Mechanism of Embrittlement of Metals by Surface-Active Elements
The nature of mechanical degradation of metals caused by surface-active elements is studied based on the effects of iodine and gallium in austenitic steels and using abinitio calculations and experimental measurements of electronic structure, X-ray diffraction, mechanical spectroscopy, and mechanica...
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| Опубліковано в: : | Металлофизика и новейшие технологии |
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| Дата: | 2018 |
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Інститут металофізики ім. Г.В. Курдюмова НАН України
2018
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| Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Цитувати: | Mechanism of Embrittlement of Metals by Surface-Active Elements / S.M. Teus, B.D. Shanina, A.A. Konchits, G.S. Mogilny, V.G. Gavriljuk // Металлофизика и новейшие технологии. — 2018. — Т. 40, № 2. — С. 201-218. — Бібліогр.: 70 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1860248211719979008 |
|---|---|
| author | Teus, S.M. Shanina, B.D. Konchits, A.A. Mogilny, G.S. Gavriljuk, V.G. |
| author_facet | Teus, S.M. Shanina, B.D. Konchits, A.A. Mogilny, G.S. Gavriljuk, V.G. |
| citation_txt | Mechanism of Embrittlement of Metals by Surface-Active Elements / S.M. Teus, B.D. Shanina, A.A. Konchits, G.S. Mogilny, V.G. Gavriljuk // Металлофизика и новейшие технологии. — 2018. — Т. 40, № 2. — С. 201-218. — Бібліогр.: 70 назв. — англ. |
| collection | DSpace DC |
| container_title | Металлофизика и новейшие технологии |
| description | The nature of mechanical degradation of metals caused by surface-active elements is studied based on the effects of iodine and gallium in austenitic steels and using abinitio calculations and experimental measurements of electronic structure, X-ray diffraction, mechanical spectroscopy, and mechanical tests. A significant increase in the density of electron states at the Fermi level for iodine in f.c.c. iron is shown that is in consistent with the measurements of the increased concentration of free electrons caused by iodine in austenitic steels. Consequently, the increase in mobility of dislocations by iodine and gallium in austenitic steels is revealed. The localization of the enhanced plastic deformation is discussed as a condition for brittleness. The obtained results are at variance with the widely spread opinion about the determining role of surface energy in a liquid-metal brittleness and, instead, are interpreted based on the correlation between atomic interactions and dislocation properties. Applicability of the available HELP and AIDE hypotheses is discussed.
Природа механической деградации металлов, обусловленной поверхностно-активными элементами, была изучена, основываясь на влиянии йода и галлия на аустенитные стали и используя abinitio-расчёты и экспериментальные исследования электронной структуры, рентгеновскую дифракцию, механическую спектроскопию и механические испытания. Показано существенное повышение плотности электронных состояний на уровне Ферми в случае йода в ГЦК-железе, что согласуется с измерениями, в которых была зафиксирована повышенная концентрация свободных электронов, вызванная йодом в аустенитных сталях. Как следствие, установлено повышение мобильности дислокаций, вызванное йодом и галлием в аустенитных сталях. Обсуждается роль локализации повышенной пластической деформации в качестве условия хрупкости. Полученные результаты противоречат широко распространённому мнению об определяющей роли поверхностной энергии в жидкометаллической хрупкости и, вместо этого, интерпретируются, основываясь на корреляции между атомными взаимодействиями и дислокационными свойствами. Обсуждается применимость гипотез HELP и AIDE.
Природу механічної деґрадації металів, яку спричинено дією поверхнево-активних елементів, було досліджено, виходячи із впливу Йоду та Ґалію на аустенітні сталі та використовуючи abinitio-розрахунки й експериментальні дослідження електронної структури, рентґенівську дифракцію, механічну спектроскопію та механічні випробування. Показано істотне підвищення густини електронних станів на рівні Фермі у випадку Йоду в ГЦК-залізі, що узгоджується з вимірюваннями, в яких було зафіксовано підвищену концентрацію вільних електронів, яку спричинено Йодом в аустенітних сталях. Як наслідок, встановлено підвищення мобільности дислокацій, спричинене Йодом і Ґалієм в аустенітних сталях. Обговорюється роль локалізації підвищеної пластичної деформації в якості умови крихкости. Одержані результати суперечать розповсюдженим твердженням про визначальну роль поверхневої енергії в рідкометалевому окрихченні і замість цього інтерпретуються, виходячи з кореляції між атомними взаємодіями та дислокаційними властивостями. Обговорюється коректність гіпотез HELP та AIDE.
|
| first_indexed | 2025-12-07T18:40:04Z |
| format | Article |
| fulltext |
PACS numbers: 61.72.Hh, 61.72.Yx, 62.20.M-, 62.40.+i, 68.35.Dv, 71.20.Be, 76.30.-v
Mechanism of Embrittlement of Metals
by Surface-Active Elements
S. M. Teus, B. D. Shanina*, A. A. Konchits*, G. S. Mogilny,
and V. G. Gavriljuk
G. V. Kurdyumov Institute for Metal Physics, N.A.S. of Ukraine,
36 Academician Vernadsky Blvd.,
UA-03142 Kyiv, Ukraine
*V. E. Lashkaryov Institute of Semiconductor Physics,
41 Nauky Ave.,
UA-03028 Kyiv, Ukraine
The nature of mechanical degradation of metals caused by surface-active el-
ements is studied based on the effects of iodine and gallium in austenitic
steels and using ab initio calculations and experimental measurements of
electronic structure, X-ray diffraction, mechanical spectroscopy, and me-
chanical tests. A significant increase in the density of electron states at the
Fermi level for iodine in f.c.c. iron is shown that is in consistent with the
measurements of the increased concentration of free electrons caused by io-
dine in austenitic steels. Consequently, the increase in mobility of disloca-
tions by iodine and gallium in austenitic steels is revealed. The localization of
the enhanced plastic deformation is discussed as a condition for brittleness.
The obtained results are at variance with the widely spread opinion about the
determining role of surface energy in a liquid-metal brittleness and, instead,
are interpreted based on the correlation between atomic interactions and dis-
location properties. Applicability of the available HELP and AIDE hypothe-
ses is discussed.
Key words: f.c.c. iron, austenitic steel, surfactants, electronic structure, dis-
locations, mechanical properties.
Природу механічної деґрадації металів, яку спричинено дією поверхнево-
Corresponding author: Valentin Gennadievich Gavriljuk
E-mail: gavr@imp.kiev.ua
Citation: S. M. Teus, B. D. Shanina, A. A. Konchits, G. S. Mogilny, and
V. G. Gavriljuk, Mechanism of Embrittlement of Metals by Surface-Active Elements,
Metallofiz. Noveishie Tekhnol., 40, No. 2: 201–218 (2018),
DOI: 10.15407/mfint.40.02.0201.
Ìåòàëëîôèç. íîâåéøèå òåõíîë. / Metallofiz. Noveishie Tekhnol.
2018, т. 40, № 2, сс. 201–218 / DOI: 10.15407/mfint.40.02.0201
Îттиски доступнû непосредственно от иçдателя
Ôотокопирование раçреøено толüко
в соответствии с лиценçиеé
2018 ÈÌÔ (Èнститут металлоôиçики
им. Ã. Â. Êурдюмова ÍÀÍ Óкраинû)
Íапечатано в Óкраине.
201
https://doi.org/10.15407/mfint.40.02.0201
https://doi.org/10.15407/mfint.40.02.0201
202 S. M. TEUS, B. D. SHANINA, A. A. KONCHITS, G. S. MOGILNY, and V. G. GAVRILJUK
активних елементів, було досліджено, виходячи іç впливу Йоду та Ґалію
на аустенітні сталі та використовуючи ab initio-роçрахунки é експериме-
нталüні дослідження електронної структури, рентґенівсüку диôракцію,
механічну спектроскопію та механічні випробування. Покаçано істотне
підвищення густини електронних станів на рівні Ôермі у випадку Йоду в
ÃЦÊ-çаліçі, що уçгоджуєтüся ç вимірюваннями, в яких було çаôіксовано
підвищену концентрацію вілüних електронів, яку спричинено Йодом в
аустенітних сталях. Як наслідок, встановлено підвищення мобілüности
дислокаціé, спричинене Йодом і Ґалієм в аустенітних сталях. Îбговорю-
єтüся ролü локаліçації підвищеної пластичної деôормації в якості умови
крихкости. Îдержані реçулüтати суперечатü роçповсюдженим тверджен-
ням про виçначалüну ролü поверхневої енергії в рідкометалевому окрих-
ченні і çамістü цüого інтерпретуютüся, виходячи ç кореляції між атомни-
ми вçаємодіями та дислокаціéними властивостями. Îбговорюєтüся коре-
ктністü гіпотеç HELP та AIDE.
Ключові слова: ÃЦÊ-çаліçо, аустенітна сталü, сурôактанти, електронна
структура, дислокації, механічні властивості.
Природа механическоé деградации металлов, обусловленноé поверхност-
но-активнûми элементами, бûла иçучена, основûваясü на влиянии éода и
галлия на аустенитнûе стали и исполüçуя ab initio-расчётû и эксперимен-
талüнûе исследования электронноé структурû, рентгеновскую диôрак-
цию, механическую спектроскопию и механические испûтания. Покаçа-
но существенное повûøение плотности электроннûх состояниé на уровне
Ôерми в случае éода в ÃЦÊ-желеçе, что согласуется с иçмерениями, в ко-
торûх бûла çаôиксирована повûøенная концентрация свободнûх элек-
тронов, вûçванная éодом в аустенитнûх сталях. Êак следствие, установ-
лено повûøение мобилüности дислокациé, вûçванное éодом и галлием в
аустенитнûх сталях. Îбсуждается ролü локалиçации повûøенноé пла-
стическоé деôормации в качестве условия хрупкости. Полученнûе ре-
çулüтатû противоречат øироко распространённому мнению об определя-
ющеé роли поверхностноé энергии в жидкометаллическоé хрупкости и,
вместо этого, интерпретируются, основûваясü на корреляции между
атомнûми вçаимодеéствиями и дислокационнûми своéствами. Îбсужда-
ется применимостü гипотеç HELP и AIDE.
Ключевые слова: ÃЦÊ-желеçо, аустенитная сталü, сурôактантû, элек-
тронная структура, дислокации, механические своéства.
(Received November 9, 2017)
1. INTRODUCTION
Phenomenon of liquid metal embrittlement (LME) is known since 1874
(see, e.g., [1]). Later on, it has been shown that solid metal films can al-
so cause brittle fracture, SME (e.g., [2]). The first physical interpreta-
tion of surface-active elements, surfactants in the following, on me-
chanical properties of solids has been proposed in 1928 [3] and desig-
MECHANISM OF EMBRITTLEMENT OF METALS BY SURFACE-ACTIVE ELEMENTS 203
nated as Rehbinder’s effect. As formulated in his short communication
at the VI Congress of Russian Physicists, Rehbinder declared ‘the ef-
fect of the surface energy of a crystal (calcite, rock salt, gypsum, or
mica) on its mechanical and other properties by decreasing the surface
tension of crystal faces via the introduction of surfactants which form
Gibbs–Langmuir layers at the interfaces’. This idea has been resulted
in the extensive practical applications, e.g., for easing the cutting of
tough materials due to their local embrittlement. Starting from the
fifties, important practical consequences were concerned with the de-
velopment of nuclear reactors using the lead-bismuth eutectic as a
coolant, where the liquid-metal embrittlement, LME, creates a serious
problem (see, e.g., [4]).
A number of original research papers, review articles and monogra-
phies are concerned with this not ordinary phenomenon, e.g., [5–10].
Nevertheless, an operating mechanism remains so far debatable. The
surfactants-induced decrease in the strength constitutes a topic of
many studies treating Rehbinder’s concept in terms of the Griffith’s
relation between the surface free energy per unit area of the crack, γ,
and the fracture strength σGr = (γE/(πc))1/2, where E is the Young modu-
lus and c is the length of the initial crack formed under applied stress.
The application of this formula suggests a decrease in strength due
to adsorption of surfactants on the crack surface, which decreases the
surface energy. This rather simple thermodynamic interpretation was,
probably, first time proposed in [11] and remains to be discussed (see,
e.g., [12–14]).
A mechanism of surfactant atoms penetration into the metal is being
preferentially related with the grain boundaries. For example, liquid-
channel grain boundary structures in ceramic materials were analysed
in [15], whereas a ‘self-indentation–internal-solution’ mechanism has
been proposed in [16], according to which the liquid metal causes grain
boundary ‘grooving’, which removes the solid material from the bulk
and dissolves it in the liquid channel.
A role of the crystal structure is also considered important for LME
appearance, e.g., the transcrystalline LME fracture occurs in marten-
sitic steels and binary ferrous alloys [17] and it is intercrystalline in
f.c.c. polycrystalline metals [18].
As a mechanism for LME, the adsorption-reduced cohesion caused
by the surfactant atoms within the crack tip was proposed by Kamdar
in [19, 20] in consistency with Rehbinder’s effect. For substantiation
of breaking the atomic bonds, this mechanism suggests a criterion of a
critical relation between normal and shear stresses, which was earlier
analysed in [21]. In these terms, the transcrystalline fracture can be
interpreted as a result of prevailing normal stresses. Nevertheless, at
variance with this idea, LME was also found in the amorphous iron-
based materials, e.g., [22, 23], where both deformation and fracture
204 S. M. TEUS, B. D. SHANINA, A. A. KONCHITS, G. S. MOGILNY, and V. G. GAVRILJUK
proceed only through the shear processes.
Important for the clarification of operative mechanisms was the ob-
servation that embrittlement by surfactants is accompanied by a local
increase of plasticity (see, e.g., [24–26]). In other words, the locally en-
hanced plastic deformation precedes the macrobrittle fracture. In the
attempt to interpret this unusual behaviour, the local disintegration of
solids resulted in colloidal disperse systems was proposed in [5, 6].
Such an approach was complemented by the ideas about liquid channels
[15, 16] and corresponding grain boundary phase transitions [27, 28].
However, such an interpretation of preceded plastic deformation is
seriously discredited by a striking similarity between LME and hydro-
gen embrittlement, HE, which has been remarked already in the first
observations of LME [1]. A significant localized plastic flow always
precedes the hydrogen-caused brittle fracture of metals.
Systematic comparative studies of LME and HE were carried out by
Lynch (see, e.g., [29]). Based on these studies and using the above men-
tioned idea of surfactant atoms adsorption within the crack tip, he has
proposed the adsorption-induced localized-slip process to be responsi-
ble for both the LME and HE phenomena [30] and, correspondingly,
developed the hypothesis of ‘adsorption-induced dislocation emission’,
AIDE, [30, 31]. Its essence amounts to the facilitated nucleation and
emission of dislocations due to adsorption of hydrogen or surfactant
atoms at the internal surface of the crack tips. Once nucleated, the dis-
locations can readily move away from the crack tip under applied
stress.
Along with AIDE hypothesis, the hydrogen embrittlement of metals
is described by the widespread hypothesis of hydrogen-enhanced local-
ized plasticity, HELP. The analysis of both hypotheses is presented,
e.g. in the review articles [32, 33].
A common feature for the variety of the above-mentioned studies is
that the analysis of LME and SME ignores the change in the electron
structure caused by surfactants, which should affect both atomic in-
teractions and properties of dislocations. The aim of this paper is to
compensate this gap.
2. CALCULATIONS AND EXPERIMENTAL
Iodine and gallium have been chosen as surfactants because of possibil-
ity to carry out the experiments at ambient temperature. Their role in
mechanical degradation of metals is well known, e.g. [13, 34]. Moreo-
ver, iodine is widely used for public demonstration of LME, e.g., ex-
trabrittle fracture of zinc crystals. The CrNi austenitic steels doped by
surfactants were investigated using theoretical and experimental
studies of the electron and crystal structures followed by the experi-
ments on dislocation properties and mechanical behaviour.
MECHANISM OF EMBRITTLEMENT OF METALS BY SURFACE-ACTIVE ELEMENTS 205
Ab initio calculations of the effect of surfactants on the electron
structure have been performed using iodine in the γ-iron. The f.c.c.
iron cluster (cell) of 32 iron atoms and that of 31 iron + 1 iodine ones
were calculated. The total potential, the electron density, and the total
energy per cell have been calculated using the computational program
package Wien2k developed by the European scientific group [35].
These calculations are based on the Kohn–Hohenberg–Sham density
functional theory (DFT) [36, 37].
The initial electron density for solving the Kohn–Sham equations
was taken in the local spin density approximation (LSDA) [38]. A pro-
cedure for solving these equations is the full-potential-linearized-
augmented plane wave method (FLAPW). The calculation of the ex-
change-correlation potential is carried out using the generalized gra-
dient approximation in the parameters of Perdew, Burke, and Ern-
zernhoff [39], where the gradient terms of electron density are added
to the exchange-correlation energy and its potential. The integration
over the Brillouin zone is carried out using the modified tetrahedron
method [40] over the 15×15×15 points in k-mesh for Fe–I system. The
wave functions, the charge densities, and the potential were expanded
with L ≤ 10 spherical harmonics inside each ‘muffin-tin’ radius, RMT,
of 2.16 a.u. and 2.39 a.u. for Fe and I atoms, respectively.
A procedure for the full relaxation has been carried out, which con-
sists of volume relaxation, shape relaxation and the relaxation of in-
ternal atomic positions. The equilibrium state and, consequently, equi-
librium lattice parameters have been obtained.
All calculations were performed in the full relativistic approach
with the spin polarized electron states at temperature T = 0 K. Self-
consistency was achieved when the root-mean square distances be-
tween the j and (j − 1) steps of the iteration procedure for the total
charges and spin densities were smaller than 1.0⋅10−4.
Using the pure iron, chromium, nickel, and manganese, four austen-
itic steels Cr15Ni15, Cr15Ni20, Cr25Ni20, and Cr15Ni25Mn15 (see
Table 1) have been melted in vacuum, as ingots of 175 g in the mass,
followed by homogenization at 1150°C for 24 hours.
TABLE 1. Chemical compositions*.
Steel Cr Ni Mn Fe
Cr15Ni15 15.4 14.4 – Balance
Cr15Ni20 16.0 19.7 – Balance
Cr15Ni25Mn15 15.3 25.6 14.8 Balance
Cr25Ni20 25.2 20.2 – Balance
*Non-purposefully added elements were not determined.
206 S. M. TEUS, B. D. SHANINA, A. A. KONCHITS, G. S. MOGILNY, and V. G. GAVRILJUK
The foils of 20 µm and 0.55 mm in thickness were prepared by roll-
ing for the measurements using electron spin resonance, ESR, and X-
ray diffraction, respectively. Wire specimens of 0.6 mm in diameter
were obtained by cold drawing with intermediate annealing for me-
chanical spectroscopy. For all specimens, the final annealing was per-
formed at 1050°C for 30 min.
The electron paramagnetic resonance spectrometer in the X-band of
the microwave field was used for experimental studies of the electron
structure. The ESR spectra were obtained at the optimum experi-
mental conditions and recorded as derivative dP/dH from the absorbed
microwave power P on the applied magnetic field H. Thereafter, all
parameters were reduced to the same conditions: modulation field am-
plitude Hm = 0.125 G, amplifying coefficient K = 104, and microwave
power P = −35 dB. A piece of the MgO:Cr3+
compound with the number
of spins 1.1⋅1016
served as a reference sample.
The analysis of experimental spectra has been carried out based on
the theory of ESR for free electrons [41] and using a technique devel-
oped in our previous studies [42, 43].
The X-ray diffraction was used for measurements of iodine and gal-
lium effects on the lattice parameters of austenitic steels. The diffrac-
tion patterns were obtained using Huber diffractometer with two-
circle goniometer and CuKα radiation under operating voltage of 30
kV. A graphite monochromator was used at the secondary beam to de-
crease the noise level. A computer program controlled the angular
movement of both goniometer and counter. The error in determination
of the angle position did not exceed 0.001°. The fitting of diffraction
reflections was carried out using the program ProFit taking into ac-
count the CuKα doublet.
Measurements of the amplitude-dependent internal friction for
studies of dislocation properties were carried out within the strain am-
plitude of 0.5⋅10−6
to 5⋅10−4
using an automated inverted pendulum op-
erating at temperatures from 80 to 580 K and frequencies of about 1
Hz.
Mechanical tests were performed at room temperature using a ma-
chine H5-K-T of Hounsfield Company, UK, with the loading rate of
1.7⋅10−3
s
−1.
To saturate the samples with iodine, they were immersed at room
temperature into a standard 5% iodine solution in the ethanol for 72
hours. Before the installation into the experimental device, EPR spec-
trometer, internal friction pendulum or mechanical test machine, the
samples were cleaned with a soft paper.
In the course of processing with gallium, the sample was kept in the
gallium bath at 35, 40 or 100°C for 5 to 68 hours. After this procedure,
the samples were cleaned with a soft paper to remove the gallium drops
from the sample surface.
MECHANISM OF EMBRITTLEMENT OF METALS BY SURFACE-ACTIVE ELEMENTS 207
3. RESULTS
3.1. Electron Structure: Calculations
The paramagnetic state of f.c.c. iron, γ-Fe, is rather complicated for
theoretical calculations, because it corresponds to a disordered spin
orientation and is not really nonmagnetic. As mentioned in [44], the
ground state of γ-Fe is located at a crossing point of ferromagnetic
(FM) and antiferromagnetic (AFM) magnetic states, which substan-
tially depends on the atomic volume. According to neutron diffraction
measurements, magnetic moments in the γ-Fe form the spin density
waves. The first-principle calculations performed using a non-
collinear spin magnetism theory confirm also that the ground state of
the γ-Fe is a spin spiral state [45, 46]. At a slight increase in the lattice
parameter, f.c.c. Fe becomes ferromagnetic. By using the collinear
magnetic moments within the DFT theory [47], it was shown that the
spin spiral state could be well described by the double layer antiferro-
magnetic (AFMD) configuration.
The theoretical description of FM states reveals two possible mag-
netic configurations: low-spin ferromagnetic (LS-FM) and high spin
ferromagnetic (HS-FM). In consistency with the arguments mentioned
in [48], we have chosen the HS-FM state to simulate the f.c.c. γ-Fe. The
reasons for that are the following: (i) the HS-FM state of the f.c.c. iron
is observed experimentally [49–51]; (ii) the HS-FM state was used to
explain the experimentally observed anti-invar effect in f.c.c. Fe [48,
49], and (iii) if properties predicted from the first-principle calcula-
tions are compared with the experimental ones obtained at finite tem-
peratures, the HS-FM state seems to be the most correct for such anal-
ysis.
Figure 1 shows the total density of states (DOS) per cell for the spin
up and spin down electron states. Numerical results of calculation are
presented in Table 2.
Iodine in the iron crystal lattice causes appearance of the bonding
states at the bottom of the metallic d-band and increases the total den-
sity of states at the Fermi level. The analysis of partial contributions to
the total DOS shows that the Fe–I atomic bonding is mainly created by
the electrons of the Fe3d and I5p orbitals. At the same time, the inser-
tion of iodine atoms into the iron crystal lattice strikingly changes the
contribution to the DOS at the Fermi level from 3d iron electrons. It
constitutes 0.88 states/(eV⋅atom) in the pure f.c.c. iron and 0.98
states/(eV⋅atom) in the Fe–I system.
This result is consistent with the data of spatial distribution of elec-
tron density in its 2D projection in Fig. 2, which has been constructed
using the XCrysden program developed in [52].
The valence states were cut off from the core and semi-core (accord-
208 S. M. TEUS, B. D. SHANINA, A. A. KONCHITS, G. S. MOGILNY, and V. G. GAVRILJUK
ing to DFT) ones, and the plane (001) was chosen for presentation. As
seen, the substitution of an iron atom for the iodine one in the iron
crystal lattice causes a distortion of electron density at the neighbour-
ing iron atoms and increases the electron density in the interstitial ar-
ea. The latter suggests the enhancement of metallic character of inter-
atomic bonds.
3.2. X-Ray Diffraction
A shift of the reflections (111)γ and (200)γ by 0.04° towards higher an-
gles occurs after holding of steel Cr25Ni20 in the iodine (Fig. 3, a). It
is by 40 times higher than the measurements precision of 0.001°, i.e.,
the lattice contraction occurs due to iodine. The estimated lattice pa-
Fig. 1. Effect of iodine on the total density of electron states per cell in the γ-
iron crystal lattice. ‘Cell’ means the calculated clusters of 32 Fe atoms and 31
Fe atoms + 1 I atom, respectively.
TABLE 2. Calculation results on the total density of states (DOS) for spin up
and spin down states in the iron and iron-doped iodine structures.
Structure
DOS (up states),
states/(cell⋅eV)
DOS (down states),
states/(cell⋅eV)
Total DOS
(up + down states),
states/(cell⋅eV)
f.c.c. Fe 5.40 28.71 34.11
f.c.c. Fe + I 27.24 16.05 43.29
MECHANISM OF EMBRITTLEMENT OF METALS BY SURFACE-ACTIVE ELEMENTS 209
rameters are equal to 0.3595 ± 0.0001 nm before and 0.3591 ± 0.0002
nm after holding in the iodine solution. A much smaller effect, nearly
within the frame of the experimental error is obtained in case of galli-
um (Fig. 3, b). This difference in the lattice response can be tentatively
attributed to a weaker penetration of gallium into the γ-iron crystal
lattice.
The iodine- and gallium-caused shift of reflections is shown in the
inserts with the peaks positions from the Kα doublet before, γ1, and af-
ter, γ2, holding in the surfactants.
After holding at 35°C, beside the reflections of the austenitic steel,
the diffraction pattern contains those of gallium. These reflections
disappear if holding occurred at 100°C, i.e., far from the gallium crys-
tallization temperature.
Remarkably, the holding in gallium changes the intensity of reflec-
tions (111)γ and (200)γ in the opposite directions. Some hint for the in-
terpretation can be derived from the calculations performed by Legris
et al. [12] who obtained different adsorption energy of surfactant at-
oms for different crystallographic orientations of the iron surface.
3.3. Electronic Structure: Experiment
As example, the spectra of electron spin resonance of austenitic steel
Cr15Ni15 measured at 77 K before and after holding in the iodine solu-
tion are presented in Fig. 4. They were recorded as derivatives from
the absorbed microwave power P on the applied magnetic field H. The
obtained data of the concentration of free electrons are presented in
Table 3. One can see that the iodine increases the concentration of free
electrons in the austenitic steels in consistency with the increase in the
density of electron states at the Fermi level of f.c.c. iron, which was
Fig. 2. 2D spatial distribution of valence electrons, ∆n(r), in the calculated
clusters: 32 Fe atoms, 31 Fe atoms + 1 I atom.
210 S. M. TEUS, B. D. SHANINA, A. A. KONCHITS, G. S. MOGILNY, and V. G. GAVRILJUK
presented in Fig. 1. It is worth noting that the ESR data are obtained
from the samples of 20 µm in thickness, i.e., this is not the surface ef-
fect.
3.4. Mobility of Dislocations
The effect of iodine and gallium on dislocation properties of austenitic
steels was studied using mechanical spectroscopy. In the absence of re-
Fig. 3. X-ray diffraction from steel Cr25Ni20 before and after immersion into
5% iodine solution in the ethanol for 72 hours (a) and gallium at 35 and 100°C
for 5 and 68 hours (b), respectively.
MECHANISM OF EMBRITTLEMENT OF METALS BY SURFACE-ACTIVE ELEMENTS 211
laxation processes, the internal friction background is controlled by
vibrations of dislocations [53, 54]. Its value is the higher the larger the
area crossed by vibrating dislocations. Therefore, under condition of
the constant frequency of the induced vibrations, it is proportional to
the velocity of dislocations.
The observed increase in the concentration of free electrons by the
surfactants suggests a weakening of interatomic bonds. This should
result in a decrease of the shear modulus µ and, correspondingly, de-
crease the specific energy of dislocations, i.e. their line tension Γ ≈
≈ [µb2/(4π)]/log(ℜ/(5b)), where ℜ is a radius of dislocation curva-
ture.
The strain-dependent internal friction in steels Cr15Ni25 and
Cr25Ni20 doped by iodine and gallium, respectively, is presented in
Fig. 5, a, b. Both surfactants increase the internal friction background
and the slope ∆Q−1/∆ε, which evidences the increase of dislocation ve-
locity in consistency with the increase in the concentration of free elec-
trons.
Fig. 4. Electron spin resonance spectra of austenitic steel Cr15Ni15: iodine-
free (a), after holding for 72 hours in the iodine solution at RT (b). A narrow
intensive line is the ESR signal of a peace of the reference sample MgO:Cr3+
with the number of spins 1.1⋅1016. Spectra are measured at 77 K.
TABLE 3. Integral intensities I/Iref of ESR signals in relation to those from
the reference sample and concentrations of free electrons Ne in austenitic
steels before (numerator) and after (denominator) holding in the iodine solu-
tion.
Steel I/Iref, 104 Ne, cm
−3, 1023
Cr15Ni15
4.01
6.32
1.7
2.67
Cr15Ni20
2.88
7.02
1.4
4.29
212 S. M. TEUS, B. D. SHANINA, A. A. KONCHITS, G. S. MOGILNY, and V. G. GAVRILJUK
3.5. Mechanical Tests
Tensile tests of studied austenitic steels have shown that, in spite of
increase of dislocation mobility, both iodine and gallium cause embrit-
tlement (Fig. 6).
As it is also usually, the case of hydrogen embrittlement in austenit-
ic steels, the local softening of the crystal lattice does not decrease the
yield strength of tested samples. This feature is clearly seen in case of
iodine.
4. DISCUSSION
4.1. Atomic Interactions, Surfactants Distribution
and Mobility of Dislocations
The iodine-caused increase in the density of electron states at the Fer-
mi level derived from the ab initio calculations (see Figs. 1 and 2) is
confirmed by the measurements of the electron spin resonance demon-
strating the increase in the concentration of free electrons (Fig. 4). It
is worth noting that the ESR data are related to the bulk of the sam-
ples, not to the surface, i.e., the obtained result cannot be explained
just by a decrease in the surface energy, which is traditionally used for
interpretation of the surfactants effect on mechanical properties.
The iodine- and gallium-caused decrease in the lattice parameter, as
shown in Fig. 3, is consistent with the usually expected negative devia-
tion from the Vegard rule for the lattice parameters of the solid solu-
tions. Possibly, because of the different iodine and gallium penetration
in steel for the experimental time, this effect is more remarkable in
Fig. 5. Strain-dependent internal friction in austenitic steels before and after
contact with surfactants: iodine, steel Cr15Ni25Mn15 (a), gallium, steel
Cr25Ni20 (b).
MECHANISM OF EMBRITTLEMENT OF METALS BY SURFACE-ACTIVE ELEMENTS 213
case of iodine and occurs to a smaller extent for gallium.
A feature of the gallium effect is a decrease in the intensity of (111)γ
reflection and the opposite tendency for the (200)γ one (Fig. 3, b). This
abnormal ratio of intensities is obviously a sign of the crystallographic
texture, which can be caused by a selective location of gallium atoms
along the (111)γ atomic planes, which decreases the intensity of (111)γ
reflections in the X-ray diffraction pattern. In other words, gallium
preferentially covers the surface of grains with a favourable orienta-
tion of their (111)γ plane in relation to the surface. The accompanying
increase in the intensity of the (200)γ peak needs a more thorough addi-
tional analysis.
At the same time, a larger shift of the (111)γ reflection to smaller
angles in comparison with the (200)γ one means that such a selectivity
in gallium atom location exists deeply under surface. In other words,
the gallium atoms prefer the (111)γ atomic planes for adsorption in the
bulk of f.c.c. iron solid solution, not only at the surface.
The next remarkable effect of iodine and gallium is the increase in
the velocity of dislocations, which evidences the enhancement of dislo-
cation slip (see Fig. 5). A similar behaviour was observed in hydrogen-
containing austenitic steels (see, e.g., [55]).
It is hardly possible that dislocation slip is accompanied by migra-
tion of surfactant atoms as it occurs in case for hydrogen as a condition
for the change of dislocation properties. Rather, the facilitated slip is
localized in some limited areas where the surfactant atoms are prefer-
entially present.
4.2. Hypotheses for Surfactants-Caused Embrittlement
A similarity of two phenomena, LME and HE, has stimulated interpre-
Fig. 6. Engineering stress-strain curves of austenitic steels Cr15Ni25Mn15 (a)
and Cr25Ni20 (b) before and after holding in iodine and gallium, respectively.
214 S. M. TEUS, B. D. SHANINA, A. A. KONCHITS, G. S. MOGILNY, and V. G. GAVRILJUK
tation of surfactants-caused embrittlement in terms of hypotheses de-
veloped for hydrogen degradation of metals. As mentioned above, the
essence of AIDE hypothesis in relation to both HE and LME is that, be
adsorbed at the internal surface of crack tips, hydrogen and surfac-
tants atoms ease the nucleation of dislocations and their emission.
Three statements in this hypothesis are remarkable: (i) a critical is the
stage of dislocation nucleation; (ii) hydrogen or surfactants atoms lo-
cated in the solid solution are not responsible for embrittlement; (ii)
the enhanced mobility of dislocations does not play any substantial role
in the embrittlement.
The following remarks can be made in relation to the ideas under-
lined in the AIDE theory. First, while starting from nucleation and
emission of dislocations from the crack tip, this hypothesis ignores the
role of hydrogen or surfactants in the stage of cracks origin under ap-
plied stress. Pre-existing cracks can occur and not occur before hydro-
gen charging or contact with surfactants. In case of hydrogen in met-
als, they are really formed in the course of cathodic charging because
of a sharp hydrogen concentration profile and corresponding stresses.
However, it is not the case for gaseous hydrogenation.
Second point concerns the crack growth. According to [32], it occurs
due to emission of dislocations from the crack tip along with formation
of nanovoids. If so, the dislocation half-loops and a definite gradient of
dislocation density should be observed under fracture surface. Howev-
er, as shown in [56] for hydrogen-charged austenitic steels, no half-
loops occur beneath the fracture surface and the uniform dislocation
structure extends to the depth of 1500 nm from the fracture surface.
It is worth noting that, similarly, the high density of dislocations is
observed under surface fracture of high-nitrogen austenitic steels, e.g.
[57], where, like hydrogen embrittlement, the quasi-cleavage occurs at
low temperatures in spite of the nitrogen-enhanced local plasticity (see
about details Ref. [33]).
Third, the hydrogen-caused formation of the voids is not properly
substantiated in the AIDE hypothesis. In fact, it does not need any
presence of second-phase particles and high stresses for dislocation
emission. Along with vacancies emitted due to intersection of screw
dislocations, like any other interstitial element in the metal solid solu-
tion, hydrogen increases the thermodynamically equilibrium concen-
tration of vacancies, which has been theoretically predicted in [58, 59],
and first time observed in the experiments on the hydrides [60] and
austenitic steels [61].
These vacancies cannot follow dislocations in the course of plastic
flow. They are expected to form nanovoids along the slip planes, which
decreases the load bearing area. In case of surfactants-caused brittle-
ness, a possible role of nanovoids has been so far not clearly substanti-
ated.
MECHANISM OF EMBRITTLEMENT OF METALS BY SURFACE-ACTIVE ELEMENTS 215
In contrast to AIDE, the HELP hypothesis of hydrogen embrittle-
ment is based on the primary role of interaction between hydrogen at-
oms and dislocations, which was first time presented by Robertson and
Birnbaum [62] in their in situ observations of hydrogen-caused in-
creased generation rate and velocity of dislocations in nickel. Later on,
Birnbaum and Sofronis have developed a theory within the frame of
continuum mechanics, of which the essence is the hydrogen-caused
shielding of the interaction between dislocations and elastic stress cen-
tres [63]. The further development of this theory was proposed in [64]
and a thorough review of theoretical and experimental data can be
found in [65].
The electronic approach to HELP phenomenon has been developed in
[33, 66, 67] taking into account the hydrogen-caused increase in the
concentration of free electrons and corresponding local decrease in the
shear modulus µ, which changes dislocation properties.
The theoretical and experimental data obtained in this study show
that, like hydrogen, surfactants in austenitic steels increase the con-
centration of free electrons in the iron and iron-based alloys.
For this reason, in both cases of hydrogen and surfactants, the fol-
lowing consequences are expected: (i) a decrease of the stress for emis-
sion of dislocations τ ≈ 2µb/L, where b is the Burgers vector and L is a
distance between pinning points; (ii) the enhancement of mobility of
dislocations due to a decrease in their specific energy, i.e. line tension
Γ ≈ [µb2/(4π)]/log(ℜ/(5b)), where ℜ is the radius of the dislocation cur-
vature; (iii) a decrease in the distance between dislocations in the pile-
ups, d ≈ (πµb)/[16(1 − ν)nτ], which assists the nucleation of cracks due
to the increase in the number of dislocations n, and, correspondingly,
the stress at the leading dislocation τL = nτ, where τ is the active shear
stress in the slip plane. This decrease in the distances between disloca-
tions was experimentally confirmed in [68] for hydrogen and should
facilitate the opening of microcracks.
Thus, the increase in mobility of dislocations eases the plastic de-
formation. A limited surfactants penetration and their non-homoge-
nous distribution in the solid solution can be a reason for localization
of plastic deformation leading to the decrease in plasticity or macro-
brittle fracture.
The obtained data also allow mentioning that, like hydrogen embrit-
tlement, LME and SME phenomena are not really the surface effects,
and term ‘surfactant’ is to some extent disputable. Therefore, one can
foresee that any chemical element enhancing metallic character of in-
teratomic bonds acts as surfactant if there are conditions for localiza-
tion of plastic deformation. At the same time, in the absence of plastic
flow localization, it should markedly increase plasticity and tough-
ness.
This idea can be illustrated at least by two examples. First, pos-
216 S. M. TEUS, B. D. SHANINA, A. A. KONCHITS, G. S. MOGILNY, and V. G. GAVRILJUK
sessing a high concentration of free electrons, copper is generally not
accepted as surfactant. At the same time, it causes LME, as well as
SME, in the artillery gun tubes be present on the projectile to provide a
gas seal and to assist its spin up for providing subsequent flight stabi-
lization (see, e.g., [10]). However, copper is successfully used as alloy-
ing element in austenitic steels for production of corrosion-resistant
wire and ropes where its occurrence substantially eases drawing of
steel wire and increases plasticity (e.g., [69]). Second example is con-
cerned with lithium which, be the well-known surface-active element,
is successfully used in Al–Li alloys for development of the advanced
structural materials (see, e.g., [70]). At the same time, due to short-
range and even long-range ordering in the Al–Li solid solutions, these
alloys are prone to localization of plastic deformation. The ageing lead-
ing to precipitation of Al3Li and Al3X particles is used to diminish the
effect of localization of plastic flow.
5. CONCLUSIONS
1. The increase in the density of electron states at the Fermi level and
corresponding increased concentration of free electrons are responsi-
ble for the local enhancement of metallic character of interatomic
bonds by iodine in f.c.c. iron and austenitic steels. The same effect is
expected for gallium.
2. As consequence, these surfactants enhance mobility of dislocations
in austenitic steels.
3. It is supposed that any chemical element enhancing the metallic
character of interatomic bonds can play the role of surfactant if the
localized plastic deformation occurs because of the limited area of its
contact with the metal or due to atomic ordering in the solid solution.
4. The nature of embrittlement of austenitic steels by surfactants can
be interpreted within the frame of the electron approach to HELP hy-
pothesis, which has been earlier developed for hydrogen embrittle-
ment.
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|
| id | nasplib_isofts_kiev_ua-123456789-140801 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1024-1809 |
| language | English |
| last_indexed | 2025-12-07T18:40:04Z |
| publishDate | 2018 |
| publisher | Інститут металофізики ім. Г.В. Курдюмова НАН України |
| record_format | dspace |
| spelling | Teus, S.M. Shanina, B.D. Konchits, A.A. Mogilny, G.S. Gavriljuk, V.G. 2018-07-15T17:24:53Z 2018-07-15T17:24:53Z 2018 Mechanism of Embrittlement of Metals by Surface-Active Elements / S.M. Teus, B.D. Shanina, A.A. Konchits, G.S. Mogilny, V.G. Gavriljuk // Металлофизика и новейшие технологии. — 2018. — Т. 40, № 2. — С. 201-218. — Бібліогр.: 70 назв. — англ. 1024-1809 PACS: 61.72.Hh, 61.72.Yx, 62.20.M-, 62.40.+i, 68.35.Dv, 71.20.Be, 76.30.-v DOI: https://doi.org/10.15407/mfint.40.02.0201 https://nasplib.isofts.kiev.ua/handle/123456789/140801 The nature of mechanical degradation of metals caused by surface-active elements is studied based on the effects of iodine and gallium in austenitic steels and using abinitio calculations and experimental measurements of electronic structure, X-ray diffraction, mechanical spectroscopy, and mechanical tests. A significant increase in the density of electron states at the Fermi level for iodine in f.c.c. iron is shown that is in consistent with the measurements of the increased concentration of free electrons caused by iodine in austenitic steels. Consequently, the increase in mobility of dislocations by iodine and gallium in austenitic steels is revealed. The localization of the enhanced plastic deformation is discussed as a condition for brittleness. The obtained results are at variance with the widely spread opinion about the determining role of surface energy in a liquid-metal brittleness and, instead, are interpreted based on the correlation between atomic interactions and dislocation properties. Applicability of the available HELP and AIDE hypotheses is discussed. Природа механической деградации металлов, обусловленной поверхностно-активными элементами, была изучена, основываясь на влиянии йода и галлия на аустенитные стали и используя abinitio-расчёты и экспериментальные исследования электронной структуры, рентгеновскую дифракцию, механическую спектроскопию и механические испытания. Показано существенное повышение плотности электронных состояний на уровне Ферми в случае йода в ГЦК-железе, что согласуется с измерениями, в которых была зафиксирована повышенная концентрация свободных электронов, вызванная йодом в аустенитных сталях. Как следствие, установлено повышение мобильности дислокаций, вызванное йодом и галлием в аустенитных сталях. Обсуждается роль локализации повышенной пластической деформации в качестве условия хрупкости. Полученные результаты противоречат широко распространённому мнению об определяющей роли поверхностной энергии в жидкометаллической хрупкости и, вместо этого, интерпретируются, основываясь на корреляции между атомными взаимодействиями и дислокационными свойствами. Обсуждается применимость гипотез HELP и AIDE. Природу механічної деґрадації металів, яку спричинено дією поверхнево-активних елементів, було досліджено, виходячи із впливу Йоду та Ґалію на аустенітні сталі та використовуючи abinitio-розрахунки й експериментальні дослідження електронної структури, рентґенівську дифракцію, механічну спектроскопію та механічні випробування. Показано істотне підвищення густини електронних станів на рівні Фермі у випадку Йоду в ГЦК-залізі, що узгоджується з вимірюваннями, в яких було зафіксовано підвищену концентрацію вільних електронів, яку спричинено Йодом в аустенітних сталях. Як наслідок, встановлено підвищення мобільности дислокацій, спричинене Йодом і Ґалієм в аустенітних сталях. Обговорюється роль локалізації підвищеної пластичної деформації в якості умови крихкости. Одержані результати суперечать розповсюдженим твердженням про визначальну роль поверхневої енергії в рідкометалевому окрихченні і замість цього інтерпретуються, виходячи з кореляції між атомними взаємодіями та дислокаційними властивостями. Обговорюється коректність гіпотез HELP та AIDE. en Інститут металофізики ім. Г.В. Курдюмова НАН України Металлофизика и новейшие технологии Физика прочности и пластичности Mechanism of Embrittlement of Metals by Surface-Active Elements Механизм охрупчивания металлов поверхностно-активными элементами Механізм окрихчення металів поверхнево-активними елементами Article published earlier |
| spellingShingle | Mechanism of Embrittlement of Metals by Surface-Active Elements Teus, S.M. Shanina, B.D. Konchits, A.A. Mogilny, G.S. Gavriljuk, V.G. Физика прочности и пластичности |
| title | Mechanism of Embrittlement of Metals by Surface-Active Elements |
| title_alt | Механизм охрупчивания металлов поверхностно-активными элементами Механізм окрихчення металів поверхнево-активними елементами |
| title_full | Mechanism of Embrittlement of Metals by Surface-Active Elements |
| title_fullStr | Mechanism of Embrittlement of Metals by Surface-Active Elements |
| title_full_unstemmed | Mechanism of Embrittlement of Metals by Surface-Active Elements |
| title_short | Mechanism of Embrittlement of Metals by Surface-Active Elements |
| title_sort | mechanism of embrittlement of metals by surface-active elements |
| topic | Физика прочности и пластичности |
| topic_facet | Физика прочности и пластичности |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/140801 |
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