ISSN 1061-8309, Russian Journal of Nondestructive Testing, 2009, Vol. 45, No. 9, pp. 636–645. © Pleiades Publishing, Ltd.

, 2009.
Original Russian Text © V.R. Skal’skii, D.V. Rudavskii, T.V. Selivonchik, 2009, published in Defektoskopiya, 2009, Vol. 45, No. 9, pp. 56–69.

ACOUSTIC
METHODS

Hydrogen Degradation of Steel 12X1MF

and Its Estimation by the Acoustic Emission Method
V. R. Skal’skii, D. V. Rudavskii, and T. V. Selivonchik
Karpenko Physicomechanical Institute, National Academy of Sciences of Ukraine, ul. Nauchnaya 5,
Lviv, 790053 Ukraine
e-mail: skal@ipm.lviv.ua
Received March 5, 2009

Abstract—The acoustic emission method for estimating damage to specimens made of thermally resis-
tant steel is described as applied in air and in a gaseous hydrogen medium. Acoustic diagrams (AD) of
steel cracking and their interpretation are presented. It is shown that thermal cycling of the steel in air
and in a hydrogen medium leads to an increase in bulk damage to the steel. It is shown that the exploited
material is more subject to micro- and macrocracking under the influence of temperature and the work-
ing environment.
DOI: 10.1134/S1061830909090071

Though a great number of various studies of different phenomena of the effect of hydrogen on properties
of structural materials have been performed, this problem is still very important. This is first of all due to
the development of hydrogen technologies and a hydrogen power industry. They should supply mankind
with new alternative forms of power and reduce pollution of the environment. However, an obstacle for wide
implementation of these technologies might be the inability to predict hydrogen degradation of structural
materials, in particular, steels. This degradation causes mostly brittle fracture in the components of struc-
tures under the effect of a hydrogen–mechanical factor. The multiparametric dependence of the hydrogen
brittleness on the composition and state of the operating environment, the surface of a metal, and its chem-
ical composition and structure on the kind and parameters of loading determines the absence of a unique
theory which would explain a wide range of concepts of this phenomenon. This determines the development
of new approaches to diagnostics of a fracture caused by hydrogen degradation of structural steels.
One of the methods of prompt estimation of a tendency of a material to hydrogen degradation is its ther-
mal cycling in hydrogen under a high pressure in the temperature range from the operating temperature typ-
ical of a particular technological process to room temperature [1]. In this case, nucleation and development
of cracks is accompanied by acoustic emission (AE) of elastic waves. The AE parameters are used to esti-
mate the intensity of crack nucleation and the equivalent area of the mentioned flaws, which nucleate during
thermal cycling. The results of the study described below concern these problems.

SOME MECHANISMS OF HYDROGEN DAMAGE TO STEELS

Hydrogen degradation of metals has been developed as a science quite recently; however, a large amount
of experimental data and theoretical studies have been accumulated [2–7]. In [8–11], some calculation mod-
els for estimating the durability of hydrated elements of structures operating under static and dynamic
mechanical loading were proposed. Manifestations of hydrogen degradation are quite versatile and pres-
ently several variants of its classification have been proposed.
According to the classification [2], two sorts and seven forms of hydrogen brittleness exist. By appear-
ance, hydrogen degradation may be classified as follows [6].
Deterioration of the strength and durability characteristics of metals caused by physical parameters of
the effect of hydrogen on deformation microprocesses in metals under load is called hydrogen embrittle-
ment. It occurs in the presence of dissolved hydrogen in metals and under the effect of hydrogen-containing
media on metals without chemical interaction of components of alloys with hydrogen and without micro-
structural changes and damage caused by application of loads.
Hydrogen degradation of a transformation is degradation of a chemical and physicochemical nature,
which is induced by chemical reactions and the formation of new phases of hydrogen-containing com-

636
 HYDROGEN DEGRADATION OF STEEL 12X1MΦ 637

pounds and accompanied by phase and structural transformations, which are possible only in the presence
of hydrogen in metals. It should be noted that these effects are stimulated by thermomechanical processes.
The phenomenon of hydrogen degradation of metallic materials appears as a result of supersaturation
with hydrogen of some areas of the metal bulk and formation of discontinuities filled with hydrogen gas
under pressure; it is not caused by an external load or by transformations due to chemical reactions.
These forms of hydrogen degradation are realized under appropriate conditions of interaction between
hydrogen and metals. Analysis of these conditions in external fields (power, strain, temperature, etc.)
described in [2, 6] has shown the possibility of latent formation of favorable conditions for hydrogen deg-
radation in local zones, while global parameters of the system metal–hydrogen-containing medium have no
warning signs as regards hydrogen degradation. A typical example of this is hydrogen degradation at low
temperatures caused by instability of temperature fields or inhomogeneity of materials.
As regards the hydrogen effect on nucleation and propagation of cracks in metals, there are hypotheses
and theoretical concepts of the mechanisms of hydrogen influence on metallic materials that associate eas-
iness of material fracture with one factor (or some factors):
the pressure of molecular hydrogen in microcavities in metals;
decohesion caused by hydrogen in a crystal lattice of a metal;
interaction of hydrogen atoms with dislocations in a metal;
chemical interaction with components of alloys and precipitation of hydrogen-containing phases
(hydrides and others); and
a surface effect (chemosorption) in the metal–hydrogen system (medium).
It is well known that the amount of hydrogen that can be dissolved in a metal depends on the temperature
and increases as the temperature increases. This phenomenon, taking into account the high diffusion mobil-
ity of hydrogen atoms in α-iron at a high temperature is used for the laboratory prompt method of acceler-
ated high-temperature hydrogen degradation of steels [1]. The abrupt decrease in the temperature at the
stages of cooling significantly impedes diffusion processes (coefficient of hydrogen diffusion in α-iron
decreases from 1.8 × 10–4 to 4.4 × 10–5 cm2/s as the temperature decreases from 813 to 373 K [12–14]). This
process is accompanied by localization of hydrogen dissolved in the metal at a lower temperature, the con-
centration of which is superequilibrium (from 0.1 to 1.0 cm3/100 g of the metal according to [15]). As a
result of this cooling, the concentration of hydrogen in the specimen is as equilibrium as at 813 K. Appar-
ently, such hydrogenation provides active migration of hydrogen to the nearest free surfaces independently
of their position (interior or exterior). In this case, excess hydrogen either goes out of the metal (from the
surface layers of the specimen) or is trapped by structural defects, grain boundaries, or interfaces, which
have energetically beneficial localizations (in the specimen). Hydrogen fills any defects and thus its migra-
tion causes motion of carbon atoms and alloying elements and their redistribution in the matrix. This hap-
pens owing to a decrease in the energy barrier for motion of any element under the effect of hydrogen [16].
It is clear that this redistribution of elements, in turn, accelerates redistribution of carbides and formation of
a net of finely dispersed special or alloyed carbides at the places with high concentrations of the alloying
elements.
During cooling, excess hydrogen is transported to traps on grain boundaries, interfaces, or structural
defects. When hydrogen migrates, it generates a trail of a high-gradient field of tensile stresses, thus provid-
ing redistribution of alloying elements and carbon in a metal and intensifying microstructural transforma-
tions of steel. The localization of hydrogen on structural defects undoubtedly causes additional tensile
stresses at interfaces. When this cycle is multiply repeated, it creates preconditions for nucleation of micro-
scopic flaws, such as small cavities and microcracks. Each subsequent thermal cycle increases the hydrogen
pressure, and deformation of walls between microcavities and microcracks and their growth by the creep
mechanism become possible under conditions of a combination of a high temperature and stresses. These
processes are certainly accompanied by emission of AE elastic waves [17].
In addition, this thermal cycling of specimens in hydrogen really creates preconditions for cyclic defor-
mation of the metal near the flaws, which have accumulated hydrogen. The strain amplitude is determined
by many factors: the distribution of flaws in their size and number, the temperature range of thermal cycling,
the pressure of hydrogen in the test chamber, the number of thermal cycles, etc.
Consequently, rapid cooling of the hydrogenated metal causes, firstly, an increase in the internal stresses
in the metal owing to a superequilibrium concentration of hydrogen in it; secondly, it promotes formation
of microcavities filled with hydrogen; and, thirdly, it causes transformation of microstructures through
intensification of diffusion, in particular, carbon diffusion. All these processes generate crack nucleation in
steels and can be effectively found from parameters of AE signals.

RUSSIAN JOURNAL OF NONDESTRUCTIVE TESTING Vol. 45 No. 9 2009