1ant and lacking
for a range ofmaterials and enüronmcnts 1102-1051.
The use of short crack specimens provides an important
benefit for cor^rosion fatiguc experimentation. Since high-
resolution crack moDitoúng is employed, crack growth
mtes arc quan¿itatively defined with small crack extensions
and the associated rcduced N- It is possible to obtain accu-
rate low growth raie CF data at low loadilg frequencies. For
example, a short crack specimen rvas employed to measure
a dald-¡V value o[ 0.5 lrm/cycle at constant A,< and f oI0.0 Hz
during a CF test time of l0 days Uó,1051. A l0- to 2o-fold
longer test time is required to obtain this measurement with
a standard long crack method.

Measurentenl of CF Crack Solution pH and Potenrial

It is important Lo measure occluded crack pH, potential,
and solution composition because these factors govem CF
by either HEE or film ruptu¡r mechanisms. Several experi- FlG. 2Hompact iension specimen and electrode arrange-
mental approaches have succeeded in this regard fo¡ simple ment for in silu measurcment ol crack electode potent¡al, pH,
ambient temperature and complex high-tempe¡ature pres- and solntion composit¡on during CF gotrrth [rA8]. @NACE
lntehalional. All rights reserved by NACE; rep.¡nted w¡th
surized water electrolyfes L|07,1081- Reference and pH elec-
permlss¡on.
trodes were located in small holes drillcd in thc compact
tension specimen to intersect the CF crack plane growing
6:om the notch, as shown i¡ Fig, 22 U081. This method nucleation and coalescencc, smali/short crack growth, a¡d
provides information on the cmck size and position long crack propagation.
dependence oI local pH and potential, as well as on the cf- Implementing the cor¡€ct method for CF life prediction
fects of AK, R, and I Additionall]¡, crack solutiori can be and CF resistant alloy developmcnt is often controversial, as
sampled ñrom cmck-intcrsecting holes for composilion existing approaches (often based on smooth specimen HCF
analysis by ion chromatography and capillary electrophore- data) are challenged by more modem approaches. A con-
sis [./09]. Impoftant data were obtained to test modcls of sensus is perhaps developing; an effective method couples
crack chemistw 172,108) aod, to understand solution- the local straiü approach to CF crack formation and carly
dissolved oxygen and metal sulfide effects on CF gro{,1h to a gi\€n detection threshold \vith the LEFM ap-
[22,23,1091. civen the very small volume of a t)pical CF proach to propagation in order to calculate the summcd
crack, solution extraction methods are likely to upset crack total component life. The recommendation is that the
electrochemistry and alter daldN. Coffin-Manson approach be employed, but that the number of
cycles to f<¡rm a (reasonably) resolvable crack size (perhaps
0.1 to I mm) be measured in place of total cvcles to failure.
APPLICATIONS OF CORROSION FATIGUE Equation 2 then describes the CF crack formation rcsis-
TEST RESULTS tance of a given allov-environment system, with the size of
the initiated crack defined operationally. These material-
Modern Approach to CF Life Prediction e¡vironmcnt pr.operty data are coupled with Neuber's
method or finite element calculations of local plastic strain
A cardinal principle is to design the CF experiment to iso- range in a component to define sen icc initiation life [7].
late and chamcterize quantitatively an¡r one of the four The ñ'acture mechanics appr-oach should be employed to
stages of fatiguc damagc defined in the De6r¡ition subsec- charactcrize CF crack propagation kinetics, with emphasis
tion of this chapter. The choice of stage depends on the on both the microstrl¡cturally small, physically short, and
problem, be it pitling-based crack nucleation in a polished conventional long crack ¡egimes [ó,8]. The Paris rclation-
and rigorously inspected medical implant o¡ steam turbine ship (Eq 3), or more complex formulations, are employed
blade, or macrocmck propagation from a u,eld defect in a u¡ith stress intensity similitude and an analysis of thc stress
targe offshore marine strucarre. If a CF experimcnt meas- and stress intensity condifions of the component to predict
ures total life, without quantifying thc four damage stages, CF propagation life, integmted from the size of the cr¡ack
then basic understanding and component life prediction are formed in the initiation stage [4.1]. A variet¡, of desktop
compromised. This is the situation for standardized high- computer programs have been developed for the LEFM po¡-
and low-cycle fatigue experiments that measure total Nfof a tion o{ the fatigue lile prediction problem [/10]. If nonde-
small laboratory specimen. The CF material properties eñ- stR¡ctive tesling so indicalcs, then the LCF initiation
bodied in the Basquil and Coffin-Manso¡ relationships portion of the problem can be equatcd to zclo, and thc frac-
(Eqs I and 2) are ¡ot directly scalable to predict the livcs of ture mechanics integr-ation stafled at the appropriate cxist-
components of alternate geometries and pelhaps containing ing flaw size.
preexisiing flaws. These data cannot be used to test models The output of an integratcd CF prcdiction method is plots
of CF because Nf embodies cl.clic deformation, microcrack of total c¡clic life
as a fu¡ction of applied strEss range, or
 CHAPTER 26- ENVIRONMENTAL CRACKING T7

crack length versus load cycles at constant applied for electrochemical rcactions, crack tip process zone damage
specific material, time, and enüronment chemistry ^d,varj- processes, and microcrack advance.
ablcs- Coffin-Manson and Paris Law data depcnd on thc 6. Fractographic anallses of CF must be improved, inclnd-
rariables citcd in the section, Factors Controlling Corosion ing quantitati\,e measurement oI crack su¡'face crystallog-
Fatigue. Since a legion of variables is important, a¡d sincc raphy [,/19], and computerized imagc analysis methods to
prolonged CF test times are often required, mechanistic characterize and reconstruct thc CF process [120].
modeling of the nucleation and cmck propagation processes 7.For mcchanistic modeling, CF results must be coupled
is a critical tool to develop algorithms for extrapolating the with tmnsient electrocher¡ical reaction kiEetics, hydro-
results oflimited laboratory expcrimcnts [111]. gen permeation, and hydrogen trapping analyses de-
scnbed elsewhere in this manual.
Examples of Component Service Life Pr€diction
with Laboratory CF Data Acknowledgments
Corrosion fatigue problems hale bcen attacked aggres- This chapte. rvas sritten based on the support of the Of-
sively in several technologies over the past decadc. The cou- fice of Naral Research (Grant N00014-91-J-41ó4, with Dr. A.
pled local stmin-forrnation and LEFM-propagation John Sedriks as the Scienlific Officer), the NASA Langley
approach has not, horvcver, been broadly employed. Early Research Center (Grant NAG-l-745, with Mr. D. L. Dicus as
codified design predictions, using elaslic smooth-specimcn Grant Monitor), and the Virginia Center for Innovative
fatigue data (HCF-SN) adjusted empirically for deleterious Technologv (Technologv Development Center for Electro-
time-depcndent enüronmental effects, are being replaced chemical Science and Engineering, with Professor G. E.
by LEFM predictions of crack propagation from an inspection- Stoner as Director).
based or estimated initial c¡ack size [.117]. Examples of this
procedure rvcre reported for CF in weldcd offshore struc-
tures in the marine em,ironment L1,3,58,111-113f, in-core BIBLIOGRAPIIY
and out-of-corc components in commercial light water nu-
clear reactors l2,22,lll,ll3l, oil and gas pipelines U141, Fatigue 'o2, Anders Blom, Ed., Eneine€ring Materials Advisorl
and aircraft [,115,1/6]. Emphases focused on the conflicting SeNices, West Midlands, UK (2002).
effect of cathodic polarization on CF cmck formation and Gangloff, R. P., "Environment Sensitive Fa(igue Crack Tip Proc-
grouth (marjnc structures), the uni§.ing role of crack tip esses and Propagation in Aerospace Aluminum A¡¡oys," in
strain rate (nuclear reactors), the dcleterious effect of sulfur Fati1ue 02, Anders Blom, Ed., Engineering Materials Adf,iso¡l
co[taminants (nuclear reaclor systems and pipelines), and Serviccs, West Midlands, UK, 2002, pp. 3401-3433.
the CF kinetics of small multiple fatigue cracks (aircraft). casem, Z. and Ganglott, R. P., "Rate-Limiting Processes in Envi
Tens of man-years are tlpically required to address a com- ronmental Fatigue Crack Propagarion in 7ooo-Series Aluminum
plex CF problem, and large databases for SCC and CF re- Alloys," in Ch€ru¡l¡-'v and Electtochemístry of Corrosiotl and
S/¡¿ss Corrosiorl Crackirg: A $nlposiunl Horlorinc the Contrib.t
sulted kom these efforts [58,117]. lions ol R.W. Slaehle, R. H. Jones, Ed., TMS, Warrendale, PA,
2001, pp.501-521.
Future Research Needs in CF Experimentation In addition, the eme¡ging body ot literature on the ettect ot precor-
rosioÍ on látigue lite, particulañy ol áerospace allovs, is impor-
Enüronmental ef[ects have not been rigorcusly incorpo- tanr. These include the tollou'ing:
rated i¡1 fatigue life prcdiction proccdures [1/O]. The timc Barler, S. A., Sharp, P. K., Holden, G., and Cla&, C., "Iniliátion and
dependence of CF, the many important interacting vari- Early Grc$,th ot Fatigue C¡acks in an Aerospace Aluminum Al-
ables, and seve¡al uncenainties confound the problem, loy," Fati9lte and Fractu-e of EkgúE¿ring Materiols and Srnc-
From the experimental perspective, LCF and LEFM-based ares, V ol. 25, 2002, pp.ltl 125.
DuQuesnay, D, L., Underhill, P. R., and Brirt, H. J., "Fátigue C¡ack
laboratory CF methods must be improved to add¡ess the
Gro\rth trom Corosion Damage in 7075-T6551I Aluminum Al-
f ollowing unceft ainties: loy Under Aitcra& Loading,' lntematíonal Joumal of Fatique,
Vol. 25, 2003, pp.37l-377.
1. Methods must bc furthcr developed to pr-obe the growth
Fawaz, F. A., "Equivalent Initial Flaw Size Testing and Analysis of
of single small CF cracks sized below 500 pm, and the in-
TÉnsport Aircraft Skin Splices," Fatigüe and Fmcl re ol Etlgi-
teraction and coalcscence of multiple small cracks must neeing Materíals and Sttuc tltre s , V ol. 26, 2OO3 , pp - 279-290.
be characterized. Both LCF and LEFM approaches must Sp€nce, S. H., Wilhams, N. M., Sronham, A. J., Bachc, M. R.,
be modified in this rcgard. Ward, A. R., Evans, W. J., Hay, D., Urbani, C., Cra$,ford, B. R.,
2. Near-threshold CF crack formation and propagation, and Loader, C-, and Clark, G., "Fatigue io the Presence of Corrosion
environmenrdependent cmck closure, must be chamcter- Pitling in an Alumunum Alloy,' in Fatigue'02, Anclers
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3, Load- and cn\.ironment-spect¡um history cffects on CF Sha¡p, P. K., Mills, T., Russo, S., Clark, G.. and Liu, O., "Effect of
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sure occluded crack chemistry, tmnsicnt cmck surface F.LtiEue , Vol. 26 , 2OO4 , pp . 615-427 .
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R. H., in Small-Crack Tesl Melhods, ASTM STP 1149, J. M. washinslon, DC, 1992.
t-arscn and J. E. AIlison, Eds-, Sociely tor Testing t.//91 Slavik, D. C., wen, J. A., and Ganslofi, R. P., Journal of Ma
^¡¡erican
and Matcrials, Philadelphia, 1992,pp. l1ó-1ó8. tcrials Research, Vol. 8 , 1993, pp.2482-2491.
[./0ó] Piascik, R. S. and Willal.(i, S. A., Fatigue and Fracture ot Engi U20l Kobayashi, T. and Shockey, D- A., "Computalional Recon-
neering Materials and Stmctures, vol. 17,1994, pp 1247 1259. struc(ion of Environmentá¡ly Acceleraled Cyclic Cra.k
[./07] Gabelta, G. and Rizzi, R., Corosion Sciencc, Vol. 23, 1983, Grc\\'th in Reactor Stecls," Paper 5ó3, Corrosion 89, NACE,
pp. 613-ó20. Houston. TX, 1989.
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oluminum alloy plote ol room lemperqture. Crqck or¡enlqlion is L-T [Reference
3.r.2.1.ó(DI.