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Marichev
Depending on the mode of inhibitor application either cornpetitive or cooperative adsorption of chloride and organic
inhibitor ions seem to occur on the metal surface. Higher inhibition efficiencies were obtained in the case of cooperative
adsorption which presumably takes place if chloride ions are
already chemisorbed on the metal surface.
The relative ranking of the inhibitor efficiencies was generally the same at high-purity iron and mild steels but most of the
substances tested were much less effective on steel than on
high-purity iron. The best results at all materials were found
with 1-naphthylmethylquinoliniumchloride.
5 Acknowledgement
6 References
1. G. Schrnift: Werkst. Korros. 34 (1983) 186.
2. G. Schmitt, B. Olbertz: Werkst. Korros. 35 (1984) 99, 106;
G. Schmitt, B . Olbertz, K.-R. Kurfz: ibid. 107, 110.
3. H . G d r , F. Richter: Z. Physik. Chem. Neue Folge 115 (1979) 69.
4. H . Gdhr: Dechema-Monographie 90 (1980) 1.
5. W. J . Lorenz, F. Munsfeld: Corr. Sci. 21 (1981) 647.
6. S. Haruyarna, F. Tsuru: Passivity of Metals, Proc. 4th Int. Congr.
Passivity, ed. by R. P. Frankenthul and J . Kruger, Electrochemical
(Received: 4. 3. 1985)
W 2362
A general theoretical and methodological approach to local dissolution and hydrogen embrittlement contributions to stress corrosion
cracking in various structural materials is discussed. According to this
approach a quantified determination of the hydrogen embrittlement
contribution to stress corrosion cracking in high-strength stecls,
titanium, aluminium, and zirconium alloys appears to be possible. On
the basis of a few postulates, a quantitative concept of hydrogen permeability of the passivating film at the tip of a crack in the metal is
developed; this concept allows for the first time a quantified determination of the relationship between critical hydrogen concentration and
stress intensity factor in steels, titanium, and aluminium alloys under
hydrogen embrittlement . Two new methods for studying adsorption
processes at the tip of a growing crack during stress corrosion cracking
are an additional outflow of this concept.
M)43-2822/85/060~0278$~.50/0
1 Introduction
At the present time each alloy-electrolyte system is considered as a particular case of stress corrosion cracking.
0 VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1985
279
Marichev
280
a = a.
+ al = a. + y [CI-] zV = a. + y$
(C1-) V,
(3)
where y, t, p are constants, (Cl-) and [Cl-] are the concentrations in the solution and on the passive film, respectively; a. is
the hydrogen permeability at V = 0 and (Cl-) = 0; a1 is the
hydrogen permeability which is proportional to [CI-] on the
passive film and to the crack growth rate. The adsorption in
this case is assumed to obey the Langmuir isotherm: [Cl-] =
p (Cl-). We propose that at very low crack growth rates (V
5 0 , O l mmh), al is independent of the crack growth rate:
a1(V = 0) = al (V 5 0,Ol). With increasing crack growth rate,
however, the latter a1 increases proportionally.
This analysis of hydrogen permeability is based on independent studies [2, 31 which show that in the absence of halide
ions no hydrogen embrittlement can be initiated in aluminium,
zirconium and titanium alloys, even at K = KIc and a cathodic
polarization of - 4 V. If, however, the passivatoridepassivator
ion ratio is optimum for each individual material, the cracking
rate increases at KHE 5 0.3 KIc and a cathodic polarization of
E = -0.7 V (hydrogen embrittlement becomes the main
stress corrosion cracking mechanism). The effect of a. in the
above materials is negligible (ao% al). In high-strength steels,
however,
can be important, because hydrogen embrittlement can occur even in the absence of aggressive ions, e. g. in
water or in sodium hydroxide of pH 10-12. In high-strength
steels, it is possible to create conditions in which a0 4 al. This
can be achieved by varying solution composition and cathodic
polarization potential. The present section is devoted to such
conditions exclusively.
In the scope of the previous discussion and from (2, 3) we
have
(4)
(5)
The experiments were carried out in a set-up with continuous resistance recording. The instrument enabled the length
and rate of cracking under stress corrosion cracking conditions
at room temperature to be measured. The uniaxial tensile
specimens (200 X 25 x 2-10 mm) were made of high-strength
steels, aluminium and titanium alloys. Their characteristics are
shown in Table 1. Each run was started in an electrolyte with
the maximum concentration of the aggressive ion. First, an
initial crack up to 1-1.5 mm in length was grown with gradually decreasing stress intensity factor, according to the method
of crack stop described elsewhere [lo]. In this way, the true
corrosion-mechanical properties of the materials (Krscc, KHE,
Vcc)were measured independent of the defects in the initial
fatigue crack and of the plastic deformation zone at its tip.
In order to obtain "n" from (5), one has to know the
dependence of the critical crack growth rate, V,,, and of Km
on the aggressive ion concentration. The unknown terms in
eqns. 4 and 5 should be constant. To ensure the latter condition:
All the experiments were conducted in buffered starting
solutions the ionic strength (and chloride activity factor) of
which were practically independent of the chloride concentration.
V,, and KHE in each run were determined using the same
cathodic polarization (ECP)and the same time lapse
between the start of polarization and the onset of accelerated crack propagation by hydrogen embrittlement.
The dependence of V, and KHEon (Cl-) was determined in
each run for the same specimen and in the same starting
solution with a regular variation of NaCl concentration.
For steel A, for example, the starting solution contained
0.03 M Na2HP04 (pH 10) 0.05 M NaN03, the NaCl
concentration being varied as follows:
Mark
Composition, weight%
A
B
C
High-strength steels
0.01 C, 18 Ni, 9 Co, 5 Mo, 1Ti
0.33 C, 3 Cr, 1Ni, 1Mo, 1V
0.38C, 3Cr, l M o , 1 V
D
E
0.40 C, 13 Cr
0.38C, 4Ni, l M o , 1 V
VT20
VT 5-1
Titanium alloys
Ti-6 AI-2Zr-1 Mo-1 V
Ti-5 Al-2.5 Sn
AL 27-1
Heat treatment
OB
Hardness,
MPa
HRC
Specimen
thickness,
mm
1900
1400
1450
1400
1500
1550
2100
1700
1780
1660
1750
175
55
48-50
50-51
46-48
50
50
2
3
3
3
2
3-5
870
850
1000
980
33
32
430
HRB 57-65
00.2
8
8
10
-e a1and [CI-]
= /3
(Cl-).
281
Table 2. K,, ( M P a 6 ) and V, (mmihr) dependence on chloride ion concentration in background clectrolyte
Tabelle 2. Abhangigkeit von der Chloridkonzentration im Grundelektrolyten
Material
Background
electrolyte,
Specimen
ET
Steel A
0.03 M Na2HP04
+ O.05M NaNO,
- 0.8V
0.3
0.03
0.01
0.003
0.001
0.0003
15.8
0
18.3
0
25.5
0
29.5
0
37.6
0
18.0
0
. 27.3
28.0
0
30.1
0
37.8
0
26.6
0
31.4
29.5
0
40.6
0
32.2
0
48.3
0
13.3
0
15.2
0
3++
VT 20
titanium
alloy
0.1
1.OM H,CrO,
-0.4 V
0.5M H2Cr0,
-0.4 V
same
31.4
36.2
- _ _ _
0.007
0.009
26.0
0.012
30.4
32.6
_
_
_
0.009
0.011
16.7
0
0
20.5
0
28.6
0
46.6
0.025
55.4
32.3
0.024
43.0
~
0.018
44.0
0.044
49.6
0.034
282
Marichev
o.ob1
/wzp3I11
0.61
(CI-),M
----r
0.1
NaC1-Konzentration
or against the assumptions made in eqn. 1 to 5 . They should
show, for example, whether n depends on the way hydrogen
penetrates into the specimen. In other words, it should
become clear whether n is identical, irrespective of the type
of hydrogen embrittlement, i. e. in connection with stress corrosion cracking or hydrogen embrittlement in gaseous hydrogen (with the same material). In the case of hydrogen
embrittlement during stress corrosion cracking, n should not
be influenced by solvent, passivator and depassivator concentrations, pH, cathodic polarization potential, etc., even
though the variation of these parameters substantially changes
V,,, KHE, 0 and other terms in eqns. (2) to (5). Since n
depends on no electrochemical parameters originating from
the solution, all data related to one material can be presented
as one curve. To do this, for a series of experiments where
(C1-) concentration is the only variable we should define a
standard solution with a maximum value of (Cl-). Then,
from (4) and (5) we have
points exhibit a considerable scatter, they all can be approximated by one straight line for each material. Their slopes - n
- for aluminium, titanium alloys and for high-strength steels
are marked accordingly: 2.1, 3 and 5.5. The relative error,
determined by the least square method, does not exceed 10%.
The value of n does not depend on the electrochemical
parameters related to the nature of the electrolyte (chemical
composition, potential and the duration of the cathodic polarization). This fact has been theoretically predicted. It does not
depend either on heat treatment (steel C), on composition,
structure and strength of titanium alloys or high-strength martensitic and marageing steels. Obviously, ,,n is an invariant
characteristic of hydrogen embrittlement in the alloys having a
given base: It depends only on the nature of the base metal. It
is further probable that the different values of n for
aluminium and titanium alloys and high-strength steels indicate different hydrogen embrittlement mechanisms. An
increase of n with increasing hydrogen embrittlement susceptibility of the aluminium-titanium-high-strength-steel line
can be noticed. Unfortunately, no evidence exists as to the
effect of the metal lattice on the response of n; this lack,
however, can be eliminated by studying titanium &alloys and
austenitic high-strength steels with the method described.
As has been pointed out earlier, the value of n should not
be affected by the way in which hydrogen enters into an alloy.
This conclusion can be verified by comparing n = 5.5
(obtained for hydrogen embrittlement during stress corrosion
cracking of high-strength steels) with a value of n obtained
during gaseous hydrogen embrittlement. Literature contains
much information about the KRE dependence on hydrogen
pressure in high-strength steels. It is limited, however, by the
high-pressure range (over 1atm). Under this pressure, the film
surface must have been covered to saturation by adsorbed
hydrogen atoms. These data cannot be used in n determination. There is only one paper [7] in which the KHEdependence
on hydrogen pressure (0.1-1000 torr) in 4340 high-strength
martensitic steel has been given. The results of this work shall
be used to determine the value of n in gaseous hydrogen
embrittlement. It seems that the hydrogen permeability, a,
must be introduced into the analysis of the gaseous hydrogen
embrittlement, since there is no exact definition of hydrogen
purity in that paper. It is known from other work [12] that
even
96 of oxygen significantly increases Km, whereas in
another paper [5] it was shown that a complete coverage of a
clean iron surface by adsorbed hydrogen was possible at 1mPa
pressure. Presuming that hydrogen contamination by oxidizers
in that experiment [7] did not depend on the hydrogen
pressure, we shall further presume that hydrogen permeability, a, is independent of the hydrogen pressure. From eqs. (1)
to (4) and Sieverts law we obtain
KHEx ,
10 l gP x = - n lg PSI
KHESt
where st and x mean standard and variable (Cl-) concentrations. According to (6), all the data pertaining to different
specimens of the same material are on one curve starting from
the origin of the coordinates Ig u x/uSt - lg KHE x / Kst,~ which
~
describe the characteristics of the standard solution. Their position is not influenced by the composition of the actual solution, by the potential, or by the time from the beginning of
cathodic polarization to the acceleration cracking.
Figure 2 shows dependence on (C1-) of V,, and KHE according to Eq. (6) for all experimental materials. Even though the
(7)
O]%QILni
Fig.
strain
0.5
a)
0 0
Alloy
Electrolyte
E,,, V,,
Points
AL27-1
0.5 M H2Cr04+
0.002-0.01 M NaCl
0.05 M H2Cr04
0.002-0.01 M NaCl
- 0.7
- 0.7
- 0.4
- 0.4
- 0.2
- 0.4
- 0.4
- 0.5
- 0.5
- 0.8
- 0.8
- 0.8
- 0.8
0.5 M H2Cr04+
0.01-0.3 NaCl
*) same
same
2.0 M H,CrO, +
0.01-0.3 M NaCl
VT 5-1
same
38 X 3 MFA (C) Borate buffer
tempered
pH 7 + G-4
250 C
20 gll +
0.003-0.1 NaCl
38X3MFA
tempered
450 C
same
0.03 M NazHPOj +
SP 33 (B)
0.05 M NaN03 +
0.001-0.03 NaCl
0.03 M Na2HP04+
0.05 M NaN03 +
0.001-0.03 NaBr
H 1 8 K 9 M S T 0.03 MNa2HP04+
0.05 M NaN03 +
(A)
0.0003-0.1 NaCl
0.03 M Na2HP04+
0.05 M NaN03 +
0.0003-0.1 M Na2S04
AISI 4340
**) gaseous hydrogen
PHZ= 0.1-600 torr
VT 20
X
0
0)
11235121
0.1
0.2
0.3
---0.L
0.
lg ( K H E ~ ~ K H E ~ ~ J
Fig. 2. KHEdependence on hydrogen permeability, a, of the passivating films at the crack tip in aluminium (a), titanium (b) alloys, and in
high-strength steels (c) during stress corrosion cracking (see eq. (5)).
Alloy compositions, electrolytes and potentials of cathodic polarization are shown in the legend below. PD is the boundary of planestrained stress rate
Abb. 2. Abhangigkeit von KlrBbei der Spannungsrifikorrosion von
Aluminiumlegierungen (a), Titanlegierungen (b) und hochfesten
Stahlen (c) von der Wasserstoffpermeation durch Passivierungsschichten an der RiBspitze (nach G1. ( 5 ) )
283
n
0
284
Marichev
~~~
Table 3. Critical stress intensity factor, KHE(MPafi), critical crack growth rate, V, (mmihr), and hydrogen permeability of the passivating
film on the metal at the crack tip, a (relative units) for high-strength steels A and B during stress corrosion cracking in solutions with pH 10,
E, = -0.8 V
Tabelle 3. Kritischer Spannungsintensitatsfaktor, kritische RiBausbildungsgeschwindigkeit und Wasserstoffdurchlassigkeit der Passivierungsschicht auf dem Metall an der RiBspitze, a fur hochfeste Stahle A (H 18KY M 5 T) und B (33 KhNMFVA) in Spannungsrifikorrosion auslosender
Losung
Concentration
Steel A
NaOH, pH 10
0.03 Na2HP04
0.03 Na2HP0, +
0.01 NaF
0.03 Na2HP04,
0.01 NaCl
0.03Na2HP0, +
0.1 NaCl
0.03 NaCH,COO
0.1 Na,SO,
0.03Na2HP0, +
0.1 H2O2
Steel B
KliE
v,,
14.6
11.1
0+
0
U++
KHE
V,,
0.002
0.006
18.0t
15.8
0.05
0.02
1
6
15.9
0.02
15.8
0.005
12
9.0
11.5
9.3
0.35
-
0.6
14.3
3.5
12
11.2
4.5
8.9
1+
4.7
0.03 Na2HP04
0.1 Na,S,O,
+)
standard.
15
285
(zr)II,
0.01
[a-],
= - -
0.0001
1 1 1 1 1 1
I , 1 1 1 1 ,
0.001
0.0 1
CNahlOg
0.001
0.01
C anion,M
0.1
(9)
WI*
286
Marichev
% at
I
0.001
0.01
1.o
C anion,M
0.003
0.01
0.03
NaCL,M
0.1
287
288
Marichev
v)
-I.-
a-
01
0.01
I
+O!&
+a12
-0.2
Ecp
jw23578/
0
J
VH
-0.4
l-
0.1-
0.01-
0.001I
+0.6
+ 0.L
+0.2
0
Ec,
-0.2
Fig. 9. Potential dependence of 0 (degree of hydrogen atom coverage of the passive film) at the crack tip during stress corrosioii cracking
of steels D (l),A (2) in 2 M CrO, 0.1 M Na,SO,
0.03 M NaCl,
and E (3) in 2 M Cr03 + 0.02 M Na2SO4
Abb. 9. Potentialabhangigkeit 0 bei Spannungsrifikorrosion der
Stahle D (1). A (2) und E (3)
289
0.01-0.1 M NaC1) can intensify hydrogen embrittlement during stress corrosion cracking.
Aluminium alloys, for example, can undergo hydrogen
embrittlement only in these electrolytes [3]. The values of KHE
for titanium alloys and high-strength steels are considerably
lower than in the presence of other oxidizers. Normally, at a
sufficiently high cathodic polarization potential, KHEis below
KIscc. These findings mean that in chromium anhydride. a
passive film developed at a crack tip effectively suppresses
local anodic dissolution controlled cracking, while maintaining
sufficiently high hydrogen permeability at the same time.
Unlike other 0x0-ions, chromates are reduced on the metal
surface. As a result, Cr3+ becomes part of the passive film
composition [16]. Its concentration on aluminium alloys is
about 5% [B].The oxide and hydroxide of the aluminium
practically do not adsorb hydrogen [3], while the heat of hydrogen adsorption on the chromium oxide can be very high
[31]. Presumably, CP creates effective adsorption sites at
which hydrogen ions are discharged. So, the passive film that
develops in the chromium anhydride electrolyte may act as a
bridge for hydrogen penetration into the metal, encouraging
hydrogen embrittlement controlled stress corrosion cracking.
At the same time it maintains its highly protective characteristics suppressing local anodic dissolution controlled stress corrosion cracking.
5 Conclusion
The quantified approach to the hydrogen permeability of a
passive film at the crack tip of a metal undergoing stress corrosion cracking is based on the following postulates:
- hydrogen embrittlement criterion selected at will,
- hydrogen permeability of the film proportional to the cracking rate and to the concentration of adsorbed activating
ions.
- coverage of the film by adsorbed hydrogen independent on
the adsorption of other ions.
Each of these postulates cannot be rigorously proved,
neither theoretically nor experimentally. They do not, however, contradict known facts, and taking them as such, one can
draw certain a priori conclusions. These conclusions have been
proven in this study. For example, it has been suggested and
experimentally proved (Section 2) that n in eqn. (1)to (5)
need not be influenced by the potential and the exposure to
cathodic polarization. It need not be affected by the composition of the solution and by other factors related to the electrolyte, although these factors have a bearing on KHEand Vcr. It
has been suggested and proved that the values of n must be
the same in hydrogen embrittlement controlled stress corrosion cracking and in gaseous hydrogen embrittlement of highstrength steels. The chloride ion adsorption isotherm for
aluminium alloy obtained from mechanical-corrosion data is
practically the same as that determined by the ESCA technique (Section 3). The slope of the hydrogen coverage vs
potential curve estimated for steel in alkaline solution is
0.25 VIO-decade and therefore close to the 0.27 and 0.20 VI
@-decade obtained for iron and nickel from direct electrochemical measurements (Section 4).
Thus, as these conclusions have been experimentally confirmed, the initial assumptions forming the foundation of this
approach may be admitted to be correct. In addition, the in
situ technique for studying competitive anion adsorption on a
passive film at a crack tip undergoing stress corrosion cracking
should be accepted as well as the technique for studying the
290
Marichev
6 References
1. V . A . Marichev, I. L. Rosenfeld: Corrosion 32 (1976) 423.
2. V. A . Marichev: Werkst. Korros. 33 (1982) 1.
3. V. A. Marichev: Werkst. Korros. 34 (1983) 300.
4. H. K. Birnbaum: Atom. Fract. Proc. NATO Adv. Res. Inst.,
New York 1981, London 1983, p. 733.
W 2357
Die Berichte iiber die Ergebnisse des Forschungs- und Entwicklungsprogramms ,,Korroion und Korrosionsschutz werden in einem der nachsten Hefte dieser
Zeitschrift fortgesetzt.
The reports on the results of the R & D-Program Corrosion and Corrosion Protection will be continued in one of the forthcoming issues of thisjournal.