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STP 1298
Effects of the Environment on the

Initiation of Crack Growth
W. Alan Van Der Sluys, Robert S. Piascik, and Robert

Zawierucha, Editors
ASTM Publication Code Number (PCN):

04-012980-30
ASTM
100 Barr Harbor Drive
West Conshohocken, PA 19428-2959
Printed in the U.S.A.
Library of Congress Cataloging-in-Publication Data
Effects of the environment on the initiation of crack growth / W. Alan

Van der Sluys, Robert S. Piascik, and Robert Zawierucha, editors.
p. cm. -- (STP : 1298)

Includes bibliographical references ( p. ) and index.
ISBN 0-8031-2408-2
1. Metals--Corrosion fatigue. 2. Metals--Cracking. 3. Metals-
-Environmental aspects. 4. Nuclear reactors--Materials--Cracking.
I. Van der Sluys, William Alan. II. Piascik, Robert S.
II1. Zawierucha, Robert, 1941-
TA462.E38 1997
620.1 '66--dc21 97-12774
CIP
Copyright 9 1997 AMERICAN SOCIETY FOR TESTING AND MATERIALS, West

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Printed in Ann Arbor

April 1997
Foreword
This publication, Effects of the Environment on the Initiation of Crack Growth, contains
papers presented at the symposium of the same name held in Orlando, Florida, on 20-21
May 1996. The symposium was sponsored by ASTM Committee E-08 on Fatigue and
Fracture, G01 on Corrosion of Metals, and Subcommittees E08.06 on Crack Growth
Behavior and G01.06 on Stress Corrosion Cracking and Corrosion Fatigue. The sympo-
sium was chaired by W. Alan Van Der Sluys, Babcock & Wilcox; Robert S. Piascik, NASA
Langley Research Center, and Robert Zawierucha, Praxair, Inc. They also served as edi-
tors of this publication.
Contents
Overview vii
STRESS CORROSIONCRACKINGINITIATION
The Role of Stress-Assisted Localized Corrosion in the Development of Short

Fatigue CrackS~ROBERT AKID
Pitting Corrosion a n d Fatigue Crack Nucleation~GIM s. CHEN, CHI-MINLIAO,

KUANG-CHUNGWAN, MINGGAO,AND ROBERTP. WEI 18
Initiation of Stress-Corrosion Cracking on Gas T r a n s m i s s i o n P i p i n g ~

B R I A N N. LEIS AND JEFFERYA. COLWELL 34
CRACK INITIATION IN AGING AIRCRAFT
O n the R e q u i r e m e n t for a Sharp Notch or P r e c r a c k to Cause

E n v i r o n m e n t a l l y Assisted C r a c k Initiation o f / ] - T i t a n i u m Alloys
Exposed to Aqueous Chloride EnvironmentsmDAViD G. KOLMANAND
JOHN R. SCULLY 61
Corrosion-Fatigue C r a c k Nucleation in Alclad 2024-T3 Commercial A i r c r a R

Skin--CHARLES G. SCHMIDT,JAMESE. CROCKER,JACQUESH. GIOVANOLA,
CHRISTINEH. KANAZAWA,DONALDA. SHOCKEY,AND THOMASH. FLOURNOY 74
Effect of P r i o r Corrosion on the S/N Fatigue P e r f o r m a n c e of A l u m i n u m

Sheet Alloys 2024-T3 a n d 2524-T3mGARY a. BRAY, ROBERTJ. 8UCCI,
EDWARD L. COLVIN, AND MICHAEL KULAK 89
STRESS CORROSION CRACK INITIATION IN NUCLEAR ENVIRONMENTS
Influence of a Mixed Nitrate Solution on the Initiation a n d Early G r o w t h of

Stress Corrosion Cracks in a Low Alloy SteeI--REDVERS N. PARKINS
AND MAHVASH MIRZAI 107
E n v i r o n m e n t a l l y Assisted C r a c k i n g of 3.5NiCrMov Low Alloy Steel U n d e r

Cyclic Straining--YOSHiYUKIKONDO, MASARU BODAI, MAO TAKEI,
YUJI SUGITA, AND HIRONOBU INAGAKI 120
C r a c k Initiation in Low Alloy Steel in High T e m p e r a t u r e W a t e r n

HARVEY D. SOLOMON, RON E. DELAIR, AND ANDY D. UNRUH 135
A Process Model for the Initiation of Stress-Corrosion Crack G r o w t h in

B W R P l a n t MaterialS--MASATSUNEAKASHIAND GUENNAKAYAMA 150
MODELING
Strain Energy Density--Distance Criterion for the Initiation of Stress

Corrosion Cracking of Alloy X-750mMERYL M. HALL,JR. AND
DOUGLAS M. SYMONS 167
Molecular Modeling of Corrosive Environments in Cracks--OTAKAR JONAS 182
CRACK INITIATION IN CORROSION F A T I G U E - - I
Interactive Effect of Dynamic Strain Ageing with High Temperature Water

on the Crack Initiation Behaviour of Reactor Pressure Vessel Steels--
JOHN D. ATKINSON, ZHI-JUN ZHAO, AND JIAN YU 199
Effects of Strain Rate Change on Fatigue Life of Carbon Steel in High-

Temperature WatermMAKOTO HIGUCHI,KUNmIROnDA, AND
YASUHIDE ASADA 216
Effects of Temperature and Dissolved Oxygen Contents on Fatigue Lives of

Carbon and Low Alloy Steels in LWR Water Environments--
GENROKU NAKAO, MAKOTO HIGUCHI, HIROSHI KANASAKI, KUNIHIRO IIDA,
AND YASUHIDE ASADA 232
CRACK INITIATION IN CORROSION F A T I G U E - - I I
Evaluation of Effects of L W R Coolant Environments on Fatigue Life of

Carbon and Low-Alloy Steels--OMESH K. CHOPRAAND WILLIAMJ, SHACK 247
Corrosion Fatigue Behavior and Life Prediction Method Under Changing

Temperature Condition--H1ROSHl KANASAKI, AKIHIKO HIRANO,
KUNIHIRO IIDA, AND YASUHIDE ASADA 267
Advances in Environmental Fatigue Evaluation for Light Water Reactor

Components--KAZUO KISHIDA,TOSHIMITSU UMAKOSHI, AND
YASUHIDE ASADA 282
Indexes 299
Overview
The initiation stage of environmentally assisted cracking can have a profound effect on
the life of a component. Little is known about the damage mechanisms that occur during the
important early stages of crack formation, e.g., nucleation and small crack growth, com-
pared to the crack propagation regime. This Special Technical Publication reviews current
understanding on the effects of the environment on the initiation of crack growth relating to
specific areas, including: (1) mechanistic modeling, (2) life prediction, (3) nuclear industry
environmental cracking, and (4) recent aging aircraft durability issues. The following is a
brief overview of the symposium papers included in this topical volume.
Session h Stress Corrosion Cracking Initiation

Akid discussed the role of stress-assisted localized corrosion on the development of short
fatigue cracks. Corrosion experiments were conducted under cyclic and static stress, using
low and high strength steels and stainless steels in chloride environments. Surface film
breakdown, pit development and growth, pit/crack transition, and environment-assisted
Stage I and Stage II crack growth were monitored. Each process is considered to be of
primary importance during the early stages of stress corrosion and corrosion fatigue crack-
ing.
Chen, Liao, Wan, Gao, and Wei assess two proposed pit to crack transition criteria: (1)
the stress intensity factor for an equivalent crack, equal, or exceeded the threshold stress
intensity factor for corrosion fatigue crack growth (CFCG), and (2) the time-based CFCG
rate exceeded the pit growth. Validation of a proposed pitting corrosion/fatigue crack
nucleation criterion is presented and discussed in terms of open hole alloy 2024-T3 experi-
ments conducted in 0.5M NaC1 solution.
Leis and Colwell studied the processes leading to the formation of crack-like features as
well as early crack growth of stress-corrosion cracking on the exterior of gas transmission
piping. Observations show that cracks with dense spacing tend towards dormancy, whereas
the sparsely spaced cracks continue to grow. Fracture mechanics based analysis is used to
rationalize the crack pattern observations.
Session II: Crack Initiation in Aging Aircraft

Kolman and Scully examined the effects of a sharp notch or crack tip on cation accumula-
tion-hydrolysis-acidification, potential drop in solution and resulting hydrogen produc-
tion, and localization on dynamic strain in titanium alloys exposed to 0.6 M NaCI. It was
shown that the drop in potential down a sharp crack is severe enough to enable hydrogen
production, even when the applied potential is more positive than the reversible potential for
hydrogen production. The effects of a sharp notch on the interplay of mechanics, film
rupture, and hydrogen uptake are also examined.
Schmidt, Crocker, Giovanola, Kanazawa, Shockey, and Flournoy investigated the pro-
cesses that influence the transition from salt water corrosion pit development to fatigue
crack formation in Alcad 2024-T3. Results suggest that the nucleation of corrosion fatigue
cracks involves two competing mechanisms: hydrogen effects in the cladding and electro-
chemical dissolution at constituent particles in alloy 2024. Cracks do not necessarily nucle-
vii
viii EFFECTS OF THE ENVIRONMENT ON THE INITIATION OF CRACK GROWTH
ate at the largest corrosion pit, suggesting that a contributing factor to crack nucleation from
a pit may be the creation of a local region of weakness.
Bray, Bucci, Colvin, and Kulak evaluate the effect of prior corrosion on the S/N fatigue
performance of 1.60 and 3.17-mm-thick aluminum sheet alloys 2524-T3 and 2024-T3. The
fatigue strength of alloy 2524 was approximately 10% greater and the lifetime to failure, 30
to 45% longer than alloy 2024. Two main factors are believed to have contributed to the
better performance of 2524: less damaging configuration of corrosion pits and its better
fatigue crack growth resistance.
Session III: Stress Corrosion Crack Initiation in Nuclear Environments

Parkins and Mirzai provide a database that will allow prediction of stress corrosion
cracking failures in nuclear reactor components exposed to the radiolysis of moist air which
produce nitric acid environments. Constant strain stress corrosion tests, at 50 or 100% yield
stress, were conducted on welded nickel based steel samples exposed to a mixed nitrate
solution for various times. Selective attack at relatively short exposure times was observed
where grain boundaries intersected the specimen surfaces.
Kondo, Bodai, Takei, Sugita, and Inagaki studied environmentally assisted cracking of
3.5NiCrMoV low alloy steel under cyclic straining in water at 60~ Test results showed
that higher strain range, lower strain rate, longer strain hold times, and higher electric
conductivity caused increased charge transfer, which resulted in shorter crack initiation life.
A prediction model tbr crack initiation life was proposed based on observed charge transfer.
Soloman, DeLair, and Unruh investigated the fatigue crack initiation of WB36, a German
low alloy steel (LAS), tested in high-temperature high-purity water. The tests were per-
formed at 177~ in water containing 8 ppm 02. H2504 additions were also used in some
tests to raise the conductivity of the water from 0.06 to 0.4-0.5 ~xS/cm. The crack initiation
and growth data are correlated with water chemistry.
Akashi and Nakayama investigated the initiation of stress corrosion cracking in boiling
water reactor materials. They suggest that stress corrosion cracking can be divided into six
(three deterministic and three stochastic) separate processes. The paper examines the influ-
ence of three stochastic processes: (1) nucleation of corrosion pits, (2) initiation of micro
cracks, and (3) the coalescence of microcracks, on the stress corrosion cracking initiation
process.
Session IV: Modeling

Hall and Symons showed that the initiation of stress corrosion cracking in alloy X-750
exposed to high-temperature-deaerated water occur at a variable distance from the notch or
crack tip. The initiation site varies from very near the crack tip, for loaded sharp cracks, to a
site that is one grain diameter from the notch, for lower loaded, blunt notches. The existence
of hydrogen gradients, which are due to strain-induced hydrogen trapping in the strain fields
of the notch and crack tips of the SCC test specimens, is argued to be responsible for
variation in the crack initiation site.
O. Jonas presented a corrosion model for iron-based alloys. Interactions of aqueous
environments in cracks are expressed as relative bonding energies for individual molecules
and other parameters. The results indicate relative aggressiveness of environments, types of
chemical/corrosion reactions, and the rate of mass transport to the crack-tip.
OVERVIEW ix
Session V and Vh Crack Initiation in Corrosion Fatigue

Atkinson, Zhao, and Yu investigated the effect of dynamic strain aging (DSA) on stress
corrosion cracking of reactor pressure vessel steels exposed to 250~ water. Results support
the coincidence of temperature and strain rate between the DSA hardening and the suscepti-
bility to environment-assisted cracking of reactor pressure steels. The mechanistic role of
DSA and its interpretation with other influential variables in the enhancement of stress
corrosion cracking are discussed.
Higuchi, Iida, and Asada studied the effect of strain rate on the fatigue life of carbon steel
exposed to high-temperature water containing dissolved oxygen. A series of strain-con-
trolled fatigue tests were conducted with strain rate changed stepwise or continuously. A
method using the product of the environmental effect and the strain increment within a unit
time interval in a transient period is integrated from the minimum strain to the maximum.
This modified strain rate approach method is discussed in detail.
Nakao, Higuchi, Kanasaki, Iida, and Asada investigated the fatigue design of pressure
vessel components. They show that decreased fatigue life of STS410 carbon in simulated
boiling water reactor water is dependent on temperature and dissolved oxygen. An environ-
ment parameter ratio, Rp, is proposed for the estimate of the fatigue life at a certain
temperature and dissolved oxygen content.
Chopra and Shack summarized the available data on the effects of various material and
loading variables such as steel type, dissolved oxygen level, strain range, strain rate, and
sulfur content on the fatigue life of carbon steel and low-alloy steels. The data have been
analyzed to define the threshold values of the five critical parameters. Methods for esti-
mating fatigue lives under actual loading histories were discussed.
Kanasaki, Hirano, Iida, and Asada performed strain controlled low cycle fatigue tests of a
carbon steel in oxygenated high-temperature water. The corrosion fatigue life prediction
method was proposed for changing temperature conditions. The method is based on the
assumption that the fatigue damage increased linearly with the fatigue cycle strain incre-
ment. The fatigue life predicted by this method was in good agreement with the test results.
Kishida, Umakoshi, and Asada proposed a method for evaluating the environmental
fatigue lives tbr the Class I reactor pressure. A revised simplified method is developed Ibr
the determination of a fatigue usage factor for a component in which loading transients
include variation of temperature, strain rate, and oxygen content in addition to the strain
range. A number of examples are presented in which an environmental effect correction
factor is determined for components in a nuclear pressure boundary.
W. Alan Van Der Sluys

Babcock & Wilcox;
Alliance Ohio; symposium chairman and
STP editor
Robert S. Piascik
NASA Langley Research Center;
P.O. Box MS 188E,
Hampton, Virginia; symposium co-
chairman and STP editor
Robert Zawierucha
Praxair, Inc., Tonawanda, New York;
symposium co-chairman and STP editor
Stress Corrosion Cracking Initiation
Robert Akid
THE ROLE OF STRESS-ASSISTED LOCALIZED CORROSION IN THE

DEVELOPMENT OF SHORT FATIGUE CRACKS
REFERENCE: Akid, R. "The Role of Stress-Assisted Localized Corrosion in the Develop-

ment of Short Fatigue Cracks," Effects of the Environment on the Initiation of Crack Growth,
ASTM STP 1298, W. A. Van Der Sluys, R. S. Piascik, and R. Zawiemcha, Eds., American
Society for Testing and Materials, 1997.
ABSTRACT: The initial development and growth of defects from 'engineered' surfaces,
i.e. fine abraded, polished, shot peened etc., often dominates the resulting component
lifetime, particularly for materials of high strength and limited ductility. When subject to
the conjoint action of stress and environment this lifetime is impaired and reductions in
fatigue strength are often observed resulting from a reduction in defect development time,
often termed 'initiation', and enhancement in defect growth rate.
A number of factors exist which influence the rate at which defects, such as pits/cracks,
develop. Included in these are; physical and chemical material surface condition, the
nature of the loading mode, test frequency and electrochemical micro-climate at the
metal/solution interface. Based upon corrosion experiments conducted under cyclic and
static stress, using low and high strength steels and stainless steels in chloride
environments, the following events; surface film breakdown, pit development and growth,
pit/crack transition and environment-assisted stage I and stage II crack growth have been
observed. Included in these experiments is that of the Scanning Reference Electrode a
technique adapted to evaluate stress-assisted localised corrosion, a process considered to
be of primary importance during the early stages of stress corrosion and corrosion fatigue
cracking; particularly for actively corroding systems.
KEYWORDS: corrosion fatigue, pitting, scanning reference electrode, microstructural

fracture mechanics, short cracks, modelling
Senior Research Fellow, SIRIUS, Structural Integrity Research Institute University of

Sheffield, Mappin Street, Sheffield, S 1 3JD, England
Copyright*
Copyright by ASTM1997 byrights
Int'l (all ASTM International
reserved); www.astm.org
Fri Dec 30 21:53:51 EST 2011
4 EFFECTS OF THE ENVIRONMENT ON INITIATION OF CRACK GROWTH
~TRODUCTION
Corrosion processes coupled with the application of an applied stress can have a profound
effect on limiting the useful lifetime of structures and components. In this respect a
number of procedures are adopted to reduce the risk of corrosion. Included in these
methods is the selection of corrosion resistance materials, the application of coatings or
the imposition of a potential, more negative than the free corrosion potential, to suppress
metal dissolution. In the latter case over protection of a structure can lead to
embrittlement through the adsorption of hydrogen. However, this mechanism is
principally restricted to components and structures containing pre-existiag defects, i.e.
cracks which are of a size appropriate for inducing hydrogen embrittlement [1-3]. Where
conditions are such that engineering surfaces, i.e. smooth polished or peened, are
essentially free from defects the process of metal dissolution can have a marked effect on
the fatigue resistance of a metal.
This paper sets out to illustrate through examples from experimental studies including the
Scanning Reference Electrode Technique (SRET) and fatigue tests conducted within air
and under corrosion conditions, how the anodic dissolution process can modify the early
stages of defect development such that the in-air fatigue limit may be eliminated. In
addition microstructural fracture mechanics based models adopted to incorporate the
influence of variables such as stress state, test frequency and electrochemical condition are
discussed.
F A T I G U E C R A C K D E V E L O P M E N T IN A I R AND AQUEOUS ENVIRONMENTS
Numerous references within the literature may be cited which emphasise a period of the
fatigue process designated as the 'initiation stage'. This term is somewhat misleading as
close attention to many of these studies shows that the term initiation refers to a period,
prior to which a defect, 'ofa specified size', may be observed. The value of this period, as
a fraction of total life; is subject to the users ability to find the defect of interest and in
many cases little attention is paid to cracking along the boundary of an inclusion or at
subsurface inclusions or defects. Recent studies [4-6] have shown that cracks can develop
within the first few percent of lifetime and grow microscopically until arrested at some
feature associated with the microstructure, e.g. a grain or phase boundary. That cracks
develop early in the lifetime and exhibit marked accelerations and decelerations in growth
is recognised through the development of Microstructural Fracture Mechanics (MFM)
models [7-8].
When smooth specimens are tested within aggressive environments the lifetime is often
reduced to a fraction of that observed in air. Observation of the early stages of defect
development [9-13] show that for carbon steels in chloride environments, pit development
and stress assisted dissolution accelerate the transfer of a stage I shear crack to that of a
fatal stage II tensile crack. Typically the processes involved during air and corrosion
fatigue are illustrated in Fig. 1.
AKID ON THE ROLE OF STRESS-ASSISTED CORROSION 5
af
0-1> 0"2 > O"3 0"3/
] Stage II cracking
0"1/
/
/ / ~ /
r
OI 9
~ / ~/
r
(D
_1
Surface film ~/Sta
ge 1/11 / /
breakdown and /
transition(air) /
(1) Pit development / ' \ \ //
E3 / / \ /
/ _.Z. ~ ........ ~ 0-2
/ ~ non-propagating
/ ~ - ~ c r a c k (fatigue limit)
I / / / \ S t a g e 1/11t r a n s i t i o n ( e n v i r o n m e n t )
;tag; / cracking
a0
Lifetime (log N)
FIG. 1 Schematic of defect development stages in air and an aggressive environment.
The ratio of corrosion fatigue to air fatigue lifetimes varies from approximately unity to
less than 0.2 depending upon the applied stress level, test frequency and solution
conditions. At high stress levels lifetimes are short and the effects of corrosion are small.
As the stress falls below that of the in-air fatigue limit the mechanical crack driving force
decreases and the relative, chemical driving force i.e. corrosion, increases. This
interaction between mechanics and corrosion is also observed as the defect approaches a
microstructural barrier [11]. Furthermore as the crack length increases, and a physically
short crack (PSC) develops, the corrosion fatigue and air fatigue crack growth rates
merge as the mechanical crack tip stress intensity controls the growth rate at the expense
of corrosion assisted growth.
The major events occurring during corrosion fatigue are discussed in detail below and
illustrated in fig 1.
M E C H A N I S M S C O N T R I B U T I N G TO I N I T I A L D E F E C T D E V E L O P M E N T .
(a) Surface film breakdown
Surface film breakdown is dependent upon the nature of the material, solution conditions,
the electrochemical state at the material/solution interface and the application of a stress.
Where dissolution is known to influence the fatigue resistance of a material the processes
leading to the formation of a pit are extremely important. A delay in the formation of pits
through a delay in film breakdown has the effect of increasing corrosion fatigue lifetime.
It has been observed during torsional corrosion fatigue tests [14], conducted in 3'A%
NaCI, using a high strength tempered martensite steel (tJy = 1440 MPa) that the lifetime
was extended on the addition of 0.1M sodium nitrite to the solution, see table 1. In this
case the effect was attributed to a delay in the development of pits.
Solution composition Applied shear stress (MPa) Fatigue lifetime (cycles)

0.6M NaCI 613 205000
0.6M NaCI + 0.001M NaNO2 613 230000
0.6M NaCI + 0.1M NaNO2 630 3.6 x 106
Table 1 Influence of NaNO2 additions on fatigue lifetime in 0.6M NaCI
Similar effects were reported by Boukerrou & Cottis [15] where it was observed that,
despite a tendency to pitting, pits were small and few in number. It should be stressed that
this phenomenon is not an increase in initiation time but an increase in the time taken for
film breakdown and subsequent pit development, which assuming a given rate constant for
film dissolution, may be associated with an increase in the thickness of the surface film in
the nitrite solution, lsaacs [16] described equivalent effects when comparing pit half
lifetimes for different degrees of surface oxidation although Ambrose and Kruger pointed
out that film thickness was not the sole factor in influencing the time to film breakdown
[17]. The effect of the addition o f a passivating solution on the initial development of pits,
using a heat treated low carbon steel, is further illustrated in tests using the scanning
reference electrode technique [ 18].
(b) Pit development and growth
Pit development and growth is similarly influenced by those factors discussed for film
breakdown with the nature of the inclusion content within the material microstructure and
the magnitude of stress both additionally influencing the rate of pit growth. The inherent
nature of material microstructures gives rise to sites at which localised corrosion processes
(pitting) can occur [19, 20]. Typical examples include non-metallic inclusions, especially
Manganese Sulphide, and inter metallic 2nd phase panicles. Depending upon the nature
of the environment, for example solution pH, localised corrosion can also take place at slip
bands developed during fatigue loading [21]. However it is curious that not all sites give
rise to pitting, a feature that may be associated with the tenacity of the surface film and the
relationship between inclusion/microstructure, local stress state and distribution of
corrosion current over the surface the metal.
The rate of pit growth may be considered to be principally governed by the material, local
solution conditions and stress state. For systems in which pitting leads to crack
development the relationship between pit propagation rate and stress state is seen to be of
paramount importance if realistic models for corrosion fatigue are to be developed.
Experimental methods are available to evaluate pitting rates [22, 23], however these
techniques fail to account for the effects of an applied stress.
Several studies have illustrated the influence of cyclic stress on the local corrosion current
[24, 25] highlighting the many fold increase in corrosion activity as bare metal is exposed
during the fracture of surface films. However, there appears to be no data available in the
literature which illustrates the change in pit current density as a function of applied stress.
Preliminary SRET studies [26] show that local pit activity increases on the application of
an applied stress. Fig. 2 shows that this activity apparently depends upon the
electrochemical conditions applied. In this recent study 316 stainless ste~l was tested in
aerated 0.6M NaCI with the specimen being held under either potentiostatic or
galvanostatic control. Local pit current density was then measured as the surface stress
was changed, in this case to a value of 90% of the material's yield strength. From fig 2a it
can be seen that pit current density decreases on the application of a stress under
galvanostatic control but increases under potentiostatic control, fig 2b. Under
galvanostatic control it is assumed that there is a limiting fixed anodic current available,
which is distributed between the pit walls and outer external surfaces.
10 .....~
Constant current (0. l m A ) 5 "Econst = OmOV (Vs SCE)
5
E
o ..................... - / . . . .
-10
,pp,~ds~,,~,P~\ //
-10
-15
o~ (a)
-20 f i i -15 i r i t
2000 4000 6000 BOOD 10(300 2000 4000 6000 8000 10000
Surface displacement (microns) Surface displacement (microns)
FIG. 2 Influence of stress on pit current density under (a) galvanostatic and
(b) potentiostatic control. 316 Stainless Steel, 0.6M NaCI.
On the application of an applied stress corrosion activity on the surface increases at the
expense of that within the pit due to the area ratios of the pit and external surfaces and the
limited availability of current. However, under potentiostatic no such current restriction
exists and the current is free to increase as the applied stress level increases, Fig. 2b.
(c) Pit to crack transition
Previous fatigue studies [27, 28] comparing the development of stage II tensile cracks
from stage I cracks, in both air and 0.6 M NaCI solution under torsional loading, show
that both the crack size and the fraction of life (N/N0, at which the stage UII transition
occurs, decreases for corrosion fatigue loading. Typically it was found that in air a
transition from stage I to stage II occurred around 120 p_m (surface crack length)
equivalent to 4 prior austenite grain diameters. Under corrosion fatigue this transition
length is reduced to 30-60 lam that is, one to two prior austenite grain:l:[iameters. The
ability of a crack to transfer, at an early stage, from the shear growth pla~e to the tensile
plane therefore has a marked effect on the resulting fatigue lifetime, as illustrated
schematically in fig 1 and experimentally in table 2.. Hence corrosion processes which
assist in bypassing or accelerating this stage give rise to a considerable reduction in fatigue
resistance; to the extent of eliminating the in-air fatigue lifetime.
Shear stress Environment transition length Cycles to Lifetime Nf

range (MPa) at/n (p.m) transition (cycles)
Nvn
854 air no transition oo
920 air 120-150 (stage I/II) 2.6 x 106 4.8 x 106
920 0.6M NaCI 30-60 (pit/stage 1) 15000 80000
Table 2 Influence of Stage 1/II transition on fatigue lifetime.
Greater attention has recently been given to the pit/crack transition stage, that is, the point
at which a crack is clearly established at a pit site. Given this criteria and based upon the
analysis of data from a wide range of corrosion fatigue studies, it would seem totally
inappropriate to assign a given fraction of lifetime (N/N 0 value to this important stage.
Fig 3 summarises the data from several sources [28-34] plotting the fraction of lifetime, at
which a crack develops during corrosion fatigue, against the applied stress level.
It can be seen from this figure that no overall trend exists and the transition point can be
independent of either the applied stress or fraction of lifetime. If however this data is
replotted, as shown in Fig. 4, in terms of the time taken for the pit/crack transition to
occur, as a function of applied stress, it is immediately apparent that a correlation exists.
The spread of data arises due to three factors, namely the nature of the loading mode, that
is, torsion, tension, or bending, the test frequency and the pit depth at which the transition
occurs. The effect of frequency on the pit/crack transition is shown in Fig. 5 which plots
the time taken for the pit/crack transition to occur against the test frequency for tests
conducted under two different loading conditions [28, 29].
0.7
zx Akid [12]
o Wu/Murtaza [28/31 ]
~ 0.6 o Wu [29]
§
o Dmytrakh [30]
0.5
.1= 9 Guilhem [32]
v Goto [33]
0.4
"~. 9 Duabler [34]
.9o 0.3 9 Nakajima [35]
Z 0.2
~-o 0.1
0.0 i n ~ ~ n n J
U. 0 200 400 600 800 1000 1200 1400
Applied Stress (MPa)
F I G . 3 Fraction of life to pit/crack transition as a function o f applied stress level for

various steels, under different loading conditions, within chloride solutions.
\ 9 Akid [12]
1 e+ 5 , Wu/Murtaza [28/31
9 Wu [29]
o Dmytrakh [30]
e~
o o Guilhem [32]
"G le+4
9 Goto [33]
Daubler [34]
v Nakajima [35]
'r. le+3 .... slope = -5
2
/
De . . . .
5
in :ed frequency ~ \\
le+2 Increase m trmlsition size 9 \
x
100 200 400 500 700 1000
Applied Stress (MPa)
F I G . 4 Relationship between the time to a pit/crack transition and applied stress level for
various steels, under different loading conditions, within chloride solution.
A reasonable approach to modelling this first stage would therefore necessarily

incorporate both frequency and stress terms as shown in equation 1.
T = A g(stress) + B g(frequency) + C (1)
where T is the time for a pit to develop into a crack and A, B and C are constants
dependent upon material and environment.
le§
\ /-J SI~ = "075
8
le+5
9 ~ 11
\ \ "-.... " t3
le+4
\~. \
? x ) \ "x7
9 Wu [29], 1200 MPa " ".
I
le+3
D Wu [14],600 MPa \
E & Wu [141,400MPa
I-- v Rollins [38], 310 MPa
le+2 i i ~ i i
0.01 0.10 1.00 10.00 100.00
Loading Frequency (Hz)
FIG. 5 Influence of test frequency on time for pit/crack transition
As previously shown in Fig. 2 it appears that the influence of stress on pit propagation rate
depends upon the imposed electrochemical conditions. It is also apparent from recent
corrosion fatigue studies [29] that the contribution to pit growth from the mechanical
driving force, i.e. stress, is also limiting. Fig. 6 shows a plot of pit growth coefficient,
derived from plots of pit growth versus time, versus applied stress level. It can be seen
from this set of results that the greatest influence of stress on pit growth rate occurs
between 800 and 1200 MPa, the lower stress value being close to the in-air fatigue limit
stress.
10-2
Q 2 N steel (0.12%C), s r = 790 M P a
y
3pt bending, R=O.01, f=O. 1Hz
v Artifieial seawater
o
0 10-3
o
n~
.c:
600 700 800 900 1000 1100 1200 1300 1400 1500
Stress Range Act, (MPa)
FIG. 6 Influence of applied stress on the rate of pit growth
From fig 6 it would appear therefore that three regimes exist, namely,
i o < 800 MPa corrosion dependent pit growth

ii o 800-1200 MPa stress dependent pit growth
iii o > 1200 MPa corrosion dependent pit growth
Regime i and iii have limiting effects on the pit growth rate suggesting threshold stress
levels for minimum and maximum pit growth rates. A feature, which it is suggested may
be related to the degree of plasticity associated with the microstructure immediately
surrounding the pit.
Based upon the previous discussion it remains for the influence of loading mode on the
pit/crack transition to be addressed in order for a unified corrosion fatigue model may be
developed. Previous work [12] shows some promise in this respect with the application of
an equivalent strain parameter. Further work [13] is now being carried out based upon
complex loading conditions of mixed tension and torsion. Preliminary results would
suggest that corrosion, i.e. pitting, dominates the microstructural fracture mechanics stage
for an actively corroding system (steel/NaCl) whereas the stress state controls the plane on
which a crack develops for passive system (stainless steel/NaCl). Tests are now being
conducted under mixed-mode stress conditions, in which the applied electrode potential is
12 EFFECTSOF THE ENVIRONMENTON INITIATIONOF CRACK GROWTH
varied so as to evaluate the role o f anodic dissolution and hydrogen embrittlement on both
the stage I and stage II crack growth regimes.
MODELLING SHORT FATIGUE CRACK GROWTH
Much of the work devoted to describing the behaviour of short cracks developed under
corrosion fatigue conditions has been based upon the processes illustrated in figure 1.
Previous studies [9, 10] adopted an approach which incorporated the summation of a
mechanical driving force and a chemical driving force, see equation 2.
(2)
~IVt....osionfatigue= ~ ....hanical+dNenviron....l
Here the mechanical crack growth term was determined from tests conducted in air while
the environment term was based upon an anodic dissolution current and the application of
Faraday's law. Assuming the continued presence of this latter term ensured that obstacles
to crack growth, i.e. microstructural barriers, could be overcome resulting in an
elimination of the in-air fatigue limit.
More recent studies, see references [2,11,18]. suggest that for steel in chloride
environments the early stages of growth are dominated by pitting and stress assisted
dissolution. Equation 2 has therefore been modified, as described in equation 3, to account
for these effects.
da (3)
~_~Ncorros,on fatigue = ~_~pmmg + dNIEMSC
da + dNIEPSC
da
here the pitting term describes the (stress-assisted) growth rate of a pit, the EMSC term
relates to the dissolution-assisted growth rate of a stage I shear crack and the EPSC term
describes the environment-assisted growth rate of a stage II, physically short tensile crack.
The crack growth rates for the EMSC and EPSC stages are described in equation 4 and 5
dd-~N = A(Ay)a(di-a) (4)

EMSC
as = B(Ar)P.- D (5)
~NEPSC
where a represents crack length, d~ a microstructural dimension e.g. grain size, i represents
the number of barriers (grains) and Ay represents the mechanical driving force term which
may be stress for uniaxial loading or an equivalent strain term for mixed mode loading [36,
39]. The term D in equation 5 represents a threshold long crack growth term. A, B, ct and
13 are constants depending upon material and environmental conditions. More detailed
descriptions of the modelling described in equations 4 and 5 is given in reference 7.
As previously discussed the first stage, that is, pit growth is not only time dependent, but
also depends upon, local solution chemistry [40], the applied stress state and
microstructural condition, assuming that the pit dissolution rate is influenced by the degree
of plasticity within the grains adjacent to the pit. A notable feature of pitting during
corrosion fatigue is the early development of a pit on the surface and then a marked
absence of progressive surface pit growth. This is not too surprising based upon a
consideration of the stress concentration of a notch and the nature of an occluded cell.
Furthermore the transition of a pit to a crack is not expected until a critical aspect ratio
has been attained; a further reason for in-depth pit development at the expense of surface
pit growth.
As discussed above a consideration of the influence of plasticity on corrosion fatigue crack

growth should be incorporated into corrosion fatigue models, particularly for those
systems where pitting is not a major consideration, for example slip band dissolution of
stainless steels.
A model based upon the development of the plastic zone ahead of h crack has been
developed [37] and takes the form shown in equation 6.
dN - C Arp (6)
here rp represents the plastic zone eliminating from a crack tip which takes on a value
depending upon the relationship between the crack length and the microstructural
dimension, e.g., grain diameter, and C and B are constants depending upon material and
environment. It is further suggested that this equation can be modified to incorporate the
influence of test frequency[29], as given in equation 7.
da _C(f)(Arp)m(f) (7)
dN
here the coefficient and exponent values C and m are dependent upon the test frequency.
SUMMARY
The early development and growth of defects, i.e., pits/cracks, at surfaces subject to the
conjoint effect of corrosion and cyclic stress can result in a drastic reduction in fatigue
performance, in effect causing an elimination of the in-air fatigue limit.
The results presented in this paper suggest that for defect development from smooth
surfaces the development of pits and the transition from a pit to a crack can dominate the
ultimate lifetime of a component. The major process involved during these stages is that
of stress-assisted dissolution, where the role of dissolution is one which assists the
development of a crack and reduces the influence of microstructural texture on crack
growth.
Based on this premise it is considered that, for systems where pitting leads to crack
development, a corrosion fatigue model should incorporate an initial stage which predicts
the influence of stress on pit growth. Assuming such an approach and given a knowledge
of the effects of test frequency, solution conditions and critical defect size for the
transition from a pit to a crack it is possible to make realistic predictio/ls of corrosion
fatigue lifetime.
ACKNOWLEDGEMENTS
The author would like to thank all his fellow researchers without whom this paper could
not have been written. In addition gratitude is expressed to both British Steel Technical
and the Royal Academy of Engineering for providing the author's current Fellowship.
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AKID ON THE ROLE OF STRESS-ASSISTEDCORROSION 17
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Response and Behaviour of Short Cracks", Submitted to Fat. F~ct. Eng,. Mat.
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226, 1994, pp 29-63
Gim S. Chen, l Chi-Min Liao, 2 Kuang-Chung Wan, 3 Ming Gao 4 and Robert P. Wei 5
PITTING C O R R O S I O N AND FATIGUE CRACK N U C L E A T I O N
R E F E R E N C E : Chen, G. S., Liao, C. M., Wan, K. C., Gao, M. and Wei, R. P., "Pitting
Corrosion a n d Fatigue C r a c k Nucleation," Effects of the Environment on the Initiation
of Crack Growth". ASTM STP 1298, W. A. Van Der Sluys, R. S. Piascik, and R.
Zawierucha, Eds., American Society for Testing and Materials, 1997.
ABSTRACT: To assess two proposed criteria for the transition from pitting to cracking,
corrosion fatigue crack nucleation experiments were conducted on open-hole specimens
of 2024-T3 (bare) alloy in a 0.5M NaCI solution at room temperature at different loading
frequencies, in conjunction with coordinated studies of pitting corrosion and corrosion
fatigue crack growth (CFCG). The proposed criteria are: (1) the stress intensity factor
AK for an equivalent crack (by modeling the pit as a semi-elliptical surface crack) equaled
or exceeded the threshold stress intensity factor (AKth) for CFCG, and (2) the time-based
CFCG rate exceeded the pit growth rate. The nucleation of fatigue cracks was found to be
associated with large corrosion pits. The size of the crack-nucleating pits was larger at
the lower frequencies. This frequency dependence reflects the competition between pit-
ting and CFCG. Validation of the proposed criteria in terms of the experimental data is
presented and discussed.
KEYWORDS: pitting corrosion, fatigue crack nucleation, corrosion fatigue crack

growth, constituent particles, cyclic-frequency effect, fatigue threshold, rate competition,
aluminum alloy, sodium chloride solution
Material degradation due to corrosion and corrosion fatigue crack nucleation and
growth has been recognized to significantly affect the airworthiness of civilian and mili-
tary aircraft, especially for the current fleet of airplanes that have served beyond their ini-
tial design life [I-3]. The ability to predict the damage development in airframe compo-
nents and structures, therefore, is of great importance in managing timely maintenance for
the aging airplanes, as well as in assisting in the design of new airplanes. Since the de-
Research Scientist, ZCSS, Lehigh University, Bethlehem, PA 18015.

2Graduate Student, Dept. of Materials Science & Engineering, Lehigh University, Bethlehem, PA 18015.
3Graduate Student, Dept. of Mechanical Engineering, Lehigh University, Bethlehem, PA 18015.
4Principal Research Scientist, ZCSS, Lehigh University, Bethlehem, PA 18015.
5Professor, Dept. of Mechanical Engineering and Mechanics, Lehigh University, Bethlehem, PA 18015.
18
Copyright*
Copyright 1997
by ASTM Int'lby(all
ASTM
rights International
reserved); Fri Dec 30www.astm.org
21:53:51 EST 2011
CHEN ET AL. ON PITTING CORROSION AND FATIGUE CRACK 19
velopment of corrosion related damage in airframe components and structures includes

(1) localized corrosion damage (pitting and exfoliation), (2) transition from pitting and/or
exfoliation to fatigue crack growth (crack nucleation), (3) early stage of corrosion fatigue
crack growth (short-crack regime), and (4) corrosion fatigue crack growth (long-crack
regime) [1], a reliable prediction would largely depend on the quantitative understanding,
characterization and modeling of these elemental processes of damage. This study is fo-
cused on the process of fatigue crack nucleation, which is viewed as the transition from
pitting to corrosion fatigue crack growth.
Because of the conjoint effects of active environment and cyclic loading, corro-
sion fatigue produces corrosion and mechanical damages and this process is inevitably
influenced by the type of corrosion and the level of mechanical loading. For example, it
has been demonstrated that at a prescribed strain amplitude, fatigue crack nucleation in an
A1-Li-Cu alloy can shift from anodic slip-bands to corrosion pits with decreasing strain
rates [4]. In another study [5], anodic slip dissolution was found to be responsible for the
nucleation of fatigue cracks in an A1-Li-Zr alloy at high stress levels, while the pitting
mechanism dominated at low stress levels. These observations suggest that a competition
between the rates of accumulation of corrosion and mechanical damages determined the
mechanism of corrosion fatigue crack nucleation. With greater strain rates or higher
stress levels, active slip-bands (the mechanical damage) can be produced more effectively
and lead to fatigue cracking before the corrosion damage (pitting) reaches a critical level
to induce crack nucleation. With reduced mechanical driving force, however, pitting cor-
rosion would predominate until the local stress condition of the pits is favorable for the
onset of fatigue crack growth.
As reported recently [6,7], pitting corrosion in a 2024-T3 (bare) aluminum alloy
in NaC1 solution was essentially associated with constituent particles. It was also evident
that individual particle-induced pits coalesced, laterally and in depth, to form larger pits
[6,7]. These corrosion pits can serve as nucleation sites for subsequent fatigue cracking
[8,9]. According to the competition concept described above, the nucleation of corrosion
fatigue cracks in the 2024-T3 alloy may be viewed as the competition between pitting
corrosion and corrosion fatigue crack growth; namely, the transition from pitting to fa-
tigue cracking occurs when fatigue crack growth outruns pit growth [10]. To develop a
quantitative understanding of the competitive nature of the crack nucleation process,
time-related factors that can affect the pit and crack growth kinetics should be taken into
account. In this investigation, therefore, fatigue experiments were carried out at different
frequencies from 0.1 to 20 Hz on open-hole specimens of a 2024-T3 (bare) aluminum
alloy in an aerated 0.5M NaC1 solution. Also, experiments of pitting corrosion and cor-
rosion fatigue crack growth were conducted independently to assist in the quantitative
analysis and modeling of the process.
EXPERIMENTAL PROCEDURES
The material used in this study is a 1.6 mm thick sheet of 2024-T3 (bare) alloy.
Its chemical composition, given in weight percent (wt%), is as follows: 4.24 Cu, 1.26 Mg,
0.65 Mn, 0.15 Fe, 0.06 Si, 0.08 Zn, 0.031 Ti, <0.01 Cr, and balance A1. The microstructure
of this alloy showed a typical elongated and flattened grain structure, with average grain
sizes of 68 ~tm, 39 ~tm and 18 I-tm in the longitudinal (L), transverse (T) and short trans-
verse (S) direction, respectively. The tensile strength, 0.2% offset yield strength, and
elongation of the alloy are 480 MPa, 355 MPa, and 17.0%, respectively.
Free corrosion experiments were conducted on a transverse (IS) surface of the
2024-T3 alloy sheet, since this surface corresponds to the maximum stressed area of the
open-hole fatigue specimen. The LS surface of each sample (about 10 mm long) was
polished, cleaned, dried and then exposed (by full immersion) to a quiescent 0.5M NaC1
solution at room temperature for prescribed periods of time (the free corrosion potential of
the alloy in this aerated solution was -600 mV). After testing, a chromic trio-xide (CrO3)
solution was used to strip oxides and corrosion products from the corroded surface. These
procedures are detailed elsewhere [6,7]. In addition, a replication technique was used to
reveal the pit morphology. An epoxy resin, mixed with proper amounts of hardener, was
cast inside a vacuum bell jar into a mounting mold in which a sample was placed with its
corroded surface facing upward. By alternating between vacuum (102 Pa) and one
atmosphere several times, the epoxy resin was fully infiltrated into the pits and was then left
to harden. The epoxy-metal assembly was removed from the mold and immersed in a 10
wt% sodium hydroxide (NaOH) solution to dissolve the 2024-T3 alloy. The epoxy replica
was then coated with carbon for examination by scanning electron microscopy (SEM).
Center-pin-loaded, dog-bone-shaped fatigue specimens, with a 31.75 • 76.2 mm
gage section, were machined from the 2024-T3 alloy sheet to make the loading axis parallel
to the rolling direction (L). All fatigue tests were conducted at room temperature (20 + 1~
in an aerated 0.5M NaC1 solution (pH = 6 and [O2] = 7 ppm) under an open-circuit condi-
tion. For the study of crack nucleation, a 5.08 mm diameter hole was drilled at the center of
the gage section of the fatigue specimens, and was polished circumferentially to produce
about 1 ~tm rms (root mean square) surface finish. The test was performed under constant-
amplitude, tension-tension loading with a maximum remote stress of 103.5 MPa and a
load ratio, R, of 0.1. Hence, the maximum stress amplitude applied at the circular hole,
(A(~ho~e)..... would be about 288 MPa when the stress concentration effect of the hole is
taken into account [11]. Cyclic-load frequencies,f, of 20, 10, 5, 1, 0.5 and 0.1 Hz were
employed. To study the effects of applied stress, two specimens were tested at (ACrho~e)ma•
of 192 and 144 MPa respectively, at f = 10 Hz. In addition, a specimen was pre-corroded
in the test solution for three days prior to fatigue testing [(A(Yhole)max= 288 MPa and f = 5
Hz]. The fracture surfaces of interest were examined by SEM. For the study of corrosion
fatigue crack growth, the dog-bone-shaped specimens with a single, through-thickness,
edge crack at the center of the gage section were employed. The K-calibration equation
for these specimens, correcting the effect of bending, is detailed elsewhere [12-14]. The
specimens were loaded under either constant-AK or increasing-AK control (R = 0 . 1 , f = 10
Hz) to cover a range AK from 5 to 10 MPaqm, and crack lengths were monitored by an
AC potential-drop technique [ 13-15].
RESULTS
Pitting Corrosion
The results of corrosion experiments recently conducted on the rolling (LT) sur-
face of the 2024-T3 alloy suggested that the pitting behavior was related to constituent
particles and could be surface dependent because of the spatial distribution of the parti-
cles [6,7]. Figure 1 is a composite SEM-micrograph (back-scattered electron contrast),
showing the morphology and distribution of constituent particles in the as-polished,
rolling (LT) and transverse (LS and TS) surfaces of the alloy sheet. Large amounts of
constituent particles were found, and their density in the LT plane was estimated to be
more than 3,000 particles/mm 2 for particles with a projected surface area greater than 1
gm 2 [6,7]. These particles tended to be clustered, with particle banding along the rolling
direction clearly evident in the LT surface. Coupled with the nature of particle distri-
butions on the other two surfaces, Fig. 1 suggests that the constituent particles in the alloy
tended to form planar clusters lying parallel to the rolling plane.
FIG. 1--Back-scattered SEM micrographs of as-polished surfaces of 2024-T3 aluminum

alloy sheet, showing the morphology and distribution of constituent particles in the roll-
ing (LT) and transverse (LS and TS) planes.
In this study, the results of corrosion experiments at the LS surface of the alloy
showed two modes of pitting damage; i.e., general pitting and severe pitting. The former
occurred over the entire specimen surface, leading to small, shallow pits which were es-
sentially associated with individual constituent particles, identical to those observed on
the LT surface [6,7]. The latter, however, occurred at selected sites, and resulted in larger
and deeper pits. Figure 2 shows the cross section of severe pits, along with an inset
showing the pit morphologies at the sample surface (after 500 h of corrosion). The larger
of the two pits is about 600 gm long and 70 gm wide at the surface, and approximately
300 gm deep at this section, indicating that the severe pit tended to grow in the L and T
directions rather than in the S direction. This behavior is attributed to the interactions of
the matrix with a cluster (or clusters) of subsurface constituent particles. Because pitting
is induced by the constituent particles and because these particles tend to be clustered
parallel to the rolling plane [6,7], the severe localized pitting would tend to develop in a
planar shape of damage and conforms to the planar clusters of constituent particles.
FIG. 2--A SEM micrograph of the cross-section (TS surface at a-b) of severe corrosion
pits in a 2024-T3 alloy, with an inset showing the appearance of the corresponding pits on
the LS surface. (Some particles associated with pitting may be seen at A,B,C and D.)
The overall features of pits may be seen more clearly from the epoxy replicas of
corrosion pits. Typical SEM micrographs tbr a sample tested for 24 h are shown in Fig.
3, showing the replica of a severe pit and several general pits. Figure 3a is the top view
of the severe pit, and Fig. 3b provides a better three-dimensional perspective of the pit by
tilting the replica 45 ~ about the pit's short axis (parallel to the S direction) and then
rotating 45 ~ clockwise with respect to the normal direction of the sample surface. It can
be seen that the morphology of this severe pit is irregular but appears overall to have the
shape of a half-discus as compared to the small, dome-like general pits (pit A, for
instance). Based on the features shown in Figs. 2 and 3, (and other observations), the
shape of severe pits in the 2024-T3 alloy may be, by and large, approximated by a flat,
semi-ellipsoid, whose aspect ratios (i.e., ratios of semi-axes) can vary considerably
depending upon the particle distributions. Because they are much larger and deeper than
general pits, severe pits are expected to be the more likely origins for corrosion fatigue
cracking.
FIG. 3--SEM micrographs of the replica of a severe pit, showing the morphology from a
view (a) normal to the sample surface, and (b) by tilting the sample 45 ~ about the S
direction, followed by a 45 ~ clockwise rotation about the sample's normal.
Corrosion Fatigue Crack Nucleation
SEM examinations of the fatigued open-hole specimens indicated that corrosion

fatigue cracks nucleated and grew from one or two larger pits at the circular hole surface
near the area of maximum stresses. For example, Fig. 4 shows the mating fracture sur-
faces of a specimen tested at 10 Hz (#A01F76, (A~hole)max = 288 MPa). The cleavage-like
river patterns emanating and diverging radially from a pit clearly indicate that the pit
served as the fatigue crack nucleus. The well matched fractographic features between
these two surfaces also suggest that the pit size must have remained unchanged after
crack nucleation and growth. For a specimen tested at 0.1 Hz (#A01F20, (A~hole)max ----
288 MPa), the corrosion fatigue process involved a long period of time because of the
low frequency. Figure 5a indicates that the fatigue crack had originated at a large pit.
Numerous small pits and general corrosion damage were found at the fracture surface
near the crack origin, suggesting that active corrosion continued after crack nucleation
over the entire fracture surface. By tilting the specimen 45 ~ about an axis parallel to the
specimen edge, the features of the crack-nucleating pit on the circular hole and fracture
surfaces can be revealed, and are reflected by the relatively deep pitting damage along the
L and T directions (Fig. 5b). The overall features of the crack-nucleating pits shown in
Figs. 4 and 5 are identical to those shown in Figs. 2 and 3. These comparisons clearly
associate severe pitting to corrosion fatigue crack nucleation in the 2024-T3 alloy.
FIG. 4--A mating pair of SEM micrographs of the fracture surface of a 2024-T3 alloy
showing the morphology of a severe corrosion pit which induced fatigue crack nuclcation
in a specimen (A01F76) which was fatigued at./"= 10 Hz.
FIG. 5--SEM micrographs of the specimen (A01F20) fatigued at f = 0.1 Hz, showing (a) a
severe corrosion pit as the fatigue crack nucleus, and (b) the planar feature of the severe
pit by tilting the sample 45 ~ about the axis parallel to the specimen edge.
Based on the fractographic results, the transition point from pitting corrosion to
corrosion fatigue crack growth may be identified with the size of the crack-nucleating
pits. In other words, fatigue cracks start to nucleate and grow continuously at these
critical pit sizes when crack growth presumably outruns pit growth. Since the severe pits
are approximated as a discus-shaped, semi-ellipsoid, they may be modeled as an equi-
valent semi-elliptical crack lying parallel to the TS plane (i.e., perpendicular to the load
axis of the fatigue sample), with a depth of a and a half-width of c, as illustrated in Fig. 6.
Hence, the pit size at transition, (c x a)~, and the corresponding half-width to depth ratio,
(c/a)t~, can be obtained from the fractographic features and are given in Table 1.
From Table 1, it may be seen that at a constant stress amplitude (288 MPa), the
transition pit size appeared to be independent of frequency for f > 5 Hz, but increased
with decreasing frequency below 5 Hz. For the tests at high frequencies (i.e., from 5 to
20 Hz), the results suggest that a threshold pit size was needed for the nucleation of fa-
tigue crack growth, consistent with a fatigue threshold theory [ ! 6,17]; namely, a corro-
sion fatigue crack is considered to have nucleated at a pit when the pit grows to a critical
size where the local mechanical condition (AK) reaches the threshold condition (kKth) for
fatigue crack growth. From a competition viewpoint', the results also imply that fatigue
crack growth had already outrun pit growth at the threshold condition so that the crack
nucleation could take place. On the other hand, the observation of frequency-dependent
pit size (c x a)tr at frequencies below 5 Hz indicates that, at low frequencies, pit growth
may have continued even though the fatigue threshold condition was reached. Fatigue
cracking could not be sustained until the time-based crack growth rate exceeded the pit
growth rate; i.e., the competition theory [ 10].
I- C C
FIG. 6--A schematic illustration of an equivalent semi-elliptical surface crack modeled

from severe corrosion pits inducing corrosion fatigue crack nucleation.
TABLE 1--Experimental results for corrosion fatigue crack nucleation.
Specimen bA~3,MPa f, Hz (c x a)tr, (c/a)t,.or 13t~ ~btr AKtr, MPa4m
A01F29 288 20 25 x 80 0.31 1.103 2.59

16 x 130 0.12 1.023 2.23
AO1F14 288 10 23 x 35 0.64 1.306 2.08
A01F76 288 10 19 • 93 0.20 1.051 2.34
AOIF05 288 5 23 • 60 0.38 1.136 2.39

AO1F39 288 5 20 • 60 0.33 1.114 2.30
A01F74 288 1 39 x 147 0.26 1.078 3.29
A01 F51 288 0.5 38 x 200 O. 19 1.045 3.35

A01F08 288 0.5 34 x 150 0.22 1.060 3.12
31 x 104 0.30 1.096 2.90
A01F20 288 0.1 50 x 250 0.20 1.051 3.85
50 • 247 0.20 1.051 3.85
A01F36* 288 5 50 x 150 0.33 1.114 3.63
AOIF62 192 10 63 • 140 0.45 1.178 2.56
A01F66 144 10 53 • 250 0.21 1.055 1.96
This specimen was subjected to 3-day corrosion in the NaCI solution prior to the
corrosion fatigue testing.
Based on these observations, two criteria are suggested to fully describe the
pitting-induced nucleation of corrosion fatigue crack growth, and they may be expressed
as follows:
zXK > AKth and -~- crack \dtJpit (1)
where g is used as a general term of pit or crack size to make distinction from the c and a
shown in Fig. 6, and dg/dt refers to appropriate time-based fatigue crack growth and pit
growth rates.
Corrosion Fatigue Crack Growth
To obtain quantitative information for time-based corrosion fatigue crack growth,

the behavior of through-thickness cracks of the 2024-T3 alloy was investigated by per-
forming increasing- and constant-AK tests in the 0.5M NaC1 solution, and the results are
used in estimating the kinetics of fatigue cracks growing from corrosion pits in the open-
hole specimens. Although short-crack effects may be of concern, the use of long-crack
data appears to be acceptable, because a recent study [9] showed that small surface cracks
(from 100 gm to 14001.tm) at the notch root of a 2024-T3 alloy exhibited crack growth
rates comparable to those of the long crack tests under identical testing conditions (i.e., in
deaerated 1% NaC1 solution with R = 0.05).
The results of the increasing-AK tests can be expressed by the power law; namely,
dg IdN = C F ( z ~ n = 3.94 x 1011 (z~3.55. The constant-2ff( tests at 5 and 10 MPa~/m in-
dicated a constant dg/dN of (1.10 + 0.09) x 10-8 and (1.10 + 0.02) x 10-7 m/cycle, respec-
tively, showing good agreement with the increasing-zXK data. These results are consistent
with those reported in the literature [9]. Since the cycle-dependent crack growth rate,
dg/dN, of 2024-T3 alloy in NaC1 solution was essentially independent of loading fre-
quency [9,13], the time-based crack growth kinetics may thus be expressed by dg/dt =
(dg/dN)xf= CF ( z ~ n x f, where CF -~ 3.94 x 10 ql and n = 3.55, suggesting that dg/dt is
proportional to the cyclic frequency.
DISCUSSION
According to the proposed criteria, a fracture mechanics parameter, AK, needs to

be used to incorporate the corrosion pit size into the criteria for crack nucleation. Due to
their small sizes relative to the radius of the circular hole, the crack-nucleating pit obser-
ved in this study may be regarded as an equivalent surface crack in the edge of a semi-
infinite plate subjected to a cyclic stress, ktAcy (i.e., (A~hole)max),where kt represents the
stress concentration factor of the circular hole and A~ the remote cyclic stress amplitude
[18]. As such, AK of each pit can be estimated using a stress intensity factor solution for
semi-elliptical surface cracks in which c/a < 1 [19-21]:
zXK = 1.12 ktA~J-4~7

q~ [sin 2
t * + (c/a)2 cos 2 , ] 1/4
(2)
= i [ s i n 2 0 + ( c / a ) 2 c o s 2 0 ] 1/2 dO
O"
where c, a and 0 are defined in Fig. 6, and d~ is a shape factor determined by the c/a ratio
of the pit. According to this equation, AK would be symmetric with respect to the a axis
and varies along the crack front. The maximum AK would occur at the intersections of
the crack front with the surface of the circular hole (i.e., at q~= rd2, see Fig. 6); namely,
(AK)max = (1.12 k t A ~ ' q ~ )/qb. For a crack-nucleating severe pit, the (AK)max at pit-to-
crack transition is defined as AKt, and is expressed as follows:
1.12 ktAo ~t r
(ZkK)max = zXKtr = (3)
qZ~tr
Using the data of (c x a)tr and (c/a)tr shown in Table 1, AKw+for each crack-nucleating pit
can be obtained by Eq. 3 at different stress levels, and is presented in the last column of
Table 1.
Fatigue threshold criterion
According to the fatigue threshold criterion [ 16,17], pitting-induced crack nuclea-

tion occurs when the AK of an equivalent crack, associated with the pit, reaches the fa-
tigue crack growth threshold zkKth; that is, pit-to-crack transition:
AKtr = AKth (4)
From Table 1, however, &Ktr= Agth is satisfied only at the higher frequencies (i.e.,f> 5
Hz), with AKtr ranging from 1.96 to 2.59 MPaqm, even at lower cyclic stresses (i.e. 192
and 144 MPa). The experimental values of AKth for long crack growth in 2024-T3 alloy
in NaC1 solution were found to range from 1.3 to 3 MPaqm, for R from 0.9 to 0.05 [9,22].
Therefore, 2tilth is estimated to be between 2 and 3 MPaqm for R = 0. I. The observed
AKtr for f > 5 Hz agrees well with the estimated z~rs range and is consistent with the fa-
tigue threshold criterion. On the other hand, the increasing values of AKt,. at the lower
frequencies (f< 5 Hz, Table 1) argues for the need of the additional rate competition cri-
terion for fatigue crack nucleation.
Rate competition criterion
According to the rate competition criterion, the time-based crack growth rate
(dg/dt)crack has to exceed the pit growth rate (dg ~dr)pit for pit-to-crack transition. For the
range of c/a shown in Table 1, crack nucleation is expected to originate at the mouth of
the equivalent semi-elliptical crack (i.e., at the end of the c axis shown in Fig. 6) where
the AK is maximal. The dimension c, therefore, would be of interest in this analysis and
will be used to replace g hereafter for the pit or crack size; namely, (dc/dt)crack >-(dc/dt)pit
for the transition.
Pit growth in the 2024-T3 alloy, in terms of a change in pit volume, was found to
vary linearly with time [7,23]; i.e., it followed a Faradaic relationship similar to that ob-
served in other aluminum alloys and steels [10,24,25]. Since the shape of the severe pits
is approximated as a flat, semi-ellipsoid (with principal dimensions of a, b and c parallel
to the T, L and S direction), the volume of the pit, gpit, may be estimated to be 2na2c/3, by
CHEN ET AL. ON PI-I-I-ING CORROSION AND FATIGUE CRACK 29
recognizing that dimension b approximately equals to dimension a (Figs. 2 and 3). Based
on Faradaic law and using 13to represent the c/a ratio, dVpit/dt = d(2na2c/3)/dt = d[(2~3)
(c/~5)2c]/dt = (2rd~2)(c)2(dc/dt) = constant = Ce. This equation can be re-arranged to give
the pit growth rate as follows:
pit 2g
where Ce is the volumetric dissolution rate depending on the pitting current and is not
known.
On the other hand, the time-based crack growth rate for the 2024-T3 alloy can be
obtained by substituting (AK)max= (1.12 ktAcr~ c )/qb into dc/dt = CF (2dQ" x f, and is
expressed in terms of the crack size c as follows:
dc) * n *
-~- crack = CF '(ktAc) . ~ - n .cn/2 . f , where C F = C F.(1.12) n.rc n/2 (6)
At transition, (dc/dt)crack should be equal to (dcldt)pit. From Eqs. 5 and 6, the rela-
tionship between the critical pit size, ctr, and load frequency, f, for crack nucleation is
obtained and given by Eq. 7:
2 2
= [ CP(~tr)2(dptr)n-
n + 4 n* " (f/n+4
(7)
Ctr 2re C F (k t Act)
Substituting the ctr of Eq. 7 into Eq. 3 leads to a relationship between z~tr a n d f a s
follows:
z~r~tr = .'/1:'(1.12 ktA(Y)4 Cp (~tr) 2 ] n+4 n+4

(8)
Equations 4 and 8 are essentially the fracture mechanics based expression of the
two criteria for pitting-induced crack nucleation, and may be shown in a log-log plot of
Z~tr as a function of l/f to demonstrate the pit-to-crack transition behavior in Fig. 7. The
fatigue threshold criterion (Eq. 4) would appear as horizontal lines in the plot, and the
rate competition criterion (Eq. 8) as oblique lines with a slope of 1/(n + 4). The ex-
perimental data of AKt~ associated with correspondingf from Table 1 are indicated by cir-
cular symbols in Fig. 7. Solid lines (based on Eqs. 4 and 8), with a slope of zero and
+ 0.132 (i.e., n = 3.55 for 1/(n + 4)) are constructed to bound the data and are consistent
with the experimental results and the estimated AKth.
10
9
9 /Xcr= 288 MPa
Crack!
O
8
7 [] 3-day precorrosion, Act = 288 MPa
9 &~r = 192 or 144 MPa
6
b-
5
e.,
,.,r &
z~
r
9
~ ~ j ~ ~ Transition Regime
"<1 9
e- Pit Growth Regime
2024-T3 Alloy in 0.5M NaC1

1. , , , ,,tJnl i i i , , l l l l ' . . . . . . . a a i i la,~
10 -2 10-1 100 101 102

Inverse of frequency, l/f (s)
FIG. 7--The relationship between the stress intensity factor range of equivalent cracks at
fatigue crack nucleation and the cyclic frequency applied.
For concurrent pitting corrosion and corrosion fatigue, therelore, the damage pro-
cess may be categorized by pit growth and crack growth dominated regimes separated by
transition regions as indicated in Fig. 7. The onset of fatigue crack nucleation (i.e., the
pit-to-crack transition) is governed by Eqs. 4 and 8, with AK~,.dependent on the variables
in these equations. For the pre-corroded specimen (indicated by the square in Fig. 7) ~Kt,
fell into the crack growth regime simply because a sufficiently large pit had been pro-
duced by precorrosion already to facilitate immediate nucleation and crack growth.
In Eqs. 4 and 8, kd~o"and f a r e determined by specimen design and loading condi-
tions and are deterministic. Other parameters, or properties, however, may vary and be
viewed as random variables. For example, AKth depends on the material, environment
and loading conditions. The parameters, CF and n, for fatigue crack growth require better
mechanistic understanding, and can be a function of frequency [26], or vary with crack
size (short cracks versus long cracks) [13]. Variations in Ce and [3or(qbtr is dependent on
13tr) are believed to be the major contributors to data scatter, as reflected by the "band" in
the transition regime (Fig. 7). A Student's t-Distribution analysis of [3tr in Table 1 gave a
value of 0.29 + 0.10 (99% confidence level) and suggested that [3t,.was not a function of
time. The variation is most likely determined by the local spatial distribution of constit-
uent particles (i.e., particle clusters). An estimation of Ce (using Eq. 8) was made based
on the information given in Table 1 and the values of CF and n. For eight nucleating pits,
(for f_< 5 Hz) Cp was estimated to be between 5.74 x 1017 and 3.72 x 10-16 m3/s. A
quantitative understanding of the probabilistic nature of the damage process, therefore, is
also needed for the development of a reliable methodology for the life prediction [27].
CONCLUSION
Based on the study of pitting corrosion and corrosion fatigue crack growth in a
2024-T3 aluminum alloy in 0.5M NaC1 solution, a quantitative understanding of corro-
sion fatigue crack nucleation has been developed in terms of the competition between
pitting corrosion and corrosion fatigue crack growth. Pitting has been attributed to the
interactions of constituent particles in the alloy with the alloy matrix, and two types of
pitting (general and severe) have been identified. General pitting is associated principally
with single particles, and is by and large benign. Severe pitting is associated with clusters
of particles, particularly those aligned parallel to the rolling plane. The volumetric rates
of pit growth followed a Faradaic relationship and were essentially independent of time.
Corrosion fatigue cracks nucleated from the larger severe pits. The size of the pit
at nucleation (i.e., the transition from pit to crack growth) depended upon the applied
stress and loading frequency, being larger at the lower stresses and frequencies. This de-
pendence reflected the competition between pitting and fatigue crack growth. By model-
ing a severe pit as an equivalent semi-elliptical surface crack, the following criteria for
pitting-induced fatigue crack nucleation were proposed and verified; namely: (1) the
stress intensity factor range (AK) must be equal to or exceed the threshold value (AKth)
for fatigue crack growth, and (2) the time-based fatigue crack growth rate must also ex-
ceed the pit growth rate. For engineering applications, the nucleation criteria may be rep-
resented by a transition AK (AKtr) which delineates the transition from pit to fatigue crack
growth, with AKtr = zS,gthat f > 5 Hz and Z~r~tr increasing with decreasing frequency below
5 Hz for this alloy-environment combination at AO = 288 MPa.
The crack nucleation criteria, taken in conjunction with information on distribu-
tions of constituent particles and pitting and crack growth kinetics, form the basis for the
development of a quantitative methodology for service life prediction.
ACKNOWLEDGMENT
Support of this research by the Federal Aviation Administration under Grant 92-
G-0006 and the Air Force Office of Scientific Research under Grant F49620-93-1-0426 is
greatly acknowledged.
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[13] Wan, K.-C., "Mechanical and Chemical Aspects of Corrosion Fatigue Crack
Growth for a 2024-T3 Aluminum Alloy in the Short Crack Regime," Ph.D.
Dissertation, Lehigh University, Bethlehem, PA, 1996.
[14] Wan, K.-C., Chen, G. S., Gao, M. and Wei, R. P., "On the Conventional K-
Calibration Equations for Single-Edge-Cracked Tension Specimens," Engineering
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Analysis, STP 738, S. J. Hudak Jr. and R. J. Bucci, Eds., American Society for
Testing and Materials, Philadelphia, PA, 1981, p. 103.
[16] Hoeppner, W., in Fatigue Mechanisms, STP 675, J. T. Fong, Ed., American Society
for Testing and Materials, Philadelphia, PA, 1979, p. 841.
[17] Muller, M., Metallurgical Transactions A, Vol. 13, 1982, p. 649.
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Astronautics, Vol. 32, 1994, p. 2073.
Brian N. Leis and Jeffery A. Colwell ~
Initiation of Stress-Corrosion Cracking on Gas Transmission Piping
REFERENCE: Leis, B. N. and Colwell, J. A., "Initiation of Stress-Corrosion CracKing

on Gas Transmission Piping," Effects of the Environment on the Initiation of Crack
Growth, ASTM STP 1298, W. A. Van Der Sluys, R. S. Piascik, and R. Zawierucha, Eds.,
American Society for Testing and Materials, 1997.
Abstract: This paper explores the initiation of stress-corrosion cracking (SCC) on the
exterior of gas transmission piping. Initiation is taken here to include processes leading
to the formation of a crack-like feature as well as early growth. Initiation is characterized
in terms of the microstructural factors and the mechanics conditions that influence
initiation and subsequent growth.
Field and laboratory data are introduced to identify features typical of, but somewhat
unique, to SCC initiation on gas-transmission pipelines. It is shown that the cracking
behavior can be grouped as a function of the crack spacing perpendicular to the maximum
principal stress. Patches of cracks are defined as sparse or dense in terms of this spacing,
with a circumferential crack spacing on the order of 0.2x (wall thickness) separating these
two cracking patterns. These results show that cracks with dense spacings tend to
dormancy whereas the sparse spacings continue to grow.
Fracture mechanics analysis is used to rationalize the field cracking patterns. It is shown
that compliance changes due to the presence of adjacent crack tips account for the field
cracking behavior. The results show that initiation patterns, which lead to closely spaced
crack arrays, will tend to a dormant state as the cracks grow, because this growth leads to
shielding of the tips from the service stresses. In contrast, growth can continue in arrays
where the conditions at initiation give rise to sparse crack spacings. In addition, the
fracture mechanics results are used to evaluate the suitability of the tapered-tension test --
a commonly used procedure to characterize SCC initiation. Laboratory and modeling
results are shown to be consistent with the field behavior.
Keywords: gas-transmission pipeline, stress-corrosion cracking, initiation, growth,

dormancy, stress intensity factor, crack aspect ratio, crack spacing, length and depth,
dense, sparse, array, SCC colony, field cracking, laboratory cracking, modeling SCC
~Research Leaders in Damage Mechanics and Corrosion, respectively, Battelle,

505 King Avenue, Columbus, OH 43201-2693.
34
Copyright*
Copyright by ASTM1997
Int'lby
(allASTM International
rights reserved); www.astm.org
Fri Dec 30 21:53:51 EST 2011
LEIS AND COLWELL ON STRESS-CORROSION CRACKING 35
INTRODUCTION
Study of colonies of stress-corrosion cracking (SCC) found in field-digs and at

mainline leaks and breaks caused by SCC reveals a wide range of crack sizes, aspect
ratios, and spacings[I,2]. For example, the aspect ratio (crack length to depth) for
cracking in the body of the pipe, away from features that focus cracking like the
longitudinal-seam weld, ranges from as small as 1 to as large as 20. Circumferential
crack spacings in colonies of SCC in the body of the pipe ranges from several grain
diameters to distances of many in. (cm). This diversity of cracking presents problems in
assessing safety and serviceability that are unique to SCC, because the merging of cracks,
termed coalescence, can control the pipeline's integrity. Whether or not coalescence
occurs depends on the driving force for cracking, which can be expressed, for example, as
a function of the linear elastic fracture mechanics (LEFM) stress intensity factor, K.
Two-dimensional (2-D) "slit" LEFM solutions for K show that its value can increase, or
decrease, or remain nearly unchanged with crack growth (e.g., see Ref. [3,4]) --
depending on the relative initial positions of the cracks and their length relative to their
spacing. Three-dimensional (3-D) LEFM results characterizing the interplay at the tips of
adjacent crack pairs[5,6] show that their behavior can be still more complex. Not only
can K either increase or decrease monotonically with growth, results of such 3-D
solutions also indicate that growth can cause an increase in K followed by a decrease in K
when shielding occurs at crack tips as the cracks grow. It follows that the cracking
behavior within colonies of SCC can be quite complex, with some initial crack sizes and
spacings supporting continued growth. Alternatively, cracks in other colonies with
different initial sizes and spacings can be expected to tend to a dormant state.
This paper explores the behavior of cracks within a class of SCC that is known to
produce quite dense "patches" of cracks as compared to other situations where the
cracking is quite sparse[I,2]. Perspective for this situation is first provided by examining
some typical field views of SCC on pipelines, followed by some definitions that are
useful in characterizing these patterns -- with a particular emphasis on trends for crack
spacings found near SCC leaks or breaks. While it will become evident that both low and
high pH 2 colonies show similar crack size, shape, and spacing tendencies, this paper tends
to emphasize the high pH situation because of the high pH bias in the colonies available
for this study. This paper draws on recently developed results derived from unpublished
measurements based on the grinding procedure of Reference 9, as well as measurements
and analysis of SCC failure reports done by and archived at Battelle. When appropriate,
consistency with the field trends is demonstrated with reference to both laboratory test
data[2] and the results of modeling[10].
2 Pipeline SCC occurs at pH levels slightly below 7, termed "low or near-neutral

pH" cracking. It also occurs at pH = 9.3, termed "high pH" cracking. Parkins[7] has
characterized these environments mad identified similarities and differences, and clearly
demonstrated that the mechanism for high pH cracking is dissolution[8], with the
interplay between repassivation and microplasticity being rate limiting.
Study of SCC colonies reveals

rather striking differences between
cracking patterns in areas where cracking
occurred remote to the failure plane for
leaks and breaks as compared to the
behavior on this plane or adjacent to
it[l,2]. This is evident, for example, in
Fig. 1, which shows views of the exterior
surfaces of a pipeline system that in this
case was suffering low pH SCC. Fig. la
is a view typical of areas remote to a line
break. Note from this figure that many
cracks have initiated at quite close
spacing -- both circumferentially and
axially. This view, as with all other such
views,
shows cracks that have initiated and
Fig. 1--Photographs illustrating some features of
the SCC on pipelines.
a) Patch of cracking with a dense spacing (-0.8X,
30 in. (762 mm) diameter x 52 pipeline operated at
72%SMYS, suffering high pH cracking).
Fig. 1--Photographs illustrating some features of the SCC on pipelines.

b) Patch of cracking with sparse spacing (-0.8X, 30 in. (762 mm) diameter x 52 pipeline
operated at 72%SMYS, suffering high pH cracking).
Fig. 1--Photographs illustrating some features of the SCC on pipelines.

c) Cross-section through failure plane (--4X, from a rupture in a 36 in. (914 mm) diameter
X65 pipeline operating at -77% of SMYS).
grown with time, with the possibility for subsequent initiation, as well as coalescence
with adjacent cracks. In contrast, Fig. lb shows a view typical of that seen along a line
break where the cracks either contributed to the failure or were drawn open by the failure
process (i.e., deeper cracks, all else being equal), wherein the cracks were quite widely
spaced, with little cracking adjacent to the failure plane. Cross-sections through such
areas along a line break, such as that presented in Fig. lc, tend to show the primary crack
(the line break) as well as several widely spaced and often rather deep "secondary" cracks.
As noted by the arrows in Fig. lc, such cross-sections occasionally also show the
presence of very shallow cracks dispersed between or beyond the deeper cracks. But, as
is evident in the figure, such shallow cracks (if present at all between the deeper cracks)
are seldom occurring and not easily seen without the use of much higher magnification.
Examination of cross-section views like that shown in Fig. 1 for the SCC failure
analyses done by or archived at Battelle are similar to that shown -- for low as well as
high pH cracking. It follows that the conditions associated with the initiation of the
sparse cracks found along failure planes and the more dense patterns found remote to
failure planes might be different. There are two points to be made in this context. First,
patches 3 of cracks appear as being either "dense" cracks or "sparse" cracks, using a
circumferential spacing equal to 20% of the wall thickness to discriminate between
them[I,2]. Second, these patches of either dense or sparse cracks tend to form in
different areas along or around the pipe, although these patches can lie quite close to each
other.
Data from a wide variety of field-digs and service and hydrotest failures have been
assembled to determine if the apparent differences in crack spacings reflect unique
populations of cracks and inherently different circumstances either at nucleation or during
3 The term "colony" herein represents an area ofpipeline's surface that shares a
common area of disbonded coating. Since not all of the area covered by a colony
develops cracks, the term "patch" is used to represent a group of cracks within a colony
that share similar sizes and spacings.
early growth, or both. Fig. 2 presents these data in terms of crack depth as a function of
the frequency of occurrence, with all data representing high pH SCC. Note that crack
depth in this figure is normalized by the wall thickness of the pipeline, so that the y axis
in this figure has values that lie between zero (no depth) and one (through-wall and
therefore a failure).
Fig. 2a presents data for sparse crack spacings based on direct measurements of
crack depth (and length) on the failure planes for 17 different hydrotest failures (one leak
and sixteen breaks), which occurred during testing of one pipeline. These 17 failures
include more than 160 cracks, results for which are presented in Fig. 2a in terms of the
average crack depth for each of the coalesced cracks involved in any leak or break. The
average depth for each coalesced crack has been grouped into intervals, with each interval
represented on the y axis by one data point that is the average for all coalesced cracks
contained in that interval. These data points have been ordered in increasing sequence
and each interval assigned its rank in this sequence. The x axis in Fig. 2a represents the
rank of the intervals, plotted as the normalized cumulative frequency, which was
determined from the cumulative frequency, ~rc, (i.e., the sum of occurrences, ~N, over all
intervals of average crack depth up to the interval of interest) divided by the sum of all
occurrences measured in all of the intervals. The y-axis is simply the average depth over
the interval of interest corresponding to ~r c. Data missing from an interval means that the
average crack depths represented by that interval were not observed in the 17 hydrotest
failures.
The data shown in Fig. 2a all lie in intervals that represent average depths much
greater than 20%of the wall thickness, which is used hereafter to distinguish between
"deep" and "shallow" cracks. 4 These average depths in no case included cracks whose
depth even approached being as shallow as 20%of the wall thickness, although in general
such could occur. It follows that the data obtained from these hydrotest failures represent
"deep" cracks. Note from the figure that, while "deep" was defined as depths greater than
20%of the wall, the crack depths included in this figure represent much greater fractions
of the wall thickness -- from about 45 through 70%.
In contrast to the results along a failure plane shown in Fig. 2a, Fig. 2b presents
data for patches of cracks found remote to the failure plane of what were in-service
ruptures. Note from Fig. 2b that the depth intervals containing these data represent quite
small differences in average crack depth. In every case, these data represent cracks whose
maximum depth was much less than 20%of the wall thickness. All cracking reflects
dense crack spacings. Crack depth was measured using optical techniques where crack
length at a given depth was revealed by the "layer-grind" technique. As detailed in
Reference 9, this technique involves locating crack positions as layers are ground
sequentially from flattened pipe sections. In all cases the depths measured with this
technique have been corrected for the thickness of the layer removed in the "first pass" of
the grind procedure. Fig. 2b has been constructed for these shallow cracks in the same
manner used for Fig. 2a. Fig. 2b indicates that the average depths for cracks found
4 Twenty percent of the wall has been chosen here as the basis to cull the data for Fig.
2 because this depth is used to distinguish between dense and sparse circumferential crack
spacings[ 1,2].
remote to the failure plane are quite shallow. Moreover, while Fig. 2a showed that cracks
with "sparse" spacings found along or near failure planes continued growing to depths
causing failures, the cracking found remote to such failure sites, which indicated "dense"
spacings also showed little evidence of growth. This is apparent by comparing the results
for the fewer than 200 cracks in the sparse population with that for the much larger
population with a "dense" spacing, which shows about an 8-fold increase in depth for the
sparse cracking.
0.80 0.50
NORMAL}ZED CRACK DEPTH VS OCCURRENCES NORMALIZED CRACK DEPTH VS OCCURRENCES
SPARSE PATCH DENSE PATCN
~3 0.70 O.40
-3
0,60 ,3 030
§ + §
+ + r
§
$
0.50 020
Cracks remote to or]gin of
Cracks remote to oflgin of service and hydrotest failures
o~ 0.40 service and hydrotest failures 01o
Z
0.3C
0.20 0.40 0.60 0..0 1.00 0 0.20 O~.O 0.80 0 80 I O0 '
Normalized Cumulative Frequency Normalized Cumulative Frequency
Fig. 2--Cumulative frequency of occurrence as a timction of crack depth(13).

a) 160 cracks from 17 hydrotest failures b) Cracking found in digs remote to failures
Data for patches of dense, shallow cracks and for sparse, deep cracks like that in
Fig. 2 can be used to further identify similarities or differences between populations of
cracking grouped accordingly. To do this quantitatively requires a means of determining
crack density or its inverse, the crack spacing, which herein is based on a line-intercept
procedure like that used to determine grain size (by analogy between multiple crack
boundaries and grain boundaries). In that the trends in Fig. 2b are very similar, with all
cracks being quite shallow, one would expect similarities in their spacings, while in light
of the differences between Figs. 2b and 2a one would expect their spacings to be
significantly different.
For the sparse cracking, found at or near failure planes where it is clear that cracks
continue to grow to a critical size, the data in Fig. 2a correspond to an average
circumferential spacing of 0.141 in. (3.58 mm). In contrast, for the first data set shown in
Fig. 2b, 88 cracks were intersected along a 1-in. (25 ram) long line drawn
circumferentially around the pipe, for a spacing between cracks of 0.011 in. (0.29 mm).
The spacing for this patch, which covered an area smaller than one square in. (- 6.5 cm z)
is more than a factor often smaller than the sparse cracking. For the second dense patch,
209 cracks were intersected along a 3 in. (76 ram) long circumferential line, leading to a
spacing of 0.014 in. (0.36 ram). This patch, which covered an area of several square in.
( - 64 cm2), was part of a much larger patch that covered about a square foot (~900 cm 2)
and had a spacing comparable to the first dense patch.
It follows that there are significant differences between crack spacings on failure
planes versus areas remote to them, as suggested in discussing Fig. 2. Note in regard to
Fig. 2b that the trends for both dense colonies would, if extended to smaller depths, pass
through zero. This means that the trends for these dense patches can be associated with
the initiation process, whereas the data in Fig. 2a start at a quite large average depth,
approaching 50%of the wall thickness. The depth of the cracking in Fig. 2a continues to
increase until ~r c gets beyond - 0.7 (i.e., the deepest crack in the population), at which
length the crack size in this sparse population becomes critical and a leak or rupture
ensues. Thus, the data in Fig. 2a do not suggest an underlying process starting with small
cracks, whereas the trends in Fig. 2b pass through zero and the behavior can be associated
with cracking that (1) initiated more recently than those that grew to failure, (2) grew
more slowly, or (3) arrested early in the growth process (i.e., dormant or zero growth-rate
cracks). Of these possibilities, dormancy seems most reasonable since the trend for both
dense patches is toward stagnation in growth at depths on the order of 5% of the wall
thickness. Part b of Fig. 3 will show conclusively the tendency for dormancy for these
data, at a quite shallow depth. It follows that the trend for cracking along the fracture
plane represented by the data in Fig. 2a involves crack growth remote to origins while the
data for dense patches can be tied back to crack initiation. Thus, the data examined for
shallow cracks (remote to fracture planes) and for deep cracks (along fracture planes)
represent apparently different cracking populations.
Given the just noted differences between crack populations in patches of SCC
defined as dense or sparse, it is reasonable to assume that other characteristic differences
also exist. One such characteristic is the shape of the crack, which is practically
significant because criteria for coalescence as well as to ensure safety and serviceability
of cracks in SCC colonies depend on crack shape. Crack shape can depend on the effects
of adjacent cracks on the stress field shared by their tips as well as the constancy of the
electrochemical conditions along the crack front, beyond initiation. When SCC initiates
at sites isolated from neighboring cracks, and while cracks are still shallow, the
electrochemical conditions along a crack's front should be nearly constant. In such cases,
the cracking occurs from a "point-source" leading to a shape where the length is twice the
depth. Thus, the ratio of crack length, L, divided by crack depth, D, (i.e., aspect ratio),
which is the slope on a plot of crack length as a function of crack depth, is two. Cracking
with an aspect ratio of near 2 has been observed for deep sparse high pH cracking that
initiated and grew along failure planes[I,2], isolated from neighboring cracks (i.e., sparse
cracking). These conditions apparently produced comparable growth rates in the L and D
directions. This possibility exists because down-crack effects, such as I-R drop, are not
an major issue in the high pH environment.
Figure 3 presents crack growth trends starting from small, initially shallow cracks,
to determine if crack shape changes significantly as the crack deepens. This figure
presents crack length, L, on the y axis and crack depth, D, on the x axis. "Point-source"
trends should be evident for initiation and early growth for all cracks when presented in
this format, but should be particularly apparent for dense patches -- at least until the
cracks grow to a length where interacting crack tips cause stress shielding and their
growth trends change accordingly. That is, the cracking trends in the format of Fig. 3
should fit the "point-source" model so long as initiation and early growth for a given
crack are "isolated" mechanically from other cracks. Crack tips are isolated when either
(1) adjacent cracks are both short and shallow or (2) there are no adjacent cracks as
occurs around the outside of a dense patch. A further requirement for "point-source"
response is that the conditions controlling SCC are equal everywhere along the crack
front, resulting in growth beyond their origins at equal rates in all directions (which
produces L/D = 2). This requirement for equal cracking conditions can be satisfied for
the high pH cracking environment and also can be expected for early growth in the low
pH environment because of the relatively dilute electrolyte and open circuit conditions in
such cases.
Figure 3a presents data for the dense patch shown in Fig. la, which extended
along the pipe for - 4 in. (- 102 mm) and around the pipe for ~ 3 in. (~76 ram).
Cracking in this colony had a circumferential spacing of 0.053 in. (1.35 mm), which for
this pipe geometry lies below the earlier defined transition from "dense" to "sparse"
spacings. The sizes of these cracks were determined using serial sections, in passes
removing about 0.003 in. (0.08 mm) whereas the corresponding lengths were measured
with the assistance of low-power stereo-optical microscopy assisted by decoration of the
cracks using wet fluorescent magnetic particle inspection.
The data in Fig. 3a start at lengths on the order of 0.006 in. (0.15 mm), which
represents the smallest length that can be reliably captured with this measurement
scheme. In excess of 75 cracks were intersected on typical serial sections through dense
patches in this colony. If the cracking shown in Fig. 3a continued with the same crack
shape, the data would track the straight line drawn through the data for the shallower
cracks. This initial cracking occurs with a length to depth ratio o f - 3, which is close to
the behavior expected for cracking from a point source. In spite of data scatter at a few
crack depths, there is a clear, continued divergence from this straight line through the data
following initiation beginning at depths slightly less than 0.01 in. (0.25 mm).
The divergence from the initial trend means that crack length continues to
increase whereas the depth does not, which indicates that crack shape changes with depth
and implies the onset of dormancy in the depth direction. Although not evident here
because replicated data points lie one upon another, the data clustered at depths less than
0.006 in. (0.30 mm) and at depths in the interval from 0.010 to 0.012 in. (0.25 to 0.30
mm). In contrast to the "sparse" cracking shown in Fig. 2a, which reached depths
approaching - 0.3 in. (7.6 mm), this dense cracking failed to grow deeper than 0.023 in.
(0.58 mm). This trend to dormant cracking in initially dense patches or patches that
become dense as the cracks grow to lengths that interact is predicted on the basis of
fracture mechanics, as detailed later in Fig. 5. While the aspect ratio for these cracks
started out at - 3, it ends at - 14. It follows that these cracks show a very strong
dependence of crack shape on crack depth. This implies that the crack aspect ratio for
SCC can depend on the depth of the cracking, which means that the aspect ratio can vary
significantly within a colony or along a pipe joint suffering SCC depending on when the
cracking environment formed and other such factors.
Crack Oeotl" ,ram

Crack Depth, mm
3 25 050 0.75
0.2S d.~O 075
§ 030 I
/
7 CRACK LENGTH VS DEPTH
DENSE PATCHES /
/ 0
0.20 x LOWpH SCC /
}= Nigh pH SCC /
, s
C: • /•
j: "- i
~5 010 - ~3
t 2
o
'
~Ol 002
Crack Oeplh, inch
i
0.05
of 0.01
Crack Depth, inch
0.02 0.03
J
Fig. 3--Crack length as a function of crack depth.

a) For the patch of cracking in Fig. la. b) For patches of low and high pH cracking.
Trends like that in Fig. 3a are also evident in Fig. 3b which presents the length
versus depth behavior for one of the high pH populations of short, shallow cracking
discussed in regard to Fig. 2b supplemented by data obtained by the layer-grind technique
applied to a patch of low pH cracking. The observation that one data set lies within the
other indicates that such cracking behavior is apparently independent of the cracking
environment, at least for these two environments. This figure also indicates that this
cracking initiated in low and high pH environments exhibits a "point-source" behavior
because the results lie on a line with a slope at or close to 2. However, as the nonlinear
least-squares curve-fit to the lower-bound data in Fig. 3b indicates, the instantaneous
slope of this data trend increases as the crack depth increases. The value of L/D for these
data increases from about 2 at initiation, which is represented here by the data for the
shallowest cracks, to a value that for these data leads to L/D - 8 for cracks that have
depths approaching - 0.025 in. (0.64 ram). These higher values of L/D are consistent
with the literature for coalesced cracks, which shows L/D values for SCC in the pipe body
ranging from 1 up to values approaching 20.(e.g., Ref.[1])
Figure 3b indicates that the transition from point-source response begins at crack
depths equal to about 0.005 in. (0.13 rnm) and based on the trends and the scatter evident
in the figure is completed at depths equal to about 0.015 in. (0.38 mm). These depths
correspond to depth to thickness ratios of 0.014 to 0.042, which places the smallest of the
cracks represented by these data in the lower left comer of Fig. 2b. Given their size and
the fact that the data lie on a trend that passes through zero, these results reflect the
initiation phase of the pipeline SCC process. Note that the data in Fig. 3b fall just slightly
below those in Fig. 3a, but otherwise the trends are comparable. Note too that the
cracking behavior shown in Fig. 3 represents the limits of the crack depths as well as
crack lengths for those patches of cracking. Although it is plausible that longer cracks
could form in such patches, the absence of longer cracks in these results suggests that
growth in the length direction becomes dormant just as it does in the depth direction. The
slightly less dense population shown in Fig. la and characterized in Fig. 3a reaches
slightly longer lengths than were developed for the patches represented in Fig. 3b.
The aspect ratio (i.e., L/D) increases from values of about 2 or 3 to as high as 15
for the data in Fig. 3 because the length is increasing without a corresponding increase in
depth. This is most evident in Fig. 3b where the low pH data trends for a given depth
show a wide range of crack length results, with this tendency becoming more evident as
the depth increases. The trends in Figs. 3a and 3b both indicate that depth is tending
toward a limiting value as the cracks lengthen. For the results in Fig. 3b, the nonlinear
least-squares curve-fit to the lower-bound data indicate that the limiting depth is 0.031 in.
(0.79 man). This corresponds to a wall-thickness normalized depth of D/t = 0.086 for the
nearly equal wall-thickness pipelines involved (i.e., the limiting depth occurs at 8.6%of
the wall thickness). Both Fig. 3a and Fig. 3b show that for these data representing dense
patches the point-source behavior breaks down. As will be shown in the next section,
mechanics analysis indicates that this breakdown is due to stress shielding, which
decreases the driving force for continued cracking. In this context, the increased crack
length occurring just after initiation can be viewed as a consequence of crack coalescence,
which is favored by the close proximity of initiated cracks in dense patches. It follows
from the trends in Fig. 3 that the L/D ratio for any dense patch will depend on the crack
depth when it was captured.
Patches of cracking in colonies that have not yet saturated in the depth direction
can have L/D approaching 2 (or less), while dense patches in colonies saturated in the
depth direction (dormant with reference to depth and possibly also length) can have
aspect ratios that approach 15 or more. Just as the results for dense patches in Fig. 3
show a range of aspect ratios, cracking along the fracture planes in the body of the
pipeline remote to longitudinal-weld seams also shows a range of crack shapes. Such
crack aspect ratios range from a low of near 2 for one in-service high pH leak and some
hydrotest breaks, through values occasionally approaching 20 for hydrotest and in-service
breaks. Even higher aspect ratios are common in situations where the SCC is focused
either by the environment or the stresses near features like the long-seam weld. However,
these high ratios, which can exceed 100 on occasion, are due more to the longitudinal
nature of the stress or environmental focus for the cracking than they are a consequence
of the SCC process. It is because the value of the L/D ratio can vary over the depth
continuously during the cracking process (and so also over time) that the analysis of L/D
for various patches of cracks falls to show any trends (i.e., nothing is constant in the
underlying database). It is also because of this variation with depth that such results
should be represented by averages, which by virtue of this variation will show scatter on
any basis for comparison.
Finally, the trends shown in Figs. 2 and 3 represent typical situations and so are
expected to represent both the macroscopic and microscopic behavior of pipeline SCC.
However, these figures represent a rather limited database because few failures have been
characterized in the detail needed for such purposes. It follows that additional studies
would be useful -- for high pH as well as low pH cracking. Such studies, which are
currently underway, could be particularly useful in understanding factors controlling low
pH cracking. This is because the SCC colonies that result from the low and high pH
environments (which create arguably different cracking processes) share spatial features
and a related depth dependence that are almost identical.
Thus far the discussion has focused on trends in field cracking. The next section
introduces fracture mechanics analyses as a means to rationalize this cracking.
Similarities and implications that follow from related laboratory as well as modeling
studies will then be presented.
FRACTURE MECHANICS ANALYSIS OF DENSE PATCHES OF SCC
To date, fracture mechanics analysis has been done to characterize the driving
force for SCC for a limited range of cracking patterns observed in field incidents and
digs. Analysis has been done to characterize isolated axial external cracks, which shows
that flat-plate solutions are suitable for the thin-walled piping typical of gas transmission
applications (e.g., see Ref. [11]). Solutions have also been generated for crack pairs to
scope the behavior of crack interaction and stress shielding (e.g., see [5]). Analysis of 3-
D crack arrays done to assess the suitability of the crack pairs approximation showed that
it was limited to crack spacings more sparse than those associated with dense patches
such as that shown in Fig. 1. This same analysis indicated that 2-D slit solutions for
generic crack arrays failed to capture the earlier discussed cracking response of such
patches, because slit solutions are through-wall idealizations and so more like the
conditions at failure as opposed to the conditions at initiation where dense patches are
populated by very shallow part-through-wall (PTW) cracks. Accordingly, solutions have
been generated with the finite element alternating method (FEAM) (e.g., see Ref. [12])
for arrays of cracks with sizes and spacings typical of dense patches.
The geometry of the array analyzed by the FEAM and used as the reference
condition for typical SCC is defined in Fig. 4, which shows the plan view of the reference
crack array. The inset to Fig. 4 shows the third dimension in terms of the usual through-
thickness crack geometry and notation. The geometric parameters addressed in Fig. 4
have been chosen to represent typical dense arrays early in the cracking process. To this
end, and in light of the trends in Fig. 3, the value ofc/a = 3 (L/D = 6) is used. Data from
a detailed analysis of the patterns and processes involved in SCC initiation and early
growth (see Ref. [13], see also Ref. [1,2]) indicate that the shift from a dense to a sparse
patch occurred at a circumferential spacing normalized by depth, 2b/t, between 20 and
33%of the wall thickness. Accordingly, a circumferential spacing equal to 20%of the
wall thickness (i.e., 2b/t = 0.2) has been selected, which gives b/t = 0.1. This choice
provides results that are representative of dense patches while also reflecting conditions
tending toward that for a sparse patch. The array has been constructed by repetition of the
same relative positions of the centers of adjacent crack pairs. The axial center spacing
depends on the row involved, or alternatively on whether one refers to the crack to the left
or the right of the reference crack. This array thus repeats in alternating rows. For cracks
to the right of the reference crack, the axial spacing between the centers of two coplanar
cracks, denoted as Su, and normalized by the thickness, t, has been chosen at S,/t = 0.4.
The corresponding axial distance between the center of the reference crack and the center
of the crack to its left, denoted a s S 1 and also normalized by the thickness, has been taken
at Sj/t = 1.
Results for fracture mechanics analysis are generally presented in terms o f the
normalized Mode I stress intensity factor, K, in the form:
KI
to facilitate their use for a range of situations. This equation makes use o f conventional
fracture mechanics notation where a --- crack depth (denoted as D in the earlier notation),
and t = pipe-wall thickness, r ---pipe radius, and P = internal pressure. As usual, the value
of Q is given as:
Q = 1 + 1.464(e/a) L65 for a/e>l , (2a)
Q = 1 + 1.464(a/e) T M for a/c<l , (2b)
where c = half crack length (equal to L/2, using the earlier notation). Note that Q in the
form of Equation (2) is supported by extensive numerical studies for a/c g 1 but only
limited results for a/c > 1. In contrast to this more general format, Fig. 5 presents the
absolute dependence of K for the reference array on the y-axis as a function o f crack
depth normalized by the crack depth on the x axis. Note that, while Fig. 5 specifically
represents b/t = 0.1, similar trends develop for other values of b/t. Further, for this view
where b/t = 0.1, the x axis can be transformed into crack depth normalized by the
thickness, a/b. This is done with a ten-to-one scaling such that the limit in this figure for
a/b is 2.5 because a/t = 0.1 (a/b), with this transformed x axis shown across the top
margin of this figure. Finally, in light of the last numerical data in Fig. 5 at a/t = 0.2, Fig.
5 specifically represents the behavior for crack depths less than 20% of the wall
thickness.
With reference to crack depth presented as a/b on the second x axis, for a fixed
crack depth the condition a/b ~ 0 represents cracks whose circumferential spacing is
decreasing and in the limit at a/b = 0 the response is that of an isolated crack. For this
eason, at small values of a/b the values of K for the array and an isolated crack must be
dentinal. Accordingly, the trends for the array and the isolated crack must converge as
a/b ~ 0, for which reason the array solutions can begin at a finite value of a/b, which
herein was chosen as 0.3. Likewise, increasing values ofa/b mean a denser array. Figure
5 thus provides two unique views into the behavior of SCC patterns: (1) at or
approaching a/b = 0, the spacing is so sparse as to reflect the response of an isolated crack
and (2) as a/b increases beyond about 0.2, the patch is tending to become dense. It
follows that the
46 E F F E C T S O F THE E N V I R O N M E N T ON INITIATION OF C R A C K G R O W T H
Normalized Flaw Oeom, ~0

o O.S qo q,~ ~,0 ~a
iso~a ~a C r a ~ ~eo
( N e w m a n a r~aiuJ
F.__2c ~'~:o
~x
I ' ! t '
t c.~(} / / I s o l a l ~ l C ,-'~41 $0(30
F,---- c~ Ix ~' /~ ( N e w m a n & Raj
i ---s~-- "t
/ ~ ~ ~ - A ~ a y (ml~ inv~tlgal~on
~;-----e ............... ~;-~ .......

....... - ,0 ~_.____~=_..~--~ ~-
I
2~ . a ~ a v ~tn,i , n v ~ l a ~ e n m j
! I ! ' |o
0.05 0~0 ) is ) ~o o~
~orma~ize~ maw olpm. ~t
Fig. 4--Array to idealize a dense patch Fig. 5--Stress intensity factor versus crack of
cracking. normalized crack depth.
trends in Fig. 5 for surface tips (qb = 0 ~ as well as at the deepest point along the front (qb
= 90 ~ can be instructive in regard to the initiation of external pipeline SCC as well as the
early growth in dense patches or patches that become dense because of crack growth.
Note that the K solutions in Fig. 5 for the array and the isolated crack tend to
converge (as they must) for the surface tips (tips in the crack length (L) direction) as well
as for the in-depth tip (tip into the depth (D) direction) as a/b ~ 0. This means that, in
spite of a potentially high crack density per unit area, the tips of very shallow and short
cracks don't influence the behavior of the adjacent crack-tips. Thus, even in a patch of
SCC with a high crack density -- that is at the birth of a dense patch -- the initiation and
early growth of the cracks occurs independent of the effects of their neighbors. But, as
these cracks lengthen and deepen or as subsequent initiation occurs, a/b increases and
cracks interact, whose effect Fig. 5 indicates through decreasing values of K.
The transition from the initial behavior as an isolated crack, shown in Fig. 5 by the
dashed line, to that of interacting crack-tips, shown as the solid lines, is indicated by the
divergence between the trends in K for the isolated crack and the array. The strength of
this divergence is a measure of the strength of this interaction. Fig. 5 shows that this
divergence begins for surface crack-tips (qb = 0 ~ at a value ofa/b that is smaller than for
the in-depth tips, because the tips of the cracks are much closer on the surface than they
are for the tips in the depth direction. This divergence becomes significant for surface
tips at about a/b = 0.2. Because Fig. 5 represents b/t = 0.1, this divergence for surface tips
occurs over the interval 0.02 ~ a/t ~ 0.04. Using an interval of pipe-wall thicknesses
between 0.2 and 0.4 in. (5.1 and 10.2 ram), which is characteristic of much of the Class I
transmission pipeline system currently in service, this range of a/t corresponds to crack
depths in the range of 0.004 through 0.016 in. (0.1 mm through 0.4 mm). Because Fig. 5
is presented in nondimensional terms, other pipe-wall thicknesses could be substituted to
better represent other pipeline applications.
Using the average of the above depths as typical for Class I transmission pipeline
applications, these results indicate that the surface tips for cracks shallower than about
0.012 in. (0.3 mm) can be considered as isolated. Such isolated cracks do not shield their
neighbors from the effects of the hoop stress in the wall so that such cracks do not
interact nor coalesce for fracture mechanics reasons. This does not mean that cracks
shallower than 0.012 in. (0.3 nun) will not grow together. Rather, it means that their
growth and eventual coalescence behavior will be as independent cracks, which in this
setting grow together by SCC. Note in this context that Fig. 3 showed a point-source
response for populations of field SCC with depths shallower than 0.005 to 0.015 in.
(0.127 to 0.38 ram). In contrast, the adjacent surface tips of cracks deeper than 0.015 in.
(0.38 mm) were found to shield each other from the effects of the hoop stress in the wall.
This shielding reduces the driving force for continued growth more and more as growth
occurs, which leads to the conclusion that cracks with dense spacings tend to dormancy
at their surface tips. Likewise, Fig. 5 shows that this tendency for the in-depth crack tips,
for cracks with depths greater than 0.4 _<a/b _<0.6, which translate to depths in the interval
from 0.008 _<depth _<0.024 in. (0.20 _<depth ~ 0.61 ram). This interval, which is
bounded above by 0.024 in. (0.96 mm), contains the data in Fig. 3a but fall just short of
the maximum depth for the curve-fit that led to a maximum depth of 0.031 in. (0.79 mm)
for Fig. 3b.
The close correspondence of the actual behavior (Fig. 3) and the analytical results
(Fig. 5) indicates that the analysis provides a viable representation of the initiation and
early growth behavior of SCC in dense patches. Figure 5 indicates that growth can be
expected at both the surface tips and the through-thickness tip at the deepest point along
the crack front beyond initiation. The analysis indicates that this early crack growth
quickly leads to interaction, at crack depths that are very shallow in comparison to the
wall thickness. It indicates that cracks deeper than about 0.024 in. (0.96 mm) shield their
neighbors from the effects of the hoop stress in the wall. This reduces the driving force
for growth both along the surface and in the depth direction, and so indicates dormancy at
the in-depth as well as surface tips within dense patches of SCC. Thus, cracks within a
dense patch at depths greater than 0.024 in. (0.61 mm) are implied to be dormant along
the full crack front -- all else being equal. Figure 3, which represents the field behavior of
dense patches, indicates the onset of dormancy in both length and depth directions at
normalized crack depths between - 0.050 and 0.086, whereas Fig. 5 implies dormancy at
both tips when the normalized depth reaches a/t = 0.067, which lies within the limits of
the observed field behavior.
It follows that the 3-D analytical analog to SCC initiation and early growth in
dense patches is consistent with field patterns for dense patches. The trends in Fig. 5
characterize the evolution of a dense patch -- they imply that dense patches begin with the
initiation of closely spaced "isolated" cracks that quickly transition to a shielded state
with very little opportunity for subsequent initiation elsewhere in the patch or growth
other than by coalescence of nearly coplanar neighbors.
Finally, as can be seen from Fig. 5, the behavior of the isolated crack (the dashed
trend) and the reference array differ significantly beyond a/b ~ 0.75. It follows that
handbook results for the often-solved isolated crack cases can badly overestimate the
driving force for cracking once interaction occurs in dense patches (i.e., at a/b ~ 0.75 or
a/t e 0.075). This means that 3-D solutions for arrays are required to adequately assess
the behavior when a/t ~ 0.15.
Consider next the extent to which the trends discussed to date for field cracking
and analysis carry over to laboratory situations or are reflected in models of SCC
initiation and early growth for pipelines.
CRACKING PATTERNS IN LABORATORY SPECIMENS
Crack initiation and early growth are typically studied under accelerated
laboratory conditions using samples that are neither notched nor precracked. Straight
sided samples can be used to explore the cracking behavior at a given stress, strain, or
strain rate condition. In contrast, data on cracking behavior can be developed at a variety
of stress levels using a sample with tapered sides, with the disadvantage of not knowing
the local strain or strain rate conditions. This section focuses on the latter type of sample
known as the "tapered-tension test" (TTT)(14), because it provides results for a range of
stressing conditions under load control, which mimics the pressure control situation in
pipelines. The maximum load is chosen to cause yielding at its minimum section, and the
stress due to this load decreases as the area increases along the taper. This test is typically
continued for seven days, with the sample subjected to a small amplitude long-period
stress cycle (often termed "ripple loading"). As shown schematically by the typical
cracking pattern in Fig. 6, many cracks form, almost immediately, with the number of
cracks increasing as time passes. The frequency of cracking decreases as the stress
decreases. A similar pattern is observed in the crack depth. Typically, the average crack
growth rate decreases with time as does the rate of subsequent crack nucleation. Analysis
indicates that this short-term cracking occurs primarily in response to creep[ 15].
Data from a wide range of tapered-tension tests have been developed at Battelle --
particularly for the high pH cracking environment. But, because the historical purpose of
the TTT was to determine a threshold stress level for SCC, to augment the screening data
from the slow strain rate test (SSRT)[ 16], the data from such tests have generally been
analyzed to determine only that threshold. Thresholds in this context were defined with
reference to a decreasing incidence of cracking (e.g., Reference [17]), although crack
depth, available from the raw data but frequently not reported, generally did not decrease
to the same extent.
Figure 6 illustrates the cracking pattern that develops in a typical TTT of line pipe
steels. In this figure the cracking incidence is overlaid schematically on the planform of a
TTT sample, denoted "typical cracking pattern". Shown with this schematic is a typical
example of actual crack incidence for cracks with depths greater than the "threshold"
depth of 0.0004 in. (0.01 mm)[17]. This typical cracking is shown in Fig. 6 laid along the
length of the specimen and denoted "occurrence histogram." The threshold stress is
defined in this context as the stress in the cross-section where the "trend line bounding
the severely cracked portion of the specimen" intersects the "threshold" depth (0.0004 in.
(0.01 mm))[17]. Thus, cracking incidence for the same test represented by the occurrence
histogram is plotted as a function of depth, in terms of"the average depth of the three
deepest cracks within an interval" along the specimen[17], denoted in Fig. 6 as "depth
histogram." With reference to this depth histogram note that the trend line bounding the
severely cracked portion of

the specimen intersects the
30FF L / BoundingTrend "threshold" depth at a
cross-section that ignores
~== ~1 t~(
JI ~~
T-...- "..,~her"
/ Threshold cracks further down the
0ii OCCURRENCE
HISTOGRAM
taper. These ignored
cracks have an average
~ 10
depth of about one-half that
o/I ~ - I ~ i'll-L, of the deepest cracks along
Distance from Shoulder the specimen and lie in
cross-sections with stresses
below the corresponding
TYPICAL CRACKING PATTERN
MAOP for Class I
ft q
operation. Assuming that
LoadI cracking was continuous
over these typically 7 day
tests, the growth rate for
cracking below the just
indicated threshold occurs
DEPTH at a rate equal to about one-
-',o |tl _J L,j l/s'o=.d Threshold HISTOGRAM
half that of the highest
rates on the sample!
Figure 7 presents
P 0H----Iqq the crack initiation and
I
Olsf~nee from Shoulder early growth behavior for
one X52 line pipe steel, as
Fig. 6--Schematic of cracking behavior in a TTT specimen. a function of applied stress,
based on raw data collected
from about 20 such tests. Similar trends develop based on data obtained for six
additional steels ranging from X52 through X70 grades, which have been tested at
Battelle in sufficient detail to support the analysis methods used herein. These data
represent tests on unflattened pipe, with the long axis of the specimen taken along the
length of the pipe. Testing was done at 75C in the "standard" high pH environment[ 17],
at the optimum potential for cracking (-650 mV SCE). The data are presented in Figs. 7a
and 7b, where the y axes are, respectively, the average axial crack spacing and the
average crack depth found over 0.2 in. (5 mm) intervals spaced sequentially along the
taper of the specimen. Because these tests were done for a comparable time, crack depth
in Fig. 7b is proportional directly to average crack speed. Axial crack spacing in the TTT
is analogous to the circumferential spacing that develops in the field whereas the depth is
analogous to that measured in field situations.
Figure 7 compiles the data developed for all specimens as a function of maximum
stress for frequencies, f, bounded by 0.0002 Hz ~ f _<0.;~Hz, and stress ratios, R, defined
as the ratio of minimum to maximum stress, equal to 0.971, 0.885, 0.808, and 0.712.
Crack spacing and depth data are presented in Fig. 7 as a function of the average
maximum stress over the corresponding 0.2 in. (5 mm) interval. All data are from
specimens loaded to produce a maximum stress of 52 Ksi (358 MPa) at the smallest
cross-section, which is comparable to the actual yield stress for the steel under test.
Figure 7a shows that the spacing of the cracks along the taper changes
significantly, with the spacing decreasing as the stress increases. The maximum spacing
for cracks in this context is set by the interval of measurement and the fact that the
minimum number of cracks in any interval is one. Thus, at the end of the TTT specimen
where cracking becomes sparse,
the spacing saturates at a
maximum of one crack per
050 interval. Because the interval for
--12 E
T'T'T: A V E R A G E C R A C K S P A C I N G VS S T R E S S e measurement here is ~ 0.2 in. (5
0.40 10 mm) and such measurements are
Stress (Max-Min), ksi
-= made on both sides of the
8
C~ 0.30 o 52-50.5 specimen (i.e., there are two
+ 5;)-46
o 52-42 -- 6 U~' intervals ~ 0.2 in. (5 mm) long
o.
~ 020 9m o ~ o*= o 52-37
within which to find only one
-- 4
+ *a o 9
crack), the maximum crack
o o
0.~0
~176 --2
~, spacing based on this analysis is
(0.2 + 0.2)/1 = 0.4 in. (10 mm).
I I 0 < Thus, the data clustered at a
0.5 0.6 0.7 0.8 0.9 t.0 1.t
N o r m a l i z e d A v e r a g e Stress O v e r Interval
spacing of 0.4 in. (10 mm) in Fig.
7a represent the largest spacing
Fig. 7--TTT data for high pH SCC, for a range of possible for this set of
stressing levels, at optimal conditions for cracking. experiments.
a) Crack spacing As the cracking becomes
more dense toward the high stress
end of the taper, the spacing is
0.015
also limited. For such high
T7-T: A V E R A G E C R A C K D E P T H V S S T R E S S stresses and cracking by an
-g 0.30
~ intergranular (IG) SCC
Stress Ratio, R _~ mechanism, this limit is the
0.010 o
§
0.971
0.885
o
,~ average grain size. At the high
O
0 0.808 ~o o o 0,20 stress end of the TTT sample, the
za 0.712 o @ = ~ ~ ~Z
data show that the crack spacing
0 ~ 1 7 6~
"~ 0.005 approaches 0.005 in. (0.13 mm),
0.10
O
g t, nit § o w which is roughly 5 times this
<
theoretical minimum for IG SCC.
<
I i I I i I 0
00. 5 0.6 0.7 0.8 0.9 1.0 1.1
N o r m a l i z e d A v e r a g e Stress O v e r Interval
Comoarison with Field Data
Fig. 7--TTT data for high pH SCC, for a range of Assuming that the
stressing levels, at optimal conditions for cracking. pipelines in Class I service
b) Crack depth represented by the data in Fig. la
operated at or near MAOP, the
minimum spacing for field
cracking is about 0.025 to 0.035 in. (0.635 mm to 0.889 mm). However, the minimum
spacing observed in the laboratory testing is five to seven times closer than this minimum
field spacing. The strong dependence of crack spacing on maximum stress, which is
evident in Fig. 7a, is critical in this context because the minimum spacing observed in the
laboratory developed at SMYS, whereas the minimum field spacing developed at 0.72 to
0.8 times SMYS. Significantly, the minimum spacing for the laboratory data at a stress
comparable to pipeline service is about 0.025 in. (0.635 ram), which is identical to the
field situation. It follows that when the laboratory crack spacings are compared to
service results at comparable stresses, the crack spacings are found to correspond -- in
spite of the laboratory process being accelerated through temperature, potential, and
concentration of the active species. This correspondence under these specific accelerated
test conditions has also been predicted using models designed to replicate the conditions
in the field and in the laboratory, as will become evident in the next section. This
modeling indicates that these short-term TTT experiments are dominated by the
maximum stress(iS). The next section will show that the maximum stress in the wall of
the pipeline controls the initial crack spacing in pipeline applications[2,10] -- but for
reasons different from that involved with the TTT procedure.
Comparison with Literature Trends
Parkins[18] points out that for laboratory data such as that in Fig. 7a, the crack
density increases over time, depending on the conditions and duration of the test, at a rate
that diminishes (in a power-law format) with time over the course of the test. Parkins'
data, which represent long gage length axial specimens tested at maximum stresses near
their yield stress (i.e., near or above SMYS), show that the maximum crack density is
about 8 cracks per mm (about 200 cracks per in.). Figure 7a indicates that the
corresponding minimum spacing is about 0.005 in. (0.13 mm) -- identical to Parkins'
result. Thus, for these similar laboratory conditions, two different laboratory tests on
different line pipe steels produce identical cracking patterns. Parkins et al.[9] also show a
range of field data that is consistent with the results presented first for field situations and
then for laboratory situations.
MODEL PREDICTIONS OF SCC I N I T I A T I O N AND EARLY G R O W T H
Modeling of SCC initiation on the surface of the pipeline has been developing as a
function of the initial crystallographic orientation of the surface grains, with provision for
the effects of the initial extent of inelastic action and redistribution of stress to the
surrounding grains due to initiation[10,15]. As detailed in References [ 10] and [ 15]
predictions of initiation and early growth show the tendency to form patches or bands of
cracks, as opposed to a uniform distribution of cracks, with a strong dependence on the
stress (pressure) in the pipeline. These pattems develop because initiation or the
incidence of cracking is related to the development of localized inelastic strains, and
because inelastic action in a grain causes it to become more compliant than its neighbors
so that load is shed to neighboring grains. At higher pipe-wall stresses, where much of
the pipe's surface under a disbond experiences inelastic action, the load-shedding in
regions where inelasticity occurs initially causes many surrounding grains to yield, which
fills in these areas with cracking creating a patchy appearance. Alternatively, at lower
stresses this load-shedding tends to affect yielding at grains confined to the region of the
crack tip, which spreads the yielding and related initiation in axial bands, or occasionally
along planes that suggest that shear also contributes to the process.
_ - -_
__-
- -_-
_ _ =
_
I
-:__ --~_ __=__= ;
- =- z- - z ~ I _ -- --
~r- At 70% Actual Yield S t r e s s ~ ~ : ~ A t 80% AcrobatY)elO S l r e s s - - - ~ " ~ ' ~ At 90% Actual Yield Stress
Fig. 8--Predicted patterns of cracking in gas-transmission piping.

a) In the pipe body, at 70, 80, and 90% of the actual yield stress
Fig. 8--Predicted patterns of cracking in gas-transmission piping.

b) Adjacent to a longitudinal seam weld at 80% of actual yield stress
Examples of patches of cracking contained within otherwise uncracked regions

are evident in Fig. 8a. These views present predictions of initiation and early growth in
the body of the pipeline just after initiation has occurred for three levels of pipeline wall
stress -- 70, 80, and 90% of the actual yield stress. Note from Fig. 8a that the density of
cracking within the patches as well as the size and number of patches increases as a
function of wall stress. The stress dependence of crack spacing apparent in Fig. 8a is
clearly evident in the trends observed in the laboratory, as was shown for example Fig. 7a
for TTT data. The pattern for the lower two stress levels shows coaxial patches of
cracking that with continued growth toward each other would lead to a banding of the
cracks. Such patterns are evident in the appearance of colonies of field cracking in the
pipe body as well as for TTT specimens, the essential difference for the TTT being the
dependence of crack spacing as a function of position (stress) along the taper of the
specimen. Predictions for the high-stress region in the TTT specimen across the range of
conditions explored in the laboratory[15] indicate that the initiation of SCC occurs very
early in the test and thereafter the growth rate quickly approaches zero, consistent with
the indicated dormant tendency for dense patches of field cracking discussed in regard to
Fig. 3.
Figure 8b shows predicted SCC adjacent to a longitudinal-weld seam, which lies
to the lower edge of this view. SCC can be focused at this location by either stress fields
or the preferential availability of the cracking environment, as occurs on tape-coated
pipelines suffering low pH cracking. Figure 8b, which is typical of results for operation
at a nominal wall-stress of 80% of the actual yield stress, indicates that the cracking will
develop in bands adjacent to the long seam with the spacing between the bands being
controlled by the distance for stress-shielding as discussed in light of Fig. 5. The width of
the strip of cracking adjacent to the long seam is determined by the width of the disbond
associated with "tenting" of the tape-coating over the long seam reinforcement. Stress
effects embedded in such predictions can be due to the shape of the reinforcement as well
as local bending related to weld-seam fit-up mismatch.
When Fig. 8b is compared to Fig. 8a, changes in the cracking pattern for initiation
and early growth in the pipe body and along weld seams become apparent. First, for
otherwise equal pipe-wall stress the pattern near the weld can be more dense. Second,
control of the potential locations for cracking due to the selective presence of the cracking
environment in a narrow strip confined by the tenting over the long seam can lead to
coaxial strings of the SCC, which appear as bands of cracking due to the effects of stress
shielding. This banding, coupled with a pattern that can be dense coaxially, can produce
very much higher aspect ratios along the weld seam as compared to that in the pipe body.
In addition to the just noted similarities in appearance between field cracking and
the predicted behavior, quantitative predictions of crack spacings closely match the
observed field and laboratory results, which implies that the models of initiation and early
growth are quite realist[2]. The success of these predictions is further supported by
empirical measurements from laboratory cracking that show a power law decrease in
crack speed, tending to saturation within days[10]. This means that cracking patterns
established over a few hours to a day or so in the laboratory with the TTT will change
very little over the duration of the test. Likewise, it implies that cracking that forms on a
pipeline will change little, with the exception of subsequent growth over the long-term
operation of the pipeline. Thus, cracking patterns developed in a test over a few days or
on a pipeline in service for many years can remain comparable to patterns formed at or
shortly after initiation, with provision for changes that occur due to subsequent growth.
This is particularly true for dense spacings for which the laboratory results show little or
no change following initiation. Analysis of the sources of inelasticity for initiation and
short-term SCC in these tests indicates that this early cracking is driven by cyclic creep,
which exhausts quickly, thereby explaining the rapid decrease in growth rates[15]. In
contrast, predictions indicate that long-term cracking on pipelines is supported by cyclic
softening at very small levels of inelastic strain per cycle[19].
DISCUSSION -- V I A B I L I T Y OF T H E T A P E R E D - T E N S I O N - T E S T
The trend to increasing crack spacing with decreasing local maximum stress
evident in Fig. 7a is associated with the decreasing trend in crack depth evident in Fig. 7b.
Comparison of these trends and the behavior of field cracking gives rise to an apparent
conflict between accelerated testing and the field situation, as follows. At the narrow end
of the TTT specimen, where the cracking is dense, the approaching adjacent crack tips are
moving toward a spacing that Figs. 4 and 5 imply will become dormant. In contrast, at
the wider end of the specimen Fig. 7b indicates that the cracking rate is about one-half of
that where cracking is fastest -- at stresses that lie at or below the corresponding Class I
MAOP. (Recall that, because the test time is the same for these TTT data, the average
growth rate is proportional directly to crack depth.) Yet, as evident in Fig. 6, this same
area is by definition(l 7) where the threshold for cracking based on crack frequency is
found. It follows that confusion can occur and conflicts develop in the interpretation of
accelerated laboratory tests to determine a threshold stress for SCC.
While similarities exist in cracking patterns between the field and the laboratory
data, there are perceived differences as well. For example, the naturally nucleated
cracking in laboratory tests accelerated by stress tends to slow to dormancy (much like the
corresponding case in the field) whereas cracks in the field do grow -- and occasionally
cause failure. This difference is, however, only perception because the dense crack
spacings that nucleate at higher stresses (due to the inelastic action that creates reactive
surface) make the area compliant, which subsequently reduces the local stresses[ 13].
This permits passivation or the formation of reaction products that block off the
environment leading to dormancy --just as observed in dense patches in the field.
Likewise, the cracking in sparse patches in laboratory specimens matches field behavior
in that cracking in both develops at rather slow rates, which is quite likely for the same
reasons. The SCC life prediction model (SCCLPM) for pipelines[20] indicates that
sparse field cracking takes years to develop to near critical depths because: (1) few
cracks initiate, which means that large amounts of growth are needed before adjacent
cracks develop to a near critical size, and (2) the mechanical conditions that support
cracking (inelastic strain and an interval of strain rate) exist over a diminishing time
fraction, which slows the average cracking speed.
Work being done to model pipeline SCC[20] suggests that tests must be done for
longer periods of time before the history-dependent microplasticity process that supports
long-term cracking becomes active and cracks of significant depth can grow in sparse
populations. This model also indicates that the dense colonies that form at the higher
stresses used to accelerate laboratory cracking will tend to become dormant -- which is
counter to the purposes of an accelerated test. (It may be for this reason that the shorter-
term laboratory testing fails to support cracking beyond a small fraction of the wall
thickness.) Finally, this model indicates that much care must be taken in designing test
geometries and in selecting "accelerating" factors in order to even approximate pipeline
cracking in the laboratory. It follows that differences between field cracking pattems as
well as the extent and method of the acceleration achieved in the laboratory should be
carefully considered in selecting or developing a laboratory test so that the results can be
transferred easily to the analysis of field cracking.
SUMMARY
Modeling for both pipelines and laboratory TTT situations[10,15] indicates that
SCC sites are activated in accordance with the random grain orientations and their
corresponding microinelastic properties. This modeling also indicates that such cracking
patterns will remain similar for dense spacings -- as the patch of cracks moves quickly
toward saturation and dormancy. The predicted pattern for dense patches of field and
T T T cracking is clearly dependent on the maximum stress in the pipeline, consistent with
Fig. 7, which showed that crack spacing (or density) was dependent on the maximum
stress. Accordingly, subtle differences in stress (for example due to differences in wall
thickness, or inelastic strain that occurs in response to stress, for example differences in
local free-surface induced microplasticity due to microstructural (or chemistry)
variations) can cause appreciable differences in crack spacing. The presence of patches
that crack within a colony under a common disbond can, therefore, be expected within
inches (cm) of each other as evident in Fig. 1. As observed in Fig. 7, the predicted
patterns of initiation and early growth are strongly dependent on maximum stress, as
shown for example in Fig. 8. As was observed in Fig. 1, dense and sparse spacings also
can be found within in. (cm) of each other. In this context, what could be interpreted as
scatter in the SCC process can equally be a direct consequence of the inherent variability
in the microstructure and other manufacturing aspects, as detailed elsewhere[13]. This
predicted cracking develops spacings that range from the order of the size of the grain
boundary to many times the thickness of the pipe --just as is observed in the field.
Likewise, as Fig. 8 indicates, these predictions show clustering of dense patches of cracks
in otherwise sparse fields even though the maximum stress is fixed. Figure 8 shows that
such clustering is more prevalent at higher stresses and also shows that dense and sparse
spacings can be found within inches (cm) of each other, again as seen in the field
cracking patterns.
CONCLUSIONS
Several conclusions can be drawn as a result of this work. The following two
conclusions are among the most significant:
When the role of stress as an accelerant is accounted for, field and laboratory
cracking features can be rationalized and are consistent with predictions based on
the underlying pipeline SCC.
Care must be taken in designing accelerated laboratory experiments to provide
data that can be used in analytical procedures that bridge the gap between the
factors controlling field cracking and the extent of their acceleration in the
laboratory.
OBSERVATIONS AND OPERATIONAL IMPLICATIONS
Low and high pH colonies showed similar crack size, shape, and spacing
tendencies.
Crack populations with circumferential spacings greater than - 20% of the wall
thickness had length, depth, and growth patterns that differed significantly from
populations with denser spacings. Such populations reflected the conditions at
SCC failures, generally contained deep cracks, and were termed sparse.
Crack populations with spacings less than ~ 20% of the wall thickness reflected
conditions away from failures, generally contained very shallow cracks, and were
termed dense and tended to dormancy whereas sparse crack spacings can continue
to grow.
Circumferential crack spacing could be correlated for field and laboratory data and
for predictions of pipeline SCC in terms of maximum stress. This implies that
operating factors, like maximum pressure, implicitly control pipeline
susceptibility to (initiation of) SCC.
Dense and sparse patches can form under a common disbonded area and can
coexist within inches of each other in an operating pipeline, which can create
situations where the dormant state in the dense patch is reactivated by the cracking
in the sparse patch.
ACKNOWLEDGMENTS
Preparation of this paper has been supported by the Engineering Mechanics Group
(EMG) at Battelle, Columbus Ohio. This work is part of work supported by the EMG at
Battelle in conjunction with extensive allied research into gas transmission pipeline SCC,
which is supported by the Line Pipe Research Supervisory Committee of the PRCI.
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[1__~.] Leis, B. N., "Characterization of Axial Flaws in Pipelines, With a Focus on

Stress-Corrosion Cracking," AGA NG-18 Report #212, 1995.
[.1~] Fessler, R. R., and Barlo, T. J., "Threshold-Stress Determination Using Tapered
Specimens and Cyclic Stresses", ASTM STP 82l, pp 368-382, 1984.
[L,5_] Leis, B. N., and Walsh, W. J., "Mechanics-Based Analysis of Stress-Corrosion

Cracking of Line-Pipe Steel in a Carbonate-Bicarbonate Environment," ASTM
STP 1049, B. W. Lisagor, T. W. Crooker, B. N. Leis, Eds., pp. 243-265, 1990.
[16] Ugiansky, G. M., and Payer, J. H., editors, "Stress-Corrosion Cracking -- The
Slow Strain-Rate Technique," ASTM STP 665, 1979.
[17] Beavers, J. A., Parkins, R. N., Koch, G. H., and Berry, W. E., "Test Method for
Defining Susceptibility of Pipeline Steels to Stress-Corrosion Cracking," AGA
NG-18 No. 146, AGA Cat. No. 51484, 1985.
[]__8_] Parkins, R. N., and Singh, P. M., "Stress-Corrosion Crack Coalescence,"

Corrosion, 46, pp. 485 (1990).
[.I~.] Leis, B. N., "Recurrent SCC in Gas Transmission Pipelines: Service History and
Material Property Considerations," AGA NG- 18 Report #210, December 1993.
[2o] Leis, B. N., Forte, T. P., and Ghadiali, N. D., "Stress-Corrosion Cracking Life
Prediction Model -- SCCLPM: Version 1.0 User's Manual and Software," AGA
NG-18 Report #217, February 1995.
Crack Initiation in Aging Aircraft
David G. Kolman I and John R. Scully 2
ON T H E R E Q U I R E M E N T F O R A S H A R P N O T C H O R P R E C R A C K TO
C A U S E E N V I R O N M E N T A L L Y A S S I S T E D C R A C K I N I T I A T I O N IN ~-
TITANIUM ALLOYS EXPOSED TO AQUEOUS CHLORIDE
ENVIRONMENTS
Kolman, D.G. and Scully, J.R., " O n The Requirement For A Sharp Notch or
Precrack To Cause Environmentally Assisted Crack Initiation Of 13-Titanium
Alloys Exposed To Aqueous Chloride E n v i r o n m e n t s " , Effects of the
Environment on the Initiation of Crack Growth, ASTM STP 1298, W.A. Van der Sluys,
R.S. Piascik, and R. Zawierucha, Eds., American Society for Testing and Materials, 1997.
A B S T R A C T : The requirement of a sharp notch or precrack to cause environmental crack

initiation of metastable [~-titanium alloys exposed to 0.6 M NaC1 has been observed. The
causal relationship has not been thoroughly examined, however. This paper seeks to
explain the sharp notch requirement by examining notch acuity effects on a variety of
parameters that affect HEAC susceptibility. These include the effects of a sharp notch on
cation accumulation - hydrolysis - acidification , potential drop in solution and resulting
hydrogen production, and localization of dynamic strain. It is shown that solution
resistance down a sharp crack is two orders of magnitude larger for a fatigue precracked
compact tension specimen than for a smooth bar. The potential drop down a sharp crack is
severe enough to enable hydrogen production even when the applied potential is more
positive than the reversible potential for hydrogen production. It also shown that a fatigue
precrack results in an acidified crack tip chemistry (approximately pH 1) which is
deleterious to HEAC resistance. The effects of a sharp notch on the interplay of
mechanics, film rupture and hydrogen uptake are also examined. It is shown that the slip
behavior at a sharp crack tip promotes localized film rupture and localized hydrogen uptake.
Localization of hydrogen uptake may be critical for HEAC susceptibility in light of the large
hydrogen concentration required to cause crack initiation (ca. 1000 wt. ppm) and the lack
of significant hydrogen uptake on filmed surfaces.
Postdoctoral Research Associate, MS G755, Los Alamos National Laboratory, Los

Alamos, NM, 87545.
2 Associate Professor, Department of Materials Science and Engineering, University of
Virginia, Charlottesville, VA 22903.
61
Copyright*
Copyright 1997
by ASTM by(all
Int'l ASTM
rightsInternational
reserved); Fri Dec www.astm.org
30 21:53:51 EST 2011
KEYWORDS: Hydrogen environmentally assisted cracking (HEAC), notch radius,

~-titanium alloys, crack tip solution acidification, ohmic loss, bare surface electrode
kinetics, film rupture, hydrogen uptake, fatigue precrack.
INTRODUCTION
Environmentally assisted cracking (EAC) of titanium alloys exposed to aqueous

chloride environments has been observed by many researchers [1,2,3,4,5,6,7,8,9,10].
EAC has been noted on (x (hcp), ~ (bcc), (x+[3 and [3+(x alloys. In the case of both (x- and
p-titanium alloys, a pre-existing sharp notch is usually required for EAC with a few
exceptions (e.g., Ti - 8 Mn and Ti - 13 V - 11 Cr - 3 AI) [6]. Beck examined the effect of
notch root radius on the EAC behavior of Ti - 8 A1 - 1 Mo - 1 V [7] and found that the alloy
was immune to EAC when exposed to 0.6 M LiCI at -0.5Vsc E for notch radii greater than
250 lam. Conversely, radii less than 250 [.tin produced EAC, with susceptibility increasing
as the notch radius decreased. Lane and Cavallaro observed the same phenomenon on Ti -
7 AI - 2 Nb - 1 Ta [11]. Several recent studies on solution treated (ST) and solution treated
and aged (STA) ~-titanium alloys, such as Ti - 15 Mo - 3 Nb - 3 AI and Ti - 3 AI - 8 V - 6
Cr - 4 Mo - 4 Zr, have employed smooth or blunt notch specimens [12, 13, 14, 15]. In
contrast to the results for precracked specimens, no EAC was observed. Further, others
have suggested that localized plastic deformation under crevice conditions may be required
for EAC [11] and a sharp notch or precrack appears to promote both these phenomena.
Although the sharp notch requirement has been widely observed and cited in titanium alloy
EAC literature, there is little discussion in the literature of the underlying reasons for the
necessity of a sharp notch. This paper seeks to explain this phenomenon.
It has been well documented that EAC of (x-titanium alloys is controlled by

hydriding of the (x phase [16, 17, 18, 19,20,21]. For the case of STA l-titanium alloys, a
hydrogen environmentally assisted cracking (HEAC) mechanism has been proposed
[1,2,3], in light of the link established between lattice and trapped hydrogen and
intergranular cracking [22]. Interestingly, EAC has been observed for both ct- and ]3-
titanium alloys during potentiostatic tests where the applied potential was more positive
than the reversible potential for hydrogen production [1,2,3,5,7]. Such results indicate that
potential drop between the reference electrode and the crack tip is required to produce
hydrogen and the resulting damage. It is possible that one requirement for a sharp notch
arises from a need to generate a restrictive solution path, increasing the potential drop in
solution. This is one focus area of this paper.
A variety of precracked (x+13and 13+(xalloys have been shown to be susceptible to

EAC in neutral pH environments [6]. It has also been shown that: 1) precracked (x+13
alloys are immune to cracking at -lVsc E in neutral solutions but are susceptible to cracking
at -1VscEwhen exposed to strongly acidic bulk environments [6,8]; 2) at potentials where
cracking is observed, cracking can be slowed or eliminated in strongly alkaline bulk
KOLMAN AND SCULLY ON REQUIREMENT FOR SHARP NOTCH 63
environments [6]; and 3) an acidic crack tip chemistry forms in a neutral bulk environment
[23]. It is likely that the pH and potential dependencies are linked. The EAC immunity of
precracked specimens observed below -1Vsc E in neutral solution appears to result from
proton or water reduction in the occluded region near the crack tip which increases the
crack tip pH. In strongly acidic environments, it is likely that the cathodic polarization is
unable to overcome the bulk acidity, uptake occurs via process zone charging (and possibly
by bulk surface ingress if oxide films are destabilized) and cracking occurs. Conversely, in
strongly alkaline environments, both process zone and filmed surface uptake is limited.
Crack tip acidification due to hydrolysis and / or oxide formation [24] is unable to
overcome the bulk alkalinity and EAC immunity results. Since the susceptibility in acidic
solutions and the immunity in alkaline solutions appears to be independent of applied
potential, it is reasonable to assert that the observed potential dependency in neutral
solutions originates from the alteration of the crack tip solution pH and not from the
electrochemical potential per s6. Since a sharp notch or crack results in an occluded region,
it is possible that a sharp notch results in an acidic crack tip chemistry which is deleterious
to the EAC resistance of titanium alloys. It is an object of this paper to examine this aspect
of sharp notches as well.
A difference in mechanics generated by varying notch acuity likely plays a role in

EAC susceptibility. Research by Young and Scully incorporating hydrogen precharged
STA Ti - 15 Mo - 3 Nb - 3 A1 circumferentially notched tensile bars (CNTBs) tested in air
showed that the increased constraint produced by reduced notch radius promoted lower
failure stress [22]. Since the CNTBs were not exposed to the embrittling environment, it is
clear that some component of EAC arises from a purely mechanical interaction of stress and
hydrogen. Moreover, notch acuity has been shown to alter the slip offset during film
rupture events [2], which may affect EAC susceptibility. Therefore, another goal of this
paper is to examine the effects of notch acuity on the interplay of stress, hydrogen
concentration and film rupture, and to relate them to observed EAC behavior.
EXPERIMENTAL PROCEDURE
The physical metallurgy of Ti - 15 Mo - 3 Nb - 3 A1 (Ti - 14.9 Mo - 2.64 Nb - 3.15

A1 (wt%)) has been described elsewhere [3,25]. Ti - 15 Mo - 3 Nb - 3 A1 was solutionized
for 8 h at 871~ (1600~ followed by an air cool. Aging of STA material comprised a
subsequent single step heat treatment at 5380 C (1000 ~ F) for 8 h followed by an air cool.
0.6 M NaC1 solutions (~: = 0.0521 (f~-cm) ~) incorporated reagent grade NaC1
added to distilled deionized water. Other 0.6 M NaC1 solutions were adjusted to alkaline
pH values with reagent grade NaOH or to acidic values with reagent grade HC1. 5 M HC1
solutions (~: = 0.602 (t2-cm) -~, calculated pH = -1.64 [26]) incorporated reagent grade
HC1 added to distilled deionized water.
Electrochemical tests incorporated a PAR 273 potentiostat and a variety of different

data recording devices. Experimental procedures and sample geometries for CNTB [2] and
compact tension (CT) specimen [1] tests are detailed elsewhere. The radius of the
circumferential notch on each CNTB was 0.544 ram.
RESULTS
Sham notch - fatigue tgrecracked CT specimen tests
Threshold stress intensities (Kth) for precracked STA ]3-titanium alloys exposed to
chloride environments at different potentials are shown in Figure 1. The fracture
toughnesses of the alloys in air are similar to the stress intensities observed at the most
negative potential shown for each alloy in Figure 1. Thus, EAC immunity is observed at
the most negative potentials. Conversely, a dramatic reduction in Ktn is observed at more
positive potentials, with a minimum observed at intermediate potentials. At these
potentials, precracked STA 13-titanium alloys are highly susceptible to EAC.
7 0 . . . . , , , , I . . . . L . . . . I ' ' ' ' i . . . .
9 Ti- 11.5 Mo- 6 Zr- 4.5 Sn I

60
50
~ ~ II Ti - 3 AI- 8 V- 6 Or- 4 Zr- 4 Mo
i- 15 M o - 3 N b - 3 AI
I
o_ 40
'~ 30
20
-1500 -1000 -500 0 500 1000 1500

Applied Potential (mVscE)
Figure 1 - Plot of threshold stress intensities for various precracked STA I~-titanium
alloys exposed to 0.6 M NaC1. (Ti - 11.5 Mo: reference 6; Ti - 3 AI: reference 5; Ti - 15
Mo: reference 3).
Blunt notch - circumferentiallv notched tensile bar tests
The ratio of the failure load in environment to the failure load in air for different
blunt notched and smooth bar ]3-titanium specimens exposed to chloride solutions at
different potentials is shown in Figure 2. It is seen that the ratio is approximately 1 for
both STA Ti - 15 Mo - 3 Nb - 3 A1 and STA Ti - 3 A1 - 8 V - 6 Cr - 4 Mo - 4 Zr, indicative
of EAC immunity. In contrast to precracked samples (Figure 1), no reductions in failure
load (Figure 2) or reduction in area (not shown) are observed at any applied potential in
environment. Thus, EAC susceptibility depends not only on applied potential, but the
presence of a sharp notch also.
K O L M A N A N D SCULLY ON R E Q U I R E M E N T FOR S H A R P N O T C H 65
1.2
[3 El--
........... ~ .....
A
Q..--
A 0.8
v
13..
0.6
= S T A T i - 15 - 3 Mo - 3 Nb - 3 AI (This Research)
- - - e - - - STA Ti - 15 - 3 Mo - 3 Nb - 3 AI (Aylor)
= STA Ti - 3 AI - 8 V - 6 Cr - 4 Mo - 4 Zr (Aylor)
[] S T A T i - 3 AI -8 V - 6 Cr - 4 Me - 4 Zr (Azkarate)
0.4 , I r I I I I I I I I I I I I I I I I I I I I I ~ I t ~
-1600 -1400 -1200 -1000 -800 -600 -400 -200 0
Potential (mVscE)
Figure 2 - Ratio of failure load in environment to that in air for blunt notch and smooth
~-titanium alloys exposed to chloride environments. A ratio of 1 is indicative of EAC
immunity. Data from Azkarate and Aylor are from references 12 and 15, respectively.
Hydrogen uotake as a function of oH
As shown in Figure 1, K~ exhibits a strong potential dependency when samples are

precracked. Since the potential dependency of HEAC is believed to be related to crack or
notch solution pH, hydrogen uptake experiments were conducted with chloride solutions of
varying pH. STA Ti - 15 Mo - 3 Nb - 3 A1 foils (0.38 mm thickness) were polarized to
-1Vsc E for 5 days. The samples were subsequently analyzed for hydrogen concentration.
The results for samples exposed to 0.6 M NaC1 adjusted to pH 10, 0.6 M NaCI, 0.6 M
NaC1 adjusted to pH 1 and 5 M HC1 are seen in Figure 3. It is seen that no hydrogen
uptake occurred on the foils exposed to pH 10, 6 and 1 solution. That is, the hydrogen
concentrations within the foils were similar to that in the as-received material. Conversely,
significant hydrogen uptake was found to occur on foils exposed to 5M HC1.
A crack tip pH of 1.8 has been measured on Ti - 8 A1 - 1 Mo - 1 V following crack

propagation at open circuit [23]. Assuming that this pH is similar to that which occurs with
~-titanium alloys, it can be inferred that hydrogen uptake through the oxide would be
precluded during EAC, even near the crack tip. In other words, there would be an almost
complete lack of "bulk" hydrogen uptake away from the crack tip. Therefore, hydrogen
uptake must occur at the bare crack tip following film rupture in order to explain EAC by
hydrogen embrittlement. Potential drop in solution, crack tip acidification and localization
of film rupture are also required. These are discussed below.
700 I I I I I l I
60O
500
c
t-.o
~ 400
aoo
0 As-received
___J~ . . . . . . . . . . . . . . . . . . . . .
2OO 9 9 Q-
IO0
0 I i I i I i I ~ [ i I i I
-2 0 2 4 6 8 10
Solution pH
Figure 3 - Hydrogen concentration measured in 0.38 mm thick STA Ti - 15 Mo - 3 Nb - 3

AI foils following cathodic polarization to -1 Vsc E for 5 days. All solutions are 0.6 M NaCI
(pH adjusted) except pH -1.64 which is 5 M HCI.
DISCUSSION
Potential drop in solution
It is apparent that potential drop in solution is necessary for HEAC when the
applied potential is more positive than the reversible potential for hydrogen production.
Since HEAC is observed in conductive solutions, a restrictive solution pathway is required
to generate significant potential drop. The presence of a sharp notch fulfills this
requirement.
Both experiment and theory predict large ohmic loss in solution when a sharp notch
or precrack is present. Experiments incorporating a model CT specimen indicated that the
solution resistance between a crack tip and the bulk solution was a minimum of 2.2 k ~ in
0.6 M NaC1 [1]. Additionally, the effect of crack angle on the solution resistance can be
estimated using a model proposed by Newman [27] (Table 1) 3. It is seen that the solution
resistance is over 2 orders of magnitude larger to a CT specimen crack tip than to a smooth
bar. At the solution resistance estimated for the Ti - 3 A1 - 8 V - 6 Cr - 4 Zr - 4 Mo CT
specimen geometry of Figure 1 (4300 ~), calculations indicate that when an area as little as
1/500th of the crack tip (5 x 10 .7 cm 2) is bared following film rupture, ohmic loss is so
severe that the crack tip potential never exceeds the reversible potential for hydrogen
3 The values for parameters in the Newman model were obtained experimentally: p = 19.2
~ - c m (0.6 M NaC1), w 0 = 1 CTOD = 5 x 10 .4 cm, i t = 270 A/cm 2 (Eapp = -0.6 Vsc E, 0.6 M
NaC1), i , = 10 7 A/cm 2 (0.6 M NaC1), L = 2.4 cm.
production regardless of the applied potential [1]. Moreover, because the model does not
account for crack tortuosity, the solution resistances are likely even larger. Further, it has
been estimated that solution resistances greater than 100 k ~ would be obtained when
preferential dissolution occurs at grain boundaries intersecting the crack tip [1]. It is
possible then to generate significant potential drop before crack initiation even when the
crack tip current is on the order of microamps. Currents on the order of microamps have
been measured preceding crack initiation [28]. Therefore, hydrogen production is possible
in a sharp notch before crack initiation, even when the applied potential is more positive
than the reversible potential for hydrogen production. This explains, in part, the HEAC
susceptibility observed in Figure 1 at potentials more positive than the reversible potential
for hydrogen production.
TABLE 1* -- Calculated crack tip l~arameters as a function of crack angle

Crack Solution Crack tip T i 3§ Crack tip
Angle Resistance concentration (near surface)
(radians) (a) (mol/1) solution pH
0.0054 7400 0.47 0.6

0.011 tt 4300 0.27 1.0
0.021 2500 0.16 1.3
0.11 640 0.040 1.9
1.1 84 0.0053 2.3
3.14 tt* 7.6 2.3 x 1 0 .6 5.6
t - Solution resistance and crack tip T i 3§ concentration were calculated from equations 8
and 7, respectively, of reference 27 and assuming currents similar to those seen preceding
crack initiation [ 1,24]. Solution pH values were correlated with T i 3+ concentrations via
reference 24. The diffusivity of Ti 3+ (= 8.5 x 10.6 cm2/s) was obtained from estimates in
the literature [29].
t t - Estimated crack angle of CT specimen at Kth in Figure i.
t t t - Smooth bar. Solution resistance calculated from ref. 30 for the smooth bar
experiments of Figure 2 from this research. Ti 3§ concentration calculated from the mass
transport limited current density, assuming a diffusion layer thickness of 30 gm.
Crack tit~ solution acidification
An acidified crack tip solution is a prerequisite for EAC of [~-titanium alloys

exposed to 0.6 M NaC1. Acidification has been shown to promote hydrogen entry in two
ways. First, it has been shown that an acidified solution enhances hydrogen production
kinetics on bare titanium following film rapture [1,24]. Enhanced hydrogen production
arises from an increased overpotential for hydrogen production following film rupture and
ohmic drop in solution [1].
Hydrogen uptake also can be enhanced on a filmed titanium surface exposed to

strongly acidic solutions (Figure 3). It is likely that the hydrogen uptake in low pH
solution results from the presence of a nonprotective film. In-situ characterization of STA
Ti - 15 Mo - 3 Nb - 3 AI exposed to 5 M HC1 indicated that that the material was

spontaneously active at open circuit even though a film was present [31]. This result is in
agreement with other research which noted that a porous film of Ti203 was present in the
active region [32]. Conversely, a passive film of TiO 2 is observed on STA Ti - 15 Mo - 3
Nb - 3 AI exposed to 0.6 M NaC1, pH 1 [31]. It appears, therefore, that there is a
transition in film properties between pH 1 and pH -1.64 wherein the film becomes
nonprotective.
It is apparent from the literature [33,34,35] and Figure 3 that bulk charging of
titanium through the oxide is unlikely in room temperature neutral solutions above -1Vscz
because the oxide (TiO2) is a strong barrier to hydrogen uptake. Moreover, the very slow
hydrogen diffusivity through the oxide and through the [3-titanium matrix itself [22,33],
makes bulk (i.e., noncrack tip) charging of the process zone unlikely for either sharp or
blunt notched specimens. Therefore, hydrogen entry must occur either at the crack tip
(where depassivation occurs) or in close proximity to the crack tip (where the pH results in
an oxide with a reduced barrier to hydrogen entry).
The concentration of Ti 3§ near the crack tip was estimated using equations
developed by Newman [27] (Table 1). The concentration of Ti 3+ was converted to a
solution pH via reference 24. Table 1 reveals that increasing notch acuity results in a
reduced crack tip solution pH, as would be expected. It is seen that the near-surface pH is
much lower for a sharp notch than a smooth bar. A crack tip pH of 1.0 was calculated for
the CT specimen test of Figure 2. At this pH, uptake on a filmed surface would not be
expected (Figure 3). Therefore, hydrogen entry is restricted to the bare crack tip surface
following mechanical depassivation.
A minimum in Kth at intermediate potentials has been observed for many different
13-titanium alloys [3,5,6], as seen in Figure 1. Since hydrogen production and crack tip
acidification are prerequisites for EAC (see Introduction), it is likely that the minimum at
-0.5Vsc E results from a maximization of the hydrogen production / crack tip acidification
combination. A maximum susceptibility to EAC would be expected at some intermediate
potential because crack tip acidification increases with potential4 while hydrogen production
decreases with potential. This is shown schematically in Figure 4.
The question arises as to how hydrogen production and crack tip acidification can
occur concurrently. The answer can be discerned from the repassivation behavior, as
follows. It has been shown that film rupture is required for EAC of [3-titanium alloys [1]
and that film rupture indeed precedes [2] crack initiation. Fractured thin film tests on
titanium5 indicate that anodic current densities greater than 100 A/cm 2 can occur during the
initial period following depassivation [24]. The majority of this current was shown to go
towards dissolution of titanium (Ti --~ Ti 3§ rather than towards film reformation [24]. The
4 Tests (not shown) have confirmed that a crack tip becomes alkaline with cathodic
polarization in a bulk solution of 0.6 M NaCI. Crevice pH values of 9.85 and 11.3 were
measured following polarization of a creviced Ti - 15 Mo - 3 Nb - 3 A1 sample to -0.65
Vsc E and - 1Vsc E, respectively.
5 Fractured thin film tests are indicative of the tree surface response following rapid film
rupture because the peak currents are less than the ohmic limit and the rapid fracture rate
eliminates depassivation speed limitations.
"o
2
0_
g
ACidic
<
Neutral
Alkaline
:=
"1"
active noble
Potential
Figure 4 - Schematic representation of hydrogen production, crack tip acidification and

EAC susceptibility vs. applied potential for a titanium alloy.
driving force for the large anodic reaction rates is the large anodic overpotential. The
overpotential is large because the bare surface open circuit potential is very negative
(-1.58Vsc E in 0.6 M NaC1) [24]. As repassivation commences, the open circuit potential of
the repassivating surface increases. When the open circuit potential becomes more positive
than the actual surface potential, the net current on the repassivating surface becomes
negative and cathodic reactions (almost entirely hydrogen production) dominate. These
current densities may be quite significant (> 1 A/cm2), depending upon potential. The
overall net charge passed on the depassivated surface is positive (anodic), however, for
applied potentials above approximately -1.2Vsc E [24]. Since the majority of this charge is
dissolution product (Ti3+), and since hydrolysis of Ti 3§ results in strong solution
acidification [24], film rupture will result in crack tip solution acidification in the absence of
strong cathodic polarization.
Film rupture (as measured by anodic current) has been shown to increase with
increasing K preceding crack initiation [2]. Since the initial film rupture events are smaller
in current amplitude, they are less likely to result in significant potential drop (i.e., ohmic
drop severe enough to lower the potential below the reversible potential for hydrogen
production). They would yield solution acidification however. As the magnitude of the
anodic current emanating from the crack tip increases, significant ohmic drop becomes
increasingly likely. Thus, hydrogen production would occur in the presence of an acidified
crack tip solution, which appears to be a prerequisite for cracking as discussed above. In
summary, solution acidification and hydrogen production are not mutually exclusive events
with both occurring following film rupture.
Mechanical effects
The resulting difference in mechanics between blunt and sharp notches may play a
role in EAC susceptibility. Research by Young and Scully showed that hydrogen
precharged STA Ti - 15 Mo - 3 Nb - 3 AI CNTBs tested in air were embrittled by hydrogen
concentrations greater than 1000 ppm and produced intergranular fracture similar to that
observed ~bllowing EAC [22]. These tests showed that the increased constraint produced
by reduced notch radius promoted lower failure loads. This result suggested that a critical
combination of local tensile stress, hydrogen concentration and governing microstructural
features may be required for HEAC of ]3-titanium alloys exposed to 0.6 M NaCI [22].
A second effect of notch acuity with respect to mechanics is the localization of slip.
High speed current recordings indicate that quasi-continuous film rupture precedes crack
initiation [2]. Moreover, it has been shown that film rupture is attributable to dislocation
intersection of the surface, as opposed to exceeding the tensile failure strain of the oxide
[2]. Since a bare surface is required for hydrogen entry, hydrogen entry on [3-titanium
alloys must occur as a result of slip. Indeed, it has been shown that dynamic straining is
required for EAC of [3-titanium alloys exposed to 0.6 M NaCI [3,4,5]. The relationship
between notch radius and HEAC may therefore be attributable in part to slip behavior, as
follows.
It is often stated that a sharp crack tip has the effect of localizing dislocation motion
to a few favorably oriented slip planes [36]. Since film rupture is attributable to slip, it may
be inferred that increasing notch acuity results in film rupture localization. This has been
confirmed through experimentation incorporating STA Ti - 15 Mo - 3 Nb - 3 AI. Tests
were performed utilizing three different geometries [2] - a smooth bar, a CNTB and a CT
specimen. The net anodic charge passed preceding cracking in 0.6 M NaCI was obtained
by integration of current - time data above the background current (the steady state or
passive current). These charges are shown in Table 26. The charge can be divided by the
surface area adjacent the plastic zone for each geometry to yield a charge density. This
charge density is directly proportional to the quantity of bare area generated adjacent the
plastic zone and, hence, the intensity of film rupture. In other words, the charge density is
a direct measure of film rupture localization. Results in Table 2 indicate that the film
rupture intensity (charge density) for the smooth bar and CNTB are similar. These
intensities are greater than one thousand times smaller than that of the CT specimen.
Therefore, film rupture is far more localized for the EAC susceptible geometry than for the
EAC immune geometries.
6 The charges shown in Table 2 actually underestimate the true anodic charge because of
the experimental method employed [2]. The underestimate is highest for the CT specimen
(as much as 50%) and lowest for the smooth bar (as much as 2%).
Slip localization has been correlated with EAC of ST [37] and STA [3] [3-titanium
alloys exposed to 0.6 M NaC1 by different researchers. There are two possible reasons
why slip localization promotes EAC. First, localization results in an increased slip offset.
It has been hypothesized (but never proven) that these larger slip steps are more difficult to
repassivate [38,39]. Second, slip localization results in film rapture localization, as shown
in Table 2. Film rupture localization results in hydrogen uptake localization because
hydrogen entry is restricted to bared surfaces as discussed above. Hydrogen uptake
localization may be critical for HEAC in light of the large hydrogen concentrations required
to embrittle [3-titanium (> 1000 wt. ppm) and the lack of "bulk" hydrogen charging. A
secondary effect may be to enhance dislocation transport of hydrogen to grain boundaries,
which may be important in light of the intergranular nature of the HEAC of [3-titanium
alloys. Since HEAC appears to result from the attainment of a critical combination of
hydrogen concentration and stress, and since a sharp crack tip increases both stress and
local hydrogen concentration, a sharp crack tip appears to promote EAC of ~-titanium
alloys.
TABLE 2 t -- Charges and plastic zone sizes for different geometries [2]
Geometry Charge Plastic Zone Charge
(c) Surface Area Density
(C/mm 2)
Smooth 4x10 -4 130 3x10 -6
CNTB 2x10 -5 14 2x10 -6
Compact 2x10 -4 0.022 8x10 -3

Tension
t - Charges were determined via integrations of the anodic currents above background
during potentiostatic mechanical testing in 0.6 M NaC1. Plastic zone sizes are calculated at
the onset of quasi-continuous film rupture [2]. The plastic zone for the smooth bar was
assumed to comprise the entire smooth section of the bar, The CNTB plastic zone surface
area / volume was obtained from finite element analysis. The CT specimen plastic zone
surface area / volume was obtained from standard fracture mechanics calculations
[40,41,42].
CONCLUSIONS
The causal relationship between notch acuity and HEAC of 13-titanium alloys
exposed to 0.6 M NaC1 was examined. It was shown that the presence of a sharp notch
produces a restricted pathway capable of generating ohmic loss in solution. This ohmic
loss can be severe enough to result in a crack tip potential below the reversible potential for
hydrogen production even when the applied potential exceeds this reversible potential.
This is a requirement for HEAC. It was also shown that a sharp notch produces an
occluded corrosion site. The solution pH at this site was shown to be lower than that
achieved in the absence of a notch. Since an acidified solution has been correlated with
EAC, a sharp crack tip may yield HEAC by forming an acidified crack tip solution. The
effect of a sharp crack tip on HEAC was examined from a mechanics standpoint also. It
was shown that a sharp crack tip enhances HEAC by a slip localization phenomenon. Slip
localization may be deleterious to the HEAC resistance of [3-titanium alloys because of
larger slip step production and localization of hydrogen uptake. In summary, a sharp notch
enhances the HEAC susceptibility in a variety of disparate ways. The enhancement of
ohmic loss in solution, crack tip acidification and localized hydrogen uptake (in the absence
of "bulk" uptake) explains the widely observed requirement of a sharp notch for HEAC. In
contrast, smooth or blunt notched samples lack sufficient potential drop, solution
acidification and strain localization to enable hydrogen uptake, resulting in EAC immunity.
ACKNOWLEDGMENTS
The authors would like to acknowledge the Office of Naval Research (Grant No.
N00014-91-J-4164) for their support of this work and TIMET for their generous donation
of alloys. The authors gratefully acknowledge R.P. Gangloff, R.G. Kelly, and F.P. Ford
for their helpful discussions and B.P. Somerday, M.A. Gaudett and D.G. Enos for their
aid with various tests.
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C h a r l e s G. Schmidt, I James E. Crocker, 2 Jacques H. Giovanola, 1 C h r i s t i n e
H. Kanazawa, I D o n a l d A. Shockey, I and Thomas H. F l o u r n o y ~
CORROSION-FATIGUE CRACK NUCLEATION IN ALCLAD 2024-T3 CO~RCIAL

AIRCRAFT SKIN
REFERENCE: Schmidt, C. G., Crocker, J. E., Giovanola, J. H., Kanazawa,

C. H., Shockey, D. A., and Flournoy, T. H., ~Corrosion-FatiQ~/e C r a c k
N u c l e a t i o n in A l c l a d 2 0 2 4 - T 3 C o m m e r c i a l A i r c r a f t S k i n , " E f f e c t s Qf the
E n v i r o n m e n t on the I n i t i a t i o n of Crack Growth. A S T M STP 1298. W.A. Van
Der Sluys, R.S. Piascik, and R. Zawierucha, Eds., A m e r i c a n S o c i e t y for
T e s t i n g and Materials, 1997.
ABSTRACT: The p r o c e s s e s that influence the t r a n s i t i o n from c o r r o s i o n

pit to crack formation in A l c l a d 2024-T3 under cyclic loads in aqueous
e n v i r o n m e n t s were e x a m i n e d in l a b o r a t o r y e x p e r i m e n t s in salt water.
Results suggest that the n u c l e a t i o n of c o r r o s i o n - f a t i g u e cracks in-
volves two c o m p e t i n g mechanisms: h y d r o g e n effects in the cladding and
e l e c t r o c h e m i c a l d i s s o l u t i o n at constituent particles in the core alloy.
Cracks in the clad did not n e c e s s a r i l y nucleate at the largest corro-
sion pit, s u g g e s t i n g that a c o n t r i b u t i n g factor to crack n u c l e a t i o n
from a pit m a y be the creation of a local region of weakness. This
paper p r e s e n t s results from e x p e r i m e n t s to assess the effects of pH and
c l a d d i n g on the n u c l e a t i o n and p r o p a g a t i o n of c o r r o s i o n - f a t i g u e cracks.
KZYWO~DS: corrosion-fatigue, crack nucleation, A l c l a d 2024-T3
M a n y studies have c h a r a c t e r i z e d the effects of e n v i r o n m e n t on

fatigue crack p r o p a g a t i o n in a l u m i n u m alloys; however, r e l a t i v e l y few
studies have e x a m i n e d the effects of e n v i r o n m e n t on crack n u c l e a t i o n
and the early stages of growth. P r i m a r y a t t e n t i o n has been given to
crack p r o p a g a t i o n because of the s e n s i t i v i t y of m o d e r n aircraft fuse-
lage d e s i g n p r a c t i c e to accurate a p p r a i s a l s of fatigue crack propaga-
tion rates. C u r r e n t design p r a c t i c e s are not d i r e c t l y based on fatigue
crack n u c l e a t i o n kinetics. Nevertheless, i m p r o v i n g our u n d e r s t a n d i n g
of e n v i r o n m e n t on fatigue crack n u c l e a t i o n has s i g n i f i c a n t value for
those s e e k i n g to develop improved measures to m i t i g a t e the effects of
e n v i r o n m e n t and fatigue.
iSenior m a t e r i a l s scientist, p r o g r a m manager, m a t e r i a l s scientist,

and a s s o c i a t e l a b o r a t o r y director, respectively, SRI International,
Menlo Park, CA 94025.
~Formerly m a t e r i a l s scientist at SRI International, c u r r e n t l y
g r a d u a t e student, U n i v e r s i t y of Connecticut, Storrs, CT 06268.
3Program monitor, FAA Technical Center, A t l a n t i c City, NJ 08405.
74
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SCHMIDT ET AL. ON CORROSION-FATIGUE NUCLEATION 75
In the p r e s e n t study, three m e c h a n i s m s for the p r o m o t i o n of c r a c k

n u c l e a t i o n by a g g r e s s i v e e n v i r o n m e n t s are considered: (i) local in-
crease in stress r e s u l t i n g from pitting, (2) local m a t e r i a l e m b r i t t l e -
ment p o s s i b l y by hydrogen, and (3) local increase in the a g g r e s s i v e n e s s
of the e n v i r o n m e n t p o s s i b l y from a c i d i f i c a t i o n w i t h i n pits. Conditions
n e c e s s a r y to n u c l e a t e cracks might result from some change i n v o l v i n g
all three processes. Most models of c o r r o s i o n - f a t i g u e crack n u c l e a t i o n
[1-5] focus on the changes in local stress that result from pitting.
In such models, a critical c o n d i t i o n is a s s u m e d to occur w h e n the
stress i n t e n s i t y p r o d u c e d by the pit is s u f f i c i e n t for crack nucle-
ation. The inherent a s s u m p t i o n is that c o n d i t i o n s of m a t e r i a l s u s c e p -
t i b i l i t y and e n v i r o n m e n t do not change over time. The p r e s e n t r e s u l t s
suggest that l o c a l i z e d e m b r i t t l e m e n t is p o s s i b l e and might e n h a n c e
c r a c k n u c l e a t i o n processes.
EXPERIMENTAL PROCEDURE
Specimen Material
Test specimen material from sections of fuselage skin w e r e ob-

t a i n e d from a r e t i r e d Boeing 737 aircraft. The a i r c r a f t e n t e r e d
s e r v i c e in 1968, e x p e r i e n c e d 56,228 flight hours, and was r e t i r e d in
F e b r u a r y 1992. Material was o b t a i n e d from above and b e l o w the 10-L a n d
10-R lap joints (i.e., the lap splice above the windows) b e t w e e n b o d y
stations 360 and 540 (i.e., from aft of the f o r w a r d door to a l o c a t i o n
r o u g h l y in line w i t h the leading edge of the wing).
A h i s t o r y of the p a i n t i n g m a i n t e n a n c e was not available; however,
the paint on the exterior surface and the zinc c h r o m a t e p r i m e r on the
interior surface were g e n e r a l l y in g o o d condition. The skin c o n s i s t e d
of a 0 . 8 1 - m m (0.032-in.)-thick core of 2024-T3, A l c l a d layers on b o t h
sides that w e r e about 0.06 mm (0.002 in.) thick, a paint layer on the
outer s u r f a c e about 0.08 m m (0.003 in.) thick, and a c o r r o s i o n inhibi-
tor layer on the inside that was about 0.10 m m (0.004 in.) thick. The
2024-T3 a l l o y and the A l c l a d (1230 alloy) have n o m i n a l w e i g h t p e r c e n t -
age c o m p o s i t i o n s of AI-4.5 Cu-0.6 Mn-l.5 Mg and A I - 0 . 1 C u ( m a x ) - 0 . 0 5
M n ( m a x ) - 0 . 7 0 Si+Fe(max), respectively.
M e t a l l o g r a p h i c e x a m i n a t i o n of the 2024-T3 core m a t e r i a l r e v e a l e d
a m i c r o s t r u c t u r e w i t h constituent p a r t i c l e s that w e r e d i s t r i b u t e d w i t h
o n l y m o d e r a t e directionality. The g r a i n s t r u c t u r e was e q u i a x e d in the
in-plane o r i e n t a t i o n w i t h a m e a n linear intercept d i s t a n c e of 30 ~m.
The t h r o u g h - t h i c k n e s s orientations w e r e similar in a p p e a r a n c e and con-
sisted of m o d e r a t e l y e l o n g a t e d grains w i t h a m e a n linear i n t e r c e p t
d i s t a n c e of 15 ~m in the t h r o u g h - t h i c k n e s s direction. The A l c l a d g r a i n
s t r u c t u r e (Fig. i), c o n t a i n e d few c o n s t i t u e n t p a r t i c l e s and h a d an
e q u i a x e d g r a i n structure, when v i e w e d normal to the plane of the sheet,
w i t h a m e a n linear intercept d i s t a n c e of 550 ~tm. In the t h r o u g h - t h i c k -
ness directions, the grains f r e q u e n t l y e n c o m p a s s e d the e n t i r e t h i c k n e s s
of the clad. The core and the A l c l a d h a d Vickers' h a r d n e s s e s of 120.4 •
1.5 and 32.2 • 2.3 kg/mm 2, respectively.
F I G . 1 - - A n o d i z e d m e t a l l o g r a p h i c cross sections
of skin material showing the grain s t r u c t u r e of
the Alclad.
Sper Desian
C o r r o s i o n - f a t i g u e specimens were e x t r a c t e d from regions of the
skin that were free of rivet holes and doublers. The gage sections
w e r e t a p e r e d from 6.35 mm (0.25 in.) to 12.7 mm (0.50 in.) over a
length of 76 m m (3.0 in.). The specimen gage length was o r i e n t e d par-
allel to the final rolling d i r e c t i o n (i.e., the L-T orientation), The
specimens were tested in two conditions: w i t h the paint r e m o v e d (the
clad condition) and w i t h the paint and clad r e m o v e d (the bare condi-
tion). The t h r o u g h - t h i c k n e s s surfaces of the gage length w e r e p o l i s h e d
w i t h 0.5 ~m alumina. Paint was r e m o v e d from the c l a d - o n l y specimens
w i t h Turco 5351 by immersion for 6 to 12 hours followed by a water
rinse. The paint and the A l c l a d layer were r e m o v e d from the bare
specimens by surface grinding.
Test P r o c e d u r e
We c o n d u c t e d c o r r o s i o n - f a t i g u e tests in stagnant, 0.5 M NaCI
solutions. Specimens were p r e t r e a t e d by soaking in the test solution
for 3 days before cyclic loading. The pH values w e r e a d j u s t e d by the
a d d i t i o n of HCI or NaOH. The fatigue tests were c o n d u c t e d at 5 Hz
w i t h a s i n u s o i d a l w a v e f o r m and an R value (= ~ m i ~ m a x ) of 0.i. Stress
levels c o m p u t e d for the clad and bare conditions w e r e c o m p u t e d on the
basis of the y i e l d n o r m a l i z e d stress, ~/~y, where O y (= 368 MPa) is the
a p p a r e n t y i e l d stress w i t h the clad, if present. The m e a s u r e d y i e l d
stress reflects y i e l d i n g of the core, so ~/~y enables us to compare
e q u i v a l e n t core stress levels.
A f t e r removal of the c o r r o s i o n deposits by i m m e r s i o n in a H3P04/

CrO 3 s o l u t i o n followed by a HNO 3 wash. The s p e c i m e n gage lengths w e r e
e x a m i n e d in an SEM. Cracks in the edges of the specimens, w e r e c o u n t e d
s t a r t i n g from the m i n i m u m w i d t h of the gage length (or fracture sur-
face, if the s p e c i m e n was loaded to final failure). In each specimen,
a l o c a t i o n along the taper was r e a c h e d w h e r e stresses w e r e too low to
cause cracking. Crack c o u n t i n g was p e r f o r m e d b y i n s p e c t i o n of images
on the SEM screen at a m a g n i f i c a t i o n of 1000X w h i c h e n a b l e d cracks as
small as 5 ~m to be r e a d i l y counted.
Data Reduction
The lengths and locations of cracks along the s p e c i m e n g a g e
lengths w e r e m e a s u r e d to obtain crack g r o w t h rates d u r i n g the e a r l y
stages of c r a c k growth. In m o s t cases, the crack p o p u l a t i o n in any
r e g i o n of the gage length c o n s i s t e d of crack lengths r a n g i n g from about
5 ~m (the d e t e c t i o n limit) to as m u c h as 0.5 m m (the m a x i m u m c r a c k
length). In the crack growth rate analysis, all cracks w e r e a s s u m e d to
n u c l e a t e and b e g i n to grow at the start of the fatigue l o a d i n g p h a s e of
e a c h test. To reduce the effect of cracks that n u c l e a t e d later in the
test, the crack g r o w t h analysis was l i m i t e d to the four longest cracks
in each 50 ~m l o n g i t u d i n a l s e c t i o n of the gage section.
In d e s c r i b i n g the crack g r o w t h rate, Paris E q u a t i o n b e h a v i o r was

a s s u m e d as follows:
da
-- = c (~)~ Cl)
dN
w h e r e a is the crack length, N is the n u m b e r of cycles, K is the stress
intensity, and C and m are constants. N e w m a n and R a j u [6] c o m p u t e d a
r e l a t i o n s h i p d e s c r i b i n g K for a c i r c u l a r corner c r a c k w i t h the c r a c k
p l a n e normal to b o t h surfaces as follows:
K = 0.722 ~ (2)
E l i m i n a t i n g K from Eqs. 1 and 2 and i n t e g r a t i n g from an i n i t i a l

crack length, a0, results in the following e q u a t i o n w h e n m is a s s u m e d
to be 2:
a = a 0 exp [(0.722 A~) 2 C N ~] (3)
The value of m was set equal to 2 b e c a u s e results from other i n v e s t i g a -

tions of similar data [~] e x h i b i t e d this value, and b e c a u s e e a r l y
analyses of the p r e s e n t data where the v a l u e of m was a l l o w e d to v a r y
r e s u l t e d in values close to 2. A least squares analysis was u s e d to
o b t a i n a fit to Eq. 3 and obtain values for C.
Pittina Characteristics
Bare m a t e r i a l e x h i b i t e d two forms of l o c a l i z e d c o r r o s i o n d a m a g e

at all pH levels i n v e s t i g a t e d (Fig. 2): deep pits (a c o n s e q u e n c e of
c o r r o s i o n of or a r o u n d constituent p a r t i c l e s [5]) and i n t e r g r a n u l a r
I,'[(]. 2 T ~ ] i c a l c o r r o s i o ~ d a m a g e on bare s p e c i m e n s (clad and c o a t i n g s

~:(~moved) of a i r c r a f t skin material. C o r r o s i o n d a m a g e is a r e s u ] t of
a 4 - d a y e x p o s u r e to 0.5 M NaCI s o l u t i o n at pH 6.
cracking. C l a d m a t e r i a l e x h i b i t e d c r y s t a l l o g r a p h i c pit c o l o n i e s on
e x p o s e d c l a d s u r f a c e s (Fig. 3). I n d i v i d u a l pits w i t h i n the c o l o n i e s
a p p e a r e d as square, block-shaped d e p r e s s i o n s a p p r o x i m a t e l y 5 ~ m on a
side. The pit c o l o n i e s w e r e u s u a l l y found on the c o r n e r s j o i n i n g the
r o l l e d s u r f a c e a n d the l o n g i t u d i n a l s u r f a c e p e r p e n d i c u l a r to the r o l l e d
s u r f a c e of the c o r r o s i o n - f a t i g u e s p e c i m e n gage lengths a n d w e r e p r e s e n t
at all pH levels tested. A f t e r e x p o s u r e to the pH 2 e n v i r o n m e n t , the
c l a d m a t e r i a l e x h i b i t e d deep pits that a p p e a r e d to n u c l e a t e at con-
s t i t u e n t p a r t i c l e s a n d w e r e s i m i l a r in a p p e a r a n c e to the p i t s f o u n d on
b a r e specimens.
FIG. 3 - - C r y s t a l l o g r a p h i c p i t s on a
t h r o u g h - t h i c k n e s s p l a n e of the A l c l a d
layer of a c o r r o s i o n - f a t i g u e specimen.
C o r r o s i o n d a m a g e is a r e s u l t of a 4 - d a y
e x p o s u r e to 0.5 M N a C I s o l u t i o n of p H 6.
Crack Nucleation Characteristics

C o r r o s i o n - f a t i g u e crack damage a p p e a r e d at (i) cracks n u c l e a t i n g
at c o n s t i t u e n t p a r t i c l e s in the bare m a t e r i a l and (2) c r y s t a l l o g r a p h i c
cracks n u c l e a t i n g in the edges of the clad material. The close p r o x i m -
ity of the c r y s t a l l o g r a p h i c pits tot he c l a d / c o r e i n t e r f a c e s u g g e s t s
that g a l v a n i c effects could p r o m o t e their formation. Cracks in the
first c a t e g o r y were r a r e l y o b s e r v e d in clad m a t e r i a l (Fig. 4); a find-
ing that has b e e n o b s e r v e d by others [~,9]. Figure 5 shows a c r a c k
that n u c l e a t e d from a pit. In this case, the pit appears to be
s l i g h t l y w i d e r (-40 ~m) than it is deep (-30 ~m) a n d has u n d e r c u t the
m a c h i n e d s u r f a c e to a small degree. I m m e d i a t e l y a h e a d of the pit are
c l e a v a g e fracture features. The r e g i o n in front of the c l e a v a g e frac-
ture is s u r r o u n d e d by a region of c l e a v a g e i n t e r s p e r s e d w i t h tear
ridges. Eventually, a fracture area in the shape of a p a r a b o l i c seg-
ment develops for w h i c h the crack depth (-300 ~m) is s l i g h t l y g r e a t e r
than the w i d t h (-250 ~m).
FIG. 4 - - C o r r o s i o n - f a t i g u e crack n u c l e a t i o n from pit in b a r e 2 0 2 4 - T 3

aluminum. The fracture surface is from a s p e c i m e n w h i c h was t e s t e d
in 0.5 M NaCI solution at pH 6 w i t h a m a x i m u m gross s e c t i o n stress
of 0.869 ~y for 24,800 cycles.
In c l a d specimens, crack i n i t i a t i o n sites e v i d e n t from f r a c t u r e

s u r f a c e features indicate that c r a c k i n g n u c l e a t e d in the c l a d and not
in the core material. In some cases, c r a c k n u c l e a t i o n o c c u r r e d at or
near c r y s t a l l o g r a p h i c pit colonies (Fig. 3). F i g u r e 5 shows a c r y s t a l -
l o g r a p h i c crack face typical of Stage I c r a c k i n g that appears to h a v e
n u c l e a t e d at a c o l o n y of c r y s t a l l o g r a p h i c pits. Once the crack was
about 40 ~m deep, the fracture surface a p p e a r a n c e c h a n g e s to d u c t i l e
ridges s e p a r a t e d plateaus that r a d i a t e d from the n u c l e a t i o n site. This
t o p o g r a p h y is typical of Stage II cracking. The m o d e of f r a c t u r e
c h a n g e d once again to large d u c t i l e v o i d c o a l e s c e n c e w h e n the c r a c k
radius r e a c h e d about 120 ~m w h i c h is i n d i c a t i v e of u n s t a b l e c r a c k i n g in
the final stage of specimen failure.
F I G . 5 - - C o r r o s i o n fatigue c r a c k n u c l e a t i o n in the c l a d d i n g of a 2024

T3 a l u m i n u m alloy. The f r a c t u r e s u r f a c e is from a s p e c i m e n wh:[ch
was t e s t e d in 0.5 M NaC] s o l u t i o n at pH 6 w i t h a maxim{ml <izoss
s e c t i o n stress of 0.958 G y for 28,600 cycles.
Crack Propaqation Characteristics
F i g u r e 6 shows v a r i a t i o n s in the c r a c k g r o w t h rate trends w i t h

p H for c l a d specimens. G r o w t h rates of small c r a c k s (i00 to 1400 ~m)
o b t a i n e d b y P i a s c i k a n d W i l l a r d [[] for 2024-T3 t e s t e d in salt w a t e r
e x h i b i t a s i m i l a r trend. In some cases, the p H 2 e n v i r o n m e n t e x h i b i t s
a h i g h e r c r a c k g r o w t h rate than the p H 6 e n v i r o n m e n t . T h e p H 10 envi-
r o n m e n t p r o d u c e s a c r a c k g r o w t h rate that is r o u g h l y equal to, or per-
h a p s s l i g h t l y below, that of the p H 6 e n v i r o n m e n t . C r a c k g r o w t h rates
c o u l d not be o b t a i n e d f r o m the b a r e s p e c i m e n s b e c a u s e too few cracks
w e r e p r e s e n t to e n a b l e an a c c u r a t e e s t i m a t e to be made.
Hvdroaen Effects
To i d e n t i f y w h e t h e r h y d r o g e n is e s s e n t i a l to the e n h a n c e m e n t of
the e a r l y s t a g e s of c r a c k i n g in A l c l a d 2024-T3 aluminum, a s e r i e s of
c o r r o s i o n - f a t i g u e e x p e r i m e n t s w e r e p e r f o r m e d u n d e r c o n d i t i o n s that w e r e
e x p e c t e d to v a r y h y d r o g e n a v a i l a b i l i t y . T h e s e tests w e r e run in a
m a n n e r s i m i l a r to that d e s c r i b e d a b o v e e x c e p t that, p r i o r to f a t i g u e
testing, test s p e c i m e n s w e r e e i t h e r e x p o s e d to 0.5 M N a C I s o l u t i o n for
3 days, e x p o s e d to 0.5 M NaCI s o l u t i o n for 3 days a n d t h e n s t o r e d in
v a c u u m for 3 days, or e x p o s e d for m a n y m o n t h s to l a b o r a t o r y air. The
first e n v i r o n m e n t w a s to i n t r o d u c e h i g h levels of hydrogen, the s e c o n d
e n v i r o n m e n t was to r e m o v e hydrogen, a n d the t h i r d e n v i r o n m e n t was to
a c h i e v e an i n t e r m e d i a t e level of hydrogen.
T h e f a t i g u e tests w e r e c o n d u c t e d in l a b o r a t o r y air a n d w e r e ini-

t i a t e d w i t h i n 15 mins. of c o m p l e t i n g the p r e t e s t e n v i r o n m e n t exposure.
, , , . | ' ', .
f.)
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lo-8
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10.9
O ~'~. 5" " i~JlI I I P ' ' I " ~ pH2

rt-
(.9
-- - pH6
v .~" . . . . . pH10
I
O
< t t
i u,,,,,aumnu data of Piascik
10-10 ~" . - and Willard
O
s t "1 l ~ i !
0.5 0.6 0.8 1 2 3

STRESS INTENSITY RANGE, ~K (MPa~Jm)
FIG. 6--Effect of pH on the c r a c k g r o w t h rate,
of small cracks in a i r c r a f t skin.
The change in h y d r o g e n c o n c e n t r a t i o n w i t h i n the s p e c i m e n s was e s t i m a t e d

to be m i n i m a l u s i n g this test procedure. B a s e d on the lattice d i f f u -
sion data of Ishikawa and M c L e l l a n [10], the a v e r a g e h y d r o g e n c o n t e n t
in the A l c l a d layer of the specimens e x p o s e d to the salt w a t e r s o l u t i o n
for 3 days was e s t i m a t e d to have d r o p p e d no m o r e than about 15% f r o m
the initial value during the fatigue tests. M e a s u r e m e n t of the h y d r o -
gen levels from these test p r o c e d u r e s is b e i n g u n d e r t a k e n in an o n g o i n g
investigation.
Figure 7 compares the cycles to failure for the three p r e t e s t

e n v i r o n m e n t s examined. On average, s p e c i m e n s that w e r e e x p o s e d to the
salt w a t e r e n v i r o n m e n t h a d the lowest n u m b e r of cycles to f a i l u r e
(-38,000 cycles). The average fatigue life i n c r e a s e d to about 81,000
cycles w h e n the salt water e n v i r o n m e n t e x p o s u r e was f o l l o w e d b y a
v a c u u m exposure. The highest a v e r a g e n u m b e r of cycles to failure w e r e
p r o d u c e d (-135,000) w h e n the sole p r e t r e a t m e n t was a l o n g - t e r m e x p o s u r e
to l a b o r a t o r y air.
D I S C U S S I O N
Pittinq Characteristics
Deep p i t t i n g damage is g e n e r a l l y a s s o c i a t e d w i t h a c c e l e r a t e d
local c o r r o s i o n of either the c o n s t i t u e n t p a r t i c l e s that are a n o d i c to
the m a t r i x or the region around c o n s t i t u e n t p a r t i c l e s w h e r e the p a r -
ticles are cathodic to the m a t r i x [~].
C r y s t a l l o g r a p h i c pits are often a s s o c i a t e d w i t h anodic c o r r o s i o n
a n d are o b s e r v e d in pure a l u m i n u m after e x p o s u r e to salt w a t e r solu-
tions where the c o r r o s i o n p o t e n t i a l is s l i g h t l y above the p i t t i n g
200,00
Corrosion environment was
0.5 M NaCI solution.
Pretreatments and vacuum
treatments were approximately
3 days each.
w 150,00 amax = 0.75 ~y
D
<
O 100,00
W
O
O 50,000
Solid lines within boxes denote
the median value. Dotted lins
denote rante of 90% of data.
Boxes denote range of data.
Corrosion Corrosion No
treatment treatment pretreament.
only. + vacuum
treatment.
FIG. 7--Cycles to failure for tests c o n d u c t e d in

air after various pretreatments.
p o t e n t i a l [12]. The c r y s t a l l o g r a p h i c c h a r a c t e r of the pits is attrib-

u t e d to an optimal shape for m a i n t e n a n c e of the pit e n v i r o n m e n t and
current d e n s i t y [13].
Cr~Gk N u c l e a t i o n Characteristics
The effect of cladding on c o r r o s i o n - f a t i g u e crack n u c l e a t i o n
kinetics appears to be a result of the d i f f e r e n c e s in the c o r r o s i o n
a t t a c k produced. C o r r o s i o n attack of bare m a t e r i a l was either p i t t i n g
c o r r o s i o n at c o n s t i t u e n t particles or i n t e r g r a n u l a r cracking. In clad
material, a t t a c k was p r i m a r i l y in the form of c r y s t a l l o g r a p h i c pits,
a l t h o u g h some pits n u c l e a t e d at c o n s t i t u e n t p a r t i c l e s in the pH 2 envi-
ronment. These o b s e r v a t i o n s of crack n u c l e a t i o n sites in clad and bare
m a t e r i a l are c o n s i s t e n t w i t h o b s e r v a t i o n s by other i n v e s t i g a t o r s [~,9] .
Evidently, the pits observed in the p r e s e n t i n v e s t i g a t i o n that formed
in the bare m a t e r i a l and n u c l e a t e d cracks were s u f f i c i e n t l y v a r i a b l e in
depth and location so that only a few of the largest (generally g r e a t e r
than 30 ~m in depth) served as crack n u c l e a t i o n sites. In the clad
material, cracks u s u a l l y n u c l e a t e d in the clad layer at or near the
c r y s t a l l o g r a p h i c pit colonies. Small cracks followed f a v o r a b l y ori-
ented crystallographic planes in a m a n n e r often r e f e r r e d to as Stage I
c r a c k i n g [14]. The p r o x i m i t y of the cracks to c r y s t a l l o g r a p h i c pit
colonies suggests that p i t t i n g promotes crack formation (although ob-
s e r v a t i o n s of Stage I cracking indicate that p i t t i n g is not essential).
The role of h y d r o g e n is d i s c u s s e d in a following section.
Crack ProDaaation Characteristics
A c c e l e r a t i o n of stress c o r r o s i o n c r a c k i n g and c o r r o s i o n - f a t i g u e
p r o p a g a t i o n rates for a l u m i n u m alloys in acidic salt s o l u t i o n s has
o f t e n b e e n observed. Sedricks et al. [15] a t t r i b u t e d the a c c e l e r a t i o n
to more rapid crack tip d i s s o l u t i o n r e s u l t i n g from an e n h a n c e d c a t h o d i c
r e a c t i o n (i.e., h y d r o g e n reduction). The effect of pH d e c l i n e s as a
c r a c k lengthens due to local a c i d i f i c a t i o n of the c r a c k tip from m e t a l
ion hydroIysis. Sedricks et al. o b s e r v e d that the d i f f e r e n c e in impact
of a pH 1 and pH 6 salt water e n v i r o n m e n t on the c r a c k g r o w t h rate of
an A 1 - Z n - M g a l l o y d i s a p p e a r e d by the time cracks r e a c h e d a l e n g t h of 1
mm. The effect of pH on the crack p r o p a g a t i o n rates o b s e r v e d in the
p r e s e n t i n v e s t i g a t i o n are consistent w i t h this finding w h e r e c o m p a r i -
sons can be m a d e (i.e., that h i g h e r crack g r o w t h rates were o b s e r v e d in
the pH 2 e n v i r o n m e n t for crack sizes b e l o w 1 mm).
In a l k a l i n e solutions, the e x p e r i m e n t a l o b s e r v a t i o n s are mixed.
In 7XXX series alloys, i n c r e a s i n g pH from 6 to l0 p r o d u c e d a g r a d u a l
increase in stress c o r r o s i o n cracking resistance, a c c o r d i n g to M c H a r d y
and H o l l i n g s w o r t h [16]. At h i g h e r pH values, the increase in stress
c o r r o s i o n c r a c k i n g r e s i s t a n c e is s u b s t a n t i a l l y enhanced. On the other
hand, de J o n g [17] reported stress c o r r o s i o n c r a c k i n g rates that n e a r l y
follow the trends in c o r r o s i o n p r o d u c t solubility: a m i n i m u m in c r a c k
g r o w t h rate at pH 6-7, where c o r r o s i o n p r o d u c t s o l u b i l i t y is low, a n d
an increase in crack growth at higher and lower pH values, w h e r e solu-
b i l i t y is high.
Our results are consistent w i t h the o b s e r v e d i n c r e a s e in c r a c k
g r o w t h rate in acidic solutions r e p o r t e d by Sedricks et al. and w i t h
the m o d e s t r e d u c t i o n in crack growth rate in a l k a l i n e s o l u t i o n s ob-
s e r v e d by M c H a r d y and Hollingsworth. However, the r e a s o n for these
trends and the role of c o r r o s i o n p r o d u c t s o l u b i l i t y has yet to be
firmly e s t a b l i s h e d [18].
The cracks n u c l e a t i n g in the clad e x h i b i t e d two e a r l y stages of
g r o w t h c o m m o n l y c a l l e d Stage I and Stage II (see F i g u r e 6). These
stages are often o b s e r v e d in a l u m i n u m and a l u m i n u m alloys s u b j e c t e d to
fatigue loading [14], w h e t h e r that l o a d i n g occurs in an a g g r e s s i v e
m e d i u m or in a vacuum. However, some i n v e s t i g a t o r s [19,20] o b s e r v e d
m o r e r a p i d g r o w t h during Stage I and Stage II c r a c k i n g by a g g r e s s i v e
media.
C r a c k n u c l e a t i o n from c r y s t a l l o g r a p h i c pits in the c l a d did not
always occur at the largest pit. Figure 8a shows a crack that n u c l e -
a t e d next to a c o l o n y of c r y s t a l l o g r a p h i c pits and Figure 8b shows
several cracks n u c l e a t i n g in d i f f e r e n t locations w i t h i n a pit colony.
This suggests that the effect of the p i t t i n g on c r a c k n u c l e a t i o n in the
c l a d was not to increase the stress locally, but to p r o m o t e c r a c k
n u c l e a t i o n in some other way. The p o s s i b l e role of h y d r o g e n is dis-
c u s s e d in the next section.
H y d r o q e n Effects
The o b s e r v a t i o n that a v a c u u m treatment after salt w a t e r e x p o s u r e
(Fig. 7) p r o d u c e d a partial r e c o v e r y in the fatigue r e s i s t a n c e s u g g e s t s
that h y d r o g e n might have p l a y e d a role in fatigue crack n u c l e a t i o n a n d
e a r l y growth. It is unclear from the p r e s e n t data w h y full r e c o v e r y
FIG. 8--Corrosion-fatigue crack nucleation in the clad

layer of Alclad 2024-T3 aircraft skin tested in 0.5 M
NaCl solution at pH 6 fatigue loaded with a maximum
gross section stress of 0.958 ~y for 28,600 cycles.
was not achieved; incomplete hydrogen removal resulting from the vacuum
treatment, detrimental effects of pitting, or detrimental effects of
intergranular attack are possibilities.
Environmentally assisted cracking of aluminum alloys in salt
water has been ascribed to the detrimental effects of hydrogen, espe-
cially for high strength alloys of the 7XXX-series. The mechanism for
hydrogen embrittlement in such alloys, while still under debate, is
associated with: (I) matrix precipitates through their influence on
slip planarity, or (2) grain boundary precipitates through their influ-
ence on local hydrogen concentration resulting from trapping [2_!].
Hydrogen effects are enhanced by microstructures that have strengthen-
ing precipitates that permit planar slip (e.g., coherent precipitates)
so that hydrogen transport from dislocation atmospheres is enhanced.
However, hydrogen induced cracking of 2XXX-series alloys has been
rarely observed and requires high levels of dissolved hydrogen [17].
H y d r o g e n c r a c k i n g in pure a l u m i n u m was r e p o r t e d in at least two

cases and is a s c r i b e d to m e c h a n i s m s that are s u b s t a n t i a l l y d i f f e r e n t
from h y d r o g e n a s s i s t e d cracking in a l u m i n u m alloys. The A l c l a d layer
is s i m i l a r to pure a l u m i n u m mechanically, e l e c t r o c h e m i c a l l y , and in
terms of the s c a r c i t y of c o n s t i t u e n t particles. B o n d et al. [2_2]
i n d u c e d c r a c k i n g in h i g h p u r i t y aluminum, t r a n s m i s s i o n e l e c t r o n m i c r o -
scope specimens by injecting small amounts of h y d r o g e n into the m i c r o -
scope. The h y d r o g e n in the m i c r o s c o p e column e n h a n c e d c r a c k i n g and
d i s l o c a t i o n activity, w h i c h suggests that e m b r i t t l e m e n t was a c t u a l l y a
r e s u l t of h y d r o g e n e n h a n c e d l o c a l i z e d p l a s t i c i t y (known as the H E L P
mechanism).
T o n g et al. [23,2,~] o b s e r v e d that h y d r o g e n u s u a l l y i n c r e a s e d the
rate of c o r r o s i o n - f a t i g u e cracking in pure a l u m i n u m single c r y s t a l s in
M o d e II and in m i x e d Mode I/Mode II loading. S u s t a i n e d c r a c k i n g was
r e s t r i c t e d to the c l o s e - p a c k e d c r y s t a l l o g r a p h i c p l a n e s and d i r e c t i o n s .
In m o s t cases, crack g r o w t h rates w e r e s u b s t a n t i a l l y h i g h e r (by as m u c h
as a factor of 100) in s a t u r a t e d air s a t u r a t e d w i t h w a t e r v a p o r w h e n
c o m p a r e d w i t h the dry air results. E x c e p t i o n s to this trend w e r e ob-
s e r v e d in specific situations w h e n the c r y s t a l l o g r a p h i c o r i e n t a t i o n was
favorable for the aqueous e n v i r o n m e n t to p r o m o t e s e c o n d a r y m i c r o c r a c k s
that e f f e c t i v e l y blunt the p r i m a r y crack tip.
U s i n g an ion microprobe, Tong et al. d e t e r m i n e d that local
d e f o r m a t i o n s u b s t a n t i a l l y i n c r e a s e d the amount of h y d r o g e n in a l u m i n u m
single crystals immersed in v a r i o u s aqueous e n v i r o n m e n t s over that
p o s s i b l e b y d i f f u s i o n alone. The h i g h h y d r o g e n contents w e r e found
n e a r fatigue fracture surfaces and w e r e a t t r i b u t e d to t r a n s p o r t en-
h a n c e d by d i s l o c a t i o n sweeping. For example, they found that p u r e
a l u m i n u m fracture surfaces fatigued in air s a t u r a t e d w i t h w a t e r v a p o r
e x h i b i t e d a h y d r o g e n content of 6.02 p p m c o m p a r e d w i t h 0.58 p p m for dry
air w i t h a relative h u m i d i t y of less than 20%.
Furthermore, they u s e d an ion m i c r o p r o b e to show that h y d r o g e n

c o u l d p r o m o t e p l a s t i c d e f o r m a t i o n by r e d u c i n g the atomic b i n d i n g e n e r g y
of aluminum. The m a g n i t u d e of this r e d u c t i o n was m e a s u r e d to be 11%
for an a v e r a g e h y d r o g e n content of 7.5 ppm. The m e c h a n i c a l w e a k e n i n g
effect of h y d r o g e n was c o n f i r m e d t h r o u g h m e a s u r e m e n t s s h o w i n g that the
c r i t i c a l r e s o l v e d shear stress of a l u m i n u m was r e d u c e d by h y d r o g e n
a b s o r b e d from aqueous solutions or moist air w h e n c o m p a r e d w i t h alumi-
n u m s t o r e d in dry air. For example, the critical r e s o l v e d shear stress
was 1.96 MPa and 1.65 MPa for a l u m i n u m w i t h h y d r o g e n levels a d j u s t e d to
0.58 and 4.43 ppm, respectively.
The w o r k of Tong et al. and B o n d et al. is e s p e c i a l l y r e l e v a n t to

our results b e c a u s e they identify c r e d i b l e m e c h a n i s m s i n v o l v e d in the
overall p r o c e s s of h y d r o g e n e n h a n c e d n u c l e a t i o n and g r o w t h of f a t i g u e
cracks in the pure a l u m i n u m A l c l a d layer on 2024-T3 skin e x p o s e d to
c o m m o n a q u e o u s environments. Their e x p e r i m e n t s w i t h pure a l u m i n u m s h o w
that: (i) aqueous environments and moist air can p r o d u c e h i g h levels
of h y d r o g e n in the lattice, e s p e c i a l l y w h e n e f f e c t i v e d i f f u s i o n rates
are e n h a n c e d by d e f o r m a t i o n - i n d u c e d d i s l o c a t i o n motion, (2) once in
the lattice, h y d r o g e n s i g n i f i c a n t l y reduces the critical r e s o l v e d shear
stress, (3) the r e d u c t i o n in shear r e s i s t a n c e is a c c o m p a n i e d by a re-
d u c t i o n in the atomic b o n d i n g e n e r g y in a l u m i n u m as a r e s u l t of
d i s s o l v e d hydrogen, and (4) h y d r o g e n in a l u m i n u m can increase the crack

g r o w t h rate s u b s t a n t i a l l y under static or fatigue loads.
SUMMARYA~D CONCLUSIONS
E x p o s u r e of A l c l a d 2024-T3 aircraft skin samples to salt water

solutions in the l a b o r a t o r y r e v e a l e d that m u c h of the c o r r o s i o n damage
was in the form of c r y s t a l l o g r a p h i c pit colonies that formed on e x p o s e d
surfaces of the clad. An acidic e n v i r o n m e n t (pH 2) i n c r e a s e d p i t t i n g
at c o n s t i t u e n t p a r t i c l e s in the core material, in a d d i t i o n to the crys-
t a l l o g r a p h i c pits in the clad.
C r a c k n u c l e a t i o n near c r y s t a l l o g r a p h i c pits in the clad did not
always occur at the largest pit. This m a y be b e c a u s e the grain where
p i t t i n g o c c u r r e d was not as favorably oriented for Stage I cracking as
a n e i g h b o r i n g grain. Thus, in this case, the local increase in stress
due to the p r e s e n c e of the pit is of little importance. Instead, the
a c c e l e r a t e d c o r r o s i o n p r o c e s s e s a s s o c i a t e d with a pit m a y encourage
crack n u c l e a t i o n by p r o d u c i n g a high, local, h y d r o g e n c o n c e n t r a t i o n
in the clad in a n e a r b y grain with c r y s t a l l o g r a p h i c planes that are
f a v o r a b l y o r i e n t e d for crack nucleation.
The c o r r o s i o n - f a t i g u e experiments on A l c l a d 2024-T3 skin m a t e r i a l
suggest two competing m e c h a n i s m s for crack nucleation: crack nucle-
ation in the clad due to h y d r o g e n effects and crack n u c l e a t i o n in the
core as a result of p i t t i n g at constituent particles. Several investi-
gators have shown that, in the clad, h y d r o g e n enhances c r a c k i n g by
e n h a n c i n g l o c a l i z e d plasticity. Pitting at c o n s t i t u e n t particles is
b e l i e v e d to form local stress risers that lead to crack formation. The
m e c h a n i s m that dominates in any given situation depends on e n v i r o n m e n t
(e.g., pH), the p r e s e n c e or absence of a clad layer, and perhaps vari-
ables not w i t h i n the scope of this i n v e s t i g a t i o n (such as material
c o m p o s i t i o n and heat treatment).
ACKNOWLEDGMENTS
This r e s e a r c h is s p o n s o r e d by the Federal A v i a t i o n A d m i n i s t r a t i o n

under Grant 93-G-065.
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Single Crystals," MeDall. Trans., Vol. 20A, 1989, pp. 925-933.
Gary H. Bray, Robert J. Bucci, Edward L. Colvin, and Michael Kulak t
E F F E C T OF P R I O R C O R R O S I O N ON THE S/N F A T I G U E
P E R F O R M A N C E OF A L U M I N U M SHEET A L L O Y S 2024-T3
A N D 2524-T3
REFERENCE: Bray, G. H., Bucci, R. J., Colvin, E. L., and Kulak, M., "Effects of Prior
Corrosion on the S/N Fatigue Performance of Aluminum Sheet Alloys 2024-T3 and
2524-T3," Effects of the Environment on the Initiation of Crack Growth, ASTM STP 1298,
W. A. Van Der Sluys, R. S. Piascik, and R. Zawierucha, Eds., American Society for Testing
and Materials, 1997.
ABSTRACT: Aviation industry demand for continuous safety improvement in the face
of trends toward increasing service life of aircraft and cost control necessitates stronger
prevention and control measures to avoid the likelihood of structural failures linked to
widespread damage involving corrosion and fatigue. New materials with improved
damage tolerance attributes can improve the margin of safety in the presence of widespread
damage. An excellent example of one such material is new aluminum alloy 2524 (formerly
C188) which has improved fracture toughness and fatigue crack growth resistance relative
to incumbent alloy 2024. In this study, the effect of prior corrosion on the S/N fatigue
performance of 1.60 and 3.17-mm thick 2524-T3 and 2024-T3 bare sheet was evaluated.
The fatigue strength of 2524 was approximately 10% greater and the lifetime to failure 30
to 45% longer than that of the 2024. Two main factors are believed to have contributed to
the better performance of 2524: a less damaging configuration of corrosion pits and its
better fatigue crack growth resistance.
KEYWORDS: fatigue initiation, fatigue crack propagation, corrosion pitting, aluminum
alloys, aircraft
The economic necessity to extend the operating lifetimes of both new and existing
aircraft has given rise to new requirements that non-pristine or aging structure be accounted
for in design and maintenance strategies. Explicit in these requirements is the upgrading of
prevention/control measures to counter the potential emergence of a widespread fatigue
damage state, that in the presence of a larger rogue crack could imperil the structure's
damage tolerance capability. As a result, corrosion is no longer viewed primarily as a
maintenance issue, but as a potential threat to aircraft safety when combined with fatigue.
This shift creates demand for affordable, replacement materials that not only can resist the
occurrence of widespread fatigue damage (WFD) from corrosion or other sources, but
which also offer improved structural damage tolerance with WFD present.
1Staff Engineer, Technical Consultant, Technical Supervisor, and Senior Technical

Specialist, respectively, Alcoa Technical Center, Aluminum Company of America, 100
Technical Dr., Alcoa Center, PA 15069
89
Copyright*
Copyright 1997
by ASTM by(all
Int'l ASTM
rightsInternational
reserved); Fri Dec www.astm.org
30 21:53:51 EST 2011
An excellent example of one such material is new aluminum alloy 2524 (formerly
C188) that was developed to meet improved fracture toughness and fatigue crack growth
property requirements set by Boeing for the 777 jetliner fuselage skin. Typical mechanical
properties for this alloy are compared to those of 2024 in Table 1. Boeing utilized the
improvements of 2524 in fracture toughness and fatigue crack growth resistance to obtain
weight saving and reduced manufacturing costs over an incumbent alloy 2024 design [ 1,2].
Table 1--Typical mechanical properties for 2524-T3 and 2024-T3 sheet

in the long-transverse direction.
UTS TYS Elong. Kca da/dN@AK=33 b

Alloy Condition MPa MPa % MPa~/m m/c),cle
2524-T3 Clad 455 310 18 174 2.3E-06

Bare 462 317 18 . . . . . .
2024-T3 Clad 455 310 18 141 7.0E-06

Bare 462 317 18 . . . . . .
a M(T) specimen, T-L orientation, W=406 mm, 2ao= 102 nun tested per ASTM B646.
b T-L orientation, tested per ASTM E647 under constant AK conditions, R=0.1, relative humidity> 00%.
In this study, the effect of prior corrosion on the S/N fatigue performance of 1.60
and 3.17-mm thick 2524-T3 and 2024-T3 bare sheet was evaluated. The two alloys
possess equivalent tensile (Table 1) and SIN fatigue properties (Fig. 1) when tested in an
uncorroded condition. The classical rating systems of evaluating corrosion performance
also rate both alloys as being nominally equivalent (Table 2). However, recent work by
Wei et al. [3] and Chen et al. [4,5] indicates fatigue initiation resistance is degraded by
pitting at large, second phase particles. Fatigue initiation as used herein refers to the
nucleation of a fatigue crack which did not previously exist. Since the number of large,
second phase particles in 2524 is significantly less than that in 2024, it was hypothesized
that the S/N fatigue performance of bare 2524 may be superior to that of 2024 in a
precorroded condition.
rt
ell
250
225
NN ,20;
200
E
,-!
.E
x 175
R=0.1
Kt=2.5
. . . . . . . . . . . - . . ,
150
10000 100000 1000000
Cycles to Failure
Fig. 1--Comparison of S/N fatigue performance of bare 2524-T3 and
2024-T3 sheet in an uncorroded condition.
BRAY ET AL. ON EFFECT OF PRIOR CORROSION 91
Table 2--Corrosion performance of several lots of bare 2524-T3 and 2024-T3 sheet.
Thickness EXCO a MASTMAASISb Type of

Alloy mm 48 h 96 h 2 week 4 week Attackc
2524-T3 0.81 P P P P P
3.17 EA EB P EB IG
6.32 EA EB P EC IG
2024-T3 1.02 P EA P EA P+iG d

2.54 EA EA P EA P+iG d
6.32 EA EA EA EA IG
a Tested at mid-thickness (t/2) per ASTM 1334.
b Tested at mid-thickness (I/2) per ASTM G85, Annex A.2 (dry bottom).
c Tested per ASTM G110.
d Pitting with slight IG attack.
Materials and Microstructural Characterization
Two thicknesses of clad 2024-T3 and 2524-T3 sheet, 1.60 mm and 3.17 mm,
fabricated by Alcoa Davenport Works were procured for this study. Since these materials
were clad and the desired test condition was bare, the cladding was removed by machining
prior to testing. The final thicknesses after removal of the cladding were 1.37 mm and
2.54 mm, respectively. The materials will be referred to by their nominal thickness, 1.60
mm and 3.17 mm, for designation purposes. The morphology of large, second phase
particles on the L-ST plane was examined using optical metallography. This plane was
normal to the direction of loading in the fatigue tests. In addition, the number of particles
and their areal size were measured with automated optical image analysis for the 3.17-mm
sheet only. The sample area was 2.525 mm 2. The minimum particle size that could be
resolved was 2 larn2.
Specimen Fabrication and Corrosion CharacteriTation
Smooth, sheet-type S/N fatigue specimens were machined in the long-transverse

(LT) direction, seven per alloy from the 1.60 mm-sheet and thirteen per alloy from the
3.17-mm sheet. A smooth geometry was selected instead of a notched one because it
samples a larger volume of material. The specimen had a gage length of 31.7 mm and a
gage width of 12.7 ram. The tool marks from removal of the cladding were eliminated by
wet sanding the specimen faces in the length direction with 600 grit paper.
The specimens were corroded by 24 h exposure to NaCI/H202 solution prepared in

accordance with ASTM Standard Practice for Evaluating Intergranular Corrosion
Resistance of Heat Treatable Aluminum Alloys by Immersion in Sodium Chloride +
Hydrogen Peroxide Solution (G 110). A study by Colvin et al. [6] indicates the fatigue
performance of 2024 sheet after 24 h exposure in NaCI/H202 is similar to that obtained
after one year exposure to a seacoast environment. Both the faces and edges were exposed
in the gage section of the specimens. The faces correspond to the L-LT plane and the edges
to the LT-ST plane.
One corroded specimen from each of the materials was cross-sectioned on a random
L-ST plane and examined using optical metallography to determine the mode of corrosion
attack. To characterize the severity of attack in the 3.17 mm-sheet, the number and depth
of the corrosion features on the perimeter of the random plane were quantified by
automated optical image analysis. The minimum depth of corrosion attack that could be
resolved was approximately 12 lam. This information was also used to estimate the area
loss due to corrosion.
Fatigue Testing and Fractography
The remaining corroded specimens were tested in laboratory air using a stress ratio
of R=0.1. Duplicate specimens for each material were tested to failure at three stress
levels, 172, 207 and 241 MPa, in order to define the S/N fatigue curve in the neighborhood
of 105 cycles. This is typically the region of the S/N curve which is of greatest interest for
design of civil transport aircraft. The load applied to achieve a given stress level was based
on the nominal specimen dimensions prior to corrosion. For the 3.17-mm sheet, four
additional specimens were tested for each alloy at the intermediate stress level to better
determine the variability in lifetime. Interrupted tests were also performed on the 3.17-mm
sheet to determine at what point in the lifetime fatigue cracking initiated. One specimen per
alloy was cycled for 15,000 cycles, and another for 25,000 cycles at 207 MPa, after which
both were pulled to failure in tension.
Six failed specimens per thickness and alloy were examined in a scanning electron
microscope (SEM) to determine primary initiating feature(s) and their sizes. The number of
secondary cracks were also counted for the 3.17-mm sheet. The interrupted test specimens
were examined in the SEM for evidence of fatigue initiation.
EXPERIMENTAL RESULTS
Microstructural and Corrosion Characteristics
The optical metallography revealed that 2524 had significantly fewer large, second
phase particles than 2024 in both sheet thicknesses as expected (Fig. 2). The distribution
of particle sizes obtained from the 3.17-mm sheet (Fig. 3) revealed that 2524 had fewer
particles over the entire size range, but that the greatest difference between the two alloys
was in the size range of 25 lam2 and less. The overall density of particles was 800/mm 2 in
2524 compared to 2290/mm 2 in 2024.
The type of corrosion attack in all materials was predominantly pitting corrosion
(Fig. 4). This type of attack is typically observed in 2X24-T3X products less than
approximately 2 mm in thickness which can be quenched rapidly enough to be resistant to
intergranular corrosion. As product thickness increases, the attack typically changes from
pitting to a mixture of pitting and intergranular corrosion to primarily intergranular
corrosion [7]. The corrosion behavior can vary considerably from lot-to-lot particularly in
the intermediate thickness range where the mode is mixed. Thus, while the lots of 3.17-
mm sheet used in this study exhibited predominantly pitting corrosion, other lots of this
same thickness may exhibit a combination of pitting and intergranular attack.
Fig. 2--Optical micrographs showing morphology of large, second phase particles

in 1.60-mm thick (a) 2524-T3 and (b) 2024-T3 sheet.
(a) 1400 (b) 200

9 2024 i 9 2024
1200
D 2524 [] 2 5 2 4
r 150
1000
tO
800 n
"3 100
b
600 ,.O
E E
z 400 Z
50
200
\
0
10 100 1000 25 125 225
Particle Area (p.m^2) Particle Area (gm^2)
Fig. 3--Histograms comparing (a) entire distribution and (b) upper tail of the distribution
of particle sizes in 3.17-mm thick 2524-T3 and 2024-T3 sheet.
Fig. 4--Optical micrographs of random plane showing pitting corrosion in bare 1.60-mm
thick (a) 2524-T3 and (b) 2024-T3 sheet after 24 h exposure to NaC1/H202 solution.
The pits on the specimen faces (L-LT plane) were hemispherical in shape, while
those on the specimen edges (LT-ST) plane were elongated. It could not be determined
whether the pitting was associated with the constituent particles, but the work of Wei et al.
[3] and Chen et al. [4,5] suggest this may have been the case. The distribution of pit
depths obtained in the 3.17-mm sheet is shown in Figure 5. The average density of
resolvable pits (12 lam) on the specimen perimeter was 2.5/mm in 2524 compared to
3.2/mm in 2024. The density of smaller pits (<12 lam deep) may have been significantly
greater in 2024, but these would be less likely to act as fatigue initiation sites. The area
loss due to corrosion in the 1.60-mm sheet was estimated to be 4.6% for 2024 and 4.0%
for 2524, while that in the 3.17-mm sheet was estimated to be 1.1 and 0.9%, respectively.
S/N Fatieue Results and Fractoeranhv
A Box-Cox equation [8] was fit to the individual fatigue test results to obtain stress-
life (S/N) curves for precorroded 2524 and 2024 (Fig. 6). The lifetime at each stress level
and the fatigue strength at 105 cycles obtained from the Box-Cox fit are given in Table 3.
The fatigue performance of precorroded 2524 was superior to that of 2024. For both
thicknesses, the lifetime to failure of precorroded 2524 was 30 to 45% longer than that of
precorroded 2024 depending on stress level, and the fatigue strength at 10 cycles
approximately 21 MPa or 10% higher. Prior corrosion reduced the fatigue strength of both
alloys approximately 140 MPa relative to the typical smooth (Kt=l) fatigue strength of 345
MPa for bare, uncorroded material [9].
(a) 16 (b) 10
9
14 9 2024 9 2024
8
12 2524 2524
7
1/)
~_1o i
~- 6
i "6
8 5
..o
E E
.-i 4
-, 6 z
Z
3
2
1
0 0
0 0.05 0.1 0.15 0 0.2 O.4
Pit Depth (mm) Pit Depth (mm)
Fig. 5--Histograms comparing distribution of pit depths (after 24 h in NaC1/H202) on

random plane (L-ST) of 3.17-mm thick 2524-T3 and 2024-T3 sheet:
(a) specimen faces and (b) specimen edges.
250
R=O.1 2024, 1.60 mm
Kt=1.0
" 2524, 1.60 mm
Precorroded
225
2024, 3.17 mm
2524, 3.17 mm
200
E
E
X
175
Brackets show scatter in six specimens
of 3.17-mm sheet tested at 207 MPa
, i = = , , i ! i
150 ' " ......
10000 100000 1000000
Cycles to Failure
Fig. 6--S/N fatigue curves for bare 2524-T3 and 2024-T3 sheet with
prior corrosion (24h in NaCI/H202).
Table 3--Comparison of S/N fatigue performance of bare 2524-T3

and 2024-T3 sheet with prior corrosiona.
Thickness Lifetime at Smax= Smax at

mm Alloy 172 MPa 207 MPa 241 MPa 105 cycles
1.60 2024 171800 82000 47900 196

2524 221900 115000 70200 216
%Improved +29% +40% +46% +10%
3.17 2024 197500 96400 57000 205

2524 252600 135000 83500 228
%Improved +28% +40% +47% +11%
a Smoo~ specimen ~s~d m l a b a i r ~ r 2 4 h i n NaCI/H202solufion(ASTMGII0),R=0.I.
SEM fractography revealed that the largest or primary fatigue cracks originated on
the specimen edges in all specimens examined (Fig. 7). The edges correspond to the
through-thickness orientation (LT-ST plane) which is representative of the surfaces of a
fastener hole or splice edge. Fatigue cracking typically initiated at 4 to 8 pits and then
coalesced to form a common crack front. Generally, the pits in 2524 were elongated and
separated by uncorroded material, while those in 2024 were partially or fully coalesced.
The maximum depth of corrosion attack in the primary origin area varied significantly from
specimen to specimen but on average was similar in the two alloys for the 1.60-mm sheet,
while in the 3.17-ram sheet, 2524 exhibited shallower attack than 2024 (Table 4). The
fracture surfaces exhibited many secondary cracks on both the faces and edges, each
typically containing multiple pit initiation sites. The number of secondary cracks in the
3.17-mm sheet also varied significandy from specimen to specimen, but on average was
slightly less in 2524.
Fig. 7--SEM fractographs from 3.17-mm thick sheet showing typical primary origin area
on sw, cimen edge in (a) 2524-T3 and (b) 2024-T3 sheet
Table 4--Maximum depth of corrosion attack in primary origin area and number of
secondary cracks on the plane of failure.
Thickness Max. Depth of Attack, mm No. Secondary Cracks

mm Alloy Rangea Averagea Rangea Averagea
1.60 2524 0.267-0.521 0.367 . . . . . .

2024 0.259-0.648 0.374 . . . . . .
3.17 2524 0.292-0.632 0.416 5-26 15

2024 0.439-0.681 0.550 6-28 16
a Range and averageof six specimensfrom each thickness and alloy.
The large number of secondary cracks and fatigue initiation sites indicates that
fatigue initiation occurred quickly and easily in the precorroded specimens and that fatigue
crack propagation comprised a significant portion of specimen lifetime. This was
confirmed by the interrupted tests in which fatigue cracking was observed emanating from
pits after only 15,000 cycles or less than 15% of the total life. Typically in a smooth,
uncorroded specimen, the plane of failure exhibits one or two initiation sites and no
secondary cracks. This is because classical initiation of the primary crack by reversal of
slip comprises approximately 80 to 90% of specimen lifetime and the primary crack
typically initiates and propagates to failure before additional cracks can form.
CRACK GROWTH ANALYSIS
Since fatigue crack propagation comprised at least 85% of the lifetime of the
precorroded specimens, a crack growth analysis was performed using CRACKS93 crack
growth analysis software [10] to investigate the effects of alloy, number of initiating pits,
pit depth, and aspect ratio on fatigue crack propagation lifetime. Fatigue crack growth data
was unavailable for these particular lots, so fatigue crack growth (FCG) curves from bare
2.54 mm sheet were substituted (Fig. 8a). The upper part of the curves are from R=0.1
tests. The near threshold data from R--'0.1 long crack data is not appropriate for short
cracks where crack closure effects are minimal so the curves were extended at low AK
using R=0.33 and constant Kmax data to approximate short crack behavior [11]. The
improvement in FCG resistance in 2524 relative to 2024 is more obvious in Fig. 8b which
shows the ratio of their crack growth rates in Fig. 8a over a range of AK.
The pits were modeled as comer flaws using symmetry. For example, for two
initiating pits, the pits were placed at if3 and 2t/3 (Fig. 9). The modeled thickness was
equal to one third of the specimen thickness, and the model width equal to the specimen
gage width. The crack was initially propagated as a comer crack using the Newman-Raiu
comer crack K-solution [12], the flaw dimension e being equal to the pit depth and the
dimension a equal to the pit half-width per their nomenclature. Once the crack propagated
through the model thickness the standard K-solution for a through crack was employed.
Using this approach, a model using only one comer flaw was used to predict the lifetime
for multiple edge flaws. This simplified the analysis, but it assumes an idealistic
distribution of flaws with no interaction between them. Due to these assumptions, the
predicted lifetimes should be viewed on a relative rather than an absolute basis. Selected
resuks of this analysis (Fig. 10) indicate that small differences in initial flaw configuration
( a ) 1E-04 1
T-L Orient. /, (b)
RH> 9 0 % . l I
1 E-05
./ A
O4
0
0.8
_~"
O
1 E-06
Od 0.6
tn
E 1E-07 ,E,,
, , ?- , ' ,[ [
z
Z 0.4
1 E-08 0
rr
1 E-09 /! - - - - - 2024
0.2
T-L Orient.
f ..... 2524 RH>90%
1E-10 0 ' = I , i i =
1 10 100 0 10 20 30 40
Z~K (MPa~/rn) AK (MPaqrn)
Fig. 8--(a) FCG curves from 2.54-mm thick 2024-T3 and C 188-T3 sheet
used for crack growth analysis. R--0.33 and constant Kmax data were used at low AK to
account for the short crack effect. (b) Ratio of 2524 to 2024 FCG rates versus AK.
t ~ ---~ 113 ~--
I I
| I
! i
t/3 2t/3
W y W
!
I
I
a~-
Idealized Representation Crack Growth Model
Fig. 9--Schematic showing simplified model for two corrosion pits

used in crack growth analysis.
and fatigue crack propagation resistance can significantly impact S/N fatigue performance
in circumstances where crack propagation comprises the majority of the specimen lifetime.
(a) 14oooo (b)1200oo

q\ 9 2024 9 2024
120000 \ [] 2524 100ooo ~ 2524
100000
~BBX \ ~
..-t
80000
\
"~ 80000 Ii
x o 60000
60000
R 40000
40000 2524
r
20000 20000 Flaw Depth (c)=0.254 mm
Aspect Ratio (c/a)=4
No. of Flaws=2 Aspect Ratio (c/a)=4
0 . . . . . . . . . ' 0
0 0.2 0.4 0 5 10
Flaw Depth (mm) Number of Initiating Flaws
Fig. 10--Results of crack growth analysis showing effect of (a) flaw depth and aspect ratio
and (b) number of initiating flaws on propagation lifetime.
DISCUSSION
Corrosion can degrade S/N fatigue performance in two ways: (1) cross-sectional
area loss resulting in increased stresses carried by uncorroded material, and (2) corrosion
features (e.g., pits) acting as stress concentrators and preferred fatigue crack initiation sites
analogous to mechanical flaws. In this study, prior corrosion approximately equivalent to
one year exposure to a seacoast environment, reduced the smooth fatigue strength of bare
2524 and 2024 sheet approximately 140 MPa or 40%. The estimated area loss was
approximately 5% in the 1.60-mm sheet and 1% in the 3.17-mm sheet. This percentage
area loss resulted in net section stresses which were approximately 9 MPa and 2 MPa
higher, respectively, than the applied gross stresses. This increase can account for less
than 14 MPa or 10% of the reduction in fatigue strength resulting from prior corrosion.
The remaining 90% or more of fatigue strength loss can be attributed to pits acting as stress
concentrators. As stress concentrators, the pits both accelerate initiation of fatigue cracks
and theft propagation while small.
Bare 2524 sheet exhibited better S/N fatigue performance with prior corrosion than
2024. The fatigue strength of 2524 was approximately 10% higher and the lifetime to
failure 30 to 45% longer than that of 2024. In view of the above mechanisms, the factors
which might contribute to 2524 having better fatigue performance than 2024 in a corroded
condition are : (1) less cross-sectional area loss; (2) a less damaging initial configuration of
initiating features (i.e., pits); and (3) better fatigue crack growth resistance. The estimated
percentage area loss in 2524 was 0.5% less than in 2024 in the 1.60-mm sheet and 0.2%
less in the 3.17-ram sheet. This slight difference can account for no more than a few
percent of the total difference in fatigue performance of the two alloys.
The remaining 95% or more of the difference in fatigue performance of the two
alloys must then be attributed to either a less damaging initial flaw configuration (i.e.,
fewer, smaller or more favorably shaped pits) in 2524 or its better fatigue crack growth
resistance or a combination of both. The improvement from a less damaging initial flaw
configuration may result both from more cycles required to initiate a crack and slower
propagation of small cracks while under the influence of the pits, the latter probably the
more dominant in this case. The improvement from better fatigue crack growth resistance
is that resulting solely from the slower crack growth rates in 2524. The superior fracture
toughness of 2524 was not a factor in this study because failure of the narrow specimens
occurred by net section yielding. This being the case, the critical crack length in both alloys
was nearly identical since their tensile strength is nominally equivalent.
First, consider the initial flaw configuration. Assuming that pits are primarily
forming at large, second phase particles, it was anticipated that 2524 would have far fewer
pits, since its particle density is only about a third of that in 2024. The density of
resolvable pits (>12 Inn) was less in 2524 but the difference was not as large as expected.
One possible explanation is that pits of resolvable depth were mainly associated with the
larger particles in the upper tail of the size distribution where the difference between the two
alloys was not as great. The number of smaller pits (<12 larn deep) may have been
significantly greater in 2024, but these would be less likely to act as fatigue initiation sites.
The average number of secondary cracks and the total number of initiation sites was also
not significantly different in the two alloys, although this may be somewhat biased against
2524 because of its longer lifetime. In any case, it does not appear that the much lower
number density of large, second phase particles in 2524 translated into far fewer fatigue
initiating pits as was expected.
However, while the advantage of 2524 with respect to the number of fatigue
initiating pits may have been less than anticipated, the pits were less damaging with respect
to their depth and/or their aspect ratio. In both thicknesses, the pits in 2024 were typically
wider at their base (i.e., lower aspect ratio) than those in 2524 due to pit coalescence in the
former. One possible explanation for this behavior is that pitting at the smaller particles
abundant in 2024 are acting to link up the larger pits. This explanation, while not proven,
is consistent with the observations of Chen et al. [2,3]. The magnitude of the stress
intensity factor along the perimeter of the pit increases with increasing depth and decreasing
aspect ratio (i.e., increasing base width). This stress intensity factor controls the crack
growth rate while the crack is small enough to be under the influence of the pit. The crack
growth analysis performed for the simplified pit configurations showed that both pit depth
and aspect ratio can significantly affect crack propagation life. However, the complexity of
measuring and modeling the actual initial pit configurations observed in the failed
specimens makes it difficult to directly evaluate the contribution of these factors to the
observed differences in S/N fatigue performance.
The contribution of fatigue crack growth resistance to the superior performance of

2524 is easier to evaluate. An estimate of the contribution of differences in the initial flaw
configuration can then be obtained indirectly by subtracting out the contribution of the
former from the total performance difference. The crack growth analysis indicates that for
an equivalent initial flaw configuration, the fatigue crack propagation lifetime is
approximately 20% longer in 2524 than 2024. This is solely due to the improved fatigue
crack growth resistance in 2524. In the precorroded specimens, nearly the entire S/N life
was crack propagation. Thus, an S/N fatigue curve obtained by fitting the 2524 data with
lifetimes reduced by this percentage represents the performance of 2524 that would be
expected if it had the same fatigue crack growth behavior as 2024. This curve and the
actual S/N curves for 2524 and 2024 are compared in Fig. 11 for the 3.17-mm thickness.
The difference in the reduced-life curve and the actual curve for 2524 is the estimated
250
Life
\~, \\ Improvement
225
k '\ \ \ from FCG
0..
200
E from IFC f N~\ \\
E
~,,ol
2024 Actual N ~N~\
\\\ \
175
....... 2524 -20%
2524 Actual
150 . . . . ' . . . . . . ' .....
10000 100000 1000000
Cycles to Failure
Fig. 11--Estimated S/N fatigue curve for 3.17-mm thick 2524 assuming same FCG
performance as 2024 compared to actual curves for precorroded 2524 and 2024.
Table 6--Estimated contributions of differences in initial flaw configuration (IFC) and FCG
resistance to improvement in S/N fatigue performance of 2524 relative to
2024 with prior corrosion.
Thickness Fatigue Life/ Estimated % Contribution

mm Strength @ IFC a FCG
1.60 172 26 74
207 42 58
241 48 52
105cycles 41 59
3.17 172 24 76
207 41 59
241 48 52
105 cycles 43 57
a Includesany conlributionfrom differences in area loss.
contribution of fatigue crack growth differences to the superior performance of 2524, while
the difference in this curve and the actual curve for 2024 is the estimated contribution of a
less damaging initial flaw configuration in 2524. The latter also includes any contribution
from the slightly lower area loss in 2524, estimated to be a few percent at most. In this
way, the improvement in fatigue strength and lifetime of precorroded 2524 relative to 2024
can be partitioned between the two contributing mechanisms (Table 6). From this analysis,
it is estimated that the better fatigue crack growth resistance of 2524 accounts for
approximately 55 to 60% of its improved fatigue strength at 105 cycles relative to 2024 and
50 to 75% of its improved fatigue life, the percentage of the latter decreasing with
increasing stress level.The remaining 40 to 45% of fatigue strength improvement and 25 to
50% of lifetime improvement can then be attributed to a less damaging initial flaw
configuration in 2524. While these should be considered rough estimates, this analysis
suggests that both mechanisms, a less damaging configuration of corrosion pits and better
fatigue crack resistance, contributed significantly to the superior S/N performance of 2524
relative to 2024 in a corroded state.
While the observed improvement in 2524 with respect to 2024 is believed to be

correct and plausible mechanisms for this improvement have been identified, it should be
recognized that the test data is limited in scope with respect to the number of lots tested (2
each alloy) and sample size (6 to 10 specimens), and therefore not sufficient to reliably
quantify the magnitude of the performance improvement. It should also be noted that the
improvement was observed for the case of pitting corrosion only and should not be
assumed to exist when other forms of corrosion such as intergranular attack are present.
However, while there may be considerable variability in the corrosion behavior of 2X24
sheet due to thickness and processing effects, the fatigue crack growth resistance of 2524 is
expected to exceed that of 2024 in nearly all cases. Thus, when fatigue crack propagation
is a significant fraction of total S/N fatigue life as is the case when stress concentrators such
as corrosion features are present, 2524 has an inherent advantage over 2024.
SUMMARY AND CONCLUSIONS
Prior corrosion, approximately equivalent to one year exposure to seacoast

environment, reduced the smooth fatigue strength of bare 2024-1"3 and 2524-T3 sheet at
105 cycles by approximately 140 MPa or 40%. The main factor, responsible for
approximately 90% of the loss in fatigue strength, was corrosion pits acting as mechanical
flaws (i.e., stress concentrators) from which fatigue cracks initiated and grew. As stress
concentrators, the pits both accelerate initiation of fatigue cracks and their propagation
while small. The primary initiating pits were located on the specimen edges (LT-ST plane)
which am representative of a splice edge or fastener hole. The pitting nearly eliminated the
classical fatigue initiation stage (i.e., reversal of slip) which typically comprises the large
majority of the life of a smooth, uncorroded specimen. Thus, the majority of life in the
corroded specimens was spent in crack propagation from corrosion-induced pitting.
Cross-sectional area loss accounted for the remaining 10% of the loss in fatigue strength.
Bare 2524-T3 sheet exhibited better fatigue performance in a precorroded state than
bare 2024-T3 sheet. The fatigue strength of 2524 was approximately 10% greater and the
lifetime to failure 30 to 45% longer than that of the 2024. Two main factors are believed to
have contributed to the better performance of 2524: a less damaging configuration of
corrosion pits (with respect to number, depth and/or shape), and its better fatigue crack
growth resistance. The improvement from a less damaging initial flaw configuration may
result both from more cycles required to initiate a crack and slower propagation of small
cracks while under the influence of the pits, the latter probably the more dominant in this
case. The improvement from better fatigue crack growth resistance is that resulting solely
from the slower crack growth rates in 2524. These two factors were estimated to account
for approximately 45 and 55% of the improvement in fatigue strength, respectively.
The results of this study suggest that bare 2524-T3 sheet is better able to delay the
onset of widespread fatigue damage ensuing from pitting corrosion. This improvement
could particularly be beneficial in small aircraft where the use of thin, bare sheet is
common. Alloy 2524 also offers improved structural damage tolerance in the presence of
widespread fatigue cracking due its superior fatigue crack growth resistance and fracture
toughness.
REFERENCES
[1] Hyatt, M.V. and Axter, S.E., "Aluminum Alloy Development for Subsonic and
Supersonic Aircraft," Science and En eineerin e of Li eht Metals (RASELM '91), Jap an
Institute of Light Metals, October 1931, pp. 2-73-280.
[2] Staley, J.T., "Aluminum Alloys for Subsonic Aircraft," Aerospace Thermal Structures
and Materials for a New Era. University of Vireinia Thermal Structures Conference
(2nd), Charlottesville, VA, October 19, 1994,-pp. 343-358.
[3] Wei, R.P, Gao, M. and Harlow, D.G., "Pitting Corrosion in Aluminum Alloys:
Experimentation and Modeling," Presentation at Air Force 3rd Aging Aircraft
Conference, Wright-Patterson Air Force Base, September 1995.
[4] Chen, G.S., Gao, M., Harlow, D.G. and Wei, R.P., "Corrosion and Corrosion
Fatigue of Airframe Aluminum Alloys," FAA/NASA International Symposium on
Advanced Structural Inte~,ritv Methods for Airframe Durability and Damaee Tolerance.
NASA Conference PubliCation 3274. Part 2, September 1994, pp. 157-173
[5] Chen, G.S., Gao, M. and Wei, R.P., "Micro-Constituents Induced Pitting Corrosion
in a 2024-T3 Aluminum Alloy," Corrosion. Vol. 52, No. 1, January 1996, pp. 8-15.
[6] Colvin, E.L, Jones, S.A. and Magnusen, P.E, "Effect of Corrosion Fatigue Initiation
and Growth in Damage Tolerant Aluminum Sheet Alloys 2024-T3 and 6013-T6,"
Effects of the Environment on the Initiation of Crack Growth. ASTM STP 1298, W.A.
Van der Sluys, R.S. Piascik, and R. Zawierucha, Eds., American Society for Testing
and Materials, 1997.
[7] Aluminum: Properties and Physical Metallurgy. J. Hatch, ed., American Society for
Metals, 1984, p. 167-169
[8] Hinlde, A.J. and Emptage, M.R., "Analysis of Fatigue Life Data Using the Box-Cox
Transformation," Fatigue and Fracture of En~ineefin~ Materials and Structures, Vol.
14, No. 5, 1991, pp. 391-600.
[9] Metallic Materials and Elements for Aerospace Vehicle Structures, Mil-Hdbk-5G,
1994.
[10] Gallagher, J.P., Miedlar, P.C., Cross, C.W. and Papp, M.L., "Cracks93 System-
PC Version," University of Dayton Research Institute, 1993 October.
[11] Herman, W.A., Hertzberg, R.W, and Jaccard, R., "A Simplified Laboratory
Approach for the Prediction of Short Crack Behavior in Engineering Structures,"
Fatigue and Fracture of En~ineerin~ Materials and Structures, Vol. 11, No. 4, 1988,
pp. 303-320. - -
[12] Newman, J.C. and Raju, I.S., "Stress Intensity Factor Equations for Cracks in
Three-Dimensional Finite Bodies," NASA Technical Memorandum 83200, Langley
Research Center, Hampton, VA, August 1981.
Stress Corrosion Crack Initiation in
Nuclear Environments
Redvers N. Parkins ~ and Mahvash Mirzai 2
INFLUENCE OF A MIXED NITRATE SOLUTION ON THE INITIATION AND

EARLY GROWTH OF STRESS CORROSION CRACKS IN A LOW ALLOY STEEL.
R E F E R E N C E : Parkins, R.N. and Mirzai, M., " I n f l u e n c e o f a M i x e d

N i t r a t e S o l u t i o n o n t h e I n i t i a t i o n a n d E a r l y G r o w t h of s t r e s s
Corrosion Cracks in a L o w A l l o y Steel," Effects of the
Environment on the Initiation of Crack Growth, A S T M STP 1298,
W.A. Van Der Sluys, R.S. Piascik, and R. Zawierucha, Eds.,
ABSTRACT: Constant strain stress corrosion tests, at 50 or

100% yield stress, were conducted on welded nickel steel
samples exposed to a mixed nitrate solution for various times.
Where grain boundaries intersected the specimen surfaces
selective attack was invariably observed, even for relatively
short exposure times. Average growth rates for the early
stages of cracking showed considerable variability, by about
an order of magnitude, for a given test time and point to the
importance of replicate tests if appropriate data are to be
collected.
KEYWORDS: Stress corrosion cracking (SCC), nitrate solution,

nickel steel, constant strain tests, crack initiation, early
growth, dormant cracks, statistical treatment.
Definition of what constitutes the initiation of a stress

corrosion crack is more difficult than may be apparent at
first sight. While it may be useful for some purposes if
crack initiation could be defined in terms of some invariably
applicable dimension, it is probably the case that initiation
needs to be defined for specific situations. Thus, the
exposure of some metals to particular environments that induce
intergranular S C C promotes instantaneous attack at the grain
boundaries, even in the absence of applied or residual stress
[!]. That raises the question as to whether or not
i Emeritus Professor of Metallurgy, Herschel Building,

University of Newcastle upon Tyne, Newcastle upon Tyne NEI
7RU, U.K.
2 Design Engineer Specialist - Materials, Ontario Hydro, 700

University Avenue, Toronto, Canada M5G IX6.
107
Copyright
Copyright by ASTM
9 1997 Int'l International
by ASTM (all rights reserved); Fri
w w w Dec
. a s t30
m . o21:53:51
EST 2011
rg
such grain boundary attack constitutes crack initiation.

Alternatively, in other systems, the formation of pits is a
forerunner of cracking and would appear to invite some
different definition of crack initiation. The association of
SCC with surface pits has sometimes been assumed to arise from
the stress concentration that accompanies pit formation.
However, pits and other geometrical discontinuities may also
result in changes in environment composition and electrode
potential, by comparison with their values outside the
discontinuity. Such changes in the environmental conditions
within a pit may promote SCC from an otherwise innoxious bulk
environment. Moreover, SCC from pits may show structural
dependence, e.g. at grain boundaries or emergent slip steps,
raising a further problem in defining initiation. It is
difficult to see how crack initiation can escape some degree
of arbitrariness in the light of such comments and,
furthermore, it appears likely that definition of initiation
will need to be system specific.
The objective of the work described below was to provide

data that would allow predictions to be made relating to the
propensity for S C C failures in components exposed in the vault
of a nuclear reactor, where radiolysis of moist air could
produce nitric acid, giving rise to a mixed, acidic nitrate
environment. Nitrates are well known to promote
intergranular SCC in ferritic steels, but any attempt to
predict the likelihood of a failure requires data relating to
the particular steel and environmental conditions involved and
such data were not available. The laboratory data obtained
relating to the early stages of SCC initiation and growth
indicated a number of matters that need to be considered in
addressing the issue of environment-assisted crack nucleation
in general.
The SCC of ferritic steels is known to depend upon the

composition [2] and temperature of nitrate solutions and upon
the associated electrode potentials, as well as upon the
composition [~] and structure [4] of the steel. While some
of those variables could be quantified for the present case,
others could not; specifically, the composition of the
environment and the potentials involved were not known with
sufficient precision. Consequently, the first task was to
obtain data relating to the influence of those variables on
the cracking propensity of the relevant steel. Chemical
analysis of a liquid from the vault sump suggested a solution
with which to start that part of the investigation, it being
recognised that the sump liquid could be appreciably diluted
by comparison with that in contact with those surfaces of
interest from the SCC viewpoint. Slow strain rate tests were
chosen as a means of assessing the effects of solution
composition and electrode potential upon cracking
susceptibility. The data from those tests were used to
identify appropriate conditions for subsequent constant strain
tests, the latter being those with which this paper is
PARKINS AND MIRZAIONINFLUENCE OFA MIXED NITRATE 109
exclusively concerned.
EXPERIMENTAL METHOD
Materials
The v a r i o u s samples, w h i c h r e f l e c t e d m a t e r i a l s e m p l o y e d
in t h e vault, w e r e p r e p a r e d f r o m A203 g r a d e B or E s t e e l s w i t h
t h e c o m p o s i t i o n s i n d i c a t e d in T a b l e i, w h i c h a l s o g i v e s t h e
c o m p o s i t i o n of the w e l d m e t a l involved.
TABLE 1 Compositions (wt%) of m a t e r i a l s .
Grade %C %Mn %P %S %Si
B 0.15 0.52 0.008 0.011 0.21 2.21
E 0.12 0.50 0.012 0.016 0.19 3.32

Weld 0.056 i.i0 0.009 0.011 0.42 3.53
The d e s i g n a t i o n s of the v a r i o u s s a m p l e s and t h e i r o r i g i n s w e r e

as follows:
A203HT - Grade E w e l d e d to G r a d e B, w i t h t h e g a g e
s e c t i o n i n v o l v i n g b o t h s t e e l s a n d t h e i r HAZ,
as w e l l as w e l d metal, and h e a t t r e a t e d at
635~ (• for 2h.
BHS - Grade B m a t e r i a l w e l d e d to G r a d e E, but the

g a g e s e c t i o n i n v o l v e d G r a d e B HAZ;
EHS - Grade E m a t e r i a l w e l d e d to G r a d e B, but the

gage s e c t i o n i n v o l v e d G r a d e E HAZ;
WSB - G r a d e E m a t e r i a l , b u t the g a g e section was

m o s t l y of w e l d metal.
Test Specimens
T h e t e n s i l e test s p e c i m e n s h a d g a g e lengths of 50 x 5 x
2.5 mm, w i t h the w e l d located so t h a t w i t h i n t h e g a g e l e n g t h
p a r e n t material, w e l d m e t a l and HAZ m a t e r i a l w e r e all present.
B e y o n d the g a g e length r a d i u s e d s h o u l d e r s led to a 12.5 m m
w i d t h for g r i p p i n g purposes. The test surfaces were polished
to a 1200 g r i t finish and d e g r e a s e d b e f o r e testing. The
specimens were strained in m o d e r a t e l y stiff frames that
incorporated a load cell, the output from which was
c o n t i n u o u s l y recorded. S t r a i n s c o r r e s p o n d i n g to two s t r e s s e s
w e r e used, 380 and 190 MPa, the f o r m e r b e i n g t h e a v e r a g e of
the y i e l d s t r e s s e s o b s e r v e d on the A 2 0 3 H T m a t e r i a l in the
e a r l i e r s l o w strain rate tests; the s t r e s s e s e m p l o y e d r e l a t e
to t h e m a x i m u m level of r e s i d u a l s t r e s s t h a t c o u l d r e m a i n in
1 10 EFFECTS OF THE ENVIRONMENT ON INITIATION OF CRACK GROWTH
some l o c a t i o n s or to a lesser level w h e r e some d e g r e e of

stress relief had b e e n achieved. In some of the t e s t s at 380
M P a there was a small a m o u n t (up to 3%) of load r e l a x a t i o n in
the first few hours after a p p l y i n g t h e strain; no a t t e m p t was
m a d e to i n c r e a s e the stress w h e r e s u c h r e l a x a t i o n occurred.
T h e e x p o s u r e t e s t s w e r e c o n d u c t e d for t i m e s up to 15 weeks,
after which they were removed from the cells and
u l t r a s o n i c a l l y c l e a n e d and dried. A d h e r e n t c o r r o s i o n p r o d u c t s
w e r e u s u a l l y p r e s e n t and w e r e r e m o v e d by e x p o s u r e to an
a l k a l i n e c y a n i d e s o l u t i o n w i t h c a t h o d i c c u r r e n t a p p l i e d to
p r e v e n t a t t a c k u p o n e x p o s e d metal. F o l l o w i n g SEM e x a m i n a t i o n
the specimens were prepared for optical microscopical
measurement of the d e p t h of cracking. Average crack
velocities were determined by d i v i d i n g the d e p t h of the
d e e p e s t crack by the e x p o s u r e time. Average crack velocities
w e r e o b t a i n e d for p a r e n t metals, w e l d metal and H A Z m a t e r i a l
in each specimen, but the r e s u l t s indicated that these
f e a t u r e s did not d i s p l a y s i g n i f i c a n t l y d i f f e r e n t d e g r e e s of
attack.
Exposure Conditions
The s p e c i m e n s w e r e c o n t a i n e d in glass cells, closed at

each end by a rubber s t o p p e r t h r o u g h w h i c h the ends of the
s p e c i m e n p r o t r u d e d for gripping. The cells w e r e h e a t e d by a
low v o l t a g e heating wire on the outer surface and the
t e m p e r a t u r e c o n t r o l l e d t h r o u g h a t h e r m o c o u p l e , c o n t a i n e d in a
glass p o c k e t in the cell, that a c t i v a t e d a c o n t r o l system; the
temperature was c o n t r o l l e d at 32~ (• T h e cells
c o n t a i n e d a Pt c o u n t e r e l e c t r o d e and a b r i d g e to an external
saturated calomel reference electrode for c o n t r o l l i n g the
potential, t h r o u g h a p o t e n t i o s t a t , at -500 mV. The latter
a p p r o x i m a t e d to the o p e n c i r c u i t potential.
The s o l u t i o n u s e d t h r o u g h o u t contained, per litre, 37 g

Ca, 1.66 g K, 1.53 g Na and 0.38 g N ~ , all a d d e d as nitrates.
The salts w e r e of 'Analar' grade and the w a t e r used was
d i s t i l l e d and deionised. The pH of the s o l u t i o n was a d j u s t e d
to 3.2 by the a d d i t i o n of n i t r i c acid. T h e cells c o n t a i n e d
about 75 ml of s o l u t i o n and in the early stages of a test the
pH t e n d e d to increase somewhat, a c c o m p a n y i n g the f o r m a t i o n of
r u s t on the s p e c i m e n surface. The solution was replaced
after the first two days and t h e r e a f t e r at w e e k l y intervals in
tests l a s t i n g m o r e t h a n 1 week, a l t h o u g h the pH c h a n g e s w e r e
small o n c e the s p e c i m e n s h a d d e v e l o p e d a f i l m of m a g n e t i t e
w i t h i n a day or two of the start of a test.
RESULTS
Structural Features of the A t t a c k
SEM e x a m i n a t i o n of every s p e c i m e n s h o w e d clear e v i d e n c e

of s t r u c t u r a l l y d e p e n d e n t a t t a c k after e x p o s u r e to the nitrate
PARKINS AND MIRZAI ON INFLUENCE OF A MIXED NITRATE 1 11
solution. Figure 1 shows part of the surface of a specimen

of A203HT, indicating obvious grain boundary attack in the
parent metal, while Figure 2 shows equivalent features in the
weld region of a similar sample but from a different specimen.
Samples of other materials showed similar effects, which were
not significantly dependent upon the stress to which the
specimens were initially strained.
Although there were little differences in the attack

apparent at the surfaces of the different samples, the latter
showed wide variations in the extent of the depthwise
penetration of the selective attack. In many specimens crack
depths were very small, Figure 3 showing a typical example in
the weld metal of a sample of EHS material tested for 500h at
100% YS. The cracks in weld metal were readily distinguished
Figure i. Scanning electron Figure 2. Surface of the

micrograph of the parent weld region of a sample of
metal surface in a sample of A203 HT after 1003 h
A203HT after 329 h exposure exposure at 100% YS.
at 100% YS.
from those in parent plate or HAZ material in that the cracks

in weld metal showed a marked tendency to develop short
branches from the main cracks at intervals appreciably less
than the grain size. The cracks in parent plate or HAZ
material, by contrast, only deviated when a grain junction was
met, as apparent from Figure 4. Such relatively deep cracks
were not often observed and where they were the specimen
contained only one or two, although in the same specimen other
regions of less deep cracking were invariably detected.
Indeed in some specimens, intergranular penetrations, to
depths of up to two grain diameters, occurred at every
boundary intersecting the surface for some twenty or so

grains, producing the appearance of what may be described as
intergranular corrosion spreading along the surface.
Figure 3. Section through Figure 4. Section through

EHS sample showing small EHS sample showing
cracks in weld region after intergranular cracking in
500 h exposure at 100% YS. parent metal after 166 h
exposure at 100% YS.
With a few specimens appreciable pitting occurred, at the

end of the gage length at the bottom of the cell and where
corrosion products collected. The pits were usually filled
with adherent magnetite below which intergranular cracks were
apparent, in some specimens constituting the deepest cracks
detected.
Averaqe Crack Velocities
A convenient way of considering the data in the first

instance is in terms of the time dependence of the average
growth rates for the deepest cracks detected in each specimen.
Figure 5 shows the results from all tests in which the stress
corresponded to 100% YS, while Figure 6 shows the equivalent
plot for the stress of 50% YS. Data are given for parent
plate and weld metal, the HAZ results being not significantly
different from those for the parent plate. Notable features
of these plots are that there is considerable scatter of the
data (by about an order of magnitude for a given test time)
and that the regression lines have slopes somewhat in excess
of -i. The implication of such slopes is that the cracks in
most specimens ceased to propagate at some time prior to the
shortest test time and the apparent reduction in growth rates
P A R K I N S A N D M I R Z A I ON I N F L U E N C E OF A M I X E D N I T R A T E 1 13
simply results from dividing the same depth by increasing

times. However, the scatter in the data suggests that, while
most cracks may have become dormant after some initial growth,
some may have continued to grow. The matter is further
complicated by the probability that not all cracks would be
initiated at the same time, despite the indications of an
inherent susceptibility to intergranular attack indicated in
Figures 1 and 2. It had been hoped to collect data for the
rates of nucleation of cracks, by examination of the surfaces
of specimens, but in the event that was not possible because
of attack at every grain boundary even after short exposure
times. Moreover, counting the number of embryonic cracks in
sections through the specimens provided no systematic change
in the rate of nucleation for the various exposure times.
Figures 5 and 6 do not indicate any significant differences
between the average velocities for cracks in parent or weld
metal, nor any marked differences resulting from the different
stresses. Thus, the general indications were that
intergranular attack in most instances occurred to some depth
(usually not more that about 0.01 m m), after which p e n e t r a t i o n
ceased, but occasionally deeper cracks were detected.
10-6 ' Parent Weld

A203HT o 9
BHS ~ 9
v) v EHS v A
E 10 -7
E WSB + x
>- x
9 +
S
>~
M
10.8
,<
<
u~ 10.9
.<
10-10
100 1000 10000
TIME hr
Figure 5. Average crack velocities for the deepest cracks in

parent plate and weld metal in various samples exposed for
different times at 100% YS. Slope of regression line = -i.i.
It is, of course, the exceptional deeper cracks that are

most important from the viewpoint of possible extension to
produce a failure. A better way of considering the data
therefore is in terms of the d i s t r i b u t i o n of velocities and
Weibull analyses are often useful in this respect.
10-7
" Parent Weld "
o A203HT o 9
8HS [] 9
~ v EHS v A
10-'
<
10.9
,<
i0-Io
100 ~000 10000
TIME hr
Figure 6. Average crack velocities for the deepest cracks in

parent plate and weld metal in various samples exposed for
different times at 50% YS. Slope of regression line = -1.3.
Weibull plots were made for the various samples, for parent
plate and weld metal and for the two stresses used. These
did not show significant differences except for the A203HT
samples showing lesser average growth rates than the
BHS/EHS/WSB samples; the latter did show differences in growth
rate with stress level, but not the A203HT samples, as shown
later. Otherwise, the data for parent and weld metals did
not show significant differences and so the data for both of
those materials were combined for all samples. In the
initial Weibull analysis of the data consideration was given
to the effect of exposure time and while the characteristic
values showed no significant change with time, the slopes of
the lines tended to increase, but with appreciable scatter, as
the test time increased. The slopes of the Weibull lines
tended to increase from a little below 1 to above 1 as the
test time increased, implying an increasing failure rate with
time.
Figure 7 shows the Weibull plot for the average crack
velocities for the A203HT specimens at both stress levels,
corrected with the location parameter shown. The
characteristic value, corresponding to the Weibull function
= 0 and often used for comparative purposes, is about 3 x i0 ~
mm/s. The equivalent plots for BHS/EHS/WSB samples, each of
which behaved similarly, are shown in Figures 8 and 9 for the
higher and lower stress levels respectively. For the stress
corresponding to 100% YS the characteristic value is 9 x i0 ~
mm/s and for 50% YS the value is 3 x 10 -9 mm/s.
PARKINS AND MIRZAI ON INFLUENCE OF A MIXED NITRATE 1 15
2 J
Data for A203HT50 & 100%YS /
Locationparameter2"9x 10"t~mm/s J 00
O<3/
ooo
u._
"%-~ i0-~ I0-9 104 10.?
AVERAGECRACKVELOCITY mm/s
Figure 7. Weibull plot of the distribution of crack velocities

for the d e e p e s t cracks in parent or weld metal f o r A203HT
samples, tested for various times at stresses of 50 or 100%
YS.
Data for BHS,EHSandWSBal I00~,,YS /
o
Z
J:E)
10 "11 10 "~~ 10 "g 10 a 10.7 10"
AVERAGECRACKVELOCITY mm/s
Figure 8. Weibull plot of the d i s t r i b u t i o n of crack velocities

for the deepest cracks in parent or weld metal for BHS/EHS/WSB
samples, tested for various times at 100% u
Data f~ BHSandEHSat 50%YS /
c
c
Z
o
_H
nn
10" 10 "~) 10.9 10~ 10.7
AVERAGECRACKVELOCITY rnm/s
Figure 9. Weibull plot of the distribution of crack velocities

for the deepest cracks in parent or weld metal for BHS/EHS
samples, tested for various times at 50% YS.
DISCUSSION
There are obvious difficulties in defining crack

initiation in the present system because attack occurred at
all exposed grain boundaries, and other structural features in
the case of welds. It is possible to adopt some arbitrary
depth of penetration to define initiation, such as the average
of the maximum depths (=0.004 mm) achieved in those specimens
that displayed the shortest cracks, such a dimension
approximating the smallest crack that can be readily measured
by optical microscopy. However, that does not reflect the
dormant condition that appears to occur with many cracks,
which simply compounds the problem of definition.
It appears likely that the growth of cracks in ferritic steels
exposed to nitrate solutions will involve the same dissolution
process as results in selective attack at grain boundaries
even in the absence of stress [!], despite possible changes in
environment composition within the crack enclave. The stress
is effective in disrupting any films that form over the crack
tip and which would otherwise prevent the continuing selective
dissolution that constitutes the growth mechanism. Accepting
such, it would appear that measurements relating to the early
stages of growth, involving relatively short cracks, are more
appropriate than debate as to what constitutes crack
initiation. That was the philosophy adopted in collecting
PARKINS AND MIRZAI ON INFLUENCE OF A MIXED NITRATE 117
the data in the present work.
The results clearly show that there is considerable

variability in the maximum crack depths developed in similar
specimens exposed for the same time. That indicates the need
for appropriate replication of tests and the subsequent
statistical treatment of the resulting data. It is possible
with laboratory tests to reduce scatter by enhancing certain
exposure conditions. For example, by applying more arduous
stressing or straining conditions, and the slow strain rate
tests conducted prior to the work reported here showed much
less scatter in the average crack velocities than were
obtained from the constant strain tests reflecting operating
conditions in the plant in question. Similarly, increases in
temperature or solution concentration, or the use of different
controlled potentials, may result in more reproducible data
and the collection of laboratory data is often accelerated by
such approaches. The problem then is that some extrapolation
towards more realistic values of those variables is necessary
if operating conditions are to be considered. That is not
essentially different from the extrapolation that needs to be
undertaken if tests near to operating conditions are conducted
for times that are invariably markedly shorter than the times
involved with plant. That is an obvious problem with the
present data, involving tests that ran for about 15 weeks at
the most, yet need to be considered in relation to plant that
has been operating for some 20 years. In considering such
laboratory crack velocity data, a few features are worth
remembering. The first is that the velocities are average
values, but that single value does not mean that the cracks
propagate at a constant rate during the exposure period, nor
that such a rate will persist to markedly longer times.
Thus, for another system [5] involving ferritic steel exposed
to a different environment, it has been shown that individual
cracks become dormant and then active again at various times
during prolonged exposure, and that the average growth rate
can show marked variations with time and crack size.
Moreover, there is the indication from the present data that
a distribution of velocities is observed for nominally
identical specimens exposed for the same time to the same
conditions. There is the further point that in obtaining the
laboratory data the exposure conditions were m a i n t a i n e d
constant, but such conditions probably do not hold in service,
where the composition of the environment and the potential may
vary with time. Nevertheless, it is useful to compare, in a
very simple way, the implications of the laboratory data to
service experience.
This may be done by calculating the time required for a

crack to reach i0 mm depth, i0 mm approximating the depth for
detection. That simple calculation has been m a d e for the
velocities observed with the various specimens involved in the
present work and the results are shown in Figure i0 as Weibull
plots.
1 18 E F F E C T S OF T H E E N V I R O N M E N T ON INITIATION OF C R A C K G R O W T H
o BHS + EHS + WSB 100%YS

o/
0 A203HT 50~- 100% YS / 8~.
Z
o
o
. . . . . %cha oe
LL
-" ~ - o . . . . . . . ~---- 10% chance
,, i~ ' . . . . . . . . . . . .
-4
10 100 1000
TIME TO REACH CRACK DEPTH OF 10 rnm years
F i g u r e i0. W e i b u l l plots of the times for cracks to reach a

d e p t h of i0 mm for B H S / E H S / W S B s a m p l e s s t r a i n e d to 50 or 100%
YS and for A 2 0 3 H T samples s t r a i n e d to e i t h e r stress.
For the c u r r e n t age of the p l a n t (=20 years) there is a i0 to

20% c h a n c e of there being i0 m m cracks p r e s e n t and that r e s u l t
led to the i n s t a l l a t i o n of h e a v y d u t y d r y e r s to remove
moisture from the vaults, even though no cracks were
detectable in the r e l e v a n t components. Of course, the
e x t r a p o l a t i o n of short t e r m l a b o r a t o r y t e s t data to long t e r m
s e r v i c e life p r e d i c t i o n s i n v a r i a b l y r a i s e s q u e s t i o n s as to the
reliability of such. However, such an a p p r o a c h to this
s y s t e m m a y be less o b j e c t i o n a b l e t h a n w i t h some other systems,
b e c a u s e of the m a r k e d p r o p e n s i t y for f e r r i t i c steels to suffer
grain boundary attack in nitrate solutions and the
c o n c e n t r a t i o n of the latter h a v i n g little i n f l u e n c e u p o n crack
g r o w t h rates once the c o n c e n t r a t i o n r e a c h e s the v a l u e u s e d in
the present experiments. That was indicated by the
p r e l i m i n a r y s l o w strain rate experiments, so that even if the
n i t r a t e c o n c e n t r a t i o n i n c r e a s e d w i t h i n c r a c k e n c l a v e s it w o u l d
h a v e little i n f l u e n c e upon g r o w t h rate.
CONCLUSIONS
I. T h e r e w i l l often be p r o b l e m s in d e f i n i n g stress c o r r o s i o n
c r a c k i n i t i a t i o n and these m a y be s u r m o u n t e d by s t u d y i n g the
early stages of crack growth.
2. The early stages of growth may show considerable

v a r i a b i l i t y , p r o b a b l y w i t h m a n y c r a c k s s o o n b e c o m i n g dormant,
especially if the conditions of e x p o s u r e and stressing
PARKINS AND MIRZAI ON INFLUENCE OF A MIXED NITRATE 119
approximate to likely service conditions. Consequently, it

is important to conduct replicate tests and apply statistical
treatment to the results.
REFERENCES
[!] Parkins, R. N., "Mechanistic Aspects of the Intergranular

Stress Corrosion Cracking of Ferritic Steels", Paper No.
183, CORROSION 95, NACE International, Houston, 1995.
[2] Parkins, R. N., and Usher, R., "The Effects of Nitrate

Solutions in Producing Stress Corrosion Cracking in Mild
Steels", First International Congress on Metallic
Corrosion, Butterworths, London, 1961, pp 289-295.
[~] Parkins, R. N., Slattery, P. W., and Poulson, B. S., "The

Effects of Alloying Additions to Ferritic Steels upon
Stress Corrosion Cracking Resistance", Corrosion, Vol.
37, 1981, pp 650-664.
[4] Parkins, R. N., Slattery, P. W., Middleton, W. R., and

Humphries, M. J., "The Effects of Quenching and Tempering
upon the Stress Corrosion Cracking of Ferritic Steels",
Britis h Corrosion Journal, Vol. 8, 1973, pp 117-123.
[5] Parkins, R. N., "Laboratory Measurements and Life

Prediction for Structures Suffering Stress Corrosion
Cracking", Proceedings of International Symposium on
Plant Aging and Life Prediction of Corrodible
Structures", Japan Society of Corrosion Engineering,
Sapporo, Japan, 1995, Paper A001, ppl3.
Y o s h i y u k i Kondo I, Masaru Bodai I, Mao Takei 2, Yuji Sugita 3,
and Hironobu Inagaki 3
ENVIRONMENTALLY ASSISTED CRACKING OF 3.5NiCrMoV LOW ALLOY STEEL UNDER

CYCLIC STRAINING
REFERENCE: Kondo Y., Bodai M., Takei M., Sugita Y., and Inagaki H., ~En-
v i r o n m e n t a l l y A s s i s t e d Cracking of 3.5NiCrMoV Low Alloy Steel Under Cy-
clic Straining, ~ Effects of the Environment on the Initiation of Crack
Growth, ASTM STP 1298, W. A. Van Der Sluys, R. S. Piascik, and R.
Zawierucha, Eds., American Society for Testing and Materials, 1997
ABSTRACT: E n v i r o n m e n t a l l y assisted cracking of 3.5NiCrMoV low alloy

steel under cyclic straining was investigated in water environments at
60~ Effects of strain range, strain rate, strain hold time and impuri-
ties in the water on the crack initiation life were investigated. The
effects of long strain hold time up to i00 hours were studied and found
to be e s p e c i a l l y significant. Lower strain rate, longer strain hold time
and higher electric c o n d u c t i v i t y resulted in shorter crack initiation
life. The corrosion current from the strained metal was measured in a
simulated electrochemical system to clarify the root cause of the life
reduction. Test results showed that higher strain range, lower strain
rate, longer strain hold time and higher electric c o n d u c t i v i t y caused
increased charge transfer, which caused shorter crack initiation life. A
prediction model for the crack initiation life was proposed based on the
charge transfer.
KEYWORDS: e n v i r o n m e n t a l l y a s s i s t e d cracking, straining electrode, corro-

sion current, charge transfer, electric conductivity, 3 . 5 N i C r M o V low
alloy steel.
INTRODUCTION
E n v i r o n m e n t a l l y assisted cracking (EAC) is one of the major con-

cerns in the integrity assessment of industrial machines which are used
in corrosive environments [!]. Stress corrosion cracking (SCC) is the
predominant failure mode in non-stop operating machines [2]. In some
cases, however, periodic start-stops can s u b s t a n t i a l l y decrease the life
of a machine. The stress variations caused by the periodic start-stops
builds up the straining electrode in the corrosive e n v i r o n m e n t [~], which
may act as an origin of the corrosion damage. The straining electrode is
reactivated by the restraining at every start-stop process. Such a coop-
erative effect of cyclic straining and the corrosive e n v i r o n m e n t may
cause a dynamic effect which enhances the e n v i r o n m e n t a l l y assisted
iAssistant chief research engineer and research engineer, respectively,

Takasago R&D Center, M i t s u b i s h i Heavy Industries, Ltd., 2-1-1, Shinhama,
Arai-cho, Takasago, Japan
2Assistant chief engineer, T a k a s a g o M a c h i n e r y Works, M i t s u b i s h i Heavy

Industries, Ltd., 2-1-1, Shinhama, Arai-cho, Takasago, Japan
~Chief r e s e a r c h engineer and r e s e a r c h engineer, respectively, Electric

Power R&D Center, Chubu Electric Power Company, Inc., 20-1,
Kitasekiyama, Ohdaka-cho, Midori-ku, Nagoya, Japan
120
C o p yCr iogph y
t r9i g h t b y bA
1997 y SASTH
T M IInntt'elr n( aatlilo nrai lg h t s
r e s e rwvwewd.)a;s tFmr.io rDg e c 3 0 2 1 : 5 3 : 5 1 E S T 2 0 1 1
KONDO ET AL. ON ENVIRONMENTALLY ASSISTED CRACKING 121
cracking.
E n v i r o n m e n t a l l y assisted cracking b e h a v i o r of a 3 . S N i C r M o V low
alloy steel under cyclic straining was i n v e s t i g a t e d in water environ-
ments at 60~ Effects of strain range, strain rate, strain hold time
and impurities in the water on crack initiation life were investigated.
Especially in this study, the effect of long strain hold time up to 100
hours was obtained. The corrosion current from the strained metal was
m e a s u r e d in a simulated e l e c t r o c h e m i c a l system. The effects of mechani-
cal and environmental factors on the amount of charge transfer were in-
vestigated. A prediction model for the crack initiation life was pro-
posed based on the charge transfer.
CRACK INITIATION AND PROPAGATION TEST
Test Procedure
Test s p e c i m e n - - T h e test material is 3 . 5 N i C r M o V low alloy steel.

The actual chemical composition and m e c h a n i c a l p r o p e r t i e s are shown in
Table 1 and Table 2, respectively. Test specimens are shown in Fig.l.
s e m i - c i r c u l a r l y notched specimen was used in the crack initiation test
and sharply notched specimen was used in the crack p r o p a g a t i o n test.
Testinq m a c h i n e - - A compact testing m a c h i n e was d e v e l o p e d as shown

in Fig,2, One end of the lever was rigidly c o n n e c t e d to the specimen.
The other end was connected to the actuator system e q u i p p e d with a com-
p u t e r i z e d stepping motor. This end of the lever was m o v e d up and down
under d i s p l a c e m e n t control condition and cyclic b e n d i n g m o m e n t was ap-
plied to the specimen. The strain wave form were saw tooth and trapezoi-
dal as shown in Fig.3. The reduction of applied m o m e n t under displace-
TABLE 1 - C h e m i c a l composition.
(%)
C SI Mn P 8 NI Cr Mo V
0,24 0.20 0.35 0.012 0.013 3.84 1.84 0.43 0.12
TABLE 2 - M e c h a n i c a l properties.
O0.2 Os El0ng~0n R~ur

of area
(MPa) (MPa) (%| (%)
804 010 24.3 69.0
150
Thickness10
150 1
Oeta~ot notch Detailof notch

(a) (b)
FIG.I - Test specimen: (a) crack initiation, (b) crack propagation.
m e n t c o n t r o l w a s u s e d for t h e d e t e c t i o n of c r a c k i n i t i a t i o n . Two percent

r e d u c t i o n of t h e m o m e n t r a n g e c o r r e s p o n d e d t o t h e i n i t i a t i o n of a 0 . 5 m m
d e e p crack. The replication technique was used to measure the crack
l e n g t h in t h e c r a c k p r o p a g a t i o n test.
The environmental media were deionized water and dilute solutions
c o n t a i n i n g NaCI. T h e v o l u m e of t h e e n v i r o n m e n t a l m e d i u m in t h e r e s e r v o i r
tank was 100L. T h e e n v i r o n m e n t a l m e d i u m w a s c i r c u l a t e d b y a p u m p at a
f l o w r a t e of 0.i L/min. T h e d i s s o l v e d o x y g e n w a s c o n t r o l l e d at 0.1ppm.
T h e t e m p e r a t u r e w a s c o n t r o l l e d at 60•176 T e s t s w e r e d o n e at t h e f r e e
corrosion condition.
./ Heatingbath I
Re!..... Electrode ~ r "-~ - , ~ i I , I '

Potentiostat CounterElectrode . i~
WorklnoElectrode Out .... Eccentric
['~II . cam Slider Linearbearing
In , ,
Wastewater Testingmachine
FIG.2 - Test equipment.
lmin tH lmin
AE
)
o 9
t t
(a) (b)
FIG.3 - Strain wave form: (a) s a w tooth, (b) t r a p e z o i d a l .
Test Results
C r a c k i n i t i a t i o n t e s t - - T h e e f f e c t of s t r a i n r a t e o n t h e c r a c k ini-
t i a t i o n l i f e is s h o w n in Fig.4. T h e A E - N c u r v e in the water environment
is a l m o s t p a r a l l e l t o t h a t in air. T h e e f f e c t of strain rate on the
r e d u c t i o n r a t i o of c r a c k i n i t i a t i o n l i f e is s h o w n in Fig.5. The lower
t h e s t r a i n rate, t h e s h o r t e r t h e c r a c k i n i t i a t i o n l i f e a n d it e x h i b i t e d a
t e n d e n c y t o l e v e l off.
T h e e f f e c t of s t r a i n h o l d t i m e o n t h e c r a c k initiation life is
3.5NiCrMoV
60~ 100ppb DO2
Deionized water
A
~'X~\ ~, In air
(% / min)
| 0.5 0.14
0.4 ()---- 0.068
(I)---- 0.034
.r 0.3 0 - - - 0.014
0.007
~ 0.2 AE
o.1 i I ~ I I i
101 102 103 104 105
Crack Initiation cycle (a = 0 . 5 r a m ) NI (cycle)
FIG.4 - Effect of strain rate on crack initiation life.
3.5NiCrMoV
~ t 60~ 100ppb DO2
Z~~ Deionizedwater
o
g
In air
/
"6 z
0,1 h I IL,,[ i , i I ,,ill

10-2 10 "I
Strainrate ~ (%/min)
FIG.5 - Effect of s t r a i n rate on the reduction of crack initiation life.
s h o w n in Fig.6, The crack initiation was substantially a c c e l e r a t e d in

the water environment. T h e l o n g e r t h e s t r a i n h o l d time, t h e s h o r t e r t h e
c r a c k i n i t i a t i o n life. T h e r e d u c t i o n r a t i o of c r a c k i n i t i a t i o n l i f e
a g a i n s t s t r a i n h o l d t i m e is s h o w n in Fig.7. Strain hold time longer than
1 h o u r h a d a s u b s t a n t i a l effect. T h e l i f e for i00 h o u r s h o l d c o n d i t i o n
d e c r e a s e d d o w n t o o n e t e n t h c o m p a r e d t o t h a t in a i r a n d m o r e r e d u c t i o n is
e x p e c t e d f o r l o n g e r h o l d time. This means that hold time effect can not
be neglected and therefore short hold time tests can give nonconservative
r e s u l t s f o r t h e a s s e s s m e n t of i n d u s t r i a l m a c h i n e .
3.5NiCrMoV
60~ 100ppb DO2
Deionized water
A
| (~/~'mIn
t. In air
1 O 0.014
0.014
0.014
0 0.014
(~ 0.014
0.5 [] 0.14 o
0.4 [] 0,14 0.5

[] o.14 1
9r 0.3 ~i~ 0.14 3

[] 0.14
[] o.14 12
0 E ~ E
0.2 9 o.14 24
9 0.007 o
0.034 o ~
/~ 0.068 o ~
0.1 I t ~ L L I t L
101 10 2 10 ~ 10 4 10s
Crack initiation cycle (a = 0.5mm) NI (cycle)
FIG.6 - Effect of h o l d time on crack initiation life.
1.0
3.5NiCrMoV
_r 60~ 100ppb DO2
o 0.5 Deionized w a t e r
LIE = 1.65%
ol
m ~ 0.3 """',~,,~ ~ . ~ = 0.14D/dmln
c
Z
"6 z
0.1
"-%
rr'
0.05
0.04
0.1 I 10 100 1000
Hold time tH (h)

FIG.7 - Effect of h o l d time on r e d u c t i o n ratio of c r a c k initiation life.
The effect of electric c o n d u c t i v i t y of the e n v i r o n m e n t a l m e d i u m on

the crack initiation life is shown in Fig.8. Higher c o n d u c t i v i t i e s re-
sulted in shorter crack initiation lives.
Fig.9(a) shows the m a g n i f i e d o b s e r v a t i o n of notch surface. Many
micro cracks were nucleated. They linked together and formed a principal
crack. Fig.9(b) shows the m i c r o s t r u c t u r e of a sectioned crack. The
crack was w i d e n e d by corrosion near the origin. The crack path seemed to
be transgranular. The fracture surface in w a t e r was c o v e r e d by thick
oxide and no cyclic pattern was observed.
104
3.SNiCrMoV tH=lh
O 60~ 100ppbDO2
o As =1.65%
=0.014%/min
tH= 1 h
e 9 NaCI solution
O H2SO4 solution
103 <) Deionized water
r-
.e
.c 9
O
O
10 2 i I , I I
10 -I 100 101 102
Conductivity K (p S/cm)
FIG.8 - Effect of electric c o n d u c t i v i t y on crack initiation life.
FIG.9 - Cracking morphology: (a) surface, (b) section.
Crack propaqation test-- Fig.10 shows the crack propagation rate

for various strain hold times, The crack propagation rate was acceler-
a t e d in t h e t e s t e n v i r o n m e n t . F i g , l l s h o w s t h e a c c e l e r a t i o n r a t i o of
c r a c k p r o p a g a t i o n r a t e c o m p a r e d t o t h a t in air. The acceleration ratio
i n c r e a s e d a s t h e h o l d t i m e i n c r e a s e d a n d it l e v e l e d off,
F i g . 1 2 s h o w s t h e e f f e c t of e l e c t r i c c o n d u c t i v i t y of t h e e n v i r o n m e n
o n t h e c r a c k p r o p a g a t i o n rate. The electric conductivity had little
e f f e c t in s u c h a d i l u t e s o l u t i o n ,
10"1
3.5NiCrMoV
6O~ 100ppb DO2
Deionized water
~ 10 "2
E
O[~/~/, In a i r
~.~ 10-0
/
/
/
/
r 10~
o
[] 7 0
9 6o o
7 ~s
~ 7
I0-~ ID 7 3
0 9 7 12
G 7 100
10-6 , ~ ~ ! , I ,,I ' ' '

10 20 30 50 100 200 300 500
Stress I n t e n s i t y f a c t o r r a n g e /,K (MPaJm)
FIG,10 - Effect of hold time on crack propagation rate.
10
~ 2
o
E tH
3.5NiCrMoV
60~ 1 0 0 p p b DO~
Deionized water t
,~ 0.5
J J i i ( i I t i 1__
0.4
0 (() lo-1 10 o 101 102 10 ~
Hold time tH (h)
FIG.II - Effect of h o l d time on t h e acceleration of c r a c k propagation.
10"I
3.5hliCrMoV
60=C, 100ppbDO2 lh t~=lh
A K=62M Pa I ~
tH=lh
E
9 NaCl solution
O H2SO4 solution
Z
De|onized water
10-2
o ~ o
0
.8
K
o
lo-3 p I I J I
10-1 100 101 102
Conductivity K (p S/cm)
FIG.12 - E f f e c t of e l e c t r i c c o n d u c t i v i t y on c r a c k p r o p a g a t i o n rate.
EASUREMENT OF CHARGE TRANSFER FROM STRAINED METAL
The a b o v e m e n t i o n e d test r e s u l t s s u g g e s t e d that c o r r o s i o n p l a y e d an

e s s e n t i a l r o l e in the s u b s t a n t i a l r e d u c t i o n of c r a c k i n i t i a t i o n life.
Therefore, the c h a r g e t r a n s f e r f r o m the s t r a i n e d m e t a l w a s m e a s u r e d in a
s i m u l a t e d e l e c t r o - c h e m i c a l s y s t e m [4]to find out the r o o t c a u s e of t h e
life reduction.
Test P r o c e d u r e
The c o n c e p t u a l d i a g r a m of the t e s t e q u i p m e n t for the m e a s u r e m e n t of

c o r r o s i o n c u r r e n t is shown in Fig.13. S i n c e the a n o d i c s i t e a n d c a t h o d i c
site s h o u l d be e l e c t r i c a l l y s e p a r a t e d in the m e a s u r e m e n t , the s u r f a c e of
the test s p e c i m e n was c o a t e d w i t h a t h i n T E F L O N T M c o a t i n g (thickness
20~m). The c o a t i n g was r e m o v e d at a w i d t h of 1 0 ~ m at t h e n o t c h root a n d
the m e t a l w a s e x p o s e d to t h e e n v i r o n m e n t . An A g / A g C I r e f e r e n c e e l e c t r o d e
w i t h L u g g i n c a p i l l a r y was set at 0 . 5 m m a w a y f r o m the n o t c h root. This
a r r a n g e m e n t was kept for 24 h o u r s at the free c o r r o s i o n c o n d i t i o n for
s t a b i l i z a t i o n b e f o r e the m e a s u r e m e n t . A f t e r the s t a b i l i z a t i o n process,
the s t r a i n i n g was s t a r t e d and t h e c o r r o s i o n c u r r e n t was m e a s u r e d u n d e r
p o t e n t i o s t a t i c c o n t r o l at the free c o r r o s i o n p o t e n t i a l .
Test R e s u l t ~
An e x a m p l e of the m e a s u r e d c o r r o s i o n c u r r e n t v a r i a t i o n for a trap-

e z o i d a l w a v e f o r m s t r a i n i n g is s h o w n in Fig.14. The c o r r o s i o n c u r r e n t
was d e t e c t e d as the s t r a i n i n g s t a r t e d and it l a s t e d d u r i n g t h e s t r a i n
hold, and t h e n it d e c a y e d w i t h u n l o a d i n g . The c h a r g e t r a n s f e r 0 = [ (i)
dt in one c y c l e is r e l a t e d to t h e a m o u n t of c o r r o s i o n g e n e r a t e d in ~
cycle.
Fig.15 shows the e f f e c t of s t r a i n r a t e on t h e c h a r g e t r a n s f e r p e r
cycle. The c h a r g e t r a n s f e r Q was n o r m a l i z e d b y Q~-0.014~/miow h e r e Q~_0.0~4,1~i,
is the c h a r g e t r a n s f e r for ~ = 0 . 0 1 4 % / m i n in e a c h e n v i r o n m e n t and p l o t t e d
a g a i n s t s t r a i n rate s The lower s t r a i n rate c a u s e d l a r g e r c h a r g e t r a n s -
fer. This i n c r e a s e of c h a r g e t r a n s f e r seems to h a v e c a u s e d t h e life
r e d u c t i o n at lower strain rate r e g i o n s h o w n in Fig.5.
0.9
3.5NICrMoV
60~ 100ppb DO2
< 6ppm NaCI solution (15 p S/cm)
v A ~ =2.35%
0.6 = 0.024 %/mln
tH=6h
Potentlostat I &. Q = 7052 pC
O
C
O
o3
0.0
Coating '(-- E O.smm i
U) 0
Time (h)
FIG.13 - Measurement of corrosion FIG.14 - Example of corrosion

current. current variation.
101
3.5NICrMoV
,E 60~ 0 3 IJ S/cm
E NaCI solution 15 ~ S/cm
9 30 p Slcm
o
10 o
10-1
e"
O
10-2
(g
E
O
Z t
10-3 i i i i i i ill I I
10"2 10"1 4X10 "1
Strain rate (%/min)
FIG.15 - Effect of strain rate on charge transfer.
Fig.16 shows the effect of strain range on the charge transfer per
cycle The charge transfer Q was n o r m a l i z e d by Q, where Q, is
the charge transfer for d~=2.35% zn each envlronment and plotted agalnst
strain range AC. The larger strain range caused larger charge transfer.
Fig.17 shows the effect of strain hold time on the charge transfer
per cycle. The charge transfer Q was n o r m a l i z e d by Qt.=~4~ where Qt,=24h, is
101
3.5NiCrMoV
o~ 60~
NaCI solution
r
<~ 100
o
c
~ 10"1
t,-
"0
.~ 10.2 Saw tooth Trapezoidal Conductivity
Q 9 3 p S/cm
A 9 15 I~Slcm
0
Z [] 9 30 p S/cm
10.3 I I I I I J Ill I I
o.t 0.2 0.3 0.5 1 ~ 3 4
Strain range ~E (%)
FIG.16 - Effect of strain range on charge transfer.
1011
3.5NiCrMoV
60~
d NaCl solution
Zl s (%) Conductivity 9
2.35 1,1
lO 0 9 <9 3 ~ Slcm
(n 9 A 15 p S/cm ~~
e-
ra 9 O 30 p Slcm A 9
10"1
o
IP E tH
"o
9
._N
m
o 1 0 .2 , I , I t
t
10"1 100 101 10 2
Hold time tH (h)
FIG.17 - Effect of hold time on charge transfer.
the charge transfer for tH=24hr in each e n v i r o n m e n t and p l o t t e d against

strain hold time tH, The longer strain hold time gave more time to cor-
rode and resulted in the increase of charge transfer per cycle. The
increase of charge transfer is almost proportional to time and seems to
be still increasing after i00 hours hold. The actual value of the charge
transfer Q for trapezoidal straining is shown in Fig.18 for electric
c o n d u c t i v i t y K = 15~S/cm.
Fig.19 shows the effect of electric conductivity on the charge
transfer per cycle. The charge transfer Q was normalized by Q~=,,,~. where
Q~. ,.,~ is the charge transfer for K=I5~S/cm for each test condition and
plotted against electric c o n d u c t i v i t y K. The higher electric conductiv-
ity caused larger charge transfer. Here, we can obtain the charge trans-
fer for any combination of strain range As strain hold time tH and elec-
tric c o n d u c t i v i t y K using Fig.18 and Fig.19 for a trapezoidal wave
straining.
These test results show that each condition which gave larger
charge transfer coincided w i t h the condition which gave shorter crack
initiation life. This indicates that the life reduction is caused by the
enhanced charge transfer by cyclic strainin 9
P R E D I C T I O N MODEL OF CRACK INITIATION LIFE BASED ON CHARGE TRANSFER
Modellinq of Crack Initiation Process
The cross section of the crack shown in Fig.9(b) suggested the

crack initiation process shown in Fig.20(a). Firstly, the anodic disso-
lution from the strained metal generated a corrosion groove in zone A.
Secondly, a crack initiated from the b o t t o m of the corrosion groove in
zone B. Let's assume that corrosion was dominant in the zone A in
Fig 20(b) and the depth of corrosion groove increased cyclicly at a con-
stant rate Ve, where Vowas defined as the corrosion amount in one cycle
of the strain variation. In zone B, however, the crack propagation rate
106
3.SNiCrMoV
60~ DO2
Conductivity K =15vS(cm
:~. tH
(~ 104
~ t0 3 1
e-
0
1o 2 I I i I ill ~ I
0.1 01.2 0'=3 0.5 1 2 3
Strain range ZX E (%)
FIG.18 - Effect of strain range and hold time on charge transfer.
K O N D O ET AL. O N E N V I R O N M E N T A L L Y ASSISTED CRACKING 131
102
Trapezoidal Saw tooth I
t H (h: ! b, ~=2.35% ~ ~=1.1% ~, ([%) [ :0,D14~4min i =0,024%lmini =0.14~minI
2,35 ~ (D
t A 1.65 ~, A
6 9 [] 1.1 ~ [] []
12 ~ V o.~ ~
101 ~4 O
o 3.5NiCrMoV
60~ 1 0 0 p p b D O 2
NaCI solution
tn
100
o
"o %P
N 10 "1
E
O
Z
! t
10 .2 ] ] I ] ] ~=1 J i
2 3 4 5 10 20 30 40
Conductivity K ( p S/cm)
FIG.19 - Effect of electric conductivity on charge transfer.
exceeded the corrosion rate and it began to p r o p a g a t e as a crack. The

crack depth can be obtained as follows.
a = ~~ + ~(da/dN~N (i)
where, a: crack depth, Vc: corrosion rate per cycle, da/dN: crack
p r o p a g a t i o n rate per cycle, No: number of cycle at which da/dN exceeded
Vc, Ni: crack initiation cycle (a=0.5mm in this study).
Zone A Zone B Z ,Z~ ,, Z o n e B
CI.
4) E
"O e-
.be
O
2
O
-~ Vo /
0
E
0 /'
Nc N i (a=0.5mm)
AK
Cycle Stress intensity factor
Ca) (b)
FIG.20 - Crack initiation process: (a) aNN, (b) da/dN-AK.
The crack propagation rate da/dN can be o b t a i n e d experimentally as

shown in Fig.10. It was verified that impurities in the environment had
little effect in dilute solution as shown in Fig.12.
The corrosion rate Vc is related to the charge transfer per cycle
based on the Faraday's law. A l t h o u g h the d e t e r m i n a t i o n of the corrosion
rate V~ should be based on the corrosion current density at the place
where the anodic dissolution takes place, the charge transfer Q measured
in this study was the sum of the corrosion current from a finite area.
The definite d e t e r m i n a t i o n of the area where the anodic dissolution oc=
curred was not possible. Therefore, it was assumed that the corrosion
rate V~ was related to the measured charge transfer Q in this study as
shown in Eq. (2).
= ~o (2)
The unknown coefficient ~ was determined by the model fitting cal-
culation to the experimental data set obtained in this study. The model
can be rewritten as shown in Eq.(3).
The model fitting calculations were done for the data of experi-
ments changing strain range and strain hold time shown in Fig.6 and
changing electric c o n d u c t i v i t y shown in Fig.8. The crack initiation
cycle Ni, charge transfer per cycle Q and the crack propagation rate da/
dN were known for these data sets. The model fitting calculation using
Eq.(3) and above m e n t i o n e d data set yielded the most suitable coefficient
for each data set. The obtained coefficient ~ is shown in Fig.21
against charge transfer Q. The result fell in a narrow band. Here we
obtained the estimation model expressed in Eq.(3) for the crack initia-
tion life, where ~ is 0.8-1.4xl0-~mm/~C, Q is obtained from Fig.18 for
K = I 5 ~ S / c m and the c o r r e c t i o n for different electric c o n d u c t i v i t y K is
obtained from Fig.19, da/dn is obtained from Fig.10.
Predictability of the Crack Initiation Life. by the Proposed Model
The p r e d i c t a b i l i t y of the crack initiation life by the proposed

model was v e r i f i e d by comparing the estimated life with the experimental
data for trapezoidal straining. Fig.22 shows the effect of strain range.
Higher strain range gave shorter crack initiation life. Fig.23 shows the
effect of strain hold time. Longer strain hold time gave shorter crack
initiation life. Fig.24 shows the effect of electric conductivity on
(X10 ~
:z
E 3.5NiCrMoV
60~ 100ppb DO2
"o
o
"B
0)
o
0 I I [ I
1000 2000 3000 4000 5000
C h a r g e transfer Q (p C)
FIG.21 - Coefficient of d i s s o l u t i o n rate.
the crack initiation life. The crack initiation life becomes short in
dirty environments where the electric c o n d u c t i v i t y is high. These re-
sults indicated that each d e p e n d e n c y of m e c h a n i c a l factors and environ-
mental factor could be well expressed in the p r o p o s e d model. This means
that the charge transfer from the strained metal p l a y e d an important role
for the crack initiation in the e n v i r o n m e n t a l l y a s s i s t e d cracking under
cyclic straining.
3.5NiCrMoV
60~ 100ppbDO2
K =1 ~S/cm
tH=12h
t,,,,
0.5
e-
0.3
0.2
0.1 I I , I r E
101 102 103 104 105
Crack initiation cycle N~ (cycle)
FIG.22 -Effect of strain range p r e d i c t e d by the p r o p o s e d model.
C
O
,m
1.0
3.5NiCrMoV
60~ DO2
._c 0.5
•= 1~S/cm
O
F~ 03
014%/min
OZ
"- 0.2
o-;
.2 ~
~ z 0.~
e..
o 1 lJ S/cm
o
9"~ 0.05
10
(9
J I p J i J ~ I
IZ 0 0.1 1 10 100 1000
Hold time tR (h)
FIG.23 - Effect of hold time p r e d i c t e d by the p r o p o s e d model.
4
E
3
::L
v-
II 2
Z
3.5NiCrM
c- 60~ ~ ~ ",~.
O
0.5
<.., Exp. Cal " ~ 4r
=_ * (~ t.= 1. . ~
/\ 6h 7~ ~,
0.3 [i 12h
o 24h
(J 0.2 <~ 48h
i 100h
O
m
rr 0.~ ~ ' ~ i__ ~ i I
10o2 10-! rod 101 102
Conductivity K ( ~ S/cm)
FIG.24 - Effect of electric conductivity predicted by the proposed model.
CONCLUSION
(i) The crack initiation life of the test alloy was substantially de-
creased in water even if the water was at low temperature. Higher strain
range, lower strain rate, longer strain hold time and higher electric
conductivity were factors which resulted in shorter crack initiation
life. Among those, long hold time effect was especially significant.
(2) The corrosion current from the strained metal was measured. Higher
strain range, lower strain rate, longer strain hold time and higher elec-
tric conductivity caused larger amount of charge transfer per cycle,
which caused the life reduction.
(3) A predietion model for the crack initiation life was proposed based
on the charge transfer per cycle. This model can incorporate mechanical
factors as well as environmental factor.
REFERENCES
[!] Staehle, R. W., ~Understanding ~Situation-Dependent Strength": A

Fundamental Objective in Assessing the History of Stress Corrosion
Cracking, Proceedings of the First International Conference on ~nvi-
ronment-Induced Crackinq of Metals, National Association of Corro-
sion Engineers, Houston, 1988.
[2] Magdowski, R. M. and Speidel, M. O., ~Clean Steels for Steam Turbine
Rotors-Their Stress Corrosion Cracking Resistance, ~Metallurgical
Transactions A, VoI.19A, June 1988, pp1583-1596.
[!] Shibata, T. and Fujimoto, S., ~Break down of Passivity on Pure Nickel
by Sulfate Ion in High Temperature Aqueous Solution," Corrosion,
Vol.41, No.3, March 1985, pp177-179.
[4] Kondo, Y., ~Electrochemical Approach to Stress Hold Time Effect in

LOW Cycle Corrosion Fatigue ~ Transactions of the Japan society of
Mechanical Engineers, Voi.58, No.554, October 1994, pp1745-1750.
Harvey D. Solomont, gon E. DeLairt and Andy D. Unruh2
Crack Initiation in Low Alloy Steel in High Temperature Water
REFERENCE: Solomon, H.D., DeLair, R.E., and Unruh, A.D., "Crack Initiation in
LowAlloy Steel in High Temperature Water", Effects of the Enviroglment on the
Initiation of Crack Growth, ASTM $TP 1298, W.A. Van Der Sluys, R.S. Piascik, and R.
Zawierucha, Eds., American Society for Testing and Materials, 1997.
ABSTRACT: This paper describes a study of fatigue crack initiation in WB36, a

German low alloy steel, tested in high temperature, high purity, water. Flat un-notched,
tensile specimens were cycled under load control, with R=0. I, and with a saw-tooth wave
form (with a loading time of 30 seconds and an unloading time of 3 seconds). Crack
initiation was followed by periodically stopping the test and replicating the surface. The
tests were performed at 177~ in water containing 8ppm 02. H2SO4 additions were also
made in some tests to raise the conductivity of the water from 0.06 gS/cm to 0.4-
0.5p.S/cm. The crack initiation and growth data are correlated with the water chemistry of
the test.
KEYWORDS: Low Alloy Steel, fatigue, high temperature water, pitting, crack
initiation, crack growth, stress intensity, ASME section III code, ASME section XI code
Crack initiation is the first step in the fatigue failure process, and failure can be
prevented if cracks can be prevented from initiating. The conditions for crack initiation must
be known to be able to prevent crack formation and to be able to set reasonable inspection
intervals. This paper details the experimental studies of crack initiation in low alloy steel
tested in high temperature, oxygenated, water. It has entailed load cycling of test specimens
in 177~ (3500F) water, with different water chemistries and the use of a replication
technique to follow crack initiation and propagation. This replication entailed stopping the
test periodically to examine the specimen and then make a cellulose replica of the surface.
This replication records the degree of pitting that has developed and the size of any cracks
that have initiated. This was done until failure or the termination of a test prior to failure,
defined as a runout. The replicas were then examined to follow the formation of specific
pits, the cracks that emanate from them, and the rate of growth of these cracks.
GE R&D Center, Schenectady, NY 12301

GE Nuclear Energy Division, San Jose, CA 95125
135
Copyright*
Fri Dec 30 21:53:51 EST 2011
By examining the replicas, it is possible to follow the initiation of cracks and their
propagation to failure. The use of replicas offers a technique which allows one to go, in
effect, backwards in time. Without replication, it is necessary to photograph virtually all
of the surface, at a high magnification, to insure that all possible cracks are being
photographed. With a replica, one can focus in on the regions where the cracks leading to
failure are located, and by examining the replicas taken at an earlier time, follow the
growth of these cracks, determine when they initiate, and the conditions leading to crack
initiation and growth.
This paper represents only part of a larger study of low alloy steel crack
initiation. ~) It is restricted to only the results obtained on WB36, a German low alloy
steel, cycled with a cycle period of 33 seconds using an asymmetric loading waveform
(i.e., the loading time was 30 seconds but the unloading time was only 3 seconds). The
complete study used other low alloy steels, different cycle periods and crack growth
measurements made with blunt notched CT specimens.
All of the results described in this paper were performed on specimens made from
WB-36 (heat #110725), a German low alloy steel. The composition and properties of the
WB-36, as determined by the manufacturer and by experiments performed as part of this
study, are given in Tables I and II. This material was received in the form of a thick
walled pipe made from Tube # 06141B.
Table I
Composition and properties of WB-36, Heat #110715, Tube #06141B
C St Mu P S AI Cu Cr Ni Me Nb N
MAn O.10 0.25 0.80 0.50 1.00 0.25 0.015
Max 0.17 0.50 1.20 0.030 0.020 0.050 0.80 0.30 1.30 0.50 0.045 0.020
Actual 0.15 0.34 1.06 0.012 0.004 0.021 0.63 0.21 1.20 0.37 0.024 0.011
Table H
Tensile Properties of WB-36
930~ (1706~ 10 m i n . --~ Air Cool + 640~176 40 min. --~ Air Cool
Temperature Yield Strength Ultimate Tensile Reduction of Area Elongation
Strength % %
KSI(MPa)
KSI(MPa)
288~ 69.7 (480.6) 96.5 (665.3) 27.0 -
177~ 74.4 (513.0) 96.2 (663.3) 62.7 17.3

RT. 82.8 (570.9) 107.5 (741.2) - 21
SOLOMON ET AL.ON CRACK INITIATION IN LOW ALLOY STEEL 137
Figure 1 shows the dimensions of the fiat specimens that were used for the tests in
high temperature water. The large size of the specimen was chosen to increase the surface
area, giving more possible sites for crack initiation. The specimens were machined with
the tensile axis oriented with the longitudinal pipe axis and with the flat surface of the
specimen oriented tangential to the pipe circumference.
#.,0
4 . 0 0 " ~ "-
, .075" R
See Note 1
A-A
.I
~ r I J
I
Figure 1. Test Specimen.
The specimen blanks were initially machined from the thick walled tube by wire
electro-discharge machining (EDM). The surfaces were then ground to remove the EDM
recast layer. The final preparation involved hand polishing with successively finer papers,
(i.e., with 60,120, 400 and then 600 grit paper) and then final polishing with 31~ diamond
paste. This procedure removed most but not all of the scratches. It was necessary to have
some fine longitudinal scratches to act as the reference points which were required to
locate the cracks from one replica to another. These fine scratches are not believed to
influence the test results. No pits or cracks (which were transverse with respect to the
tensile axis) were observed to emanate from these longitudinal scratches.
The testing was performed under load control with the peak load fixed to give a
nominal stress of 90KSI (620.5 MPa). The radius of the specimen gave a stress
concentration~ factor of approximately 1.05, raising the stress to 94.5KSI (651.6MPa).
This load cycling was performed with R=loadmin/loadmax=0.1 and with a saw tooth
wave form, consisting of loading to the maximum load in 30 seconds and an unloading in
three seconds.
The testing was broken down into test blocks, defined by the periodic cessation of
cycling in order to cool the specimen, remove it from the autoclave, and then replicate the
surface. After replication(x), the specimen was reinstalled in the testing machine, the
autoclave sealed, the water pressurized and heated, and another block of fatigue cycling
performed. This cycling was continued until another replication sequence was performed,
or until the specimen failed or testing was stopped and the specimen declared a runout.
Cylindrical tensile specimens were tested in sir at 177~ to determine the base line
fatigue life for specimens not exposed to high temperature water. The flat tensile
specimens used in the replication studies were tested in water in a pressurized autoclave
run at 1500 PSI (103.4 bar) to prevent steam formation. Different water chemistries and
procedures were utilized for different tests.
A mixture of 3 parts N 2 to one part 0 2 was added to the water, for all of the tests
run in water, to produce an oxygen content of 8000ppb. In some tests the oxygen
additions were started while the autoclave was at room temperature, continued as the
temperature was increased to 177~ continued during the testing, and while the autoclave
was cooled back to room temperature. In other tests the water was oxygenated only after
reaching 177~ and oxygenation was discontinued after cycling, and prior to cooling to
room temperature. A 1 gallon (3.79 liter)autoclave was utilized with an exchange rate of
1 gallon/hr (3.791/hr). The autoclave was 5 inches (127ram) in diameter, so the linear flow
rate past the specimen was 0.5 cm/min.
A dilute H2SO 4 solution was added in some tests to alter the conductivity of the
water. Without these additions, an inlet conductivity approaching 0.06 pS/cm (the
theoretical conductivity of pure water) could be achieved. The outlet conductivity was,
however, not as high. At the start of a test block, the outlet conductivity was about 0.5
pS/cm, decreasing to about 0.25pS/cm within about three hours after reaching 177~ at
which point load cycling was started. The outlet conductivity further decreased to about
0. I I~S/cm within about 48 hours, which was a terminal outlet value for the tests that were
run without acid additions. With acid additions, the inlet conductivity was controlled at
0.4-0.5 pS/cm The inlet and outlet conductivities were the same and reached the control
value prior to the start of heating to 177~
RESULTS
Oxygenating prior to heating to the 177~ test temperature resulted in the
development of ferric oxide/hydroxide, analogous to the rust which forms due to
atmospheric corrosion. The determination of the exact nature of the oxide is difficult and
beyond the scope of this study, so for simplicity, the red oxide which forms will be
referred to as rust. This rust is shown in Figure 2. The streaks are all rust red in color,
which is unfortunately not shown here in color. These streaks emanate from pits which
were quite numerous in specimens exposed to water which was oxygenated at room
temperature. Over time at 177~ this red oxide is converted to black oxide, presumably
Magnetite (black Fe304) or a mixture of Fe203 and Fe304. The initial streaked pattern is,
however, still readily apparent, but is now black rather than red. The pits that caused the
red streaks to develop are also not significantly changed. Specimens which were never
exposed to oxygenated water below 177~ never exhibited the rusting that was typical of
those specimens which did. This is illustrated in Figure 3. The specimen is blue black and
no rust streaks are visible. The magnification of Figure 3 is greater than that of Figure 2
so that some of the few pits which were present could be resolved. Far fewer pits were
formed than in the specimens which were exposed to oxygenated water prior to heating to
177~
Figure 2. Tested specimen which formed "rust".
Figure 3. Test specimen which did not rust.
Figure 4 shows the development of cracks from the pits, as followed by continued
replication. This specimen (#5) was heated and cooled in oxygenated water, with no acid
additions to raise the conductivity. Other specimens were similarly examined and the
cycles to the first observation of a crack and the rate at which the cracks grew were
determined from these replicas. Table HI summarizes these results.
Figure 4. Examples of successive replicas.
Table HI gives the cycle number at which cracks were firstobserved and cycle
number of the previous replica on which a crack was not clearly noted. (In some cases
this was zero, denoting that the crack was observed on the firstreplica that was made).
The approximate size of the pit,or pitted region, which initiatedthe crack is also shown.
In some cases this is larger than the size of the crack which was initiatedfrom it. This
occurred when the pitswere illdefined (as was the case when the conductivity was raised
by acid additions). In these cases, cracks initiated~ the pitted region, and were
therefore initiallysmaller than the size of this region. The table also liststhe size of the
crack when it was first observed, and surface crack growth rate (d(2c)/dN) at two stress
intensities. The cracks are distinguished as to whether they were observed on the edge of
the specimen or on its face. (In the case of specimens 6 and 8, both types of cracks were
followed, whereas in specimen #5 only edge cracks were observed.)
Table m
S u m m a r ' o f Initiation a n d Early C r a c k G r o w t h D a t a
spechn~ N fer ~ flr~ App~mate 8izo of tho cr~:k d(2c)/~ at d(~yr Cyde. to
(~v~ty of me ~ t w ~ h It the tim 6.K=2-SlvINm"~ AK~J~,INm"~ Failure
and kah---~ the m ~ ohm'ration ~er~W~,de
Mkor~e
or for g ~ i m e m #3 Microns
oxygm snd II the si~ of
~mel~
Micmm
5 140S5(12000) 100 238 0.065 at 4.5 0.19 3~222
MNm"~
RT. oxysm
~h~ition)
15085(14O85) 3O 363 0.058 at o.~4 (IS,3s4
edp 5 MNm"~ cyr to
failure ia a
4O0O(3O0O) 470 211 0.3 1-2 7833

face
(0.4-0.5pS/c~ 4000 (3000) 425 192 0.6 I-2 (7079
RT. oxygm face cycles to
~Idit/o~) failure in a
.pecim~)
50o~o) 70 286 0.2 0.5
8 20o0(o)face 125 50 0.05 0.2 at 10,105
10 MNm"~
(o.4-o.5~s/~ 60O0 (5000) 160 161 o.o~ 0.18 at (11030
I T / ' C oxYSm face 3 MNm"~ 10 MNm"~ cyctm to
failure in a
_2_~o_~~ _ 170 48 0.16 0,4

20oo~o~ ~d~ 225 82 0.16 0.35
3 nogowing 50-150
(O.O6 ~ / c m , cracks
with I?'PC at 155,000
oxygm cyclm
add~t~a)
failure
II ~were 20-120
(o.o~ t~S/aa etmcved ~ ~nnima~
pre.~tted w~h 24.000cycle*, 200.000
~T. themn~v have r
followedby bern i slieht wit~at
testing w~th W,Mh by 44,000
o~:lm,but withno failure
st 17~c)
The replication measurements yielded the surface crack length, 2c, where c is the
half length. The calculation of the stress intensity required the determination of the crack
shape, which was done with the aid of an examination of the fracture surface. This is
illustrated in Figure 5, which shows the fracture surface of the same specimen (#5) whose
surface cracks are shown in Figure 4. The final crack developed by the merger of two
cracks, the growth of one of which is shown in Figure 4. The fracture surface also shows
the crack shape at intermediate crack lengths. This was supplemented with an SEM
examination of the fracture surface, from which one can estimate the crack shape when the
crack was small. Figure 6 shows the estimated crack depth, a, divided by the half length
of the crack, c. These estimates were made for both of the cracks which made up the
final, merged, crack. As can be seen, the initial a/c ratio was about 0.2-0.5, and as the
crack grew its aspect ratio (i.e., a/c) increased.
Figure 5. Fracture surface of specimen #5.
00
0e
OXacaa%ttn/ /s
07
06
O O5
04
0.0
O2.
01-
O0 ,
'": .... : .... : .... [ .... I .... [ .... I
200 400 600 800 1000 1200 1400
2c (microns)
Figure 6. a/c ratio for the cracks of specimen #5.
The stress intensity was calculated using the equations developed by Newman and
gaju(3"s) for elliptical surface defects. The stress intensity varies with position around the
crack, as measured by the angle between the normal to the crack surface and the specimen
surface. The zero degree value represents the stress intensity at the surface of the
specimen, at the maximum surface crack length, c. The 90 degree value represents the
stress intensity at the maximum crack depth, a. With an aspect ratio of 0.1, the stress
intensity at the maximum crack depth is about twice as large as that on the surface. As a/c
increases, the difference between the two stress intensities decreases. They are
approximately equal when a/c=0.826 (although there is still some variation in the stress
intensity around the crack). Where possible, the aspect ratios determined from the
fracture surfaces were utilized for the stress intensity calculations. In the case (specimen
#6), where the oxidation on the fracture surface prevented such a measurement, the results
were bracketed for a/c=0.1 to 0.826.
Figure 7 illustrates one of the crack growth calculations. This figure shows the
surface and depth crack growth rates for one of the cracks which made up the final crack
of specimen #5. The depth crack growth rate was determined from the a/c ratio and the
surface crack growth rate. This procedure was also applied to the crack observed in
specimens 6 and 8. The general behavior for all of the crack growth observations was
similar to that shown in Figure 7. Table III summarizes the surface crack growth rate
observed at high (20MNm"3/2) or low (2-5MNm"3t2 depending upon the test) stress
intensities. The increase in the stress intensity was primarily due to the growth of the
crack, as maximum load being cyclically applied was kept constant, and the increase in
stress due to the decrease in load bearing area was relatively small.
10 i i i l l l l l [ i i i i
ASME Sectian Xl C u r ~ ,
Blunt Notched CT Data 3 ..xk/

(Group 2-3b, 200ppb O ~ ///
"O - 0.06 ,uS/cm)
O
r Surface Crack Growth v
o (Specimen #5, left crack
O.O
g
c-
0.1
8000 ppb 02
0.06 ,uS/cm)
Y
0.01 - -
All t e s t s on WB36
tested at 177C
/ \
kSME Section Xl Curve \
0.001
U /'Oep,.CrackOrowt0 (Specimen #5, left crack
I 8000 ppb 02
I o.o6/~S/cm)
0.0001
lO
Stress Intensity Range (MN m "3/2)
Figure 7. Crack growth versus stress intensity.
Figure 7 summarizes several important features of the crack growth behavior

observed in the smooth specimens (specimen #5), and in blunt notched CT specimens (run
as part of the rest of the overall study~l)), and compares this data with the ASME section
XI curve(s). Both types of specimens were tested at 177~ in 0.06 ~tS/cm water. A
somewhat lower oxygen content was used with the CT specimens than with specimen #5
(200 vs. 8000 ppb). The CT specimens also used a 1000 second loading time versus only
a 30 second loading time for specimen #5. These differences in the oxygen content and
the loading time (particularly the latter) influence the crack growth, so direct comparisons
between the CT specimens and specimen #5 are not possible. This figure is meant to
show the difference in the general trends in the data.
DISCUSSION
The four water chemistry variations utilized in this study are listed in Table III.
Oxygenation was done either at room temperature, prior to heating, or a~er the test
temperature (177~ was reached. Furthermore, some specimens were tested in water
whose conductivity was increased to 0.4-0.5~tS/cm by acid additions, whereas in other
tests, no acid additions were made. Combinations of these two variations yield a total of
four water chemistry variations, with two specimens being tested for each variation. Table
III shows that these differences in the water chemistry altered both the number of cycles
before a crack could be resolved and the growth rate of this crack.
(Several factors should be kept in mind when assessing the data in Table III. The
observation of the first crack is, in part at least, determined by the replication interval.
The cycle where a growing crack is observed represents the upper limit of the real value,
which could only be determined by examining the specimen after each cycle. In general,
this uncertainty was about 500-2000 cycles, depending upon the replica interval. The
crack growth rates shown in Table III were determined from the slope of a curve fit to a
relatively small amount of crack length data. As such, the growth rates should only be
given order of magnitude significance.) With these caveats in mind, Table III shows the
following:
1. The environment influences both the number of cycles to first observe a crack
and the overall life, and the influence on the overall life is not just accounted
for by the difference in the number of cycles to first observe a crack. Thus, the
environment influences both crack initiation and growth.
2. Cracks tend to form on the edge of the specimens prior to their formation on
the face. For a given crack length and aspect ratio, the calculated stress
intensity for a crack on the edge of the specimen is the same as for one on the
face. This calculation, however, neglects the roundness of the edge of the
specimen.
3. There is relatively good agreement between the crack growth rate at a stress
intensity range of 20 MNm"v2 and the ASME section XI data curves, for all of
the data generated, except for that of specimens #6, which exhibited a crack
growth rate which was about 2-5 times that of the ASME section XI data
curve.
The observations of the replicas yield the following:

1. Oxygen saturation of the water below 177~ allows rust pits to form and this
promotes cracking.
2. The degree of pitting is greatly reduced if there is no low temperature
oxygenation. Specimen #3 shows that a few pits can still develop, but that in
low conductivity water these pits do not reduce the fatigue fife below the range
of the air reference specimens (which was measured at 150,000-200,000
cycles)
3. Specimen #11 fin'ther shows that the development of a rust pit will not
necessarily reduce the fatigue life. If subsequent oxygenation is prevented
below 177~ and the conductivity of the water is kept low, then the few cracks
which develop from rust pits do not appear to propagate, and the fatigue life
remains in the range of the air control specimens.
4. Pits were developed by the initial exposure to water, especially to room
temperature oxygenated water. Most of these pits did not initiate cracks, and
their morphology did not change significantly with further testing.
Furthermore, those pits which did serve as crack initiation sites also failed to
exhibit a change in their morphology with subsequent crack initiation and
growth. The exception to this was in the tests run in higher conductivity, room
temperature oxygenated water. In these tests (specimen #6 and its companion)
the cracks were widened by corrosion, but pits not associated with cracks were
not enlarged.
5. If the oxygenation below 177~ is continued with each cycle of cooling,
replication and re-heating, then specimen #5 shows that the fatigue life is
significantly reduced even if the conductiviw is kent low. This is true even
though much of the rust appears to be converted to Magnetite, or a mixture of
Fe203 and Fe304, and there appears to be little additional rust pit formation
over that which is produced by the initial exposure. While the nature of the
pits do not change significantly, a differential aeration cell can be developed
when the specimen is heated in the oxygenated water, and the corrosion that
this produces can concentrate whatever impurities are present in the water at
the crack tip.
6. Increasing the conductivity of the water to 0.4-0.5 pS/cm by acid additions
resulted in the development of irregular pitted regions, rather than well defined
pits.
7. The fatigue life is low and the crack growth rate is relatively high if the
conductivity of the water is allowed to increase to 0.4-0.5/~S/cm. This is
accompanied by much more corrosion (irregular pit formation), with or
without low temperature oxygenation.
8. The combination of high conductivity and low temperature oxygenation
produced the lowest fatigue lives (specimen #6 and its companion) and highest
crack growth rates.
9. The cracks which were developed, initially grew at stress intensities which
were far below that required in crack growth tests run in high temperature
water on CT specimens. This is indicative of"short crack" growth behavior.
These observations can be compared to those of Kondoc~ who studied

2.5NiCrMoV and 3.5NiCrMoV low alloy steels load cycled (R=0.8) at 90~ in 100-1600
ppb oxygenated water with a relatively high conductivity (<5.0~S/cm). Kondo's tests
were performed with lower stress amplitudes than those discussed here and, in spite of the
high R ratio, resulted in fatigue lives of6• s cycles. This required the use of a 50 Hz
cycle frequency instead of the 0.03 Hz employed here. In spite of these differences, there
were some interesting similarities between the present results (which were low cycle
fatigue tests) and those of Kondo (which were performed in the high cycle fatigue
regime). Kondo observed short crack behavior with a threshold stress intensity of
2.4MNm3~. This stress intensity was also about the lowest stress intensity at which
cracks were observed in the present study. The critical pit fize required for crack
initiation was also about the same size (0.1-0.25ram) as the pits observed in this study,
although the higher stresses employed here allowed somewhat smaller pits (0.05ram) to
initiate cracks. The chief difference between these studies was that in Kondo's tests, crack
initiation was governed by pit growth (i.e., the pits had to grow to a critical size before
cracks would initiate), whereas in the present study, the crack initiation did not require pit
growth (after their initial formation there was little or no additional pit growth, except for
that which appeared to follow crack growth in the specimens tested in low temperature
oxygenated, 0.4-0.5 I~S/cm conductivity water). The higher stresses may have allowed the
pits which formed from the initial water exposure to initiate a crack without the
requirement of further pit growth.
All of the tests described here were performed on WB36 which had a very low
sulfur content. A few replication tests were also run on higher sulfur A533B, which
exhibited a lower fatigue life when tested at the same fraction of the ultimate tensile
strength. The A533B also exhibited a faster crack growth rate in CT specimens. This
increased crack growth rate and decreased fatigue life is in agreement with the newly
proposed modifications to section XI of the ASME pressure vessel code,~8'9) a
considerable amount of experimental data<~~ and the proposed model developed by
Andresen and Ford.tu4"l~)
Figure 7 shows both the surface crack growth and the depth crack growth for the
left crack of specimen #5. As can be seen, the crack growth rate is lower for the crack
depth than that observed on the surface. This reflects the fact that the surface crack length
being measured is the total crack length_, 2c. It should be divided by two to get dc/dN
rather than d(2c)/dn. The dc/dN crack growth rate is the one which should be compared
with the depth crack growth rate daJdN. Furthermore, aJc is initially small (see Figure 6),
which further reduces da/dN. These factors act to reduce da/dN to 0.125*d(2c)/dN for
a/c=0.25, and to 0.413*d(2c)/dN for a/c=0.826. At some points the crack growth rates
differ by different amounts from those predicted by a/c, reflecting differences in the curve
fits to the crack length versus cycle number, from which the growth rates are determined.
Figure 7 also shows that the stress intensity is greater at the center of the crack than for
the surface of the crack. This is true for a/c<0.826, and this makes a/c increase until a/c
reaches 0.826.
Figure 7 shows that at high stress intensities (greater than 18 MN m'3/2), there is a
reasonable correspondence between the ASME section XI curve and the test data (also
see Table III for the correlation with the rest of the smooth specimen crack growth data).
The ASME curve breaks below about 18 MN m"3t2, exhibiting a much lower crack growth
rate. The crack growth rate measured on the smooth specimens is much greater than that
of the section XI curve. These specimens exhibit typical "short crack" behavior~16'17),
which is typified by being higher than that observed in long crack specimens and
sometimes with a slowdown in growth, followed by an acceleration.
The CT data exhibits a crack growth rate which averages at about the level
predicted by the ASME section IX curve, but is much steeper with respect to the
dependence of the crack growth rate with the stress intensity. To a large degree, this
steepness is an artifact of how the CT tests were run. The load that was applied and the
nature of the specimen meant that the stress intensity range of a crack emanating out of
the blunt notch was at 33MN m"3t2. The slowdown in the crack growth, developed in
most of the CT specimens after the initial crack formation from the blunt notch, caused
very low crack growth rates to be developed at high stress intensities. This is the cause of
the almost vertical nature of the CT crack growth curve. If a lower load were used, the
initial stress intensity would have been lower, and the vertical portion of the CT crack
growth curve would have been shifted to a lower stress intensity. To develop a truer
crack growth curve, it is necessary to establish a steady state crack growth rate for a given
load and then reduce the load to reduce the crack growth rate, and in this way trace out
the crack growth rate down to lower stress intensities.
While exact comparisons between the CT, smooth bar and ASME Section XI curves
are not possible, Figure 7, does clearly illustrate that:
1. the smooth specimens exhibit "short crack" behavior, at stress intensities of 2-5
MNm "3r2. The ASME Section XI curve predicts a crack growth rate of less than
lx104 microns/cycle which is several orders of magnitude lower than the crack
growth rates listed in Table III
2. at high stress intensities the CT, smooth bar and section IX curves all predict a
crack growth rate of about 1 micron/cycle
3. the smooth bar data is in better general agreement with the section XI data than
with the CT data, but the discrepancy that is developed with the CT data is
largely due to the way in which the CT specimens were tested.
Figure 8 compares the fatigue lives measured in these tests (the last column of
Table III) with the ASTM section III design curve.(n) The ASTM curve was developed
for fully strain controlled, fully reversed, cycling, i.e., R=-I, whereas these tests were run
under load control with R--0.1. It was therefore necessary to correct for this mean stress
effect, and this was done using the Goodman approach. (~9) The results of air fatigue tests,
also run in smooth specimens with R=0.1, are also shown. Figure 8 shows that while the
fatigue life was influenced by the environment, the fatigue lives were correlated by the
data curve and were greater than the design curves. The tests run in the best water
chemistry (low conductivity water, with 177~ oxygenation) had lives which were longer
than that of the data curve, and were in the range of the air reference data. This was even
true for the specimen (#11) which was pre-pitted prior to further testing in the best water
chemistry. This generated a runout that was within the range of the air data.
148 E F F E C T S OF T H E E N V I R O N M E N T ON INITIATION OF C R A C K G R O W T H
ASME LAS Data Curve

u~
o.
/ (R=-I)
lo 105
m
o.
E
<
_ \ \\
U)
U) - \\ \ "'" \ \ WB36 Data
L_ \ \ ter
\ \
o 105 /)f\.\ "",,,
10 /' "\ \ \
u)
rt ASM/E " ~-,~.~_._
Design Curve ------~""'--Aiu t
Data Obtained with ---~
R=0.1 and corrected using |
the Goodman Equation |
104 ~ ,,,,,,,I , ,,,..1 , ,,,,,.I , ,,,,,,,I ,,, /.i
I I I I /
101 102 103 104 105 10e
N (cycles)
Figure 8. Comparison of the fatigue lives with the ASTM section HI
design curve.
CONCLUSIONS
1. The fatigue lives of the WB36 specimens were all above the ASME design curve.
2. The fatigue lives of the WB36 specimens were reduced by raising the conductivity of
the water from 0.06 I~S/cm to 0.51~S/cm (produced by acid additions), and by
oxygenation at room temperature rather than at 177~
3. Pit growth was not required for crack initiation.
4. Pre-pitting did not reduce the fatigue life of a specimen which was subsequently tested
in low conductivity water, with oxygenation only at 177~
5. "Short crack" growth behavior was observed in the cracks which initiated in the un-
notched specimens tested in this study.
6. When these short cracks grew enough to raise the stress intensity to about 20 MNm "3rz
the crack growth behavior was similar to that of the ASME section XI curve and to
that measured in blunt notched CT specimens.
7. A533B specimens exhibited shorter fatigue lives than similarly tested WB36
specimens. This was related to the higher S content of the A533B material.
Acknowledgments
The Authors gratefully acknowledge VGB and EPRI for their support of this work
and specifically to Erich Tolksdorf (VGB) and Raj Pathania (EPRI) for their
encouragement and support. The authors also gratefully acknowledge the fruitful
discussions with Gumer Brummer, Otto Wachtcr, Peter Ford and John I-Iiclding.
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14) Solomon. H. D., Um'uh, A. D., DeLair, R. E., Ford, F. P., and Weinstein, D,
"Environmentally-AssistedFatigue Crack Initiation in Low Alloy Steels, Interim
Technical Report", April 1994.
15) Andresen, P. L., and Ford, F. P., Private communication, 1992.
16) Suresh, S."Fatigue of Materials", Cambridge University Press, 1991.
17) Suresh, S. and Ritchi, R. O., International Metals Reviews. V29, 1984, pp. 445-476.
18) Cooper, W. E. "Basis and Intent of Section III Design Curves", PVRC Workshop on
Cyclic Life and Environmental Effects in Nuclear Applications, Welding Research
Council, Clearwater Beach, FL, January 20-21, 1992.
19) Bannantine, J. A., Comer, J. J., and Handrock, J. L., "Fundamentals of Metal Fatigue
Analysis", Prentice Hall, 1990.
Masatsune Akashi I and Guen Nakayama I
A PROCESS MODEL FOR THE INITIATION OF STRESS-CORROSION CRACK

GROWTH IN BWR PLANT MATERIALS
REFERENCE: Akashi, M and Nakayama, G., "A P r o c e s s M o d e l f o r the

Initiation of Stress-Corrosion Crack Growth in BWR Plant
M a t e r i a l s , " Effects of the Environment on the Initiation of Crac~ Growth.
A S T M STP 1298. W.A. Van Der Sluys, R.S. Piascik, and R. Zawierucha, Eds.,
ABSTRACT: The process of initiating the s t r e s s - c o r r o s i o n crack growth

comprises f o l l o w i n g six e l e m e n t a r y processes; namely, (I) the incubation
period, (IX) the process of nucleating the corrosion pits (or corrosion
crevices), (Ill) the process of the growth of pits (or crevices), (IV) the
process of initiating microcracks, (V) the process of the p r o p a g a t i o n of
microcracks, (Vl) the process of c o a l e s c i n g the microcracks, leading into
the process of steady p r o p a g a t i o n of the main crack. The processes I, IXI,
and V fall into the category of the d e t e r m i n i s t i c process, while the proc-
esses If, IV, and VI the stochastic process. This paper deals with the
last three stochastic elementary processes by analyzing the stress-
corrosion c r a c k i n g behavior for each stage, and examines the models
d e v e l o p e d t h e r e b y to predict the initiation life of each. Following
observations and conclu-sions have been made: (i) the critical pit depth to
initiate the m i c r o c r a c k is approximately 20 ~m for the carbon steel, and
the m i c r o - c r a c k s are n o n - p r o p a g a t i v e semicircular cracks of a p p r o x i m a t e l y
50 ~m in depth; (2) the processes IX of the pit nucleation, IV of the
m i c r o c r a c k initiation, and VI of the m i c r o c r a c k coalescence can all be
represented to the Poissonian stochastic process; (3) inasmuch as the total
c r a c k - i n i t i a t i o n life is d e t e r m i n e d by a stochastic process comprising
these P o i s s o n i a n processes c o n c a t e n a t e d in series, the p r o b a b i l i t y
d i s t r i b u t i o n of the life leading to the onset of steady propagation of a
m a i n crack can be represented by the e x p o n e n t i a l distribution; (4) the
applied stress exerts its influence m a i n l y on the rate of proliferation of
microcracks, but h a r d l y on the p r o p a g a t i o n of microcrack, critical pit
depth, and the p r o b a b i l i t y of the pit's g e n e r - a t i n g microcrack3; and (5)
inasmuch as the p r o l i f e r a t i o n rate of m i c r o c r a c k is represented by a linear
function in a p p l i e d stress, the d i s t r i b u t i o n lower limit of the m a i n - c r a c k
initiation life is in inverse proportion to the applied stress.
Keywords: s t r e s s - c o r r o s i o n cracking, b o i l i n g water reactor,

initi-ation process, crack coalescence, P o i s s o n i a n stochastic process,
exponential distribution, life prediction,
iSenior research engineer and research engineer, respectively, Research

Institute, I s h i k a w a j i m a - H a r i m a Heavy Industries Co, Ltd., Toyosu, Kotoku,
Tokyo 135, Japan.
150
C o p yCr iogph y
t r9i g h t b y bA
1997 y SASTH
T M IInntt'elr n( aatlilo nrai lg h t s
r e s e rwvwewd.)a;s tFmr.io rDg e c 3 0 2 1 : 5 3 : 5 1 E S T 2 0 1 1
AKASHI AND NAKAYAMA ON A PROCESS MODEL 151
INTRODUCTION
As r0~y be r e p r e s e n t e d by the s t r e s s - c o r r o s i o n c r a c k i n g that takes p l a c e

in a u s t e n i t i c s t a i n l e s s steels in neutral c h l o r i d e s o l u t i o n e n v i r o n m e n t s ,
the s t r e s s - c o r r o s i o n crack has been o b s e r v e d to i n i t i a t e in v a r i o u s sorts
of p r a c t i c a l service e n v i r o n m e n t via c o r r o s i o n pits or c o r r o s i o n c r e v i c e s
[i-~]- It has been shown also that the m i c r o c r a c k s that have b e e n
i n i t i a t e d are n o n p r o p a g a t i v e by nature, so that the s t e a d y p r o p a g a t i o n of a
m a i n crack is p o s s i b l e only when it has b e e n f o r m e d t h r o u g h c o a l e s c e n c e of
these m i c r o - c r a c k s [I, ~]. Much the same has b e e n o b s e r v e d to o p e r a t e in
c a r b o n steels, s t a i n l e s s steels, and n i c k e l - b a s e s t a i n l e s s alloys w h e n
t e s t e d in h i g h - t e m p e r a t u r e , h i g h - p u r i t y water e n v i r o n m e n t s p r e p a r e d in
s i m u l a t i o n of BWR p r i m a r y coolant e n v i r o n m e n t [~-12].
Such a s t r e s s - c o r r o s i o n c r a c k i n g b e h a v i o r is i l l u s t r a t e d in Fig. i [~]
in terms of the time d e p e n d e n c y of the mode of the m a x i m u m c r a c k - d e p t h dis-
t r i b u t i o n found for a s e n s i t i z e d Type 304 s t a i n l e s s steel s p e c i m e n s t e s t e d
by the CBB m e t h o d [~] in a 250 C h i g h - p u r i t y w a t e r e n v i - r o n m e n t . The
m i c r o - c r a c k s that have been i n i t i a t e d early in the test remain b e l o w the
c r i t i c a l depth for a vary long time. A crack b e c o m e s able to start its
steady p r o p - a g a t i o n if and when its depth e x c e e d s a c e r t a i n c r i t i c a l value.
The authors define the process p r o c e e d i n g in the time s t a r t i n g f r o m the
i m m e r s i o n of the specimen in the test e n v i r o n m e n t to the onset of steady
p r o p a g a t i o n of the f r a c t u r i n g crack as the s t r e s s - c o r r o s i o n crack
i n i t i a t i o n process.
t (h)
0 100 200
1.5
E
E Sensitized Type 304
C a B t,est d a t a ~
x:" ----,nitiati'0n~-~/propaglti--on--/
=o
O
E= 0 . 5
/ da/dt--2.01xl0.9m/s
. . _
- -~o~<:~ ...... v~',, I . . . .

0.5
t (Ms)
Fig. 1 Progress of s t r e s s - c o r r o s i o n c r a c k i n g in s e n s i t i z e d Type 304

stainless steel in 250 C h i g h - p u r i t y water e n v i r o n m e n t as r e v e a l e d
by the CBB test in terms of the m a x i m u m crack depth.
It s h o u l d be n o t e d that the p r o p a g a t i o n rate of fatigue crack is the

smaller, the s m a l l e r its size, b e c a u s e the stress i n t e n s i t y at the crack
tip is the s m a l l e r then, and that this affords the d e v e l o p m e n t of an effec-
tive m e t h o d of r e m a i n i n g life p r e d i c t i o n by c o m b i n i n g the n o n - d e s t r u c t i v e
e v a l u a t i o n of as small a crack as p o s s i b l e and the w e l l - f o r m u l a t e d crack
p r o p a g a t i o n analysis. For the p r o p a g a t i o n of s t r e s s - c o r r o s i o n crack, on
the other hand, two o b s e r v a t i o n s s h o u l d be a c c e p t e d as c h a r a c t e r - i s t i c : one
is that the d e p e n d e n c y of the crack p r o p a g a t i o n on m e c h a n i c a l factors is
very little, and the other is that the rate of steady propagation, b e i n g
n o r m a l l y on the order of 10 -9 m/s, or a p p r o x i m a t e l y 30 mm/y, is far too
large to allow the crack to remain u n t e n d e d until the time of next regular
outage. This means that the initiation process, i.e., that lifetime which
leads to the onset of steady p r o p a g a t i o n of crack, has to be q u a n t i t a t i v e l y
m o d e l l e d in order to e s t a b l i s h a truly reliable life a s s e s s m e n t in the case
of s t r e s s - c o r r o s i o n cracking.
This paper intends to analyze the i n i t i a t i o n process so as to p r o v i d e
s c i e n t i f i c grounds to the p r e d i c t i v e modelling, and so to q u a n t i f y the life
p r e d i c t i o n model.
THE INITIATION PROCESS
As s t a t e d e a r l i e r on and as shown in Fig. I, the m i c r o c r a c k s of depths

smaller than the critical size are i n i t i a t e d c o m p a r a t i v e l y early in the
whole life. Since they are n o n p r o p a g a t i v e by nature, the crack p r o p a g a t i o n
is p o s s i b l e only when they p r o p a g a t e into larger cracks by c o a l e s c i n g with
n e a r b y microcracks, and one of the large cracks thus f o r m e d makes the
steady p r o p a g a t i o n as the main crack, by which the final fracture is
b r o u g h t about. In the case of s e n s i t i z e d Type 304 stainless steel in 250 C
h i g h - p u r i t y water environment, the depth of the m i c r o c r a c k s has b e e n
o b s e r v e d to remain g e n e r a l l y less than 50 ~n [~]. The surface length of
these m i c r o c r a c k s is, on the other hand, g e n e r a l l y of the order of I00 ~2n
as e x e m p l i f i e d in Fig. 2, which shows the d i s t r i b u t i o n of surface lengths
of m i c r o c r a c k s as d e t e r - m i n e d in an SEM surface survey of a s e n s i t i z e d Type
304 stainless steel specimen after the c o n s t a n t - l o a d test in an 250 C high-
p u r i t y water environ-ment. These results indicate u n a n i m o u s l y that the
aspect ratio of micro-cracks, a/c,i.e., the ratio of the crack depth, a, to
the h a l f - l e n g t h of the surface crack,c, is a p p r o x i m a t e l y unity. On the
other hand, however, the CBB tests c o n d u c t e d in 250 C h i g h - p u r i t y water
e n v i r o n m e n t for s e n s i t i z e d Type 304 stainless steel specimens have
revealed, as shown in Fig. 3 [~], that the aspect ratio, a/c, of stress-
c o r r o s i o n crack p r o p a g a t i n g at a steady rate remains at about 1 to 3, i.e.,
1/3, i r r e s p e c t i v e of the extent of progress.
The s t r e s s - c o r r o s i o n crack i n i t i a t i o n p r o c e s s can be regarded as com-
p r i s i n g six separate stages as i l l u s t r a t e d in Fig. 4. In terms of their
basic processes, these six stages can be c l a s s i f i e d into two groups: one
group of stages which are d e t e r m i n i s t i c in their nature, and the other
which are s t o c h a s t i c in the working. The stages that b e l o n g to the
d e t e r m i n i s t i c g r o u p are: the Stage I, the i n c u b a t i o n period, in which the
c o r r o s i o n p o t e n t i a l rises to the critical value at which l o c a l i z e d corro-
sion (or, p i t - t i n g corrosion) is initiated; the Stage III, the p e r i o d of
A K A S H I AND N A K A Y A M A ON A P R O C E S S M O D E L 153
pit growth, in which the corrosion pits grow into the critical size for
cracking [9-12]; and the Stage V, the period of microcrack propagation, in
which the micro-cracks initiated at pit bottoms attain the critical size
for coalescing [6.10.12].
Fig. 2 Distribution of the surface length of microcracks generated in

sensitized Type 304 stainless steel by the constant-load test in
250 C high-purity water environment.
T--
250 C, ZO ppm DO c i
, !
d
~ 0.5
"6
-!i 0 .... 9
< "~E ........ o o .............. ~ . . . . . . . ~ : ~ - ; ) ~ 2 ~~-
O
L~
II
0 3 ~'
i i
0 5OO 1000 1500

Crackdepth, a (~m)
Fig. 3 Relation between the aspect ratio and the depth of stress-
corrosion cracks generated in sensitized Type 304 stainless steel
by the CBB test in 250 C high-purity water environment.
steady
Stage II III IV V VI propaclation
E
0
0
C
~ b ~
~- E r~
ac, scc r / ........,
aC, PIT
Fig. 4 A stress-corrosion crack i n i t i a t i o n p r o c e s s model.
Of these, the t i m e p e r i o d s e x p e n d e d in Stages III and V are small enough to

be safely i g n o r e d in practice. The stages that b e l o n g to the stochastic
group are: the Stage II, the p e r i o d of pit nucleation, in which the pit
p r e c u r s o r s have to survive the c o m p e t i t i o n of the birth process on local-
ized b r e a k d o w n of p a s s i v a t i o n film and the death p r o c e s s of r e s t o r a t i o n of
the film; the Stage IV, the p e r i o d of m i c r o c r a c k initiation, in which
m i c r o - c r a c k s are g e n e r a t e d by some of those c o r r o s i o n pits that have grown
b e y o n d the critical size; and the Stage VI, the p e r i o d of m i c r o c r a c k
coalescence, in which the m i c r o c r a c k s coalesce each other into forming a
m a i n crack that u n d e r g o e s steady p r o p a g a t i o n subsequently. These p r o c e s s e s
can be r e p r e - s e n t e d by the P o i s s o n i a n s t o c h a s t i c p r o c e s s [6.9.12] or by the
b i r t h - a n d - d e a t h s t o c h a s t i c process [13.14].
EXPONENTIAL DISTRIBUTION OF LIFETIME
C o n s i d e r an event that takes place obeying the P o i s s o n i a n stochastic

process. Then, it can be shown that the probability, p(x), of that event
occurring x times within a time span of t is given by eq. (I);
p(x) = [(kt)x/(x!)]exp(-lt), [x = 0,1,2,3, .... ], (i)
where ~ is the o c c u r r e n c e rate of this event, i.e., the failure rate. The
r e l i a b i l i t y function, R(t), which is:
R(t) = exp(-it), (2)
is the p r o b a b i l i t y given by eq. (i) for x=0. Therefore, the c u m u l a t i v e

p r o b a b i l i t y of the o c c u r r e n c e of the event under consideration, F(t), is
given as:
F(t) = l-R(t)
= l-exp(-kt), (3)
which is n o t h i n g but the c u m u l a t i v e distribution function of the

exponential distribution.
Here, F(t) is g e n e r a l i z e d as:
F(t) = ]-exp[-(t-a)/8], (4)
where a, which is t e r m e d as the location parameter, is the lower limit of

the d i s t r i b u t i o n , i.e., the induction time, and 8=i/~, which is c a l l e d the
scale parameter, is the s t a n d a r d d e v i a t i o n of the d i s t r i b u t i o n . Inasmuch
as F(t) can be given in terms of the c u m u l a t i v e hazard, H(t), as:
F(t) = l-exp[-H(t)], (5)
eq. (4) can be r e w r i t t e n as:
H(t) = (t-a) /8, or

= l(t-a) . (6)
Since this means that H(t) and t are in a linear relationship, p l o t t i n g

H(t) a g a i n s t time t on an e x p o n e n t i a l d i s t r i b u t i o n paper, which is con-
s t r u c t e d as shown in Fig. 5, s h o u l d p r o d u c e a straight line for a p a r t i c -
ular d i s t r i b u - t i o n , w h e r e i n the t-cut of the feature line gives a, the
l o w e r - l i m i t life, and the slop of the line, 8, the scale p a r a m e t e r (or l,
the f a i l u r e rate, for that matter).
The e x p o n e n t i a l p r o b a b i l i t y plots of field as well as l a b o r a t o r y data

reveal that the d i s t r i b u t i o n of s t r e s s - c o r r o s i o n c r a c k i n g life can be
r e p r e s e n t e d by the e x p o n e n t i a l d i s t r i b u t i o n [~, ~-I, 4-12, 15, 16].
EFFECTS OF APPLIED STRESS
The effect of a p p l i e d stress on the d i s t r i b u t i o n of s t r e s s - c o r r o s i o n

c r a c k i n g life of carbon steel weld m e t a l is shown by means of an e x p o -
n e n t i a l p r o b a b i l i t y plot of the data a c q u i r e d in the c o n s t a n t - l o a d tests
c o n d u c t e d in a 250 C h i g h - p u r i t y water e n v i r o n m e n t in Fig. 6 [12], w h i c h
e x h i b i t s c l e a r l y a t r e n d that a b e c o m e s larger and l, smaller w i t h
d e c r e a s i n g a p p l i e d stress.
In a n o t h e r attempt at e x a m i n i n g the role of the a p p l i e d stress p l a y s in

each of the e l e m e n t a r y processes, the f r a c t u r e d s p e c i m e n s u s e d in the test
of Fig. 6 were s t u d i e d with an SEM for the n u m b e r and size of c o r r o s i o n
pits or m i c r o c r a c k s . Figures 7 and 8 r e s p e c t i v e l y reveal the e f f e c t s of
test d u r a t i o n and a p p l i e d stress on the a v e r a g e diameter, 2h, of c o r r o s i o n
pits and the a v e r a g e surface length, 2c, of m i c r o c r a c k s . It w i l l be n o t e d
4 / 0.99
3 0.95
1
0.9 ~-
2
a
0.5
0 0
t
Fig. 5 Construction of e x p o n e n t i a l probability paper.
t ///t Jl
Carbon Steel ] [] > / , ~ - ~ MP~ / I
3 - Weld Metal I 541 M P a / / / / ~ 0.95
250 C 8 ppm DO
...... '1 /// / I
94 MPa 0.90
2
S/ / o 070
0 1 2 3
t (Ms)
Fig. 6 Effects of a p p l i e d stress on the d i s t r i b u t i o n of s t r e s s - c o r r o s i o n
c r a c k i n g life of carbon steel weld metal u n d e r c o n s t a n t - l o a d test
[12].
that the a p p l i e d stress affects the g r o w t h of pits or p r o p a g a t i o n of m i c r o -

racks v e r y little, if ever. The previous paper [12] shows that the crit-
ical d i a m e t e r for the pit to b e c o m e able to initiate the m i c r o c r a c k does
not d e p e n d on the stress, and suggests that the role of the c o r r o s i o n pit
as a m i c r o c r a o k i n i t i a t o r is not as a stress c o n c e n t r a t o r but as a p r o v i d e r
of the n e c e s s a r y c i r c u m s t a n c e for g e n e r a t i n g the m i c r o c r a c k locally within
itself.
. . . . . . . . I - , ..... I-
E ~Carbon Steel Weld Metal I

v100-- L 250 O, 8 p p m DO ] _
04 0 n=0.204 541 MPa
. ~ ~ / b ~ ~ 565 MPa
~- ~ 424 MPa
~(~ 0 "=0" 15~dk,"

-
"0
-~. 565 MPa
0~ 541 MPa
10- 471 MPa
424 MPa
>
<C 541 MPa-static
' "1 ........ I ......... I-
0,1 1 10
t (Ms)
Fig. 7 Effects of test duration and a p p l i e d stress on the a v e r a g e pit
diameter, 2h, as d e t e r m i n e d for carbon steel w e l d m e t a l a f t e r the
test.
E
::L
','1
v
O
OJ ........ ' i +][.~++ +sMPa
471
424
+ +a +,
541 +ic 1 +.
100- O 0 0
O
n = 0.053
2
._o
E
(D
l Carbon Steel Weld Metall
250 c, 8 ppm DO l
>
<[ 10 . . . . I. . . . . . . . . I .......... I--
0.1 1 10
t (Ms)
Fig. 8 E f f e c t s of test d u r a t i o n and a p p l i e d stress on the a v e r a g e s u r f a c e
length of microcrack, 2c, as d e t e r m i n e d for c a r b o n steel w e l d
m e t a l after the test.
C o n t r a r y to these, the p r o l i f e r a t i o n of m i c r o c r a c k is a p p a r e n t l y
a f f e c t e d by the a p p l i e d stress. This is shown in Fig. 9 in terms of the
n u m b e r of m i c r o c r a c k s as d e t e r m i n e d at the surface after the test.
A l t h o u g h the n u m b e r of data is a d m i t t e d l y insufficient, the t r e n d s that the
n u m b e r increases l i n e a r l y with the test d u r a t i o n and that the p r o l i f e r a t i o n
rate s t r o n g l y d e p e n d s on the stress level are indubitable. Figure I0

p r e s e n t s the p r o l i f e r a t i o n rate of microcracks, ~, as e s t i m a t e d in Fig. 9
by the slope of each best-fit feature line, as a function of a p p l i e d
stress. The data plots fall on a straight line a g r e e a b l y enough, so that:
= m~ + (~th (7)
holds true. For this P a r t i c u l a r case shown herein, m=l15 (MPa~ and the
lower limit, or the threshold, stress for m i c r o c r a c k i n i t i a t i o n can be
e s t i - m a t e d from the i n t e r s e c t i o n on the o r d i n a t e as ~th=378 (MPa) .
25 .... ~ :::::::::::::::::::::: .......I - H - 7-~
(.,) != = r b O . Stool WOJd MO~m| ~

z
2O
<) (static) 4711~Pa Mpa.~/ !.
(,,,)
o 15
0
,5 P. I
!= # .M / _ I <,],~ 471 MPa -t
z
rl ~ ' ~ /k L [] 541 MPa static)
0i ....... + t- . . . . . . . . + ~ - - -I- . . . . !
0 1 2 3 4 5
t (Ms)
Fig. 9 Effects of test d u r a t i o n and a p p l i e d stress on the number of

microcracks.
All in all, it can be c o n c l u d e d that the i n c r e a s i n g the a p p l i e d stress

means p r i n c i p a l l y i n c r e a s i n g the p r o l i f e r a t i o n rate of microcracks. On the
other hand, Fig. 6 indicates that i n c r e a s i n g the stress also means shorten-
ing the time to a l l o w the m a i n crack to start its steady propagation. This
observation, then, will be the subject of next chapter.
A POISSONIAN SERIES MODEL
C o n s i d e r a p r o c e s s c o m p o s e d of two e l e m e n t a r y p r o c e s s e s A and B, each

b e i n g of the P o i s s o n i a n stochastic occurrence. M a t h e m a t i c a l l y , the distri-
b u t i o n of the time e x p e n d e d b e f o r e a c e r t a i n event has m a d e its first
a p p e a r a n c e in each of the p r o c e s s e s A and B, i.e., the d i s t r i b u t i o n of
lifetime to the o c c u r r e n c e of that p a r t i c u l a r event, is given by:
FA(t ) = l-pA(0) = l-exp(-IAt) , and (8)

FB(t) = l-pB(0) = l-exp(-IBt) , (9)
700 .... I .... I .... I , I I I ....
Carbon Steel Weld Metal

Constant.Load Test
(" 6 0 0 -
B_ 2 5 0 C, 8 ppm DO
"1~ o= 115 ~+378
r
r
<I: C,h:378 (MPa)
300 '''1 .... I '''1 l l i IIIII

0 1 2
Microcrack initiation rate, (m-~s -1)
Fig. 10 Effects of a p p l i e d stress on the p r o l i f e r a t i o n rate of m i c r o -

cracks, I.
S u p p o s i n g the p r o c e s s e s A and B to be i n d e p e n d e n t a n d to be c o n c a t e n a t e d in
series, and l e t t i n g IB=kkA, the life d i s t r i b u t i o n of the serial p r o c e s s is
g i v e n as:
FAB(t ) = FA(t ) ~
= l-e xp (- ~A t ) -e xp (-kIAt ) +e xp {- (1 +k) ~A t }, (i0)
an event that is i l l u s t r a t e d in Fig. ll as e x p o n e n t i a l p r o b a b i l i t y plots

for a case of k=0.5. Here, it will be o b s e r v e d that, while the life
d i s t r i b u t i o n of the p r o c e s s A, b e i n g of an e x p o n e n t i a l d i s t r i b u t i o n , is
r e p r e s e n t e d by a straight line naturally, that of the p r o c e s s AxB does not.
However, as m a y be judged in the figure, this life d i s t r i b u t i o n can,
e x c e p t i n g for very small F(t) or v e r y small H(t), be a p p r o x i m a t e d well by a
straight line shown in the figure as the thick s o l i d line. Namely, the
a s s u m p t i o n of:
FAB(t ) = l-exp{-lM(t-aM) } (11)
s h o u l d h o l d true without m u c h reservations. This figure a f f o r d s a n o t h e r

i n t e r e s t i n g observation. If k is equal to 0.5 as e x e m p l i f i e d here, the
slope of the c o n v e r g e n t straight line and its cut on the a b s c i s s a give
f u r t h e r a p p r o x i m a t i o n s of IM=kA/2 and aM=i/(21A). This has b e e n r e p e a t e d in
Fig. 12 for p r o c e s s e s A and AxB with k as a parameter. It will be seen in
the figure that the a b s c i s s a - c u t is always i/(21A) r e g a r d l e s s of the chang-
ing k. The r e l a t i o n s h i p that is h e l d b e t w e e n kM, w h i c h can be d e r i v e d from
the e s t i m a t e of the slope of the a p p r o x i m a t i o n line, and k can be viewed,
as shown in Fig. 13, as linear, as:
160 EFFECTSOF THE ENVIRONMENT ON INITIATION OF CRACK GROWTH
i i I } / J
ProcessA I / ~
3- F,(t) = 1-exp(-;~Atl/ ' '
", 2 _
!
II -
4.A
I
I II i
0 ' ~ ' '

I I
/ T / ; / :
-i/k 0 Ilk 2/k 31k 4/k 5/k
t
Fig. 11 Exponential probability plots for P r o c e s s A and Process AxB.
k=l
-- F(t)=l-exp(-ktV / / k=0.75
/ lJ j,_-o.,
II < --
g :: /F(t)~l)-6Xp(-I~.l)+e'xp[-( l*k)klt
-1/x o ]/x 2/~, 3/x 4/~, s/~,

t
Fig. 12 Exponential probability plots for Process A and Process AxB with k
v a r i e d as a parameter.
FAB(t) = l - e x p [ - k ~ A{t-(21 A)-I}] . (12)
This r e a s o n i n g explains how and with what m a g n i t u d e an " i n c u b a t i o n

time" m a k e s its a p p e a r a n c e in a c o n c a t e n a t e d p r o c e s s c o m p r i s i n g s e r i a l l y
two e l e m e n t a r y p r o c e s s e s of b o t h P o i s s o n i a n s t o c h a s t i c in nature, such as
the p r o c e s s of c o r r o s i o n - p i t n u c l e a t i o n and the p r o c e s s of m i c r o c r a c k

i n i t i a t i o n f r o m the pits or the m i c r o c r a c k i n i t i a t i o n p r o c e s s and the
m i c r o c r a c k c o a l e s c e n c e process, the length of the i n c u b a t i o n time b e i n g
d e p e n d e n t on the failure rate of that p r o c e s s which p r e c e d e s in the pair.
This rule s h o u l d h o l d true also for the case where three p r o c e s s e s are
c o n c a t e n a t e d in series. Thus, in the d i s t r i b u t i o n of the lifetime r e c k o n e d
on the onset of m i c r o c r a c k i n i t i a t i o n and that of m i c r o c r a c k coalescence,
the failure rate, iM, and the d i s t r i b u t i o n lower limit, aM, can be
approximated by:
IM = k~A, and (13)

a M = i/(2l A) , (14)
05k-
0 i i i i - I I i i__ ~
0 0.5
k
Fig. 13 Relation between the e s t i m a t e of k M and k.
where ~A is i d e n t i f i e d as the p r o l i f e r a t i o n rate, and k~ A, the c o a l e s c e n c e

rate, pertaining to f o r m a t i o n of m i c r o c r a c k s .
As seen in Fig. 9, and r e c a l l i n g eq. (7), k A can be l i n e a r l y r e l a t e d to

the a p p l i e d stress, ~, as:
IA = (l/m)((~-~th), and (15)

aM = [ (2/m) ((~-(~th)]-i. (16)
This r e l a t i o n s h i p is f u r t h e r d e m o n s t r a t e d in Fig. 14 on the data shown in

Fig. 6. It will be a g r e e d that ~th=378 (Mpa), i.e., the value w h i c h was
d e d u c e d in Fig. 9, is a r e a s o n a b l e e s t i m a t e for the a s y m p t o t e of the
inverse p r o p o r t i o n a l i t y r e g r e s s i o n curve. Thus, eq. (16) can be o f f e r e d as
a h i g h l y rational a n d i n d u s t r i a l l y r e l i a b l e m o d e l to e v a l u a t e the s t r e s s -
c o r r o s i o n cracking life. That the lower-limit life is inversely propor-

tional to the a p p l i e d stress, ~-~th, should be a convenient practical a x i o m
to go by.
700 -
Cmrbon Steel Weld Metal 1
Conltent-Lomd Telt /
a. 600 2 8 0 C , O p p m D O ...... I
v
(n
5oo
"0
._~
~- 400
<
o,.=378 (MPa)
300
0 0.5 1 1.5 2
Lower-limit lifetime, a (Ms)
Fig. 14 Effect of applied stress on the lower-limit life of stress-

corrosion cracking of carbon steel weld metal under c o n s t a n t - l o a d
test.
CONCLUDING REMARKS
Previous studies have shown that the process of initiating stress-

corrosion cracking in materials used in the p r i m a r y coolant environment of
b o i l i n g water reactor plants proceeds through six e l e m e n t a r y subprocesses
of: (I) the incubation period, (II) the process of n u c l e a t i n g the corrosion
pits (or c o r r o s i o n crevices), (III) the process of the g r o w t h of pits (or
crevices), (IV) the process of initiating microcracks, (V) the process of
the p r o p a g a t i o n of microcracks, (VI) the process of c o a l e s c i n g the m i c r o -
cracks, leading into the process of steady propagation of the main crack.
Of these, the p r o c e s s e s (1), (III), and (V) are d e t e r m i n i s t i c by nature,
whereas (If), (IV), and (VI) are P o i s s o n i a n stochastic in nature. The
present paper has p h e n o m e n o l o g i c a l l y a n a l y z e d the last three stochastic
processes and p r e s e n t e d a model to estimate the stress-corrosion cracking
initiation life, which virtually determines the whole service life of the
material concerned.
Following observations have been made and conclusions reached:
(i) The critical depth of corrosion pit to initiate m i c r o c r a c k is approxi-

m a t e l y 20 ~rn in the case of carbon steel, and the microcracks then
generated are nonpropagative in nature, semicircular in form, and of a

depth of approximately 50 ~m.
(2) Inasmuch as the total crack initiation life is determined by a stoch-
astic process composed of the Poissonian processes concatenated in
series, the probability distribution of the time leading to the onset
of the steady propagation of the main crack, i.e., the distribution of
the stress-corrosion cracking life, can be represented by the exponen-
tial distribution.
(3) The applied stress hardly exerts influence on the propagation behavior
of the microcrack, the critical depth of corrosion pit, the probability
of the pit's initiating microcrack, and related properties, its influ-
ence being confined to the proliferation rate of microcracks.
(4) AS the proliferation rate of microcracks is linearly related to the
applied stress, the lower-limit life of stress-corrosion cracking is in
inverse proportion of the stress.
REFERENCES
[i] Tsujikawa, S., Shinohara, T., Hisamatsu, Y., "The Role of Crevices in
Comparison to Pits in Initiating Stress Corrosion Craacks of Type 310S
steel in Different Concentrations of MgCI 2 solutions at 80 C," C o r r o -
sion Cracking, Goel, V.S., Eds., AMS, No. 86-071193, 1986, pp. 35-41.
[~] Tamaki, S., Tsujikawa, S., Hisamatsu, Y., "Development of a New Test
Method for Chloride Stress Corrosion Cracking of Stainless Steels in
Dilute NaCI Solutions," A d v a n c e s in L o c a l i z e d Corrosion, Isaacs, H.S.,
Bertocci, U., Kruger, J., Smialowska, S., Eds., NACE, No. 90-62155,
1990, pp. 207-214.
[~] Nakayama, G., Akashi, M, and Ohtomo, A., I S I J International, Vol. 31,
No. 2, 1991, pp. 223-228.
[~] Nakayama, G., Lian, C., and Akashi, M, "Repassivation Method for Deter-
mining the Critical Potential of Stress-Corrosion Cracking," CORRO-
SION/94, NACE International, 1994, Paper No. 226.
[~] Nakayama, G., and Akashi, M., "Effects of Electrode Potential and
Degree of Sensitization on the Initiation Lifetime of Crevice Corrosion
and Intergranular Stress-Corrosion Cracking for Sensitized 304 Stain-
less Steels in Neutral Chloride Environments," presented at Inter-
n a t i o n a l S y m p o s i u m on Plant A g i n g and Life P r e d i c t i o n of C o r r o d i b l e
structures, Shibata, T., and Shoji, T., Eds., Jap. Soc. Corr. Eng.,
Tokyo, Japan, and NACE International, Houston, TX.,1995, Paper NO.
AII20.
[~] Akashi, M., "CBB Test Method for Assessing the Stress Corrosion
Cracking Susceptibility of stainless steels in high-Temperature, High-
Purity Water Wnvironments," L o c a l i z e d C o r r o s i o n -Current J a p a n e s e
M a t e r i a l s R e s e a r c h 4, Hine, H., Komai, K., and Yamakawa, K., Eds.,Soc.
Mat. Sci. Jpn., Elsevier Applied Science, London-New York, 1988, pp.
175-196.
[I] Akashi, M., "An Exponential Distribution Model for Assessing the Stress
Corrosion Cracking Lifetime of BWR Component Materials," Life P r e d i c -
tion of C o r r o d i b l e Structures, Vol. II, Parkins, R.N., Eds., NACE
International, Houston, TX., 1995, pp. 1040-1049.

[~] Nakayama, G., and Akashi, M., "Effect of Electrode Potential on the
Susceptibility of Alloy 182 Weld Metal to Stress-Corrosion Cracking in
Simulated BWR Environment," P r o c . 6 t h I n t e r n a t i o n a l S v m p o s i u m on
E n v i r o n m e n t a l D e g r a d a t i o n o f M a t e r i a l s in Nuclear Power Svstems -Water
Reactors, Gold, R.E., and Simonen, P., Eds., TMS, 1993, pp. 883-887.
[4] Nakanishi, K., Tanaka, Y., Yoshida, K., Nakayama, G., and Akashi, M.,
"Stress-Corrosion Crack Initiation Behavior of Carbon Steel in Simul-
ated BWR Environment," Q Q ~ R O S I O N / 9 4 , NACE International, Houston, TX.,
1994, Paper No. 156.
[10] Nakayama, G., Akashi, M., "Stress-Corrosion Crack Initiation Process
for Alloy 182 Weld Metal in Simulated BWR Environments," CORROSION~95,
NACE International, Houston, TX., 1995, Paper No. 406.
[ii] Akashi, M, and Nakayama, G., "Stress-Corrosion Crack Initiation Process
Model for BWR Plant Materials," q.v. [5], 1996, Paper No. AI08.
[12] Nakanishi, K., Tanaka, Y., Yoshida, K., Akashi, M., "Effects of Applied
Stress on the Stress-Corrosion Cracking Lifetime of Carbon Steel Weld
Metal in High-purity Water Environment at 250 C," ibid., Paper No.
BVI01.
[13] Shibata, T., Takeyama, T., Proc. 8Th Inter. Con~r_ Met. Corrosion,
DECHEMA, Frankfurt/Main, 1981, p. 146.
[14] Shibata, T., Corros. Sci., Vol. 31, 1990, p. 413.
[15] Okamoto, A., Akashi, M., Kitagawa, M., "Probabilistic Approarch for the
Defect Identification in BWR Pipings," presented at The Pressure Vessel
and Piping Conf., ASME, 1987, Paper No. 87-PVP-30.
[16] Akaahi, M., "Acceleration of Stress-Corrosion Cracking Test for High-
Temperature, High-Purity Water Environments by Means of Artificial
Crevice Application," A p p l i c a t i o n of A c c e l e r a t e d C o r r o s i o n Tests to
S e r v i c e L i f e P r e d i c t i o n of M a t e r i a l s , ASTM STP 1194, Cragnolino, G.,
Sridhar, N., Eds., American Society for Testing and Materials,
Philadelphia, 1993, pp. 313-324.
Modeling
CopyrightbyASTMInt'l(allrightsreserved);FriDec3021:53:51EST2011
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Meryl M. Hall, Jr. 1 and Douglas M. Symons l.
STRAIN E N E R G Y D E N S I T Y - D I S T A N C E C R I T E R I O N FOR T H E
I N I T I A T I O N OF STRESS CORROSION CRACKING OF ALLOY X-750
REFERENCE: Hall, M. M., Jr., Symons, D. M., "Strain Energy Density -

Distance Criterion for the Initiation of Stress Corrosion Cracking of Alloy
X-750," Effects of the Environment on the Initiation of Crack Growth, ASTM STP
1298, W. A. Van Der Sluys, R. S. Piascik, and R. Zawierucha, Eds., American
ABSTRACT: A strain energy density-distance criterion2 was previously developed

and used to correlate rising-load K c initiation data for notched and fatigue precracked
specimens of hydrogen precharged Alloy X-750. This criterion, which was developed
for hydrogen embrittlement (HE) cracking at 93~ is used here to correlate static-load
stress corrosion cracking (SCC) initiation times obtained at 360~ in deaerated water
using smooth geometry, notched and fatigue precracked specimens. According to this
initiation criterion, the onset of crack growth occurs when a critical strain energy
density is attained at a microstructurally characteristic distance from notch and crack
tips. In the previous HE study the characteristic distance for crack initiation was
found to be one grain diameter, independent of notch radius, applied stress intensity
factor and hydrogen level. For the current SCC study, initiation is shown to occur at a
variable distance from notch and crack tips. The initiation site varies from very near
the crack tip, for highly loaded sharp cracks, to a site that is one grain diameter from
the notch, for lower loaded, blunt notches. The existence of hydrogen gradients,
which are due to strain-induced hydrogen trapping in the strain fields of the notch and
crack tips of the SCC test specimens, is argued to be responsible for variation in the
crack initiation site. A variable crack initiation site for the SCC specimens is shown
to be consistent with a fixed initiation site for the HE specimens by considering the
source of the hydrogen, which is external to the specimen in the SCC study and
internal to the specimen in the HE study.
KEYWORDS: SCC initiation, strain energy density criterion, hydrogen
l Manager and Senior Engineer, respectively, Bettis Atomic Power Laboratory,

Westinghouse Electric Corporation, PO Box 79, West Mifflin, PA 15122
z M. M. Hall, Jr., D. M. Symons and J. J. Keams, in The Parkins Symposium on

Fundamental Aspects of Stress Corrosion Cracking, The Minerals, Metals & Materials
Society, 1992.
167
Copyright*
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Int'l (all International
Fri Dec 30 21:53:51 EST 2011
Designers of nuclear reactors must consider the potential for stress corrosion
cracking (SCC) failures of reactor components that have sharp, crack-like
manufacturing defects. Fatigue precracked fracture mechanics test specimens are
commonly tested to determine the threshold stress intensity factors, elapsed times and
crack growth rates for the onset and propagation of SCC in these defected
components. Notched and smooth geometry specimens also must be tested as SCC
failures have been reported for highly loaded components, such as age-hardened
NiCrFe Alloy X-750 fasteners and pins, even though they were nominally free of
manufacturing defects [1-3].
The stress parameter that is used to correlate SCC initiation data is chosen to
suit the test specimen geometry. The fracture mechanics stress intensity factor, K, is
available to correlate times for the onset of SCC crack growth for precracked
specimens. A quantity K/~/p, which is a ratio of the stress intensity factor and the
square root of the notch root radius, has been used to correlate SCC initiation times
for notched specimens [4]. The applied tensile stress is commonly used for uniaxial
tension and bend specimens. A purpose of the work reported here is to develop a
single fracture mechanics stress parameter that is capable of describing simultaneously
the stress conditions for initiation of SCC crack growth in smooth, notched and
precracked geometry test specimens. A further purpose is to use test results obtained
from these specimen types to infer aspects of the mechanisms for initiation of SCC
crack growth in Alloy X-750.
PREVIOUS WORK - HYDROGEN EMBRITTLEMENT
A criterion for the initiation of intergranular cracking due to hydrogen

embrittlement of Alloy X-750 was developed and reported by Hall et al. in a previous
publication [5]. As-notched and fatigue precracked three-point bend specimens were
hydrogen precharged and tested in air at 93~ under rising load to determine the
critical applied stress intensity factors, Kpc and K c (the stress intensity factors at
maximum load for notched and precracked specimens, respectively). Analysis of these
data, using an elastic-plastic analysis of the strain energy density distributions about a
notch, showed that the critical condition for the onset of crack growth is the
attainment of a critical strain energy density (SEDEN), Wc, at a microstructurally
characteristic distance, Xc, from the notch and fatigue crack tips. This characteristic
distance was found by analysis of the data to be one grain diameter, independent of
stress intensity factor, notch radius, and hydrogen concentration. This result was
obtained for two heat treatment conditions of Alloy X-750, HTH and AH, having grain
diameters of about 125 lam and 20 am, respectively.
There is additional information, obtained since first publication of the HE
analysis results, that supports the existence of a characteristic distance for crack
initiation. Fig. I is a photomicrograph that shows a detached grain boundary
microcrack located one grain diameter below the notch of an HTH specimen. The
rising load test of this specimen was interrupted just prior to the onset of crack
growth. Serial grinding and polishing of the specimen revealed no evidence that the
microcrack in Fig. 1 was connected to the notch surface. Therefor, this micrograph
supports the analysis result that crack initiation occurs within the specimen interior and
that the characteristic distance is o n e grain diameter.
HALL AND SYMONS ON STRAIN ENERGY DENSITY 169
Fig. 1--Initiation of a grain boundary

crack at a distance of one grain
diameter below the notch tip.
The critical stress intensity factor, Kpc, for initiation of HE crack growth in as-
notched specimens was successfully modelled as
(1)
Kpc = ~-~p(l+(1-V) xcl i (l-v)
The critical stress intensity factor increases in direct proportion to the square root of
the notch root radius, p, for notch root radii that are large compared to the
characteristic distance, X c. As the notch root radius decreases to zero, the plastic
correction factor, C_, approaches a value of 2, and Kpc approaches the critical stress
9 . P
intensity factor for a crack, K c, where
I nE'WcX~ (2)
Kc -- (l-v)
In these equations E' = E/(1-v 2) where E and v are the usual elastic constants. Eq. 1
defines a notch similarity function, Fp, such that
(3)
P Cp~ 4 )~"
Then Eq. 1 becomes

Kpc = FpKc" (4)
170 EFFECTSOFTHE ENVIRONMENTON INITIATIONOF CRACKGROWTH
A P P L I C A T I O N TO SCC I N I T I A T I O N
Eq. 4 was developed for the time-independent rising load HE tests. We

assume that this similarity relationship between notches and sharp cracks holds at all
times for the time-dependent SCC test. This means that for any given notch, having a
radius p and an applied stress intensity factor Kp, there is an equivalent crack, having
an applied stress intensity factor, K e , that initiates SCC at the same time, t i , as the
notch. (Note that K o is calculated using stress intensity factor equations for cracks
and assuming a crack length that is equal to the depth of the notch being analyzed.)
Then K e is the effective notch stress intensity factor. To obtain an expression for K e
in terms of the applied notch stress intensity factor, K 0 , we rearrange Eq. 3, let K c =
K e and Kpc = Kp and obtain
K = KplFp. (5)
This relationship is illustrated in Fig. 2.
~,~ . Precracked
ti . . . . . . . . . . . . . . . . . i
i m
, , " , ' e v ~P v \ ,\
Stress Intensity Factor

Fig. 2--Schematic illustration of the effective notch stress intensity factor concept.
Once K e has been determined by combining notched with precracked data and using
the method illustrated in Fig. 2, the characteristic distance can be obtained by
combining Eq. 3 with Eq. 5 and solving:
(1- v)-~
Xc -
(6)
) - 1
Using the strain energy density equations previously developed [5], we can
now calculate the strain energy density at this characteristic distance:
1-v CpK:
(7)
This equation also applies to cracks when P = 0. When the notch radius is large
relative to X c , the strain energy density is given by
4@K: (8)
Wp- rc E/O
This equation establishes the relationship between the strain energy density, used in
this work, and the ratio KJx/p, which has been used by others [4] to correlate notch
fracture toughness and SCgC initiation data9
For smooth geometry uniaxial test specimens, the strain energy is uniformly
distributed across the test section so that strain energy density is no longer dependent
on position within the gage section9 In this case,
2
w -
10o +
ff ode, (9)
2E ~
where ~o and % respectively are the yield stress and yield strain at the proportional
limit. The first term on the right hand side of equation is the yield strain energy
density, Wo, and the second term is an elastic-plastic (post-yield) component. Eq. 7
and Eq. 9 are used below for correlating the stress conditions for initiation of SCC
crack growth in as-notched, precraeked and smooth geometry test specimens. Use of
Eq. 6 to determine the characteristic distance for SCC and comparison to the
characteristic distances previously found for HE cracking provides further insight into
the micromechanics and mechanisms for deaerated water SCC initiation in
Alloy X-7509
MATERIALS AND EXPERIMENTAL PROCEDURE
Three heats of material were tested. The ranges of chemical composition are
given in Table 1. Heat 1 was given the HTH heat treatment, which consists of a
solution anneal at 1094~ for 1 hour, air cool and age at 704~ for 20 hours. Heats 2
and 3 were given the AH heat treatment, which consists of a stress equalization heat
treatment at 885~ for 24 hours, air cool and age at 704~ for 20 hours. Table 2
provides the mechanical properties.
Table 1--Materials Compositions [wt. %]
Ni Cr Nb + Ti A1 Fe C S
Ta
70.7- 14.9- 0.96- 2.37- 0.75- 6.45- 0.03- 0.01 HT l&2
73.6 15.4 1.05 2.58 0.78 7.90 0.04 0.07 HT 3
Table 2--Mechanical Properties
Heat Test Kjc UTS Yield Prop. Elong RA Gage Gage

Direction Strength Limit ation Dia. Length
MPa {m MPa MPa MPa % % mm mm
HT 1 Long. 147 1186 775 414 28 36 1 2 . 8 8 50.8
HT 2 Long. 150 1150 710 552 29 ..... 12.85 50.8

HT 3 Long. 150 1186 752 552 24 34 1 2 . 8 3 50.8
Microstructural features relevant to this study include grain size and grain boundary
carbide size and spacing. Both the HTH and the AH heat treatments result in
equiaxed grain microstructures with the mean intercept grain sizes being 127 tim for
HTH and 19 tim for AH. The predominant intergranular precipitate for condition
HTH is closely spaced (about 90% grain boundary coverage) M23C6 carbides having a
range of size typically 0.1 p.m to 0.3 tim. The predominant intergranular precipitate
for condition AH is less closely spaced (less than about 60% grain boundary coverage)
MC carbides having a size typically less than or equal to approximately 0.1 tim.
The superior SCC resistance of the HTH material in water precludes obtaining
SCC initiation on smooth tensile specimens for sensible loads and reasonable times.
Tests of the HTH material were performed, therefore, on as-notched and precracked
compact tension specimens having a width of 20.3 mm and a thickness of 10.2 nun.
The notch and crack depth to specimen width ratios were nominally 0.5. The notch
root radii were 0.127 mm, 0.254 mm and 0.756 ram. Precracked specimens loaded to
33 MPa~/m were precracked with a final maximum K I of 20 MPax/m and those loaded
to below 33 MPa~/m were precracked with a maximum K~ of 11 MPa~/m. All

specimens were bolt loaded using a load transfer technique. The specimen was loaded
to 95% of the final load in a tensile machine, then the load was transferred to the
specimen while maintaining the CMOD constant [6]. The load transfer technique was
used in reverse to measure the remaining load on the specimen at specific intervals,
thereby allowing the internal crack length to be calculated by standard compliance
techniques [7]. SCC incubation was measured as the time to grow an average crack of
125 ~m. The SCC initiation time for the notched specimens was taken as the time
when a crack could be detected using a stereo microscope by viewing the notch tip
along the thickness. Once initiation was observed, the specimen was inserted into the
autoclave for one additional cycle. In every case, the additional cycle resulted in
extensive crack growth.
Testing of the AH material Heat 3 was performed using the bolt-loaded as-
notched compact tension specimens and test methods discussed above. Testing of
Heat 2 was performed using constant load round tensile specimens. Tensile specimens
included smooth, circumferentially notched and single edge notched (saw cut) fatigue
precracked specimens. Testing of notched and precracked rounds was conducted in
order to facilitate comparisons to results obtained on the smooth surface uniaxial
tension specimens. Testing under constant load facilitated detection of SCC initiation
for the very long lived uniaxial smooth and circumferentially notched tensile
specimens. In this case, SCC initiation time was taken as the specimen failure time
corrected for crack growth. The maximum correction was about 19% for the shortest
lived notched specimen. The smooth tensile specimens had a diameter of 10.6 mm.
The as-notched tensile specimens had a major diameter of 10.6 mm and a minor
diameter of 6.4 mm. The precracked tensile specimens had a diameter of 4.57 mm
with a saw cut edge notch 0.30 mm deep. The onset of crack growth and the crack
growth rate in the precracked specimens were determined by interim examinations to
detect crack extension at the specimen surface.
The intergranular fracture surfaces for HE and SCC have the appearance of an
intergranular microvoid initiation process initiating at the grain boundary carbides
followed by void growth and coalescence [8]. The effect of internal hydrogen (HE
tests) is to reduce the apparent level of strain associated with microvoid growth. The
SCC fracture surfaces have the appearance of less void growth than the HE fracture
surfaces.
All specimens were tested in an autoclave at 360~ The aqueous environment
was prepared from high purity water (conductivity below 0.1 laS/cm). The water
contained 40-60 STP cc H2/kg H20. The room temperature pH was controlled
between 10.1 and 10.3 with the oxygen less than 100 ppb, normally below 40 ppb, and
the conductivity was approximately 80 ~tS/cm due to the additive used for pH control.
ANALYSIS PROCEDURE AND RESULTS
Fig. 3 shows the SCC initiation times that were obtained on both the
Condition AH and HTH heats plotted versus strain energy density. The data reduction
began with the smooth tensile specimens of AH Heat 2. Since for tensile specimens
the strain energy is not dependent on position within the gage section, these data can
be analyzed independent of a knowledge of the characteristic distance. Eq. 9 was used

to calculate the applied strain energy densities for the tensile specimens. In order to
obtain the best fit and to account for the survival of the longest exposed specimens, a
threshold strain energy value, Wth, having a magnitude of about 0.86 M N - m / m 3 had to
be subtracted from the calculated value of the applied strain energy for each. The
magnitude of Wth is about 7 % greater than the strain energy required for yielding (at
the proportional limit), Wo. This result implies that plastic strain is a necessary
condition for SCC initiation for this material. The threshold tensile stress
corresponding to Wth is about 572 MPa.
1,000,000
Closed Symbols - HTH
o Half Open (Heat 2) and
o
0 100,000 Open (Heat 3) Symbols - AH
CO
O3
"~ 10,000
t-
ai 1,ooo
100
V 0 Ji ~i
~'~Z 10
t-
1
0.01 o.1 1 lO lOO 1,ooo lO,OOO
W- Wth, MN-m/m 3
Notch Smooth 0.762 0.254 0.152 0.127 0.064 PC
Rad 9 (mm) ~' []
9
~
9
~ Q
o ~7
9
Fig. 3--SCC initiation time as a function of the applied strain energy density. Smooth,
notched and precracked specimen data are correlated with a single stress parameter.
Next, using Eq. 7, the applied strain energy densities for the precracked tensile
specimens were determined. A value for the sum r c = X c + (1-v)p/4 found in the
denominator of Eq. 7 was adjusted so as to obtain the best fit with the smooth tensile
test results. A value for r c o f about 2.3 ~tm was obtained. Note that this is
significantly smaller than the comparable value found for the condition AH material in
the HE studies. In the HE studies X c was found to be equal to the grain size o f about
20 ~tm and the effective crack tip radius for precracked specimens was found to be
about 11.4 ~tm, which gives a value for r c of about 20.5 ~tm. If we assume that the
effective crack tip radius in the SCC tests is as large as 11.4 ~tm as found for the HE
tests, we find that X c for the precracked SCC specimens is about 0.1 ~tm. As is
discussed in more detail below, X c for SCC is found by analysis o f the SCC data to
be variable, having a range o f values, from a minimum o f about 0.1 Ilm for highly
loaded cracks to a value approximately equal to the grain size for lower loaded blunt
notches.
No tensile SCC initiation tests were conducted for the more SCC resistant
condition HTH heat. Consequently, there are no tensile SCC data for use in
establishing r c for precracked specimens. Therefore, strain energy density values were
calculated for the precracked HTH specimens assuming the value o f r c found for the
precracked AH specimens. In this way the upper curve in Fig. 3 was constructed.
Note that with this assumption, the HTH and AH curves intersect at a time of about 3
hours and a SEDEN value o f about 10,000 MN-m/m 3. Using this SEDEN value and
Eq. 2, a K c of about 153 MPa ~]m is calculated. This is within 4% of the inert
environment Kjc fracture toughness for both heat treatment conditions of Alloy X-750.
These results imply, as is expected, that the toughness Kjc is little effected by the
environment for tests of short duration.
The characteristic distances were determined next for the as-notched CT
specimens o f both the AH and the HTH heats using Eq. 6. The Kpe values were
determined in a manner consistent with the method illustrated in Fig. 2. With X c for
each specimen determined, Eq. 7 was used to plot the position o f each notched
specimen on Fig. 3. Note that the AH Heat 3 data fall below the best fit curve
obtained for Heat 2 by about 30%. This difference is well within the normal heat-to-
heat variability observed for this heat treatment of Alloy X-750.
Fig. 4 is a plot o f the X c values plotted versus a normalized applied strain
energy density, W N = (W-Wth)/(Wjc-Wth). Wjc is the SEDEN value corresponding to
Kjc. This figure shows that, for the AH heats, Xc increases as W decreases, with X c
approaching a value approximately equal to the AH grain size as W approaches the
threshold value, Wth. For the HTH heat, there are no data at the lower W values from
which to judge data trends near threshold. However, for both AH and HTH heats, X c
decreases as W increases.
As shown by the data trend curves in this figure, both the AH and HTH data
sets are consistent with X c approaching the grain size as W N approaches 0. As
discussed above, the AH data are consistent with a value o f X c o f about 0.1 ~tm when
W N approaches 1. A value of 0.1 ktm is typical of the size o f grain boundary carbides.
Recalling the relationship, Eq. 8, between SEDEN and the ratio K J ' 4 p , Fig. 4 shows
that X c decreases with either a decrease in P or an increase in the applied K.
Increases in P and decreases in K both lead to increases in X c.
176 EFFECTSOF THE ENVIRONMENTON INITIATIONOF CRACKGROWTH
25
HTH Grain Size 127 IJm
2o AH Grain Size
Closed Symbols - HTH Heat 1

Half Open (Heat 2) and
Open (Heat 3) Symbols- AH
10
~ o ..,. 9 Gram Boundary

5
~-~. 9 Carbide Size
........ .O .............
o I i i ~ '
0 0.02 0.04 0.06

(W- Wth ) / ( W j c - Wth )
Notch 0.762 0.254 0.152 0.127 0.064
Rad.(mm) ~ ~ ~ o
Fig. 4--The microstructurally characteristic distance for fracture initiation as a function

the normalized applied strain energy density.
DISCUSSION
Mechanical Effects on SCC Initiation
A comparison of the HE and SCC fracture behaviors of AH and HTH heat

treatments of Alloy X-750 provides insight relative to the micromechanics and
mechanisms of environment-induced intergranular cracking in this alloy. Although
these heat treatment conditions have very similar inert environment mechanical
properties of yield strength and fracture toughness, the larger grained HTH condition
has superior HE and SCC resistance. In the HE study, the notch fracture toughness of
hydrogen charged HTH specimens was found to be superior to that of AH specimens
in spite of its apparent lower critical SEDEN, Wc. The superior HE toughness of
condition HTH was attributed to its much larger grain size. The larger
microstructurally characteristic distance, Xc, results in a substantially lower applied
SEDEN at the grain boundary fracture initiation site, which more than compensates for
the lower Wc (see Eq. 2.) The lower Wc for the HTH condition is consistent with
the larger grain size as there is significantly less grain boundary area for segregation
of embrittling elements known to lower the resistance of high nickel alloys to
intergranular fracture [9,10].
The importance of mechanical effects on the initiation of SCC for Alloy X-750
is readily apparent in Fig. 4. There appears to be a mechanical threshold for initiation.
For the AH heats, the threshold stress for smooth tensile specimens is about 4%
higher than the proportional limit. Due to the superior SCC resistance of the HTH
heat, there are no data near threshold to determine threshold stress for this heat
treatment. The data trends for both heat treatments show that, for short exposure
times, the apparent toughness extrapolates to the inert environment Kjc toughness of
Alloy X-750. In between these limits of SCC and Kjc thresholds, the time dependent
SCC initiation behavior is well behaved and can be correlated with equations of the
form
(w w,h)-m r K ,2. (10)

t,= to
K c-K,J
o - - ,
where, at 360~ in deaerated hydrogenated water, t o = 3.3 h for both conditions AH

and HTH, m = 0.7 for condition AH and m = 2.0 for condition HTH. This equation
implies that the same mechanism for initiation of fracture applies over the entire stress
range from the SCC threshold to stress intensities approaching Kjc fast fracture.
Enviroumentallv Enhanced Creep Fracture Model
From Eq. 10, which describes the initiation behavior shown in Fig. 3, we
conclude that the superior SCC initiation resistance of condition HTH can be attributed
to whatever is responsible for the much stronger associated stress parameter
dependence. One of the authors (MMH) recently developed an SCC crack growth rate
model for Alloy X-750 and Alloy 600 that accounts for the stress intensity factor
dependence of crack growth [11]. This model assumes that a hydrogen enhanced
creep fracture mechanism controls the rate of crack advance. The model accounts for
large effects of stress intensity factor and cold prestrain on the apparent activation
energy. The model also accounts for the effects of these variables and temperature on
the stress dependence of the crack growth rate.
Development of a similar model for SCC initiation is considered here. This
model is based on the assumption of a transient creep constitutive equation that allows
for creep hardening:
1_ 1
_o
9
(o/7,/-" (11)
-- NE Oo) o -IOo)l%)
- 9
In this equation N is the usual time-independent strain hardening exponent, q is the
creep strain hardening exponent, and n is the creep stress exponent. Reidel [12] has
derived the crack tip stress distributions for materials that obey Eq. 11. He also
provided an expression for the time dependence of the creep zone size:
1
K2 (12)
=
Eo o
where
p - N n - 1- q (13)
I+N
and ct is a function of N, n and q. Consistent with the time-independent model for HE

cracking, we consider that SCC initiation occurs when the creep strain exceeds a
critical value at a microstructurally characteristic distance from notch and crack tips.
This requires that rcz > X c. Then the SCC initiation time is given by
> ~-~(EOoXr] t' (14)
In this equation eo is a temperature dependent material parameter, that, along with n

and q, is expected to be environmentally sensitive.
Comparison of Eq. 14 with Eq. 10 implies that the stress parameter exponent in
Eq. 10 can be obtained from Eq. 14. The strain hardening exponent, N, is about 0.167
for both AH and HTH conditions and the creep strain hardening exponent is typically
1 for low temperature-high stress dislocation creep [13]. We conclude then that it is
the transient creep stress exponent, n, that distinguishes the AH and HTH conditions
and is the deformation parameter associated with the superior SCC resistance of the
HTH condition. Assuming these values for N, q and the values for p determined from
Eq. 9, the creep stress exponents, n, are determined to be about 17 and 26 for AH and
HTH conditions, respectively. There are no low temperature transient creep data for
Alloy X-750 to give a comparison to these results. However, transient creep stress
exponents this large indicate "exponential creep" [14], which is consistent with the
expected low-temperature high-stress creep mechanism for SCC [11].
Effect of Source of Hydrogen on Crack Nucleation Site
An important difference to note between HE and SCC initiation for Alloy X-

750 is in the sources of hydrogen. For the hydrogen precharged specimens of the HE
experiments, the hydrogen is internal to the specimens and crack nucleation occurs at a
grain boundary located at a distance of one grain diameter from the notch and crack
tips. This initiation site is independent of notch radius, applied stress intensity factor
and the hydrogen concentration. For the specimens used in the SCC experiments, the
source of hydrogen is external to the specimen. In this case analysis of the data shows
that the crack initiation site varies systematically with notch radius, from about 0.1 ~tm
for sharp notches to one grain diameter for blunt notches.
While the role of hydrogen in SCC remains controversial, crack initiation due
to hydrogen enhanced local plasticity is consistent with the observations and
conclusions regarding the location of the initiation site. Variation in the initiation site
can be rationalized in terms of the hydrogen and strain gradients. For the HE case,
the specimens are first precharged with a uniform distribution of hydrogen and then
strained to initiation. In this case of initially uniform hydrogen, a microcrack should
first nucleate at a distance of one grain diameter if the crack nucleation occurs by a
Stroh [15]-Cottrell [16]-Petch [17]-type crack nucleation mechanism. In this
mechanism cracks nucleate at the terminus of a dislocation pile-up. The strength of
the pile-up is proportional to ~/l, where l is the length of the pile-up. Then microcracks
will first nucleate at a distance of one grain diameter from a source of dislocations,
such as a notch, since the maximum length of a dislocation pile-up is one grain
diameter.
For the SCC case, specimens are first strained and then exposed to a source of
hydrogen by exposure to high temperature deaerated water. A uniform hydrogen
distribution is not expected for sharply notched specimens. Hydrogen that enters at a
notch tip will be trapped by dislocations and precipitates in the strain field of the
notch in proportion to the local strain level [18,19]. The notch strain at the
characteristic distance is a function of the ratio K/~/p, which is a measure of the
maximum local strain and magnitude of the strain gradient [20,21 ]. As this ratio
increases, either by an increase in K or a decrease in p, the maximum strain and the
strain gradient increase, and consequently, so will also the hydrogen concentration and
hydrogen gradient. Then crack nucleation should occur near the notch tip where the
strength of a dislocation pile-up first exceeds the local hydrogen affected fracture
strength. In the limit of large KA/p, which is approached with a sharp crack, the crack
nucleation site approaches very near the surface for the external hydrogen case.
For very blunt notches the strain distributions, and consequently, the hydrogen
distributions, will be more uniform. In the limit of the unnotched tensile specimen,
the hydrogen distribution is uniform and the specimen is expected to behave in a way
similar to the internal hydrogen case. Therefore, as the notch radius increases we
expect that the crack initiation will occur at a site that approaches one grain diameter
from the notch tip.
CONCLUSIONS
Use of the strain energy density-distance criterion, which was developed for
rising-load K c initiation of cracking due to hydrogen embrittlement, shows that stress
corrosion cracking, like HE cracking, also initiates at an interior site. This supports an
assumption that hydrogen plays an important role in SCC initiation as the water
environment has no direct access to the initiation site. Since initiation occurs under
static load, time-dependent creep strain appears to be necessary. Since the threshold
stress for crack initiation is just above the proportional limit, dislocation creep
mechanisms, such as thermally activated glide, are most likely. Consideration of the
analytical solutions available for crack tip deformation under creep conditions suggest
that the SCC stress dependence is a function of the time-independent strain exponent
and creep hardening exponent but is likely controlled by the transient-creep stress
exponent.
Unlike HE, the site for SCC initiation depends on the notch radius and the
applied stress intensity factor. The existence of hydrogen gradients, which are due to
strain-induced trapping of hydrogen at notch and cracks tips, can qualitatively account
for variation in the site for microcrack nucleation. These observations and conclusions
can then be seen to be consistent with the observations from a previous HE study in
which the characteristic distance for microcrack nucleation was found to be
independent of notch radius, applied stress intensity factor and hydrogen level.
ACKNOWLEDGMENTS
The authors wish to acknowledge H. K. Shen and J. J. Kearns whose data were used
in this study. This work was supported by the United States Department of Energy
through Contract No. DE-AC 11-93PN38195,
REFERENCES
[I] Berge, P., "Experience with Alloy X-750 in PWRs," Proceedings: 1986
Workshop on Advanced High Strength Materials, EPRI NP-6363, 1989.
[2] Camahan, R. A. and Gordon, G. M., "Summary of Alloy X-750 Behavior in
General Electric BWRs," .Proceedings: 1986 Workshop on Advanced High
Strength Materials, EPRI NP-6363, 1989.
[3] Benhamou, C. and P0itrenaud, P., "Framatome Experience and Programs in
Relation to Guide Tube Support Pin Cracking," Proceedings: 1986 Workshop
on Advanced High Strength Materials, EPRI NP-6363, 1989.
[4] Hirose, Y. and Mura, T., "Nucleation Mechanism of Stress Corrosion Cracking
from Notches," Engineering Fracture Mechanics, Vol. 19, No.2, 1984, pp. 317-
329.
[5] Hall, M. M., Jr., Symons, D. M. and Kearns, J. J., "Strain Energy Density -
Distance Criterion for the Initiation of Hydrogen - Induced Cracking of Alloy
X-750," Proceedings of the Parkins Symposium on Fundamental Aspects of
Stress Corrosion Cracking, S. M. Bruemmer, E. I. Meletis, R. H. Jones, W. W.
Gerberich, F. P. Ford, and R. W. Staehle, Ed., The Minerals, Metals and
Materials Society, 1992, pp. 231-244.
[6] Mills, W. J. et al., "Effect of Irradiation on the Stress Corrosion Cracking
Behavior of Alloy X-750 and Alloy 625," Sixth International Symposium on
Environmental Degradation of Materials in Nuclear Power Systems - Water
Reactors, R. E. Gold and E. P. Simonen, Ed., 1993, pp. 633-643.
[7] Saxena, A. and Hudak, S. J., "Review and Extension of Compliance
Information for Common Crack growth Specimens," International Journal of
Fracture, Vol. 14, No. 5, 1978, pp. 453-468.
[8] Symons, D. M. and Thompson, A. W., "The Effect of Hydrogen on the
Fracture of Alloy X-750," Metallurgical and Materials Transactions A, Vol.
27A, January 1996, pp. 101-110.
[9] Grove, C. A. and Petzold, L. D., Corrosion of Nickel-Base Alloys, American

Society for Metals, 1985, pp. 165-180.
[10] Elliot-t,C. K., "Effect of Thermal Treatment on the Fracture Properties of
Alloy X-750 in Aqueous Environments," Ph.D. Thesis, Massachusetts Institute
of Technology, 1985.
[11] Hall, M. M. Jr., "Thermally Activated Dislocation Creep Model for Primary
Water Stress Corrosion Cracking of NiCrFe Alloys," Presented at the
Intemationa! Symposium on Plant Aging and Life Prediction of Corrodible
Structures, Japan Society of Corrosion Engineering, Sapporo, Japan, 1995,
WAPD-T-3045.
[12] H. Riedel, Creep Deformation at Crack Tips in Elastic-Viscoplastic Solids,"
Journal of the Mechanics and Physics of Solids, Vol. 29, 1981, 35-49.
[13] Feltham, P., "Creep and Stress Relaxation in Alpha-Brass at Low
Temperatures," Philosophical Magazine, Vol. 6, 1961, pp. 259-270.
[14] Sherby, O. D. and Burke, P. M., Mechanical Behavior of Crystalline Solids at
Elevated Temperature, Pergamon Press Ltd., London, 1968, p. 340.
[15] Stroh, A. N., Proceedings of the Royal SocieW, Vol. A223, 1954, p. 404-414.
[16] Cottrell, A. H., Transactions of the American Institute of Mining, Metallurgy
and Petroleum Engineers, Vol. 212, 1958, pp. 192-203.
[17] Petch, N. J., Philosophical Magazine, Vol. 3, 1958, p. 1089.
[18] Boursier, J. M., de Bouvier, O., Gras, J. M., Noel, D., Rios, R. and Vaillant, F.,
"SCC of Alloy 600 in High Temperature Water: A Study of Mechanisms,"
Corrosion-Deformation Interactions CD 92, Les Editions de Physics, Les Ulis,
France, 1992, pp. 117-137.
[19] Yonezawa, T., Yamaguchi, Y. and Iijima, Y., "Electron Micro
Autoradiographic Observation of Tritium Distribution on Alloy X750," Sixth
.International Symposium on Environmental Degradation of Materials in
Nuclear Power Systems - Water Reactors, R. E. Gold and E. P. Simonen, Ed.,
1993, pp. 799-804.
[20] Rice, J. R., "A Path Independent Integral and the Approximate Analysis of
Strain Concentration by Notches and Cracks," Journal of Applied Mechanics,
Vol. 35, June 1968, pp. 379-386.
[21] Samhanam, A. T. and Bates, R. C., "The Influence of Notch-tip Geometry on
the Distribution of Stress and Strain," Materials Science and Engineering, Vol.
41, 1979, pp. 243-250.
Otakar Jonas 1
MOLECULAR MODELING OF CORROSIVE ENVIRONMENTS IN C R A C K S
REFERENCE: Jonas, Otakar, "Molecular Modeling of Corrosive Environments

in Cracks," Efffcts of the Environment on the Initiation of Crack Growth, ASTM
STP 1298, W.A. Van Der Sluys, R.S. Piascik, and R. Zawierucha, Eds., American
ABSTRACT: Presented are concepts and results of molecular modeling of the

chemistry of the environment - crack interactions. Water, salt and acid solutions,
hydrogen, and hydrogen sulfide were evaluated on magnetite and hematite covered
open surface and crack tip. Interactions of these environments with the oxides are
expressed as relative interaction energies. Individual molecules and ions of the
environment equilibrate in their preferred positions within the crack and other
surfaces. When different crystallographic planes are present, the chemical species
often separate, forming groups of cations, anions, and neua-al molecules. The results
indicate relative aggressivity of the environments, types of chemical/corrosion
reactions, and the rate of mass transport to the crack tip. They may lead to models of
the mechanisms of stress corrosion and corrosion fatigue.
KEY WORDS: corrosion, cracking, stress corrosion, initiation, molecular modeling

solutions, salts, acids, adsorption, ion separation, hydrogen, magnetite, hematite
!. INTRODUCTION
It has been amply documented that different corrosive environments can differ by
orders of magnitude in their effects on the crack initiation and incubation times and
the crack propagation rate |l to 5]. For carbon and low alloy steels, there are at least
9 classes of environments producing significantly different results in corrosion
cracking, i.e., stress corrosion, intergranular attack, and corrosion fatigue. These
environments include nitrates, hydroxides, carbonates, phosphates, CO + CO2 +
H20, NOx containing sulfates, non-oxidizing acid environments, cyanides, and
sulfides. Corrosion cracking processes also strongly depend on many other parameters
such as temperature, pressure, concentration, pH, potential, stress, inhibitors,
promoters, surface treatments, and crack overloading.
Metal oxides are usually present during the crack initiation stage on the open metal
surfaces exposed to air or aqueous environments. On carbon and low alloy steels,
1 Consultant, Jonas, Inc., 1113 Faun Road, Wilmington, DE 19803
182
Copyright*
Fri Dec 30 21:53:51 EST 2011
JONAS ON MOLECULAR MODELING 183
typical oxides are magnetite (Fig. 1) and hematite. On stainless steels and
superalloys, spinnels form the passivating layer (see Fig. 2). Even slow propagating
stress corrosion and corrosion fatigue cracks are almost always covered with oxides.
FIG. 1--Magnetite on carbon steel FIG. 2--Oxide on 304 stainless steel
The equilibrium state of a metal surface in specific environments can be predicted by

the potential - pH diagrams [6] which can be used to determine what oxide or other
type of surface are present for a specific metal-environment-pH-potential-temperature
combination.
Several corrosion crack initiation and propagation models have been proposed
during the last decades [1, 7, 8, 9]. However, these mostly qualitative models have
not been developed down to the molecular scale where the environment - metal/oxide
interactions occur. Admittedly, there are macroscopic effects such as corrosion cells,
potentials, and stresses, but in corrosion cracking, these effects only influence the
molecular scale phenomena.
The stages of corrosion crack initiation, incubation, and propagation can be divided
as follows (see Fig. 3):
ENVIRONMENT
1. Transport of environment to a crack
p
2. Sorption
3. Corrosion reactions (electrochemical)
STRESS
4. Transport of soluble reacted species
and gasses away from the crack
5. Crack propagation
FIG. 3--Stages of corrosion crack initiation, incubation, and propagation
For the stages 1, and 2, molecular modeling has been applied and is described in
this paper. The more aggressive corrosive situations, such as acidic dissolution and
pitting where the oxide is chemically dissolved, have not been studied because the
technology for modeling of these chemical reactions is not yet sufficiently advanced.
For the molecular modeling of the impurity - surface and crack interactions
described in this paper, several configurations of magnetite and hematite crystals
exposed to water, water with ionized and nonionized impurities, and single and
hydrated molecules of typical impurities encountered in aqueous corrosion have been
studied.
The modeling has been done without any representations of metal oxide defects, and
the effects of temperature and pressure were not fully investigated.
2. MOLECULAR MODELING METHODS [10 to 19]
All molecular modeling methods involve the definition and calculation of a potential
energy surface which depends on the atoms which comprise the system, their
locations, and the distribution of the electrons in the system. The configurations at
which the energy is at a minimum are found by iteration. Two classes of molecular
modeling methods have been used here:
Molecular Mechanics--an empirical method based on classical physics which does

not explicitly include the electrons in the calculation. As a result, these methods
cannot be used to study processes involving bond formation or bond breaking. They
can be used to study the interactions between molecules or between parts of a
molecule that do not involve changes in bonding.
Semi-empirical methods--approximate methods based on quantum mechanics. The

electron distribution is explicitly calculated. These methods can be used to study
processes involving changes in bonding.
Both molecular mechanics and semi-empirical methods use parameters in their

potential energy expressions which are determined by fitting to experimental data.
Parameters are not available for all elements in all situations and the applicability of
these methods is often limited to systems for which parameters have been determined.
Molecular Mechanics
Molecular mechanics is an empirical method which uses equations derived from the
laws of classical physics to model the interactions of molecules and atoms in
molecules. Calculations do not explicitly involve the electrons in the molecules. As
such, molecular mechanics cannot be used to study processes involving bond
formation and bond breaking.
A potential energy function, U, is defined from which the forces acting on each
atom in the system can be calculated. The potential energy function includes terms
for bonded interactions (bond stretching, bond angle bending, torsion angle rotation)
and non-bonded interactions (van der Waals repulsion, London attraction and
electrostatic interactions between charged particles, some functions also include terms
to explicitly account for dipole-dipole interactions and hydrogen-bonding). Typical
bonding and non-bonding interaction contributions to the potential are outlined below.
Terms in the Potential Energy Funr
Bond stretching and bond angle bending are treated as if the atoms were connected
by springs. A symmeU'ic quadratic potential about an equilibrium bond length or
bond angle typically represents the energy required to distort the bond or angle from
its equilibrium position. The bond and angle constants (Kr and Ko) reflect the ease or
difficulty with which the bond length or angle may be distorted from their equilibrium
values (r0 and 00). The MM+ [10, 11, 12] forcefield includes a cubic term in the
bond-stretching contribution to better model the asymmetry of the bond dissociation
potential.
Ubond = K r (r-to)2 Uangle = I4,o(0-00)2
Torsion angle rotation is represented by a cosine function with a phase factor (~b0)
to shift the minimum of the function to the appropriate angle. The barrier (Vn) to
rotation about the bond is also a parameter in the equation (n is the symmetry of the
rotational barrier, typically 2 or 3).
Utorsion = (Vn/2)(1 +cos(n~-~0))
van der Waals and London interactions are usually combined into a single
non-bonded potential with a term for the repulsive vdW interaction and another ter~n
for the attractive London interaction. The repulsive p2tential is modeled as a I/r "~- or
exponential function and the attractive potential as 1/ru. Two typical non-bonded
potentials are shown below: r i is the van der Waals radius of an atom, rij is the sum
of the van der Waals radii of two interacting atoms, ei is a hardness factor (which
determines the depth of the potential well and how easy or difficult it is to push the
atoms together), ~ij is the geometric mean of the hardness factors, i.e. (ei ei)I/2, A,
B, C, Aij and Bij are method-specific parameters for each pair of interactin~ atoms,
Rij is the interatomic distance and Pij =Rij/rij-
Unon-bonded (MM+) = ~ij (A e-C rij . B rij-6 )
Unon-bonded (LJ) = Aij/Rij 12- Bij/Rij6
The last major non-bonded interaction is the electrostatic interaction between atoms
bearing full or partial charges. These electrostatic interactions are very important for
polar and ionic systems. The electrostatic interaction is determined simply by using
Coulomb's law: qi is the charge on atom i, and e is the dielectric constant.
Uelectrostatic = qi qj/c Rij
Some forcefields (AMBER [14]) also include a term to explicitly account for
hydrogen-bonding.
UH_bond = Cij/Rijl2 _ Dij/RijlO
The partial charges used in molecular mechanics calculations must be set manually.
These charges are often determined from quantum mechanical calculations of the
electron distribution of the molecule, or in the case of commonly studied molecules,
such as water, charges are chosen which reproduce the structure and behavior of water
in aqueous systems.
Default MM + ForcefieM--The constants present in the expression for the potential

energy used in molecular mechanics calculations are determined by fitting the
properties of a selected set of molecules predicted using a particular potential energy
function to experimentally determined values. This parametrization of a method using
experimental data can make up for the approximations made in treating the system
according to the laws of classical mechanics (as opposed to quantum mechanics).
Molecular mechanics parameters for an atom in a molecule depend not only on what
element it is but also on its chemical environment (the number and types of bonds an
atom makes to other types of atoms in the molecule). As a result, possibly the largest
barrier to the use of molecular mechanics forcefieids in areas other than those for
which they were developed is the lack of parameters for atoms in molecules that are
very different from those used to generate the parameters.
The MM + molecular mechanics method has the ability to generate "default"
parameters in situations where they are lacking [15]. The non-bonded parameters are
the most important for the work in this study, as intermolecular interactions are the
focus of this work. The default non-bonded parameters are determined based on the
element involved. Default values allow the method to be broadly applied.
Semi-Emoirical Methods
Semi-empirical methods are based on quantum mechanics, the laws of physics

which govern the behavior of subatomic particles such as electrons. Unlike molecular
mechanics, which considers only the atomic nuclei, quantum mechanics explicitly
considers the electrons in the system being studied. Electrons, being much smaller
and lighter than nuclei, move rapidly in comparison to the atomic centers. As a
result, almost all quantum mechanical calculations treat the motion of the electrons
around the nuclei as though the nuclear positions were fixed (the Born-Oppenheimer
approximation). For any given arrangement of nuclei (molecular geometry) the
electrons adjust instantaneously to the best (lowest energy) distribution for that
geometry. The electronic energy is calculated by approximately solving the quantum
mechanical Schr/Sdinger equation (below).
HW =EtP
H is the Hamiltonian operator; it contains terms describing the potential and kinetic
energies of the electrons and the potential energy of the nuclei in the system. The
solutions to the Schr&linger equation (a multi-variable, second-order, partial
differential equation) are functions, ~P, called wavefunctions, which describe the
electron distribution (the motion of the electrons and where they are most likely to be
found) of the molecule. Each function that is a solution to the Schr&linger equation
for a given molecular geometry has an energy, E, associated with it. The lowest
energy solution is called the ground-state wavefunction. All of the semi-empirical
calculations in this study involve the ground-state wavefunction.
Semi-empirical calculations provide approximate solutions to the Schr/Sdinger
equation. The Schr&linger equation for a system containing more than one electron
cannot be solved exactly. As a result, all quantum mechanical calculations involving
more than one electron must involve some approximations in order to obtain solutions.
The exact solution of the Schr&linger equation involves calculation of all electron-
electron, electron-nucleus and nucleus-nucleus interactions. As the size of the system
increases, the number of interactions to consider and the computer time required to
obtain a solution increases rapidly. To simplify the equations that must be solved and
decrease the computer time needed to solve these problems, semi-empirical methods
neglect some of the smaller interactions and approximate other with parameters which
depend on the dements involved in the interactions. These parameters are derived
from empirical data or ab initio quantum mechanics calculations (which make minimal
approximations and use no empirical data). Unlike molecular mechanics methods,
these parameters depend only on the element and not on its chemical environment.
Additionally semi-empirical calculations require no information about the location or
types of bonds in the system or partial charges on individual atoms.
Since we enter only the initial position of the atoms and no information about
bonding or charges into the calculation (other than the overall charge on the system,
which determines the total number of electrons present), the electron distribution
functions (wavefunctions) obtained from semi-empirical calculations can be used to
calculate partial charges (average number of electrons around an atom compared to its
nuclear charge) and to study bonding. Semi-empirical calculations can also be used to
study processes involving changes in bonding, however they are significantly more
computationally intensive and cannot readily be applied to extremely large systems.
To simplify the calculation, and reduce the computer time required, some of the
terms in the Schrrdinger equation are approximated with parameters for the different
elements in the system. As with molecular mechanics, these parameters are
determined by fitting the properties of a selected set of molecules predicted using this
approximate SchrOdinger equation to experimental values. The semi-empirical
methods used in this work are discussed briefly below.
AM1 and PM3--AM1 was developed by M.J.S. Dewar and co-workers [16, 17].
PM3 is a reparameterization, by J.J.P. Stewart [18], of AM1 (i.e. - the same
equations and approximations are used in each method, only the values of the
parameters differ). AMI is generally considered to be the most accurate semi-

empirical method (for most problems) |19] available for our use. PM3 is typically
used for organic molecules. There are parameters for main-group elements through
Xe. These methods were used to determine partial charges on small molecules
composed of main-group elements (NH3, CO2, OH-, etc.) for use in molecular
mechanics studies.
3. M O D E L S R E L A T E D T O E N V I R O N M E N T A L CRACKING
The models described in this paper include the following oxides and their
configurations:
9 cubic magnetite
9 truncated tetrahedral magnetite
9 cubic hematite
9 cracked magnetite
The environments studied include pure water and single molecules and ions,
hydrated molecules, groups of molecules, and molecules in aqueous solutions of the
following impurities: NaCl, HCI, NaOH, SiO2, H2S, Na2S305, Ca + , H2, H + . . . .
Both ionized and nonionized substances were studied.
In each computer run in the equilibrium configuration studies using the MM+
method described in Section 2, stable and metastable equilibrium configurations and
the corresponding system energies were determined. In the molecular dynamic
computations, the rate of change of the initial configuration and the final
configurations and energies were determined. All systems studied were isolated (in
vacuo). No distance-based force cutoffs or periodic boundary conditions were
imposed. For the molecular species for which structure was not well known, the
semi-empirical quantum mechanics method was applied before the other modeling.
Transport of Environment to a Crllck Tin and Oxidized Surface
Transport of corrosive species and water molecules to an open magnetite surface,

tetrahedral magnetite, and oxidized cracks is very fast. This has been experimentally
demonstrated by sorption experiments even at very high vacuum. Figure 4 gives
results of molecular dynamics modeling of transport of 32 water molecules from a
droplet configuration into a magnetite covered crack tip at 300~ The equilibrium
configuration has been reached in less than 5 picoseconds.
FIG. 4--Transport of 32 water molecules from a droplet to a crack tip
How quickly the environment will reach its equilibrium at a surface or in a crack
depends on its chemical characteristics, such as ionization and hydration, on the oxide
crystallographic planes, and on temperature. In relation to the observed times for
crack nucleation, incubation, and propagation, this transport is not the rate-controlling
phenomenon.
$0rption and Ion Senaration
Magnetite and hematite strongly adsorb all the chemical species we have
investigated. Ions are adsorbed much more strongly than neutral molecules. When
different crystallographic surfaces are present, such as for the tetrahedral magnetite
and a magnetite wedge representing oxidized crack tip, ionic and neutral species
separate and each adsorbs preferentially on its preferred magnetite plane.
Two examples of the separation of chemical species are shown in Figures 5 and 6.
Figure 5 is an equilibrium configuration of sodium hydroxide solution represented by
20 water molecules and 10 Na § ion pairs, on a truncated magnetite tetrahedron.
Na +, OH-, and H20 separated, each on a different crystallographic plane. The total
energy of interaction is -51,629 kcal/mol. Figure 6 gives similar results for a solution
of hydrochloric acid represented by 20 molecules of H20 and 10 ion pairs of H+CI -.
The energy of this interaction is -53,306 kcal/mol. The bonding energies for a group
of chemicals on tetrahedral magnetite are tabulated in Table 1. In the table, large
differences between ionized and neutral species can be seen.
FIG. 5--Adsorption of NaOH solution FIG. 6--Adsorption of HC! solution on

on magnetite tea'ahedron and separation magnetite tetrahedron and separation of
of H20 - Na + - OH-. H20-H +-CI-.
An example of equilibrium configuration of a solution of sodium chloride

represented by 10 molecules of water and 5 ionic pairs of Na+C! - at an oxidized
crack tip represented by a magnetite wedge is shown in Figure 7. Similarly as for the
tetrahedron, there is separation of the three chemical species. Interaction energies for
l0 molecules of impurities in a magnetite wedge representing oxidized crack tip are
given in Table 2.
FIG. 7--Sodium chloride solution at the FIG. 8--Preferential adsorption of calcium

tip of oxidized crack represented by a ion on the oxygen-rich plane of magnetite
magnetite wedge. tetrahedron.
TABLE 1--Interaction energies for maanetite tetrahedron

v
Impurity Energy (kcal/rnol)
H20 -4,395
Ca + + -41,963
Na + CI- -65,270
Na + OH- -83,950
HC1 -3,761
H+CI - -88,967
H+ -40,062
H2S -402
SiO2 -331
TABLE 2--Interaction enereies for imnurities in oxidized crack tio
Impurity Energy (kcal/mol)
H20 -274
Ca + + -550
Na+CI - -5,166
Na+OH - -3,736
HCI -667
H+CI - -6,260
H+ -3,901
H2S -113
SiO2 -45
Somtion of buffers and corrosion inhibitors--can also be investigated by molecular

modeling. It is known from the production of magnetite pigment that calcium ion can
stabilize the pigment particles and it has been observed in corrosion of water systems
that precipitated hardness acts as a buffer to acid corrosion. Results of our modeling
of Ca + § adsorption on magnetite are illustrated in Figure 8. Calcium ions
preferentially adsorbed on the oxygen-rich plane.
Corrosion Reactions
Generally, it is possible to model corrosion reactions on oxide-covered surfaces and

within oxidized cracks with the use of quantum mechanics models. This modeling has
not been performed yet in our project. However, possible reactions can be inferred
from the configurations of corrosive species as described above and from the
deformation of the adsorbed molecular species and of the crystal lattice of magnetite.
Our studies show that in all cases, the adsorbed species are pulling the iron ions out
from their positions in the magnetite crystal. The mechanical forces exerted by these
adsorbed impurities are, in relation to the loading by stresses, very low. The
maximum force was -0.15 N/cm, for water molecules in a crack tip.
Hvdrogen--has been considered to be responsible for crack initiation and

propagation in many corrosion cracking situations. It is produced by many corrosion
reactions in aqueous environments with a large variety of corrodents including acids,
salts, and hydroxides. For general and pitting corrosion in boilers and heat
exchangers, it can be measured and is usually in low ppb range in water. As shown
in Figure 6, hydrogen is also available after adsorption of acids and separation of
anions and cations.
We have not modeled the mechanisms of hydrogen participation in the later stages
of crack initiation and propagation.
4. DISCUSSION
This paper describes the concepts and selected results of molecular modeling of the
environment - oxidized metal surface interactions, applied to corrosion cracking (stress
corrosion and corrosion fatigue). It concentrates on chemical aspects of the crack
initiation and incubation process (see Figure 5) which need to be combined with
corrosion and material/stress aspects of the crack growth phenomena to develop a
complete model of corrosion cracking. There have been studies of the oxide-impurity
interactions [20, 21, 22] and molecular dynamics has been used to model crack
formation and crack-vacancy and intersticial atom interaction [23 to 26].
In practical applications of steels and other materials, in aqueous environments and
air, there are almost always conditions favorable to oxide formation, i.e., environment
and time. Rapid stress corrosion component failures are today an exception indicating
bad design, bad material selection, or unexpectedly aggressive environment. The
crack initiation from undamaged surfaces and crack initiation from manufacturing
defects typically take tens of thousands of hours and practical crack propagation rates
are in the range of 10-4 to 1@7 mm/hour.
The selection of metal oxides and environments used in this study represents
situations in the steam generation industry, such as in boilers, steam generators, steam
turbines, heat exchangers, and piping.
While the studies performed so far have many limitations, they help to understand
the interactions of various environments with metal component and crack surfaces.
Current advancements of the computational quantum mechanics, chemical reactions
and electrochemistry of corrosion will result in larger and more qualitative models.
The ultimate approach for modeling of crack initiation and propagation will have to
include the chemical interactions of impurities with metal and crack surfaces, transport
of these impurities into the region of the crack tip and their effect on local corrosion
and metal bond interruption in the crack tip region.
In practical corrosion cracking situations, particularly in the steam generation
industry, numerous other environmental processes are involved which may also
control the crack initiation, incubation, and propagation. These processes include:
9 deposition from liquid and gaseous environments
9 evaporation on hot surfaces
9 concentration in condensed phases in two-phase environments
9 concentration on oxides - sorption
9 l i q u i d - vapor chemical transport
9 surface diffusion
9 diffusion through protective oxide layers
9 dissociation and chemical reactions
9 gradient of the potential along a crack
Surface analytical techniques such as SIMS, ESCA, and Auger spectroscopy and
atomic force microscopy are providing experimental input to the understanding of
surface interactions and reactions active in corrosion cracking.
It is hoped that a combination of molecular modeling, surface chemistry, corrosion
science, thermodynamics, metal physics, and fracture mechanics will finally lead to
the development of a comprehensive model of stress corrosion cracking and corrosion
fatigue.
5. CONCLUSIONS
1. Molecular modeling provides an insight into the chemistry of corrosion crack

nucleation from oxidized surfaces and the chemistry within cracks at crack tips.
Different corrosive and noncorrosive environments and corrosive inhibitors and
buffers can be rated as far as their:
aggressivity
rate of transport
chemical reactions with surfaces
electrochemical interactions within cracks
behavior of reaction products and their effects on cracking
stress - chemistry interactions
Gaseous and liquid environments containing organic or inorganic chemical species
can be modeled.
At the present, this fast developing technology gives semiquantitative results based
on molecular mechanics - an empirical method which uses equations derived from the
laws of classical physics to model the interactions of molecules and atoms in
molecules and semi-empirical methods based on quantum mechanics where the
electron distribution is explicitly calculated. Molecular mechanics can provide
equilibrium configurations as well as models of real time changes from one
configuration to another (molecular dynamics).
2. For modeling of corrosion crack initiation and incubation, inputs from chemical
thermodynamics, i.e., solution equilibria and potential - pH diagrams, are useful. For
corrosion crack incubation from existing oxidized cracks, the thermodynamic models
need to be modified for the crack tip geometry.
3. Aggressivity of an environment can be judged from the energy difference

between the interacting and noninteracting systems, from the reaction products which
can be evaluated using semi-empirical methods, and from the attractive forces between
the oxidized metal surface and the molecules and ions of the environment.
4. The rate processes of crack initiation, incubation, and propagation can be
evaluated from the modeling of:
sorption on oxides or other surfaces
micro reactions (passivation or corrosion)
generation and diffusion of atomic hydrogen
diffusion and mass transport towards and away from a crack tip
Temperature and concentrations of chemical species can be included in the models.
Near a crack tip (magnetite wedge), the speed of unobstructed migration calculated for
water and HCI and NaOH solutions was from 0.8 to 1100 m/s. In ionized solutions,
anions, cations, and water migrated at different speed.
5. For the interactions with magnetite we have investigated, i.e., NaCI, HCI,
NaOH, H2S, and pure water, the corrosion cracking mechanism seems to be
hydrogen-related. Ionic compounds dissociate, anions react with the iron cation, and
H + or H ~ can easily migrate through magnetite and/or metallic iron.
6. On an oxidized iron or steel surface covered with a magnetite layer, anions,
cations, and polar molecules separate to different crystallographic surfaces, forming
adjacent islands of reactive species which can become microscopic corrosion cells.
This is especially pronounced on tetrahedral magnetite (which is often found on
carbon and low alloy steels exposed to aqueous environments) and at a crack tip.
7. The interaction energy of chemical species with iron oxides and the preferred
adsorption sites is strongly dependent on the crystallographic orientation of the oxide
surfaces and on ionization. For the ionized species, the interaction is about order of
magnitude stronger than for neutral molecules.
8. Foreign ions and molecules have a tendency to migrate to the oxidized crack tip.
All investigated chemical species exhibited forces which tend to close the crack tip or
pull ions of Fe + + out of the magnetite lattice. Maximum force was exerted by H20
molecules: -0.15 N/cm (per 1 centimeter of the crack front).
9. Inhibiting effects of nonreactive (SiO2) species and cations (Ca + +) can be
demonstrated with molecular modeling. These species prevent migration of hydrogen-
producing corrodents to the oxidized surfaces or cracks.
Acknowledgement
The author wishes to acknowledge the help of Ivo Jiricek, Pamela Seida, and Petra
Klimoszova in performing the modeling computations. A part of this work was
sponsored by the Electric Power Research Institute, project on Turbine Steam
Chemistry and Corrosion; EPRI project manager, Dr. Barry Dooley.
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Crack Initiation in Corrosion Fatigue ml
(PDVSA Los Teques) pursuant to License Agreement. No further reproductions authorize
J o h n D. A t k i n s o n I , Z h i - j u n Zhao 2 a n d J i a n Y u 3
INTERACTIVE EFFECT oF DYNAMIC STRAIN AGEING WITH HIGH TEMPERATURE

WATER ON THE CRACK INITIATION BEHAVIOUR OF REACTOR PRESSURE VESSEL
STEELS
REFERENCE: A t k i n s o n , J. D., Zhao, Z. J. a n d Yu, J., ~ I n t e r a c t i v e E f f e c t

of Dynamic Strain Ageing with High Temperature Water on the Crack
I n i t i a t i o n B e h a v i o u r o f R e a c t o r P r e s s u r e V e s s e l S t e e l s , " E f f e c t s of
the E n v i r o n m e n t on the I n i t i a t i o n of C r a c k Growth, A S T M STP 1298, W. A.
V a n D e r Sluys, R. S. Piascik, a n d R. Z a w i e r u c h a , Eds., A m e r i c a n S o c i e t y
for T e s t i n g a n d M a t e r i a l s , 1997.
A B S T R A C T : T h e e f f e c t of d y n a m i c s t r a i n a g e i n g (DSA) o n s t r e s s c o r r o s i o n
c r a c k i n g (SCC) of r e a c t o r p r e s s u r e v e s s e l ( R P V ) s t e e l s h a s b e e n
i n v e s t i g a t e d . T h e e x p e r i m e n t a l i n v e s t i g a t i o n w a s c o n d u c t e d o n an A 5 3 3 B
C l a s s 1 steel s u b j e c t e d to s l o w s t r a i n r a t e test (SSRT) at a n o m i n a l
9 -6 . .
s t r a l n rate of 2x10 /s in s t a g n a n t p r l m a r y w a t e r at 250~ Various DSA
r e s p o n s e s of the s t e e l w e r e a c h i e v e d b y a p p r o p r i a t e h e a t - t r e a t m e n t
processes. The evaluation was made under identical environmental
c o n d i t i o n s . T h e r e s u l t s d e m o n s t r a t e d that D S A e n h a n c e d the S C C w h i c h w a s
c o n s i s t e n t l y o b s e r v e d o n l y in the s t e e l that w a s h e a t - t r e a t e d to g i v e
the m o s t s i g n i f i c a n t D S A h a r d e n i n g effect. T h e S S R T a n d f r a c t o g r a p h i c
e v i d e n c e s u p p o r t s the p r e v i o u s o b s e r v a t i o n s b a s e d o n the d a t a analysis,
i.e. t h e r e w a s a c o i n c i d e n c e of t e m p e r a t u r e a n d s t r a i n r a t e b e t w e e n the
D S A h a r d e n i n g a n d the s u s c e p t i b i l i t y to e n v i r o n m e n t - a s s i s t e d c r a c k i n g
(EAC) of R P V steels. The m e c h a n i s t i c r o l e of D S A a n d its i n t e r a c t i o n
w i t h o t h e r i n f l u e n t i a l v a r i a b l e s in the e n h a n c e m e n t of S C C are
discussed.
K e y w o r d s : d y n a m i c s t r a i n ageing, e n v i r o n m e n t a s s i s t e d c r a c k i n g , s t r e s s
c o r r o s i o n cracking, s l o w s t r a i n r a t e test, r e a c t o r p r e s s u r e v e s s e l
steel, A533B, h i g h t e m p e r a t u r e w a t e r
It is w e l l e s t a b l i s h e d that a m a j o r d i f f i c u l t y in p r e v e n t i n g
f a i l u r e of e n g i n e e r i n g c o m p o n e n t s f r o m e n v i r o n m e n t - a s s i s t e d c r a c k i n g
(EAC) is due to the fact that the c r a c k i n g r e s u l t s f r o m the s y n e r g i s t i c
e f f e c t of m a t e r i a l , e n v i r o n m e n t a l a n d m e c h a n i c a l factors; the
i n t e r a c t i v e v a r i a b l e s i n v o l v e d are so n u m e r o u s t h a t a m u l t i d i s c i p l i n a r y
i P r o f e s s o r , S c h o o l of E n g i n e e r i n g , Sheffield Hallam University,

Sheffield, S1 IWB, UK.
2 PhD Student, S c h o o l of E n g i n e e r i n g , Sheffield Hallam University,

Sheffield, S1 IWB, UK.
3 P r o f e s s o r , S h a n g h a i R e s e a r c h I n s t i t u t e of M a t e r i a l s , S h a n g h a i ,
200437, China; c u r r e n t l y on l e a v e at S c h o o l of E n g i n e e r i n g , S h e f f i e l d
H a l l a m U n i v e r s i t y , Sheffield, S1 IWB, UK.
199
Copyright
Copyright by ASTM
9 1997 Int'l (all
by ASTM rights reserved); Friwww.astm.org
International Dec 30 21:53:51 EST 2011
p r o g r a m m e is n e e d e d to i d e n t i f y the r e l a t i v e r o l e s in the c a s e of
r e a c t o r p r e s s u r e v e s s e l ( R P V ) . D u e to the s t r i n g e n t s a f e t y r e q u i r e m e n t s
of n u c l e a r p o w e r plant, e x t e n s i v e s t u d i e s h a v e b e e n d e v o t e d in the last
t w e n t y y e a r s to u n d e r s t a n d i n g the f a c t o r s c o n t r o l l i n g the E A C of R P V
steels. Of all the v a r i a b l e s i n v e s t i g a t e d , it h a s b e e n e s t a b l i s h e d that
the s u l p h u r c o n t e n t a n d s u l p h i d e m o r p h o l o g y of s t e e l [ l - 9 ] , e n v i r o n m e n t a l
temperature[10-19], p o t e n t i a l or o x y g e n c o n c e n t r a t i o n [ l , 2 , 1 9 - 3 1 ] ,
p o t e n t i a l / p H I 1 9 , 2 3 , 2 5 , 2 7 ] , s t r e s s i n t e n s i t y l e v e l [15] , s t r a i n rate [19],
l o a d i n g f r e q u e n c y [ l l , 1 8 , 2 1 ] a n d l o a d ratio[28] are the m o s t s i g n i f i c a n t
f a c t o r s a f f e c t i n g the EAC.
It is n o t e d that in p a r a l l e l to the r e s e a r c h o n EAC, the e f f e c t of

d y n a m i c s t r a i n a g e i n g (DSA) on the loss of d u c t i l i t y of R P V steele has
a l s o b e e n of a g r e a t c o n c e r n in the a r e a s of f r a c t u r e [ 3 2 - 3 4 ] a n d
r a d i a t i o n d a m a g e [ 3 5 - 3 9 ] . T h i s is b e c a u s e R P V steels, s u c h as A 5 3 3 B or
A508, i n e v i t a b l y c o n t a i n i n t e r s t i t i a l c a r b o n a n d n i t r o g e n a t o m s and
s u f f e r r a t h e r s e n s i t i v e D S A h a r d e n i n g in c e r t a i n r a n g e s of t e m p e r a t u r e
a n d s t r a i n rate[41,42] . However, the D S A has o n l y b e e n s t u d i e d in air
envirorunents. The p o s s i b l e e f f e c t of D S A o n the E A C s u s c e p t i b i l i t y has
not y e t b e e n e x p e r i m e n t a l l y i n v e s t i g a t e d .
B a s e d o n the D S A d a t a of A 5 3 3 B s t e e l o b t a i n e d o v e r a w i d e range of
s t r a i n r a t e s f r o m 3x10 "~ to 3x10-3/s a n d t e m p e r a t u r e s f r o m 20 to 350~
A t k i n s o n a n d Y u reported[42] that the m o s t m a r k e d D S A a p p e a r e d at 250~
w h e n the steel w a s s u b j e c t e d to s t r a i n i n g at 3.3x10-8/s, as s h o w n in
Figure 1, w h e r e it is a l s o a p p a r e n t that there is a n e g a t i v e s e n s i t i v i t y
to s t r a i n r a t e s i m i l a r to the e f f e c t s r e p o r t e d b y R o s e n et al. [43] in
A I - C u - M g alloys.
680 -
660 -
:2
6~o
8(]0 2
580
560
54O ~- 3.3E-3/sec. I
• 3.3E-4/sec. I
3.3E-5/sec, [
520 3.3E-6/sec. I
o 3.3E-7/sec. I
500 ...... = . . . . . , . . . . . . . , , L . . . . , . . . . . , ,......
50 1(30 150 200 250 300 350 4(30
Temperature =C
Fig. 1 - - T h e e f f e c t of t e m p e r a t u r e a n d s t r a i n r a t e o n D S A
h a r d e n i n g of A 5 3 3 B C l a s s 1 steel[4_22].
ATKINSON ET AL. O N E F F E C T O F D Y N A M I C STRAIN 201
100" 650
90- 600
o
80"
550
70"
5O0 r
60-
<
50- ~o ~
o 40- -400
30
-350 i~
"300
0: 9250
0 50 100 150 200 250 300 350 400
Temperature ~
Fig. 2 - - D a t a s h o w i n g t h e c o i n c i d e n c e b e t w e e n D S A h a r d e n i n g (at s t r a i n
r a t e o f 3x10-6/s) a n d the s u s c e p t i b i l i t y to S C C (at s t r a i n r a t e o f
2 x 1 0 -6 s -I) o f A 5 3 3 B C l a s s 1 s t e e l [ 4 2 ] (the S C C d a t a a f t e r C o n g l e t o n e t
a1.[19]).
T "C
300 i~0 100 0
I0-2 ~ ONSET AT 0.01/$ J
"~ ~-3f
i I .,I IV (SW~l I
, I J~.AI results |
b ~ Prater (A.~3-.6)|
9 L. . . . Kor.~o ~ze}l
I CP~R~ ! ! |
~'~'| l" I r~s c~L~ ~/
,.5 '~ro ~:~ ' ~:o ~:~ ~r
Fig. 3 - - S u m m a r i s e d d a t a s h o w i n g t h e e f f e c t o f t e m p e r a t u r e o n d a / d N o f
R P V s t e e l s i n r e l a t i o n to the o n s e t o f D S A [ 4 2 ] (the d a / d N d a t a w a s
sununarised b y K a t a d a a n d N a g a t a [ 1 5 ] ) .
The same a u t h o r s a l s o a n a l y s e d the SCC r e s u l t s o b t a i n e d b y

C o n g l e t o n et al. f r o m the s a m e heat of s t e e l b y s l o w s t r a i n rate tests
(SSRT) at s i m i l a r s t r a i n rate of 2x10-6/s in P W R w a t e r w i t h o x y g e n
c o n c e n t r a t i o n b e l o w 600 p p b [19], a n d f o u n d that the m o s t s u s c e p t i b l e
SCC c o i n c i d e n t a l l y took p l a c e at 250~ as s h o w n in Fig.2. M o r e
i n t e r e s t i n g l y , as s h o w n in Fig.3142], the c o r r e l a t i o n b e t w e e n the
t e m p e r a t u r e d e p e n d e n c e of the s u s c e p t i b i l i t y of R P V s t e e l s to c o r r o s i o n
f a t i g u e c r a c k g r o w t h a n d D S A also a p p e a r s to exist.
In o r d e r to c o n f i r m the a b o v e a r g u m e n t b y e x p e r i m e n t a l evidence~
the p r e s e n t w o r k a i m e d to test the e f f e c t of D S A o n the c r a c k i n i t i a t i o n
of A 5 3 3 B C l a s s 1 s t e e l in h i g h t e m p e r a t u r e w a t e r at 250~ at s t r a i n rate
of 2x10 6/s. V a r i o u s D S A r e s p o n s e s of the same c h e m i c a l c o m p o s i t i o n of
steel w a s a c h i e v e d b y d i f f e r e n t h e a t - t r e a t m e n t p r o c e s s e s u s e d b y L i t t l e
a n d Hudson[41] .
EXPERIMENTAL METHOD
Material
The m a t e r i a l t e s t e d was an A 5 3 3 B C l a s s 1 steel, s u p p l i e d in the

f o r m of p l a t e of 150 nun thickness. The c h e m i c a l c o m p o s i t i o n of the steel
w a s analysed, as l i s t e d in T a b l e i.
T a b l e i: C h e m i c a l C o m p o s i t i o n of A 5 3 3 B C l a s s 1 R P V steel(wt%).
C Mn P S Si Mo Ni Cu V N Fe
T h e a v e r a g e c a r b o n c o n t e n t w a s a b o u t 0 . 0 4 % h i g h e r t h a n that of the
steel r e p o r t e d p r e v i o u s l y b y A t k i n s o n [ 4 2 ] a n d C o n g l e t o n et al. [19], but
still s a t i s f i e d the A S T M s t a n d a r d for the m a x i m u m c a r b o n c o n t e n t a l l o w e d
(0.25%) in A 5 3 3 B C l a s s 1 steel[44].
The free i n t e r s t i t i a l n i t r o g e n c o n t e n t of 5• p p m in as r e c e i v e d
steel was analysed, b y m e a n s of the m e t h o d b a s e d on the s y n t h e t i c
a m m o n i a f o r m a t i o n in h y d r o g e n a t m o s p h e r e at ~ 450~
Specimens
T w o k i n d s of c y l i n d r i c a l t e n s i l e s p e c i m e n s w e r e used. One was a

c o n v e n t i o n a l , p a r a l l e l - s i d e d type w i t h the g a u g e l e n g t h of 18 m m and the
d i a m e t e r of 3.6 nun, w h i c h w a s m a i n l y for e v a l u a t i n g the D S A r e s p o n s e in
air. The o t h e r w a s a t a p e r e d type w i t h the s e m i - a n g l e of the taper, ~ =
2 ~ , the g a u g e l e n g t h of 18 m m a n d the d i a m e t e r of 3.6 n~n at the s m a l l e s t
end. The t a p e r e d s p e c i m e n s w e r e t e s t e d in h i g h t e m p e r a t u r e water, as it
has b e e n s h o w n that t e n s i l e s p e c i m e n s w i t h s m a l l t a p e r e d a n g l e are
u s e f u l for d e t e c t i n g s t r e s s c o r r o s i o n c r a c k i n i t i a t i o n [ 4 5 ] .
The s p e c i m e n s w e r e m a c h i n e d f r o m the steel plate with the gauge

l e n g t h in p a r a l l e l to the r o l l i n g d i r e c t i o n .
Heat Treatments
In o r d e r to a c h i e v e v a r i o u s D S A r e s p o n s e s of the steel, the

specimens were heat-treated by different heat treatment processes based
on the w o r k b y L i t t l e a n d H u d s o n [ 4 1 ] . T h e m a j o r e f f e c t of the heat
t r e a t m e n t w a s b e l i e v e d to be o n the g r a i n s i z e a n d free i n t e r s t i t i a l of
the steel. T h e h e a t t r e a t m e n t was c a r r i e d o u t in an a r g o n - p r o t e c t e d
furnace after the machining of specimen. Table 2 shows the h e a t
t r e a t m e n t c o n d i t i o n s employed.
ATKINSON ET AL. ON EFFECT OF DYNAMIC STRAIN 203
T a b l e 2: H e a t T r e a t m e n t P r o c e s s e s .
(AC = air cooling; FC = f u r n a c e c o o l i n g ; W Q = w a t e r q u e n c h i n g . )
Condition Heat Treatment

A 25 min./85~-5~, A C + 45 min./650~ AC
B 25 min./1050~ FC + 15 m i n . / 8 5 0 ~ + 45 min./650~ AC
C 25 min./850~ A C + 45 min./650~ WQ
D As Received
C o n d i t i o n A r e p r e s e n t s the b a s i c a u s t e n i s e d (at 850~ and

t e m p e r e d (at 650~ state, g i v i n g the m i c r o s t r u c t u r e of b a i n i t e .
C o n d i t i o n B p r o d u c e d l a r g e r g r a i n size of p r i o r a u s t e n i t e b u t w i t h the
s a m e t r a n s f o r m a t i o n k i n e t i c s as f r o m 850~ in c o n d i t i o n A. A r e d u c e d D S A
e f f e c t was e x p e c t e d in c o a r s e r g r a i n e d s t e e l b e c a u s e D S A h a r d e n i n g is a
c o n s e q u e n c e of the r a p i d r i s e in total l o c k e d - i n d i s l o c a t i o n d e n s i t y a n d
f i n e r g r a i n e d steel d e v e l o p s a h i g h e r d i s l o c a t i o n d e n s i t y t h a n d o e s
c o a r s e g r a i n e d o n e [ 4 1 ] . C o n d i t i o n C w a s u s e d to g i v e an e n h a n c e d
i n t e r s t i t i a l c a r b o n c o n t e n t c o m p a r e d w i t h c o n d i t i o n A. C o n d i t i o n D
d e s i g n a t e s as r e c e i v e d state, of w h i c h the steel w a s h o t - r o l l e d a n d
supplied with stress relieved condition.
Environments
S i n c e the m o s t s i g n i f i c a n t D S A of A 5 3 3 B o c c u r s at 250~ w h e n
s u b j e c t e d to s l o w - s t r a i n i n g at 10-6/s (Fig.l), b o t h air t e s t s a n d S C C
tests w e r e c a r r i e d out at 250~ t h r o u g h o u t the p r e s e n t i n v e s t i g a t i o n .
T h e t e m p e r a t u r e of air tests w a s c o n t r o l l e d b y a h e a t i n g f u r n a c e o n the
t e n s i l e t e s t i n g m a c h i n e . The SCC tests w e r e p e r f o r m e d in a s t a t i c
a u t o c l a v e w i t h h e a t i n g e l e m e n t a n d c o n t r o l u n i t to k e e p the t e m p e r a t u r e
constant.
The S C C w a s t e s t e d in a s t a g n a n t p r i m a r y w a t e r c o n t a i n i n g 6000 p p m
h i g h p u r i t y b o r i c a c i d a n d 4 p p m A n a l a r g r a d e l i t h i u m h y d r o x i d e , pH7. As
it w a s d i f f i c u l t to control, or m o n i t o r , the o x y g e n c o n t e n t in a s t a t i c
autoclave, the s o l u t i o n w a s a d d e d w i t h 0.75 p p m h y d r o g e n p e r o x i d e to
a s s u r e the u n i f o r m i t y of o x y g e n level, to p r o v i d e m o r e c o n v i n c i n g b a s i s
in terms of the c o n s i s t e n c e of e n v i r o n m e n t a l c o n d i t i o n for e v a l u a t i n g
the e f f e c t of D S A on SCC. A l l o w i n g for the t h e r m a l e x p a n s i o n of the
water, the m a x i m u m v o l u m e of test s o l u t i o n a d d e d at r o o m t e m p e r a t u r e w a s
no m o r e t h a n 75% of the total v o l u m e of the a u t o c l a v e . A l l SCC tests
were carried out under open circuit conditions.
T e s t Procedllre
P r i o r to test c o m m e n c e m e n t , e a c h s p e c i m e n w a s p o l i s h e d d o w n to 3/0
f i n i s h w i t h e m e r y paper, then d e g r e a s e d . T h e d i a m e t e r of e a c h s p e c i m e n
w a s c a r e f u l l y m e a s u r e d . T e n s i l e t e s t s w e r e c o m m e n c e d w h e n the d e s i r e d
t e m p e r a t u r e w a s reached, a n d s t a b i l i s e d , for at l e a s t one hour. The
n o m i n a l s t r a i n r a t e a p p l i e d w a s 2x10-6/s. T h e S S R T t e s t s w e r e c o n d u c t e d
on Mayes testing machines.
I m m e d i a t e l y f o l l o w i n g the t e r m i n a t i o n of SSRT, the s p e c i m e n t e s t e d

was examined under both optical microscope and scanning electron
microscope (SEM)~ When the specimen suffered SCC, the true crack
i n i t i a t i o n stress, ~tl, w a s d e t e r m i n e d b y the m a x i m u m l o a d d i v i d e d b y the
cross section area where the minimum crack length was measured
m e t a l l o g r a p h i c a l l y . The a v e r a g e c r a c k v e l o c i t y w a s c a l c u l a t e d b y the
m a x i m u m c r a c k l e n g t h d i v i d e d b y the c r a c k p r o p a g a t i o n time, i.e. the
d i f f e r e n c e b e t w e e n the total f a i l u r e time, tf, a n d the c r a c k i n i t i a t i o n
time, t•
RERITLTS
Characterisation of DSA
The DSA responses of steel were characterised by tensile t e s t s at

250~ in air. Fig. 4 s h o w s t h e s t r e s s - s t r a i n c u r v e s o b t a i n e d f r o m the
parallel specimens under various heat treatment conditions.
1000
800
~- 600 H T-C
~E
400 HT-D
CO
200
0 . . . . . . . . . ' . . . . . . . . . . . . . .
0.0 5.0 10.0 15 0 20 0 25 0
Strain (%)
Fig. 4 - - S t r e s s - s t r a i n curves of A533B Class 1 steel under various heat

treatment conditions, f r o m p a r a l l e l cylindrical s p e c i m e n s , 250~
2 x 1 0 -6 s -I "
O b v i o u s l y , a l l the c u r v e s d i s p l a y t h e s e r r a t i o n b e y o n d y i e l d i n g ,
f e a t u r i n g the o c c u r r e n c e of D S A . C o m p a r e d w i t h t h e as r e c e i v e d
condition, all of the heat treatments used increased the strength of
s t e e l s i g n i f i c a n t l y . I t is n o t e d t h a t t h e e f f e c t o f h e a t t r e a t m e n t o n
the i n c r e a s e o f s t r e n g t h w a s m u c h m o r e s i g n i f i c a n t i n t h e p r e s e n t s t e e l
t h a n i n t h e s a m e c l a s s o f s t e e l s t e s t e d b y p r e v i o u s w o r k e r s [41,42]. It
is m o s t l i k e l y t h a t s u c h a s i g n i f i c a n t e f f e c t o f h e a t t r e a t m e n t w a s
a t t r i b u t e d to h i g h e r c a r b o n c o n t e n t o f the p r e s e n t s t e e l . N e v e r t h e l e s s ,
the e f f e c t o f h e a t t r e a t m e n t o n t h e D S A c a n b e c l a s s i f i e d i n the
following order.
C > A > B > D(As received) (I)
This order is i n a g r e e m e n t with that reported by Little and

Hudson[41], as expected by the experimental design. T a b l e 3 s h o w s the
q u a n t i t a t i v e d a t a m e a s u r e d f r o m the t e n s i l e c u r v e s . A s it w a s d i f f i c u l t
to d i s t i n g u i s h different DSA hardening s o l e l y b y the s e r r a t i o n , the
effect of heat treatment on DSA hardening was further evaluated by a
normalised parameter of ~/~t. CD>' w h e r e ~ u t . is t h e d i f f e r e n c e in
ultimate tensile (flow) stress between heat treated a n d as r e c e i v e d
s t e e l w h i l e O~t.(D] is the u l t i m a t e t e n s i l e (flow) s t r e s s o f as r e c e i v e d
steel.
Table 3: E f f e c t of heat treatments on tensile properties of A533B Class

1 s t e e l i n a i r at 250~ 2xi0-6 s
Heat Treatment ~u~s (MPa} ACuts/~u~A{D ~ (%) t~ (h)

A 793 22.8 26.5
B 759 17.5 27.6
C 818 26.6 31.6
D 646 0.0 27.8
T O c h a r a c t e r i s e the D S A h a r d e n i n g m o r e q u a n t i t a t i v e l y , the strain

h a r d e n i n g e x p o n e n t w a s c a l c u l a t e d u s i n g a c u r v e f i t t i n g m e t h o d i n the
uniform plastic deformation region by the following equation[46].
= k n (2)
w h e r e ~ is s t r e s s , k is s t r e n g t h c o e f f i c i e n t , 8 is p l a s t i c s t r a i n a n d n
is s t r a i n h a r d e n i n g e x p o n e n t . E q u a t i o n (2) h o l d s f o r b o t h t r u e a n d
engineering (nominal) s t r e s s - s t r a i n r e l a t i o n s h i p s . T r u e s t r a i n c a n b e
e x p r e s s e d b y e n g i n e e r i n g s t r a i n i n t h e form:
~t = in(~ + 1) (3)
where ~t is t r u e s t r a i n a n d E is e n g i n e e r i n g or nominal strain.
Table 4 shows the values of strain hardening exponent and strength

. . . . . . 2
coefflcxent, together wlth the values of correlatlon coefficient, R ,
f r o m t h e c o r r e s p o n d i n g c u r v e s . It is c l e a r t h a t t h e e f f e c t o f h e a t
treatment on strain hardening in terms of strain hardening exponent
h o l d s t h e s a m e o r d e r as t h a t o n outs o r ~uts/~uts(o).
T a b l e 4: A n a l y s e d d a t a c h a r a c t e r i s i n g t h e e f f e c t o f h e a t t r e a t m e n t o n
strain hardening exponent and strength coefficient ( s u b s c r i p t t is
d e s i g n a t e d to values from the true stress - strain curves).
Heat Treatment nt ~ (MPa) Rt 2 n k(MPa) R2
A 0.18 1308 0.9836 0.14 1088 0.9928

B 0.16 1238 0.9973 0.13 1042 0.9942
C 0.20 1427 0.9968 0.16 1185 0.9958
D 0.ii 915 0.9965 0.07 783 0.9909
A g a i n , b a s e d o n the d a t a i n T a b l e 4 a n d the s t r e s s - s t r a i n curves shown

i n Fig. 4, it is n o t d i f f i c u l t to i n f e r t h a t t h e s a m e o r d e r is o b e y e d i n
terms of the effect of heat treatment on strain hardening r a t e , d~/d~.
T h i s is s i m p l y b e c a u s e
dc/d~ = na/~ (4)
a n d f o r a g i v e n s t r a i n , d ~ / d ~ is d i r e c t l y p r o p o r t i o n a l to t h e p r o d u c t o f
n a n d ~. F o r e x a m p l e , it is o b v i o u s t h a t h e a t t r e a t m e n t C g a v e r i s e to
the h i g h e s t s t r a i n h a r d e n i n g r a t e as b o t h n a n d c o f t h e s t e e l h e a t -
treated under this condition were the highest in the uniform plastic
deformation region.
SCC
I n a n a t t e m p t to d e t e c t t h e c r a c k i n i t i a t i o n stress, a series of
SCC tests were conducted on the tapered tensile specimens. After
exposure to t h e w a t e r e n v i r o n m e n t , all the specimen surfaces exhibited
black oxide films but small pits were observed at inclusions. Of all t h e
SCC tests, only the specimens heat-treated by condition C, w h i c h g a v e
the highest DSA response, suffered SCC. T h e r e s u l t s w e r e c o n f i r m e d by
repeated tests, particularly, for the conditions of C and D. The
reproducibility was satisfactory. The true crack initiation s t r e s s , el,
measured f r o m t h e t a p e r e d s p e c i m e n s of c o n d i t i o n C w a s 896 a n d 899 M P a .
In o r d e r to o b t a i n t h e p l a s t i c s t r a i n f o r c r a c k i n i t i a t i o n , ~:~, a n d a l s o
to c o m p a r e the crack initiation s t r e s s w i t h Cut 8, a c o n v e r s i o n between
true crack initiation stress (~ti) a n d e n g i n e e r i n g stress or strain was
necessary. Strictly speaking, as t h e g a u g e length of tapered specimen
was not subjected to u n i f o r m d e f o r m a t i o n , such a conversion must invoke
the stress-strain relationship established from the parallel specimens.
Thus, u s i n g E q u a t i o n s (2) a n d (3) a n d t h e p a r a m e t e r s of C in T a b l e 4,
both the engineering crack initiation stress, ~i, a n d t h e e n g i n e e r i n g
plastic strain required for the crack initiation, ~i, o f t h e s p e c i m e n s
with condition C were converted from the true crack initiation stress,
ctt- T h e c I c a l c u l a t e d w a s 823 - 825 M P a , b e i n g v e r y c l o s e to the v a l u e
of Cut" m e a s u r e d in t h e a i r test. T h e r e f o r e , t h e t i m e to r e a c h the p e a k
load on tapered specimen, i.e. tut., w a s t a k e n as t h e c r a c k i n i t i a t i o n
time, t~. T h e a v e r a g e c r a c k v e l o c i t y , CV, w a s c a l c u l a t e d b y
CV = a~x /( tf - t~t.) (5)
where a m x is the maximum crack length and tf is the total failure time.
T a b l e 5 s h o w s the d e t a i l s of t h e S C C r e s u l t s . It c a n b e s e e n t h a t
although the crack initiation was late and required more than 10%
plastic strain, the crack propagation rate following the initiation was
high, r e a c h i n g m o r e t h a n 2 x l 0 - ~ m m / s .
Table 5: T h e SCC results from tapered specimens in primary water at

250~ nominal s t r a i n r a t e 2 x 1 0 -6 s- .
H.T. SCC tf tutB ct i ~i 8z amx C V (mm/s)

..................................(-h~.
... .......(h) ........(MPa) .......( M P a) .........j.% ) ..........(m~) .....................................
A NO 24.40 16.30 - - 0 0
B NO 23.75 16.00 - - - 0 0
C YES 23.35 17.70 896 823 10.3 0.491 2 . 3 x i 0 -s
C YES 25.30 18.90 899 825 10.4 0.504 2 . 2 x i 0 -5
D NO 22.10 13.55 - - 0 0
D NO 26.10 14.70 - - 0 0
A typical view of initiated cracks at the surface of tapered

specimen heat-treated b y c o n d i t i o n C is s h o w n i n Fig. 5. I t is
noticeable t h a t a s m a l l c r a c k i n i t i a t e d j u s t at t h e l o c a t i o n b e t w e e n the
specimen portions of necking and unnecking. The indication is t h a t t h e
~ , w h i c h w a s a l m o s t e q u a l to cut B, is a r e l i a b l e m e a s u r e m e n t . Fig. 6
s h o w s an i n i t i a t e d c r a c k a t h i g h e r m a g n i f i c a t i o n under SEM: As indicated
by the arrows, the pits which were either associated with the crack
i n i t i a t i o n o r at u n c r a c k e d s u r f a c e s a r e v i s i b l e .
After the SCC tests, the fractographic examinations revealed

typical transgranular SCC on the fracture surfaces of the specimens
heat-treated b y c o n d i t i o n C. F o r t h e s p e c i m e n s t h a t w e r e h e a t - t r e a t e d by
the other conditions (A, B a n d D) a n d d i d n o t s u f f e r SCC, o n l y d u c t i l e
d i m p l e s w e r e o b s e r v e d o n t h e f r a c t u r e s u r f a c e s . Fig. 7 s h o w s t h e a r e a
c r a c k e d by SCC on the fracture surface of the s p e c i m e n (condition C),

d i s p l a y i n g a f a n - s h a p e d crack propagation. The SEM e v i d e n c e of
t r a n s g r a n u l a r c r a c k i n g p a t h or quasi c l e a v a g e in the s p e c i m e n s s u f f e r e d
SCC is g i v e n in Fig. 8 at h i g h e r m a g n i f i c a t i o n .
Fig. 5 - - O p t i c a l p h o t o g r a p h s h o w i n g a typical v i e w of the crack

i n i t i a t i o n of A 5 3 3 B Class 1 steel, t a p e r e d tensile s p e c i m e n h e a t - t r e a t e d
by c o n d i t i o n C, in P r i m a r y w a t e r at 250~ s t r a i n rate of 2x10 -6 s -I.
Fig. 6--A c l o s e - u p v i e w of an i n i t i a t e d crack by SEM. N o t e the pits

i n d i c a t e d by the arrows.
Fig. 7 S E M f r a c t o g r a p h s h o w i n g the f r a c t u r e s u r f a c e of SCC, f r o m a

A533B Class 1 tapered specimen, heat-treated b y conditlion C, in P r i m a r y
w a t e r at 250~ s t r a i n r a t e of 2 x 1 0 s
Fig~ 8 SEM fractograph at h i g h e r m a g n i f i c a t i o n s h o w i n g the q u a s i

c l e a v a g e of t r a n s g r a n u l a r SCC; t h e s a m e t e s t i n g c o n d i t i o n as in Fig.7.
DISCUSSION
The Effect of D S A
T h e m a i n o b j e c t i v e o f t h i s w o r k w a s to i d e n t i f y t h e e f f e c t of D S A
o n the e n h a n c e m e n t of S C C i n R P V s t e e l . T h e k e y s to r e a c h t h i s t a r g e t
i n v o k e d t w o t e c h n i c a l r o u t e s : O n e w a s to o b t a i n d i f f e r e n t D S A r e s p o n s e s
o f the s t e e l , a n d t h e o t h e r w a s to s e l e c t a n a p p r o p r i a t e environment to
reveal the DSA effect.
R e g a r d i n g the first t e c h n i c a l route, d i f f e r e n t D S A r e s p o n s e s c o u l d

a l t e r n a t i v e l y b e a c h i e v e d b y a d d i n g v a r i o u s a m o u n t s of i n t e r s t i t i a l
atoms, e.g. C a n d N, into the steel. C o m p a r e d w i t h the a d d i t i o n of
a l l o y i n g e l e m e n t s , the a d v a n t a g e of the p r e s e n t m e t h o d u s i n g h e a t
t r e a t m e n t is: It a l l o w s the r e s u l t s to b e e v a l u a t e d b a s e d o n e x a c t l y the
same c h e m i c a l c o m p o s i t i o n of steel, and, also, is m o r e c o s t - e f f e c t i v e .
It m a y b e a r g u e d that h e a t t r e a t m e n t m i g h t h a r d e n the s t e e l b y some
m e c h a n i s m s o t h e r than DSA. It is true t h a t D S A is o n l y o n e o f the
s o l u t i o n h a r d e n i n g m e c h a n i s m s . It is a l s o true t h a t it c o u l d b e
m i s l e a d i n g if the e f f e c t of D S A w a s m e r e l y j u s t i f i e d b y the i n c r e m e n t of
cuta9 e s p e c i a l l y w h e n the tests w e r e c a r r i e d o u t o n l y at a s i n g l e
t e m p e r a t u r e a n d s t r a i n rate, b e c a u s e o t h e r p o s s i b l e s t r e n g t h e n i n g
m e c h a n i s m s m a y a f f e c t ~ut~ as well. H o w e v e r , the p a r a m e t e r s
characterising d y n a m i c s t r a i n h a r d e n i n g b e h a v i o u r h a v e b e e n a n a l y s e d in
the p r e s e n t work. In c o n j u n c t i o n w i t h the d a t a of ~ut. in T a b l e 3, the
r e s u l t s c h a r a c t e r i e a d f r o m s t r e s s - s t r a i n c u r v e s in T a b l e 4
i n d i s p u t a b l y s u p p o r t the fact that the p r i n c i p l e e f f e c t of h e a t
t r e a t m e n t o n h a r d e n i n g the steel w a s a t t r i b u t e d to DSA.
As far as the e n v i r o n m e n t is c o n c e r n e d , it w a s r e a l i s e d that it

w o u l d be d i f f i c u l t to i d e n t i f y the e f f e c t of D S A o n S C C if the
e n v i r o n m e n t a l c o n d i t i o n w a s too a g g r e s s i v e or v i c e v e r s a . If the
e n v i r o n m e n t w a s too a g g r e s s i v e , all s p e c i m e n s w o u l d h a v e c r a c k e d thus
m a s k i n g the e f f e c t of DSA. U n d e r the o p p o s i t e e x t r e m e of t e s t c o n d i t i o n ,
the e n v i r o n m e n t m i g h t b e too w e a k to c r a c k a n y s p e c i m e n . F o r t u n a t e l y ,
the e n v i r o n m e n t u s e d in the p r e s e n t w o r k a p p e a r s a p p r o p r i a t e . It w a s
b a s i c a l l y m a d e f r o m P W R p r i m a r y w a t e r c h e m i s t r y w i t h a d d i t i o n s of 0.75
p p m H202 a n d h e a t e d in the w a y of B W R c o n d i t i o n . A c c o r d i n g to A n z a i a n d
K u n i y a [ 4 7 ] , the a d d i t i o n of 0.75 p p m H202 i n t o P W R w a t e r w o u l d r e s u l t in
at l e a s t 375 p p h of e f f e c t i v e o x y g e n c o n c e n t r a t i o n in the w a t e r b e c a u s e :
[O2]off = [02] + I/2[H202] (6)
As the o x y g e n c o n t e n t in the s t a g n a n t a u t o c l a v e w a s n o t m o n i t o r e d
and the w a t e r w a s n o t h e a t e d u n d e r p r e s s u r i s e d c o n d i t i o n in the p r e s e n t
e x p e r i m e n t , the o x y g e n c o n t e n t w a s n o t m e a s u r e d . B a s e d o n the p r e v i o u s
r e s u l t s [ 1 9 ] , it a p p e a r e d that the a c t u a l o x y g e n c o n t e n t in the w a t e r w a s
w e l l b e l o w 375 ppb. O n the o t h e r hand, H202 has an e f f e c t o n
d e c o n t a m i n a t i o n of s u l p h i d e in the s o l u t i o n [ 4 8 ] , w h i c h m i g h t m o r e or
less r e d u c e the s u s c e p t i b i l i t y of the s t e e l to SCC.
N e v e r t h e l e s s , the p r e s e n t e v a l u a t i o n of the e f f e c t of D S A is v a l i d
as all the SCC t e s t s w e r e p e r f o r m e d in an i d e n t i c a l e n v i r o n m e n t .
The S t r a i n R a t e of T a p e r e d S p e c i m e n
T a p e r e d s p e c i m e n s are u s e f u l in d e t e c t i n g the c r a c k i n i t i a t i o n of
EAC. T h e m a j o r c o n c e r n in u s i n g this type of s p e c i m e n h a s b e e n of the
d e g r e e of v a r i a t i o n of s t r a i n rate a l o n g the g a u g e length. In o t h e r
words, the q u e s t i o n is w h e t h e r the s t r a i n r a t e in the c r a c k e d p o r t i o n of
g a u g e l e n g t h is r e p r e s e n t a t i v e of the d e s i r e d s t r a i n r a t e for the
c o n v e n t i o n a l , p a r a l l e l specimen. A m e a s u r e m e n t of the s t r a i n r a t e a l o n g
the g a u g e l e n g t h of t a p e r e d s p e c i m e n s w i t h e=3 ~ s h o w e d that the m a x i m u m
v a r i a t i o n of s t r a i n r a t e w a s w i t h i n the f a c t o r of 1.6149]. In the
p r e s e n t case, this k i n d of v a r i a t i o n w a s e x p e c t e d to be e v e n s m a l l e r as
the ~ a d o p t e d w a s o n l y 2 ~ . F o r a g i v e n c r o s s - h e a d speed, the m a x i m u m
d i f f e r e n c e in s t r a i n r a t e b e t w e e n t a p e r e d a n d p a r a l l e l s p e c i m e n s c a n b e
a s s e s s e d b y the r a t i o of f a i l u r e time, w h i c h is:
r t = tf(T.W)/t~(P.A) (7)
w h e r e r t is the f a i l u r e time ratio, t~(T.W) is the f a i l u r e time of the

t a p e r e d s p e c i m e n (G=2 ~ e x p o s e d to the w a t e r a n d tf(P.A) is the f a i l u r e
time of the p a r a l l e l s p e c i m e n in air. B a s e d o n the d a t a in T a b l e s 3 and
5, the v a l u e of r t for v a r i o u s h e a t t r e a t m e n t c o n d i t i o n s are c a l c u l a t e d
and s h o w n in T a b l e 6.
T a b l e 6: T h e r a t i o (rt) of the f a i l u r e time of the t a p e r e d s p e c i m e n

(e=2 ~ e x p o s e d to the water, tf(T.W), to the f a i l u r e time of the
p a r a l l e l s p e c i m e n in air, t~(P.A), for a g i v e n a p p l i e d c r o s s - h e a d s p e e d
at 250~
Heat Treatment r t = tf(T.W)/tf(P.A)

A 0.92
B 0.86
C* 0.77
D* 0.87
*: C a l c u l a t e d b y the m e a n v a l u e of r e p e a t e d tests.
The i m p l i c a t i o n of T a b l e 6 c o n s i s t s of two i n t e r e s t i n g points:

Firstly, for the n o n - S C C c o n d i t i o n s of A, B and D, the f a i l u r e time of
the t a p e r e d s p e c i m e n w a s m o r e t h a n 85% of the f a i l u r e time of the
p a r a l l e l specimen. This i m p l i e s that the m a x i m u m s t r a i n rate of the
f o r m e r s p e c i m e n is less t h a n 1.16 times that of the l a t t e r specimen. In
o t h e r words, the m a x i m u m s t r a i n r a t e at the s m a l l e s t e n d of the t a p e r e d
s p e c i m e n w i t h 0=2 ~ w a s no m o r e than 2.32x10-~/s w h e n the t a p e r e d s p e c i m e n
w a s s u b j e c t e d to the s t r a i n rate of 2x10-6/s at the s a m e c r o s s - h e a d
speed. S u c h a d i f f e r e n c e in s t r a i n rate is n o r m a l l y i n s i g n i f i c a n t for
SSRT. It s h o u l d a l s o be r e m e m b e r e d that the s t r a i n r a t e at a t a p e r e d
g a u g e l e n g t h d e c r e a s e s as the c r o s s s e c t i o n a r e a i n c r e a s e s . T h i s m e a n s
that in t a p e r e d specimens, the s t r a i n rate at the s i t e s w h e r e the c r a c k
i n i t i a t i o n w a s o b s e r v e d c o u l d be m u c h c l o s e r to the s t r a i n r a t e of the
p a r a l l e l s p e c i m e n t h a n the f r a c t u r e surface.
Secondly, c o m p a r e d w i t h the v a l u e s of u n c r a c k e d c o n d i t i o n s , the r t

u n d e r c o n d i t i o n C is c o n s i d e r a b l y lower b e c a u s e of the o c c u r r e n c e of
SCC.
The M e c h a n i s t i c R o l e of D S A
T h i s s t u d y has c o n f i r m e d that D S A has a l a r g e i n f l u e n c e of

m e c h a n i c a l p r o p e r t i e s of A 5 3 3 B C l a s s 1 steel a n d i n d i c a t e s a p o s s i b l e
role in the i n i t i a t i o n of SCC. A l l four h e a t t r e a t m e n t v a r i a n t s (A, B,
C, D) i n d i c a t e d s i g n s of p i t t i n g a l o n g the g a u g e l e n g t h b u t o n l y C type
s p e c i m e n s s h o w e d SCC w h i c h n u c l e a t e d at the i n c l u s i o n c e n t r e d pits (Fig.
6). T h e r e are two p o s s i b l e i n f l u e n c e s of D S A on the SCC p r o c e s s e s .
1. T h r o u g h a s t r e s s r e l a t e d i n i t i a t i o n p r o c e s s f r o m a pit. The role of

s t r e s s c o u l d s i m p l y be one of s t r e s s i n t e n s i t y f a c t o r K e l e v a t i o n
due to the i n c r e a s e d f l o w stress. T h i s c o u l d f a c i l i t a t e the c r a c k
i n i t i a t i o n at s t r e s s c o n c e n t r a t o r s like pits, in the D S A regime.
2. T h r o u g h an i n f l u e n c e of the d a m a g e p r o c e s s in DSA, w h i c h a p p e a r s to
c o n s i s t of i n c r e a s e d d i s l o c a t i o n density[50] a n d r e d u c e d ductility.
For c o n d i t i o n s i n v o l v i n g h y d r o g e n e m b r i t t l e m e n t (HE) w h i c h m i g h t be
the c a s e for s u l p h u r s p e c i e s p r e s e n t w i t h i n an a c i d i f i e d pit in
A 5 3 3 B C l a s s 1 steels, there is the p o s s i b i l i t y that the two
d e g r a d a t i o n p r o c e s s e s , i.e. D S A a n d HE m a y i n t e r a c t to p r o d u c e the
t r a n s g r a n u l a r facets. H i g h c r a c k i n i t i a t i o n s t r e s s / s t r a i n , fast
c r a c k v e l o c i t y a n d a small n u m b e r of i n i t i a t e d c r a c k s are o f t e n the
s y m p t o m s of HE. T h e s e s y m p t o m s can be f o u n d f r o m the p r e s e n t
r e s u l t s , as s h o w n b y the d a t a in T a b l e 5 a n d the f r a c t o g r a p h in
Fig. 5 r e s p e c t i v e l y .
D u r i n g S C C t e s t i n g w i t h g r e a t e r e n v i r o n m e n t a l s e v e r i t y t h a n the
p r e s e n t work, C o n g l e t o n et al. o b s e r v e d s e v e r e S C C in c o n d i t i o n D (Fig.
2), so it a p p e a r s that D S A is a s e c o n d a r y f a c t o r c o m p a r e d w i t h s t e e l
s u l p h u r c o n t e n t a n d e n v i r o n m e n t severity, b u t it d o e s h a v e the r o l e in
e n h a n c i n g the S C C s u s c e p t i b i l i t y zone. S i n c e m o s t R P V s t e e l s c o n t a i n
free n i t r o g e n a n d e x h i b i t D S A e f f e c t s , the c o n t r o l of C a n d N is
d e s i r a b l e to m i n i m i s e the o c c u r r e n c e of SCC. It m i g h t b e m o r e
i n t e r e s t i n g to s t u d y the e f f e c t of D S A on e n v i r o n m e n t - a s s i s t e d c r a c k
p r o p a g a t i o n in the n e a r future. T h i s is for the r e a s o n that c r a c k
b r a n c h i n g has b e e n f r e q u e n t l y o b s e r v e d d u r i n g t e s t i n g the E A C of R P V
s t e e l s in the r a n g e of t e m p e r a t u r e f r o m 200 to 250~ u s i n g p r e c r a c k e d
specimens, i m p l y i n g a p o s s i b i l i t y that D S A m i g h t h a v e a s t r o n g e r
i n f l u e n c e o n the c r a c k tip w i t h h i g h s t r e s s / s t r a i n c o n c e n t r a t i o n ,
e n h a n c i n g the c r a c k p r o p a g a t i o n a l o n g p r e f e r e n t i a l l y d e f o r m e d
d i r e c t i o n s , thus c r e a t i n g m i c r o - b r a n c h e s . S u c h d e f o r m a t i o n b r a n c h i n g m a y
be s t r o n g l y a s s i s t e d b y the n e g a t i v e s t r a i n r a t e s e n s i t i v i t y o b s e r v e d in
the r e g i o n of 200-250~
CONCLUSION
V a r i o u s D S A r e s p o n s e s of an A 5 3 3 B C l a s s 1 s t e e l w i t h 0 . 2 3 % c a r b o n
c o n t e n t a n d a b o u t 5 p p m free n i t r o g e n w e r e o b t a i n e d b y a p p r o p r i a t e h e a t
t r e a t m e n t p r o c e s s e s . The D S A h a r d e n i n g b e h a v i o u r at 250~ w e r e
q u a n t i t a t i v e l y c h a r a c t s r i s e d b y b o t h the i n c r e m e n t of u l t i m a t e t e n s i l e
s t r e s s a n d s t r a i n h a r d e n i n g e x p o n e n t . T h e r e s u l t s of S C C t e s t s at s l o w
s t r a i n r a t e of 2x10-6/s c o n f i r m e d t h a t D S A has the e f f e c t of p r o d u c i n g a
n e g a t i v e s e n s i t i v i t y to s t r a i n r a t e a n d on e n h a n c i n g the s u s c e p t i b i l i t y
of the s t e e l to SCC: U n d e r i d e n t i c a l e n v i r o n m e n t a l c o n d i t i o n , i.e.
p r i m a r y w a t e r w i t h 0.75 p p m H202 in s t a t i c a u t o c l a v e at 250~ the c r a c k
i n i t i a t i o n w a s o n l y o b s e r v e d in the c o n d i t i o n that e x h i b i t e d the o p t i m u m
D S A r e s p o n s e . It w a s a s s e s s e d that the c r a c k i n i t i a t e d at u l t i m a t e
t e n s i l e s t r e s s a n d a b o u t 10.3% p l a s t i c strain; the a v e r a g e c r a c k
v e l o c i t y r e a c h e d 2x10 -5 mm/s. It is b e l i e v e d that the r o l e of D S A in the
e n h a n c e m e n t of SCC w a s t h r o u g h the i n c r e a s e of s t r e s s i n t e n s i t y f a c t o r
at p i t s a n d the i n t e r a c t i o n of r e d u c e d d u c t i l i t y w i t h the h y d r o g e n
r e l e a s e d b y s u l p h i d e d i s s o l u t i o n . T h e p r e s e n t w o r k s u g g e s t s that the
e f f e c t of D S A on the SCC of R P V s t e e l is s i g n i f i c a n t a n d s h o u l d be
a s s e s s e d in a w i d e r r a n g e of A 5 3 3 B a n d A 5 0 8 steels.
ACKNOWLEDGEMENT
T h e a u t h o r s w i s h to t h a n k M s A n i t a C l a r k for h e r a s s i s t a n c e o n the
s c a n n i n g e l e c t r o n m i c r o s c o p y . T h e y are g r a t e f u l to M r C. Hague, M r K.
Wright, M r B. P a l m e r and M r D. L a t i m e r for the i n s t a l m e n t of a u t o c l a v e s
a n d h e a t i n g f a c i l i t i e s . T h e t i m e l y h e l p f r o m M r D. W i l k i n s o n a n d M r D.
w o o d h e a d , as w e l l as f r o m the U n i v e r s i t y of N e w c a s t l e u p o n Tyne, s h o u l d
a l s o be a c k n o w l e d g e d for the p r e p a r a t i o n of s p e c i m e n s .
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[45] Yu, J., Xue, L. J., Zhao, Z. J., Chi, G. X. and Parkins, R. N.,
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Crack V e l o c i t i e s U s i n g Slowly S t r a i n e d T a p e r e d Specimens, F a t i q u e
and F r a c t u r e of E n q i n e e r i n g M a t e r i a l s and Structures, Vol. 12, No.
6, 1989, pp 481-493.
[46] Dieter, G. E., ~Mechanical M e t a l l u r g y " , International Edition,

1986, M c G r a w - H i l l , Inc., p 287.
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Makoto Higuchi 1, Kunihiro Iida2, and Yasuhide Asada3
EFFECTS OF STRAIN RATE CHANGE ON FATIGUE LIFE OF CARBON

STEEL IN H I G H - T E M P E R A T U R E WATER
R E F E R E N C E : Higuchi, M., Iida, K., and Asada, Y., "Effects of Strain Rate
Change on Fatigue Life of Carbon Steel in High-Temperature Water", Effects
of the Environment on the Initiation of Crack Growth, ASTM STP 1298, W. A. Van Der
Sluys, R. S. Piascik, and R. Zawierucha, eds., American Society for Testing and
Materials, 1997
ABSTRACT: In high temperature waters that contain dissolved oxygen (DO) to certain
content, the fatigue life of carbon steel is strongly affected by strain rate. A formula has
been advanced to quantify this effect when the strain rate is held constant. However, the
strain rate changes continuously in most of transients of actual plant operation. There is no
way currently to assess the effects of strain rate when the strain rate is varied as in the
actual plant transients. To find a solution to this problem, a series of strain controlled
fatigue tests have been conducted with the strain rate changed stepwise or continuously. It
is shown that a method, in which the product of the environmental effect and the strain
increment within a unit time interval in a transient period is integrated from the minimum
strain to the maximum, evaluates the environmental effect with satisfactorily high accuracy.
This method is called the modified rate approach method. It is shown also that the
procedure of taking the strain rate as averaged over the minimum to peak of the strain
change as giving rise to more conservative evaluations than the ones the modified rate
approach method produces.
KEYWORDS: fatigue life, strain vs. life (S-N) curve, environmental fatigue, light water
reactor environment, strain rate dependency factor, carbon steel, nuclear power plant,
fatigue degradation
INTRODUCTION
The fatigue life of carbon steel and low alloy steel in high temperature water that
contains dissolved oxygen (DO) above a certain content is known to be strongly affected by
strain rate, temperature, DO content, and possibly several other factors. Much has been
made known on this phenomenon, and many a fatigue life prediction formula to quantify
the effects of these factors has been proposed to the date [1,2,3]. Nevertheless, current
1 Manager, Production Engineering dept., Ishikawajima-Harima Heavy Industrie Co.,

Ltd., 1 Shin-nakahara, Isogo-ku, Yokohama, 235 Japan
2 Doctor, Professor Emeritus of the University of Tokyo, Japan Power Engineering and
Inspection Corporation, 1-5-11 Akasaka, Minato-ku, Tokyo, 107 Japan
3 Doctor, Professor, Department of Mechanical Engineering, University of Tokyo, 7-3-1

Hongo, Bunkyo-ku, Tokyo, 113 Japan
216
Copyright*
Copyright by ASTM1997
Int'l by
(allASTM International
Fri Dec 30 21:53:51 EST 2011
HIGUCHI ET AL. ON EFFECTS OF STRAIN RATE CHANGE 217
status is that, since these formulas have all been advanced on the basis of test data obtained
within the constant test conditions of strain rate, temperature, and DO content individually,
they are not fit to evaluating the damage incurred under changing strain rate. This means
that, for example, the damage evaluation conducted based on the partial slow strain rate in
the transient period will allow the cumulative damage to become excessively high, thereby
destroying the whole idea of plant designing.
On the other hand, however, it has not been determined whether designing on the
average strain rate is conservative or not. To obtain a better understanding for this
problem, a series of fatigue tests on carbon steel have been conducted in oxygen containing
high temperature water with the strain rate changed in several different ways, and have
been able to develop a method to evaluate the effect of changing strain rate in quantitative
terms. As a part of this work has been reported previously to ASME/JSME Joint PVP
Conference of 1995 [4], the present report constitutes its sequel.
In addition, information pertaining to initiation of fatigue crackes and their subsequent
propagation have been examined by means of the beachmark imprinting technique. On the
basis of the observation, it is concluded that the marked degradation of fatigue life in high
temperature, DO containing water is due to shortened crack initiation lifetime or to
acceleration of the crack growth rate, or both.
TESTING METHOD
M~tterials Tested
The main material was the JIS G3455 STS410 carbon steel pipe (equivalent to ASME
SA333 Gr. 6), which came in two different heats: one with a relatively high sulfur content
(Hi-S), and the other a regular low sulfur variety (Lo-S). The chemical compositions and
mechanical properties of them are presented in Table 1. This table lists two other carbon
steel pipes for reference: one is a JIS G3455 STS42 steel that was used in the previous
work by authors[l], and the fourth is an American made ASME SA106 Gr. B steel, which
is the same heat as the one used by Chopra, et al. in their study at ANL [3].
Table 1 Chemical compositions and mechanical properties of tested steels

Chemical Compositions (mass %) Mechanical Properties
Steel Sce. C Si Mn P S Cr Ni Mo
YS UTS Elong. RA
(MPa) (aPa) (%) (%)
STS410(HS) 1) 0.21 0.31 1.14 0.016 0.012 383 549 35
STPT480(LS) 1) 0.24 0.29 0.91 0.010 0.007 333 559 34
SFVQ2A(HS) 1) 0.21 0.25 0.68 0.010 0.011 0.36 0.84 0.65 469 629 28 68
STS42(HS) 2) 0.20 0.31 0.93 0.020 0.015 302 489 41 80
STS410(LS) 3) 0.15 0.20 1.25 0.019 0.006 314 490 41
A106-B(HS) 4) 0.29 0.25 0.88 0.013 0.015 0.19 0.09 0.05 301 572 23.5 44
1) Present study 2) Higuchi and lida (Ref. 1)
3) Higuchi and lida (to be published in 8th ICPVT) 4) Chopra et al. (Ref. 5)
(STS410 and STS42 eq. to A333-6, STPT480 eq. to A106-C, SFVQ2A eq. to A508-2)
Tgst Piece
The test piece was a solid, smooth, and round bar specimen in the form shown in Fig.
1. All the specimens were machined off the pipes as received, at their central wall
thickness, and with the specimen axis laid parallel to the pipe's axis.
FBti~ue Test
"l~he fatigue test was conducted in the fully reversible, axial strain controlled mode in an
autoclave with a pressurized high temperature water recirculated through it. Figure 2
presents the testing setup schematically. The testing temperature was held constant at 288
~ and the DO content was either 8 or 0.8 ppm. The tests included various straining
waveforms, including a triangular waveform, sawtooth waveform, stepwise varying
waveform of either convex or concave disposition, and a sinusoidal waveform.
In addition to these, experiments to produce beachmarks at appropriate intervals were
conducted for the study of the behavior of cracking. This was done by alternating the main
fatigue cycles of low strain rate (0.004 %/s) and the beachmark imprinting cycles of high
strain rate (0.4 %/s), each for an appropriate duration. From the observation of
beachmarks on the fracture surface, the determination of the cycles for crack initiation and
the growth rate of subsequent crack propagation was done with ease.
Monitor
,., ....
~ ~. ,,, i $pec met
L ,I ILI ILl,
o': o ~ ~
l-7 i
I :~ i',
::,,
-~] 5 I " "1( 76 "1" " 1>51"
Pump
Fig. 1 Specimen Fig. 2 0 u d i n e of environmental fatigue test machine
T E S T R E S U L T S AND D I S C U S S I O N S
In total, fatigue tests were conducted on 44 test pieces of Hi-S STS410, five of Lo-S
STS410, and 14 of ANL's A106-B steel. The results obtained are summarized in Table 2
for Hi-S 410, in Table 3 for Lo-S 410, and in Table 4 for A106-B.
Effect of b4aterial ~rld Strain Amolitude on the Environment Fati~e Life

It has been shown in the previous work [1] that the fatigue life in the environment of
high temperature water is inversely related to the strain rate, so that, for a given strain
amplitude, a good linearity holds true between the fatigue life and the strain rate on log-log
scale. This is represented by:
N25 W = A(~T)P (I)

where
the fatigue life in the water environment,
N25 w =
A = a constant calculated by the least squares best fitting as the cut on ordinate
(it is approximately equal to N25A, the fatigue life determined at the same strain
amplitude in the room temperature air environment),
~r = the strain rate on the straining (i.e., strain increasing) leg of the strain cycle,
P = exponent.
Here, the P term, which should be defined as the strain rate dependency index,
represents the effect of environment on the fatigue life quite well. This is seen in Fig. 3,
and better still, in Fig. 4, which present the four fitted lines of these four steels together
with their tensile strengths, S contents, and P values. The variation in P values is
particularly well depicted in Fig. 4, where these four lines have been replotted with the
fatigue life ratio (N25w/N25A) in the ordinate, because, thus plotted, all lines are made to
converge on a single point, which is ~T = 1%/s.
Table 2 Fatigue test results in high temperature water for carbon steel
(STS410(HS), 288"C, R=-I; wave shape:triangle; saw tooth; stepx~ise changed)
Test DO Strain Amp. (%) Strain Rate (%/s) N25 "1 *2 *3 *4 *5
No. ~a r ~2 ~T1 ~'T2 ~73 ~c tT Fent Fenc Fenav N25P
ppm cycles (s)3 cycles
I-1 8 0.6 0.4 0.4 1875 1.47 1.49 - 1792
I-9 0.6 0.4 0.4 1826 3 1.51 1.49 1792
I-2 0.6 0,004 0.4 258 300 10.68 11.04 136
I-8 0.6 0.004 0.4 242 300 11,38 11.04 - 136
I-11 0.6 0.5 0.4 0.004 0.4 1056 27,8 2.61 2.29 3.92 515
I-7 0.6 0.4 0.4 0.004 0.4 754 52.5 3.65 3.08 5.17 361
1-10 0.6 0.4 0.4 0.004 0.4 795 52,5 3.47 3.08 5.17 361
I-3 0.6 0.2 0.4 0.004 0.4 686 102 4.02 4.67 6.91 249
I-6 0,6 0 0.4 0.004 0.4 496 152 5.55 6.27 8.20 199
1-13 0.6 -0.1 0.4 0.004 0.4 438 176 6.29 7.06 8.76 183
I-4 0.6 -0.2 0.4 0.004 0.4 328 201 8.40 7.86 9.28 170
1-12 0.6 -0.3 0.4 0.004 0.4 386 226 7.14 8.66 9.76 159
1-14 0.6 -0.3 0.4 0.004 0.4 326 226 8,45 8.66 9,76 159
I-5 0.6 -0.4 0.4 0.004 0.4 305 251 9.03 9.45 10.21 150
1-19 0.6 -0.491 0.4 0.004 0.4 286 273 9.63 10.18 10.60 143
1-15 0.6 0.527 0.4 0.004 0.4 0.4 1426 21 1.93 2.07 3.47 603
1-16 0.6 -0.2 -0.127 0.4 0.004 0.4 1284 21 2.15 2.07 3.47 603
1-17 0.6 -0.2 0.4 0.04 0.4 942 21 2.93 3.20 3.47 603
1-18 0.6 0.491 0.4 0.004 0.4 1085 30 2.54 2.36 4.06 494
1-20 0,6 0.04 0.4 624 30 4.42 4.06 - 494
1-21 0,6 -0.491 0.004 0.4 0.4 1146 30 2.40 2.36 4.06 494
1-27 8 0.4 0.4 0.4 4570 2 1.78 1.63 - 4646
1-28 0.4 0.04 0.4 1654 20 4.92 5.58 - 1280
1-34 0.4 0.004 0,4 393 200 20,71 19.08 - 352
1-32 0.4 0.327 0.4 0.004 0.4 1208 20 6.74 3.22 5.58 1280
1-25 0.4 -0.327 0.004 0.4 0.4 1839 20 4.43 3.22 5.58 1280
1-29 0.3 0.4 0.4 10627 1.5 1.69 1.76 - 9622
1-30 0.3 0.04 0.4 2334 15 7.71 7.29 - 2650
1-31 0.3 0.004 0.4 618 150 29.11 30.17 730
1-33 0.3 0.245 0.4 0.004 0.4 2684 15 6.70 4.36 7,29 2650
1-26 0.3 -0.245 0.004 0.4 0.4 2746 15 6.55 4.36 7.29 2650
141 0.25 0,4 0,4 46830 1.25 1.87 1.87 - 15793
1-35 0.25 0.004 0.4 2032 125 43.03 42.95 1198
1-40 0.6 0.4 0.4 648 300 5.03 1.49 136
1-42 0.6 0.004 0.4 236 300 11.67 11.04 136
1-37 0.8 0.4 0.4 0.4 4450 2 1.66 1.66 4646
1-36 0.4 0.004 0.4 344 200 21.53 21.54 352
1-39 0.4 0.327 0.4 0.004 0,4 1460 20 5.07 3.49 5.99 1280
1-38 0.4 -0.327 0.004 0.4 0.4 2265 20 3.27 3.49 5.99 1280
"1 : tT= T, A a n/~ Tn *2: Fent=A / N25
*3: Font = T, ( ~ Tn)'Px A ~ n / A ~ , P=0.435 DO 8 8 8 8 0.8
*4: Fen=v=(A E: / tT)"P, P=0.435 9 0.6 0.4 0.3 0.25 0.4
*5: N25p=(ASME Best Fit N) x ( ~ =v)P, A 2755 8134 17990 87426 7405
( ~ = v ) P=A ~ / tT, P=0.56 P 0.44 0.534 0,617 0.681 0.556
| | |174
| | |
§ +0. 6 +0. 6
E 0 ~ 0
t
~ C ~ 72
-0. 6 -0.6 -0.6
Table 3 Fatigue test results in high-temperature water for carbon steel

(STS410(LS), 288~ DO=8ppm; R=-I, wave shape:triangle & saw tooth)
Test ~a Strain Rate Stress at N -[kl25 "1 *2 *3 *4
T1 ~; C N O"max. G rain. tx Fern Fenav N25p
No. (%) %/S %/s cycles MPa MPa cycles (s) c~/cles
LC-1 0.6 0.4 0.4 1800 361 -366 3480 3 1.61 1.64 1792
LC-2 0.6 0.004 0.4 130 419 -432 258 300 21.78 20.04 136
LC-3 0.6 0.001 04 70 460 -472 140 1200 40.14 42.56 62
LC-4 0.3 0.4 0.4 6500 292 -312 12840 1.5 1,5t 1.51 9622
LC-5 0.3 0.004 0.4 850 445 -450 1632 150 11,86 11.86 730
"1 : tr = ~ A & n/& rn *2:Fent=A/N25
"3: Fenav=(A (E~T)-P &a 0.6 0.4
*4: N25p=(ASMEBestFitN)X(&av) P, A 5620 19355
( E av)P=~ & ' / t T , P=0.56 P 0.543 0.448
Table 4 Fatigue test results in high temperature water for carbon steel
(AI06-B, 288*(2, R=-I, wave shape:triangle, saw tooth, stepwise changed)
Test DO Strain Amp. Strain Rate (%/s) N25 "1 *2 *3 *4 *5
No. ~a ~r ~T1 ~T2 ~c tT Fent Fenc Fenav N25P
pp.rn (%) (%1 cycles (s) cycles
(IHI)
11 8 0.6 0.4 0.4 1185 3 1.53 1.51 1792
10 0.6 0.004 0.4 148 300 12.24 1206 136
7 0.6 - 0,04 0.4 433 30 4.18 4.27 494
6 0.6 0.527 0.4 0.004 0.4 378 30 6.74 3.22 4.27 494
9 0.6 -0.527 0.004 0.4 0.4 524 30 4.43 3.22 4.27 494
1 0.8 0.4 0.4 0.4 1765 2 1.39 1.36 4646
2 0.4 0,004 0.4 342 200 7.16 6.38 352
5 0.4 0.00792 0.4 553 101 4.43 5.07 516
3 0.4 0 0.4 0.004 0.4 418 101 5.86 3.87 516
4 0,4 0 0.004 0.4 0.4 682 101 3.59 3.87 516
12 8 0.3 -0.245 0.004 0.4 0.4 5320 15 1.85 2.51 4.32 2650
13 0,3 0245 0.4 0.004 0.4 2975 15 3.3 2.51 4.32 2650
14 0.3 0.004 0.4 797 150 12.33 12.33 730
15 0.3 0.4 0.4 6480 1.5 1.52 1.52 9621
(ANL)
J7-27 0.8 0.370 0.4 0.4 2077 1.8 1.41 1.41 5716
J7-62 0.6 0.373 0.004 0.4 363 187.3 8.02 8.02 417
J7-35 0.8 0.381 0 0.4 0.004 0.4 545 96.2 4.71 4.71 6.19 582
J7-52 0.7 0.381 0 0.004 0.4 0.4 1935 96.2 4.71 4.71 6.19 582
J7-62 0.8 0.396 0.004 - 0.004 338 198 8.02 8.02 361
J7-22 0.8 0.400 0.0004 - 0.4 153 2000 19.16 19.1 97
J7-42 0.7 0.390 0.195 0.4 0.004 0.4 615 50.2 3.06 3.06 4.81 801
J7-15 0.7 0.380 0.190 0.4 0.004 0.4 553 48.9 3.06 3.06 4.81 855
J7-73 0.6 0.367 -0.184 0.004 0.4 0.4 2080 47.1 3.06 3.06 4.8 933
.m
"1: tT=Z A ~n/~Tn
*2:Fent=A/N25 Lab, IHI IHI IHI ANL
*3: Fenc=~,, (~Tn) "PX /~ ~n/A G DO 8 0.8 8 0.6-0.8
*4: Fenav=(A 6/tT) "P ~= 0.6 0.4 0.3 0.4
*5: N25p=(ASME Best Fit N) x (~ av)P, A 2755 8134 17990 7405
( &"=v)P=A ~ttT, P=0.56 P 0.435 0.534 0.617 0.556
t/)
10 4 ........ i ........ i ........ i ...... 'i'll
(D
O N 2 5 w = ~
o.I
10 3
Z
"J 10 2
(%) Water(ppm) A i r (MPa) (%)
-I
$TS410(HS) 0 . 6 0 8 O 549 0.0120.435
STS410(LS) 0.6 ~ 8 t 4890 0.0160.543
LL 8TS42 (HS} 0.6 8 0.015 0.660
A-106B(HS) 0.375 [ ] , 0.8 [ ] 572 0.0150.375
101 ........ I . . . . . . . . . . . . . . . . i 9 9 i = .... i
10 .4 10 -3 10 -2 10 -1 10 ~
Strain Rate E T (%/S) (Air)
Fig. 3 Relation between strain rate and fatigue life
101 ......... . ........ . ....... , . . .. .....
E a 288~ DO UTS S P
Z
(%) Water(ppm)(MPa) (%)
STS410(HS) 0 . 6 0 8 549 0.012 0.435
i;Ss~22iLS!) 0:6 ~ ~ 49~0000016 0:543 ~-~"~
10 0
Z
O
a~
n-
0-1
_J
. ~ oo - ~"
._~ .~'" N25w/N25A=( ~ T)P
u- 10 2 . . . . . . . . I 9 i iiI1~.1 . . . . . . . . I . . . . . . .
1 0 "4 10 .3 102 10 1 10 ~
Strain Rate E T (~176
Fig. 4 Relation between strain rate and fatigue life ratio
It was found that, relatively speaking, the hi-S, high-strength heat of STS410 exhibits a
short fatigue life in air environment coupled with a small P value, the hi-S, low-strength
STS42, a long fatigue life and a large P value, the lo-S, low-strength heat of STS410, the
longest fatigue life and a low P value (this evidently on account of its low S content), and
the highest-strength A106-B shows the shortest fatigue life and a small P value. From
these observations, the effects of such factors are summarized as follows:
9 The higher the strength, the lower becomes the P value;
9 With the strength held to the same level, the higher the S content, the higher the P; and
9 The effect by the strength is stronger than by the S content.
The authors have not tried to quantify these relations further because of insufficient data.
Figure 5 presents the fatigue data obtained for 288 "C and 8 ppm DO with the strain rate
changed variously, as plotted in terms of the strain amplitude vs fatigue life. Reference to
the data from the ambient air, room temperature fatigue test will show that the S-N curve
for high temperature water environment is shifted toward the shorter life with decreasing
strain rate. This effect of strain rate on N25W is shown in Fig. 6 with the strain amplitude
222 EFFECTSOF THE ENVIRONMENTON INITIATIONOF CRACKGROWTH
as a parameter. The relationship is again linear in a log-log scale and the P value is seen to
increase with decreasing strain amplitude.
10-1 . . . . . . . . i . . . . . . . . i ........ i ........ i ........
Mat.:STS410(HS) Envi. '~ T ~ C
t.tj 2S8~Water (%/s) (%Is)

DO=8ppm O Water
Water
0.4
0.04
0.4
0.4
[] Water 0.004 0.4
9 RT Air 0.4 0.4
~_10.2
<E F'IA ~
t- [] A O9
[] O9
ff)
1 0 -3 ........ L ........ i ........ i ........ i . . . . . . .
101 10 2 10 3 10 4 105 106

Fatigue Life N25w (cycles)
Fig. 5 Relation between fatigue life and strain amplitude
105 . . . . .
E a DO . .
P. i
,E a 9 DO9 9 # .... i . . . . . . . .
(%)(ppm) (%) (ppm)

tO
0 0.6 8 0.435 ~ 0.26 8 0.681
-/~ 0.4 8 0.534 9 0.4 0.8 0.556 J /
[ ] 0.3 8 0.617
tO
Od
z
._1
"I 103104~ ~ . . . 288~ Water

.t.-,
II
102 .........................
10.3 10.2 10-1 10~
Strain Rate E T (%/s)
Fig. 6 Relation between strain rate and fatigue life
Figure 7 shows the P values of the four carbon steels as a function of the testing
conditions given in terms of strain amplitude, temperature, and DO content. It is observed
here that the hi-S version of the STS410 exhibits a tendency of having its P value
monotonically decrease with increasing strain amplitude, but other steels exhibit various
trends. For example, the P value of STS42 (Hi-S) at 288 ~ as well as that of A106-B, is
higher for a strain amplitude of 0.6 % than for 0.3 %, whereas the behavior of P value of
STS42 (Hi-S) is more complex: when the strain amplitude is less than 0.4 %, it behaves
like that of STS42 (Hi-S), but when it is over 0.4 %, the trend is reversed, Thus, even
though it is quite certain that the strain amplitude does exert some influence on the P value,
its effect can not be evaluated quantitatively.
Thus, it is shown that, even while it has been demonstrated that the S content,
mechanical properties and strain amplitude do exert some influence on the P value,
individually or in combination, neither their effects can be too great, nor quantification of
them is possible at this time. Therefore, it is concluded that the average of the thirteen P
values given in Fig. 7 for the Japanese made steels as P = 0.56 can be taken as the P value
for the environments of high temperature, high DO content water (e.g., 288 *C and from
0.8 to 8 ppm DO), for the time being.
1.0
IX.
>,0.8
O
r Q~
Average O~1~..~...................................
"~ 0 . 6
..... 0.56 ................ :" : . : ' ~ ' ~ L " . . . . . . . . . -'-::-~" ......
Q. (Except A106B) __" " . ~
a 0.4
Temp. DO ""'"-~, ................ Temp. DO
(~C) (ppm) (~) (ppm)
O STS410(HS) 288 8 ~ STS42 (HS) 288 8
~t'-" 0.2 O STS410(HS) 288 0.8 ~ A106-B(HS) 288 8
/~ STS410(LS) 288 8 9 A106-B(HS) 288 0.8
co 0 . 0 [ ~ STS42 (HS)1288 8 , I J I
0.0 0.2 0.4 0.6

Strain Amplitude E a (%)
Fig. 7 Relation between strain amplitude and P value
Existence of Strain Domains Devoid of the Environment Effect

Because it is quite possible that the environment effect would fail to manifest itself under
compressive stress, fatigue tests have been conducted in search of such environment-
insensitive domain or domains by varying the manner of straining but holding the strain
amplitude at 0.6 % constant. Namely, the loading was done in two steps so as to give rise
to a fast/slow convex straining, holding the strain rate high at 0.4 %/s in the first step of the
straining, or the rise period, and holding it low at 0.004 %/s in the second step, with the
duration of each step being controlled so as to give rise to the same total strain amplitude
(A~) as designated. Here, the variation was given in terms of the proportion the first step
strain amplitude (A~I) occupied in Delta epsilon.
15 ~ . . . .
,, O.O04~/s
10 (~)o
"~ ' ' ~ -0 6 .... 3
" "~ ~ i~' O~N25A / N2sw

5
.- 9 uu=eppm max.. ,
0 ~" , I , J , i , t , ~,1
0.0 0.2 0.4 0.6 0.8 1.0
/ k ~ I / A E
Fig. 8 Relation between ,5~1/A~ and Fentest
The results are shown in Fig. 8, where the term Fentest, which is called the environment
effect coefficient (to be discussed again later on), is defined as:
Fentest = N25A/N25w or = A/N25w (2)
Now, should a domain of environment-insensitivity exists, it would be either under

compressive stress as mentioned earlier on, or at least, for stresses lower than the yield
strength. It follows then that such a domain, if exists, not only should be found near the
lowest strain range, which is indicated in Fig. 8 by a broken line, but in that domain, the
Fentest value should become constant.
However, no such tendency is found in the figure: the Fentest value changes linearly
from the minimum strain to the maximum, indicating that the environment effect is uniform
all through the strain range tested. Therefore, it is concluded that the presence or absence
of an environment-insensitive domain need not be taken into consideration. This is
different from the conclusion determined by Chopra and Shack [5].
Effects of Strain Rate as Varied Stepwise

If the strain rates that have changed in certain way can be represented by a single
effective strain rate, such an "average" strain rate, the analysis and evaluation will be much
simpler. This proposition has been tested by a series of stepwise changing strain rate
fatigue tests conducted with three different waveforms (i.e., fast/slow-convex; slow/fast-
concave, and constant strain rate sawtooth), keeping the same rise time (i.e., the time spent
in the increasing strain part of a cycle).
Then, from the examination of the data as classified by the magnitude level of strain
amplitude, a term Fenca 1, called the environment effect coefficient (more specifically, the
coefficient to calibrate the fatigue life for the environment effect) is obtained. It is defined,
in accordance with what has been described earlier as:
Fenca 1 = E{ ( eTn) -p x Ae n / A E } (3)
where P's are those which have been determined for each of the strain amplitude level, and
are listed as a footnote in each table.
15 2a8~ water ' ,~. 60 ' ' /
/
(%) (ppm) /
9 STS410(HS)0.6 8 /
L.~ STS410(HS)0.4 8
9 STS410(HS) 0.4 0.8
10 [ ] STS410(HS)0.3 8 A ~
~ A106"B(HS)0"3750 ~ ~)~J
| ZX~
U..
~ F~n,~,=N~./ N~w
encal=2( E Tn)-PxA ~n/A
-
0 i I m I m
0 5 10 15
Fencal
Fig. 9 Relation between Fencal and Fentest
It will be seen that, although Fenca1 agrees quite well with Fentest for a strain amplitude
of 0.6 %, Fentest tends to become larger than Fenca1 at smaller amplitudes, and that while
the Fentest in the fast/slow-convex straining agrees well with that in the slow/fast-concave
straining for strain amplitudes of 0.6 and 0.3 %, Fentest in the fast/slow-convex is larger
than that in the slow/fast-concave for an amplitude of 0.4 %.
Figure 9 summarizes these observations in terms of the relation between Fencal and
Fentest. It is noted here that even while Fentest tends to become larger than Fencal for
small strain amplitudes, the overall relationship may be regarded as a linear
correspondence. Therefor, it is concluded that the two coefficients agree each other
satisfactorily well.
Figure 10 shows the effect of rise time on fatigue life ratio. When the strain rate is
constant, the fatigue life ratio can be correlated to the rise time on the log-log scale so that
the three trend lines are drawn for each of the three strain amplitudes tested, and that the
data from the stepwise changing strain rate tests are found to be above these straight lines.
This means that constant strain rate gives the shortest fatigue life if the rise time is the same.
< 101
i'M !O '~ a"--0~6~/0'V'a'riableRate " , A ' ~ "a-0.4% C'onstant Rate'
z
1,O ~ a=0.6% Constant Rate [ ] ~ a=0.3% Variable Rate
'~ ~Ea=0.4% Variable Rate 9 E a=0.3% Constant Rate
od 100
Z
O
n- 0 o
~ lO 1
.-I
288 Water . . . . . .
p.... -
DO=8ppm
, ,
le 10 2
10 ~ 101 10 2 10 3
Rise T i m e t T (s)
Fig. 10 Relation between rise time and fatigue life ratio
Effect of Unstrainin~ Strain Rate
The effects of the strain rate in the unstraining (i.e., decreasing strain) part of the loading
cycle were investigated by seven sets of fatigue data obtained in tests conducted with the
strain amplitude kept the same at 0.6 % but differing in the strain waveform: fast/fast
triangular, slow/fast positive sawtooth, fast/slow negative sawtooth, and slow/slow
triangular. The fatigue life obtained by the slow/slow test was about the same as that the
slow/fast test produced, so that essentially no effect was seen for the unstraining strain rate.
However, the life obtained in the fast/slow test was markedly shorter than that of the
fast/fast test. These observations show that the effect of strain rate of the unstraining part of
the loading cycle manifests itself only when the strain rate in the unstraining part is slow
enough, when the effect of the latter overwhelms that of the former. In fact, the P value for
the unstraining strain rate was about one half of that for the straining strain rate.
Effects of Frequency in the Sinusoidal Waveform Test

The effects of frequency in the sinusoidal waveform fatigue test conducted with the
strain amplitude held constant are summarized in Fig. 11. The fatigue life can be related to
the frequency linearly on the log-log scale through a formula inscribed in the figure. The P
value that represents the frequency effects is much smaller than those that represent the
effects o f the constant strain rate in the cases of triangular or positive sawtooth waveform
tests conducted with other conditions held the same.
The effects of the rise time are shown in Fig. 12 together with the results of the constant
strain rate test. It is to be seen that the longer the rise time, the shorter the fatigue live, and
that, except for the cases o f very short rise times, the constant strain rate gives rise to
shorter fatigue lives.
10 4 . . . . . . . . i . . . . . . . . i . . . . . . . . i . . . . . .
m Mat. : STS410(HS)
0
2889C Water
DO=8ppm 2 a=0.6%
Sine Wave
Z
10 a
J
~ ~ 2 5 w = 2 5 9 4 f 0.223
U-
10 2
10 .4 1 0 .3 10 2 10 1 10 ~
F r e q u e n c y f (Hz)
Fig. 11 Relation between frequency and fatigue life
10 4 . . . . . . . . ! . . . . . . . . i . . . . . . . .
O Sine Wave Mat.:STS410(HS)

A Constant Rate 288% Water
a=0.6% DO=8ppm
" "--L~.... ....... N25W~2221tT0'223

Z 103
...I
........ O--
N25W=2983tT'0"435~
I.L
10 2 . . . . . . . . i . . . . . . . . i . . . . . . . .
10 0 101 10 2 10 3
Rise Time t T (s)
Fig. 12 Relation between rise time and fatigue life
The Case of A106-B Steel

The results o f tests conducted in Japan for American made A106-B steel agreed quite
nicely with those obtained by A N L except for one case. The exception was the 4/4 cycle
slow test of A N L vs. its Japanese counterpart, where the results were that, where test J7-
52 on ANL's material gave a fatigue life of 1,935 cycles for a strain amplitude of 0.381%,
compared to a life of 682 cycles in the authors' test for an amplitude of 0.4 % (Table 4,
No. 4). Similar result was seen in authors' test No. 9 (a life o f 524 cycles for a strain
amplitude of 0.6 %). Most probably, these observations should be taken as indicating that
the low strain rate straining in raising the strain from the minimum strain, which means a
compressive stress field, exerts a strong effect on the fatigue life.
The metallography revealed that the A106-B had by and large the same sort of
microstructure as ordinary Japanese carbon steels. Its environmental behavior, too, was
much the same as those of Japanese carbon steels, though A106's P value was slightly
smaller. All in all, it is concluded that no essential difference can be found between
American A106-B steel and Japanese counterparts.
Effect of Environment on the Crack Initiation and Crack Prooa~ation Lifetimes

As stated earlier on, the use of the beachmark imprinting technique turned out to be quite
effective to study the cracking habit. Table 5 presents the results obtained in terms of the
crack initiation lifetime and crack propagation behavior together with the loading history.
An example of fractography conducted on the fracture surface after completion of test is
illustrated in Fig. 13, while Figs. 14 and 15 present the crack depths and lengths, as
determined by the beachmark imprinting method, as arranged in relation to the usage factor,
i.e., the rate of fatigue damage accumulation, which was computed by the Miner's law.
As shown in Fig. 14, which collects the high temperature, high DO tests, that when the
environmental effect is intense, the beachmark makes its appearance in the very first step
regardless of the strain amplitude. Extrapolation of the trend line for the crack depth (or
length) vs. usage factor relationship to zero crack depth suggests that the crack was initiated
very early in the cyclic loading. As N25 tends to be reached before the usage factor
becomes unity, moreover, the introduction of beachmarks is suspected to accelerate the
environment effect.
Table 5 Fatigue test conditions and results for beach mark tests
(STS410 H-S, 288~ R=-I, wave shape: triangle)
Strain Strain Num, Num. Num. Cycles N2s by Cure.
Test DO Step Amp. Rate of of of at Const. Damage
No. sa ~ Cyc./ Steps Beach N25 Cndtn. at N2s
/ppm) (%) (%/s) 1 Step Marks (cycles) (cycles)
1 1 Main 0.6 0.004 25 8 8 104 242 0.430
B.M. 0.3 0.4 25 100 10627 0.009
5 Main 0.6 0.004 10 16 16 118 242 0.488
BM. 0.3 0.4 25 275 10627 0.026
6 Main 0.6 0,004 10 5 5 242
B.M. 0.3 0.4 25 10627
2 Main 0.3 0.004 60 7 6 370 618 0.599
B.M. 0.3 0.4 60 360 10627 0.034
7 Main 0.3 0.004 20 10 9 618
B.M. 0.3 0.4 60 10627
8 0.2 Main 0.6 0,004 30 7 5 186 470 0,396
B.M. 0.3 0.4 30 180 13699 * 0.013
9 Main 0.3 0.004 60 32 16 1530 1303 1,174
BM. 0.3 0.4 60 1500 13699 * 0.109
3 0.005 Main 0.6 0.004 100 9 8 702 1208 0.581
B.M. 0.3 0.4 100 700 18430 * 0.038
4 Main 0.3 0,004 200 14 4 2830 3028 0,935
B.M. 0.3 0.4 100 1400 18430 * 0,076
B.M.: B e a c h M a r k *: E s t i m a t e d V a l u e
Fig. 13 A sample of beach marks on fractured surface

5 i i i i
E" SIS410 Depth Length

E -O- ~ ~ a=0.6%
4 in 288% Water
DO=lppm, ~ =0"004%/s--A
A . . . . A__ ~(.a=0.3%
3 N25 ,'~ ,~-~(:~J~
O
0.0 0.2 0.4 0.6 0.8 1.0
Cumulative Fatigue Damage Ratio
Fig. 14 Relation between crack depth, length and cumulative fatigue damage
5 [STS410 ' ' 'N '

v Lin 288~ water i% A
EL'4 /DO=0.00Sppm, ~ =0.004%/s l/O ,;
~-Depth Length II t4(" ,'
/--O-- " 0 - - ~ a=0.6%m~" ~ ,"
0
0.0 0.2 0.4 0.6 0.8 1.0
Cumulative Fatigue Damage Ratio
Fig. 15 Relation between crack depth, length and cumulative fatigue damage
In Fig. 15, which represents the low DO tests, on the other hand, it is noted that, if the
environment effect is not very intense, the crack initiation is affected by strain amplitude, so
much so that, where the beachmark was observed from the first step for an amplitude of
0.6 %, it was delayed to late in the fatigue life (in fact, as late as 80 % of total life) when
the amplitude was 0.3 %, though the initial velocity of crack propagation was clearly
slower than in the high DO environment even for a strain amplitude of 0.6 %.
Therefore, it is concluded that in the high temperature, high DO water environments,
both the initiation and the propagation of crack are accelerated, so that the initiation lifetime
is shortened to virtually zero.
FATIGUE LIFE EVALUATION METHOD FOR STRAIN RATE CHANGE

As stated earlier in 3.3, Fencai generally agrees well with Fentest. On the strength of
this observation, the modified rate approach method is proposed as a method to evaluate the
environmental effect through the transient period encountered in actual operations. As may
be recalled, in the modified rate approach method, the parameter Fenca i is computed out by
eq. (3) through integration of the product of the environmental effect (determined for a
strain rate averaged over the unit time interval) and the strain increment from the minimum
strain to the maximum strain. Mathematically, eq. (3) can be generalized as:
I~max
Fen = S { (ST) "P / (emax-emin) }dE (4)
~min
A remaining problem is that, when the strain amplitude is comparatively small, the
prediction that FencaI makes often tends to be not conservative enough. In trying to amend
this fault, authors have noted a fact that when P value is less than unity, Fen takes on a
maximum when the strain rate remains constant all the way through from the minimum
strain to the maximum. As the P values obtained empirically are always smaller than unity,
this observation would mean that adoption of an average strain rate should ensure the
evaluation to be on the conservative side. Such a parameter, called Fenav, is given as:
Fenav - (AE/tT) -P (5)
The Fenav'S that have been computed on the data acquired in the stepwise changing
strain rate tests are presented in Tables 1, 2, and 5. As may be seen in these tables, the
value of Fenav is calculated to be larger than Fencal, thereby alleviating the non-
conservatism of Fentest. On the other hand, this method, though certainly simpler, may
give rise to excessively conservative evaluations. For example, among the Fenav'S listed in
Table 3 as obtained from the results of sinusoidal waveform tests, the ones for lower
speeds are clearly overly conservative.
SUMMARY AND CONCLUSIONS

Formulation of the effects of changing strain rate on the environment effect has been
attempted by conducting environmental fatigue tests for carbon steels in the environment of
high temperature water containing dissolved oxygen (DO). Evaluating such effects by
means of the strain rate dependency index called the parameter P, following conclusions are
obtained:
(1) The parameter P is affected by the sulfur content, mechanical properties as represented
by the strength, and strain amplitude, though no quantification was possible because of
insufficient data. For this reason, P = 0.56, which is an average of data taken of the
four Japanese made sample steels (i.e., excepting the American made A106-B steel),
was adopted. This convention appears to work quite well.
(2) When the strain amplitude is 0.6 % or more, no environment-insensitive domain can be
found anywhere, not even near the minimum strain which should be in the compressive
stress field, the effect of environment on the fatigue life being uniform all the way
through from the minimum strain to the maximum.
(3) On the strength of satisfactory agreement obtained between the theoretical values
(Fencal) and the experimental determinations (Fentest), the modified rate approach
method, which computes Fen, the environment effect coefficient (more specifically, the
coefficient to correct the fatigue life for the effect of environment) by integrating the
product of the environment effect determined assuming a constant strain rate during a
unit time interval and the strain increment gained in that time from the minimum strain
to the maximum, has been proposed for evaluating the environment effect in the
transient periods which are often encountered in the actual operations.
(4) The environmental fatigue life obtained by holding the strain rate constant in the strain
increasing part of a loading cycle tends to become the shortest among tests for the same
rise time. Also, the Fenca 1 takes on a maximum when the strain rate is held constant,
provided P remains to be smaller than unity.
(5) The strain rate in the unstraining, or strain decreasing, part of cycle does not affect the
environmental fatigue life unless it becomes smaller than that of the increasing straining
part of cycle. When it is smaller than the latter, it tends to shorten the environmental
fatigue life, but the P value is only about one half of that for the increasing straining
part.
(6) The results of tests conducted for an American made A106-B steel in Japan agreed quite
well with the results of ANL, all except one case. As far as can be judged from the
acquired data, both mechanical and metallographical, no essential difference was seen
between this steel and its Japanese counterparts, because the data were much the same
as those obtained from Japanese made carbon steels, including even the ones where
discrepancies were noted.
(7) The beachmark imprinting method of study of the cracking behavior conducted
particularly to study crack initiation and propagation has revealed that environment of
high temperature and high DO content water accelerates both the initiation and the
propagation of crack, so much so that the initiation lifetime can be shortened to virtually
zero.
ACKNOWLEDGMENT
The research project described in this paper has been conducted sponsored by the Joint
Research Fund which had been established by the ten utilities and the three plant fabricators
in Japan. The test results have been examined by the EFD Committee of the Thermal and
Nuclear Power Engineering Society. The authors wish to sincerely thank our fellow
committee members for their valuable discussions and comments.
REFERENCES
[1] M. Higuchi and K. Iida, Nuclear Engineering and Design, 129 (1991), 239-306.
[2] M. Higuchi and K. Iida, "Effects of Isothermal Aging on Low Cycle Fatigue Properties
of SA533B-1 Steel in High Temperature Water Environment," Manuscript, Post
SMiRT Conference, Construction Code and Associated Engineering Mechanics,
August, 1993.
[3] O. K. Chopra, W. F. Michaud, and W. J. Shack, "Fatigue of Carbon and Low Alloy
Steels in LWR Environments," Proc., 21st Water Reactor Safety Information Meeting,
October 25-27, 1993.
[4] M. Higuchi, K. Iida, and Y. Asada, ASME, PVP-Vol. 306, p. 111, 1995
[5] O. K. Chopra and W. J. Shack, ASME, PVP-Vol. 306, p. 95, 1995
Genroku Nakao ~, Makoto Higuchi 2, Hiroshi Kanasaki 3, Kunihiro Iida 4, Yasuhide Asada 5
EFFECTS OF TEMPERATURE AND DISSOLVED OXYGEN CONTENTS ON FATIGUE LIVES

OF CARBON AND LOW ALLOY STEELS IN L W R WATER ENVIRONMENTS
REFERENCE: Nakao, G., Higuchi. M., Kanasaki, H., lida, K. and Asada. Y., "Effects of
Temperature and Dissolved Oxygen Contents on Fatigue Lives of Carbon and Lo~ Alloy Steels in
LWR Water Environments," Effects of the environments on the Initiation of Crack Growth" ASTM
STP 1298 W.A. VanDer Sluys. R.S Piascik, and R. Zawierucha, Eds.. American Society for Testing and
Materials, 1997.
ABSTRACT : In order to modify tile fatigue design method for pressure vessel components of light ~ater
reaclors(LWRs), strain controlled fatigue tests were carried out under various environmental conditions,
and the effects of temperature and dissolved oxygen (DO) contents on fatigue lives of carbon steel in
LWR-simulated water environments were evaluated and analyzed.
The results of the present study are summarized as follows;
1) The decrease in fatigue life of carbon steel STS410 in BWR-simulated water environments occurs at
temperatures above 2t)0'(: and with DO higher than 0. Ippm The rate of decrease is greater at higher
temperatures and higher DO concentrations.
2) To offset differences in test condition such as temperature, DO, strain amplitude etc., an new index, Rp,
which represents a ratio of the environmental index P-values previously proposed, was introduced. Also
a new fatigue life equation based on Rp was proposed.
3) By the new equation, the fatigue life of carbon steel under a certain environmental condition of
temperature and DO can be predicted better than by the previously proposed method.
KEYWORDS: corrosion fatigue, fatigue life, environmental effect, temperature, dissolved oxygen content,
carbon steel, low alloy steel, light water reactor component, environmental factor
Nomenclature
~: strain amplitude(ratio or %) T: strain rate(~
Senior Research Engineer, Kure Research Laboratory, Babcock-Hitachi K.K., 3-36 Takara-machi,
Kure-shi, Hiroshima, 737 Japan.
Manager, Material Processing & Evaluation Group, Product Engineering Center, Ishikawajima-
Harima Heavy Industries Ltd, 1, Shin-Nakahara-cho, Isogo-ku, Yokohama 235 Japan.
3 Senior Research Engineer, Takasago R&D Center, Mitsubishi Heavy. Industries Ltd, 2-1-1
Shinhama, Arai-cho, Takasago-shi, Hyogo 676 Japan.
4 Advisor, Doctor, Japan Power Engineering and Inspection Corporation, Shin-Tranomon BLDG,
1-5-11, Akasaka, Minato-ku, Tokyo 107 Japan.
Professor, Department of Mechanical Engineer, Universit).- of To~'o, 7-3-1, Hongo, Bunkyo-ku,

Tokyo 113 Japan.
232
Copyright by ASTM Int'l (all rights

Copyright9 reserved); Friwww.astm.org
International Dec 30 21:53:51 EST 2011
NAKAO ET AL. ON LWR WATER ENVIRONMENTS 233
Nzsw: fatigue life in an environment(number) N25A: fatigue life in air(number of 25% load drop)
DO: dissolved oxygen content(ppm) T: water temperature(~
S: sulfur content(%) Ps: Pc value under 290~ DO=8ppm
P,Pc: environmental parameter based on the strain rate dependence of fatigue life
Rp: environmental parameter ratio(Rp=P/Ps)
a,b and c: factors and constants refer to material's strength.
LWR:lighi water Reactor MITI:ministry of international trade and indust~'
At present, in Japan, fatigue design of LWR components has been perfunned according to the official
announcement No.501 of M1TI, which was prepared with reference to ASME Section m. The fatigue
design curves in ASME Code Section m had been based on the regression analysis of fatigue life test data
in air and established with a certain safety factor. Although the safety factor, in terms of one-half of the
strain amplitude and one-twentieth of the numbers to failure, is reflecting scattering in data, effects of test
specimen size and surface roughness etc., other effects such as water environments are not considered.
Since corrosion fatigue had been recognized as an important phenomenon, extensive corrosion
fatigue studies have been done at many research centers to access the reliability of LWRs' primary
components in high temperature pure water, as well as to consider life extension of existing plants. By such
efforts, influences such as environmental conditions (temperature, DO etc,), material conditions (material
quality, sulfur content, non-metallic inclusions etc.) and stress conditions (strain amplitude, strain rate,
stress ratio etc.) were identified[I][2][3]. Among such studies, the most detailed research on the effect of
environments on the fatigue life of carbon steel pipe in high temperature pure water for nuclear power plant,
especially with respect to the influence of temperature and DO, were those done by Higuchi et a1.[4][5].
From their experimental data, a P-value, which is a function of temperature and DO and appears as an
exponent of strain rate( ~ z) in a Stromeyer type fatigue life equation was introduced.
Although such approach can yield estimates of minimum fatigue life, the thus predicted life could be
too conservative, because the data analyzed were mainly from the test results of high temperature and high
DO test conditions, and the proposed equation was made based on such data as strictly as possible. In actual
structures, however, both strain rate and temperature change with time during operation and DO levels are
rather low. Therefore it is reasonable to say that the proposed fatigue life prediction equation is still early to
apply to fatigue designs for actual components until it is verified to be valid at mid-temperatures and low
DO conditions by experimental data at these conditions.
In the present study, the influences of temperatures and DOs on the low cycle fatigue life of carbon
steel in high temperature pure water were studied as part of a joint program between the LWR related
parties in Japan. At the same time, the estimation method mentioned above was reevaluated by available
data including the newly acquired. Based on such evaluation, a new index and a new process was proposed
to obtain more reliable estimates of fatigue lives than the P-value method.
ExperimentalProcedure
Material and Specimens
As the influence of high temperature water environments on the fatigue life of carbon steel is
especially remarkable, STS410(A333-6), carbon steel pipe for high pressure service, was used as a main
test material, STPT480(A106-C), carbon steel pipe for high temperature service and SFVQ2A(A508-2),
quenched and tempered alloy steel forging for pressure vessels, were partly employed. Table 1 shows the
chemical compositions and mechanical properties at room temperature of the test materials. The sulfur
content of STS410 was intentionally controlled to be in the range of 0.010-0.015%, because sulfur in metal
is said to influence the fatigue life in water environment, and the range mentioned here had been typical for
materials used for older plants construction.
Fig. 1 shows the shapes and dimensions of test specimens for fatigue tests in high temperature water.
Because each participating party, uses its own loading and strain detection ~'stem, three types of specimens
were employed to fit each test apparatus. Type A has ridges for attaching a strain meter inside an autoclave.
Type-B is a solid smooth cylindrical specimen for which two strain detection bars were pressed against the
specimen with a non-seal differential transducer. Type-C is a tubular specimen through which high
temperature and high pressure water flows. Each specimen was machined from the mid-wall section of
pipes or plate such that its tensile axis was parallel with the pipe axis or with the roiled direction of the
plate.
Table 1 Chemical Compositions and Mechanical Properties of Test Materials
Steel I.' St Ila P $ Cr NI Iio Cu O. 2~YS IJTS El
.V,TS41II0~:L~I3 6) O,~l 11.31 1. 14 O. Ule n. 012 ~t~ 649 :~

.~'TI"I'4140{AI06 C) O. ) 4 o. ~ 0. 91 0. 010 0. 007 3:]:1 .rdil~ :M
,'r163 ;~) 0. i~1 (I.;~/:i 0.68 O. OIO O. Ol I O. 36 O. 114 O. 6FJ O. l ) 469 1:121) ).R
Type A R5
l~':~,
125
8 106 i,..4
Type C 1
Fig. 1 Shape and D i m e n s i o n s o f T e s t S p e c i m e n s
Fatigue Test in LWR Simulated Water Environments
All the fatigue tests in high temperature water in the present study were done with axially controlled
and fully reversed strain (R=-I) in triangular or saw-tooth wave mode.
Main test conditions are as follows;
9Temperature : 100 ~ 290~
9DO :0.01 ~ 8ppm for BWR-simulat ed environment or
<0.005ppm (including 0.5ppm NH3, pH9.2) for PWR-simulated environment
9Strain amplitude :0.1541.0%
9Strain rate :0.4 or 0.004%/s
Fig.2 is an outline of .typical apparatus for high temperature water fatigue test. During each fatigue
test, the strain rate, temperature and DO concentration were kept constant.
The main purpose of this experiment was to apprehend low ~-cle fatigue lives in mid-temperature
and low DO environments, for which comparatively little data has so far been collected. In order to obtain a
basis for comparison, in-air fatigue tests at both room temperature and high temperatures were also
performed.
Monitor
D0 EC pH _ _
J \" ~ J Pressure [ I
1141
Pump High Pressure Pump
Fig. 2 High Temperature Water Fatigue Test Equipment
Results and Discussion
Low cycle fatigue life of carbon steel in BWR-simulated water environments
Indicated in Fig.3 are the in-air low cycle fatigue lives of STS410 at room temperature, 100 ~C and
200 ~C. As is clearly shown, the fatigue lives at higher temperatures are almost the same as that at room
temperature. This result is in agreement with the previous research stating that the influence of temperature
on in-air fatigue life is small up to 300~ A regression analysis using all the fatigue data plotted in Fig.3
can yield a Stromeyer type equation ( E a=aN~+c) as follows;
a = 0.345N~sA,"~176+ 0.00182. (1)
In the present study, equation(I) is defined as a basis to discuss the environmental effect of high
temperature water.
Figs.4 and 5 indicate the low cycle fatigue lives of STS410 at 100, 150 and 200~ in pure water with
0.2ppmDO. According to Fig.4, the low cycle fatigue life at 100~ in pure water is a little shorter at large
strain amplitudes than that in air. This tendency was also observed by Higuchi et al.[4]. At 100~
practically no environmental effect is seen, even if the strain rate is reduced from 0.4%/s to 0.004~
Contrary to this, at 150 and 200~ a two order decrease in strain rate produced a marked environmental
effect:the fatigue lives decrease to 1/2~ 1/4 of those in air or those by the high strain rate.
Low cycle fatigue life of carbon steel in PWR-simulated water environments
Figs.6 and Fig.7 show the fatigue lives of STPT480 and SFVQ2A in a PWR-simulated water
environment (secondary water). With these materials, tubular specimens were employed and their fatigue
lives were defined as number of cycles (Nl,~) to the appearance of a crack on the tubular specimen's outer
surface which can be found by high temperature water leakage.
These results indicate that little environmental effect of cooling water was noted with both carbon
and low-alloy steels in a PWR-simulated water environment
236 EFFECTS OF THE ENVIRONMENT ON INITIATION OF CRACK GROW]
4
'i ~i [Carbon Steel (STS410)
i i Jin Air, E T=0.4%/S
! i t Type A Specimen
1 ........... : ......... ~ ~ ~
<
I '
{). l ! !
(/. 03 ~
10() 1, ()()(/ 1(1, ()()() 1()0, ()()() 1, 0()0, (ll)()
Fatigue IJfe N:;~ (cycles)
Fig. 3 Strata A m p l i t u d e vs. F a t i g u e Life Data o f S T S 4 1 0 Steel in Air
i [Carbon Steel (STS4'O)

i ! ~ 100%, D O 0.2ppm Water
1 "" ! i [Type A Specimen
0. I -- J- - J .......... ~
l()0OCq}.~4%/sIO0~149 100~-Air A_!r ]
0.03
loo 1,000 lo, ooo lOO, o0o 1, 0o0, ooo
Fatigue Life N25w (cycles)
Fig.4 Strain A m p l i t u d e vs. Fatigue Life D a m o f S T S 4 1 0 Steel
m B W R W a t e r (100~
i ',[Carbon Steel (STS410)

i DO=0.2ppm Water
9 i i Type A and B Specimen
,~ i i i
m nnAo/~''~"lb~ Air Data Line i
........ 9............... c . . . . _._.

! 5oOc 5oOc 2ooOc 2ooOc . I
I 0 4~/sO 00~4%/s0 4%/s0 004%/sAlr I
O.
100 1,000 10, 000 100, 000 1,000, 000
Fatigue Life Nzsw (cycles)
Fig. 5 Strata A m p l i t u d e vs. F a t i g u e Life D a t a of STS410 Steel in
B W R W a t e r (150~ and 200~
4
i i[Carbon
Steel (STPT480)
ii i/Do<00sppm,o s p , m N . ,
i i TypeC Speoimen
1 . . . . . . . ;. . . . . . . . q . . . . . . . . . . ~- . . . . . . . . . .
' i i
, i i I
i
<
O. 1 . . . . . !- 29o~c, o. 4%/s 29o*c, 0. oo4~/s ...... i _..
lO0'C, O. 4%/s IO0~ O. 004%/s i

! @ 9 i
O. 03
1 00 1,000 10, 0 0 0 100, 0 0 0 1,000, 000
Fatigue Life Nleak (cycles)
Fig.6 Strain Amplitude vs. Fatigue Life Data of STPT480 Steel in
PWR Simulated Water
4
! i [L~ AII~ Steel (SFVQ2A)
' i [DO 0.005ppm, 0.5ppmNH3
/
i i p
.4 O. 1 . . . . . . . . . . . ~ ........... ~ ............ !. . . . . . . . . . . ~- -
I ~oo~-o.,~,,';~o~-o.o.~,.ioo~-o.,.,,'~,oo~-o.oo..,,-A,/I
o. oa I .... ~> ~ e 9 o [
100 1,000 10, 0 0 0 100, 0 0 0 1,000, 000
Fatigue Life Nl~k (cycles)

Fig.7 Strain Amplitude vs. Fatigue Life Data of SFVQ2A Steel in
P W R Simulated Water
Effects of temperature and DO on fatimae life of carbon steel
One of our aims was to supplement experimental data at mid-temperatures and low DO levels and to
evaluate quantitatively the influence of temperature and DO in a wide range. In the present study, a number
of experiments were done with STS410 under various temperature-DO conditions at a large strain
amplitude( E a=0.6%) and a low strain rate( ~ r=0.004~ In Table 2, the fatigue lives in each test
condition are summarized. For comparison, the test results by Higuchi et al. [4] is cited in Table 3.
Fig.8 is the log-log plots of the test results in Table 2 as a function of DO. It seems that there would
be an almost linear relation between DO and the fatigue life of carbon steel under the employed strain
condition. A similar relation between DO and the fatigue life on a log-log plot is also found in the report by
Patterson et al. [7] who evaluated the corrosion fatigue of boiler tubes in water-walls. Especially the effect
of DO becomes remarkable at temperatures above 200~ As discussed later, a linear relation between
temperature and the fatigue life of carbon steel exists in this temperature zone on a log-log plot. This
finding agrees with the result by Higuchi et al.[4].
238 EFFECTS OF THE ENVIRONMENT ON INITIATION OF CRACK GROWTF
Table 2 Numbers of Cycles to Falure of Fatigue of Carbon Steel in Pure Water

(STS41010.012%S), t T=0. 004%/s, ~ a=0. 6%, N2sw)
Temperature Dissolved Oxygen Content (ppm)

(~ 0.01 0.05 0.1 0.15 0.2 0.3 0.4 1 8
290 1,203 926 4 524 430~ 290 280 195 4

1,141 972 658 640 415 258
250 1,278 1,088 734 428 394
200 1,267 1,261 1.128 1,082 96() 707 741
1511 1,325 1.260 1,182 1.284 984 1.180

1,275 1.295 1.124
lO0 1,246 1,217 1,325 1.054 1,140
25 1.627
'lablc 3 Previous l't,..st Data ; Effects of l'empcrature and Dissolved ()xygenon Fat{gut: l,ili: of
oft'arbon Stt:cl in t~urc Watcr(STS42(0.015%~";), ~ : 0. 004%/s, ~ ~ 0. t~%, N,~) l,I ]
Temperature Dissolved Oxygen Conltmt (ppm)

(of?) 0.111 11.{15 0.1 {).15 0.2 (1.3 0.4 1 8
290 1,896 1,005 43() 377 280 2117

1.768
250 2.239 1,850 2.126 515 994 418

452
200 1,574 1,664 1,725 2,100

1,060
150 2,298 1,580 948
100 1,385 1,065
25 2,214
Temperature
3, 0 0 0
100'13
150~
1,000
9 ,l+:+ , i ~j
250~C
29~C
i
i i
C a r b o n Steel ( S T S 4 1 0 ) i
...... r ........... i .-
100 t a=0.6%" ~ r = 0 . 0 0 4 % / s i
i
Types A & B S p e c i m e n
lii i i i i i i ill i ....... , i i i llilll
0.01 0.1 1 10
Dissolved Oxygen Content (ppm)
Fig. 8 Effect of Dissolved Oxygen Content on Fatigue Life
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N A K A O ET AL. ON LWR WATER E N V I R O N M E N T S 239
Reconsideration on environmental parameters and proposal of a new equation
(1) Result of evaluation of former P-value

The existing equation for environmental fatigue life estimation, previously" proposed by Higuchi-
Iida[4], is such as shown below.
~ = A(N2~w" ~ P)B + C (2)
In this equation, the influences of temperature and DO in high temperature pure water were reflected in the
exponent, P, of the strain rate, which originally represents the dependency of fatigue life on strain rate.
The value of P (hereafter referred to as P-value) is generally calculated using the slope of a line
defined by a linear regression analysis on a log-log plot of fatigue lives and strain rate. Such data can be
obtained from fatigue experiments in which the strain rate is varied while the environmental conditions are
fixed constant. A ~pical expression of the relation is as follows;
N2sw = A( ~ T)r~ (3)
Where, Nesw is the fatigue life in water environment, A a constant calculated by" the least square
method (almost equal to fatigue life (N25a) in room temperature air) and ~ T the strain rate on the tension
side.
In the present research, as experiments were not conduct at every. environmental condition, the P-
value was calculated by assuming A in equation (3) as the regression life N25A=2,648 from the in-air fatigue
test (in reference [41, N25A=3,480 was used).
Figs.9 indicates the relation of DO, temperature and P-value calculated by the way described above.
In this figure, the lines depicted by the formerly proposed P-value and data by Higuch-Iida [4] are also
shown. It can be seen that the results from the present study mostly agree with the data and proposed P-
value lines by Higuchi-Iida. However, by looking at the data more closely, differences can be detected: most
data from the present experiments are plotted to a lower region than the line proposed by Higuchi-Iida.
Consequently" the present data should be regarded as much more conservative. Conversely, at low DO
concentrations, there are some plots which are located above the Higuchi-lida line. This fact means that if
the formerly proposed P-value line is used, then potentially dangerous predictions may be made.
Higuchi-IidaEquation Nzsw=A(~'T) P ~ N 2 5 A ( ~ ' T ) p

Proposed P% Line
P=0.1 + M ' N . . . . . .
D.O~ M T(~ N
---<0.1 ---0-- . . . . . < ]00 0.21"/100
0.1~0.2 (Do-0.1)/0.1 100~200 0.2
>=0.2 I >200 0.2+0.4(T-200~q00
0.8
Carbon Steel ( S T S 4 1 0 ) i @i
Solid m a r l s , Present Study ,'-................. i......290~........_~ [
Open marks;PreviousStudyby I ! i i 250~C
0.6 T. []
g~
HiguchMida . 1- j~. . . . . . . . . . . . .~. k. .
! , 250 ~
~.I
mi
12o,o
P's Line Proposed i~/~ • ! ~! 150~
4,
0.4 100~
PWR 2rvWater 4 ~ s 100~200~2 ~!
'~ 0.2
k~a
0 , , ,,,,HI t t ..... ~ ........ i ........ i

0. 001 0.01 0. I 1 10
DissolvedOxygenContent (ppm)
Fig. 9 Relation between Dissolved Oxygen Content and Environmental Factor P
As described above, the P-value here is simply an exponent of the strain rate. However, from the
present results where the strain rate was changed in the course of the run, and from the results by Higuchi et
al. where the influence of material quality was evaluated, it becomes clear that the P-value, influenced by
the sulfur content and the tensile strength of the tested materials as well as by the strain rate employed,
cannot be evaluated simply. The scattering in data found in Fig.9 are considered to be connected to these
factors.
(2) Introduction of a new index for evaluation

As the P-value depends on strain amplitude and material qualiD, it is not possible to simply define
the P-value xxith reference to temperature and DO. To overcome this problem, an indcx.Rp, which is a ratio
of the P-value of a given condition to the P-value of a certain base was introduced The reason for this is
that the influence of each parameter would be nornmlized by this index and the faligue life in various
environments and loading conditions could be cvaluated by a single equation.
It will be shown below how experimental data can be adjusted by this ratio.
As a basis. Ihc test condition of 29()'(~ and 8ppmDO was chosen, because lots of data were collectcd
for this particular condition and its cnvironmental effect on thc fatigue life of carbon steel is well
established
The ratio Rp can bc calculated by an equation shown below.
Rp = P/Pc 29,,i;.[y, Sppm= P/Ps (4)
Where, Pc.2,~,c.t~, spl,,,, is the P-value to be a basis. Using equation(3), it was calculated from the
result of the fatigue experiment where the strain rate was varied in 2 9 0 C pure water with 8ppmDO. For
simplicity, Ps for PC,291,c.D~, 8ppmwill be used in the later part of the present paper.
As a representative example. Fig l0 shows the relation between DO and Rp, calculated from the
faligue data in pure water environmenls at 290:t;. This clearly indicales that different sets of data are
plotted within a narrow range even though there are noticeable difference in material quality and loading
condition. This was just what was expected when Rp was introduced.
With the data at 290'C (Fig.10), the plots show a certain relation between Rp-value and DO. As
was with P-value. the data were divided into the three zones of DO level and equations to express the data
were determined as follows:
DO=0.05ppm or lower: Rp=0.2 (5)
DO=0.05~ 0.8ppm: Rp=0.30 9In(DO) + 1.13 (6)
DO=0.08ppm or higher: Rp= 1.0 (7)
Corresponding P-values for these DO level and given temperatures can be calculated by the equation shown
in Fig9. Fig. 11 indicates the maximum values of Rp (hereafter Rp(max)) of each temperalure. For these
plots, the following equation was determined with temperature T in ~
Rp(max)=0.198exp(0.00557T) (8)
(3) Correlation between estimated and experimental fatigue lives

Now the fatigue lives at each test condition can be estimated from equation (2) using P-values
modified by Rp. To find whether or not an estimated fatigue life agrees with the experimentally determined
result, correlation between those two types of fatigue lives was evaluated.
The standard equations used for estimating the fatigue life are listed below. Equation (10) was
simply derived from equations (1) and (3).
From the study by Higuchi: ~ a=0.231(N 25w" ~ ~ P)-~ + 0.00108 (9)
From this study : E a=0.345(N 2sw" E T -P)-~176+ 0.00182 (10)
Since the tested materials in both cases were carbon steel pipes of different heats, the variations seen
in coefficient and constant are probably due to material quali .ty or condition.
To obtain N 2sw by Higuchi-Iida method, the P-value was calculated first by the method shown in
Fig. 9, and then using the thus calculated P-values and ~ T, N 25w was gained from equation (9) or(10).
On the other hand, to obtain N25w by the new method, the Rp-value at each test condition was calculated
by equations (5)~(8), and the P-value was derived by equation(4). Using this normalized P-value, N 25w
was calculated by equation (9) or (10). Fig.12 shows relation between dissolved oxygen content and P
ratio (Rp) at various temperatures.
In Fig.13, the correlation between experimental and estimated fatigue lives calculated by the two
methods is indicated. As is seen obviously, the equation proposed by Higuchi-Iida gave us some evaluations
which fall deep into the lower side of the one-to-one relation (see the open marks). Contrary to this, the new
method produced far accurate predictions(see the solid marks). Thus fatigue life evaluation with
reasonable results can be made by using the P-value modified by Rp, within the scope of the present design
rules.
It should be noted here that all the research conducted so far (including the present paper) has been
based on experimental results at conditions of constant temperature, constant DO, and of comparatively
large strain amplitude and therefore to make the environmental fatigue evaluation method more accurate,
further tests are required at various conditions which precisely simulate actual plant operation. For example,
a test at a low strain amplitude (0.2~0.3%) while temperature is decreasing which is to be done after
prolonged immersion in high temperature and low DO water may be interesting. Or an experiment where
strain pattern and environmental conditions change simultaneously would be also valuable.
Fig. 10 RelationbetweenDissolvedOxygenContentand P Ratio (Rp)
Fig. 11 Relation between Temperature and Maximum value o f Rp
Fig 12 Relation between Dissolved Oxygen Content and Rp
Conclusions
In order to modify the fatigue design method for actual components in high temperature water
environments, fatigue tests in LWR-simulated water conditions at mid-temperatures and low DO levels
were performed with carbon and low alloy steels, and the results were analyzed and discussed. From the
present study ,the following conclusions can be drawn.
1) Fatigue lives of STS410 steel in air are nearly the same over the range from room temperature to 200~
and the effect of temperature on in-air fatigue life is considered negligible in this temperature range.
2) In a pure water environment at 100"C and with 0.2ppmDO, the decrease in fatigue life was not
noticeable, even if the strain rate was reduced from 0.4 to 0.004~ However, at 150 and 200~ and
with 0.2ppmDO, the fatigue life decreases to 1/2 to 1/4, i.e. a marked environmental effect appears,
when the strain rate is reduced in the same way.
3) In PWR-simulated water, neither environmental effect of water nor influence of temperature and strain
rate on fatigue life was observed with both carbon steel(STPT480) and low alloy steeI(SFVQ2A).
4) The decrease in fatigue life in high temperature pure water of carbon steel(STS410) was remarkable at
temperatures above 200~ and with DO higher than 0. lppm. The rate in reduction was larger at higher
DO levels, but below 150~ no significant decrease in fatigue life was seen even with high DOs.
5) A new equation was proposed for evaluating the environmental effects, where the P-value to be used for
calculation is normalized by Rp, a ratio of P-values of a given and a base condition. When the condition
of 290~ and 8ppmDO is chosen as a basis, Rp is expressed as follows;
Rp - P/P C,290Oc,DO~mn
Rp = 0.30*In(DO) + 1.13 (ifRp<0.2 then it is assumed to be 0.2.)
Rp(max)=0.198exp(0.00557T)
1) Environmental fatigue life equations

9Previous report ~ a-0. 231 (N2sw" g +-p)-0.472 + O. 00108
9Present study ~ a=0. 345 (N2sw" ~ r -P ) 0. 560 + 0. 00182
2) Caluculation method of P
9Previous report P-0. 1 +M"N
DO(ppm) M T (%) N
~0. 1 0 < 100 0.2T/100
O. 1 ~ 0 . 2 (DO-().1)/0.1 100~200 0.2
->0.2 1 >200 0.2+0.4 (T 200)/100
9Present study P-Rp'Pc, ~o~cDo-e~m
Rp--O, 30"ln(O0) + 1.13
i f Rp<0.2 then Rp-0.2
Maximum of Rp : Rp-O. 198exp(O. 00557T)
Fig. 13 Comparison of the correlation between the Estimated and the Experimental
Fatigue Lives by Rp method and original P methods
With the help of this parameter, more accurate estimates of fatigue life of carbon steel in high
temperature water can be made at various conditions of temperature, DO and strain amplitude by
the following equation.
a=0.345(N 2sw" e T -P)-os6o+ 0.00182
Acknowledgment
The present research project has been supported by a research fund for the joint utility, stud3' composed of
the Japanese utilities and the three plant fabricators. The test results were discussed at FED Committee of
TENPES. The authors wish to thank gratefully the members of the committee.
References
[/] EPRI Report. "'Application of Environmental Fatigue Stress Rules to Carbon Steel Reactor Piping",
NP-4544M Vol. l&2,1986
121 O'Donnel. "Synthesis of S-N and da/dN Life Evaluation Technologies". ASME PVP-88. T-10.
Pittsburgh. Pennsylvania. 1988
[31 NRC. "'Discussion Paper on Fatigue (Revision 1)". 1991
14_1 Higuchi M. and lida K. "Fatigue Strenglh Correction Factor for Carbon and Low-alloy Steels in
Oxygen-containing High-temperature Water" ,Nuclear Eng. & Desig.n 129. P293-306, 1991
[5] Higuchi M and Sakamoto H,Jr. Iron and Steel Inst. of Japan, vol.71 No.8. P86. 1985
16] Hale D.A. el al.,"Low Cycle Fatigue of Commercial Piping Steels in a BWR Primary Water
Enviromnenf', Trans. of ASME, Vol. 102, No, 1, PI02. 1981
[7] Patterson R. W. et al.,"Boiler Tube Failures in Waterwalls and Economizers : Vol,4", Summery.
Report EPRI TR-100455, 1993
[_8] ANL Report,"Fatigue of Carbon and Low-Alloy Steels in LWR Environment", 21st Water Safety
Information Meeting, 1994
[_9] Higuchi M. et al.,'Effects of Strain Rate Change on Fatigue Life of Carbon Steel in High Temperature
Water", ASME PVP-95 Conference Vol.306, PI 11. 1995
[I_LQ]Chopra O. K. and Shack W. J.,"Effect of LWR Environments on Fatigue Life of Carbon and Low
Alloy Steels", ASME PVP-95 Conference Vol.306, P95, 1995
Crack Initiation in Corrosion Fatigue--II
Omesh K. Chopra 1 and William J. Shack 1
EVALUATION OF EFFECTS OF LWR COOLANT ENVIRONMENTS ON

F A T I G U E L I F E O F C A R B O N AND L O W - A L L O Y S T E E L S
R E F E R E N C E : Chopra, O. K., and Shack, W. J., "Evaluation of Effects of L W R

Coolant Environments on Fatigue Life of Carbon and Low-Alloy Steels," Effects of
the Environment on the Initiation of Crack Growth, ASTM STP 1298, W. A. Van Der
Sluys, R. S. Piascik, and R. Zawierucha, eds., American Society for Testing and
Materials, 1997.
A B S T R A C T : The ASME Boiler and Pressure Vessel Code provides rules for the
construction of nuclear power plant components. Figu :e 1-90 of Appendix I to Section
III of the Code specifies fatigue design curves for structural materials. However, the
effects of light water reactor (LWR) coolant environments are not explicitly addressed by
the Code design curves. Recent test data indicate a significant decrease in fatigue life of
carbon and low-alloy steels in L W R environments when five conditions are satisfied
simultaneously, viz., applied strain range, temperature, dissolved oxygen in the water,
and sulfur content of the steel are above a minimum threshold level, and the loading
strain rate is below a threshold value. Only a moderate decrease in fatigue life is
observed when any one of these conditions is not satisfied. This paper summarizes
available data on the effects of various material and loading variables such as steel type,
dissolved oxygen level, strain range, strain rate, and sulfur content on the fatigue life of
carbon and low-alloy steels. The data have been analyzed to define the threshold values
of the five critical parameters. Methods for estimating fatigue lives under actual loading
histories are discussed.
KEYWORDS: fatigue crack initiation, strain vs. life (S-N) curve, L W R environment,
carbon steel, low-alloy steel, strain rate, dissolved oxygen, sulfur content
INTRODUCTION
Plain carbon and low-alloy steels are used extensively in light water reactor (LWR)
steam supply systems as piping and pressure-vessel materials. The ASME Boiler and
Pressure Vessel Code Section III, which contains rules for the construction of Class 1
components for nuclear power plants, recognizes fatigue as a possible mode of failure in
pressure vessel steels and piping materials. Cyclic loadings on a structural component
1Metallurgistand Associate Director, respectively, Energy Technology Division, Argonne National

Laboratory, Argonne, IL 60439
247
Copyright*
Copyright 1997
by ASTM Int'lby(all
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occur as a system moves from one load set (e.g., pressure, temperature, moment, and
force loading) to any other load set. For each pair of load sets, an individual fatigue
usage factor is determined by the ratio of the number of cycles anticipated during the
lifetime of the component to the allowable cycles. Figure 1-90 of Appendix I to
Section III of the Code specifies fatigue design curves that define the allowable number
of cycles as a function of applied stress amplitude. The cumulative usage factor (CUF) is
the sum of the individual usage factors. The ASME Code Section 111 requires that the
CUF at each location must not exceed a value of 1.
The current Code fatigue design curves are based on strain-controlled tests of small
polished specimens at room temperature (RT) in air. In most studies, the fatigue life of a
test specimen is defined as the number of cycles for the tensile stress to drop 25% from
its peak value, which corresponds to a =3-mm~teep crack. Consequently, fatigue life N
represents the number of cycles required to initiate a crack ---3 mm deep. The best-fit
curves to the experimental data are expressed in terms of the Langer equation [1]
ea = B(N) -b + A, (1)
where Ea is applied strain amplitude and A, B, and b are parameters of the model. The
fatigue design curves were obtained by decreasing the best-fit curves to the experimental
data by a factor of 2 on stress or 20 on cycles, whichever was more conservative, at each
point on the best-fit curve. These factors are not safety margins but rather adjustment
factors that must be applied to the experimental data to obtain estimates of the lives of
reactor components. The effect of LWR coolant environments on fatigue resistance of
the material are not explicitly addressed in the Code design fatigue curves.
Recent fatigue strain vs. life (S-N) data from the U.S. [2-7] and Japan [8-12]
illustrate potentially significant effects of LWR coolant environments on the fatigue
resistance of carbon steels (CSs) and low-alloy steels (LASs). Environmental effects on
fatigue life are significant when five conditions are satisfied simultaneously, viz., applied
strain range, service temperature, dissolved oxygen (DO) in the water, and sulfur content
of the steel are above a minimum threshold level, and the loading strain rate is below a
threshold value. Although these are the minimum conditions that must be met to produce
significant degradation in fatigue life, the actual dependence of fatigue life on these
variables involves complex synergistic interactions. Also, studies on the effect of high-
temperature aqueous environment on fatigue crack growth behavior of carbon and l o w -
alloy steels indicate that flow rate is an important parameter for environmental effects on
fatigue life in water [13,14]. However, experimental data to establish either the
dependence of fatigue life on flow rate or the threshold flow rate for environmental
effects on fatigue life are not available. When any one of the threshold conditions is not
satisfied, environmental effects on fatigue life are modest. Interim fatigue design curves
have been developed that take into account temperature, DO content in water, sulfur level
in steel, and strain rate [15]. Statistical models have also been developed for estimating
the effects of various material and loading conditions on fatigue life of materials used in
the construction of nuclear power plant components [16]. Results of the statistical
analysis have been used to estimate the probability of fatigue cracking in reactor
components [ 16]. The Pressure Vessel Research Council (PVRC) has also been
compiling and evaluating fatigue S - N data related to the effects of LWR coolant
environments on the fatigue life of pressure boundary materials; the results have been
presented by Van Der Sluys [17].
This paper summarizes available data on the effects of various material and loading
variables such as steel type, dissolved oxygen level, strain range, strain rate, and sulfur
CHOPRA AND SHACK ON LWR ENVIRONMENTS 249
content on the fatigue life of CSs and LASs. The data have been analyzed to define the
threshold values of the five critical parameters. Methods for evaluating the effects of
LWR coolant environments on the fatigue life of these steels are presented, and
estimations of fatigue lives under actual loading histories are discussed.
AIR ENVIRONMENT
The fatigue life of CSs and LASs in air depends on steel type, temperature,
orientation, and strain rate. For LASs, the fatigue life is greater and fatigue endurance
limit is higher than it is for CSs. For both steels, fatigue life decreases as temperature
increases. Some steels show very poor fatigue properties in the transverse orientation.
The fatigue lives of A302-Gr B steel in the rolling (R) and radial (T2) orientations are
shown in Fig. 1. The fatigue life in the T2 orientation is nearly one order of magnitude
lower than in the R orientation. Also, endurance limit in the T2 orientation is lower than
it is in the R orientation. Metallographic examination of the specimens indicates that
structural factors, such as distribution and morphology of sulfides, are responsible for the
poor fatigue resistance of steels in transverse orientations, in which fatigue crack
propagates preferentially along the sulfide stringers. The results also indicate that some
heats of CS and LAS are sensitive to strain rate. For example, in an air environment at
288~ the fatigue life of A302-Gr B steel (Fig. 1) decreases with a decrease in strain
rate. The effect of strain rate is quite significant for the T2 orientation. A similar strain
rate effect has also been observed in A333-Gr 6 carbon steel [7]. However, two heats of
CS and LAS showed no effect of strain rate on fatigue life in air at 288~ [5,6].
The cyclic stress-strain response of CSs and LASs varies with steel type and
temperature. In general, these steels show initial cyclic hardening followed by cyclic
softening or a saturation stage at all strain rates. Significant initial hardening is seen in
the CSs with a pearlite and ferrite structure and low yield stress. The LASs, which
consist of tempered ferrite and bainitic structure, have a relatively high yield stress, and
show little or no initial hardening, may exhibit cyclic softening during testing. For both
steels, maximum stress increases as applied strain increases and generally decreases as
temperature increases. However, at 200-370~ these steels exhibit dynamic strain
aging, which results in enhanced cyclic hardening, a secondary hardening stage, and
negative strain rate sensitivity [18-20]. The temperature range and extent of dynamic
strain aging vary with composition and structure. Effect of strain rate and temperature on
the cyclic stress of CSs and LASs is shown in Fig. 2. For both steels, cyclic stresses are
' ....... I , ,,'-,q , , ...... I ........ I ' ','""1 ' ''""

A302--Gr B L o w - A h o y S t e e l
,.G"
~1.0 Figure 1 -
Effect of material orientation on
.r
fatigue life of A302-Gr B low-alloy
Strain Rate (%/s) steel in air at 288~
O 0.4/0.4
~, 0.004/0.4
o Open Symbols: R orientation
I-- Closed Symbols: T2 orientation
. . . . . . . . i , ,,,,,,,i , , ...... i ........ i ........ i .... ,
0.1
1 0~ 1 02 1 0~ 1 04 1 05 1 06 1 07
Cycles to Failure, N2 5
1100 . , , , ..... i ........ i ' '''""1 ...... '~1 - ' ....... I ' ' ...... I . . . . . . vq ' ' ''""1
: A 1 0 6 - G r B Carbon Steel ~ (a) : A 5 3 3 - G t B Low-Alloy Steel (b)
~ ' I 000 ~-~ ~ = o . 7 5 %
13.-
900 9 ~ e~ DO 00o o
00 ~ 0 0
- 800 00 ~ ~
0
t~ 700
0 288~ Air 0 288~ Air A
600 o z~ RT Air ~. RT Air
Strain Rate (~ Strain Rate (%/s)
500 Open Symbols: 0.4 Open Symbols: 0.4
Ctosed Symbols: 0.004 Closed Symbols: 0 0 0 4
400
00 1 01 1 02 1 03 1 04 00 1 01 1 02 1 03 1 04
Number of Cycles Number of Cycles
Figure 2--Effect of strain rate and temperature on cyclic stress of carbon and low-alloy
steels in air
1200 ' ~....... I ......... I .... ~''' ' I ......
Carbon Steels ,,,~ o Low-Alloy Steels .... :
~" 1000 288~176
~ ~ e~'~~o.oo~o/as
0 800
c~) 6 0 0
y u'o o.oN%ls o,4"/~s
/~
~ v
Ae~(%)
~
= (A~/1965) ~- (Ao/C) 9 ~
0A~
t~ C = 1080 - 50.9Log(~ C = 962 - 30.3Log(E)

4O0 / TenJComp.
$ /
/ Ten/Comp.
Strain Rate (%/s) / Strain Rate (%/s)
200
/ o 0.4/0.4 / O 0,4t0.4
/ z~ 0.04/0.4 / A 0.01/0.4
O 0 004/0.4 / o 0.00410.4
iiiil,,,i,, ....... [,,,, ..... I,,,,,,,,
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
Total Strain Range, A~ (%) Total Strain Range, Aet ( % )
Figure 3--Cyclic stress-strain curve for carbon and low-alloy steels at 288~ in air
higher at 288~ than at room temperature. At 288~ all steels exhibit greater cyclic and
secondary hardening. The extent of hardening increases as applied strain rate decreases.
The cyclic stress vs. strain curves for CSs and LASs at 288~ are shown in Fig. 3;
cyclic stress corresponds to the value at half life. The total strain range AEt(%) for CSs
can be represented in terms of the cyclic stress range A~ (MPa) and applied strain rate b
(%/s) with the equation
A(~ (_~/TM ' (2a)

A e t - 1965
where the constant C is expressed as
C = 1080 - 50.9Log(k); (2b)
and for LASs, with the equation

A(~ (_~)9,09, (3a)
Aet - 1965
C H O P R A A N D S H A C K ON LWR E N V I R O N M E N T S 251
where the constant D is expressed as
D = 962 - 30.3Log(e). (3b)
The fatigue life of CSs and LASs in air and LWR environments can be estimated
from statistical models [18]. In air, the fatigue life N, defined as the number o f c y c l e s to
form a 3-mm-deep crack, o f C S s is expressed as
In(N) = 6.570 - 0 . 0 0 1 3 3 T - 1.871 ln(ea - 0.11) (4a)
and that of LASs as
In(N) = 6.667 - 0.00133 T - 1.687 ln(ea - 0.15), (4b)
where e a is the strain amplitude in % and T is the temperature in ~ The fatigue lives of
CSs and LASs in air at room temperature and 288~ are compared with the values
estimated from Eqs. 4a and 4b in Fig. 4. The results indicate significant heat-to-heat
variation. At 288~ fatigue life may vary up to a factor of 5 above or below the mean
value. The results also indicate that the ASME mean curve for CSs is not consistent with
the experimental data; at strain amplitudes <0.2%, the mean curve predicts significantly
........ i ........ l ........ [ ........ i ........ I ........
........ i ........ i ........ i ........ i ........ i ......
Carbon Steels zx Data used to define Carbon Steels

zx Room Temp. Air ASME Mean Curve 2 9 0 ~ Air
g A
~ L ~ 6. -
O
- - - -
Other Data
Statistical Model
- - Statistical Model
.0"~ 0 0 0 25(~-299 ~
..... ASME Mean Curve
. 1,0 ..... Higuchi & lida ~\_
"o
.-2
<
E
~.o
o.1
, ,,,,,,,i , ,H,,,,I , ....... i , ,,,,,,,i ........ i , ..... , , ,,i,,,I , ,,,,lld ........ I , ,,l,,.l ........ I ' ''''
1 02 1 03 1 04 1 05 1 06 1 07 1 08 1 02 1 03 1 04 1 05 1 06 1 07 1 08
C y c l e s to Failure, N 2 5 Cycles to Failure, N2 5
........ i ........ i ........ i ........ i ........ i .......

........ i ........ i , , ...... i ........ i ........ i ........
I / , n l ~ ~,ll~w ga==~=l~ & Data used to develop ' Low-Alloy Steels
),O
~% _ =v---" "v3 . . . . . . . . . . . . .
Room Temp. Air iv
A~Mt Mean ~u e 290~ Air
o~ b;]l~_ O Other Data X~ - - Statistical Model
Statistical Model
- - - - -
O 286-300~
J. 9 - , ~ j ~ = = ~ ..... ASME Mean Curve
E
1.0
% _. - .... Higuchi & lida
<
._E
/X
, ,,,,,,.i .... ,,,d i , ...... i , ,,,,..i ........ I , ,,,, , ,,,,Hd I ,lllml n pL,,n,d , ,,,,,nl [ n ,,,,,,I ,
10 2 10 3 10 4 10 5 10 6 10 7 10 8 10 2 10 3 10 4 10 5 10 6 1 07 1 08
Cycles to Failure, N2 5 Cycles to Failure, N2 5
Figure 4--Fatigue S-N behavior for carbon and low-alloy steels in air at room
temperature and 2900(?
lower fatigue lives than those observed experimentally. The estimated curve for LASs is
comparable with the ASME mean curve. For both steels, Eq. 4 shows good agreement
with the average curves of Higuchi and Iida [8]. The existing fatigue S - N data base for
CSs and LASs does not include information regarding the size and distribution of
inclusions in the steel. Consequently the effect of orientation could not be incorporated
into the statistical model.
The fatigue data indicate that in the temperature range for dynamic strain aging,
strain rate may influence fatigue life of some steels even in an inert environment; the
fatigue life may be either unaffected [5,7], decrease for some heats [18,19], or increase
for others [20]. The relatively large variation in life observed in the tests at 288~ may
be due to differences in the extent of dynamic strain aging in the steel. Because of the
conflicting possibilities, strain rate effects were not explicitly considered in the statistical
model. Inhomogeneous plastic deformation can result in localized plastic strains, this
localization retards blunting of propagating cracks that is usually expected when plastic
deformation occurs and can result in higher crack growth rates [18]. The increases in
fatigue life have been attributed to retardation of crack growth rates due to crack
branching and suppression of plastic zone. Formation of cracks is easy in the presence of
dynamic strain aging [20]. In an air environment, Eqs. 4a and 4b consider only the
effects of steel type and temperature on fatigue life.
LWR ENVIRONMENTS
The fatigue data in LWR environments indicate a significant decrease in fatigue life
of CSs and LASs when five conditions are satisfied simultaneously, viz., applied strain
range, service temperature, DO in the water, and sulfur content of the steel are above a
minimum threshold level, and the loading strain rate is below a threshold value.
Although the microstructures and cyclic-hardening behavior of CSs and LASs are
significantly different, environmental degradation of fatigue life of these steels is
identical. For both steels, environmental effects on fatigue life are minimal if any one of
these conditions is not satisfied. The effects of these parameters on fatigue life are
discussed below in greater detail to define the threshold values.
Temperature
The change in fatigue life of two heats of A333-Gr 6 CS with test temperature at
different levels of DO [8,9,12] is shown in Fig. 5. Other parameters, e.g., strain
amplitude and strain rate, were kept constant; the applied strain amplitude was above and
strain rate was below the critical threshold value. In air, the two heats have a fatigue life
of =3300 cycles. The results indicate a threshold temperature of 150~ above which
environment decreases fatigue life if DO in water is also above the critical level. In the
temperature range of 150-320~ fatigue life decreases linearly with temperature; the
decrease in life is greater at high temperatures and DO levels. Only moderate decrease in
fatigue life is observed in water at temperatures below the threshold value of 150~ or at
DO levels <0.05 ppm. Under these conditions, fatigue life in water is 30-50% lower than
in air; Fig. 5 shows an average life of-~2100 cycles for the heat with 0.015 wt.% sulfur
and =1200 cycles for the 0.012 wt.% sulfur steel. For the latter, the larger decrease in
fatigue life in l o w - D O water relative to RT air, is most likely due to strain rate effects.
As was discussed in the preceding section, the A333-Gr 6 steel with 0.012 wt.% sulfur is
sensitive to strain rate even in air; life decreases with a decrease in strain rate [7].
1 0' .... I .... I .... I .... I .... I .......

A 3 3 3 - G r 6 Carbon Steel ' . ~ 3 3 3 ~ r '6'Cah~on 'Ste~l . . . . . . . . I .... !1 . . . . .
~a = 0.6%, S = 0.012 wt.% ~o =0~O,o, s =00,5~O,o i i
9 ~ zxi
: ! :: v e i ~ :
, * : mi,
O.~10;
...... ........... i ........... .......... * .......... ........ ...........
== DO {ppm) :: ~, 7: ?i~i
._~ o _0.05 ! i ~' i
0 ' 0.05 ~ i ~ @
[] o.lo i :: u ~i [] '0.1 i i V::
o " 0.20 ::Strain Rate (%/si ~ ~r i O 0.2 i Strain Rate (%/S) ::
1 0: v ' _>l.0-----iOpen Symbols: 0.004-----~' ......... v.: ............ v _>1.0-..-i-Open Symbols: 0.01 .................... ~............
9 " Air ::Closed Symbols: 0.4 :: V i zx A r :: Closed Symbols: 0.4 :: !
,,,t .... J .... i .... J . . . . . . . . . . . . -
5 0 100 150 200 250 300 350 5 0 100 150 200 250 300 350
Temperature (~ Temperature (~
Figure 5--Change in fatigue life of A333-Gr 6 carbon steel with temperature and DO
The strain rate effects are similar in air and in water when any one of the threshold
conditions is not satisfied.
Fatigue S - N data on high-sulfur LASs are inadequate to determine the temperature

dependence of fatigue life in water. Available data indicate that the threshold value of
150~ and a linear dependence of fatigue life on temperature may also be applicable to
LASs.
Strain Rate
A slow strain rate applied during the tensile-loading cycle is primarily responsible
for environmentally assisted reduction in fatigue life. Slow strain rate applied during
both tensile- and compressive-loading cycles does not cause further decrease in fatigue
life. However, limited data indicate that a slow strain rate during the compressive-
loading cycle also decreases fatigue life, although the decrease in life is relatively small.
The fatigue life of A533-Gr B steel at 288~ 0.5-0.8 ppm DO, and =0.5% strain range
decreased by factors of 5, 8, and 35 for the fast/fast, fast/slow, and slow/fast tests [5].
Similar results have been observed for A333-Gr 6 carbon steel; relative to the fast/fast
test, fatigue life for slow/fast and fast/slow tests at 288~ 8 ppm DO, and 1.2% strain
range decreased by factors of 3.5 and 7.5, respectively [ 10].
The S - N data indicate that strain rates above 1%/s have little or no effect on fatigue
life of CSs and LASs in LWR environments. For strain rates <1%/s, fatigue life
decreases rapidly with decreasing strain rate. The fatigue lives of several heats of CSs
and LASs [5-10] are plotted as a function of strain rate in Fig. 6. The results indicate that
when threshold conditions for the five parameters are satisfied, fatigue life decreases with
decreasing strain rate and increasing levels of DO in water. Only a moderate decrease in
fatigue life is observed in low-DO water, e.g., at DO levels of _<0.05 ppm. For two heats
of steel, e.g., A 1 0 6 - G r B CS and A533-Gr B LAS, the effect of strain rate on fatigue life
appears to saturate at =0.001%/s strain rate. This is consistent with the predictions of a
crack growth model [15]. However, a heat of A 3 3 3 - G r 6 CS did not show saturation at
this strain rate at 250~ and 8 ppm DO. Saturation strain rates are likely to depend both
on material and environmental variables; their experimental determination is very time
consuming.
O~ ........ l ........ I ........ I ' ....... I '

Carbon Steel !. x ')('"'! A'333"G 'r'!6 C a ~ o 'n"~teel . . . . . . . i! ........ I! .......
! : ~ ! x i lm - 25oo c : _ _ y~__ A_+r__ _ L - - -++ - q
Strain Amplitude: 0.6% +~ ~ ~+~'I
Sulfur: 0.015 wt.% i ~ +J@ 1
! ..~.~ ~,: .A333-Gr6
ol o o ~ ! b 0.7
gl 0; .... ; ............... ~ 9 i. . . . . . . . V 8.0 . . . . . . . i .......... ~ * ...................... b 0.05+=
2880C : ' i A106-Gr B-+ i ~ u O.lO
LL Strain Amplitude: =0.38% i 'A 0.01 A 0.20
S u l f u r : A 3 3 3 - G r e = 0.012 Wt.% ! 0 0.70 o 8+0
A106~3r B = 0.015 wt.% X Air X Air
........ i ........ i ........ i ........ + ....... ........ I ........ I ........ ] ........ I .......
0 .5 1 0 .4 1 0 -3 1 0 .2 1 0-1 00 1 0 -5 1 0 .4 1 0 .3 1 0 .2 1 0 "1 00
Strain Rate (%/s) Strain Rate (%/s)
10'
Carbon Steel :: ': :: ;re'e;'"'", ........ i ........ " ....... 1
288~ ' i ~: Air i rl nJ 288~ " ! i :: J
Strain Amplitude: 0.8% - - -~ ~ - ~ :: j~ Strain Amplitude: 0.6% i i l
+oo++,o i Sulfur: ~0,01 wt.% i PW RWater i . ~ 1
~1 0:
O0 (ppm) i ,~ ~ : q
A333-Gr 6 i ~'+"~ + '
.J o o.ot i ~r : q i ~.../r 4
o.1o ;/v i i I
.~ 1 0; 0.20 .............. ~ ..... ! .... t
o 8.o i ~ 1 ......... ii ~ ~ .~. ~ . . i~ ~ - - ~ . . + i+ ~ . . . AS33~3r B
1
u_ • Air i i ~ t
i ~:o.2 1
v 0.o i I
t 0 ,m ...... I ........ I ....... I ........ I ~ ,n,4 ........ [ ........ [ ........ ~ ..... ill ?'?t ,,,l]
1 0-5 1 0 .4 1 0 .3 1 0 .2 1 0 -t 1 00 1 0 -5 1 0 .4 1 0 .3 1 0-2 1 0 -1 t 00
Strain Rate (%/s) Strain Rate (%/s)
Figure 6--Dependence of fatigue life of several heats of carbon and low-alloy steels
on strain rate at several dissolved oxygen levels
1 04 i , r,,,,, I i , ,,,,,r I , , ,,,,,,I i ; +,,,,t ' ' ',,",1 r , ''""1 ' ' ''""1 J , i,i,u
A 3 3 3 - G r 6 Carbon Steel i 288~ A 3 3 3 - G r 6 Carbon Steel 250~
] Strain Amplitude: 0.6% Strain Amplitude: 0.6%
i Sulfur: 0.012 or 0015 wi% Sulfur: 0.012 or 0.015 wt.%
A
~,.~ 1 03 .................. L ........ o..,, i ............ • .... , ................
o i
0
14. Strain Rate (*/*Is) ~ Strain Rate (*/ds) O
102 O O 064 ....................................... ~ ................ O 0 ' 0(}4
"i ......... +...................... | ................
A o.ot o i A O.O i i
........ J ........ ~ ........ i .... ........ i ........ i ........ i . . . . . .
1 0 -3 t 0-2 I 0-I I 00 1 01 1 0 .3 1 0 -2 1 0 "1 1 00 1 01
Dissolved Oxygen (ppm) Dissolved O x y g e n (ppm}
Figure 7--Dependence of fatigue life of carbon steel on dissolved oxygen
D i s s o l v e d Oxv~,en
T h e d e p e n d e n c e o f fatigue life o f carbon steel on D O c o n t e n t in w a t e r [9,12] is

s h o w n in Fig. 7. T h e test temperature, a p p l i e d strain a m p l i t u d e , and sulfur c o n t e n t in
steel w e r e a b o v e , and strain rate w a s b e l o w , the critical t h r e s h o l d v a l u e s . T h e results
indicate a minimum DO level of 0.05 ppm, above which environment decreases fatigue
life of the steel. The effect of DO content on fatigue life saturates at 0.5 ppm, i.e.,
increases in DO levels above 0.5 ppm do not cause further decreases in fatigue life. In
Fig. 7, for DO levels between 0.05 and 0.5 ppm, fatigue life appears to decrease
logarithmically with DO.
Sulfur Content in Steel
The fatigue S - N data indicate that when all the threshold conditions are satisfied,
environmental effects on the fatigue life of CSs and LASs increase with increased sulfur
content in the steel. However, the available data are inadequate to establish the
dependence of fatigue life on sulfur content and either a lower threshold for sulfur content
below which environmental effects are unimportant or an upper limit above which the
effect of sulfur on fatigue life may saturate. Limited data suggest that environmental
effects on fatigue life may saturate at sulfur contents above 0.015 wt.%. For example, a
A 3 0 2 - G r B steel with 0.027 wt.% sulfur and A533-Gr B steel with 0.012 wt.% sulfur
yield identical fatigue lives in water at 288~ and =0.7 ppm DO [7]. The probability of
environmental enhancement of fatigue crack growth rates in precracked specimens
appears to diminish markedly for sulfur contents <0.005 wt.% [23-26], but enhanced
growth rates have been observed in isolated heats with very low sulfur levels.
10.0
" " ' 0.015 wt.% Sulfur A533-B I Steel 0.012 wt.% Sulfur
A106-B Steel DO = 0.5-0.8 ppm
288 ~ Strain Rate (%/s) 288oc DO = 0.5-0.8 ppm
O 0.4/0.4 Sirain Rate ~*/*fs)
[] .04/.4 O 0.4/0.4
< 0 0.004/0.4
O 0.004/0.4
Air Z~ 0.0004/0.4 , ~ L . ~\\, L,~ .r A 0.0004,0.4
I~ 1.0
.E o "~,~" L.,
EstimatedCurver,~-
Str~. Ra~e
" ~ ?5~,-,
(o/~,l"-..~o. "-. ~"e-~ E0i,mat~e,& " - ~ - , ~ _ ~
.- 0.4 - - - - ~ . ~ - . ~ . ~.-..,..:=
-
o
..... 0.04 . . . . . 0.04 .
F- . . . . . 0,004 -- -- - 0.004
0.001
0. 1 t---L~sn"--
1 01 1 02 1 03 1 04 1 05 1 06 1 07 1 01 1 02 1 03 1 04 1 05 1 06 1 07
Cycles to Failure, N25 Cycles to Failure, N25
Figure 8--Fatigue S-N behavior for AIO6-Gr B and A533-Gr B steels estimated from
model and determined experimentally in high-DO water at 288 ~
Strain Amplitude
A minimum threshold strain is required for environmentally assisted decrease in

fatigue life. This threshold value most likely depends both on material parameters such
as amount and distribution of sulfides, and on parameters such as temperature, strain rate,
and DO level in water. The fatigue life of A106-Gr B and A 5 3 3 - G r B steels in h i g h - D O
water at 288~ and different strain rates is shown in Fig. 8, For these heats of carbon and
low-alloy steels, the threshold strain range appears to be at =0.36%. This behavior is
consistent with the slip-dissolution model for crack propagation [22]; the applied strain
must exceed a threshold value to rupture the passive surface film in order for
environmental effects to occur. However, this does not imply that the observed threshold
strain is the actual film rupture strain. Film rupture occurs at the crack tip and is
256 EFFECTS OF THE E N V I R O N M E N T ON INITIATION OF C R A C K G R O W T H
controlled by the crack tip strain. The threshold strain measured in smooth-specimen
tests is a surrogate that in essence controls the crack tip strain, but no numerical equality
between the two need be implied.
Low Dissolved Oxygen
Only a moderate decrease in fatigue life is observed in water when any one of the
threshold conditions is not satisfied, e.g., low-DO pressurized water reactor (PWR)
environments [4-8]. The fatigue life of CSs and LASs in simulated PWR water is shown
in Fig. 9. For both steels, fatigue lives in a PWR environment are lower than those in air
by a factor of less than 2. Similar behavior is expected in water at temperatures below
150~ even when the DO levels are above 0.05 ppm and strain rates are below l%/s. In
PWR water, the effects of orientation and strain rate are similar to those in air; heats of
CS and LAS that are sensitive to strain rate in air, also show a decrease in fatigue life in
PWR water with decreasing strain rate. For some heats, fatigue life decreased by a factor
of =4 when strain rate decreased from 0.4 to 0.004%/s [7]. On the other hand, for some
heats, a decrease in the strain rate by three orders of magnitude does not cause an
additional decrease in fatigue life, e.g., results for A 106-Gr B and A533-Gr B steels in
Fig. 9. The results also suggest that even the high-sulfur steels, e.g., A302-Gr B steel
with 0.027 wt.% sulfur, which exhibit enhanced crack growth rates in PWR water [21],
show only modest decreases of fatigue life in low-DO PWR water [5,7].
A106-Gr B Carbon Steel (a) Low-Alloy Steels Strain Rate (%Is) (b)
o~ 0 0.4/0.4
o3- ,5. 0.004/0.4
0 0.4/0.004
<3
o/
o•
"q~l~.
Statistical Model
-<0.05 ppm DO
O ~ All Strain Rates Statistical Model
c 1.0
c~ 9 ~il <0.05 ppm DO
03
rr A N L Strain Rate f31r~'~C~
~ ~ . J , ~ All Strain Rates
o o.~ ~,D/f <1oppboo ~ o,~./
0004 %15 ~_ 1000 ppm Boron "'"~_Pc~
2 ppm Lithium
Terrell Freq. < 1 0 oob DO
O 1 Hz v pp- Open Symbols: A533-Gr B
"6 1000 ppm Boron Closed Symbols: A302-Gr B
I-- A 0.~ Hz 2 ppm Lithium Crossed Symbols: w/o B & Li
[] 0.017 Hz
0.1 I j~,,,,,I , ,tH.d = ,,,Hd ........ i i i ...... I , ,~,, t ,,H.,I , ,,H,.I .... ,,,,b , , ...... i ........ i , ,,H.
01 1 02 1 03 1 04 1 05 1 0s 07 1 01 1 02 1 03 1 04 1 0s 1 06 07
Cycles to Failure, N25 Cycles to Failure, N2 5
Figure 9--Fatigue S-N behavior for (a) carbon steel and (b) low-alloy steels estimated
from model and determined experimentally in PWR water at 288 ~
E S T I M A T I O N OF FATIGUE LIFE
For service conditions that satisfy all critical threshold values, the fatigue life of
carbon and low-alloy steels can be estimated from the statistical models [ 16]. The
fatigue life of CSs is expressed as
In(N) = 6.186 - 1.871 l n ( e a - 0.11) + 0.554 S* T* O* e* (5a)
and that of LASs as
In(N) = 5.901 - 1.687 ln(ea- 0.15) + 0.554 S* T* O* g*, (5b)
where S*, T*, O*, and k* = transformed sulfur content, temperature, DO, and strain rate,
respectively, defined as follows:
S* = S (0 < S < 0.015 wt.%)

S* = 0.015 (S >0.015 wt.%) (6a)
T* = 0 (T <150~
T* = T - 150 (T = 150-350~ (6b)
O* = 0 (DO <0.05 ppm)

O* = DO (0.05 ppm <DO <0.5 ppm)
O* = 0.5 (DO >0.5 ppm) (6c)
g* = 0 ( g > 1%/s)
g * = In(g) (0.001 < g <1%/s)
~* = In(0.001) (g <0.001%/s) (6d)
The functional forms for S*, T*, O*, and g* were defined on the basis of the
experimental data. Equations 6b and 6d are consistent with the data in Figs. 5 and 6,
respectively. In Eq. 6c, a linear rather than a logarithmic function of DO was used to
define O*. As discussed previously, the available data are inadequate to establish the
dependence of fatigue life on sulfur content. The data suggest a linear dependence of life
on sulfur; the effect of sulfur content was assumed to saturate at 0.015 wt.% sulfur. The
last term in Eqs. 5a and 5b is zero when any one of the critical threshold conditions is not
satisfied, e.g., in a PWR environment the low DO would imply that environmental effects
are small even for low strain rates. The fatigue life of CSs and LASs in simulated PWR
water is compared with values estimated from Eq. 5 in Fig. 9. The fatigue lives in high-
DO water at 288~ are compared with the estimated values in Fig. 8. The predicted
fatigue lives show good agreement with the experimental results.
FATIGUE EVALUATION
The fatigue S-N correlations of Eqs. 4 and 5 show excellent agreement with data
obtained under loading histories with constant strain rate, temperature, and strain
amplitude. Actual loading histories are far more complex. Exploratory fatigue tests have
been conducted with waveforms where the strain rate or temperature was varied during
the loading cycle. The results of such tests provide guidance for developing procedures
and rules for fatigue evaluation of components under complex loading histories.
Strain Rate
Exploratory fatigue tests have been conducted with waveforms where the slow
strain rate is applied during only a fraction of the tensile loading cycle. Sample results
for A106-Gr B steel tested in air and low- and high-DO environments at 288~ and
=0.75% strain range are summarized in Fig. 10. The waveforms consist of segments of
loading and unloading at fast and slow strain rates. The variation in fatigue life of
Fraction of strain at slow rate: 1 Fraction of strain at slow rate: 0.83 Fraction of strain at slow rate: 0.65
C D
Air: 3,721; 3,424; 6,275 Air: 3,893 Air: 4,356
PWR: 2,141 PWR: - PWR: -
Hi DO: 303; 469 Hi DO: 340 Hi DO: 615
Fraction of strain at slow rata: 0.666 Fraction of strain at slow rate: 0.334 Fraction of strain at slow rate: 0.347
E G
Air: 5,261 Air: - Air: 5,139
PWR: - PWR: - PWR: -
Hi DO: 545 Hi DO: 1,935 Hi DO: 615; 553
Fraction of strain at slow rate: 0.167 Fraction of strain at slow rate: 0.170 Fraction of strain at slow rate: 0.084
Air: 4,087
VVV
Air: 4,122
K
Air: 4,105
PWR: - PWR: PWR: -
Hi DO: 1,649;2,080 Hi DO: 888 Hi DO: 2,093
Figure lO--Fatigue life of AlO6-Gr B carbon steel at 288~ and O.75% strain range in
air and water environments under different loading waveforms
A 1 0 6 - G r B and A 3 3 3 - G r 6 CSs is plotted as a function of the fraction of loading strain at

slow strain rate in Fig. 12 [5-7,10]. Open symbols indicate tests where the slow portions
occurred near the m a x i m u m tensile strain. Closed symbols indicate tests where the slow
portions occurred near the m a x i m u m compressive strain. In Fig. 11, if the relative
damage were totally independent of strain amplitude, fatigue life should decrease linearly
from A to C along the chain-dot line. Instead, the results indicate that the relative
damage due to slow strain rate is independent of strain amplitude once the amplitude
exceeds the threshold value. The threshold strain range is 0.36 % for A 1 0 6 - G r B steel; a
value of 0.25% was assumed for A 3 3 3 - G r 6 steel. Loading histories with slow strain rate
applied near m a x i m u m compressive strain (i.e., waveforms D, F, H, or K) produce no
damage (line AD) until the fraction of the strain is sufficiently large that slow strain rates
are occurring for strain amplitudes greater than the threshold. In contrast, loading
histories with slow strain rate applied near the m a x i m u m tensile strain (i.e., waveforms C,
E, G, or J) show continuous decreases in life (line AB) and then saturation when a portion
of the slow strain rate occurs at amplitudes below the threshold value (line BC). For
C H O P R A A N D S H A C K ON LWR E N V I R O N M E N T S 259
,,, i , , , i , , , i , , , i , '(a )
--
104
f
I
- Q - - I O . . . . . . . . . . .O
Average Life in Air J
~
s
Average Life in PWR Water
....
A
__El
9
[]
. . . . . . . . . . . . . . . . . . . .
9 Average Lifein Air
.',=-r A I, O
J103
~ ._~.__. . .~_t_
i
. . ~. . . . . . . . . . . . D" .......................
O
"- ".
A 't--" ~ : 2 - - - ' ~ -~-
t~ A~ o.6% - " -Z ..... _--__

LI_ ,~ ~4 =0.75% B <> ! O IHI Air B ~ - 0 25~
O Air Eth = 0.36% F A IHI 8 p p m DO th- . to
A PWR [- O IHI 0.8 ppm DO
[] IHI 0.8 ppm DO [] ANL Air
k ~7 ANLO.8ppm DO
lo2 , ?, ,AN,Lp.8, pp,%O9` I,,, I,, L~_ i i i ~ i i I ~ i i i ~ i i I i i i
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8

Fraction of Strain at Slow Fraction of Strain at Slow
Strain Rate Strain Rate
Figure 11 Fatigue life of(a) AIO6-Gr B and (b) A333-Gr 6 steels at 288~ tested with
waveforms where slow strain rate is applied during part of tensile loading
cycle. Slow strain rate (0.004%/s) occurred either near peak tensile strain
(open symbols) or near peak compressive strain (closed symbols). Fast
strain rate was 0.4%/s in all tests. ANL: Argonne National Laboratory and
IHI: lshikawajima-Harima Heavy Industries Co. Japan
A 1 0 6 - G r B steel, the decrease in fatigue life follows line ABC when a slow rate occurs
near the maximum tensile strain and line ADC when it occurs near maximum
compressive strain.
The A333-Gr 6 steel exhibits a somewhat different trend. For example, a slow
strain rate near peak compressive strain appears to cause a significant reduction in fatigue
life, while as discussed previously, slow strain rate had a significant effect on fatigue life
of A 1 0 6 - G r B steel only when they occurred at strains greater than the threshold strain.
For this heat of A333-Gr 6 CS, a threshold strain for environmental effects has not been
observed for tests in high-DO water at 288~ and 0.6% strain amplitude, i.e., fatigue
damage was independent of strain amplitude[10]. The apparent disagreement may be
attributed to the effect of strain rate on fatigue life. This heat exhibits a strain rate effect
in air, e.g., fatigue life of the steel in air decreased =20% when the strain rate decreases
from 0.4 to 0.004 %/s [7]. The cyclic hardening behavior of the steel is also quite
different than that of the A106-Gr B steel. In Fig. 11, the decrease in fatigue life from A
to A' is most likely caused by a strain rate effect that is independent of the environment.
If the hypothesis that each portion of the loading cycle above the threshold strain is
equally damaging is valid, the decrease in fatigue life due to environmental effects should
follow line A BC when a slow rate is applied near peak tensile strain, and line A'DC when
it is applied near peak compressive strain. This behavior is consistent with the s l i p -
dissolution model [22], i.e., the applied strain must exceed a threshold value to rupture
the passive surface film in order for environmental effects to occur.
104
~ ' ' ! .... = .... I .... ! .... ! .... ! ....
A333-Gr 6 Carbon Steel Tube specimen; 3-ram wall A333-LGr 6 carbon Steel Temperature
: e a = 0.6%;'c = 0.002 %Is
i S = 0.012 wt.%; 130 = 1 ppm Tube s~oecimen;:l-mm wall O: Cons:rant
a = 0,6%; c = 0002 %Is : /x In ph:ase
S = 0.0"~2 wt.%; DO = 1 ppm ! 9 Out ~t phase
~ 1 03 ....................... , .......... qr----:------! ......................................

........... ~ .......... 6 ............ !-----*----i ........................... i ...........
_.1
}
Temperature ~ --~. : : A t
u- o : Constant : i
102 . ,,, t. phase ........... ! .......... :: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................................... :.............. ~.......... O ........ a i ............
9 Out of phase i
50 100 150 200 250 300 350 50 100 150 200 250 300 350
Temperature (~ Temperature (~
Figure 12--Effect of varying temperature on fatigue life of A333-Gr 6 carbon steel
Temperature
Fatigue tests have been conducted on tube specimens (1 or 3 mm wall thickness) of

A 3 3 3 - G r 6 carbon steel in oxygenated water under combined mechanical and thermal
cycling [ 11]. Two sequences were selected for temperature cycling: an in-phase
sequence in which temperature cycling was synchronized with mechanical strain cycling,
and another sequence in which temperature and strain were out of phase, i.e., maximum
temperature occurred at minimum strain level and vice-versa. Three temperature ranges,
50-290~ 50-200~ and 200-290~ were selected for the tests. The results are shown
in Fig. 12. An average temperature is used for the thermal cycling tests. Because
environmental effects on fatigue life are moderate and independent of temperature below
150~ the temperature for the tests that were cycled in the range of 50-290~ or 50-
200~ was determined as the average of 150~ and the maximum temperature.
The results of constant temperature tests are consistent with the results in Fig. 5 and
confirm that environmental effects on fatigue life are minimal at temperatures below
150~ The results also indicate that the fatigue life for in-phase temperature cycling is
comparable to that for out-of-phase cycling. At first glance, these results are somewhat
surprising. If we consider that the tensile-loading cycle is primarily responsible for
environmentally assisted reduction in fatigue life and that the applied strain must be
above a minimum threshold value for environmental effects to occur, then life for the
out--of-phase tests should be longer than for the in-phase tests, because applied strains
above the threshold strain occur at temperatures above 150~ for in-phase tests, whereas
they occur at temperatures below 150~ for the out--of-phase tests. If environmental
effects on fatigue life are considered to be minimal at temperatures < 150~ and at strain
levels <0.25 %, the average temperatures for the out--of-phase tests at 50-290~ 5 0 -
200~ and 200--290~ temperature ranges should be 195, 160, and 236~ respectively,
instead of 220, 175, and 245~ as plotted in Fig. 12. The fatigue lives of out-of-phase
tests should be at least 50% higher than those of the in-phase tests.
The nearly identical fatigue lives for the two sequences suggest that environmental
effects can occur at strain levels below the threshold strain. However, the results may be
explained by considering the effect of compressive-loading cycle on fatigue life. The
fatigue data suggest that a slow strain rate during the compressive-loading cycle could
also decrease fatigue life, although the effect of slow strain rate during a compressive
cycle is smaller than that during a tensile cycle [5,10]. The thermal cycling test results
shown in Fig. 12 were obtained with a triangular waveform. For out-of-phase tests,
although maximum temperatures occur at strain levels that are below the threshold value
for the tensile-loading cycle, they occur at maximum strain levels for the compressive-
loading cycle. The contribution of compressive loading cycle on fatigue life may result
in nearly the same fatigue life for in-phase and out-of-phase tests. For in-phase tests,
maximum temperatures occur at strain levels that are below the threshold value for the
compressive-loading cycle; contribution of compressive cycle on fatigue life would be
negligible. However, the decrease in fatigue life because of a slow strain rate during
compressive-loading cycle is difficult to reconcile in terms of the slip-dissolution model.
Strain Amplitude
The fatigue S-N curves specify, for a given strain or stress amplitude, the number
of cycles needed to form an "engineering" crack (e.g., a 3-ram-deep crack). These
allowable number of cycles may be divided into two stages: cycles for formation of
microcracks ( a few micrometers deep) on the surface, and cycles for propagation of the
shallow surface cracks to an engineering size. The reduction in fatigue life in LWR
environments may arise from a decrease in the period for formation of surface cracks
and/or an increase in growth rates of the microcracks. The former is quite sensitive to
applied strain amplitude.
The fatigue crack growth behavior of ferritic steels in high-temperature oxygenated

water and the effects of sulfur content and loading rate are well known [23-27].
Dissolution of MnS inclusions changes the water chemistry near the crack tip, making it
more aggressive. This results in enhanced crack growth rates because either (a) the
dissolved sulfides decrease the repassivation rate, which increases the amount of metal
dissolution for a given oxide rupture rate [23]; or (b) the dissolved sulfide poisons the
recombination of H atoms liberated by corrosion, which enhances H uptake by the steel at
the crack tip [27]. In addition to the effects of environment on crack growth, the water
environment may also enhance crack nucleation. For example, corrosion pits or cavities
produced by dissolution of MnS inclusions can act as sites for nucleation of fatigue
cracks.
All fatigue specimens tested in water show surface micropitting. The specimens
also contain an abundance of surface cracks, their surface length may vary from <10 to
several hundred micrometers. These cracks may consist of several cracks that formed at
different sites and then merged, or they may represent a single crack. A detailed
evaluation of the test specimens did not show any evidence that fatigue cracks form
preferentially at the micropits [28]. Examination of the fatigue specimens indicates that
irrespective of environment, cracks in carbon and low-alloy steels form along slip bands,
carbide particles, or at the ferrite/peaflite phase boundaries. The cracking frequency,
defined as the number of cracks along longitudinal sections of the gauge length, for
fatigue specimens tested in different environments has also been measured [28]. The
results show that environment has no effect on the frequency of cracking. For similar
loading conditions, the number of cracks in the specimens tested in air and oxygenated
water with 0.8 ppm DO are identical, although fatigue life in water is lower by a factor of
=8. If the reduction in life is due to an enhancement in the formation of surface
microcracks, the specimens tested in high DO water should show more surface cracks.
Exploratory tests have also been conducted to evaluate the contributions of

environment to the formation of surface microcracks. Figure 13 shows the fatigue life of
A106-Gr B steel in air (dashed line) and in high-DO water at 0.4 and 0.004%/s strain
rates (circle and diamond symbols, respectively). Fatigue tests were conducted on
10.0
........ ' ........ ~ ........ ' ' ' 'S't';ain ' r a t e ' s . . . . . . . . . . . . !
288 ~ S: 0,004 *MS F: 0.4 *tcJs~
0.6-0.8 ppm DO
O F/F
~f O S/F
288~ Air V Preoxidized
then F/F in air Figure 1 3 -
cr 1.0
\,,/ s , F toho,eoo, Environmental effects on formation of
surface microcracks. Preoxidized
~ . [] 570 cycles S/F
.~_ then FIF in air specimens were exposed at 288~ for
30-100 h in water with 0.6-0.8 ppm DO.
x Preoxidized then
F/F in ~10 ppb DO ~ " ......
o
+ Preoxidized then
SIF in <10 ppb DO
~ . . i ..... ,.~ , ....... I , ,,,,.d i llmld i hlu
0.1
1 01 1 02 1 03 1 04 1 05 1 06 1 07
Cycles to Failure, N2 5
specimens that were preexposed at 288~ for 30-100 h in water with 0.6-0.8 ppm DO
and then tested either in air or <10 ppb DO water. At 0.4% strain range, nearly half the
fatigue life may be spent in the formation of surface cracks. Fatigue lives of the
preoxidized specimens are identical to those of nonoxidized specimens; life would be
expected to decrease if surface micropits facilitate surface cracking. Preoxidized
specimens of A533-Gr B low-alloy steel also show a similar behavior. Sequential tests
have been conducted to check the possibility that both the high DO and slow strain rate
are required to influence surface cracking. Fatigue specimens were first tested in high-
DO water at 0.4% strain range and 0.004%/s strain rate for 570 cycles (=25% of the life
at these loading conditions) and then tested in either air or high-DO water at 0.4%/s
strain rate. Fatigue life of these tests should be lower if formation of surface cracks
contributes in any way to environmental effects. Once again, no reduction in life is
observed; the tests yield a CUF value of >1. These results suggest that the reduction in
fatigue life in high-DO water is primarily due to environmental effects on fatigue crack
propagation.
CONCLUSIONS
The available data on the effects of various material and loading variables such as
steel type, orientation, dissolved oxygen level, strain range, strain rate, loading waveform,
and surface morphology on the fatigue life of carbon and low-alloy steels in air and water
environments have been summarized. In air, the fatigue life of carbon and low-alloy
steels depends on steel type, temperature, orientation (rolling or transverse), and strain
rate. The fatigue life of CSs is a factor of =1.5 lower than that of LASs. For both steels,
fatigue life decreases with increase in temperature up to 320~ Strain rate and
orientation are important in some heats of CSs and LASs. For these heats, fatigue life
decreases with decreasing strain rate. Also, the fatigue properties in transverse
orientation may be inferior to those in the rolling orientation. Structural factors, e.g.,
distribution and morphology of sulfides, are responsible for the poor fatigue resistance in
transverse orientations. In an air environment, the fatigue S - N curves for carbon and
low-alloy steels indicate significant heat-heat-variation. At 288~ fatigue life may vary
up to a factor of 5 above or below the mean value. The results also indicate that the
ASME mean curve for CSs is somewhat conservative with respect to the experimental
data; at strain amplitudes <0.2%, the mean curve predicts significantly lower fatigue lives
than those observed experimentally. The ASME mean curve for LASs shows good
agreement with the experimental data.
Both carbon and low-alloy steels exhibit dynamic strain aging at temperatures
between 200-370~ which leads to enhanced cyclic hardening, a secondary hardening
stage, and negative strain rate sensitivity, i.e., cyclic stress increases with decreases in
strain rate. The temperature range and extent of dynamic strain aging vary with
compositional and structural factors. The large variation in fatigue life that has been
observed in the tests at 288~ may be due to differences in the extent of dynamic strain
aging in the steel.
The available fatigue strain vs. life (S-N) data in LWR environments suggest that
the reduction in fatigue life in high-DO water is primarily due to environmental effects
on the growth of shallow cracks. The results show that environmental effects on fatigue
life are significant when five conditions are satisfied simuItaneously, viz., applied strain
range, temperature, dissolved oxygen in water, and sulfur content in steel are above a
minimum threshold level, and strain rate is below a critical value. Although the structure
and cyclic-hardening behavior of carbon and low-alloy steels are distinctly different,
there is little or no difference in susceptibility to environmental degradation of fatigue life
of these steels. The fatigue life of carbon and low-alloy steels in air and L W R
environments can be estimated from the statistical models.
For both steels, the fatigue data indicate threshold values of 150~ for temperature
and 0.05 ppm for DO, above which fatigue life is decreased significantly in L W R
environments if the other three threshold conditions are also satisfied. At 150-320~
fatigue life decreases linearly with temperature. The effect of DO content on life
saturates at 0.5 ppm; higher DO levels do not cause further decreases in fatigue life. For
DO levels between 0.05 and 0.5 ppm, the fatigue life may be represented equally well by
a logarithmic dependence of life on DO content. The data indicate a maximum threshold
value of 1%/s for strain rate below which environmental effects on life are significant.
When the threshold conditions for all five parameters are satisfied, fatigue life decreases
logarithmically with decreasing strain rate. For some heats of carbon and low-alloy
steels, the effect of strain rate on life saturates at =0.001%/s strain rate. The existing
fatigue data are inadequate to establish a lower threshold for sulfur content below which
environmental effects are unimportant or to define the saturation level. The minimum
threshold value for strain also can not be defined from the existing fatigue data. Most
likely it depends on material parameters, e.g., size and distribution of sulfides, and on
service parameters, e.g., temperature, strain rate, and DO level in water. Limited data
suggest that the threshold strain is either equal to or slightly greater than the endurance
limit of the material.
Only a moderate decrease in fatigue life is observed in L W R environments when

any one of the threshold conditions is not satisfied, e.g., at temperatures <_150~ or in
l o w - D O PWR environments (<0.05 ppm DO), or for low-sulfur steels (containing
<0.003 wt.% sulfur). Under these conditions, life in water is 30-50% lower than that in
air. The effects of orientation and strain rate are similar to those in air. For example, in a
PWR environment at 288~ heats of steel that are sensitive to strain rate also show a
decrease in life as strain rate decreases, whereas heats that are not sensitive to strain rate
do not show a change in life even when strain rate decreases by three orders of
magnitude.
In L W R environments, when all of the threshold conditions are satisfied, both the
tensile- and compressive-loading cycles are responsible for environmentally assisted
reduction in fatigue life, although the effect of the compressive cycle is smaller than that
of the tensile cycle. For loading cycles in which strain rate and temperature also vary
with strain, the results indicate that environmental effects on fatigue life occur only when
the five threshold conditions are satisfied. For example, a slow strain rate is effective in
decreasing fatigue life only when it occurs at strains greater than the threshold strain.
Also, slow strain rates applied during any portion of the loading cycle above the
minimum threshold strain are equally effective in decreasing life. The fatigue S-N
behavior for loading cycles where both temperature and strain change may be represented
by an average temperature, determined from only that portion of the cycle where all five
threshold conditions are satisfied. Limited data suggest that a linear summation of
individual usage factors to determine CUF for a location is applicable for LWR
environments; the results of sequential loading tests yield CUF values of >1, i.e., the
linear damage model is conservative. However, additional data are needed to verify these
results.
ACKNOWLEDGMENTS
This work was supported by the Office of Nuclear Regulatory Research of the U.S.
Nuclear Regulatory Commission, FIN Number A2212; Program Manager: Dr. M. McNeil
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Hiroshi Kanasaki, I Akihiko Hirano, 2 Kunihiro Iida, 3 Yasuhide Asada, 4
CORROSION FATIGUE BEHAVIOR AND LIFE PREDICTION METHOD UNDER

CHANGING TEMPERATURE CONDITION
REFERENCE: Kanasaki, H., Hirano, A., Iida, K., and Asada, Y., ~ C o r r o -
sion F a t i g u e B e h a v i o r and Life P r e d i c t i o n Method under changing
Temperature C o n d i t i o n , " Effects of the Environment on the Initiation
of Crack Growth ~, ASTM STP 1298, W.A. Van Der Sluys, R.S. Piascik, and
R.Zawierucha, Eds., American Society for Testing and Materials, 1997.
ABSTRACT: Axially strain controlled low cycle fatigue tests of a car-

bon steel in oxygenated high temperature water were carried out under
changing temperature conditions. Two patterns of triangular wave were
selected for temperature cycling. One was in-phase pattern synchronizing
with strain cycling and the other was an out-of-phase pattern in which
temperature was changed in anti-phase to the strain cycling. The fa-
tigue life under changing temperature condition was in the range of the
fatigue life under various constant temperature within the range of the
changing temperature. The fatigue life of in-phase pattern was equiva-
lent to that of out-of-phase pattern.
The corrosion fatigue life prediction method was proposed for
changing temperature condition, and was based on the assumption that the
fatigue damage increased in linear proportion to increment of strain
during cycling. The fatigue life predicted by this method was in good
agreement with the test results.
KEYWORD: corrosion fatigue, high temperature water, carbon steel,

changing temperature condition, life prediction
Recently it has been recognized that the fatigue life of carbon and
low alloy steels is affected by strain rate,temperature and dissolved
oxygen in high temperature water. In this regard a good many data ob-
tained by environmental fatigue tests of carbon and low alloy steels
have been released and the quantative equations of fatigue life taking
account for these three parameters were proposed [!], [~]. In these paper,
higher temperature resulted in shorter fatigue life in oxygenated high
temperature water. However, almost all the data were obtained at con-
stant temperature, and they were difficult to be applied for evaluation
of the strain cycling behavior of actual plant components, in which tem-
iSenior research engineer, Takasago R&D Center, Mitubishi Heavy

Industries Ltd., 2-1-1, Shinhama, Arai-eho, Takasago, Hyogo, 676 Japan
2Researcher, Hitachi Laboratory, Hitachi, Ltd.,l-l, Saiwai-cho

3-chome, Hitachi, Ibaraki, 316 Japan
3Professor Emeritus of the University of Tokyo, Japan Power Engi-

neering and Inspection Corporation, 1-5-11, Akasaka, Minato-ku, Tokyo,
107 Japan
4Professor, Department of Mechanical Engineer, University of Tokyo,

7-3-1, Hongo, Bunkyo-ku, Tokyo, 113 Japan
267
Copyright
Copyright 9 by ASTM
1997 byInt'l
ASTM(all rights reserved); Fri Dec 30 www.astm.org
International 21:53:51 EST 2011
268 EFFECTS OF THE ENVIRONMENT ON LNtTLATION OF CRACK GROWTH
p e r a t u r e is g e n e r a l l y not c o n s t a n t b u t i r r e g u l a r l y changing. For evalu-

a t i o n u n d e r a c h a n g i n g temperature condition, a q u e s t i o n is w h e t h e r a
s i n g l e t e m p e r a t u r e can be used in the e v a l u a t i o n and if so, h o w to s e l e c t
this t e m p e r a t u r e . Therefore, t h e r e was a s t r o n g need for a c c u m u l a t i n g
m o r e data on the e f f e c t of t e m p e r a t u r e c h a n g e in e n v i r o n m e n t a l c o n d i t i o n
to c o n s i d e r the a c c u r a t e life p r e d i c t i o n m e t h o d u n d e r c h a n g i n g tempera-
ture condition.
A c c o r d i n g l y an e x p e r i m e n t a l s t u d y was c a r r i e d out to d e t e r m i n e ef-
fects of t e m p e r a t u r e c h a n g e s y n c h r o n o u s l y c o m b i n e d w i t h m e c h a n i c a l cy-
c l i n g in the m a n n e r of i n - p h a s e and o u t - o f - p h a s e and the f a t i g u e life
p r e d i c t i o n m e t h o d u n d e r t e m p e r a t u r e c h a n g i n g c o n d i t i o n was proposed.
A t e n t a t i v e r e s u l t s of this s t u d y was r e p o r t e d A S M E / J S M E J o i n t PVP Con-
f e r e n c e of 1995 [!]. All the data w e r e e x a m i n e d and final c o n c l u s i o n s
w e r e s u m m a r i z e d in this paper.
EXPERIMENTAL METHOD
Material
B e c a u s e e f f e c t s of t e m p e r a t u r e c h a n g e on f a t i g u e life w e r e investi-
g a t e d in the p r e s e n t study, a m a t e r i a l w h i c h has r e m a r k a b l e d e p e n d e n c y
of f a t i g u e life a g a i n s t test t e m p e r a t u r e was d e s i r a b l e as a m a t e r i a l to
be tested. A c a r b o n steel pipe of JIS G 3 4 5 5 S T S 4 1 0 ( e q u i v a l e n t to ASME
SA333 Gr6) was s e l e c t e d in the p r e s e n t s t u d y r e f e r r i n g to the results of
a p r e v i o u s s t u d y [i], in w h i c h the STS410 s h o w e d r e m a r k a b l e i n f l u e n c e of
t e m p e r a t u r e on f a t i g u e life in o x y g e n a t e d water.
The c h e m i c a l c o m p o s i t i o n and the m e c h a n i c a l p r o p e r t i e s of the ma-
terial are l i s t e d in T A B L E ~ and T A B L E 2, respectively.
Specimens
T w o t y p e s of h o l l o w c y l i n d e r specimens, of w h i c h c o n f i g u r a t i o n s are
shown in FIG. i, w e r e u s e d for f a t i g u e tests. T h e o u t e r d i a m e t e r s of b o t h
s p e c i m e n s at test s e c t i o n are 12 mm, and the t h i c k n e s s is 1 m m and 3 mm,
respectively.
The s p e c i m e n s w e r e m a c h i n e d from the m i d - t h i c k n e s s l o c a t i o n of the
T A B L E 1 -- C h e m i c a l c o m p o s i t i o n of the test m a t e r i a l (wt.%)
C Si Mn P S
0.21 0.31 1.14 0.016 0.012
T A B L E 2 -- M e c h a n i c a l p r o p e r t i e s of the t e s t m a t e r i a l
0.2% YS UTS Elongation

(MPa) (MPa) (%)
383 549 35
15
R2o
R40
160
(1) t=3mm
(2) t=l|
F I G . I -- Shapes and d i m e n s i o n s of t e s t s p e c i m e n
K A N A S A K I ET AL. O N C O R R O S I O N FATIGUE BEHAVIOR 269
p i p e in the a s - r e c e i v e d condition, w i t h the a x i s c o i n c i d i n g w i t h t h a t of

the pipe. The o u t e r and inner s u r f a c e of the s p e c i m e n w e r e p o l l i s h e d in
the as same d i r e c t i o n as the s p e c i m e n w i t h e m e r y paper.
Test apparatus
In the p r e s e n t study, the t e m p e r a t u r e of the t e s t s e c t i o n of a spec-

imen s h o u l d be c h a n g e d s y n c h r o n o u s l y w i t h the m e c h a n i c a l s t r a i n cycle.
F a t i g u e tests in h i g h t e m p e r a t u r e w a t e r are u s u a l l y c a r r i e d o u t in
an autoclave, b u t it is d i f f i c u l t to c h a n g e the t e m p e r a t u r e of a speci-
m e n w i t h i n a s h o r t p e r i o d in this method. In the p r e s e n t s t u d y an auto-
c l a v e was not used, and the m e t h o d u s i n g the h o l l o w - c y l i n d e r s p e c i m e n
was a p p l i e d as s h o w n in FIG 2. The h o l l o w c y l i n d e r s p e c i m e n w a s p r e s s u r -
ized by hot w a t e r h e a t e d from r o o m t e m p e r a t u r e b y the h e a t e r to p r o d u c e
the d e s i g n a t e d t e m p e r a t u r e change. The t e m p e r a t u r e of w a t e r and the
s p e c i m e n s u r f a c e t e m p e r a t u r e at t e s t s e c t i o n w e r e m o n i t o r e d b y t h e r m o -
couples, of w h i c h e l e c t r o m o t i v e forces w e r e t r a n s m i t t e d to the f e e d b a c k
c i r c u i t of the t e m p e r a t u r e c o n t r o l l i n g d e v i c e c o n n e c t e d to the heater.
Monitor I I
Wat~--~
er
Ar 8L_
or 0,}'~
N,VVI '~
~ Pressure
Induction
heatin, co,
U
Upper grip -t_~r
Ill
89176
ell/Thermocouple
~ Specimen
~Extensometer
9ow.r 7111" The

mocou0,.
3ressure o
~i 6"E..~
Pump
~ If_Control
Do. l Heater ir~"~ ~
FIG.2 -- O u t l i n e of a p p a r a t u s for f a t i g u e t e s t
Upper g ~ i 9 ~ 0 -- ring
Induction ~ [ ~ Water out

heating~ -~-LIIIJZZi::::V--~Thermocouple
coil ol ~ I t ~ Specirnen
~Thermocouple
,~ Water in
Lower Grip LIJIlll l
FIG.3 -- V e r t i c a l s e c t i o n of a p p a r a t u s
The s p e c i m e n was s u b s i d a r i l y h e a t e d up by an i n d u c t i o n coil so as to m a k e

the t e m p e r a t u r e d i s t r i b u t i o n t h r o u g h the s p e c i m e n t h i c k n e s s as u n i f o r m
as p o s s i b l e w h e n the s p e c i m e n w i t h t h i c k n e s s of 3mm was tested. FIG.3
i l l u s t r a t e s a vertical, s e c t i o n a l v i e w of s p e c i m e n set up w i t h h e a t i n g
apparatus. The p r e s s u r i z e d w a t e r was s e a l e d w i t h m e t a l i c O - r i n g s b e t w e e n
b o t h ends of the s p e c i m e n and the grips.
As an example, c o m p a r a t i v e t r a c e s of the t e m p e r a t u r e c h a n g e of the
p r e s s u r i z e d w a t e r and the t e m p e r a t u r e c h a n g e of the s p e c i m e n s u r f a c e at
test s e c t i o n of a s p e c i m e n are s h o w n in FIG.4. The t e m p e r a t u r e range was
50~ to 350~ and the p a t t e r n of t e m p e r a t u r e c h a n g e was t r i a n g u l a r w a v e
w i t h a p e r i o d of 20 minutes. The o r i g i n s of b o t h t e m p e r a t u r e t r a c e s are
r e l a t i v e l y s h i f t e d in FIG.4 for easy observation of temperature profiles.
The m a x i m u m d i f f e r e n c e b e t w e e n b o t h t e m p e r a t u r e s was a b o u t 5~ w h i c h is
a d e q u a t e for test p u r p o s e s w i t h a c a p a b i l i t y of t e m p e r a t u r e c y c l i n g a
test s p e c i m e n w i t h a p e r i o d of 20 m i n u t e s and t e m p e r a t u r e r a n g e of 300~
Axial s t r a i n c o n t r o l l e d f a t i g u e tests w e r e c a r r i e d out w i t h an ex-
t e n s o m e t e r a t t a c h e d on the o u t e r s u r f a c e of the specimen. The total
waterat test
section outersurfaceof
400~ ~ /~estspecimen
A 300
4 200
I- 100 20rnin.
0U
FIG.4 -- T e m p e r a t u r e c h a n g e m e a s u r e d by t h e r m o c o u p l e
temperatureat outersurfaceof
! lstreste~t speiimen
0.
t--
20min.
FIG. 5 -- Stress measurement during temperature cycling when

mechanical strain controlled to be constant
KANASAKI ET AL. ON CORROSION FATIGUE BEHAVIOR 271
e l o n g a t i o n m e a s u r e d w i t h the e x t e n s o m e t e r i n c l u d e d t h e r m a l e x p a n s i o n of
the specimen, w h i c h was g e n e r a t e d d u r i n g t h e r m a l cycle. For the p u r p o s e
of e l i m i n a t i n g t h e r m a l e x p a n s i o n component, a s p e c i a l function, w h i c h
c o u l d c a n c e l the t h e r m a l e x p a n s i o n on the b a s i s of m e a s u r e d t e m p e r a t u r e
and c a l i b r a t e d r e l a t i o n b e t w e e n t e m p e r a t u r e and t h e r m a l expansion, was
f i t t e d to the e x t e n s i o n m e a s u r i n g system. In o r d e r to c o n f i r m the per-
f o r m a n c e of this function, the s t r e s s c h a n g e in the s p e c i m e n was mea-
s u r e d w h e n the t e m p e r a t u r e was c y c l i c a l l y changed, w h i l e t h e m e c h a n i c a l
s t r a i n was c o n s t a n t l y k e p t 0%. If this f u n c t i o n o p e r a t e s e f f i c i e n t l y ,
the c h a n g e of the stress will not occur. An e x a m p l e of s t r e s s m e a s u r e -
m e n t s is s h o w n in FIG.5. In this case, t e m p e r a t u r e was c h a n g e d b e t w e e n
50~ and 350~ cyclically. The o b s e r v e d s t r e s s a m p l i t u d e was 6 MPa, t h a t
c o r r e s p o n d s to s t r a i n a m p l i t u d e of 0.003% for Y o u n g ' s m o d u l u s of 183 GPa.
This v e r i f i e d that m e c h a n i c a l s t r a i n c o n t r o l l e d f a t i g u e t e s t s c o u l d be
p e r f o r m e d w i t h g o o d a c c u r a c y e v e n u n d e r c h a n g i n g t e m p e r a t u r e condition.
Fatique test
F u l l y r e v e r s e d axial s t r a i n c o n t r o l l e d f a t i g u e tests w e r e c a r r i e d
out in p u r e w a t e r c o n t a i n i n g 1 p p m oxygen. The f l o w r a t e of t e s t w a t e r
was a b o u t 30 ~/hr and a v e r a g e f l u i d v e l o c i t y was 0 . 1 2 m / s e c in 3mm thick-
ness s p e c i m e n and 0 . 1 m / s e c in i m m t h i c k n e s s specimen. The w a v e s h a p e of
stain c y c l i n g was triangular, and s t r a i n r a t e was a l w a y s 0 . 0 0 2 % / s e c in
the p r e s e n t tests. Two p a t t e r n s of t r i a n g u l a r w a v e w e r e s e l e c t e d for
t e m p e r a t u r e c y c l i n g as s h o w n in FIG.6. One w a s an i n - p h a s e p a t t e r n w h i c h
was s y n c h r o n i z e d w i t h m e c h a n i c a l s t r a i n c y c l i n g and the o t h e r w a s an
o u t - o f - p h a s e pattern, in w h i c h t e m p e r a t u r e was c h a n g e d in a n t i - p h a s e to
the m e c h a n i c a l strain. T h r e e t e m p e r a t u r e ranges, 50~ to 290~ 50~ t o
200~ and 2 0 0 ~ to 2 9 0 ~ w e r e s e l e c t e d for the test.
F a t i g u e tests u n d e r c o n s t a n t t e m p e r a t u r e c o n d i t i o n w e r e a l s o car-
r i e d out at a t e m p e r a t u r e r a n g i n g from 50~ to 290~
~" Temperature Strain

0.6
v
o _
= 0 o
-0.6 .... _o.~
(1) In -- phase o
~
m
( 2 ) O u t - of - phase o
~
m
FIG.6 -- P a t t e r n s of t e m p e r a t u r e c h a n g e
Fig.7 -- E x a m p l e of f r a c t u r e d s u r f a c e of t e s t e d s p e c i m e n
D a r k areas w e r e p r o d u c t e d in h i g h t e m p e r a t u r e w a t e r
and b r i g h t aras w e r e p r o d u c e d in air a f t e r test.
Because of the water environment on the inside surface of the hollow

cylinder specimen, fatigue cracks initiated on the inner surface, propa-
gated toward outer surface, and finally penetrated through the thickness
o f t h e w a l l , a s s h o w n in F I G . 7 . F a t i g u e l i f e w a s d e f i n e d as NLEAK, w h i c h
was the number of cycles to the full thickness penetration of a c r a c k in
both constant temperature test and changing temperature test.
TEST RESULT AND DISCUSSION
Fatigue tests at constant temperature
TABLE 3 -- R e s u l t s of fatique tests at constant temperature
Temp. DO Strain rate (%/s) s O. NL~ ~ thickness

(~ (ppm) ~',' ~l; {%/ {M~a 1 (c~cles~ Imm 1
50 364 994 3
367 787 1
i00 354 816 3
364 745 1
150 380 1487 3
387 950 1
200 426 611 3
i 0.002 0.002 0.6 427 389 1
486 225 3
250 416 i01 1
456 152 1
475 162 3
481 80 1
290 481 108 1
476 175 3
195 3
.... i .... i .... i .... i .... i ....
STS410
C o n s t a n t temp. I
I
DO=lpm
O ~=0.002%/s
A 1000 O 9
Z
O
O t=3mm
9 t = l mm 9 O.
100
| ~ . , i . . . . i . . . . I , . . i I . . . . i , i i
0 50 100 150 200 250 300

T e m p e r a t u r e (~
FIG.8 -- E f f e c t s of temperature on fatigue life
R e s u l t s of f a t i g u e tests at c o n s t a n t t e m p e r a t u r e a r e l i s t e d in
T A B L E 3. ~ in T A B L E 3 was the s t r e s s a m p l i t u d e at N=I/2NLEAK. The rela-
tion b e t w e e n f a t i g u e life NL~ K a n d t e s t t e m p e r a t u r e is s h o w n in FIG.8.
T o t a l s i x t e e n s p e c i m e n s w e r e t e s t e d w h i c h c o n s i s t e d of e i g h t s p e c i m e n s
of e a c h thickness.
F a t i g u e life b e t w e e n 50~ to 1 5 0 ~ was a l m o s t c o n s t a n t and t h a t de-
c r e a s e d w i t h an i n c e a s e of t e m p e r a t u r e a b o v e 200~ p r o m i n a n t e f f e c t of
t e m p e r a t u r e on f a t i g u e life was o b s e r v e d in o x y g e n a t e d w a t e r [1],[2],[4]
a n d f a t i g u e life at 2 9 0 ~ was a b o u t one s i x t h of t h a t at 50~ This
t e n d e n c y a g a i n s t t e m p e r a t u r e was o b s e r v e d in 3mm and I m m t h i c n e s s speci-
m e n s a l t h o u g h the f a t i g u e life of 3mm t h i c k n e s s s p e c i m e n w a s a b o u t 1.5
times t h a t of imm t h i c k n e s s specimen.
T A B L E 4 -- R e s u l t s of f a t i q u e t e s t s u n d e r c h a n q i n q t e m p e r a t u r e c o n d i t i o n
Temperature (~ DO Strain rate(%/s) s Ua NLmK thickness

min. max. Pattern (ppm) e, ~ (%) (Mpa) (cycles) (mm)
in 580 403 3
50 290 phase 472 195 1
out of 523 361 3
phase 494 211 1
in 427 1297 3
50 200 phase 1 0.002 0.002 0.6 422 750 1
out of 410 962 3
phase 418 776 1
in 496 218 3
200 290 phase 486 176 1
out of 485 213 3
phase 481 131 1
Fatigue tests under chanqinq temperature condition
R e s u l t s of f a t i g u e tests u n d e r c h a n g i n g t e m p e r a t u r e c o n d i t i o n are
l i s t e d in T A B L E 4. T o t a l t w e l v e s p e c i m e n s w e r e t e s t e d w h i c h c o n s i s t e d of
six s p e c i m e n s of e a c h thickness. C o m p a r i s o n of f a t i g u e life of 3mm
t h i c k n e s s s p e c i m e n b e t w e e n c o n s t a n t and c h a n g i n g t e m p e r a t u r e c o n d i t i o n
is shown in FIG.9. The d i f f e r e n c e of f a t i g u e life b e t w e e n 3mm and i m m
t h i c k n e s s s p e c i m e n was a l s o a b o u t 1.5 times u n d e r c h a n g i n g t e m p e r a t u r e
condition.
F a t i g u e life of t e m p e r a t u r e r a n g e of 50~ to 2 9 0 ~ or 2 0 0 ~ to 2 9 0 ~
was in the r a n g e of f a t i g u e life b e t w e e n t h a t at t h e h i g h e s t t e m p e r a t u r e
and that at the l o w e s t t e m p e r a t u r e in e a c h t e m p e r a t u r e cycling. Fatigue
life of t e m p e r a t u r e r a n g e of 50~ to 2 0 0 ~ w a s b e t w e e n 611 c y c l e s and
1487 c y c l e s w h i c h w e r e the s h o r t e s t a n d l o n g e s t f a t i g u e lives u n d e r
v a r i o u s c o n s t a n t t e m p e r a t u r e w i t h i n t h e r a n g e of t h e c h a n g i n g t e m p e r a -
ture. T h e s e r e s u l t s s h o w e d t h a t f a t i g u e life u n d e r c h a n g i n g t e m p e r a t u r e
was u s u a l l y l o n g e r t h a n t h a t at the h i g h e s t t e m p e r a t u r e in t h e r a n g e of
t e m p e r a t u r e c h a n g e and e v a l u a t i o n w i t h f a t i g u e data at the h i g h e s t tem-
p e r a t u r e of the a c t u a l p l a n t r e s u l t s in c o n s e r v a t i s m .
F a t i g u e life of i n - p h a s e p a t t e r n was e q u i v a l e n t to t h a t of o u t - o f -
p h a s e p a t t e r n in all t e m p e r a t u r e range. An e x p e r i m e n t a l s t u d y on the
e f f e c t s of s t r a i n rate c h a n g e s h o w e d t h a t an i n s e n s i t i v e s t r a i n r a n g e on
e n v i r o n m e n t a l e f f e c t s does not exist.[5] T h e r e s u l t of the p r e s e n t
s t u d y s u p p o r t e d this conclusion, b e c a u s e the m a x i m u m and a v e r a g e tem-
p e r a t u r e in the s e n s i t i v e s t r a i n r a n g e w a s h i g h e r in the i n - p h a s e
p a t t e r n t h a n the o u t - o f - p h a s e p a t t e r n a n d t h e f a t i g u e l i f e of t h e in-
p h a s e p a t t e r n s h o u l d be s h o r t e r t h a n t h a t of the o u t - o f - p h a s e pattern,
if the i n s e n s i t i v e s t r a i n r a n g e on e n v i r o n m e n t a l e f f e c t s e x i s t s near
m i n i m u m strain.
T h e s e t e n d e n c i e s w e r e o b s e r v e d in imm t h i c k n e s s s p e c i m e n as w e l l as
3mm t h i c k n e s s s p e c i m e n as shown in FIG.10.
t=3mm
I STS410 I
DO=I ppm
s
[] ...................... "El
1000
'
t 00 changing temp. (in-phase)
changing temp. (out-of-phase)
r 9 9 - I . . , , I , = i 9 i . . . . i i i i i . . . .
0 50 100 t 50 200 250 300
Temperature (~
FIG.9 -- C o m p a r i s o n of f a t i g u e life b e t w e e n c o n s t a n t and c h a n g i n g

t e m p e r a t u r e c o n d i t i o n (t=3mm)
.... i .... i .... i .... I .... i ....

t=l mm STS410 I
DO= 1ppm
~-0,002%/s I
1000
m=...~-,-=-=~l = = . . . . . , , = = = . . . . -,-,~
?.,
o
9 constant temp. I:R.................I, .......... . ~

100 - ' { 3 - changing temp. (in-phase) I 9
-,-lB.,- changing temp. (out-of-phase) I 9
, , , , i , , , , i ....
, - 9 - i . . . . i . . . . i
50 1O0 150 200 250 300
Temperature (~
F I G . 1 0 -- Comparison of f a t i g u e life b e t w e e n c o n s t a n t and c h a n g i n g

t e m p e r a t u r e c o n d i t i o n (t=imm)
E f f e c t of t h i c k n e s s on f a t i g u e life
The c r a c k p r o p a g a t i o n b e h a v i o r was e x a m i n e d u s i n g the b e a c h - m a r k
method. The t h i c k n e s s of specimen was 3mm, t e m p e r a t u r e was 290~ and

fully r e v e r s e d s t r a i n i n g of 50 cycles and high strain ratio ( g ~ n / E ~ = 0 . 5 )
s t r a i n i n g of 20 cycles w e r e a p p l i e d to the s p e c i m e n a l t e r n a t i n g each
other.
The fatigue life of this specimen was 237 cycles of fully r e v e r s e d
s t r a i n i n g and large three cracks were o b s e r v e d on the f r a c t u r e d surface.
The e x a m p l e of these cracks is shown in FIG.If and four clear beach-
marks w e r e observed. Relation b e t w e e n number of fully r e v e r s e d strain-
ing cycles and crack depth d e t e r m i n e d from the b e a c h - m a r k s is shown in
FIG.12. The fatigue lives of Imm t h i c k n e s s s p e c i m e n are also p l o t t e d at
the v e r t i c a l p o s i t i o n of imm. The results s u g g e s t e d that the crack ini-
tiated at very early stage of fatigue life ,the crack p r o p a g a t i o n life
was d o m i n a n t in the total fatigue life and the d i f f e r e n c e of fatigue
life b e t w e e n imm and 3mm thickness was caused by the d i f f e r e n c e of crack
p r o p a g a t i o n life.
In the p r e s e n t study, the f a t i g u e life o b t a i n e d w i t h im~n t h i c k n e s s
specimen was m u l t i p l i e d by 1.56 w h i c h was an a v e r a g e of the ratio of 3mm
t h i c k n e s s to that of Imm, for c o r r e c t i o n of the effect of thickness.
FIG.II -- B e a c h - m a r k s on f r a c t u r e d s u r f a c e
3,0
2.5 ,-O.- Crack No,2

%- .-A.- Crack No,3 j~" <2
E 2,0 9 Leak {t=lmm) / ,,,~:'~
Q.
cD
1.5
"lD
1.0
O
0.5
0,0
(3 50 100 150 200 250
Number of cycles (cycles)
FIG.12 -- Relation b e t w e e n crack d e p t h and n u m b e r of cycles
Q b s e r v a t i o n of f r a c t u r e d s p e c i m e n s
F r a c t o g r a p h s of the f r a c t u r e d s u r f a c e of 3mm t h i c k n e s s s p e c i m e n s
t e s t e d at 5 0 ~ 1 7 6 and 290~ u n d e r c o n s t a n t t e m p e r a t u r e c o n d i t i o n are
shown in FIG.13. The o b s e r v e d p o s i t i o n was Imm d e e p f r o m the inner sur-
face of the specimen. The c r a c k s u r f a c e m o r p h o l o g y was d e p e n d e d on temp-
erature, that is, q u a s i - c l e a v a g e p a t t e r n at 50~ d u c t i l e s t r i a t i o n s at
150~ and f a n - s h a p e d p a t t e r n at 290~ w e r e observed. The f a n - s h a p e d
pattern, w h i c h was the e v i d e n c e of e n v i r o n m e n t a l a s s i s t e d cracking, in-
d i c a t e d that the c r a c k p r o p a g a t i o n rate was a c c e l e r a t e d and this accel-
e r a t i o n r e s u l t e d in large r e d u c t i o n of f a t i g u e life at 290~ The duc-
tile s t r i a t i o n s i n d i c a t e d small or no a c c e l e r a t i o n of c r a c k p r o p a g a t i o n
rate and r e d u c t i o n of f a t i g u e life at 150~ The f r a c t u r e d s u r f a c e s of
s p e c i m e n s u n d e r c h a n g i n g t e m p e r a t u r e s p e c i m e n s w e r e c o v e r e d w i t h thick
oxide.
P h o t o g r a p h s of the inner s u r f a c e of 3mm t h i c k n e s s s p e c i m e n s t e s t e d
at 50~ 150~ and 290~ under c o n s t a n t t e m p e r a t u r e c o n d i t i o n and t e s t e d
in the t e m p e r a t u r e r a n g e f r o m 50~ to 290~ u n d e r c h a n g i n g t e m p e r a t u r e
c o n d i t i o n are shown in FIG.14. and FIG.15, r e s p e c t i v e l y . The n u m b e r of
cracks was s t r o n g l y d e p e n d e d on t e m p e r a t u r e and p a t t e r n of t e m p e r a t u r e
change. The r e l a t i o n b e t w e e n the n u m b e r of cracks and t e m p e r a t u r e is
s h o w n in FIG.16. The m a x i m u m n u m b e r of cracks was o b s e r v e d at 150~ and
the m i n i m u m
n u m b e r was o b s e r v e d at 290~ u n d e r c o n s t a n t t e m p e r a t u r e . The n u m b e r of
c r a c k s of o u t - o f - p h a s e p a t t e r n was m o r e than that of i n - p h a s e p a t t e r n
u n d e r c h a n g i n g t e m p e r a t u r e condition.
F I G . 1 3 -- F r a c t o g r a p h s of f r a c t u r e d s p e c i m e n s at c o n s t a n t
temperature
The c o m p a r i s o n w i t h the number of cracks and fatigue life in FIG.15

showed that there w e r e no r e l a t i o n b e t w e e n the number of cracks and fa-
tigue life and s u g g e s t e d that t e m p e r a t u r e i n f l u e n c e d crack i n i t i a t i o n in
o x y g e n a t e d w a t e r but crack i n i t i a t i o n life was not d o m i n a n t in total fa-
tigue life as s u g g e s t e d from the r e s u l t b e a c h - m a r k test at 290QC.
FIG.14 -- P h o t o g r a p h s of inner s u r f a c e of specimens at

constant t e m p e r a t u r e
FIG.15 -- P h o t o g r a p h s of inner s u r f a c e of s p e c i m e n s under c h a n g i n g

t e m p e r a t u r e c o n d i t i o n (temperature r a n g e = 5 0 ~ to 290~
NLEAK Num.ofcracks
constant temp. []
10000 in-phase I~'---~ ~ ' - - - ~
out-of-phase I~'---~] ~'--'~
do
~ I000 . . . . . . 4~
E3 ' E}.................. -::- -::::::~'
~oo ~ 4~
Z
~ ...... ~ t
,I
z~E= 10- . . t
10 100 200 300

Temperature(~
FIG.16 -- R e l a t i o n between n u m b e r of c r a c k s and t e m p e r a t u r e
Modified rate approach method
M o d i f i e d r a t e a p p r o a c h m e t h o d is to p r e d i c t t h e f a t i g u e life reduc-
tion f a c t o r u n d e r c h a n g i n g t e m p e r a t u r e , d i s s o l v e d o x y g e n c o n t e n t and
s t r a i n r a t e c o n d i t i o n , Fen' f r o m t h e f a t i g u e l i f e r e d u c t i o n factor, Fen
w h i c h w a s d e v e l o p e d b y H i g u c h i & Iida for the c o n d i t i o n w h e r e t h e s e pa-
r a m e t e r s a r e c o n s t a n t [~]. The m e t h o d was o r i g i n a l l y d e v e l o p e d by A s a d a
a n d i m p r o v e d b a s e on t h e f o l l o w i n g a s s u m p t i o n [!], [~], [~]
Fe~ w a s d e f i n e d b y H i g u c h i & lida a s
<o : N~sA = (<)~ C1)

N25w
where
N25A = f a t i g u e in a i r at r o o m t e m p e r a t u r e , c y c l e s
N2sw = f a t i g u e l i f e in h i g h - t e m p e r a t u r e water, c y c l e s
s = s t r a i n r a t e in r i s i n g p h a s e of s t r a i n i n g , %/s
P = s t r a i n r a t e d e p e n d e n c e f a c t o r of f a t i g u e l i f e w h i c h is f u n c t i o n
of t e m p e r a t u r e a n d d i s s o l v e d oxygen.
T h i s e q u a t i o n c a n b e c h a n g e d as
I/N25 ~ = Fen-i/N~s A (2)
From the above equation, fatigue damage accumulated during one strain
c y c l i n g in h i g h - t e m p e r a t u r e w a t e r is Fen t i m e s as l a r g e as t h a t in a i r a t
r o o m t e m p e r a t u r e . If t h e m a g n i f i c a t i o n r a t e o f f a t i g u e d a m a g e , Fen is as-
s u m e d t o i n c r e a s e f r o m 1 to Fen in l i n e a r p r o p o r t i o n t o i n c r e m e n t s of
s t r a i n f r o m m i n i m u m s t r a i n ~min (%) t o m a x i m u m s t r a i n s increments
o f Fen, dFen d u r i n g i n c r e m e n t s o f s t r a i n d~ is c a l c u l a t e d as
F -i
d ~ n -- "~ d~ (3)
I n t e g r a t i o n of dF.n f r o m s t o emx p r o v i d e s t h e m a g n i f i c a t i o n of f a t i g u e
damage or fatigue life reduction factor under changing temperature,
o x y g e n c o n t e n t a n d s t r a i n r a t e c o n d i t i o n , Fen' as
F '= 1 +
F<oI - -- dE =
.p
dE (4)
en mln ~ x -- Emi n mi~ E ~ X -- ~min
In t h e p r e s e n t study, Fen' c o u l d n o t b e c a l c u l a t e d b e c a u s e P v a l u e s
at temperature ranging 50~ to 290~ were not determined. Accordingly,
t h e f o l l o w i n g e q u a t i o n is o b t a i n e d w h e n e q u a t i o n (i) is s u b s t i t u t e d in
e q u a t i o n (4).
N~sx ~=~N~ A dr
or
N~sw, - ~ o N~5~ - ( ~
C .~ . )
1 _ ~o. 1 d8 (5)
where
N2sw' = f a t i g u e l i f e in h i g h - t e m p e r a t u r e water under changing tem-
perature condition, cycles
The following equations are obtained the in-phase pattern and out-of-
p h a s e p a t t e r n in t h e p r e s e n t test.
ds dT
(in - phase)
(~~ - <,~ -
(~_ - <j
d~ -dT (6)
=.~ _ <o) (out - of - phase)
where
T = temperature, ~
T=x = m a x i m u m t e m p e r a t u r e , ~
Tmin = m i n i m u m t e m p e r a t u r e , ~
E q u a t i o n (5) a n d ( 6 ) p r o v i d e t h e e q u a t i o n b y w h i c h I/N25w, u n d e r c h a n g i n g
t e m p e r a t u r e c o n d i t i o n c a n b e p r e d i c t e d as
1 _ c~,~ 1 d3
N..: J.~o N... ( T T~~ (7)
R e l a t i o n b e t w e e n i/Nnm K a n d T w h i c h w a s o b t a i n e d a t c o n s t a n t tem-
p e r a t u r e is s h o w n in F I G . 1 7 . T h e e q u a t i o n is d e t e r m i n e d a s
1/. .... = 8.755 x lo-' (T~176~

(8)
= 4 . 8 5 X 10-ST - 7 . 6 8 X I0-3(176~ < T ~290~
R e l a t i o n b e t w e e n t h e p r e d i c t e d Npred a n d t h e e x p e r i m e n t a l Ntest is s h o w n in
F I G . 1 8 . Npr~d w a s c a l c u l a t e d b y e q u a t i o n s (7) a n d (8) j u d g i n g t h a t NLEAK w a s
e q u i v a l e n t t o N25w. As s h o w n in F I G 18, g o o d c o r r e l a t i o n b e t w e e n Npr~d a n d
Nte~t w a s o b s e r v e d a n d f a t i g u e l i f e u n d e r c h a n g i n g t e m p e r a t u r e c o n d i t i o n
c o u l d b e a c c u r a t e l y p r e d i c t e d b y m o d i f i e d r a t e a p p r o a c h m e t h o d w i t h fa-
t i g u e l i v e s at c o n s t a n t t e m p e r a t u r e .
10-2
STS'10 I IO
DO=1ppm
~=0.002%/s 9
t=3mm
t=lmm I 9 1
o,~ 5x10~ 1/NLEAK

z
I/NLEAK=8,755X10~
Q
g *
O
10.3 I I I I I
50 100 150 200 250 300
Temperature (~
FIG.17 -- R e l a t i o n b e t w e e n I/NLEAK and t e m p e r a t u r e
= = = =1 = i = = = = = =1 i i =
[/ Changing
lO temp. II /
/
/ DO-lppm I
[ ~.o,oo~%,s I
103
102 L_~__ t=lmm J

9 I I I I I I I i , , i I ii , i i
102 103
Ntest(cycles)
FIG.18 -- R e l a t i o n b e t w e e n the p r e d i c t e d and a c t u a l f a t i g u e life
CONCLUSIONS
Axially strain controlled low cycle fatigue tests of a carbon steel

in oxygenated high temperature water were carried out under the changing
temperature conditions. The obtained obervations and conclusions were
as follows:
(i) Fatigue lives in oxygenated water tended to decrease with increasing
temperature under constant temperature condition.
(2) Fatigue life under changing temperature condition was in the range
of the fatigue life under various constant temperature within the range
of the changing temperature.
(3) Fatigue life of in-phase pattern was almost equivalent to that of
out-of-phase pattern.
(4) Fatigue life under changing temperature condition could be accurate-

ly predicted by modified rate approach method with fatigue lives at con-
stant temperature.
ACKNOWLEDGMENT
The present study has been supported by a research fund from the
joint utility study composed of the ten Japanese electric utilities and
the three plant fabricators. The test results were discussed at EFD
Committee of the Thermal and Nuclear Power Engineering Society.
The authors wish to thank gratefully the members of the committee.
REFERENCES
[!] Higuchi, M.and Iida, K., ~Fatigue Strength Correlation Facters for
Carbon and Low-Alloy Steels in Oxygen-Containing High-Temperature
Water," Nuclear Enqineerinq and Design., 129 1991, pp293-306
[2] Chopra, O. K.and Shack W. J., ~Effects of LWR Environment on Fa-

tigue Life of Carbon Steel in High Temperature Water, ~ ASME PVP
Vol.30~, 1995, pp95-110
[!] Kanasaki, H.,Hayashi, M.,Iida K. and Asada Y., ~Effects of Tempera-
ture Change on Fatigue Life of Carbon Steel in High Temperature
Water, M ASME PVP Voi.306, 1995, ppi17-122
[4] Nakao, O.,Higuchi, M.,Kanasaki, H.,Iida, K. and Asada,Y., ~Effects

of Temperature and Dissolved Oxygen Content on Fatigue Life of Car-
bon and Low Alloy Steels in LWR Water Environment," ASM~ PVP Vol.
306, 1995, pp
[~] Higuchi, M.,Iida K. and Asada Y., ~Effects of Strain Rate Change on
Fatigue Life of carbon Steel in High Temperature Water," ASME PVP
Voi.306, 1995, pplll-ll6
[6] Kishida, k.,Suzuki, S. and Asada, Y., ~Evaluation of Environmental

Fatigue Life for Light Water Reactor Component." ASME ~VP Voi.306,
1995, pp129-138
Kazuo Kishida, 1 Toshimitsu Umakoshi, 2 Yasuhide Asada 3
Advances in Environmental Fatigue Evaluation for Light Water Reactor Components
REFERENCE: Kishida, K., Umakoshi, T., and Asada, Y, "Advances in Environmental

Fatigue Evaluation for Light Water Reactor Components," Effects of the Environment
on the Initiation of Crack Growth, ASTM STP 1298, W.A Van Der Sluys, R.S. Piascik, and
R. Zawiemcha, Eds., American Society for Testing and Materials, 1997.
ABSTRACT: The recently acquired fatigue test data have indicated that the low cycle
fatigue lives attained in light water reactor environments can be markedly shorter than those
determined in the ambient atmospheric air. Of the various factors that are known to exert
influence on the fatigue life, the present authors have noted strain rate, temperature, and
dissolved oxygen (DO) content, and proposed a method of evaluating the environmental
fatigue lives for the Class 1 vessels when they vary with time. In this paper, this method is
examined against, and revised in view of, the fatigue data acquired since then, and
subsequently simplified so as to become adaptable to the Class l piping besides the Class l
vessels. Then, these two versions of this evaluation method are combined into a
methodological system by their respective nature, and, in doing so, have proved their worth
by applying themselves to several different sorts of component. The results show that the
effects of the light water reactor environments on the fatigue life is a factor of 2 or so in terms
of the increase of the usage factor (i.e., the environmental effect correction factor Fen = ca.
2).
KEYWORDS: ASME Code, fatigue life, fatigue evaluation, light water reactor
component, environmental effect, strain rate
The fatigue design of the components and piping of the primary cooling system of
light water reactors (LWR) is being conducted in accordance with ASME Boiler & Pressure
Vessel Code, Section III [!]. It is to be borne in mind here that the design fatigue curves
adopted in Section III are the ones that have been drawn by best fitting the data obtained in
1 Technical Manager, Nuclear Power Division, Ishikawajima-Harima Heavy Industries

Co., Ltd. 1,Shin-Nakahara-Cho, Isogo-Ku, Yokohama, 235, Japan.
2 Engineer, Kobe Shipyard and Machinery Works, Mitsubishi Heavy Industries Co.,
Ltd. 1-1-1, Wadasaki-Cho, Hyogo-Ku, Kobe, 652, Japan.
3 Professor, Doctor of Engineering, Department of Mechanical Engineering, University
of Tokyo, 7-3-1, Hongo, Bunkyo-Ku, Tokyo, 113, Japan.
282
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Int'l (all International
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KAZUO ET AL. ON ADVANCES IN ENVIRONMENTAL FATIGUE 283
the strain controlled, atmospheric air fatigue tests, and that necessary design values are
derived from these curves by applying a multiplication factor of 2 for the stress range, and 20
for the cyclic life. Well organized though this code is, there is no denying the fact that it does
not provide for the effects of the high temperature, high pressure water environments of the
reactor at all.
Now, performing a series of low cycle fatigue tests in a simulated reactor high
temperature water environment, Higuchi and Iida [2] have shown that in certain cases the
fatigue life can be degraded markedly as compared with the life attainable in ambient air.
Then, they have proceeded to quantify the effects of the reactor water on the fatigue life from
the data they obtained, and have proposed a formula to calculate what they called the
environmental effect correction factors.
Their method proved to be quite workable as the environmental effect correction
factors were defined in it as a function of strain rate, temperature, and DO content, but it was
marred with an intrinsic difficulty: because their formulation was done on the basis of the
test data obtained with all these three parameters held constant individually, the
environmental effect correction factors cannot be calculated unless these parameters remain
invariable through any one cycle of fatigue. This means that, inasmuch as these factors vary
with time in actual components of operating LWR plants, their factors can hardly apply to the
real cases.
To overcome this difficulty, we have proposed previously new evaluation methods [3],
which comprise following two different formulations: the effective strain range method and
the modified rate approach method.
The effective strain range method is defined by eq. (1) as:
AEneq = ~, 6Ew(dET /dO e" + AEin
t max
= f(de~/dO e'§ + Ae,, (1)
tin
where Ae a,q is the effective strain range. Here, Ken, the multiplier for the stress range, is
obtained by dividing Ae~,q with Aeze.
The modified rate approach method, on the other hand, is defined by eq. (2) as:
max
Fen = f(a T / at)-" / ( E max - E in. ) d E (2)
Though this formula calculates Fen, the multiplier for the usage factor directly, the time
histories of the strain rate, temperature, and DO content are required. As these histories can
be deduced readily enough from the results of the mandatory analysis if the component
concerned is one of the Class 1 vessels and likes, i.e., those for which finite element method
(FEM.) analysis is a matter of routine, they are unavailable, not immediately anyway, for
Class 1 piping for which no such detailed analysis is demanded. For this reason, this method
remains applicable only to the Class 1 vessels.
In this paper, we intend to present and discuss a simplified method of computing
the environmental effect correction factor, Fen, that we have developed so as to be
applicable to Class 1 piping on such information that is readily available even for them. Then,
we will proceed to present and discuss a comprehensive methodological system we have
formulated by combining the detailed evaluation formula and the simplified formula to be
used taking advantage of their respective nature.

Concurrent with the theoretical development, we have conducted a series of
environmental fatigue tests with strain rate and temperature varied programmatically and
differing in the DO content[4-6]. As these tests have underwritten the conclusion made by
Kanasaki, et al. [5] (i.e., that the modified rate approach method is quite capable of
evaluating the environmental effect even when temperature is variable) as well as the
authenticity of the P factor as revised by Nakao, et al. [7], we have decided to resort to the
modified rate approach method using the revised P factor in calculating the environmental
effects.
Finally, we will present and discuss the results of sample calculations we have
conducted on several different vessels and piping using these formulas, all in quantitative
terms.
FATIGUE EVALUATION F O R VESSELS
The fatigue evaluation of Class 1 vessels is being conducted in accordance with the
NB-3200 of Section III, the ASME Boiler & Pressure Code. Generally speaking, the fatigue
evaluation consists of determining Sa, the cyclic stress range, for every load set pair that is
defined in the design specification, calculate UFi, the usage factor, for every pair by
comparing the number of the load set pairs expended so far and the allowable number of
cycles as read offthe design fatigue curve, and see if they sum up to exceed unity.
Here, Sa is computed through following steps: First, the designer calculates the peak
stress for each of the load sets using the FEM. analysis; second, he determines the three
principal stresses, S~, Sz, and $3 ; from these three principal stresses, he calculates the three
stress differences as: S~2 m S~ - $2 , $23 - $2 - $3, and $3~ - $3 - S~, of which the largest
absolute value is defined as the peak stress intensity, Sp; finally, Sa is given as:
S~ - ! K, Se (3)
2
where Ke is the augmentation factor to compensate for the plastic deformation effect.
Now, as mentioned earlier on, we need to know the strain history for each load
set pair as a first requisite to calculate Fen. This can be done by dividing the Sp with the
Young's modulus. Next, inasmuch as the Higuchi-Iida's method, which constitutes the
modified rate approach method, is built on their observation that the strain rate of the strain
increasing phase of the strain history controls the environmental effect, we need to know
which of the strain history determined above is the strain increasing process. This is done by
equating the positive/negative sign to that of the larger of the two principal stresses which
have constituted Sp. For example, if the principal stress differential that gave rise to Sp was
S3J, compare S~ and S~ by the absolute value, and if S~ > $3 andS~ > 0 , S~ is tensile, and
$3 is compressive. Each strain history can be determined by setting its profile this way.
Concurrent therewith, the metal temperature history is determined in correspondence
to the strain increase process that has been obtained from the FEM. analysis. The data for the
DO content, which are also necessary to compute Fen, are obtainable from the plant
operation experience.
Next, as stated earlier on, we have elected to use the P factor as revised by Nakao, et al.
[7], which is defined as
P=Rp xPc
(4)
Rp = M I N { O . 3 O l n ( D O ) + 1.13,0.198exp(0.0055T)}
where Rp is set to 0.2 if it is less than 0.2, and Pc is to be determined for each heat on the
fatigue data obtained for 280 C and 8 ppm DO, though it is set to 0.56 in the absence of such
data.
Furthermore, we have introduced following assumptions:
1) There exist domains both for the strain range and for the strain rate wherein the effect of
environment does not manifest itself." they are strain ranges of less than 0.1% and strain rates
of over 1%/s [8].
2) Though the environmental effects become acute the more, the lower the strain rate, it gets
saturated for a strain rate of0.001%/s [6].
3) When computing out the strain history, Ke can be set to unity in eq. (3).
4) e ~m.is taken as e ~, in eq.(2) on calculating Fen.
In this work, we have elected to examine the feedwater nozzle of the reactor pressure
vessel (RPV) in the case of BWR and the feedwater nozzle of the steam generator (SG) in
the case of PWR. The reasons for the choice are that the they are the components which are
in constant contact with the reactor water, that they are known to work to high usage
factors, and that they are made either of carbon steel or low alloy steels, the species that are
known to be sensitive to the environmental effects. Though these reasoning are essentially
the same as the preceding work [3_], we differ from it here in the matter of P factor and the
prerequisites for Fen calculation.
For calculating Fen for the feedwater nozzle ofBWR's RPV, we show the case of a
load set pair that is composed of shutdown and turbine roll for BWR 5 as an example.
Namely, first, we present in Fig. 1 the strain history as we have determined from the stress
report. It will be noted here that the load set which gives rise to a positive strain is the shut
down condition. The temperature history that corresponds to this strain history is shown in
Fig. 2. Here, it is to be noticed that large tensile strains are always associated with rapid
decrease in temperature.
Then, we have conducted the progressive integration using these as inputs for eq. (2).
This is shown in Table 1 in terms of Fen given against increasing strain. Here, the term
&Fen stands for the Fen calculated for that time interval concerned on the assumption that
the strain rate, temperature, and DO content remain unchanged during that time interval,
while the term 6 F e n • 8~ / e ,o,,ais obtained by multiplying &Fen with fie, the increment in
strain attained in the same time interval, then by dividing the product by a,o,,1, which is the
differential between the maximum and minimum of strain. The total summation of
&Fen x ?3E / E,o,,~gives Fen. An example of calculating Fen for feedwater nozzle of an SG of
PWR is presented in Table 2. Here, the load set pair was the combination of shutdown and
upset in the 4-loop SG. It will be seen that the strain rate is rather low: in fact it is smaller
than the saturation rate in many of the processes.
Now, for a given part, evaluation completes itself by calculating Fen through the
identical steps for such load set pairs that give rise to a value of the strain amplitude that
exceeds 0.1%. The Fen's thus obtained are shown in Table 3 for the feedwater nozzles of
RPVs o f B W R 4 and 5, and in Table 4 for the feedwater nozzles of 2-loop, 3-loop, and 4-
loop SGs o f a PWR. We observe that while Fen is 1.3 to 1.7 in the case of BWR, it is 1.8 to
2.2 for PWR.
0.30
0.20
O.lO
0.00
-0.10
0 10 20 30 40 50 60 70
Time(min.)
FIG. 1-- Strain Time History Calculation at Combination of
Shut down and Turbine roll for BWR RPV.
300
"~ 200 l ......
e'L
100
[-
0
0 10 20 30 40 50 60 70
Time(min.)
FIG2-- Temperature Time History Calculation at Combination
of Shut down and Turbine roll in BWR RPV.
The method of calculating Fen presented above may be considered the most detailed
one available today. However, there is an intrinsic difficulty associated with it it demands the
FEM. analysis to be performed as many times over as the number of time intervals used for
obtaining the strain history and the temperature history that this method calls for to calculate
the strain (or stress) and temperature at that time. On the other hand, Higuchi, et al.[4]
stated on the fatigue life of the variable strain rate tests they have conducted that, if the rising
time of the strain is the same, the constant strain rate gives rise to the shortest fatigue
life.This means that calculation of Fen with an assumption that the strain rate to remain
invariable in the time between the moment at which the strain has become minimum and that
at which it attained its maximum should give rise to the largest Fen. Also, it should afford
considerable saving of computer time because determination of these characteristic moments

would be much easier than determining the strain history. Since the load sets as defined in the
design specification lack mutual continuity to constitute a strain history, however, the
following information has to be acquired: the moment at which the minimum strain occurs,
the moment at which that load set which has given rise to the minimum strain is brought to an
end, the magnitude of the strain at that moment, the moment at which the maximum strain
occurs, the moment at which that load set which has given rise to the maximum strain has
started, and the magnitude of the strain at that moment.
TABLE 1-- Fen Calculation for Load Set Pair of Shutdown and Turbine roll in BWR5 RPV.
Time Strain Strain Rate Used Strain Temperature DO P 8Fen 6Fen*de
(Second) (%) (%/see.) Rate (%/see.) ((2) Tpm) /etotal
0 0.0494
46 -0.0324
71 -0.0333
82 -0.0327 5.57E-05 1.00E-03 119.1 0.04 0.112 2.17 0.0048
1788 -0.0124 1.19E-05 1.00E-03 120.4 0.04 0,112 2.17 0.1634
3588 0.0118 1.34E-05 1.00E-03 215.5 0,04 0.112 2,17 0.1950
3600 0,0171
3601 0.1431 1.26E-01 1.26E-01 228.1 0.04 0.112 1.26 0,5909
3602 0.2098 6.67E-02 6.67E-02 193.8 0,04 0.112 1.35 0.3361
3603 0.2456 3.57E-02 3.57E-02 172.9 0.04 0.112 1,45 0.1930
3604 0.2651 1.95E-02 1.95E-02 159.2 0.04 0.112 1.55 0.1127
3605 0.2752 1.02E-02 1.02E-02 149.3 0.04 0,112 1.67 0.0633
3606 0.2806 5.36E-03 5.36E-03 141,7 0.04 0.112 1.80 0,0358
3607 0.2834 2.84E-03 2.84E-03 135.6 0,04 0,112 1.93 0.0203
3608 0.2850 1,57E-03 1.57E-03 130.5 0.04 0.112 2.06 0,012(3
3609 0.2854 3,65E-04 1.00E-03 126.2 0.04 0,112 2.17 0.0025
Fen= 1.73
TABLE 2-- Fen Calculation for Load Set Pair of Shutdown and U )set in PWR 4 Loop SG.
Time Strain Strain Rate Used Strain d Fen d Fen*d e
(Second) (%0) (%/sec.) Rate (%/see.) / ~ total
21600 2.19E-03
21605 2.97E-03 1.63E-02 1.63E-02 0.112 1.59 1.0116
21615 2.98E-03 2.46E-04 1.00E-03 0,112 2,17 0.0236
21630 2.99E-03 6,38E-05 1.00E-03 0.112 2.t7 0,0055
21650 2.99E-03 6.38E-05 1.00E-03 0.112 2.17 0.0055
21680 2.99E-03 6.00E-05 1.0OE-03 0.112 2.17 0.0108
21740 3,02E-03 5.78E-05 1.00E-03 0.112 2.17 0.0306
21860 3.04E-03 5.27E-05 1.00E-03 0.112 2.17 0,056C
22160 3.12E-03 4.22E-05 1.00E-03 0.112 2.17 0.1346
22760 3.21E-03 2.87E-05 1.00E-03 0,112 2.17 0.1527
23660 3.26E-03 1.85E-05 1,00E-03 0.112 2.17 0.0985
24860 3.30E-03 1.31E-05 1.00E-03 0.112 2.17 0.0696
2666(3 3.35E-03 8.50E-06 1.00E-03 0,112 2.17 0.0903
2906(3 3.38E-03 5.19E-06 1.00E-03 0.112 2.17 0.0551
32060 3.40E-03 3.15E-06 1.00E-03 0.112 2.17 0.033~
35660 3.41E-03 1.96E-06 1.00E-03 0,112 2.17 0.0205
Fen= 1.80
TABLE 3--Detailed Calculations of Fen for each load set

of BWR reactor pressure vessel feedwater nozzle
NO. Load set hair F~n
1 Turbine roll Turbine trip 1.27
BWR4 2 Turbine roll Shut down 1.27
3 Shut down Shut down 1.29
1 Shut down Turbine generator trip 1.43
2 Shut down Turbine roll 1.73
3 Shut down Hot standby 1.33
4 Shut down Hot standby 1.33
BWR5 5 Shut down Turbine trip 1.49
6 Shut down Scram 1.4S
8 Hot standby Shut down 1.43
9 Turbine roll Shut down 1.4~
10 Feedwater pump trip Shut down 1.42
11 Turbine generator trip Shut down 1.4";
TABLE 4--Detailed Calculations of Fen for each load set

of PWR steam generator feedwater nozzle
NO. Load set )air Fen
1 Cooldown Upset 1.79
2 Loop 2 Heatup Upset 2.05
3 Hot standby Upset 1.79
4 Turbine roll Upset 1.79
1 Leak test Upset 2.17
2 Cooldown Upset 2.17
3 Hot standby Upset 2. i 7
3 Loop 4 Reactor trip Upset 2. ! 7
6 Depressurization Upset 2.17
7 Reactor trip Upset 2.17
1 Cooldown Upset !.8{}
2 Heatup Upset 2.05
3 Hot standby Upset 1.8{}
4 Loop 4 Reactor trip Upset 1.83
5 Depressurization Upset 1.81
7 Inadvertent safety injection actior Upset 1.80
We have done this as follows: Calling the load set that gives rise to the maximum
strain 'i', and that which is for the minimum strain 'j', letting the strain rate, assumed constant
in each for the rising phase of straining, be (de / dt)i and (dr / dr)j, respectively, using the
maximum value encountered in the rising phase o f straining both for the temperature and for
the DO content (this is to ensure the P factor become to assume the maximum for every load
set), and letting such P factors be Pi and Pj, respectively, we write:
E max -- E start E end -- E mm

F e n = Feni + Fenj (5)
(1~ max -- ~ start ) "l" ( E end -- ~ min ) (E maX -- I~ start ) "F ( E end -- E rain )
where Feni,j = ( d E / d ~ ) i , j P m a x i ' j , Pmax i,j = f ( Tm= ~,j , DOm~x i,j ) , e,~o.is the strain at the
moment the load set which gave rise to the maximum strain has started, and e end is the
minimum strain counterpart of it.
As eq. (5) is evidently much simpler than eq. (2), we shall designate it as the
simplified method. We have duly applied this method to the parts shown in Tables 3 and 4,
and have obtained Fen's as presented in Table 5 for BWR and in Table 6 for PWR. It will be
noticed that where Table 5 gives Sa, Fen, (de /dt)i,j , maximum temperature, maximum
DO, and the largest P factor for each of the load sets, Table 6 lacks the maximum
temperature and maximum DO in reflection of the fact that in PWR the DO concentration is
so low that P is assigned with a constant value regardless the temperature. It will be further
noted that the strain rate is faster for BWR than for PWR, for which the strain rates are all
smaller than the saturation value of 0.001%/s. Finally, we observe that all the Fen's, both for
BWR, which is 1.4 to 1.9, and for PWR, which is 2.2, are higher than those that have been
obtained in the detailed evaluation.
T A B L E 5-- S i m p l i f i e d Calculations o f F e n for e a c h load set p a i r o f B W R r e a c t o r p r e s s u r e

v e s s e l f e e d w a t e r nozzle.
NO. Load set pair Sa Strain rate Tmax DOmax Pmax Fen i,j Fen
MPa) (%/see) (C) (ppm)
1 Turbine roll 662 9.72E-02 283 0.04 0.112 1.30 1.36
BWR4 Turbine trip 1.15E-03 166 0.04 0.112 2.13
2 Turbine roll 505 9.72E-02 283 0.04 0.112 1.30 1.36
Shutdown 1.15E-03 166 0.04 0.112! 2.13
3 Shut down 480 9.64E-.02 286 0.04 0.112 1.30 1.3~
Shutdown 1.15E-03 166 0.04 0.112 2.13
4 Shut down 287 7.93E-02 199 0.04 0.112 1.33 1.6&
Shutdown 1.15E-03 166 0.08 0.208 4.10
1 Shutdown 819 2.98E-02 289 0.04 0.112 1.48 1.53
Turbine senerator trip 2.72E-04 214 0.04 0.112 2.17
BWR5 2 Shut down 555 2.98E-02 289 0.04 0.112 1.48 1.88
Turbine roll 1.28E-04 215 0.08 0.208 4.22
3 Shut down 48C 2.98E-02 289 0.04 0.112 1.48 1.4/4
Hot standby 3.71E-01 289 0.04 0.112 1.12
4 Shut down 466 2.98E-02 289 0.04 0.112 1.48 1.44
Hot standby 3.71E-01 289 0.04 0.112 1.12
5 Shutdown 502 2.98E-02 289 0.04 0.112 1.48 1.52
Turbine trip 4.94E-04 215 0.04 0.112 2.17
6 Shutdown 502 2.98E-02 289 0.04 0.112 1.48 1.52
Scram 4.94 E-04 215 0.04 0.112 2.17
7 Shut down 465 2.98E-02 289 0.04 0.112 1.48 1.54
Shut down 4.26E-05 273 0.04 0.112 2.17
8 Hot standby 465 2.98E-02 289 0.04 0.112 1.48 1.54
Shut down 4.26E-05 273 0.04 0.112 2.17
9 Turbine roll 448 2.23E-02 287 0.04 0.112 1.53 1.58
Shut down 4.26E-05 273 0.04 0.112 2.17
10 Feedwater pump trip 449 2.98E-02 289 0.04 0.112 1.48 1.54
Shutdown 4.26E-05 273 0.04 0.112 2.17
11 Turbine generator trip 345 2.02E-02 214 0.04 0.112 1.55 1.5-~
Shut down 4.26E-05 289 0.04 0.112 2.17
Note: If the strain rate is less than 1.0E-03(%/sec), the strain rate for the calculations is taken as 1.0E-03(%/sec.).
TABLE 6-- SimplifiedCalculationsof Fen for each load set pair of PWR steam
~edwaternozzle.
NO. Load set pair Sa Strain rate Pmax Fen i,j Fen
(MPa) (~
1 Cooldown 349 3.30E-07 0.112 2.17 2.17!
2 L~x~p Upset 1.78E-O5 0.112 2.17
2 Heatup 347 2.12E-05 0.112 2.17 2.17
Upset 1.78E-05 0.112 2.17
3 Hot standby 340 0.00E+00 0.112 2.17 2.17
Upset 1.78E-05 0.112 2.17
4 Turbine roll 208 0.00E+00 0.112 2.17 2.17
Upset 1.78E-O5 0.112 2.17
1 Leak test 332 4.32E-07 0.112 2.17 2.17
Upset 6.86E-06 0.112 2.17
2 Ctxddown 327 2.47E-07 0.112 2.17 2.17
Upset 6.86E-06 0.112 2.17
3 Ltx~p 3 Hot standby 310 0.00E*00 0.112 1.00 2.17
Upset 6.86E--06 0.112 2.17
4 Reactor trip 251 4.24E-05 0.112 2.17 2.17
Upset 6.86E-O6 0. I 12 2.17
5 Turbine roll 209 0.00E +00 0. I 12 1.00 2.17
Upset 6.86E-O6 0.112 2.17
6 Depressurization 205 8.47E-06 0.112 2.17 2.17
Upset 6.86E-O6 0. I 12 2.17
7 Reactor trip 196 2.36E-04 0. I 12 2.17 2.17
Upset 6.86E-06 0.112 2.17
1 ttot standby 333 2.04E-07 0.112 2.17 2.17
Upset 1.78E-05 0. I 12 2.17
2 Heatup 332 1.90E--05 0.112 2.17 2.17
Upset 1.78E-05 0.112 2.17
4 L~a~p 3 Hot standby 330 0.00E~O0 0.112 1.00 2.17
Upset 1.78E-05 0.112 2.17
4 Reactor trip 252 3.29E-05 0.112 2.17 2.17
Upset 1.78E-05 0.112 2.17
5 Depressurization 215 ! 1.86E-05 0.112 2.17 2.17
Upset 1.78E-O5 0.112 2.17
6 Turbine roll 201 0.00E+O0 0.112 1.00 2.17
Upset 1.78E-05 0.112 2.17
7 Inadvertent safety injection action 191 6.30E-O6 0.112 2.17 2.17
Upset 1.78E-05 0.112 2.17
Note: If the strain rate is less than 1.0E-03(~ the strain rate fiw the calculations is taken as 1.0E-03( Fdsee.
o
FATIGUE EVALUATION FOR PIPING
The current practice of fatigue evaluation for Class 1 piping is accorded to the NB-
3600 of Section III, the ASME Boiler & Pressure Vessel Code. Though it is essentially the
same as for Class 1 vessels, difference lies in the way Sp, the peak stress intensity, is
determined. Here, Sp is defined as [!]:
Sp = KICI DoPo + K2C2 Do Mi + K3CsEabJo. ar~ -~brbJ
2t 2I
1 1 (6)
+
zU-v )
K,E<A I +
1- V
I
where, K's are the local stress indices, C's, the secondary stress indices, Po, the range of
operating pressure, Mi, the range of moment, Eo~, the average Young's modulus for side a
and side b when there exists a material or structural discontinuity, a's, the thermal expansion
coefficient for sides a and b, respectively, when there exists a material or structural
discontinuity, T's, the average temperature for sides a and b when there exists a material or
structural discontinuity, A/i, the temperature differential across the pipe wall when the
temperature distribution in the thickness direction is linear, ATz, that with the AT~
subtracted when the temperature distribution in the thickness direction is nonlinear, nu, the
Poisson ratio, and Do, t, and I are as defined in the NB-3600 [i]. Here, it is to be appreciated
that the first term of eq. (6) gives the stress due to internal pressure, the second, the stress
due to the moment (which is given rise to mainly by the constrained thermal expansion), and
the third to the fifth, the stresses arising from the temperature distribution in the thickness
direction.
Now, in the piping analysis, each term is individually calculated for every load set, and
the peak stress intensity is determined for every load set pair, and none of the stress
calculations in eq. (6) is done through such detailed analysis as FEM. as required of the Class
1 vessels. This is because the object of analysis is far too many for the piping than for the
vessel, making not only the adoption of simpler calculation method inevitable on one hand,
and direct application of eq. (2) impracticable on the other hand.
In the simplified method we have developed piping, we make use of the constant
strain rate again as we did for vessels. Inasmuch as the five terms of eq. (6) are to be
calculated individually, however, the information on at what moment the summed up stress
has attained its maximum is unavailable. To cover this deficit, we have noted the term that
calculates the stress due to moment and the one that returns the stress due to ATe. This
convention should be considered reasonable because experience tells us that, in general, the
stress due to moment predominates in the peak stress intensity if the transient change takes
place slowly as in the case of start-up, whereas that due to AT~ is dominant if the transient
change takes place quickly.
Here, the constant strain rate is computed out in the following procedure:
1) First, between the moment term and the AT~ pick up the one that rises larger peak stress
intensity.
2) Calculate the stress for each of the two load sets that have given rise to that stress term
chosen above, and pick up the larger stress of the two.
3) Determine the following quantities: the moment at which that stress is being given birth
to, the magnitude of that strain at that moment, the moment at which the stress attains its
maximum, and the magnitude of the maximum stress.
4) Determine the strain rate for that time interval, assuming the stress change is linear
therein.
5) Finally, if the term due to moment has been selected, take the startup for the load set in
which to calculate the constant strain rate.
The rest of the calculation is straightforward: once the strain rate has been determined
this way, enter eq. (4) with the maximum temperature and the maximum DO content of that
load set which gives rise to that strain rate to calculate the P factor, then calculate Fen as:
Fen = (dEr ~dr)-" (7)
We have examined the efficacy of this method by applying it to the feedwater line of
BWR and the main feedwater piping of PWR with results presented in Tables 7 and 8,
respectively. It will be seen that Fen was 1.7 to 2.1 for BWR and 2.2 for all load sets for
PWR, where the strain rate was lower than the saturation value in all the cases. The fact that
these Fen's turned out to be equal to or larger than those obtained by the simplified method
for the vessels has been held to attest to the appropriateness of this simplified method as for
the piping.
TABLE 7-- Fen Calculations for each load set pair of BWR feedwaterpiping.
NO. I Load set pair Sa Fen
(MPa)
i Turbine ~enerator trip Shut down 1430 1.91
Turbine trip Shut down ... 73{} 1.70
3 Turbine l~eneratortrip Shut down 651 2.08
4 Bypass of feedwater heater Shut down 371 2.09
5 Wrongoperation o.fsafe~ relief valve Wrong operation of safety relief valve 30O 1.82
6 Bypass of feedwater heater Shut down 291 1.95
7 Turbine roll Shut down 268 1.86
8 Turbine roll Shut down 266 1.66
9 Null Turbine roll 241 1.70
I0 Null Turbine trip 232 1.85
11 Turbine trip Turbine trip 221 1.89
TABLE 8-- Fen Calculations for each load set pair ofPWR SG feedwater pipinl~.
i NO. Load set pair Sa Fen
m
(MPa)
1 Upset Upset 105 2.17
2 Cooldown Upset 94 2.17
3 primary leak test Upset 94 2.17
4 Seeondray leak test Upset 94 2.17
As the present simplified method gives larger Fen's than should be, reduction o f Fen so
as to bring its value closer to the one that is obtainable with the detailed method for the
vessels has been attempted by resorting to the three later terms of eq. (6). Here, we have
been able to determine the needed history of the summation stress, not from the ordinary
pipeline analysis methods, because none of which can yield this kind of information, but
using the temperature distribution analysis model. An example of the strain history of BWR
piping as converted from the stress history due to A/i, ]T~ - Tb] and AT2 is shown in Fig. 3.
This strain history and eq. (2) have produced an Fen of 1.61, i.e., a value which is
satisfactorily smaller than those given in Table 7.
As it is evident that this method is quite capable of calculating Fen to a reasonable value, we
shall call it the detailed method for the piping. This method is expected to prove its worth
whenever the simplified method has given rise to such an Fen that makes the sum of the
usage factor of every load set pair exceed unity.
0.5
0.4
,/ '\N
0.3
0.2
0.1
f
/
0.0
0 2 4 6 8 10
Time(min.)
FIG.3--Strain Time History Calculation at Feedwater
Heater Trip o f B W R Feedwater Piping.
M E T H O D O L O G I C A L SYSTEMATIZATION OF EVALUATION M E T H O D
The environment fatigue evaluation is a lengthy work, and to conduct it for all the Class
1 vessels and piping of an LWR plant takes unbearably long time. On the other hand,
however, it is also true that many of their parts do not work up to such a high a usage factor
as makes us to worry about. This calls for a reliable method of screening out those parts for
which the fatigue evaluation is really necessary. We have done this by developing a screening
criterion on the basis of the Fen's that we have obtained in this work, then have proceeded
further to construct a comprehensive methodological system by combining this screening
criterion and the detailed and the simplified methods as follows:
First, we note two important observations acquired in the study: one, that all fatigue
evaluations are brought to conclusion if and when the summation of the usage factors
determined for every load set pair turns out to be less than unity, and two, the more
simplified the evaluation formulation is, the larger becomes the Fen. Therefore, we start out
our comprehensive evaluation by setting up an Fen so as to be larger than what has been
obtained by the simplified method and multiply the sum of the usage factors with it.
Fig. 4 presents our methodological system for comprehensively evaluating
environmental fatigue occurring in the vessels and piping of LWR plants by a flowchart. The
work proceeds as follows:
1) Multiply UF~o,,a(o,),the sum of the original usage factors for the object part, with Fensc,
Fen for screening. If the resultant UF~ot,a,, is less than unity, terminate the evaluation. If
not, proceed to the next step.
2) Eliminate from the load set pairs the seismic load states because of their excessively fast
strain rates and those pairs that do not have to consider the environment effect because
their values of Sa are too small.
3) Select an appropriate simplified method depending on if the object is a vessel or a piping.
4) Determine the constant strain rate, maximum operating temperature, and maximum DO
content for every load set pair, and calculate Fen on them.
5) Calculate UE,, by multiplying the original UEor with the Fen determined above.
6) Sum up all of UE,, into UF,o,~,, for all the load set pairs, including those that have been
eliminated once in 2), and see if it exceeds unity. If not, terminate the evaluation. If does,
proceed to the next step.
7)Determine the temperature history and the DO content history, and calculate Fen by the
detailed method.
8) Sum up all of U F , , into UF,o,~d,, for all the load set pairs, including those that have been
eliminated once in 2), and see if it exceeds unity. If not, terminate the evaluation. If does,
the load set should be reviewed for revising. For example, reset them, not on the design
operation specifications, but on the actual operation history.
F OriginalUsageFactor
"4r Yes
~F,o,o,(o,., • F ..... 1 l. . . . . . . . . . . . .
+ No
~ LoadSet Pair "i" [
9~" Yes
Seismic Load States
~r No Yes
i S"' < S~176 [
"6" No
[ DetermineFen using [ [ DetermineFen using [
the SimplifiedMethod the DetailedMethod
I MultiplyUFior. by Fen ]
I k[
i--n ~ g ~ =UE~(~_~)+UF,,
[ * Yes
UF,o,~ < 1 0
9~, Yes
[ End
FIG,4-- Flow Diagramfor EnvironmentalFatigueEvaluation.
KAZUO ET AL, ON ADVANCES IN ENVIRONMENTAL FATIGUE 295
In the flowchart described above, we have used a value o f 3.0 for Fensc, in view of
the Fen's listed in Tables 5 to 8. Though reasonable this value appears to be, there can be
portions in the B W R plants where the D O content is not regulated to as low a value as it is in,
for example, the feedwater lines we have considered above. In order to cover these high DO
cases by the same flowchart, we have calculated Fen for 0.1 ppm and 0.3 ppm DO with the
strain rate and temperature held the same as in Tables 5 and 7. Taking the rounded up version
o f the Fen thus obtained as Fensc of BWR, we have summarized this in Table 9.
We believe this concludes our comprehensive and methodological systematization o f the
methods for evaluating the environmental fatigue for Classl vessels and pipelines o f LWR
plants.
TABLE 9-- Fen Calculations for Screening of BWR Fatigue Evaluation.

NO. Load set pair Fen
DO=0.3ppml DO=0.1ppm
1 Shut down Turbine generator trip 5.12 2.60
BWR5 2 Shut down Turbine roll 5.72 2.82
RPV 3 Shut down Hot standby 4.17 2.24
4 Shut down Hot standby 4.17 2.24
5 Shut down Turbine trip 4.96 2.53
6 Shut down Scram 4.96 2.53
7 Shut down Shutdown 5.75 2.62
8 Hot standb~r Shut down 5.75 2.62
9 Turbine roll Shut down 6.31 2.78
10 Feedwater pump trip Shut down 5.75 2.62
11 Turbine generator trip Shut down 4.18 2.61
1 Turbine roll Turbine trip 3.02 2.03
BWR4 2 Turbine roll Shut down 3.02 2.03
RPV 3 Shut down Shut down 3.03 2.04
4 Shut down Shut down 2.89 2.30
1 Turbine senerator trip Shut down 8.46 4.15
BWR 2 Turbine trip Shut down 5.78 3.22
3 Turbine ~enerator trip Shut down 10.02 4.64
Piping 4 Bypass offeedwater heater Shut down 9.75 4.56
5 Wrong operating of Wrong operating of 5.03 2.93
safety relief valve safety relief valve
6 Bypass of feedwater heater Shut down 9.79 4.57
9 Null Turbine roll 3.67 3.20
10 Null Turbine roll 4.53 3.86
11 Turbine trip Turbine trip 4.79 4.79
Fensc for BWR 10 for 5 for
DO>0. lppm DO=<0. lppm
CONCLUSION
The modified rate approach method has been found to be quite effect for evaluating the
fatigue taking the environment effect into consideration. The difficulty associated with this
method, i.e., that of having to prepare the histories of strain, temperature, and DO content by
reiterating the FEM analysis at considerable expense in time and labor, can be avoided by the
two simplified methods, one for the vessels, and the other for the piping, that we have
developed and presented herewith. Sample calculations have shown that these simplified
methods apply quite well to LWR vessels and piping, respectively. Furthermore, a flowchart
of comprehensively evaluating the environmental fatigue occurring in components and parts
of LWR plants has been developed by methodologically systematizing the detailed formulas
and the simplified ones and by combining in it a function of screening out those parts which
really need evaluating fatigue. Trial calculations have shown that the increment of the usage
factor due to the environment effect remains a factor of 2 or thereabout.
ACKNOWLEDGMENT
This paper has been compiled on a part of the data that have been acquired by the
Committee on Environmental Fatigue Data (EFD) of the Thermal and Nuclear Power
Engineering Society The authors earnestly wish to extend their sincere thanks to the fellow
members of the Committee of EFD for their valuable discussion and comments.
REFERENCES
[1] "Rules for Construction of Nuclear Power Plant Components." Section III,
Divisionl,1995 ASME Boiler and Pressure Vessel Code. American Society of
Mechanical Engineers.
[2] Higuchi, M., and Iida, K.. "Fatigue Strength Correction Factors for Carbon and Low-
Alloy Steels in Oxygen-Containing High-Temperature Water." Nuclear Engineering and
Design. 129, 1991, pp.293-306.
[3] Kishida, K , Suzuki, S., and Asada, Y., "Evaluation of Environmental Fatigue Life for
Light Water Reactor Components." ASME PVP V01.306, 1995, pp. 139-147.
[4] Higuchi, M., Iida, K , and Asada, Y., "Effects of Strain Rate Change on Fatigue Life of
Carbon Steel in High Temperature Water." ASME PVP Vol.306, 1995, pp 111-116.
[5] Kanasaki, H., Hayashi, M., Iida, K., and Asada, Y., "Effects of Temperature Change on
Fatigue Life of Carbon Steel High Temperature Water. " ASME PVP Vol.306 1995
pp117-122.
[6] Chopra, O. K., and Shack, W. J., "Effects of LWR Environments on Fatigue Life of
Carbon and Low-Alloy Steels." ASME PVP Vol.306, 1995, pp.95-110.
[7] Nakao, G., Higuchi, M., Kanasaki, H., Iida, K., and Asada, Y., "Effects of Temperature
and Dissolved Oxygen Content on Fatigue Life of Carbon and Low Alloy Steels in LWR
Water Environment." Presented at ASTM Symposium on Effects of the Environment on
the Initiation of Crack Growth. Orlando, FL., May 20-21, 1996
[8_] Van Der Sluys, W. A., and Yukawa, S., "Status of PVRC Evaluation of LWR Coolant
Environmental Effects on the S-N Fatigue Properties of Pressure Boundary Materials."
ASME PVP Vol.306, 1995, pp.47-58.
STP1298-EB/Apr. 1997
Author Index
A J
Akashi, M., 150 Jonas, O.,182
Aldd, R., 3
Asada, Y., 216, 232, 267, 282 K
Atkinson, J. D., 189
Kanasaki, H., 232, 267
B Kanazawa, C. H., 74
Kishida, K., 282
Bodai, M., 120 Kolman, D. G., 61
Bray, G. H., 89 Kondo, Y., 120
Bucci, R. J., 89 Kulak, M., 89
C L
Chen, G. S., 18 I_~is, B. N., 34
Chopra, O. K., 247 Liao, C.-M., 18
Colvin, E. L., 89
Colwell, J. A., 34 M
Crocker, J. E., 74
Mirzai, M., 107
D
DeLair, R. E., 135 N

Nakao, G., 232
F Nakayama, G., 150
Flournoy, T. H., 74
P
G
Parkins, R. N., 107
Gao, M., 18
Giovanola, J. H., 74
S
H Schmidt, C. G., 74
Scully, J. R., 61
Hall, M. M., Jr., 167 Shack, W. J., 247
Higuchi, M., 216, 232 Shockey, D. A., 74
Hirano, A., 267 Solomon, H. D., 135
Sugita, Y., 120
Symons, D. M., 167
I
T
Iida, K., 216, 232, 267
Inagaki, H., 120 Takei, M., 120
299
Copyright by ASTM
Copyright Int'lby
9 1997 (allASTM
rights reserved); Fri Dec 30 21:53:51
International EST 2011
www.astm.org
300 THE INITIATION OF CRACK GROWTH
U Y
Umakoshi, T., 282
Unruh, A. D., 135 Yu, J., 189
W
Z
Wan, K.-C., 18
Wei, R. P., 18 Zhao, Z.-J., 189
STP1298-EB/Apr. 1997
Subject Index
A F
Aircraft, 89 Fatigue
skin, 74 corrosion, 18, 74, 182, 232,
Alclad 2024-T3, 74 267
Aluminum alloy, 18, 74, 89 crack growth resistance, 89
American Society for Mechanical crack initiation, 135, 247
Engineers, 135, 232, 247, crack nucleation, 18
267, 282 crack propagation, 89
cracks, short, 3
C damage, 89, 267
degradation, 216
Chloride environments, 3, 61 environmental, 216
sodium chloride, 18 life, 247, 267, 282
Conductivity, electric, 120 precrack, 61, 167
Corrosion cracking, stress, 34, strength, 3
107, 150, 167, 182, 189 threshold, 18
Corrosion current, 120 Film rupture, 61
Corrosion fatigue, 3, 34, 232, Fracture toughness, 89
267
aluminum alloy, 74, 89
carbon steel, 267 G
crack growth, 18
Corrosion pitting, 89 Gas transmission piping, 34
Crevice growth, 150
Cyclic-frequency effect, 18 H
Cyclic straining, 120
Hematite, 182
Hydrogen
D embrittlement, 74, 167
sulfide, 182
Defect growth rate, 3 uptake, 61
Degradation, fatigue, 216
Dormancy, 34, 107
Ion separation, 182
E
Electrode L
bare surface, kinetics, 61
scanning reference, 3
Environmental effect correction Life prediction method, 267
factor, 282 Load control, 135
Environmentally assisted Load frequency, 189
cracking, 61, 120 Loading, 247
Exponential distribution, 150 cyclic, 74
301
302 THE INITIATION OF CRACK GROWTH
Magnetite, 182 Salt water, 74

Microstructural fracture Scanning reference electrode,
mechanics, 3 3
Modeling, 3 Sodium chloride, 18, 61
crack initiation life, 120 Steel, 107, 150, 167, 182
molecular, 182 A533B, 189
process, crack initiation, carbon, 216, 232, 247, 267
150 low alloy, 120, 135, 232,
stress corrosion cracking, 34 247
Strain aging, 189
N Strain amplitude, 232
Strain energy density, 167
Nickel steel, 107 Strain rate, 107, 247, 282
Nitrate solution, 107 change, 216
Notch radius, 61 Strain tests, 107, 267
cyclic, 120
O slow strain rate, 189
Stress corrosion, 3
Oxygen, dissolved, 216, 232, 247, cracking, 34, 107, 150, 167,
282 182, 189
Stress intensity, 135
P factor, 18, 34, 167
Sulfur, 247
Piping, gas transmission, 34 Sulfuric acid, 135
Pitting, 3, 74, 135 Surface film breakdown, 3
corrosion, 18, 89
growth, 150 T
Poissonian stochastic process,
150 Tapered tension test, 34
Titanium, 61
R
W
Reactor, 189
boiling water, 150 Water, high temperature, 135,
light water, 216, 232, 247, 216
282 Water reactor, boiling, 150
ISBN 0-8031-2408-2

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Copyright by ASTM Int'l (all rights reserved); Fri Dec 30 21:53:51 EST 2011

Effects of the Environment on the

W. Alan Van Der Sluys, Robert S. Piascik, and Robert

ASTM Publication Code Number (PCN):

Effects of the environment on the initiation of crack growth / W. Alan

p. cm. -- (STP : 1298)

Copyright 9 1997 AMERICAN SOCIETY FOR TESTING AND MATERIALS, West

Peer Review Policy

Printed in Ann Arbor

The Role of Stress-Assisted Localized Corrosion in the Development of Short

Pitting Corrosion a n d Fatigue Crack Nucleation~GIM s. CHEN, CHI-MINLIAO,

Initiation of Stress-Corrosion Cracking on Gas T r a n s m i s s i o n P i p i n g ~

CRACK INITIATION IN AGING AIRCRAFT

O n the R e q u i r e m e n t for a Sharp Notch or P r e c r a c k to Cause

Corrosion-Fatigue C r a c k Nucleation in Alclad 2024-T3 Commercial A i r c r a R

Effect of P r i o r Corrosion on the S/N Fatigue P e r f o r m a n c e of A l u m i n u m

STRESS CORROSION CRACK INITIATION IN NUCLEAR ENVIRONMENTS

Influence of a Mixed Nitrate Solution on the Initiation a n d Early G r o w t h of

E n v i r o n m e n t a l l y Assisted C r a c k i n g of 3.5NiCrMov Low Alloy Steel U n d e r

C r a c k Initiation in Low Alloy Steel in High T e m p e r a t u r e W a t e r n

A Process Model for the Initiation of Stress-Corrosion Crack G r o w t h in

Strain Energy Density--Distance Criterion for the Initiation of Stress

Molecular Modeling of Corrosive Environments in Cracks--OTAKAR JONAS 182

CRACK INITIATION IN CORROSION F A T I G U E - - I

Interactive Effect of Dynamic Strain Ageing with High Temperature Water

Effects of Strain Rate Change on Fatigue Life of Carbon Steel in High-

Effects of Temperature and Dissolved Oxygen Contents on Fatigue Lives of

CRACK INITIATION IN CORROSION F A T I G U E - - I I

Evaluation of Effects of L W R Coolant Environments on Fatigue Life of

Corrosion Fatigue Behavior and Life Prediction Method Under Changing

Advances in Environmental Fatigue Evaluation for Light Water Reactor

Session h Stress Corrosion Cracking Initiation

Session II: Crack Initiation in Aging Aircraft

Session III: Stress Corrosion Crack Initiation in Nuclear Environments

Session IV: Modeling

Session V and Vh Crack Initiation in Corrosion Fatigue

W. Alan Van Der Sluys

THE ROLE OF STRESS-ASSISTED LOCALIZED CORROSION IN THE

REFERENCE: Akid, R. "The Role of Stress-Assisted Localized Corrosion in the Develop-

KEYWORDS: corrosion fatigue, pitting, scanning reference electrode, microstructural

Senior Research Fellow, SIRIUS, Structural Integrity Research Institute University of

F A T I G U E C R A C K D E V E L O P M E N T IN A I R AND AQUEOUS ENVIRONMENTS

FIG. 1 Schematic of defect development stages in air and an aggressive environment.

(a) Surface film breakdown

Solution composition Applied shear stress (MPa) Fatigue lifetime (cycles)

Table 1 Influence of NaNO2 additions on fatigue lifetime in 0.6M NaCI

(b) Pit development and growth

Surface displacement (microns) Surface displacement (microns)

(c) Pit to crack transition

Shear stress Environment transition length Cycles to Lifetime Nf

Table 2 Influence of Stage 1/II transition on fatigue lifetime.

Applied Stress (MPa)

F I G . 3 Fraction of life to pit/crack transition as a function o f applied stress level for

Applied Stress (MPa)

A reasonable approach to modelling this first stage would therefore necessarily

T = A g(stress) + B g(frequency) + C (1)

0.01 0.10 1.00 10.00 100.00

Loading Frequency (Hz)

FIG. 5 Influence of test frequency on time for pit/crack transition

Stress Range Act, (MPa)

FIG. 6 Influence of applied stress on the rate of pit growth

i o < 800 MPa corrosion dependent pit growth

MODELLING SHORT FATIGUE CRACK GROWTH