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1. Introduction
Failures of riveted steel pressurc vessels have
fr equently b een attributed to stress-corrosion cracking, called in these instances "caustic embrittlemen t."
The construction of pressure vessels by welding has
prevented the leaks that wer e a factor in causing the
cracking of riveted structures but has by no m eans
eliminated stress-colTosion cracking of low-carbon
steel vessels. The m ech anism of the initiation and
propagation of str css-corrosion crackin g in low-carbon
steels is not wcll understood . Sevcral theories hav e
b een advanccd to explain the m echanism ; none ar e
universally accep ted. The data r epor tcd in this
paper are used for th e r eexamination and r efin emen t
of som e of thc curren t theories of stress-corrosion
crackin g.
A brief review of conditions under which str esscorrosion cracking has b een reported in low-carbon
steels was given in an carlicr papcr [1) .1 Conod cnts
have included h ydroxides, nitrates, cyanidcs, complex organics, and even humid weather conditiol1s. 2
In our earlier laboratory study of th e stresscorrosion crackin g of low-carbon steels [1) extensive
exposure pcriods were requucd to produce failures in
conventional (but subsize) tensile specunens in a
boiling aq ueous solu tion of N"H 4N0 3 . Failures of
specimens in lcss than 300 hI' were rare and some
specimens were r emoved from the corrodent after
1,800 hr exposure with no evidence of the development of str ess-corrosion cracks . Failures, when they
occurred, were in regions of str ess concen trations
resulting from th e combined action of stress and the
general attack of the corrodent. A typical failed
sp ecimen is shown in figure 1.
Anodic polarization of specimens produced preferential grain boundary attack at a small number of
boundaries, whether or not the specimens were
1 Figures in brackets indicate the literature references at th e end of thi s paper.
2 Failure of steel hooks, odesigned to h old in place the concrcte block facing on
the B ureau of Engraving and P rinting Annex, \Vashington, D.C ., was attributed
to stresscorrosion cracking [2].
347
FI GU RE 1.
Conventional st1'ess-corrosion speci men that fail ed af teT 300 hI' i n the aqueous boiling
N H 4 ~0 3
solution .
Cracki ng was l imited to reduced sectio n containing regions oC stress con centration .
TABLE
Carbon
A
B
0.20
.22
. 19
. 19
C
D
M a nganese
J1 hosphorus
0. 01
. 008
. 008
. 008
0. 41
.44
. 43
.54
Sulfur
Aluminum
Silicon
0. 029
. 025
.022
. 029
C hromium
0. 03
.061
. 17
.018
0.070
.016
< . 01
.04
Copper
0.02
. 009
0. 02
. 009
ND
ND
ND
ND
Lot
A
B
C
D
Yield
stre ngt h
Ultimate
Red uction
te nsile
in area
'r ransition
te mperature
strength
psi
psi
45, 400
32,800
49, 700
46,200
60, 200
62,500
66, 800
63, 200
63
59
66)1
68
348
OF .
37
98
:--J' D
ND
H ardness
Rockwell B
scale
62
70)1
72
71
Grain s ize
AST M N o.
7. 5
6. 0
8.0
8. 0
. 015
0. 05
ND
ND
Nickel
-~4"-
- -- 2 " - - - -1
1- - - -- - 3f- - - - - - -1
FIG U RE 2.
TABT,E
Lot
Average
standard
deviation
to faUurc
min.
min.
240
85
422
101
255
2,2
204
17,6
an y ti me t.
349
ll .
--
---
------
- - -- --
FIGURE
5.
Void in the center of the figu re resulted from shearing action at failure.
Appearance of fail eel surface at the left of the voiel indicateel that a stress
corrosion crack probably penetrated to t. hat poin t.
X 50.
FIGU R E
FIGURE
4.
350
-.46
. . i '
:! : :
. . . !
, I .
"i .
::~!
I ~; e
I-
...
:i: ; ~ ::
>
::!
::'" 1\:
~.
...J
....
.1
j.
j .;
:i :!
:ij i ;;:;.~~~i
Hil
.. , ij'lt 1[::
t , ~:
T
!. I I
-.
tl::l~ if:;
1 1'
, -,
i" i :
j . :'"
1 "
f"
.. i l
: : !: .
::~~
; ~
:.: :!
I.,
~-:..~ ; ..
- . 36
la
} ' I C:UH I"
6.
,.
5 min
.;:, :
.\ l ar kill !!s on lower scull' illdietlt c successive m inutes. lrregula ri ti cs ill potell ti a l (:urvc at., equilihriulll positio.ll s arC' ea llsco h:,; hoilin g of th(, sol ut ion .
351
rodin g m cdium afte r v arious ex posu re per iods sec~ion ed lOllgit udinall.\", a lld e""ft illi ll ed me Lftllog;'apllJeally fo l' cVId cll ce of s lr ess-co rros ion cracks . In
th is m an ll cr , it w as cl clcl'lll ill cd t ha t c rac ks m ay
s tart to d evelop with in 20 mi n a fter Ll lc sp cc imc'll
w as s t rcsscd . F igu re 7 s hows a s tr ess-corrosion
crack ill a Holch ed specimcn r cm ov ed a fter :30 min
exposure uncl eI' s t ress . E xalll ill a t ioll s o r ncwly
i ni tial ed s t ress-corrosion crac ks Ilav c us ually
vealed cor1'osio n p roci llcls 011 lhe s urfacc of th e
m eLal a t Lhe mouth s or l ite cracks i ll th ese sp ec im ell s.
Cracks followed i nLcrcr,)'s Lall ill e p at hs (see flg. 8)
and us ually d evelopcd in pairs in a 1I 0 lched s pecimen
fts is s how n in fig ures 8, 9, 10, a nd 11. H ctcnyi
aJ ld Li u [7] h av e s hown Ll la t Lhe maximu m s hear ilig
s tress is n ot at t he r oo t of t he n otch b u t is d isplaced
abou t }6 th e roo t raci ius fr OI1l t hftL point. T hi s
may explain t h e location of th e s Lr ess-corrosion
cracks in figures 8, 9, 10, and 11. K ies, S mit h,
and Irwin [8] h ave pos t ulated t h at t he direction
of th e maximum tensile str ess near t h e r oot of t he
not ch is n ot p ar allel t o th e t en sion axis b u t m ak es
an angle of a bout 60 d egr ees with it . This may
expl ain t h e direction tak en b v th e crack s .
The r esults ob tain ed by str'essin g a sp ecimen in
th e corroden t prior t o h ea ting i t were d iffer ent in
some r esp ec ts than those r eported ab ove. F or
example, applyin g th e s tress to sp ecim ens at room
tem p er at ure did not produ ce any apprecia ble ch an ge
Th e
m t he elec tr och emical solu tion p oten tial.
pote n Lial of t he s tr essed sp ecimen, how ever, b ecame m or e p osi tiv e wit h in creasill g temp erat ure as
was noLed ab ove for t he Ull s t ressed s pecim en h eated
in t hc COl'rod ent . Sp ecim ens r ema in ed in tile soluLioll at t emperat ure for 60 m in afte r rap id bo ilin g
h ad begun a nd dur ing t hi s p eriod t her e wcre n o
ch an ges in p oten tial, in t he ac t ive d irection , indicative of film r up ture. Sp ecim ens wer e the n r emoved
re-
1)
'it
f'
\) '
j)~
'iJ
r:-'
II
".
FIG U RE
.,
un cLe hcc!.
FIG U RE
7.
X 100.
X 500 .
FIGU RE
FIG U RE
{"net ched .
X 250.
un etchcd . X 100.
352
mm
F I GU R E 11 .
Unctc hcd.
X 90 .
Most inves tigators in the fi eld agree that str esscorrosion cracking is initia ted by an elec trochemical
process. The fact t hat no cracks developed in a
specimen to whi ch cathodic pro tec tion was applied
during the en tire exposure p eriod under str ess substantia tes this idea for low carbon steels.
If a con tinuous anodic region exists a t the gr ain
boundaries, and jf this r egion is attacked in the
cOl'roclent in t h e absence of str ess, ther e is no probl em in explaining t he init iation of in tercrystallin e
str ess-corrosion crackin g. M aterial at grain boundaries m ay b e in a higher en ergy s tate (and h ence
more active) th an t hat on the exposed faces of
crys tals . There was no eviden ce in this inves tiga tion , however , that the grain boundaries were
sufficien tly energe tic, in the absence of stress, to
provide a con tinuous anodi c pa th for either the
initiatio n or propaga tion of str ess-corrosion cr acks.
H ence, tbe appearan ce of active anodic areas wher e
cer tain grain boundaries con tact t he surface of the
m etal must be associa ted wi th the application of
th e stress. Two explanations of this m echanism
have b een proposed .
Th e first of th ese postulates that the polarized
condi tion on the s urface film develop ed during t he
h eating of the cOlTodent pro tec ts the sp ecimen from
corrosion generally as long as it is intact. Applying
str ess to the specimen imm ersed in th e boiling
conodent destroys the polarized condi tion (or
r up tures the film) in th e highly str essed r egion at
th e root of t he no tch . E lectroch emical solu tion
potential meas urem ents obtained at the fin al failure
of specimens indica ted tha t t his exposed surface
may ac tually be 0.20 to 0.2 5 anodic to th e ma terial
on the sides of the notch. Thus, an ideal condi tion
exists for corrosion by an electroc hemical process
wi th all of the r equired elements prese nt: a r ela-
9 Dlitial loading ruptures an area at the root o f the notch that is rela tivel y
la rge, probably cont.aining both crystal boundaries and crys tal interio rs. Intercrys ta ll ine corrosion can ta ke place , howe ver, onl y if t he exposed crystal faces
are cathodic to the material at or adjacent to the crystal boundaries .
353
10
One D specimen extended abruptly d uring the 60th min, , ee figure 10.
:TI1~d
,i} ;:!
::i
:::::
:jr:
FIG U R E
j
l
)-
12.
i'!)
,i . ,::,,'.:
.... ..
:,'.::: :,'.'.:.
I,..
::
'lliTl!i I T~ijii Hi
' .. , i,!!!,
'''I
....
:......., .
~
.. :,:, - .:.c
, ::i:: ;~'.:-.: ::::
....
I:!; :.'.::.:.
'i'
-::~
:,:.':.:
,-
i,',::
"It
;'..
:i::"
..
,,"
:!j
. .:~~~ ~1fi f:j:
j'
:::1 ,,_.
:-:::~:
..
"
..
".
""
"._.'
.
-: " , " .i I .::: ), ::~!
. . _.
,. .. . . . ::::
5 min
Oscillographic charts showing increases in elongation oj specimen (u pp er curve) and accom panying change in potential
(lower curve)
355
4. Summary
1. The mechanism of stress-corrosion cracking
and the relative susceptibility to cracking of four
low-carbon steels (carbon content 0.20 %) have been
studied using notched specimens and boiling 20
percent NI-I4 N03 as the corrodent.
2. Stress-corrosion cracking failures of these steels,
stressed to produce a small amount of plastic extension at the roots of the notches, occurred in 4 to
8 hr compared to several hundred hours for unnotched specimens.
3. At a temperature well above the transition
temperature (for either steel) a steel with a high
trans ition temperature from ductile to brittle fracture, in the (, harpy V notch test, was more resistant
to stress-corrosion cmcking than a steel with a much
lower transition tem perature. There was no correlation between tbe resistance of the four steels to
stress-corrosion cracking and their chem istry.
4. Cracks ftt the root of the notch were most probably initifttcd after major damage to polarizfttion or
th e protective film (th at resulted from initial stressing) had been r epaired . Cracks generally develop
in pairs on opposite sides of the root or the notch
and in the areas where th e shear stresses are postulated to be the greatest.
5. Crack ini tiation is at grain boundaries and is
postulated to be b~- an electrocllemi(" ~ll reaction with
submicroscopic anodes formed as the result of plastic
extension at the str ftin rate of the order of m ag nitude of O.OOl /sec.
6. In its early stages crack propagation is intercrystalline. It is postulated to be an electrochemical
process requiring a current density of about 0.15
amp /cm 2 at the tip of the crftck. The ftnode ftt the
tip of the crack m ay result from plas tic extension at
a stmin rate of the ord er of magnitude of O.OOl /sec or
from a stress-induced cathodic precipitate at the
grain boundary.
7. Tensile fracture, r esulting from overload, was
initiated as mftny as five times before it went to
completion. Earlier failures were prevented by the
strain hardening and strain aging of the metal ahead
of the tips of the stress-corrosion cmcks.
8. Cathodic protection can prevent the initiation
of stress-corrosion cracking in these steels and can
stop or delay propagation of cracks in m a terial
already severely damaged . This fact is considered
to be a very strong argument for an electrochemical
mechfwism for the initiation and propagation of
stress-corrosion cracks.
"I
5. References
[1] Logan, H. L. , Physical M etallurgy of Stress Corrosion
Fract ure, Ed. Thor ~. Rbod in, p. 295 (Intel'science
Publishers, ~e\y York, 1959).
[2] Holshouser, W. L. , and Staugait is, C., private communication.
[3] Logan, H. 1,. , J. Research , NBS 61, 503 ( 1958) RP2 29 1.
[4] Edmunds, Gerald, i::lymposium on Stress Corrosion
Cracking of Metals, p. 67, ASTM-AIME, Philad elphia (1944).
[5] Parkins, R . )[., Stress Corrosion Cracking a nd Embri t tlement, Ed. W. D. Robertso n, p . 140 (J ohn
'Wiley & Sons, Inc. , New York, 1956).
[6] Logan, H. L. , Physical M ctallurg.v of Stress Corrosion
Fracture, Ed. Thor ~. Rhodin, p . 145 (Interscience
Publi shers, New York, 1959) .
[7] H ete nyi, M. and Liu, T. D. , J. Appl. Mechanics 23, 451
(1956) .
[8] IGes, J . A. , Smith, H . L., and Irwin, G. R., Mem .
Sci. Rev. Metallurgie 57,101 (1960) .
[9] Logan, H. L., J. R esearch, NBS 48, 99 (1952) RP2291.
[10] Hoar, T. P., a nd West, J . M., Nature 181, 835 (1958).
[11] Hines, J . H., Corrosion Sci. 1, 21 (1961).
[12] W a ber, J. 1'., and McDonald, H. J., Stress Corrosion
Cracking of Mild Steel (Corrosion Pub!. Co., Pittsburgh, 1947) .
[13] Uhlig, H . H ., a nd White, R. A. , Trans. ASM 52, 830n
(1960) .
[14] K eating, F. H., Symp . on Internal Stresses in Metals
a nd Alloys, p. 3 11, Inst. Metals, London (1948).
[15] Harwood , J. J. , Stress Corrosion Cracking and Embrittlement, Ed. W. D. Robertson , p. 1 (John Wiley &
Sons, Inc ., New York, N.Y., 1956)
[16] Perryman, E. C. W., ibid., p. 61.
[17] Coleman, E. G., vVei nstein, D. , and Ro stok er, W. , Acta
Met. 5, 491 (1961).
[18] Engell, H.-J., and Ba um el, A., Ph ys ical Metallurgy of
Stress Corrosion Fracture, Ed. Thor N. Rhodin,
p. 363 (Interscience Publishers, New York, 1959).
[19] Gei l, G. W., and Candle, N. L ., J. Research, N BS 45,
129 (1950) RP2119.
356
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