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278

Werkstoffe und Korrosion 36, 278-290 (1985)

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.

and Corrosion Protection (FE-KKs) and by the Fond der


Chemischen Industrie.

5 Acknowledgement

Society, 1978, p. 564.


7. B. Olbertz: Dissertation, Technical University of Aachen, F.R.G.,
1980.

This work was supported by the Arbeitsgemeinschaft


Industrieller Forschung (AIF), by the Bundesminister fur
Forschung und Technologie within the project Corrosion

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 quantified concept of the hydrogen permeability


of passivating films at a crack tip during
stress corrosion cracking of structural materials
Quantitatives Konzept der Wasserstoffpermeation durch Passivierungsschichtenan der
RiBspitze bei der SpannungsriBkorrosion von Konstruktionswerkstoffen
V. A. Marichev*

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.

* Corrosion Department, Institute of physical Chemistry, Academy


of Sciences of the USSR, Leninski Prospekt 31, USSR-117071
Moscow.

M)43-2822/85/060~0278$~.50/0

Mit Hilfe einer allgemeinen theoretischen und methodologischen


Behandlung wird versucht, die Rolle der Wasserstoffversprodung und
die lokale anodische Auflosung bei der SpannungsriBkorrosion verschiedener Konstruktionswerkstoffe zu klaren. Die Moglichkeit einer
Quantifizierung der Rolle der Wasserstoffversprodung bei der SpannungsriRkorrosion von hochfesten Stahlen, Titan-, Aluminium- und
Zirkoniumlegierungen wurde daher nachgewiesen. Ein quantitatives
Konzept der Wasserstoffpermeation durch passivierende Filme auf
Metallen an der RiBspitze bei SpannungsriRkorrosion wird aus einigen
grundlegcnden Postulaten entwickelt. Damit wird zum ersten Ma1 ein
Zusammenhang zwischen der kritischen Wasserstoffkonzentration
und dem Spannungsintensitatsfaktor bei der Wasserstoffversprodung
von Stahlen, Al- und Ti-Legierungen gefunden. Aus diesem Konzept
werden zwei neue Methoden fur Adsorptionsuntersuchungen an der
RiBspitze bei Spannungsriljkorrosion abgeleitet.

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

Werkstoffe und Korrosion 36, 278-290 (1985)

A quantified concept of the hydrogen permeability of passivating films

Moreover, no generally accepted theory or methodology is


available for identifying the cracking mechanism for an! Structural material, irrespective of its base or structure. Many
investigations in this field have been based on a rather simplifying approach: the predominant role of one possible
mechanism was emphasized without considering probable
competitive cracking mechanisms. An attempt was made elsewhere [l-31 to work out a general electrochemical approach
on the basis of the following assumption:

- Joint action of two basic processes at a crack tip is possible:


namely local anodic dissolution and hydrogen embrittlement.
- Their contributions depend on the nature of alloy, electrolyte, heat treatment, potential, etc. The crack growth rate
and the stress intensity factor are additional important parameters.
- The crack growth rate reflects the similarity of the metal
properties at the crack tip and on a newly generated surface
and also controls the permeability of the passivating films.
A regularity of the effect of cathodic polarization on cracking was discovered in the case of high-strength martensitic
steels [l]:
The same potential of cathodic polarization being similar
(alloy, electrolyte, temperature, etc.) either inhibits cracking
if the initial crack growth rate and the stress intensity factor at
the corrosion potential are below a certain critical level, or
accelerates cracking if the crack growth rate and the stress
intensity factor exeed this level.
The effect of cathodic polarization is thus ambiguous, and
this finding has been used as a basis for the experimental backup of this work.
The critical values of the crack growth rate, V,,, and the
corresponding critical values of the stress intensity factor, KHE,
are quantitative characteristics of local anodic dissolution and
hydrogen embrittlement. At crack growth rates less than V,,,
and stress intensity factors less than KHE, local anodic dissolution is the main mechanism, whereas at crack growth rates
greater than V,, and stress intensity factors greater than KHE,
hydrogen embrittlement is the main mechanism of stress corrosion cracking. V,, and KHEdepend on alloy and electrolyte
compositions, potential, etc. Changes in the alloy-electrolyte system resulting in less stable passive films or a lower
critical hydrogen concentration give rise to a decrease of V,,
and KHE and thus enhance hydrogen embrittlement in stress
corrosion cracking. This conclusion was proved by the establishment of the relations between V,, and KHE for highstrength steels stress corrosion cracking and the corresponding
concentrations of chlorides, hydrogenation promoters and
oxidizers in the electrolyte. Heat treatment of the steels affects
the critical values in a similar way [I, 21.
This novel interpretation of stress corrosion cracking is obviously free from constraints imposed by the nature of alloy or
electrolyte. It is significant that the ambiguous effect of
cathodic polarization on stress corrosion cracking in austenitic
high-strength steels, titanium, zirconium and aluminium alloys
can be predicted [2, 31. Based on these experiments, a general
theory and methodology of local anodic dissolution and hydrogen embrittlement contributions to stress corrosion cracking
can be formulated.
The main aim of this work is to formulate a quantified concept of the hydrogen permeability of the passive film at the
crack tip and to determine the relation between the electrochemical conditions, i. e. V,, and Km, and the critical hydrogen concentration in stress corrosion cracking.

279

2 Critical hydrogen concentration (CHcr)


vs critical stress
intensity factor (Km) in the hydrogen embrittlementof
structural materials
The fundamental terms in the theory of hydrogen embrittlement in structural materials are the critical hydrogen concentration (CHa) and the critical stress intensity factor (Km) for
hydrogen embrittlement . Km can be determined experimentally, both in gaseous hydrogen and under stress corrosion
cracking conditions. However, neither a generally accepted
technique suitable for physico-chemical analysis, nor a theory
of hydrogen embrittlement is available for the determination
of absolute values of CHcrrdespite the interdependence of CHcr
and KRE [3-91. This is why only the qualitative aspect of this
relation can be considered today as being definitely established: the higher K, the lower CHa.
The method of studying the relation between CHcrand KHE
evolved from a general understanding of the stress corrosion
cracking as described elsewhere (see 1). The experimental
determination of the critical values of crack growth rate, V,,,
and their KHE counterpart was another element of this
method.
The main postulate of the hydrogen embrittlement theory (a
crack grows when a critical hydrogen concentration, CH,,, and
a critical stress intensity factor, KHE, develop ahead of the
crack tip), supposing that CHa decreases when K increases,
can be written as follows:

This dependence is one of the possible ways of describing


the rupture criterion under hydrogen embrittlement conditions; no specific physical model of hydrogen embrittlement is
required. Formally, it is close to a power law discussed elsewhere [8] in terms of the hydrogen embrittlement decohesion
theory [7]. Hydrogen penetration into the metal at the crack
tip can take place in a sequence of steps:
1. Electrochemical reactions resulting in a certain concentration of adsorbed hydrogen atoms on the passive film: 0,
degree of coverage;
2. Migration of the hydrogen through the film, building up a
certain concentration underneath (CHmf).This concentration is controlled by the hydrogen permeability a of the
film: CHmf= @a.
3. Hydrogen transport in the bulk of the metal and buildup of
a critical hydrogen concentration within a strictly limited
time
cHcr = cHmfE = OaE
just at the crack tip (E = l), or a little ahead (5 # 1).
In this formal description the localization of CHcris not very
relevant, since it is not related to any particular physical model
of hydrogen embrittlement. On the other hand, it should be
more useful to define a mechanism and a transport coefficient
(5) applicable to variable experimental conditions (chloride
ion concentration, or cathodic polarization).
Expression (1) is a hydrogen embrittlement criterion in the
alloy-hydrogen system. It can be used as a criterion of stress
corrosion cracking connected with hydrogen embrittlement
when transformed accordingly

Here, 0 and a depend on the composition of alloy and


electrolyte, pH, temperature, potential, etc. Hydrogen per-

Marichev

280

Werkstoffe und Korrosion 36,278-290 (1985)

meability depends on the crack growth rate and aggressive ion


(e. g. chloride) concentration

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

tive units i. e. in terms of the slope of expression (5) Ig K


[(Cl-) V,,], "n" can be determined.

2.1 Experimental techniques

OEy$ (Cl-) V,, K;IE = const.

(4)

lg [(Cl-)Vcr] = const. - n Ig KHE.

(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:

Since the constants in (4) are unknown, no absolute values


of hydrogen permeability can be obtained. If expressed in rela-

0.1 - 0.03 - 0.01 - 0.003 - 0.001 - 0.0003 - 0.1 - 0.03 - 0.01


- 0.003 M.

Table 1. Test materials


Tabelle 1. Versuchswerkstoffe

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

Cast aluminium alloy


A1-10 Mg-0.5 Si

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

Natural ageing, 12 years 260

430

HRB 57-65

ageing, 500 "C


tempering, 300 "C
tempering, 250 "C
same, 450 "C
tempering, 400 "C
tempering, 350 "C
Hot-rolled plate

00.2

8
8

10

A quantified concept of the hydrogen permeability of passivating films

Werkstoffe und Korrosion 36,278-290 (1985)

When a new solution was introduced the electrochemical


cell and the specimen were washed with water and solution at
a rate of ten times. Concurrently, the crack in each new solution was extended for another 0,l-0.15 mm under low-cycle
load (about 100 cycles). This pulsing load made the sides of the
crack work as a pump (R = 0.1), providing for a rather fast
replacement of the solution inside the crack [ll].V, and KHE
were determined for each new electrolyte. When the readouts
became stable, the electrolyte was replaced again. This technique substantially reduced the scatter of the data. The relative error was 10% for V, and 4% for KHE. Table 2 shows the
reproducibility of the measurements on the same specimen in
varying solutions. Since diffusion may be important for CHcrr
and since the results of other works [9] had shown that the
distance of the rupture zone from the crack tip depends, in the
case of hydrogen embrittlement, on stress intensity factor, we
had to strictly maintain the same time interval from the beginning of cathodic polarization of the onset of accelerated cracking. The rupture zone tends to shift with time. Presumably, it
should be located at the same distance from the crack tip,
when the polarization time is constant during V, and KHE
determination. The constancy of E, in eqn (2) can be ensured in
this way. In all the experiments this time interval was 150 s
(exceptions will be shown separately (see Fig. 2 ) ) . The potentials were measured with reference to the standard hydrogen electrode.

2.2 Experimental results and discussion


Any experimental verification of Eqs. (4) and (5) can only
be made on the assumptions stated before. In the first place it
is true for the conditions described as follows:
a0

-e a1and [CI-]

= /3

(Cl-).

281

The first is automatically satisfied for titanium and


aluminium alloys: hydrogen embrittlement is impossible in the
absence of aggressive anions. In high-strength steels this condition can be created by the addition 0.02-0.05 M of an
inhibitor to the starting solution, e. g. G-4, K2Cr04, or
NaN03. The range of the chloride ion concentrations which
meets the requirements of the second condition was determined by estimating V,, and Km with respect to the C1- concentration. As follows from Fig. 1, the KHE vs (Cl-)-curve has
two sections: one section where KHEis independent of (Cl-),
and another one where KHEdecreases with increasing (Cl-).
Obviously, according to [Cl-] = p (Cl-)/I
(Cl-), the
gradual increase of the chloride ion concentration increases
chloride adsorption by the passive film at the crack tip. The
hydrogen permeability of this film then increases, while Km
drops. The film surface then becomes saturated with adsorbed
[Cl-] chloride ions at specific values of (Cl-) in each alloyelectrolyte system. Any further increase of (Cl-) does not
result in a change of hydrogen permeability or of KHE. In the
case of the titanium alloy VT 20, for example, the saturation
and the maximum admissible concentration of chloride ions in
0.5 M C r 0 3 are about 0.3 M (see Fig. 1, curves I and 1).The
requirement for a minimum value of (Cl-) originates from the
need to maintain the plainstrain state of the specimen with
increasing KHE and decreasing (Cl-) [lo]. Table 2 illustrates
the behaviour of V, and K Hwith
~ reference to the chloride ion
concentration in the media mentioned above.
In view of the above considerations, % in eqn. 1 to 5
exclusively characterizes hydrogen embrittlement in the particular alloy-hydrogen system. It has no relation to the corrosion resistance of an alloy in an electrolyte. Consequently,
n may depend on alloy base, alloy composition, structure,
heat treatment and temperature, but not on any electrochemical parameter of the electrolyte. Any experimental proof of
these conclusions could be interpreted as an evidence in favour

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

Chloride ion concentration (M)

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

Werkstoffe und Korrosion 36,278-290 (1985)

0.61
(CI-),M

----r

0.1

Fig. 1. KHEdependence on NaCl concentration in background solutions:


1 - VT 20 titanium alloy (0.1 M H2Cr04;E
, = -0,4 VH);
2 - AL27-1 aluminium alloy (0.5 M H2Cr04;E, = - 0.7 V);
3 - 38X 3 MFA steel (borate buffer pH 7.4 + inhibitor G-4, 10 g/l,
E,, = -0.5 V);
4 - 18HK9M5T steel (0.03 M Na,HP04 + 0.05 M NaN03,
E,, = -0.8 V)
1- hypothetical adsorption curve for chloride ion from the solution to
the surface of the passivating film at the crack tip during stress
corrosion cracking of the titanium alloy VT 20
Abb. 1. Kritischer Spannungsintensitatfaktor K,, fur die Wasserstoffversprodung bei SpannungsriRkorrosion in Abhangigkeit von der

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)

where st and x refer to maximum (600 torr) and the lower


pressures of hydrogen, respectively. As Fig. 2c shows, the
results from [7] that have been treated by eq. (7) and appear in
the graph as asterisks fall into the band of other types of the
high-strength steels under hydrogen embrittlement accompanied by stress corrosion cracking. The value of n, determined separately from these results, is 5.1. This is in good
agreement with the value of n for hydrogen embrittlement
accompanied by stress corrosion cracking (5.5 k 0.6).

A quantified concept of the hydrogen permeability of passivating films

Werkstoffe und Korrosion 36,278-290 (1985)

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 ) )

Despite the empirical nature of eqs. (1) to (5) which are


based on no specific physical model of hydrogen embrittlement, the values of n in this work can help to construct such
a model for some materials. The identity of n in stress corrosion cracking accompanied by hydrogen embrittlement in
gaseous hydrogen for high-strength steels suggests that the
mechanism is the same in these environments. Eqs. (1) to ( 5 )
are based on the following postulates:
- hydrogen embrittlement criterion selected at will,
- hydrogen permeability proportional to crack growth rate
and to the chloride ion concentration on the passive film,
- 0 independent of [Cl-1.
These postulates do not contradict known theories, but they
cannot be quantitatively evaluated or experimentally tested.
Considering the present state-of-the-art it is e. g. impossible to
check the values of n obtained in this work. This is so
because the modern hydrogen embrittlement theory allows
but a qualitative explanation of the CHcrvs KHE relation.
Nonetheless, since the values of n are known, they can be
used to draw some a priori conclusions from the concept of
hydrogen permeability of the passive film at a crack tip. These
conclusions which will be discussed in Sections 3 and 4 below,
can be checked experimentally.

283

n
0

*) Time from the start of cathodic polarization to the acceleration of


crack growth is 10 s (in the other experiments 150 s).
**) Experimental results obtained elsewhere [7] and treated by
Eq. (7).

3 Hydrogen permeability of the passive film at a crack


tip in a metal under stress corrosion cracking conditions
Hydrogen permeability, a, has been introduced as a term in
this work. It is a dimensionless parameter which shows the
proportion of the hydrogen adsorbed by the surface film and
penetrates to the metal-film interface, causing hydrogen
embrittlement. The physics of the hydrogen permeability is
not yet clear. We can only say so far that hydrogen diffusion
through a passive film may not be decisive. For example, an
acceleration of stress corrosion cracking upon cathodic polarization starts in aluminium and titanium alloys within 0.8-1 s
when K > KHE, but does not start even after lo4 when
K < KHE,other conditions being exactly the same.
The absolute values of a cannot be determined from experimental values of V,, and Km, because 0 and constants in eqs.
(2) to (4) are unknown (with the exception of n). Assuming,
however, a = 1 for some randomly set standard conditions,
its relative variations (a,) with changing chloride ion concentrations can be determined from

284

Marichev

Werkstoffe und Korrosion 36, 278-290 (1985)


~

~~~

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

variation of u upon addition of 0.05 M NaN03 to the electrolyte.

Here, st and x are standard and real conditions of the


experiment, respectively. Presumably, small variations of electrolyte composition (within 0.05 M of the activator or the passivator) do not change 0 which depends mainly on specimen
potential and electrolyte pH [13].
Experiments with high-strength steel provided the most
complete information about a and its components, uOand al,
with respect to the electrolyte composition (see eq. (3)). This
is due to the fact that in water and NaOH solutions hydrogen
embrittlement-controlled cracking of such steels occurs at sufficiently negative potentials of cathodic polarization without
the presence of activating ions. The standard conditions of the
experiments were ( a = a. = 1):
- NaOH pH 10,
- cathodic polarization potential E, = - 0.8 V in V,, and KHE
determinations,
- time from the beginning of cathodic polarization to the
cracking acceleration in hydrogen embrittlement conditions
150 s.
The corrosion potential of these steels was approximately
- 0.2 V in NaOH of pH 10, and - 0.15 V in 0.03 M Na2HP04.
It vaned insignificantly (k 0.05 V) when 0.05 M of an activator
or passivator were added.
Table 3 shows KHE and V,, for steels A and B in some
electrolytes. a was calculated from these values for n = 5.5,
using eqn. (8). Such evaluations of the variation of a with
varying electrolyte composition can be made only for the same
steel: by definition, the standard includes not only electrolyte and potential, but also the specimen material. This means
that the standard conditions for different steels are different in
the same solutions.
As follows from Table 3, the hydrogen permeability is significantly increased by phosphate, acetate, and chloride and
sulphate, while nitrate gives rise to a sharp reduction. It is
interesting to compare the effects produced by phosphate and
nitrate.

Although phosphate is considered to be a corrosion


inhibitor, it increases a by a factor of 5 to 6. Nitrate, though
normally considered as corrosion activator, sharply reduces a
in solutions containing chloride and sulphate and also completely suppresses hydrogen embrittlement in high-strength
steels in a standard NaOH. Some other papers [ll, 141, however, demonstrated its inhibiting effect on stress corrosion
cracking and corrosion fatigue. Some long-term experiments
(up to one months duration) showed that the values of KHE
and Krscc are considerably increased in the presence of nitrates.
Figure 3 gives a more detailed information concerning the
effect of nitrate on the hydrogen permeability of the passive
film at the crack tip in steel B. It shows that as little as 0.0001
M NaN03 added to the standard NaOH solution of pH 10,
give rise to a noticeable reduction of hydrogen permeability.
With 0.003 M NaN03, a decreases by a factor of 100 (curve l),
while addition of 0.03 M Na2HP04 to the standard solution
increases a by a factor of 6 and addition of 0.01 M NaCl by
more than two. The effect of NaN03 on a is influenced by
other ions: while 0.001 M NaN03 decrease a in NaOH by a
factor of 15 (curve l),a remains practically unchanged in the
presence of 0.01 M NaCl (curve 3).
In addition to nitrates, other anions, too, decrease a: they
are preferentially oxidizers such as chromates, nitrites, nitrobenzoates, etc. There is no correlation, however, between
their oxidizing strength and their effect on hydrogen permeability. For example, the strongest oxidizers, H2O2 and
Na2S208(up to 0.1 M concentration), do not decrease the
value of a for steel A in 0.03 M Na21-IP04.Na2S208,on the
other hand, gives rise to an increase of Q because it is reduced
to sulphate which, like the chloride ion, increases hydrogen
permeability. Addition of 0.05 M NaN03, for example,
decreases Q by as much as three orders of magnitude (Table
3), although it is a much weaker oxidizer; its effect is based on
its ability to effectively displace chloride ions from the steel

Werkstoffe und Korrosion 36,278-290 (1985)

A quantified concept of the hydrogen permeability of passivating films

285

experimental determination of KHE and V,, in standard and


real conditions, followed by a calculation of the variation of
the chloride concentration at the crack tip. In standard conditions [Cl-I,, is assumed to be 1. In real conditions, the chloride
or nitrate ion concentrations may be different. The constants
in eqn. (2) to (4) are assumed to be the same in both conditions. From eqn. (2) to (4) we obtain
d

(zr)II,

0.01

[a-],
= - -

0.0001

1 1 1 1 1 1

I , 1 1 1 1 ,

0.001

0.0 1

CNahlOg

Fig. 3, Hydrogen permeability, a, of the passivating layers on the


metal at the crack tip during stress corrosion cracking of high-strength
steel B in various solutions with pH 10: 1 - NaOH; 2 - 0.03 M
Na,HP04; 3 - 0.03 M Na,HP04 + 0.01 M NaCl vs NaNO, concentration. a = 1 in NaOH, E,, = - 0.8 V
Ahh. 3. Abhangigkeit der Wasserstoffpermeation a durch Passivierungsschichten an der RiBspitze bei der SpannungsriRkorrosion des
hochfesten Stahls B von der NaN0,-Konzentration

0.001

0.01

C anion,M

0.1

Fig. 4. Relation between adsorbed chloride ion (CI-] concentration


on the passive film at the crack tip in steel B during stress corrosion
cracking in 0.03 M Na,HPO, + 0.01 M NaCl and inhibitor concentration: 1 - Na2Cr04,2 - hexamethylenamine 3.5 dinitrobenzoate (G-4),
3 - NaNO,, 4 - NaN03 . [Cl-I,, = 1 for 0.03 M Na2HP0, + 0.01 M
NaCl, E,, = - 0.8 V
Ahb. 4. Abhangigkeit der Konzentration der auf der Passivierungsschicht an der Riaspitze adsorbierten Chlorionen [Cl-] bei der SpannungsriBkorrosion des hochfesten Stahls B in 0,03 M Na,HP04 + 0,Ol
M NaCl yon der Inhibitorkonzentration

surface in a competitive adsorption [15]. Obviously, it is its


adsorption and ability to substitute chlorides, which controls
the drop of a, rather than its oxidizing strength or ionic
charge. The increase of a with increasing chloride concentration in 0.03 M Na,HPO, and its decrease in the presence of
NaN03 follow the respective increase and decrease of the
amount of chloride adsorbed on the passive film. One of the
consequences of the theory concerning the hydrogen permeability of passive films is the finding that it is useful to study
chloride ion concentration directly on the passive film at a
crack tip in structural materials. This technique is based on an

(9)

defining the isotherms of the chloride adsorption on the film


surface (from data in Fig. 1).It also defines the drop of [Cl-]
as a result of a competitive adsorption, if other anions are
added to the standard solution (inhibitors, in particular). This
technique can be applied not only to chloride; adsorption of
other anions can be studied as well, if the stress corrosion
cracking of alloys in their presence is controlled by the hydrogen embrittlement mechanism. The method for different
materials is the same, but the value of n in eq. (9) should be
5.5 for steels, 3 for titanium, and 2 for aluminium alloys.
Figures 4 and 5 illustrate the competitive adsorption of
chloride ion at a crack tip in high-strength steel B, titanium
alloy VT 20 and aluminium alloy AL 27-1. Fig. 4 shows that an
addition of oxidizing anions obstructs the adsorption of the
chloride ions. Nitrate is the most effective inhibitor and even
stronger than the known inhibitors of general corrosion - chromates, nitrites and the organic inhibitor G-4. The same effect
of nitrate is observed with titanium and aluminium alloys (Fig.
5). In another paper [14] it had been shown that at high rates
of cracking the nitrates are effective inhibitors for highstrength steels in distilled water, being superior to nitrites,
while 0.01 M chromates had no inhibiting action. In another
paper [11] nitrate was shown to inhibit corrosion fatigue of the
high-strength aluminium alloy 7075 in chloride solution. It is
possible that the adsorption in the conditions of the stress
corrosion cracking is more specific than in general corrosion.
The nitrate ions seem to be in a favourite position with respect
to the chloride ions on the passive film at a crack tip. As has
been shown above, this specificity is not connected to the ionic
charge or to the oxidizing capacity. Obviously, it is not directly
related to the 0x0-ion reduction either, because chromate ion
is not only reduced at the steel surface but is incorporated into
the passive film as C? [16]. It has less influence on a than
nitrate, however. In the stress corrosion cracking of
aluminium alloys the effectiveness of the chromate is lower
than that of nitrate, vanadate and molybdate [17], even though
it is part of the film [18].
Some of the estimates of the chloride adsorption on A1 27-1
alloy were made using the ESCA method. Figure 5, for example, shows that addition of 0.01 M NaN03 to 0.5 M Cr03 +
0.01 M NaCl reduces the chloride ion concentration on the
film by a factor of 5. The [Cl-] concentrations were as follows:
1.5 at% in the initial solution, and 5 0.5 at% when 0.01 M
NaN03 was added (the accuracy of the ESCA method was
0.5%). In these measurements the results obtained in another
study [17] were confirmed: chloride ion adsorption on the passive film is essentially stopped in 0.5 M Cr03 solution at equal
concentrations of chloride and nitrate ions (0.01-0.1 M range)

WI*

Earlier (Section 2) it has been suggested that the reduction


and stabilization of K H with
~ increasing chloride concentration
is a result of an adsorptive saturation, with chloride passive
film at the crack tip (Fig. 1). For AL 27-1 in 0.5 M CrOJ +

286

Werkstoffe und Korrosion 36, 278-290 (1985)

Marichev

% at
I

0.001

0.01

1.o

C anion,M

Fig. 5. Concentration of adsorbed chloride ion [CI-] on the passive


film at the crack tip in the alloy AL 27-1 during stress corrosion crakking in 0.5 M CrO, + 0.01 M NaCl (- - -), E, = - 0.73 V, and in BTZO
under stress corrosion cracking in 0.5 M CrO, + 0.1 M NaCl (-),
E,, = - 0.4 V in its relation to NaNO, and C r 0 3 concentrations
Abb. 5. Abhangigkeit der Konzentration der auf der Passivierungsschicht an der RiBspitze adsorbierten Chlorionen [Cl-] von der
NaNO,-Konzentration. Aluminiumlegierung AL 27-1 in 0,5 M C r 0 3
+ 0,Ol M NaCl (-- -), Titanlegierung VT 20 in 0,5 M CrO, + 0,1 M
NaCl (-)

0.003-0.2 M NaCl, for example, this saturation occurs at


0.01-0.02 M NaCl (curve 2). For this case, a chloride ion
adsorption isotherm was calculated using eqn. (9). The estimates were in relative units at [Cl-I,, = 1for 0.01 M NaCl. The
real concentrations of the [Cl-] were determined by the ESCA
method. Figure 6 shows that the estimates and the experimental adsorption data agree well enough - both isotherms have
saturation effects in the range of 0.01-0.02 M NaCl [lo].

0.003

0.01

0.03
NaCL,M

0.1

Fig. 6 . Estimated (-- -) and experimentally determined (-)


adsorption isotherms for chloride ions on the surface of the passive film on
AL27-1 in 0.5 M CrO, 0.003 - 0.1 M NaCl
Abb. 6. Theoretische (- - -) und experimentelle (-1
Isothermen der
Adsorption von Chlorionen auf der Passivierungsschicht an der
Riaspitze bei der SpannungsriRkorrosion der Aluminiumlegierung
AL27-1 in 0,5 M Cr03 + 0,003-0.1 M NaCl

if @, is assumed to be 1. From eqn. (1) and (2) it follows that

where W and x refer to standard and real potentials resp.


of the cathodic polarization during KHE and V, determinations. All other conditions are unchanged. A standard
potential for every alloy-electrolyte system is selected at random. Normally, it is the most negative potential in each series
of experiments.
4 Adsorbed hydrogen atoms on the surface of a passive
In this section the potential dependence of the degree of
film. The degree of coverage
coverage, 0 ,is studied for steels A, D and E, and the titanium
alloy BT 20. Steel A is especially convenient because of its
The first two most important stages of hydrogen embrittle- high hydrogen ernbrittlement susceptibility. Hydrogen
embrittlernent of the steel can be caused at K 5 KIscc in
ment are
- hydrogen ion discharge and development of a certain degree alkaline solution at E, = - (0.2-0.8) V, that is in the absence
of coverage on the passive film, 0 ,
of a growing crack at the corrosion potential. Figure 7 shows
- hydrogen transport through the film to the film-metal inter- the potential dependence of 0 for steel A in various solutions
at pH 10. E, = - 0.8 V is a standard potential for all electroface.
Both these stages can become limiting under certain condi- lytes. It should be noted that 0 = 1 in standard conditions
tions. It should particularly be emphasized that the degree of does not imply full coverage of the film surface by adsorbed
coverage of the film-solution interface, 0,can be significantly hydrogen because this technique cannot determine the absohigher than that of the film-metal interface. This is due to the lute value of the 0 . Chloride ion adsorption is significantly
fact that the passive film acts as a barrier to hydrogen entering inhibited by nitrate. The decrease of 0 in electrolytes containinto the metal during stress corrosion cracking and gaseous ing no chloride ions and in 0.03 M Na2HP04 f 0.05 M NaN03
hydrogen embrittlement. The presence of 2 to 3 oxide layers
0.1 M NaCl is represented by curve 2. Its mean slope in the
on a tantalum surface, for example, reduces the rate of hydro- range from - 0.3 to - 0.8 V is 0.25 V per order of magnitude
gen adsorption by a factor of 10 [19]. The known experirnen- of 0.The decrease of 0 with the potential increase from - 0.8
tal work [13, 20, 211 on the coverage of iron, steel and nickel to - 0.4 V is less intensive in 0.03 M Na2HP04 0.1 M NaCl
surfaces did not consider the role of the passive film.
at - (0.4-0.8) V. In the - (0.2-0.4) V range the rate of the
One of the requirements of a quantified approach to hydro- decrease is accelerated (curves 1 and 2 have appr. the same
gen permeability is a technique to determine @. For an alloy- slope - 0.25 V per order of magnitude of 0).
electrolyte system the coefficients in eqs. (1) to (4) are
It has been shown elsewhere [20] that in conditions very
assumed to be constant. Then the relation KHEand V,, vs. E,, similar to ours (iron in 0.0001 M NaOH + 0.1 M Na2S04,pH
can be used for calculation of the potential dependence of 0. 9.5) 0 shifts from 5 to 12% in the - (0.3-0.4) potential range.
The relative variations of 0 with varying potential can be The slope of lg 0 vs potential curve was 0.27 V per order of
obtained for a standard system (alloy, electrolyte, potential) magnitude of 0.For nickel (the main alloying element of steel

A quantified concept of the hydrogen permeability of passivating films

Werkstoffe und Korrosion 36,278-290 (1985)

287

cracking at negative potentials, in some steels [221 and


titanium alloys [9] hydrogen embrittlement also occurs at
l:
+ (0.1-0.15) V in acidic solutions (pH 0 to 1).No additional
I n .c
acidification
of the electrolyte is possible under these condi3
tions due to corrosion product hydrolysis in the crack.
E The theory of hydrogen overvoltage is based on two conajoint
reactions: hydrogen ion discharge with subsequent
0.1:
recombination of the atoms, and hydrogen evolution according to a few possible mechanisms. The first reaction gives rise
to the adsorption of hydrogen atoms at the electrode surface;
these ad-atoms can penetrate passive layers and initiate hydrogen embrittlement. This primary reaction is most important
for hydrogen embrittlement to occur and may, on well adsorb0.01
ing and absorbing materials, produce high degrees of hydro1
I
I
I
I
I
I
gen coverage at fairly positive potentials, up to 0.4 V (Pt), 0.3
0.2
0.3
0.4
0.5
0.6
0.7
0.8
V
(Pd), 0.27 V (Rh) and 0.21 V (Ni). At a zero n.h.e. the
[w2)sT!j
-E,,,V,
values of 0 for these metals may be close to unity in 1 M
Fig. 7. Dependence of the potential on the degree of surface cover- H2S04[23-251. The effect of hydrogen evolution at negative
age, 0,by adsorbed hydrogen atoms on the passive film at the crack potentials on hydrogen embrittlement during stress corrosion
tip in steel A during stress corrosion cracking in solutions with pH 10: cracking is similar to the effect of the discharge and evolution
1 - 0.03 M Na2HP04+ 0.1 M NaC1, 2 - NaOH, 0.03 M Na2HP04,
reaction rate ratio on 0.
0.03 M Na2HP04+ 0.05 M NaNO, + 0.1 M NaCl
The theory of the hydrogen electrode does not account for
Abb. 7. Potentialabhangigkeit des Wasserstoffbedeckungsgrades 0
the
energy of hydrogen atoms adsorption on the electrode.
auf der Passivierungsschicht an der RiBspitze bei der SpannungsriaLiterature 124, 261 provides some information on the depenkorrosion des Stahls A
dence of hydrogen overpotential and 0 on adsorption energy
and the presence of oxides. For example, free energies
reported for TiH2 and TiH formation are - 87 and - 63 kJI
A), the slope is 0.20 V per order of magnitude of 0 in the mole showing a thermodynamical possibility of formation of
range of low coverage (up to 30 at.% H) in alkaline solution the respective hydrides (via hydrogen atom adsorption) at
[21]. The fact that the slopes obtained in these experiments by + 0.45 and + 0.65 V [27]. According to various studies 15, 8,
direct electrochemical analyses are similar to those obtained 291, the enthalpy of hydrogen adsorption on refined iron is
by us emphasizes the correctness of the assumptions forming - (52 to 120) kJ/mole Hz. This means that the formation of the
the basis of this technique.
hydrogen atoms on the iron surface is possible at as high as
The theory of hydrogen permeability and its outcome - the
(0.27 to 0.61) V during their discharge from an acidic electechnique of 0 determination - have no fundamental limita- trolyte. It should be pointed out, too, that the potential of
tions related to the nature of an alloy. Both can be used with sodium deposition from neutral or alkaline solutions on merany alloy-electrolyte system when stress corrosion cracking is cury increases [29]. The reversible potential of sodium is
controlled by hydrogen embrittlement and in which cathodic - 2.71 V, but a noticeable discharge of the sodium ions during
polarization accelerates crack growth. The latter is a basis for amalgam formation begins at - 1.2 V, that is from a potential
the experimental determination of KHE and Vcr. Only high- by 1.5 V more positive than the standard. This phenomenon is
strength steels can meet the above conditions in the majority caused by a reduction of the free energy of sodium during
of aqueous solutions. However, by purposefully selecting elec- amalgamation. It has probably the same nature as the hydrotrolytes, the range of convenient materials can be substantially gen ion discharge at positive potentials at platinum, palladium,
expanded, and austenitic stainless high-strength stee1,tita- nickel and other metals with a high hydrogen adsorption
nium, zirconium and aluminium alloys can be included (see energy.
section 1). During this work we have found that chromium
When hydrogen embrittlement was studied in chromium
anhydride-based solutions are universally applicable to all anhydride-based solutions, the concentration of the solution
these materials.
for each alloy were empirically selected and the following
requirements were met:

4.1 Stress corrosion cracking accompanied by hydrogen


embrittlement at positive potentials
Studying hydrogen embrittlement in chromium anhydridebased solutions (@ dependence on the potential, in particular)
can be of particular interest. They can give an insight into the
possibility of hydrogen embrittlement at potentials more positive than zero. The corrosion potential of steel and titanium
alloys in such electrolytes is (0.5-0.8) V. Thus, KHEand V,,
can be determined for a broad range of potentials, including
very positive ones. Hydrogen embrittlement is considered to
be impossible at positive potentials, because the electro-chemical evolution of hydrogen is then thermodynamically impossible. Although the majority of alloy-electrolyte systems are
susceptible to hydrogen embrittlement aided stress corrosion

1. activator/passivator concentration ratio (NaCI, Na2S04/


Cr03) as high as possible,
2. alloy in a stable passive state at corrosion potentials from
+0.5 to +0.8 V,
3. current density not more than 0.3 mA/cmZat the most negative (standard) potential of cathodic polarization.
As a result, we obtained:
- high hydrogen permeability of the passive film at the crack
tip
- low, or even zero, cracking rate controlled by local anodic
dissolution at corrosion potential,
- high value of stress intensity factor,
- insignificant changes in the electrolyte composition during
short-term cathodic polarization.
I

288

Werkstoffe und Korrosion 36,278-290 (1985)

Marichev

For example, the titanium alloy BT 20 was tested in 0.5 to 2

M Cr03 + 0.1 M NaCl (pH 1-0, E,,, = + 0.75 to 0.85 V, Ecpst


= - 0.4 V, K H E s t = 28-33 MPa t/;;;). The KHEvs E, relation

v)

-I.-

a-

01

0.01
I

+O!&

+a12

-0.2
Ecp

jw23578/

0
J

VH

-0.4

Fig. 8. Potential dependence of 0 (degrec of coverage by adsorbed


hydrogen) on the passive film at the crack tip in VT 20 during stress
corrosion cracking in 0.1 M NaCl + CrO,: 1- 2 M; 2 - 1 M; 3 - 0.5 M
Abb. 8. Potentialabhangigkeit des Wasserstoffbedeckungsgrades 0
bei SpannungsriBkorrosion der Titanlegierung VT20 in Cr0,-Losungen

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)

and the relative variation of 0 were calculated from eq. (10).


It follows from Fig. 8, that the increase of the potential from
- 0.4 to 0 V is associated with a gradual decrease of 0 in all
electrolytes. A further growth of the potential produces a
sharp decline of 0 .The value of K H E corresponding to 0 > 0.2
was obtained under plane straining. The conditions were
changed to mixed deformation in the range of lower 0. We
assume, therefore, that 0 as estimated in the 0.01 to 0.2 range
in this figure is too low. Within the scope of this study aimed at
hydrogen embrittlement at positive potential, however, it is
more important to note that at potentials up to +0.45 V
(curve 3) the degree of the passive film coverage with
adsorbed hydrogen atoms exceeds 0.01. This level is high
enough to accelerate cracking in titanium alloys under hydrogen embrittlement during stress corrosion cracking.
High-strength steels are less susceptible to passivation in
chromium anhydride solutions than is titanium. Reduction of
the chromate ions at the metal surface is more intensive than
on the alloy BT 20. Because of this, the dependence on the
potential at hydrogen embrittlement was determined in solutions with a low NaCl/Cr03 ratio. To this end the high alloy
steels A and D were tested in 2 M CrO? + 0.03 M NaCl + 0.2
M Na2S04 (E, = +0.5 to +0.65 V). Steel E, which is less
resistant to corrosion, was tested in 2 M Cr03
0.02 M
Na2S04 (E, = 0.75 to + 0.85 V). The passivation of the
steels was very stable and at a maximum K = 40-55 MPa 6
no local anodic dissolution controlled cracking under stress
corrosion cracking conditions was observed. Short-term
cathodic polarization at positive potentials was insufficient to
initiate hydrogen embrittlement controlled cracking. Therefore, the technique of electrochemical crack arrest was applied
to determine the dependence of K H E on Ecp.The technique
consists in initiating crack growth at EfP = -0-0.2) V, followed by stepping up the cathodic polarization potential. The
cracking rate is continuously recorded until the process comes
to a complete stop.
Figure 9 shows that 0 sharply decreases with increasing
potential. With all steels, 0 was 0.003 to - 0.001 at very positive potentials (from +0.1 to +0.5 V) and was sufficient to
maintain hydrogen embrittlement controlled cracking. The
technique proposed in this work is characterized by a very high
sensitivity to meet the requirements resulting from measuring
such low values of 0 and has turned out to be much superior to
the known electro-chemical techniques. Hydrogen embrittlement of high-strength steel is used in this method as a sensor
for hydrogen adsorbed at a crack tip. Since the steel is most
susceptible to hydrogen embrittlement, the hydrogen concentration on its surface (0= 0.0001) is by several orders of
magnitude higher than hydrogen solubility. Hence this high
sensitivity of the technique which obviously should become
even higher with growing steel strength (which is accompanied
by growing susceptibility to hydrogen embrittlement). At K
close to KIc in calculations of 0 the sensitivity should increase
as well. This was confirmed in 0 determinations for an ultrahard tool steel (oB = 2700 MPa, HRC = 63) in 2 M Cr03
without activating ions. In the range from + 0.25 to + 0.55 V,
0 decreased monotonously from 0.001 to 0.0001.
In this study, probable variations of the electrolyte pH
inside the crack (due to hydrolysis or incomplete propagation
of external cathodic polarization to the tip) was not considered. The true pH and potential, therefore, may be different
from those on the specimen surface. The titanium alloy and

Werkstoffe und Korrosion 36, 278-290 (1985)

A quantified concept of the hydrogen permeability of passivating films

the high-strength steels exhibited stable passivity in chromium


anhydride. The dissolution and the hydrolysis of the dissolution products were almost completely stopped. At E, =
+ (0.2 to 0.5) V, the density of the external polarization current did not exceed 10 mcA/cm2. This means that this current
can cause only an insignificant drop of the voltage due to the
resistance inside the crack. The solution had high electric conductivity (pH 0), the crack had maximum opening, and K was
approximately 0.9 Klc.
Figures 8 and 9 should be taken as an experimental proof of
hydrogen embrittlement in titanium alloys and high-strength
steels at potentials significantly higher than zero, i. e. when
electrochemical evolution of hydrogen is thermodynamically
impossible. The experiments have therefore shown that discharge of hydrogen ions and formation of adsorbed atoms on a
passive film should not be overlooked.
4.3 Hydrogen ion discharge as a cathodic depolarization
process
The results discussed above suggest that the hydrogen ion
discharge (without hydrogen evolution) can be considered as a
possible process of cathodic depolarization. The process is
similar to oxygen and hydrogen depolarization. The high rates
of cracking under hydrogen embrittlement during stress corrosion cracking imply that hydrogen ions can be discharged at
high speed within a broad range of potentials (including very
positive potentials). The adsorptive nature of the process,
however, limits its depolarizing effect. At a maximum degree
of coverage (1 at HI1 at Me), the electricity produced cannot
be greater than 160-100 pC/cm2, depending on the lattice constant of the metal. This means that in normal corrosion, the
hydrogen ion discharge is quickly stopped and plays an insignificant role as a cathodic depolarization process. It can be
important, however, in corrosion mechanisms involving constantly renewed attack surfaces.
The hydrogen ion discharge (without evolution) may play a
substantial role and influence metal hydrogenation in stress
corrosion cracking, corrosion fatigue, electropolishing and
chemical milling. Obviously, it is the main cathodic process on
fresh metal surfaces shortly exposed to electrolytes (80 to
100 ps).
The studies of the electrochemical properties of the fresh
surfaces have shown that the corrosion potential of many metals (iron, aluminium, titanium and others) is noble immediately upon cutting. It rapidly shifts (within 80 to 150 ps) to the
level close to that of the standard potentials of these metals
[30]. During these 80 to 150 ys, the potentials of the fresh
surface in neutral solutions were by 0.1 to 0.3 V more positive
than the potential of hydrogen evolution. The densities of the
anodic and cathodic currents at this time reach hundreds of
mA/cm2. The authors of [30] were not able to explain the
origin of this very intensive cathodic process. Because of the
diffusion limitations it cannot be a reduction of dissolved oxygen, while the thermodynamics preclude it be an electrochemical hydrogen evolution. Thus the hydrogen ion discharge at
positive potentials becomes the most probable cathodic process. Inspite of the limitations imposed by its adsorptive
nature, the process is capable of producing high-density currents (up to 1 A i m 2 ) for 200 ps.
Some of the features of stress corrosion cracking and hydrogen embrittlement in structural materials in chromium anhydride solutions can be explained by the adsorptive characteristics of the process. Such electrolytes (0.5-2 M CrOs

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

potential dependence of the relative variations of the coverage


by adsorbed hydrogen atoms.

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.

5 . R. A. Oriani: Ann. Rev. Mater. Sci. 8 (1978) 327.


6. D. L. Dull, L. Raymond: Met. Trans. 3 (1972) 2943.
7. R. A. Oriani, P. H . .Josephic: Aca Met. 22 (1975) 1065.
8. H . P. Van Leeuwen: Coating and Corrosion 4 (1979) 5.
9. V. A . Marichev: Werkst. Korros. 32 (1981) 537.
10. GOST 9.903-81. Stali i splavy visokoprochnie. Mctodi uskorennih
ispitanii na korrozionnoe reastreskivanie (Hochfeste Stahle und
Legierungen: Methoden fur bcschleunigte Prufung der Spannungsril3korrosionsanfalligkeit)
11. M. Khobaib, C. T. Lynch, F. W . Vuhldick: Corrosion 37 (1981)
285.
12. W , T. Chandler, R. J. Walter: Hydrogen embrittlement testing,
ASTM STP N 543, Baltimore, 1974, p. 170.
13. B. E. Wilde, C. D. Kim: Corrosion 37 (1981) 449.
14. 0. N.Romaniv, G . h. Nikoforchin, A. T. Tzirulnik: Fiziki-khimicheskaja mehanika materialov 17 (1981) 1; 46.
15. V . V . Gerasimov: Korrozia reaktornikh materialov, M. Atomizdat 1980, 250 str. (Korrosion von Reaktonverkstoffen (Buch,
250 S.).
16. I. L. Rosenfeld, L. J . Kazanskii, A . G . Akimov, L. V . Frolova:
Zashita metallov 15 (1979) 349.

Werkstoffe und Korrosion 36, 278-290 (1985)


17. V . A. Marichev: Werkst. Korrosion. 34 (1983) 112.
18. V. A . Marichev, A . N. Khodan, S. V . Novikov, I. A . Stepanov:
Proc. 9 Intern. Congress on Metal Corrosion, Toronto 1984,
Vol. 3, p. 505.
19. E. Fromrn: Collected Abstracts 11 JIM-Intern. Symp. Hydrogen
in Metals, Minakami, Japan, 1979, 147 S.
20. C. D. Kim, B. E. Wilde: J. Electrochem. SOC.118 (1971) 202.
21. M. A . V. Devanatan, M . Selvaratham: Trans. Faraday Soc. 56
(1960) 1820.
22. M. N . Fakin, D. I. Starosvetsky, R. L. Baru, V .A. Timonin: DAN
SSSR 251 (1980) 1182.
23. E. N. Khruscheva, M. R . Tarasevich: Uspehi Khimii 47 (1978)
805.
24. L. I. Krishtalik: Dvoinoi sloi i elektrokhimicheskaja kinetika, sb.
pir Kazarinova V. E., M. Nauka. 1981, 370 str. (Elektrolytische
Doppelschicht und elektrochemische Kinetik (Monographie)).
25. A. G. Pshenichnikov, Z . I. Kudrjavtseva: Elektrokhimija 16
(1980) 161.
26. N. E. Homutov: Itogi nauki, Elektrokhimija, M. Viniti, 1969, 95.
27. A. M. Sukhotin, L. I. Tungusova: Zashita metallov 4 (1968) 8.
28. G. Wedler, K.-P. Gems, K . G. Kolb, G . McElhiney: Appl. Surface Sci. 1 (1978) 471.
29. S. Gleston: Vvedenie v elektrokhimiu, M., IL, 1951. 767 str. (Einfuhrung in die Elektrochemiel.
30. I. L. Rozeafeld, K . I. Afanasjev: ltogi nauki, Korrozija i zashita ot
korrozii, t. 7, M., VINITI, 1978, 42 (Brennpunkte der Wissenschaft: Korrosion und Korrosionsschutz, Band 7).
31. J . H . deBur: Kataliz. Nekotorie voprosi teorii i tekhnologii organicheskih reaktsii, pir A. A. Balandina, M. IL, 1959, 367 str.
(Katalyse: Einige Fragen der Theorie und Technik organischer
Reaktionen).

(Received: 11.01. 1985)

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.