ISSN 1063-780X, Plasma Physics Reports, 2023, Vol. 49, No. 5, pp. 563–574. © The Author(s), 2023.

This article is an open access publication.

Russian Text © The Author(s), 2023, published in Fizika Plazmy, 2023, Vol. 49, No. 5, pp. 412–424.

LOW-TEMPERATURE
PLASMA

Iron Corrosion in the Radiative Plasma of Moist Air

V. N. Babicheva, K. E. Galeevaa, A. N. Kirichenkoa, A. A. Nekrasova, A. V. Ugodchikovaa,
N. I. Trushkina,*, A. V. Filippova,b, Yu. V. Cherepanovaa, and V. E. Cherkovetsa
a Troitsk Institute of Innovative and Thermonuclear Research, Moscow, Troitsk, 108840 Russia
b Joint Institute for High Temperatures, Russian Academy of Sciences, Moscow, 125412 Russia
*e-mail: trushkin@triniti.ru
Received November 14, 2022; revised December 12, 2022; accepted December 26, 2022

Abstract—The rate of iron corrosion in a low-temperature plasma of moist air formed under the action of a
fast electron beam, depending on the relative air humidity, was measured. It is shown that a beam of fast elec-
trons (radioactive β-radiation) significantly intensifies the corrosion of iron in a plasma-forming gas medium
in which oxygen and water vapour are simultaneously present. It has been established that the rate of corro-
sion under conditions of radioactive irradiation increases sharply when the relative air humidity exceeds 10%.
Numerical simulation of the ionic composition of the plasma is carried out taking into account 12 types of
positive and 12 types of negative hydrated ions at different intensities of the external ionization source and at
different values of relative humidity from 10–6 to 100%. A hypothesis has been put forward about the deter-
mining role of cluster hydrated ions, which are formed in the plasma of moist air at atmospheric pressure, in
heterogeneous processes of iron oxidation.

Keywords: plasma, electron beam, radiation, corrosion, iron

DOI: 10.1134/S1063780X22601924

1. INTRODUCTION plasma excited by a stationary fast electron beam as a

The problem of long-term and reliable storage of
radioactive waste (RW) is an urgent task of the nuclear
industry, which has a significant impact on the devel-
opment of the entire nuclear industry, and above all
nuclear energy, worldwide. A radiation chemically
active low-temperature plasma is formed during the
processing and storage of radioactive waste in installa-
tions and containers under the influence of radiation
arising from the decay of radioactive elements of
radioactive waste. This leads to the initiation and
intensification of ion–molecular processes of plasma
chemical corrosion of metal walls of equipment and
storage facilities and a significant reduction in their
safe operation. The current level of understanding of
complex processes and phenomena occurring in
closed volumes of RW storage facilities is very limited
and far from meeting the increasing needs of practice
[1, 2]. In this regard, the study of the mechanisms and
kinetics of physics–chemical corrosion processes
under increased radioactive radiation conditions is
important for the development methods for protecting
the walls of equipment and containers from destruc-
tion and, accordingly, preventing radiation leakage
into the environment and ensuring the maximum level
of safety of radioactive waste storage. This paper pres-
ents the results of experimental studies of the corro-
sion rate of iron, which is the main component of most
structural alloys of container walls, in a moist air
high-energy ionizing beta radiation simulator for
decay products of radioactive elements of spent
nuclear fuel. The effect of the number density of water
vapor in the air on the rate of iron corrosion has been
studied. The results of numerical simulation of the
plasma composition in moist air irradiated by a fast
electron beam at different values of relative humidity
are also presented.
It should be noted that the type of ionizing radia-
tion that creates a plasma has practically no effect on
the physicochemical processes in such a plasma,
therefore, all of the following is also true for the
plasma generated in humid air by γ-quanta, α-parti-
cles, or other high-energy charged particles at equality
of the production rate of electron-ion pairs per unit
volume.
2. EXPERIMENTAL
Figure 1 shows a schematic diagram of an experi-
mental setup designed to study the rate of iron corro-
sion in a radiation plasma of moist air formed by fast
electron beam at different number densities of water
vapor. The setup allows experiments to be carried out
at different number densities of water vapor in air or
other gases and at different gas ionization rates.
The main module of the experimental setup is an
electron accelerator (electron gun) with an incandes-

563
564
Humid air chamber
Humid air flow
Fig. 1. Schematic diagram of an experimental setup for studying the rate of iron corrosion in a radiation plasma of moist air gen-
erated by fast electron beam.
cent cathode, which generates a continuous (station-
ary) fast electron beam. The electron energy and the
beam current could be varied in the range W = 80–
140 keV and I = 0.1–1.5 mA, respectively. A fast elec-
tron beam formed in the high-vacuum chamber of the
accelerator is extracted into the plasma chemical reac-
tor (high-pressure region) through an aluminum foil
with a thickness of 14 microns. The cylindrical
plasma-chemical reactor was made of a glass tube with
an internal diameter of 175 mm and a height of 70 mm,
with one end closed with a metal flange, and the other
vacuum tightly docked to the output of the electronic
accelerator. The reactor is equipped with vacuum
ports for pumping the internal volume to a pre-vac-
uum pressure of P = 10–3 Torr and subsequent injec-
tion of a working plasma-forming gas of a given com-
position and pressure. In this paper, all experiments
were carried out at a pressure of P = 1 bar, weak pump-
ing of gas with a volume flow rate of vf = 100 cm3/s and
a processing time of t = 20 min. A massive steel cylin-
der with a diameter of 100 mm was placed on the bot-
tom of the plasma chemical reactor, which together
with the flange of the chamber served as a refrigerator
for the iron sample being processed. A chromel—
copel thermocouple was inserted into the upper end of
the steel cylinder, with the help of which the tempera-
ture of the processed metal sample was measured. The
processed samples were plates of technically pure
ARMCO iron with transverse dimensions of 10 ×
10 mm2, 20 × 70 mm2 and 70 × 70 mm2 and a thick-
ness of 0.5 mm, which were placed on a massive ther-
mostat that allows maintaining a constant temperature
of iron samples equal to approximately 300 K. The
choice of several geometric dimensions for the pro-
cessed samples is due to the requirements of the diag-
nostic methods used, as well as the spatially heteroge-
neous nature of the radiation corrosion phenomenon
under study. Chemical composition of iron (wt %),
according to the manufacturer’s passport, was as fol-
BABICHEV et al.
Vacuum chamber
e-beam
Thin foil
Out
Humid
air plasma Sample
Iron
cooler
lows: Fe 99.92, C 0.010, Mn 0, 010, P 0.010, S 0.008,
N 0.006, Cu 0.03, Sn 0.010.
Before installation into the chamber, iron samples
were mechanically ground using fine sandpaper and
washed with acetone and isopropyl alcohol. Experi-
mental studies of the rate of iron corrosion in a moist
air plasma excited by a stationary fast electron beam
were carried out at an absolute air humidity of ε, vary-
ing within the range of ε = 0.01–2.5%. When the air
temperature in the laboratory room in which the
experimental installation is located is equal to T =
295 K, the specified absolute humidity corresponds to
the relative humidity RH = 0.4–94%. Obtaining a
given level of humidity in the air was achieved by pass-
ing it through a humidifying system consisting of sev-
eral sequentially connected containers with distilled
water. In the case of a high level of relative humidity
RH ≥ 60%, dust-free indoor air was used as the
pumped gas. At RH <60%, dry synthetic air was
pumped through the humidification system, obtained
by mixing nitrogen and oxygen in a ratio of 0.79 : 0.21.
The water vapor content in the air was measured at the
inlet and outlet of the plasma chemical reactor. At a
low humidity level (ε ≤ 0.1% = 1000 ppm) measure-
ments were carried out using a Baikal MK coulometric
hygrometer at ε > 0.1% used a thermometer –
hygrometer “Testo 623” with a humidity sensor of the
capacitive type. In order to form a complete picture of
the studied phenomenon of radiation corrosion of
iron, a number of experiments were carried out in the
inert gas argon, as well as in nitrogen with a water
vapor content of ε = 0.005 and 1.2%.
After penetrating through the aluminum foil of the
accelerator and entering the plasma chemical reactor,
the fast electron beam becomes divergent due to the
elastic and inelastic scattering of electrons on foil neu-
tral atoms and air molecules [3, 4]. In this paper, the
spatial distribution of the current density of fast elec-
trons in the plane of the processed samples was mea-
PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023
 IRON CORROSION IN THE RADIATIVE PLASMA 565

sured using a multi-element electrical probe. The 10

measuring sections of the probe were isolated from (а)
each other by a dielectric gap 0.5 mm wide, they had 1
transverse dimensions of 5 × 5 mm2 and were arranged 8
in one row (line) and connected through an individual

Jb, PA/сm2
measuring resistance to a grounded bus. An electrical 6
signal from each measuring resistance was applied to
the input of a multichannel recorder. The entire line of 2
probes was surrounded by a protective grounded cop- 4
per electrode, which prevents the influence of external
electric fields on the data of the probes. The probe
2
module was placed on a two-coordinate moving sys-
tem, with the help of which it moved in a plane in two
mutually perpendicular directions during measure-
ments. In turn, the displacement system could be 0 2 4 6 8 10
x, сm
installed at any given distance from the entrance of the 2.0
electron beam to the plasma-chemical reactor. 1
Figure 2a shows, for example, the measured distri- (b)
butions of the beam current density at the total current 1.5

Qion, 1016 сm3 s1

of the gun I = 0.5 mA and I = 1.0 mA. It can be seen
that the beam current density has a maximum value on
the beam axis (x = 5.5 cm) and monotonically
decreases with increasing distance from the axis (with
increasing radius). The obtained electron beam cur-
rent density distributions were taken into account
when choosing the sizes of the processed samples and
their location in the processing zone in order to obtain
various scenarios and the most complete picture of
radiation corrosion. Large samples (70 × 70 mm2) fell
into areas with significant differences in radiation
intensity, while small samples (10 × 10 mm2) were in
areas with fairly uniform, but different in magnitude,
radiation.
The rate of iron corrosion in the plasma of moist
air, depending on the number density of water vapor,
was estimated using three independent diagnostic
methods:
1. Change in the mass of the corroding sample
(gravimetric method).
2. Qualitative and quantitative changes in the ele-
mental chemical composition of the upper surface
layer of the sample.
3. Evolution of the spatial structure (morphology)
of the sample surface in the corrosion process.
To measure the weight gain of the processed sam-
ple, digital analytical scales of the CCS Services
A-250A brand were used with a measurement accu-
racy of 10–4 g, which have automatic calibration and
control of zero readings. Qualitative and quantitative
changes in the elemental chemical composition of the
upper surface layer of the sample, occurring during
corrosion, were investigated by X-ray microanalysis
using a high-resolution scanning electron microscope
of the brand Axia ChemiSEM (Thermo Scientific),
equipped with a detector for elemental analysis Ever-
hart–Thornley SE. The evolution of the spatial struc-
ture (morphology) of the corroding surface of the
samples was also studied using this microscope. The
1.0 2
0.5
0 2 4 6 8 10
x, сm
Fig. 2. Radial distribution of the current density of fast
electrons in the plane of processing iron samples (a) at dif-
ferent values of the total beam current I = 1 mA (circles
and curve 1) and 0.5 mA (triangles and curve 2) and the
corresponding gas ionization rate distributions (b).
change in the spatial structure of the sample surface
during its processing was also studied using an Altami
MET 5T digital optical microscope. This microscope
allows analysis of the surface in polarized light using
various light filters and adjustable aperture and field
diaphragms.
3. RESULTS AND DISCUSSION
Figures 3a–3h show photographs of the surface of
the initial (untreated) iron sample and samples
exposed to an electron beam and radiation plasma in
air with different humidity, as well as photographs of
samples treated in an atmosphere of nitrogen and
argon (Fig. 3i) at relative humidity RH = 50%. It is
clearly seen from the presented photos that relative
humidity has a significant effect on the processes of
radiation corrosion of iron in the air. At low relative
humidity RH ≤ 10%, no visible traces of corrosion are
detected on iron samples (Fig. 3b). Noticeable traces
of corrosion processes begin at a relative humidity of

PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023

566
(a)
(d)
(g)
Fig. 3. Photos of iron samples processed in moist air plasma. (a) Initial (untreated) sample; relative air humidity RH = (b) 0–10,
(c) 15, (d) 23, (e) 37, (f) 63, (g) 80, and (h) 90%; (i) Ar, N2, RH = 50%. The sample sizes are 70 × 70 mm2.
RH = 15%, while, as can be seen from Fig. 3c, the dis-
tribution of corrosion products over the surface of the
sample is significantly heterogeneous. From the com-
parison of Figs. 3 and 2, it follows that with the
selected total beam current I = 1 mA, the maximum
current density corresponds to the minimum corro-
sion of the sample. Note that the heterogeneous
nature of corrosion is observed only when the total
beam current exceeds a certain critical value of Icr ≈
0.5 mA. With an increase in relative air humidity, the
heterogeneous nature of corrosion persists, but the
size of the area of heterogeneous corrosion decreases.
At the same time, even at a high level of RH = 90%,
the area of heterogeneous corrosion does not com-
pletely disappear. A more detailed study shows that
corrosion actually occurs in the central part of the
sample, but unlike its peripheral areas, where corro-
sion is fairly uniform (but with different intensity), in
the center it has a point (pitting) character. The most
probable reason for the decrease in the corrosion rate
BABICHEV et al.
(b) (c)
(e) (f)
(h) (i)
in the central region of the electron beam, where the
maximum current density and accordingly the maxi-
mum gas ionization rate (see Fig. 2) is observed, is the
appearance of a passive state of iron [5], in which an
increase in the corrosive properties of the medium
leads to reducing the rate of corrosion. Also note that
in the absence of oxygen, the presence of water vapor
in the plasma-forming mixture (nitrogen, argon) does
not lead to the appearance of visible corrosion prod-
ucts (Fig. 3i).
Figures 4a–4e show images of the surface of the
initial (untreated) iron sample and samples exposed to
an electron beam and radiation plasma in air with dif-
ferent humidity, as well as in nitrogen and argon,
obtained using a scanning electron microscope at
magnification k = 5000. From the presented photo-
graphs it can be seen that under the influence of radi-
ation in a humid oxygen-containing environment
(air), a yellow-brown loose flaky layer of rust forms
very quickly (compared to atmospheric conditions) on
PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023
 IRON CORROSION IN THE RADIATIVE PLASMA 567

(a) (b) (c)

10 nm 10 nm 20 nm

(d) (e) (f)

20 nm 20 nm 20 nm

Fig. 4. Images of the surface of iron samples obtained using a scanning electron microscope. (a) The original (unprocessed) sam-
ple; (b–e) wet air plasma treatment, relative air humidity RH = (b) 10, (c) 23, (d) 40, and (e) 85%; (f) Ar, N2, RH = 50%. Sample
sizes are 10 × 10 mm2, magnification k = 5000. Electron beam current I = 1 mA, electron energy W = 115 keV, processing time
t = 20 min.

the surface of the samples. With other similar process-
ing conditions in wet nitrogen and argon, such a layer
of rust does not form on the samples.
Figure 5 shows experimental data on the increase in
the mass of iron samples treated in moist air plasma
depending on the relative humidity of the air, obtained
with a constant current of a fast electron beam I =
1 mA and a constant processing time t = 20 min. The
dimensions of the processed samples were 70 ×
70 mm2. The samples were weighed 10 minutes after
their extraction from the plasma chemical reactor.
From the data presented, it can be seen that at a rela-
tive humidity of the plasma-forming air RH <10%, the
increase in the ΔM mass of the treated sample is below
the sensitivity limit of the ΔM weights <0.1 mg. The
results obtained by the gravimetric method are in good
agreement with the results of microscopic and optical
in oxygen content is detected already at relative
humidity RH = 5%. The contradiction is resolved if
we estimate the depth of the Δh layer analyzed by
X-ray microanalysis using a scanning electron micro-
scope. With the electron energy in the diagnostic beam
equal to W = 1.5 keV, the depth of analysis is Δx =
2 nm. Estimates show that the increase in the mass of
the sample due to the introduction of oxygen atoms
into the surface layer with a thickness of 2 nm is at the
level of 5 × 10–6 g/cm2, which is below the measure-
0.3
'm/S , mg/сm2

studies (Figs. 3b and 4b). Also, Fig. 5 clearly shows 0.2

that there is a “critical” relative humidity RH ≈10%,
above which the rate of mass gain of an iron sample
treated in a radiation plasma of moist air increases sig-
nificantly.
0.1
Figure 6 shows experimental data on the oxygen
content in the near-surface oxidized layer of iron sam-
ples treated in moist air plasma, depending on the rel-
ative humidity of the air. The results of measurements
for two samples with a size of 10 × 10 mm2, which were 0
placed in different areas of the irradiation zone during 0 20 40 60 80
processing, are presented. Sample 1 was located on the RH, %
axis of the electron beam, where the minimum corro-
sion rate is observed, and sample 2 was located at a
distance of 3 cm from the beam axis, where the corro- Fig. 5. The specific increase in the mass of iron samples
treated in moist air plasma, depending on the relative air
sion rate is higher. humidity. Electron beam current I = 1 mA, electron
At first glance, these data do not agree with the energy W = 115 keV, processing time t = 20 min. The size
results presented in Figs. 3b and 4b, since an increase of the samples is 70 × 70 mm2.

PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023

568 BABICHEV et al.

60 model from [4] and the ionization rate was calculated

by the relation:
50 jb ρ dE
Qion = φ ( r, z ) F ( E0 ) , (1)
e εion dz
40
1 where jb is the beam current density, e is the absolute
value of the electron charge, εion is the energy cost of
[O], %

2
30 the ion-electron pair production, which is close to two
ionization potentials of atoms and molecules of gas
20 (for humid air εion ≈ 33 eV [7]), dE/dz is the specific
energy loss by a fast electron per unit path length, φ is
10
the function that takes into account diffusion spread-
ing of the beam, z, r are the coordinates in a cylindrical
coordinate system with the origin at the center of the
0 foil, F is the quantity that takes into account the effect
0 10 20 30 40 50 60 70 80 90 of the electric field E0 applied to the discharge gap. In
RH, %
[4], to determine the specific energy loss and electron
range, approximate relations were proposed, obtained
Fig. 6. The oxygen content in the oxidized near-surface as a result of approximation of the data calculated by
layer of iron samples treated in moist air plasma, depend- the Monte Carlo method:
ing on the relative air humidity. 1—the sample was located
on the axis of the electron beam, 2—the sample was
located on the periphery of the beam, the size of the sam- ( b ) [
dE E , Z = 0.78 − 0.0005E
b]
ples is 10 × 10 mm2. Electron beam current I = 1 mA, elec- dZ
(2)
tron energy W = 115 keV, processing time t = 20 min. E   Z + Z 
× b 1 + sin 1.29π f  ,
Re   Re 
ment limit. At the same time, the thickness of the oxi- Re = 0.00753Eb1.661, (3)
dized layer of iron (rust) at high levels of relative air
humidity, measured using an optical profilometer, where Re is the beam electron range in mg/cm2, Eb is
turns out to be 10–200 times greater. the beam electron energy in keV, dE/dZ is the specific
energy loss in keV cm2/mg, Zf is the foil thickness in
mg/cm2, Z = ρz is the electron range in gas in mg/cm2
4. NUMERICAL SIMULATION (foil is at z = 0), ρ is the gas density.
OF THE PLASMA COMPOSITION After a fast electron has passed a certain path in a
AND ESTIMATION decelerating medium (according to [8], approximately
OF THE CORROSION RATE equal to half the electron range in gas), the spreading
function φ is described by the Laplace equation:
As follows from the data presented in Fig. 5, the
rate of radiation corrosion of iron increases sharply at Δφ = 0 (4)
a relative humidity RH ≥ 10%. At such low humidity with the following boundary conditions [4]:
values, continuous water films do not form on the
metal surface [6] and, accordingly, the electrochemi- 1, r ≤ a,
φ ( r, z = 0) =  lim φ ( z, r ) → 0, (5)
cal mechanism of corrosion does not work under these 0, r > a, z →∞
conditions. In [2], it was suggested that hydrated pos-
itive ions can play a significant role in the mechanism where a is the radius (half-width in the case of a win-
of radiation corrosion, while no specific processes of dow in the form of an infinite strip) of the exit window
ion participation in the mechanism of corrosion were of the electron gun.
proposed. To clarify the role of cluster hydrated ions in In our experiments, the exit window of the electron
heterogeneous processes of iron oxidation, numerical gun had a shape close to round; therefore, the solution
modeling of plasma composition in moist air irradi- of the Laplace equation (4) can be represented in the
ated by a fast electron beam at different values of rela- following form [3] (see also [9]):
tive humidity and different electron beam ionization π
rates was carried out in this paper. φ=z 
1
π 0 [z 2 + r 2 sin 2 ψ]
The calculation of the rate of gas ionization by a (6)
beam of fast electrons Qion was carried out according to  2 r + z − ar cos ψ
2 2

× (r + z ) − 2 d ψ.
2 1/2
1/2 
the model described in detail in [3]. It is similar to the  (r + z + a − 2ar cos ψ) 
2 2

PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023

 IRON CORROSION IN THE RADIATIVE PLASMA 569

100 (а)
102 6
1 101
2 7 5
8 9
3 100
4 4
ni/n6, %

np, i /n6, %
50 5
6 101 3
7 2
2 1
8 10
10 11
103
0 104
106 105 104 103 102 105
GH2O 20 40 60 80 100
RH, %
(b)
Fig. 7. The number densities of O4+ ions (curve 1), 102 5
NO2+ (2), NO+O2 (3), H3O+(OH) (4), NO+(H2O) (5), 9
12
8
H3O+ (6), O4− (7), O2− (8) at Qion = 1016 cm–3 s–1. 1 10
10
6 11
By integrating the spreading function, the current nn, i /n6, % 100 4
density per individual section of the probe was deter- 7
mined in the form of squares 0.5×0.5 cm2 in size: 1 3
10 2
x + ap 2 y + ap 2
1
j p ( x, y, z ) = jb   φ ( x ', y ', z ' ) dx ' dy ', (7)
102
x −ap 2 y −ap 2

where h = ap/2, ap is the section size: ap = 0.5 cm. Fig-

ure 2 shows the beam current density distributions cal-
culated by Eq. (7). One can see a good agreement
between the calculated and experimental data. To
achieve the best agreement, two parameters were var-
ied in the calculations: the value of the beam current
density jb passing through the foil, since a part of the
total beam current I fell on the structural elements of
the electron gun supporting and cooling the foil, and
also the coordinate z, since the spreading function,
which has already been noted above, is described by
the Laplace equation only from a certain distance after
the passage of the foil [8]. It turned out that a good
agreement between the beam current densities at the
maximum in the calculation and experiment is
achieved if we assume that 46.5% of the beam current
is released at I = 1 mA, and it is 40.7% at I = 0.5 mA.
And the form of the dependence on the x coordinate in
the experiment and in the calculation practically coin-
cide with each other, as can be seen in Fig. 2, at
z' = 3 cm, i.e., the shift was 2.5 cm: z – z' = 2.5 cm.
Therefore, the air ionization rate was calculated using
formula (1) with this shift and with the found values of
the beam current density. The calculation results are
shown in Figs. 2b. It can be seen that the rate of gas
ionization on the axis of the working chamber reaches
2 × 1016 cm–3 s–1.
The kinetic model of ion-molecular processes
described in detail in [7] was used to calculate the ionic
103
0 20 40 60 80 100
RH, %
Fig. 8. Relative number densities of positive H+(H2O)n (a)
and negative O2− (H2O)n (b) ions with different numbers of
water molecules in the radiation plasma of moist air,
depending on relative humidity (the numbers on the right
are equal to the value of the number of water molecules in
the complex n). The ionization rate of Qion = 1016 cm–3 s–1.
composition of moist air plasma. The main calcula-
tions were performed at the ionization rate
Qion=1016 cm–3 s–1. Figure 7 shows the relative number
densities of non-hydrated positive and negative ions in
the radiative plasma of humid air as a function of rela-
tive humidity. It can be seen from the presented results
that the fraction of non-hydrated ions is noticeable
only at low relative humidity RH ≤ 0.1%, and already
at RH ≥ 1%, the total fraction of non-hydrated both
positive and negative ions becomes less than 10%.
Figure 8 shows the relative number densities of
positive H+(H2O)n (a) and negative O2− (H2O)n (b) ions
in radiative plasma of humid air as a function of rela-
tive humidity at a constant rate of gas ionization by an
electron beam. It can be seen that as the relative
humidity increases, the number n in the cluster com-

PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023

570 BABICHEV et al.

1011 ing radiation, the process of chemical corrosion is

considered in more detail. The analysis will be carried
1 out on the basis of the Langmuir–Hinshelwood
model [2, 10]. The process of corrosion by neutral
2 molecules of oxygen and water vapor in the Langmuir-
1010 Hinshelwood model is described as a bimolecular pro-
3 cess on the surface:
ni, сm3

O2 + S ↔ O2 − S, (8)

109 H2O + S ↔ H2O − S, (9)

108 6
10 105 104 103 102 101
RH, %
Fig. 9. Dependences of (solid curves) the total concentra-
tion of all ions of the same sign, (dashed curves) the total
concentration of positive hydrated ions, and (dash-dotted
curves) the total concentration of negative hydrated ions
on the relative air humidity at an ionization rate Qion =
(1) 1016, (2) 1015, and (3) 1014 cm–3 s–1.
plex increases (i.e., the cluster ions “get heavier”), and
for negative ions this process begins much earlier (at
lower RH) than for positive ions and accordingly at a
fixed RH value, the fraction of negative ions with high
n is greater than the fraction of positive ions. For
example, at relative humidity RH = 80%, the fraction
of O2− (H2O)12 ions is 11–14%, depending on the gas
ionization rate, while the proportion of positive
H+(H2O)9 is at the level of 1%.
Figure 9 shows the total number density of positive
ions and the total number density of negative ions
equal to each other, as well as the total number densi-
ties of hydrated positive and negative ions in the radi-
ative plasma of humid air depending on relative
humidity at three gas ionization rates of 1014, 1015, and
1016 cm–3 s–1. As can be seen from Fig. 9, at a constant
rate of gas ionization by an electron beam, the total
number densities of positive and negative ions practi-
cally do not change with changes in air humidity, and
hydrated complex ions become the predominant ions
at RH > 10%.
In the range of RH > 20%, the composition of the
predominant ions, as can be seen from Fig. 8 changes
insignificantly, while the number of molecules in the
complex changes by 1–2 units. Also in this area,
according to Fig. 9, the total number densities of
hydrated complex ions do not change. Therefore, we
can conclude that the change in the corrosion rate and
its maximum at RH ~ 45%, established in [2], are not
associated with a change in the type of hydrated ions.
To establish the reasons for the appearance of the
noted features of corrosion under the action of ioniz-
where “S” means the surface, followed by a two-step
process
2+ −
2Fe → 2Fe + 4e , (10)
100
O2 + 4e − + 2H2O → 4OH−, (11)
which can be written as one process
2Fe + O2 + 2H2O ↔ 2Fe2 + + 4OH−. (12)
The overall corrosion equation in the first stage is:
2Fe + О2 + 2Н2О → 2Fe (ОН)2
(13)
(white rust).
Under the influence of atmospheric oxygen, the
further oxidation of iron will occur with the formation
of iron (III) hydroxide (the second stage) according to
the reaction:
4Fe (OH)2 + O2 + 2H2O = 4Fe (OH)3 . (14)
Iron (III) hydroxide is unstable and decomposes
with the release of water according to the following
reaction:
Fe(OH)3 → FeOOH + Н2О, (15)
where FeOOH is the leaf rust, the end product of iron
corrosion in a neutral environment (рН 7) [11].
The rate of absorption of oxygen and water mole-
cules by the surface is described by the balance equa-
tions [2]:
d ΘO2
= ka1 (1 − ΘO2 − ΘH2O ) nO2 − kd1ΘO2 ,
dt (16)
d ΘH2O
= ka2 (1 − ΘO2 − ΘH2O ) nH2O − kd 2ΘH2O,
dt
where ka1, kd1 are the rate constants of adhesion and
evaporation of oxygen and ka2, kd2 of water molecules,
respectively, nO2 and nH2O are the volume number den-
sities of oxygen and water molecules in air, respec-
tively, ΘO2 and ΘH2O are the fraction of surface sites
occupied by oxygen and water molecules, respectively.
The iron density under normal conditions is ρFe =
7.874 g/cm3, the iron lattice structure is body-centered
cubic with a lattice parameter a = 2.866 Å. The density
of surface sites ns depends on the type of lattice face;

PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023

 IRON CORROSION IN THE RADIATIVE PLASMA 571

for estimates, it was assumed that it is determined by 8kBT 8kBT

the expression: vth,O2 = , vth,H2O = . (19)
πmO2 πmH2O
ρFea −2
ns = = 1.2 × 10 cm ,
15 The accommodation coefficient is usually on the
(17)
2mFe order of 10–3−10–4. In the stationary state, from (16)
we find:
where mFe is the mass of iron atoms. When the fluxes
of molecules to the surface and from the surface are ka1nO2 kd1
not very different (i.e., for small values of the accom- ΘO2 = ,
1 + ka1nO2 kd1 + ka2nH2O kd 2
modation coefficient), the sticking rate constants can (20)
be determined using the kinetic flux of molecules to ka2nH2O kd 2
ΘH2O = .
the surface: 1 + ka1nO2 kd1 + ka2nH2O kd 2
vth,O2 vth,H2O The rust growth rate R in the process of chemical
ka1 = γO2 , ka2 = γ H2O , (18) corrosion is determined by the expression [2, 10]
4ns 4ns
K1K 2nO2 nH2O
where γO2 and γ H2O are the accommodation coeffi- R = k ΘO2 ΘH2O ≡ k , (21)
cients (probabilities of adhesion) to the iron surface of (1 + K1nO2
+ K 2nH2O )
2

oxygen molecules and water molecules, respectively, where k is the growth rate constant of the corroded
vth,O2 and vth,H2O are the directed thermal velocities of layer, K1 = ka1/kd1, K2 = ka2/kd2. Expression (21) can be
oxygen and water molecules: reduced to the form:

kka1ka2nO2 nH2O
R= . (22)
 kd1   kd 2 
k
 d1 + k n + k n k + k n + k n
kd 2  
a1 O2 a2 H2O d2 a1 O2 a2 H2O 
 kd1 

It can be expected that, under normal conditions, source can be carried out not only by oxygen mole-
all sites on the iron surface will be occupied by water cules, but also by positively charged H3O+(H2O)n ions
and oxygen molecules: ΘO2 + ΘH2O ≈ 1. In this case, [2]
the first terms in brackets in the denominator (22)
(terms kd1 and kd2) can be neglected. Also, for esti- H3O+ (H2O)n + e − → 1/2H2 + (n + 1)H2O. (24)
mates, we can assume that ka1 ≈ ka2. Then, to estimate If the efficiency of oxygen as a depolarizer is suffi-
the growth rate of the corrosion layer from (22), using ciently low, then the ion will neutralize the negative
(18) and (19), we obtain: charge of the electrode with almost unity probability.
The flux of positive ions to the surface in the kinetic
γnO2 nH2O γ H2O mO2 region is given by
R≈k , γ= . (23)
( nO + γnH2O )
2
γO2 mH2O 8kBT
2
J k + = 1 n+ , (25)
The corrosion rate under normal conditions varies 4 πm+
within 50–200 μm/year [12]. For estimates, we where n+, m+ are the number density and mass of pos-
assume that at a relative humidity of 95% (the corro- itive ions. And in the diffusion region, the ion flux is
sion growth rate at this humidity is maximum), the determined by the expression
growth rate is 200 μm/year. Estimates show that the
rate of growth of the corrosion layer in the atmosphere π2D+
on the relative humidity of the air depends on the value J d + = n+
, (26)
2Rsh
of the parameter γ and this dependence has a maxi-
mum at γ ≈ 8, which is quite explainable by the higher where D+ is the diffusion coefficient of positive ions,
accommodation coefficient of water molecules, which which can be determined from the mobilities given in
have a constant dipole moment, than the accommo- Table 1 using the Einstein relation: D+/μ+ = kBT/e, Rsh
dation coefficient of oxygen molecules, having only a is the characteristic screening length in nonequilib-
constant quadrupole moment. In this case, the rate rium plasma [7]. According to the equally accessible
constant turned out to be equal to k = 800 μm/year. surface method [13], in the general case, the ion flux
Let us now consider the corrosion in plasma. In will be determined by the expression:
this case, the process of cathodic depolarization −1
 2πm+ 2Rsh 
( )
−1
during electrochemical corrosion of metals in humid J+ = J k−+1 + J d−+1 = n+  + 2  . (27)
air under the influence of an external ionization  kBT π D+ 
PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023
572 BABICHEV et al.

Table 1. Parameters for calculating the growth rate of the corrosion layer under the action of positive hydrated ions at the
gas ionization rate Qion = 2 × 1016 cm–3 s–1
Designation and unit
Parameter Value
measurements
Number density of positive ions n+, cm–3 8.0 × 1010
Mass of H3O+(H2O)7 m+, amu 145
Mobility of H3O+(H2O)7 μ+, cm2/V s 1.95

Ion-ion recombination coefficient of H3O+(H2O)7 and O2− (H2O)9 βii, cm /s

3
3.17 × 10–6
Diffusion coefficient of H3O+(H2O)7 D+, cm2/s 0.0493

Mass of O2− (H2O)9 m_, amu 194

Mobility of O2− (H2O)9 μ_, cm2/V s 2.1

Diffusion coefficient of O2− (H2O)9 D_, cm2/s 0.052

Screening length (28) [7] Rsh, μm 3.2
Flux of positive ions to the iron surface J+, cm–2 s–1 5.4 × 1013
Surface density of iron atoms ns, cm–2 1.20 × 1015
Iron lattice parameter a, Å 2.87
The probability of neutralization of the negative charge of the electrode by γ+ 1
a positive ion
Corrosion layer growth rate (29) R+, cm/s 6.4 × 10–10
Mass of positive ions reaching the surface in 20 minutes Δm+, mg/cm2 0.016

This expression determines the rate of heteroge-
neous processes involving ions.
The screening length in Eqs. (26) and (27) is 1/ks
(see [7]), the expression for which is generally given
in [7]. In the case of one predominant sort of both
positive and negative ions, it goes into the following
expression:
−1/2
  
Rsh = βii n+  1 + 1  , (28)
  D+ D− 
where βii is the coefficient of ion-ion recombination,
D– is the diffusion coefficient of negative ions.
The growth rate of the corrosion layer under the
action of a positive ion flux is ultimately determined by
the expression
−1
γ J a γ n a  2πm+ 2Rsh 
R+ = 1 + + ≡ 1 + +  +  . (29)
2 ns 2 ns  kBT π2D+ 
Table 1 shows the parameters used in the calcula-
tion of the growth rate of the corrosion layer under the
action of negative hydrated ions from expression (29).
According to the calculations performed in this sec-
tion, at a gas ionization rate Qion ~ 1016 cm–3 s–1 and a
relative humidity RH > 20%, the main positive ions
are H3O+(H2O)6, H3O+(H2O)7 and H3O+(H2O)8, and
the dominant sort of negative ions are O2− (H2O)5 and
O2− (H2O)9 ions (see Fig. 8). Therefore, the calculations
were carried out for H3O+(H2O)7 and O2− (H2O)9 ions,
since both the mobilities (diffusion coefficients) and
the ion–ion recombination coefficients for all the
named ions are very close.
As can be seen from Table 1, the increase in the
mass of the iron plate due to the flow of positive ions
in 20 minutes turns out to be an order of magnitude
less than those observed in the experiment (see Fig. 5).
It should be noted that the above estimates did not
take into account the formation of an ambipolar diffu-
sion layer near the plate, since the mobilities of nega-
tive and positive ions are close to each other. Near the
plate, the rate of electron loss due to escape to it can
exceed the rate of loss in the process of three-body
attachment to oxygen molecules. According to [14],
the condition for the dominance of the electron flux
over the flux of negative ions to the wall (this condition
is the condition for the formation of an ambipolar dif-
fusion layer, in which the diffusion and drift compo-
nents of the flux of more mobile charge carriers in
plasma are approximately equal to each other) has
the form:
2
μ ν 
Qion @ Qion,cr = 1  − a  , (30)
βii  μe 

PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023

 IRON CORROSION IN THE RADIATIVE PLASMA
where νa is the frequency of three-body electron
attachment, βii, μ−, μe are the mobilities of negative
ions and electrons. Calculations with the use of the
BOLSIG+ program [15] with cross sections from [16,
17] showed that the diffusion coefficient of electrons
in air at atmospheric pressure and at a reduced electric
field strength E/n = 0.1 Td (n is the total number den-
sity of air molecules) is equal to De = 460 cm2/s
(mobility μe = 1.43 × 104 cm2/V s). During the charac-
teristic time of the process of three-body attachment
of electrons, the main channel of their loss in the bulk
plasma, equal to τa =1/νa = 18 ns (νa ≈ 5.5 × 107 s–1)
at atmospheric pressure in air, they manage to cover a
distance of Ra = 2D e τa ≈ 40 μm, which significantly
exceeds both the Debye screening length and the
screening length (24). From (30) we find that Qion,cr ≈
1013 cm–3 s–1, therefore, at Qion ≈ 1016 cm–3 s–1 in our
experiments, an ambipolar diffusion layer will form
near the iron plate under study. In this layer, in which
the density of negative charge carriers will be strongly
suppressed due to the action of the ambipolar electric
field that slows them down, the main channel for the
loss of positive ions will be their escape to the wall.
Consequently, the positive ion flux will be of the order
of QionRa ≈ 8 × 1013 cm–2 s–1, which is almost two times
higher than the ion flux given in Table 1. This shows
the need for more accurate calculations of the ion flux
using the balance equations, taking into account the
processes of charge exchange and ion conversions.
4. CONCLUSIONS
In this paper, experimental studies of the corrosion
rate of iron samples placed in a chemically active
plasma of moist air generated by fast electron beam as
a simulator of radiation from the decay radioactive
products of spent nuclear fuel, depending on the rela-
tive air humidity, are carried out. It was found that
radioactive β-radiation (fast electron beam) signifi-
cantly intensifies iron corrosion in a working gas envi-
ronment in which oxygen and water vapor is simulta-
neously present. It has been found that the rate of cor-
rosion under conditions of radioactive irradiation
increases sharply when the relative humidity of the air
exceeds RH > 10%. The existence of a “critical” air
humidity RH ~ 60% for the rate of iron corrosion
under atmospheric conditions (in the absence of radi-
ation) is well known [18] and is explained by the
change of the corrosion mechanism from chemical to
electrochemical during the formation of a continuous
film of water on the metal surface. At a relative humid-
ity of RH ~ 10% continuous films of water do not form
on the metal surface, therefore, an increase in the cor-
rosion rate under these conditions has a different
nature. In [1] it was shown that the effect of fast elec-
trons on metal corrosion processes in a vapor-gas
medium occurs through radiolysis of this medium,
PLASMA PHYSICS REPORTS Vol. 49 No. 5 2023
573
and not through activation of the metal surface by
electrons. The mechanism of this effect remains
unclear to date. Numerical calculations of the compo-
sition of the radiation plasma in humid atmospheric
air performed in this paper indicate that the main ions
at a relative humidity RH > 10% are hydrated ion clus-
ters H+(H2O)n and O2− (H2O)n with n = 6−8 for positive
and n = 9–12 for negative ions. The close correlation
between the behavior of the corrosion rate and the
composition of hydrated ions in moist air plasma indi-
cates the decisive role of cluster hydrated ions in het-
erogeneous iron oxidation processes. Numerical sim-
ulation of the corrosion process based on the Lang-
muir–Hinshelwood model showed that hydrated ions
significantly increase the corrosion rate, however, to
achieve a quantitative agreement between the simula-
tion results and experimental data, more accurate cal-
culations of ion fluxes are required, taking into
account the conversion and charge exchange pro-
cesses.
FUNDING
The work was supported by the Rosatom State Corpo-
ration (state contract no. N.4ch.241.09.21.1074 dated
April 20, 2021).
CONFLICT OF INTEREST
The authors declare that they have no conflicts of interest.
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Vol. 49 No. 5 2023