Beruflich Dokumente
Kultur Dokumente
Volume 176
Series Editors
Leonid Pinchuk
Micromechanisms
of Friction and Wear
Introduction to Relativistic Tribology
123
Dmitrij Lyubimov Leonid Pinchuk
Kirill Dolgopolov National Academy of Sciences of Belarus
Department of Antifrictional Materials Metal-Polymer Research Institute
South-Russian State University Gomel
Shahty Belarus
Russia
ISSN 0933-033X
ISBN 978-3-642-35147-1 ISBN 978-3-642-35148-8 (eBook)
DOI 10.1007/978-3-642-35148-8
Springer Heidelberg New York Dordrecht London
The progress of engineering and technology stimulated the ideas of friction from
the simplest mechanistic views of Leonardo da Vinci and Charles-Augustin de
Coulomb to the modern tribophysical viewpoint considering the friction as the
superposition of adhesive and cohesive forces. It presumes that friction belongs to
the category of nanotheories, though now we are more accustomed to using the
terms microlevel, micromechanisms, etc.
Unfortunately, the development of models describing the process of friction and
wear using the ideas of the matter electron molecular structure confronts if not
principal then considerable challenges. The fact can be related to them that the
matter structure changes during friction at the microlevel which is hard to trace
and, therefore, hard to study. The structure of the substance exposed to friction is
in the dynamically mobile variable state having the properties hard to assess or
predict.
v
vi Preface
The contents of the present monograph are at the borderline between different
trends of natural and engineering sciences, like electrodynamics, the theory of
relativity, the quantum mechanics, the solid body and the surface physics, the
physical and chemical kinetics, and others. Each of the above-listed sections
contains a long established system of common designations, constants, and values.
These designations coincide sometimes. For instance, one and the same symbol
S designates the fundamental values, such as action in the mechanics,
entropy in the thermodynamics, spin in the quantum theory, Umov-Pointing
vector in the electrodynamics, and others. This symbolic designation is so much
common that any effort to change it can cause confusion in the perception of
formulas like the use of similar symbols can be misleading. Therefore, the for-
mulas are deciphered the way they are written in the text; in addition, the book
contains at the end the list of main designations included into the formulas in each
chapter.
With sincere respect to our readers who open this book for the first time,
ix
x Contents
4 Friction Microdynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.1 Friction Effect on Solid Body Surface . . . . . . . . . . . . . . . . . . . 95
4.2 Diffusive Triboprocesses in Friction . . . . . . . . . . . . . . . . . . . . 101
4.3 Motion of Dislocations in Friction . . . . . . . . . . . . . . . . . . . . . . 111
4.4 Relativistic Effects in Friction. . . . . . . . . . . . . . . . . . . . . . . . . 116
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Afterword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
Chapter 1
Interaction Between Atoms in the Substance
Each science discovers the things which are far beyond the
immediate observation,
Ch. Kittel, American philosopher
In fact, the physics of solids reduces to the establishment of
relations between the behavior of individual atoms and
molecules they manifest when the atoms and molecules combine
into huge associations like regularly ordered crystals
Ch. Kittel, American philosopher
From the viewpoint of the physical principles, the most
interesting phenomena occur in the new spots where the rules
are not suitable or where they are ineffective,
Richard Phillips Feynman, American physicist
When two solid bodies approach mutually, the attraction forces begin to act due to
the Van der Waals interactions or the Van der Waals forces (J. van der Waals is the
Dutch physicist, the Nobel Prize winner). These forces ate intrinsic to the neutral
electric systems and they appear due to the fluctuations in the distribution of charges
in atoms or molecules of the converging bodies. These charges produce momentary
continually displacing dipoles in the adjacent atoms. The Van der Waals forces are
divided into three types [1].
A. Dutch physicist A. W. Keesom, was the first to treat the interaction between
constant dipoles within the framework of the classic electromagnetic theory and
which he termed the orientation interaction. Keesom studied the orientation of
two dipoles corresponding to the least potential energy in this system. The energy
of their interactions is
2 p12 p22 6
Uor = r , (1.1)
3 kT
Thus, the orientations forces is inversely proportional to the spacing to the order
of the seventh power and they can be both be the forces of attraction and the forces
of repulsion in response to the orientation of dipoles. The so-called Keesom effect
means that the attraction of dipoles comes to prevail when the temperature lowers.
B. The experiment did not confirm the temperature dependence (1.1). In real-
ity, the energy Uor reduces much slower as the temperature drops. P. Debye,
German physicist, the Nobel Prize winner, assumed that the molecule with the
constant dipole moment produces the induced moment in the adjacent molecule.
Therefore, the expression to calculate the energy of dipole-to-dipole interactions
should contain the second term independent of the temperature. This interaction
was called induction or polarization. The term originates from the displacement
of the centers of gravity of electric charges of a particle under the external field
effect from the adjacent atoms and molecules. The values of the induced electric
models in this case are relatively insignificant bearing in mind the weakness of
the molecular fields. The energy of interactions depends on the magnitude of the
moment in the system, the polarization coefficient and inversely proportional
to the spacing to the power of six:
1.1 Van der Waals Forces 3
p2
Uind = . (1.3)
r6
C. The model of P. Debye was unfit to the molecules without any constant dipole
moment. The problem how the forces of attraction appear between two neutral
particles was solved by German physicists W. Hatler and F. London using the
quantum mechanics apparatus. Afterwards, this type of the Van der Waals forces
was called the dispersion or London forces.
The result to which London arrived is, in general, that the energy of attraction
between two particles is inversely proportional to the spacing between them to the
power of six.
B
Udisp = , (1.4)
r6
where Bthe constant for this type of atoms.
London proposed the approximate formula for simple molecules:
3 n 0 2
Udisp = , (1.5)
4 r6
where = h/2 the Plank constant; n 0 the so-called characteristic quantum
or the term which is found experimentally using the light dispersion equations.
The measurements have shown that the term values are close to the value of the
ionization potential i that is why formula (1.5) is often rewritten in the following
way:
3 i 2
Udisp = . (1.6)
4 r6
J. Slater and E. Kirkwood develop the ideas of London further and obtained the
expressions well correlating with the experiment:
3e N 3
Udisp = , (1.7)
4 r6 me
where e, m e electron charge and mass; N number of electrons in the atom external
shell.
The improvement of the quantum models of the Van der Waals forces has enabled
to explain why atoms repulse one another. As the spacing between two atoms gets
shorter, the electron clouds begin to overlap so the systems electrostatic energy
changes. If the spacing is rather intimate, the energy of interactions transforms
into the energy of repulsion due to the overlapping electron clouds. The energy
of interactions is the energy of repulsion at any spacing whatsoever between the
atoms with filled electron shells. It results mainly from the Pauli Exclusion Principle
4 1 Interaction Between Atoms in the Substance
(W. Paulithe Swiss physicist-theoretician, the Nobel Prize winner) [2, 3] which
states that two electrons cannot stay in the same quantum state. The Pauli Exclusion
Principle precludes multiple occupation of this state; the electron clouds of two inti-
mate atoms can overlap when the electrons leap into a higher energy state. Thus, the
process of overlapping of electron clouds boosts the full energy of the system and
corresponds to the appearance of repulsion forces. The potential repulsion forces 0
in inert gases can be represented in the following way:
B1
0 = , (1.8)
r 12
where B1 the empirical parameter determined by independent measurements.
The expression of full potential energy of interactions between two atoms at the
spacing r is usually recorded as [3]:
12 6
B3 B4
U (r ) = 4 B2 , (1.9)
r r
derived the equation to estimate the adhesive interactions between mirror planes
under the effect of the Van der Waals forces [4]:
hc A
FA = , (1.11)
480 r 4
where Athe surface area.
The attraction induced by the Van der Waals forces is compensated by the repulsion
forces which inhibit the mutual penetration of electron clouds of atoms or molecules.
Because the emerging Van der Waals forces do not cause any electron exchange, the
molecular structure of crystals appearing when particles converge is determined
mainly by the geometrical factors. Since Van der Waals forces are not directional,
the atoms tend to pack densely in the lattice. The resulting crystals are dielectric
because the electrons are tightly bonded.
The Van der Waals forces are described using the classic electrodynamic appa-
ratus containing some elements of the quantum mechanics: the Planck constant
(M. PlanckGerman physicist, The Nobel Prize winner) and the Pauli principle
of exclusion. The latter opens a new class of interactions between the particles hav-
ing the non-Coulomb nature, or the exchange forces. The particles proper, irre-
spective of their nature, possess simultaneously the wave and corpuscular properties
according to the de Broglie hypothesis (L. de BroglieFrench physicist-theoretician,
the Nobel Prize winner). The principle of mechanical determinism becomes upset
instead of being customary from the classic thermodynamic viewpoint. It com-
pelled W. Heisenberg (W. HeisenbergGerman physicist-theoretician, the Nobel
Prize winner) to develop the uncertainty principle. A new class of physical values
was added to the physical theory; these values are impossible to measure concur-
rently: the energy and the time; the pulse and the coordinate. It is impossible to
know simultaneously the object parameters like the coordinate, the velocity and the
time following the uncertainty principle. Hence, the body location in the space-time
coordinates is unknown validly, it is known with some probability. That is why
A. Einstein (A. Einsteinthe founder of the modern physics) called the quantum
mechanics the Gods game of dice. This game demanded to invent the vector of
state as the new physical value in order to describe physical systems. This value
has several names: the wave function, the probability density, the wave vector, and
others; whence it is assumed that the lacks any strict physical sense. In fact, the
vector of state represents some information field or a quantum object which is the
complex function of the coordinate and the time acquiring a single-valued physical
sense only for a particular physical problem. For instance, when models of solid
6 1 Interaction Between Atoms in the Substance
bodies are considered, the value 2 is the charge density, while it is the probability
density in the quantum statistical physics.
The main equation of the quantum mechanics permitting to combine the vector
with any system using the analytic expression = (x, y, z, t) is the equation
of Schrdinger (E. Schrdingeran Austrian physicist-theoretician, the Nobel Prize
winner). The Schrdinger equation derived in 1926 for motion of electrons has the
following general look:
(x, y, z, t)
i = H , (1.12)
t
where ithe imaginary unity; H the Hamilton (Hamiltonian) operator named after
the Irish mathematician W. Hamilton.
The precise solution of the Schrdinger equation as it looks (1.12) was found only
for the limited class of quantum objects, like the hydrogen atom. The electron in these
quantum systems moves in respect to the atom nucleus in the central coulomb field
within which the potential electron energy U depends only on the distance r to the
atom nucleus. The relevant wave functions characterizing the electron state and its
energy are obtained by solving the Schrdinger equation (1.12):
h c R p Z 2
Un = ,
n 2 (1.13)
(r ) = R (r ) Y (, ) ,
where c the light speed; R p the Rydberg constant equal to 3.29 1015 Hz
(J. Rydberga Swedish physicist); Z atom nucleus charge; n = 1, 2, 3 . . . , main
quantum number; (r )wave function; R(r )wave function radial portion; ,
angles, spherical coordinates of the electron radius-vector.
The value h c R p is the energy of ionization of the hydrogen atom in the
main state taken with the opposite sign. In addition to the main quantum number n ,
the atom state is set by the azimuth or orbital quantum number l = n 1 which
determines the moment of electron pulse in respect to the atom nucleus. Because the
moment value has different projections in the randomly selected direction, still one
more: the magnetic quantum number m e = l , l 1, . . . , l is introduced. The
numbers n , l , m e characterize fully the electron state in the hydrogen atom. The
electron state in the atom has the following alphabetic designations in the quantum
mechanics, chemistry and spectroscopy:
n = 1, 2, 3. . ., s, p, d. . .
l = 0, 1, 2. . ., K, L, M. . .
smeared in the space forming the electronic cloud with the dimensions proportional
to n 2 . Then the value R 2 (r ) determines the radial and the Y 2 (, ) determines the
angular distribution of the electron density.
The atoms containing two or more electrons have the wave functions to describe
which of the interelectron interactions should be taken into account including the
interelectron repulsion, the magnetic interactions, and the exchange forces. It is
because the electron has the spin which is the quantum mechanic analogue of the
proper moment of rotation and the Pauli moment of exclusion. This spin produces an
additional quantum number m s = 1/2, 1/2 complicating significantly the electron
state description in the multielectron atom. Equation (1.12) has no accurate analytic
solution for these objects. That is why the solutions like (1.13) serve for the similar
quantum systems.
The electron energy in the complex atom can be represented similarly to (1.13):
h c R p (Z )2
Un = , (1.14)
n 2
where the screening constant taking into account approximately the interaction
between electrons.
The perturbation theory apparatus yields more accurate results; this apparatus
is one of the most common methods of approximate calculation in the quantum
mechanics. The perturbation theory is applied to the physical systems which with a
number of simplifications can be represented as the object which has a precise ana-
lytic solution of the Schrdinger equation. A certain value is added to the obtained
expression to take into account the additional interaction (perturbation) discriminat-
ing the atom in question from the hydrogen-like analog. It looks mathematically in
the following way. Equation (1.12) is represented as
(t)
i = H0 + U (t) (t), (1.15)
t
where H0 the hydrogen-like atom operator; U (t)the perturbation operator.
Initially the moment of the quantum system is in one of the steady states deter-
mined by the vector m0 as the plane wave with the energy Um0 . Then the solution
(1.15) looks like a series:
i
(t) = Cmn (t)m0 exp Um0 t , (1.16)
m
Cmn
i = Umk (t)Ckn (t),
t
k
(1.17)
i
where (m0 ) the wave vector of the unperturbed state conjugated in complex with
the unperturbed wave vector m0 ; k, mthe indices of the steady state of the
quantum system.
The function |Cmn (t)|2 determines the probability of transition of the quantum
system characterized by the Hamiltonian H0 , from the initial state m to another state
n under the effect of perturbation U (t).
A particular case of solving the quantum mechanical problems of the theory of
perturbation is stationary problems independent of the time of perturbation. In this
case, Eq. (1.15) is rewritten as follows:
H0 + U m = Um m . (1.18)
The solution of this equation corresponds to type (1.16) which is much simplified
for the stationary case:
n = Cm m0 . (1.19)
m
The stationary theory of perturbations illustrates well the shifts and splits of the
atomic levels. Equations (1.151.17) is applied to the study of transitions from one
quantum system state to another.
Atoms with Z 2 have the electrons each exposed to the action of fields of
other electrons of this atom. Their energies can be determined only on the basis
of approximate quantum mechanical calculations. The Hartree-Fok method is the
most popular (D. Hartree, V. Fok are the British and the soviet physicists) [5], who
proposed the approximate quantum mechanical solution of the multielectron atom
states. The solution can be obtained by reducing the original equations to the already
known and solved problem for the single electron atom. A system of equations is
solved for each electron moving in the averaged field of the remaining electrons.
The obtained electron density distribution reflects the structure of electron shells.
Because the solution algorithms are well tried out, it can be assumed that the wave
functions and the energies of the stationary atom states are known. More complicated
quantum systems, molecules among them, are considered by making the following
assumptions [6]:
1.2 Quantum Mechanical Description of Atom Interactions 9
(1) the solution of Schrdinger equations for molecules yields the wave functions
describing the energy levels of molecules (the molecular orbitals);
(2) the molecular orbitals embrace all nuclei of molecules and have the same physical
sense as the atomic wave functions;
(3) the electronic structure of the molecular orbital follows the same law of the
atomic quantum mechanics as the atomic orbital.
It follows from these assumptions that the molecular orbital is a single electron
multicenter wave function describing the state of individual electrons in the molecule
moving in the averaged field of other electrons and in the field of the molecules
nuclear carcass. The molecular orbital includes the spatial 1 (r ) and the spin 2 (S)
components, hence, they are often called the spin-orbitals (r, S) [7]:
The designations of the molecular orbitals differ from those of the atomic orbitals.
For instance, the orbitals with the quantum number l = 0, 1, 2, 3 are designated as
-, -, -orbitals (the Greek characters replace the Latin ones). Since the molecules
can have several orbitals of one type, the additional indexes 1, 2, 3, 4, are introduced
to show how the orbitals rank by energy. Special calculation methods are used to
find the molecular orbitals. Most often they are the method of a linear combination
of atomic orbitals (LCAO) and the method of valent schemes.
Following the LCAO method, the molecular orbital m of the molecule consisting
of N atoms is represented as the linear combination of the atomic orbitals n :
N
m = Cn n , (1.21)
n=1
Un
= 0. (1.22)
Cn
If the combination of orbitals boosts the electron density among the nuclei,
the combined orbital is called the connective and its designation is + . If the super-
position of orbitals reduces the electron density, it is the loosening orbital . The
higher energy states with the electron density offset from the internuclear region
correspond to the loosening orbitals. Following the LCAO method, interelectron
repulsion is ignored leading to the equal contribution to the energy of ion and cova-
lent summands, though it is not always true.
The method of valent bonds expands the LCAO method implying that each wave
function incorporated into the linear combination describes the state of a specific
configuration of protons and electrons. For instance, the LCAO method dictates that
the orbital of hydrogen molecules should be (1.21): = C1 1 + C2 2 . The orbital
according to the method o valent bonds looks more complicated:
10 1 Interaction Between Atoms in the Substance
= 1 1 + 2 2 + 1 2 + 1 2 , (1.23)
where 1 , 2 the system in which the first electron is bonded to the nuclei A and
B, respectively; 1 , 2 the system in which the second electron is bonded to the
nuclei A and B.
The exhaustive consideration of all the interactions augments the number of terms
in relation (1.23). Paper [6] provides the information about the equation and the
molecular orbitals of the hydrogen atom containing 50 terms.
The Van der Waals forces are too weak to form the structures of solid and fluid
bodies. Their structure and behavior are governed by stronger cohesive interactions
which are described with the quantum mechanics apparatus. Let us briefly consider
their main regularities.
The ion bonds result from the electrostatic attraction of oppositely charged ions.
When they approach intimately enough, the electron shells touch, but without mutual
penetration because the Pauli Exclusion Principle imposes limitations [7]. That is
why it is believed that the distribution of charges in the substances with ion bonds has
a spherical symmetry which is somewhat upset in the areas of contact with adjacent
atoms (Fig. 1.2).
Ch. Kittel (Ch. Kittelthe American physicist) comments that we are likely
to make mistake believing that the energy and the bonds in ion crystals are mostly
due to the Coulomb interaction The spacing between the positive ion and the
nearest negative ion in the sodium chloride crystal equals to 2.81 108 cm, that is
why the potential attraction energy is equal to 5.1 eV. This energy can be compared
with the energy of bonds of the crystal NaCl7.9 eV [3]. It can be concluded
from the above-said, that it is advisable to use the electrostatic approaching when
calculating the energy of ion bonds. This energy is termed the Madelung energy
(E. Madelung) [8].
If we designate the energy of interactions between ions i and j with Ui j , then the
full ion energy Ui with the account of all interactions is equal to
Ui = Ui j . (1.24)
j
j=i
1.3 Strong Chemical Bonds 11
Fig. 1.2 Distribution of electron density in common salt crystal basic plane
Let us assume that the Ui j can be represented as the sum of two Coulomb potential
and some potential of the repulsion forces variable following the exponential law
ri j q2
Ui j = B5 exp , (1.25)
B6 ri j
where B5 , B6 are the constants determined experimentally; q is the ion charge (the
plus sign corresponds to the same ad the minus sign corresponds to the opposite
charges).
The full energy of the lattice comprising the N ions can be written in the following
way:
Ufull = N Ui , (1.26)
where z is the number of the neighbors nearest to the ion selected as the coordinate
start; M is the Madelung constant (E. MadelungGerman physicist-theoretician).
12 1 Interaction Between Atoms in the Substance
The classic definition of the covalent bonds is the bonding of electron couples with
covalent bonds [911]. These bonds are called in the chemistry and particularly in
the organic chemistry homopolar (homeopolar) bonds. The covalent bonds are strong
bonds because the energy of bonds between the carbon atoms in the diamond is equal
to 7.3 eV. This value is comparable with the energy of ion bonds, notwithstanding
the fact that the covalent bonds appear between neutral atoms.
When a common electron pair bonds following the Pauli Exclusion Principle,
the bonded electrons should have oppositely directed spins. Hence, these bonds can
be represented as the interaction between atoms and electrons when both electrons
cease virtually to be bonded to particular atoms. Double or triple bonds can appear
in this way when two or three electrons come into common use.
All covalent bonds originating from each atom bond it rigidly to other atoms
and possess vividly pronounced directivity. Each atom in the carbon, silicon and
germanium crystals locates in the tetrahedron center which is formed by four nearest
atoms (Fig. 1.3).
The precise angular arrangement of the bonds depends on their number and the
type of electrons involved in the formation of covalent bonds. For instance, the
electron clouds of the s-orbitals are spherically symmetric; the electron clouds of
three p-orbitals in three mutually perpendicularly directions, those of the d- and
f-orbitals have a more intricately structured cloud (Fig. 1.4).
The electrons located over the hybrid orbitals are involved in the bond formation
of the majority of crystals. The bond direction depends on which orbitals dominate.
For instance, one of the diamond electrons can pass to the p-orbital so that all four
outer electrons happen to get unpaired. When three p-orbitals arrange at an angle
90 one to another and the s-orbital is unidirectional, four hybrid sp-orbitals appear
directed towards the tetrahedron apexes (Fig. 1.3) typically for the diamond.
1.3 Strong Chemical Bonds 13
The crystals appearing similarly to the diamond are mainly the covalent bonds so
tat they feature high strength, melting point and hardness. They are dielectric like
the ion crystals because all outer electrons bond strongly into the covalent bonds.
The dielectric characteristics of the covalent crystals withstand the melting and
dissolution unlike the substances with the ion bonds.
The metallic bonds appear due to the forces of attraction between the lattice of pos-
itively charged ions and the surrounding gas of free electrons. The free electrons
(the electrons of conductance) move under the external field effect through the metal
like a gas molecule in some volume. This idea agrees poorly with the habitual chem-
ical notion of bonds; the latter states that the bonded valent electrons localize in the
ion islands. It leads to the ion bonds which distribute between atoms forming lig-
ands or behave like the covalent bonds. The valent bonds are saturated in both cases
because the valent electron has to remain all the time in the localized bonded state,
or electrons form pairs following the Pauli Exclusion Principle.
The free electrons possess high motility not bonded to any particular atom; they
render the bodies with metallic bonds highly heat and current conductive. The ideas
14 1 Interaction Between Atoms in the Substance
were that the metallic bonds evolution would explain the magnitude of forces of
adhesion between the atoms in the metallic crystalline lattice rather than the physical
properties of metals. The energy of interactions between the atoms in the system
with metallic bonds is determined by the following relation [2, 8]:
A1 e2 A2 A3 e2
Umet = + + , (1.29)
3
1 2
3
Since the neutral hydrogen atom has just one electron, it should possess one bond
which permits it to interact just with one alien atom. But the hydrogen atom combines
with two atoms under some circumstances producing the so-called hydrogen bond
with the energy about 0.1 eV. It is believed that the oxygen bond has mainly the
ion nature because it appears only between the most electrically negative atoms
like those of fluorine or oxygen. In the extreme case, when the oxygen bonds are
purely of the ion nature, the hydrogen atom gives away its electron transforming into
a proton which bonds with two electrically negative atoms (Fig. 1.6a). The proton
Fig. 1.6 Examples of hydrogen bonds: a molecule of hydrogen fluoride; b protein molecules
small dimensions permit to the proton to have only two adjacent atoms; therefore,
the oxygen bonds are achievable only between two atoms.
The oxygen bonds are the most essential type of interactions between water mole-
cules governing to large extents its abnormal behavior when heated. The oxygen
bonds limit the size of protein molecules and govern their geometrical structure
(Fig. 1.6b).
L. Pauling discovered the resonance bonds (L. PaulingAmerican physicist
and chemist) in transitional metals [11]. He assumed that the electrons of the
(n1) dsubshell distribute between the atomic and bonding orbitals. The electrons
within the atomic orbitals bond with individual atoms and influence the magnetic
properties of the substance. The electrons at the bonding orbitals form the covalent
bonds which resonate between a great numbers of directions of the bonds.
The resonance idea presumes existence of single- and triple-electron covalent
bonds with the energy equal to half of that of the relevant single and triple bonds.
The latter takes place in the benzene cycle structure. Whence the conclusion is that,
if several configurations of the covalent bonds, the resonance are able to produce the
structure corresponding to a smaller energy, it is thus more stable compared with the
original structures.
The cohesive forces bonding the atoms and the molecules in the solid body are quite
hard to measure experimentally. The chemical bonds in crystalline bodies have a
mixed nature with bonds of one type dominating. Therefore, the solids can be iden-
tified by the dominating type of cohesive interactions [12] (Fig. 1.7). It is intrinsic to
metals to have the metallic type of bonds little ion or covalent contribution. Chemical
compounds of various metals (intermetallides) are often characterized by a consider-
able covalent component. Ceramic and polymeric materials contain mixed types of
bonds. For instance, covalent bonds are effective in polymeric chains; Van der Waals
forces are effective between chains producing a supramolecular structure. The latter
forces can be strong enough to induce crystallization of polymers.
16 1 Interaction Between Atoms in the Substance
Fig. 1.7 Schematic of contribution of different types of bonds into structures of most common
materials [12]
Hence, the theoretical models permitting to estimate the forces which act between
particles in the solid bodies become ever essential. A.S. Akhmatov emphasizes that
the essential theoretically and practically problem emerges how the law of inter-
actions between the condensed system and the isolated particle close to its surface
produces its effect and how two systems of particles interact. These laws are obvi-
ously the foundation of all phenomena of interactions between the surface of this
phase and the environment the theory of boundary friction and lubrication has
particularly fundamental significance [1].
The energy and interactions between condensed bodies (the term of
A.S. Akhmatov) are determined using the models representing the energy as a sum
of paired interactions between isolated atoms and molecules. The drawbacks of this
assumption are apparent. The external forces field on the solid body surface cannot be
represented as a simple sum of elementary fields of individual particles. It is hardly
doubtful that the phase interactions of the substance in the gaseous, fluid or sold state
are different categories of phenomena. At the same time, the interaction between con-
densed media should be determined by the common properties of the substance. The
best fitting models of calculation are those of Kazimir and Soviet physicist E.M.
Livshits which permit to calculate the energy of interactions between condensed
bodies independently of paired interactions. For instance, Kazimir obtained the fol-
lowing relations for the metallic placed spaced at r one from the other (SGSE) [4]:
0.013
F= . (1.30)
r4
E.M. Livshits treats the interphase field assuming that both solid phases are iden-
tical semispaces separated by a narrow slot r wide [13]. He considered two extreme
cases: r is small and r is larger compared with the main wavelength of the spectrum
of absorption (emission) of the substance. For the r < , the forces of interactions
between phases can be represented in the following way:
1.4 Collective Interaction Between Atoms 17
2
1
F= d,
8 2 r 3 +1
0
for r >
2
c 2 1
F= (), (1.31)
r 4 240 +1
c 2 0.013
F= = , (1.32)
240 r 4 r4
which is identical to Kazimir equation (1.30).
E.M. Livshits investigated also the dependence of force F on temperature T . For
metals under the condition r < the following relation was obtained:
c 2 r kT 4
F= 4 1 5.33 . (1.33)
r 240 c
Fig. 1.8 Melting temperature variations in response to number of subgroup in periodic system [8]
the elements of group IV of the periodic system. When these forces are used as a
measure of forces of cohesion in crystals, it is essential to remember the solid and
fluid phases are at equilibrium at the melting point, while the heat of sublimation is
determined by the amount of work needed to transform one gram-atom of the solid
substance into stem consisting of neutral atoms. Therefore, both physical constants
of the elements are the properties of the substance in all solid, fluid and gaseous
states.
The compressibility of the solid body cm is a relative reduction of its volume as
the hydrostatic pressure augment, i.e. it is a measure of the possibility that the atoms
approach. Hence, the compressibility is the inverse value to the forces of cohesion
in the crystal (Fig. 1.9).
The thermal expansion coefficient of the solid body characterizes the variations of
dimensions (length, volume) of the specimen when the temperature changes by one
degree; hence, it is a measure of the amplitude of thermal oscillations of atoms. The
low thermal expansion coefficient indicates considerable forces of adhesion between
atoms. The dependence of the thermal expansion coefficient on the element atomic
number resembles the similar dependence for compressibility.
1.4 Collective Interaction Between Atoms 19
The electronic cloud enveloping the atom nucleus is not a rigid sphere and can
change its size and shape in response to the nature of forces of interatomic inter-
action involving the external electrons of atoms in the solid body. The interatomic
distance d can be assumed a measure of strength of interatomic bonding. However,
direct comparison of the value d among the elements with different crystalline struc-
tures is complicated, the general tendency of this parameter is to reduce when the
coordination number (CN) diminishes.
Norwegian geochemist V. Goldschmidt demonstrated, in particular, that reduction
of the CN from 12 to 8, 6 or 4 shortens the interatomic distance by 12 %. So, he
proposed to reduce the interatomic distances in crystals to the CN equal to 12 and
hold half of this value of the atomic radius. The value of the atomic radii obtained
in this way suits well to the metals with comparatively simple structures, but it
is unsuitable for calculation of the group of transitional metals. Another method to
estimate the atomic radius is to exclude the CN effect o the obtained result. It is based
on the definition of the volume (
) of the substance per atom; if the linear parameter
is needed, then the atomic radius is calculated with the expression
= 43 r03 .
The idea about the atomic volume is convenient because this value can be easily
determined for any structure dividing the elementary cell volume by the number of
atoms the cell contains. Figure 1.10 shows the values of atomic radii.
20 1 Interaction Between Atoms in the Substance
Fig. 1.10 Variations of atomic radius r0 in response to subgroup number in periodic systems [8]
1.5 Crystallization
The collective effect of atoms on the cohesive forces produces ordered structure or
crystals. The process of formation of crystals from the melt, gas, solution or another
crystal is called crystallization [5]. The crystallization as a physical phenomenon
means that original atoms, molecules or ions are packed into the crystalline lattice.
The ordered structure lattice implies that is entropy and chemical potential diminishes
versus the original medium. In other words, the formation of the crystalline structure
is determined by the principle of energy expediency: the full energy of a single
crystal is less than the combined energy of its individual components so the process
of crystallization is accompanied by liberation of latent heat.
The growth of crystals is a multistage process: gas or fluid atoms and molecules
interact and produce specific structures or nucleus at the initial stage which can be
spontaneously disintegrate, but, after a certain of number of Ncr atoms (it is called
the nucleus of critical size) has been collected, they will only grow. The rate of
nucleation is determined by the following relation:
Unu
Jnu = Bnu exp , (1.35)
kT
2
Umb = N chm + p (c Ncr ) 3 , (1.36)
where chm the difference between chemical potentials; p the specific fee
energy over the nucleusmedium interface; the averaged surface energy; c
the specific substance in the crystalline state.
P
chm = kT ln 1 + , (1.37)
P
2 p
Ncr = , (1.38)
3chm
According to the classic theory of crystallization, the nuclei appear due to tem-
perature fluctuations initiating aggregation of a new daughter phase. Einstein used
the principles of statistic physics to demonstrate the probability that the fluctuations
alter the equilibrium system entropy proportionally to exp(S/k); soviet physicist-
theoretician, Nobel Prize winner, L.D. Landau verified this provision demonstrating
that entropy changes S are equal to S = W/T , where W is the lest work needed
for fluctuations, T is the medium temperature [14]. The energy W can be replaced
with the energy of Gibbs G or free energy in a number of cases.
The formal theory of heterogeneous nucleation assumes that the nucleus on the
alien substrate has a dome shape with the spherical symmetry and it is character-
ized by the equilibrium contact angle . This angle is determined by the following
relation:
m = nu + s cos , (1.39)
where m , nu , s is the averaged surface energy relating to the melt, nucleus and
substrate.
The nucleation on the easily wettable substrate requires the overcoming of a
weaker potential barrier than on the non-wettable one, so the overchilling is less.
The temperature reduction slows down nucleation because the melt viscosity grows
exponentially so that the nuclei adhere to new particles less frequently. At first the
rate of nucleation is the maximum; it slows down as the temperature reduces and may
become so slow that the melt hardens remaining amorphous. Thus, the packing of
particles in smaller nuclei may differ from that in heavier nuclei. That is spontaneous
nucleation is avoided when growing larger crystals [15].
Crystals can grow layer by layer or normal to the crystal surface depending if it
smooth or rough in the atomic scale (Fig. 1.11). The atomic planes form a smooth
surface of almost fully packed atoms; the planes contain rather few vacancies and
atoms adsorbed in the spots of the relevant crystalline lattice nodes in the next layer.
22 1 Interaction Between Atoms in the Substance
Fig. 1.11 Atom smooth (a) and atom rough (b) surfaces
The edges of incomplete atomic planes form steps containing some three dimensional
angles. When new particles adhere to them, the energy of the atom smooth surface
remains unchanged.
The surface roughness (in the atomic scale) consists of multiple steps. When
a new atom attaches to any its point, but the three-dimensional angle of the step
changing its energy, this growth of crystals is termed directional. The filling of few
vacancies reducing the rough surface energy cannot start any new atomic layer. The
concentration of in the relevant crystalline lattice nodes augments the surface energy
and that is why it is small. The crystal can grow only when the three-dimensional
angles arrange dense on the surface.
The density of steps depends on whether they are generated by two-dimensional
nuclei or dislocations. The nucleation requires the overcoming of a barrier determined
by the step energy. If the spiral dislocation grows, its step acquires a spiral shape
(Fig. 1.12).
The layerwise crystallization from the gaseous phase does not evolve through
direct targeting of atoms at the steps due to a low density it evolves through diffusion
of particles adsorbed on the atom smooth surfaces called terraces.
The shape of growth of crystals (habitus) is determined by the anisotropy of the
crystallization rate and the conditions of heat and mass transfer. The crystals with
rough surfaces have usually a circular shape with rough surfaces. The atom smooth
surfaces appear like facets. The stationary shape of the crystalline polyhedron is such
that the distance from its geometrical center to each facet is proportional to its growth
rate. The crystal results formed by the facets with the least growth rates.
The perfect crystal can be constructed by endless regular repetition in space of similar
structural unities. The structural unity of simple crystals consists of one atom, for
instance, copper, gold and others. The structural unity of crystals in more complicated
substances may contain several atoms or molecules. For instance, their number may
reach 104 atoms in crystal. The crystal can consist of several chemical elements
(the common salt NaCl) or contain combined groups of atoms (hydrogen H2 ). The
crystalline structure is described using the elementary portion of the crystalline lattice
periodically repeating in space called the elementary or primitive cell.
The perfect crystal is a body consisting of atoms arranged in the spatial lattice
cfollows the rule
so that the vector of main translations a , b,
r = r + n 1 a + n 2 b + n 3 c, (1.40)
called translation.
If the individual perfect crystal is assumed as the integrity of atoms, then it fol-
lows from relations (1.40) and (1.41) that their arrangement should obey definite
rules of symmetry; French crystallographer O. Bravais reduced them to 14 types of
elementary cells (Fig. 1.13).
The so-called triclinic crystal lacks the symmetry. Both the angles and the stretches
of the crystal axes are unequal. The cubic crystals are the most symmetric because
all the facets are equally long and the angles between them are right.
In addition to the elementary lattices which coincide only in apexes, there centered
lattices which, depending on the symmetry type, contain structural entities in the
center of facets or in the crystal center. The cubic cells (I and F in Fig. 1.13) are
(BCC) body-centered and (FCC) face-centered cubic lattices.
The number of ways of arranging atoms which satisfy the rules of symmetry is
limited to 230 variants termed spatial groups. The spatial groups differ from the
pinpointed classes of symmetry that the operation of symmetry is conducted in them
not in respect to the beginning of coordinates but in respect to any point in the lattice.
All spatial groups are described in the crystallographic table and designated with
alphabetic symbols and numeric index correspond to the set of elements of symme-
try. The letter designates the crystal chemical composition: Asimple substances,
B, C, Dcompounds, Lalloys, Oorganic substances, Ssilicates. The numeric
index designates the structure type. For instance, A1 designates the cubic FCC.
24 1 Interaction Between Atoms in the Substance
l
L chain = n mon , (1.42)
2
where n mon is the number of monomers in the polymeric chain (Fig. 1.15).
The molecular chain length is usually assumed as the shortest distance between
the terminals atoms of the macromolecule stretched without deformation. This value
extensively used in publications is the structural characteristic of the carbon skeleton
of the polymer molecule.
Geometrically there are polymeric chains of linear, ramified and reticular struc-
tures (Fig. 1.16). The macromolecules of linear polymers are long nonramified
molecular chains containing similar or dissimilar monomeric chains. The ramified
polymers have the basic (main) molecular and lateral chains. Chemically the main
chain has homogeneous-chain and heterogeneous-chain polymers. The macromole-
26 1 Interaction Between Atoms in the Substance
Fig. 1.16 Schematic view of structures of polymeric chains: a linear; b ramified; c reticular
1 1 1
, , = h, k, l , (1.43)
m n q
for the free atom. From the quantum mechanics viewpoint, it is exactly this fact
which proves that the kinetic energy of electrons is smaller in the main crystal states.
It is impossible to calculate the mechanical characteristics of solid materials rely-
ing just on the regularities of atomic interactions due to the reasons disclosed in
Sect. 1.6. But these problems are solved rather easily for perfect crystals [3]. For
instance, the volume modulus of elasticity of ion crystals E y is found in the follow-
ing way:
M e2
E y = Aq , (1.44)
18ri4j
where Aq the constant depending on the electron structure of solids; ri j the spac-
ing between nearest ions; M the Madelung constant (see 1.27); ethe electron
charge.
The common salt perfect crystals have the constant Aq equal to 10.2; it corresponds
to the domination of forces of repulsion at distances 0.3 108 cm [3]. To proceed
to the engineering materials, the deviations from the periodicity of their crystalline
structure and the collective action of cohesive forces should be taken into account.
1
W Wf
f (E) = exp +1 , (1.45)
kT
N
1
N
2 2
H= i + Ui (r ) + Ui j , (1.46)
2m 2
i=1 i, j
kinetic energy operator; i = xi + yi + z i Laplace operator
2
where 2m
(P. Laplacea French physicist); Ui (r )potential energy of the interactions between
the ith electron and the nucleus; Ui j the energy of interactions between electron.
This problem cannot be solved without certain approximation of the problems
already solved. The best elaborated approximation of free electrons is the one which
excellently describes the structure of metals.
The model of the potential of free electrons added by the ions and electrons of
the crystalline lattice is represented as a homogeneous background with its mean
potential energy being a constant value U(r ) = const. It is counted from U(r ) = 0,
then the Hamiltonian value from (1.46) depends only on the kinetic energy of elec-
trons:
Fig. 1.19 Fermi distribution view: 1 at absolute zero; 2 at limit temperature satisfying condition
kT
W f
1.7 Electronic Structure of Materials 31
2 2
H = . (1.47)
2m
The kinetic energy corresponding to the Hamiltonian is the following:
2 2
Wk = , (1.48)
2m
where wave number, = 1/; wave length.
The wave function proper describing the electron state in the crystal is the fol-
lowing:
1
= ei r , (1.49)
where
crystal volume.
For the three-dimensional lattice, equation (1.49) can be rewritten as
3
1 2 2
= exp i (n x x + n y y + n z z) . (1.50)
L cr L cr
2
= n, (1.52)
L cr
The density of states N (W ) per single energy interval is found from the equality
W f
N= N (W )dW , (1.54)
0
32 1 Interaction Between Atoms in the Substance
W f 3
1 2m 2 3
N (W )dW = W f2 . (1.55)
3 2 2
0
Now the mean kinetic energy of free electrons or the electrons of conductivity
can be calculated.
W f
1 2
Wmean = WN(W )dW = W f . (1.57)
N 5
0
The following expression was obtained experimentally for the heat capacity of
metals:
C v = a1 T + a2 T 2 + a3 T 3 . (1.58)
The second and third summands in expression (1.58) can be ignored at low tem-
peratures, then:
2 N k2
a1 = ,
2W f (1.59)
W f = kT f ,
The existence of the long-range forces in the metals lattice can be explained from
the viewpoint of interactions between electrons. Let us consider the following system:
the electron gas with the density eN against the homogeneous background of
the positive charge +eN. Let us displace the electrons radially in respect to the
charged background so that the U (r ) acts as the function of displacement r . Then
the charge value moving away from the sphere with radius r is approximately equal
to 4 e2 Nr 2 U (r ). Since the coulomb forces follow the law of inverse squares, the
1.7 Electronic Structure of Materials 33
electron at a distance r from the coordinate start is exposed to the force of attraction
..
equal to 4 e2 NU (r ). Application of U (r ) and the second Newtonian law yield the
equation describing electron motion:
.. 4 e2 N
U (r ) + U (r ) = 0. (1.61)
m
Equation (1.61) is the equation of harmonic oscillations with the frequency
4 e2 N
p = . (1.62)
m
The frequency p , calculated with formula (1.62) is called plasma frequency and
similar oscillations induced by far acting interactions between electrons are called
plasma interactions. Their energy amounts to about 4 eV, the heat oscillations change
somewhat the value p .
The interactions between molecular chains of polymers within the SMS are compli-
cated and more varied than similar processes in metals. It is shown in Sect. 1.6; the
SMS structure of polymers resembles the crystalline structure. The crystal energy U
in the calculation per 1g/mole of the substance is measured by the work of is isother-
mal sublimation during transition into the gaseous state [3]:
1
U = U + f 1 f 1 + f 2 f 2 + . (1.63)
n t t
where f the specific surface energy on the crystal facet; W f the total value of
the surfaces of the crystal of this class, the indexes f designate the crystal phase
surfaces.
If these ideas are expanded to the crystallizing polymers, the first term in the
formula can be called the volume energy of the molecular lattice because this portion
of the full energy is determined by the potential energy of macromolecules that are
beyond the action of the surface forces. The second term (the polynomial) expresses
the sum of specific surface energies o the facets of the molecular crystallite (nthe
number of grammoles of the substance). Its value in respect to the first term can be
estimated knowing the relation between the number of particles in the surface layers
and the total number of particles making up the crystallite.
The energy of attraction and repulsion between the links of molecular chains
determines the crystalline lattice energy, hence, the physical and chemical polymer
characteristics too, the melting point in the first place, the constants of elasticity
34 1 Interaction Between Atoms in the Substance
and the plastic flow parameters. This energy can be expressed through the magnetic
susceptibility of the atomic groups [18]:
6mc2 1 2
UA = r 6 , (1.64)
11 1 + 21 2
The first and third terms in formula (1.65) express the energy of interactions
between similar atomic groups, he second term expresses the energy of interac-
tion between dissimilar atomic groups. The components in these formulas are the
following:
3
i = Mr
Na
1 np (1.66)
Mr =
2 + n 2p
3
U A = mc2 i r 6 = B A r 6 , (1.67)
2
and between dissimilar groups
3 1 2
UAB = mc2 1 r 6 = B AB r 6 .
2 1 1 + 21 2
1.8 Interactions Between Molecular Chains 35
The calculations show that BCH2 0.4 1010 erg cm6 , and BCH2 CH3 0.5
1010 erg cm6 . The energy of attraction of the CHn -groups turned out within 0.6
1012 erg [1].
In addition to the forces of attraction of polymeric molecules, there are forces of
repulsion; to calculate them the repulsion potential r ep is used. According to the
Slater formula (J. SlaterAmerican physicist-theoretician) the following is obtained:
r ep = M er , (1.68)
where M = 7.7 1010 ; = 2.43rB1 ; rB the Bohr radius called so after N. Bohr,
one of the founders of modern physics; r the spacing between atoms (nuclei).
The energy of repulsion within the molecular chains governing the elasticity (or
compressibility) of macromolecules is calculated with the formula:
U = B ri6 + r ep . (1.69)
i
The calculations show that the full potential of the repulsion value for the
macromolecules consisting of the CHn -groups amounts to 0.2 1013 erg and
the full potential of the interactions of these molecules is approximately equal to
1.3 1013 erg.
The above-listed formulas [1] served to calculate the Youngs modules of elas-
ticity (T. Younga British physicist) among three axes of the coordinates x, y, z,
yielding good agreement with the experimental values. The modulus of elasticity of
the molecular chain of paraffins turned out equal to E x = 1.25 1011 din/cm2 ,
E y = 1.25 1011 din/cm2 , E z 33.3 1011 din/cm2 .
References
1. A.S. Akhmatov, Molecular Physics of Boundary Friction (physical and mathematical literature,
Moscow, 1963), p. 472
2. D.N. Lyubimov, V.A. Ryzhikov, Processes in Friction: Manual (South Russia State Engineering
University, Novochherkask, 2006), p. 147 (Phys. Chem.)
3. Ch. Kittel, Introduction into Solid Body Physics (Mir, Moscow, 1978), p. 791
4. H. Casimir, Proc. Ned. Ac. Watensch. 51, 793 (1948)
5. A.M. Prokhorov (ed.), Physical Encyclopedia, vol. 2 (Sov. Encyclopedia, Moscow, 1990), p.
703c
6. E. Cartnell, G.V.A. Fowls, Valence and Structure of Molecules (English translation) ed. by
M.V. Bazilevsky (Chemistry, Moscow, 1978), p. 360
7. A.M. Prokhorov (ed.), Physical Encyclopedia, vol. 3 (Sov. Encyclopedia, Moscow, 1992), pp.
672672c
8. R. Kana, Physical Science of Metals, vol. 1 (Mir, Moscow, 1967), p. 329
9. N.L. Glinka, (ed.), in General Chemistry: University Manual, 23 edn, ed. by V.A. Rabinovich.
Chemistry (Khimiya, Leningrad, 1983) p. 704
10. M.K. Strougatskii, B.P. Nadeyensky, General Chemistry (Vysshaya Shkola, Moscow, 1962),
p. 407
36 1 Interaction Between Atoms in the Substance
Material point, absolutely solid body, perfect gas, heat machine of Nicolas Carno, are
physical models intended to help researchers study natural phenomena by simplifying
the objects of material world. The perfect crystal treated in the first chapter belongs to
the models. Solid materials are different because their crystalline space is distorted.
That is why additional notions were needed in the near and far order to describe
materials; the notion which were unnecessary before for perfect crystals. The near
order is the substance condensed state in which the ordered arrangement of particles
appears at distances comparable with atomic distances. The far order is the strict
reproducibility of one and the same structural element in all directions throughout
hundreds and thousands of periods of the crystalline lattice. The imperfect structure
of engineering materials governs the values of effective cohesive forces.
The structure of the majority of natural solid bodies is far from that of the perfect
crystal because they contain a great number of defects. British physicist D. Griffiths
believes that the solid body is a collection of cracks [1]. Unless the irregularities
of the structure are taken into account, the modern theory of the solid body would
be unable to assess adequately and quantitatively the physical properties of natural
materials.
Cracks, imperfections, deviations from perfect structure called defects
appear when substances crystallize deforming the physical and chemical homogeneity
of the lattice structure. There are three main types of defects of tribosystems: chemical
composition inhomogeneity, dislocations, and voids [13].
The chemical composition inhomogeneity appears due to the foreign atoms and
molecules in the crystallizing substances. They can occupy the nodes in the crys-
talline lattice under formation producing pinpointed defects which modify the crystal
parameters. Such modifications occur because the extrinsic atom has the dimensions
incompatible with those of the main atoms in crystals. These distortions of the crys-
talline lattice reduce the crystal full energy.
The changes in the crystal volume V due to the intrusion of extrinsic atoms are
calculated using formula [4]
V = 4 Pcr , (2.1)
where Wd the full energy for point defect appearance; Wr the energy of repul-
sion of atoms in closed shells; We changes in the energy of electrons.
4 V
We = Wf z , (2.3)
15
where zthe charge number; V the volume change around the defect in the
infinite crystal; atom volume.
The constant is = 1 for the infinite crystal in (2.1), hence, according to (2.1):
V = 4P, (2.4)
2.1 Defects of Crystalline Structure 39
The point defects imply both cases when the extrinsic atom is present and absent
in the crystalline lattice node. This phenomenon acquired vacancy or the Schottky
defect (W. SchottkyGerman physicist) [5]. It is probable that this lattice node is
vacant in the thermal equilibrium state, when the energy is equal to
Wv
pe = exp , (2.5)
kT
where Wv the energy needed to displace the atom from the crystalline lattice node
of the surface crystal; kthe Boltzmann constant.
Another type is the Frenkel defect (Ya.I. Frenkelsoviet physicist-theoretician):
it is the atom displaced into the internode position uncommon for the atom. The
number of defects according to Frenkel is the following:
1 Wy
N F = N N 2 exp , (2.6)
2kT
Fig. 2.1 Effect of point defects on crystalline space: a vacancy; b internodal atom; c slight inden-
tation defect; d slight displacement defect; e Frenkel defect; f Schottky defect (pair of vacancies in
cation and anion sublattices)
40 2 Crystalline Materials: Surfaces of Solid Bodies
Fig. 2.2 Arrangement of atoms around boundary dislocation: a schematic image; b electron
microscope image of dislocations in crystal
where Cv the gradient of point vacancies; dthe lattice period of the main sub-
stance (the solvent); dthe difference between lattice periods of the solvent and
the soluble component; Ethe modulus of the solvent elasticity.
The solvent implies the substance in which crystallization takes place; the soluble
component is the extrinsic substance. If the concentration of the extrinsic phase is
high enough, the distribution of the extrinsic substance in the solvent solid phase is
laminar, the isoconcentrates (the lines equal to the concentration of vacancies) being
parallel to the crystallization front in the plane in which the interface surface moves.
The process evolves more intensively of the interface surface is due to absorption of
extrinsic elements.
Dislocations are another type of defects of the crystalline structure [2, 57]. The
dislocations are the crystalline structure defects along some line. Three mechanisms
determine mainly the dislocations appearing when crystals grow: thermal stresses due
to the stresses induced by the fluctuations in the solid phase and the oversaturation of
the lattice with vacancies. The simplest types are boundary and helical dislocations.
The simplest presentation of the boundary dislocation is the line along which the
crystallographic semiplane breaks (Fig. 2.2). The electron microscopes with high
resolution power enable to observe arrangement of atom rows specific for boundary
dislocations in some crystals (Fig. 2.2b).
The helical type dislocations result when crystal portions displace parallel to the
broken crystalline semiplane rather than perpendicularly (Fig. 2.3). These disloca-
tions are called so because their contour on the plane perpendicular to the line of
break (the line of dislocations) is a helix around the line of dislocations.
The dislocation of crystalline structure fragments in the break plane can occur
at any angle to the line of dislocation rather than parallel or perpendicular. These
mixed dislocations can be considered consisting two types of boundary and helical
dislocations.
2.1 Defects of Crystalline Structure 41
The geometrical dislocations are characterized by the linear element S and the
Burgers vector b (see Fig. 2.3) called after British physicist J. Burgers.
The linear element is the vector tangent to the line of dislocations. If the line is
curved, the direction S is variable. The value and direction of the Burgers vector
coincide with vector towards which the crystal portion above and beneath the plane
of dislocations displace mutually. The modulus of the Burgers vector is usually equal
to the least spacing between atoms in the lattice.
Since the linear element vector S can vary, while the vector b remains constant, the
type of dislocations along its line can vary too. The boundary and helical components
of the mixed dislocation characterized by the Burgers vectors b and be , respectively,
depend on the orientation of the mixed dislocation Burgers vector b to S. If the angle
between them is equal to , then:
b = S b S = b cos S,
(2.8)
be = S b S = b sin n,
Fig. 2.4 Origination of dislocation loop: a view of rectangular closed dislocation loop (sectioned
through AACD plane); b arrangement of atoms in upper plane; c arrangement of atoms in lower
plane
crystal coincide, the ABCD boundary of this section represents the dislocation loop.
It is characterized by identical value of the Burgers vector. The loop in Fig. 2.4. can
be represented composed of two boundary AB and CD and two helical dislocations
BC and DA. Both the boundary and helical components are antiparallel.
The closed dislocation loop changes direction at least in two points, but the vector
b remains constant along all loop portions that is why it can consist only of heli-
cal dislocations. The closed loop can be plotted with only boundary dislocations if
the Burgers vector is parallel to the loop plane. These dislocations were called pris-
matic or FrankReed dislocations (J. FrankGerman physicist, W. ReedAmerican
physicist). If the loop ends are fixed, the FrankReed dislocations can multiply under
the effect of sufficiently strong stresses.
The expanding dislocation loop reaches the critical state when its radius becomes
equal to the distance l between the points where the lop ends are fixed. The relevant
displacement stress cr can be calculated with the formula:
Gs b
cr = , (2.9)
l
where G s the shear modulus; bthe Burgers vector modulus.
The continuum physics apparatus is usually used to treat the effect of dislocations
on elastic characteristics of solid bodies [8].
If the shear dislocations u i are known in the Cartesian system of coordinates,
the tensor component of the shear stresses jk , appearing when dislocations move
following the Hook law. The approximation of the isotropic crystal can be rerecorded
as follows [3]:
jj = + 2G s ejj ,
(2.10)
jk = G s ejk ,
2.1 Defects of Crystalline Structure 43
u j u k u j
ejk = + ; ejj = ;
k j j
= ejj ; = 2G s (1 2)1 ,
j
The solutions for stresses and deformations relating to the helical dislocations can
be obtained with the three stage routine:
1. Let us apply the Hook law (2.10) and determine the stresses which result from
the deformation due to the appearing helical dislocations which can bee recorded as
follows:
b y
u x = u y = 0; u z = arctg , (2.13)
2 x
where x, ythe Cartesian coordinates of dislocations.
Hence, the only non-vanishing stress components are the following:
G s by
x z = zx = ,
2 x 2 + y 2
(2.14)
G s bx
zy = yz = .
2 x 2 + y 2
equilibrium can be made directly by substitution providing Eqs. (2.11) and (2.14) are
fulfilled if [4]
2uz 2uz
+ = 0. (2.16)
x2 y2
Due to the stresses zx and zy , the dislocations can be twisted into the loop with
the value equal to
1
M= G s b R0disl 2 r0disl
2
, (2.17)
2
where R0disl , r0disl are internal and external radii of the helical dislocations.
3. Then the component of stresses z after correction for twisting becomes equal to
Gs b 1 1
z = . (2.18)
2r0disl 2
R0disl + r0disl
2
To find the deformations following the method applied to the helical dislocations
is impossible when applied to the boundary dislocations. Instead the so-called Airy
function of stresses , is used which subordinates the following equation:
2 2 2 2
+ + = 0. (2.19)
x2 y2 x2 y2
G s by 1
2
= ln x 2 + y 2 . (2.20)
2 (1 )
To calculate the stresses and displacements induced in the crystal the following
expressions are used:
G s by 3x 2 + y 2
x x = ,
2 (1 ) x 2 + y 2 2
G s by x 2 y2
yy = ,
2 (1 ) x 2 + y 2 2
(2.21)
G s by y
zz = ,
(1 ) x + y 2
2
G s bx x 2 y2
x y = ,
2 (1 ) x 2 + y 2 2
2.1 Defects of Crystalline Structure 45
b 1 bxy
ux = + ,
2 2 4 (1 ) x 2 + y 2
(2.22)
b (1 2) x 2 + y2 b x2
uy = ln .
8 (1 ) 2
r0 4 (1 ) x + y 2
2
No matter what mechanism causes stresses in the crystal, it results in the deforma-
tion which would be partly elastic, in the general case, and partly plastic. The relative
value of each of these components depends on the material yield strength Y . The
plastic deformation p resulting in generation of dislocations is determined by he
relation:
Y
p = , (2.23)
E
where Ethe elasticity modulus.
The number of dislocations d per unit of the crystal volume is determined with
the following formula:
p
d = ae , (2.24)
b
where ae the experimental coefficient.
Usually d is inversely proportional to the distance between dislocations.
The energy of the field of elastic stresses around dislocations can be found by
integrating the elastic energy density through the crystal volume. Incase of the helical
dislocations located in the hollow cylinder L long with the radii R0disl and r0disl ,
this energy is
G s b2 L R0disl
Uv = ln . (2.25)
4 r0disl
G s b2 L R0disl
Uc = ln . (2.26)
4 (1 ) r0disl
The elastic energy of the mixed dislocation is the superposition of boundary and
helical dislocations is found in the following way:
G s b2 L R0disl
Uc = ln 1 cos2 , (2.27)
4 (1 ) r0disl
where the angle between the Burgers vector and the axis of dislocations.
Thus, the dislocations possess a certain energy activity. Their interaction with
point defects in the crystal concentrates them close to the axes of dislocations.
46 2 Crystalline Materials: Surfaces of Solid Bodies
concentrating around dislocations the point defects form cloud or the Kottrell
atmosphere (A. KottrellBritish metallurgist) [7, 9]. The concentration of impu-
rities in the Kottrell atmosphere around the mixed dislocation is calculated from the
following relation [3]:
4 (1 + )
1
Cimp = C0 exp G s b sin Rat Rat Rimp sin (r kT )
2
,
3 (1 )
(2.28)
where C0 pre-exponential multiplier; Ram the atom radius of the main substance;
Rimp the atom radius of the impurity; p the angle of disagreement; r the
dislocation nucleus radius.
The concretion of the Kottrell atmosphere in transparent crystals results in
decoration of dislocations making them visually perceptible. The defect of the Kot-
trell atmosphere can coagulate in the oversaturated solid solutions. Hey are likely to
condense into single-, double-, or triple-layered loops parallel to the densest packed
planes (Fig. 2.5). After the loop diameter exceeds some critical size, the loop sides
flatten and join together. Exactly this defect is called the FrankReed dislocation.
If the flattening does not result in the joining of the boundary loops, the dislocation
originated in the Kottrell atmosphere is the boundary dislocation. If the flattening of
disk is accompanied by the tangential dislocation, then the dislocation loop is of the
partly mixed and partly boundary type.
Dislocations can move and interact fortifying or annihilating themselves. Concur-
rently the crystal full energy changes. The regularities of motions and interactions
of dislocations are considered below.
The following group of defects in the structure and in the solid bodies confirms
the Griffiths thesis that the natural crystal is most often a collection cracks or the
defects of the type of voids. These defects cover the microcracks or Smekal voids
(A. Smekalchzeck physicist) and extrinsic inclusions [1].
Fig. 2.6 Shapes of microcracks: a planar wedge-like; b wedge-like double sharpened; c elliptic
section
The microcrack is the defect in the solid body which can be characterize as a
rupture in the form of slot of micro- and submicrosize. These defects appear when
wet crystals dry under thermal or mechanical effect on the structure, disorders of
growth of crystals, foreign inclusion in the mother medium, etc.
The geometrical shape of cracks in crystalline bodies is different. Two shapes
prevail: wedge-like and elliptical (Fig. 2.6).
A high concentration of mechanical stresses endangering the solid body strength
appears at the top of microcracks. Any variable external deforming stresses pro-
mote the crack propagation encumbered with fatigue fracture of the solid body [10].
The Griffiths theory stipulates that the mechanical stress needed for the crack to
develop is
2Ed
= , (2.29)
l0.5
hence, foreign substances can penetrate into them and strongly affect the physical
and chemical characteristics of the solid body.
The foreign substances in the crystalline lattice resulting from the release of
microscopic and ultramicroscopic particles in the crystal are a special type of defects.
They appear due to a broad variety of mechanisms. They can appear as the crystal
grows at the initial stages of crystallization, or due to a variety of secondary processes
like artificial introduction of foreign substances into the crystal.
Thus, the structure of crystalline materials differs from its perfect model by the
existing structural defects. They can have a decisive effect on the physical, chemical
and mechanical characteristics of materials. The engineering materials are more
active chemically than perfect crystals but their strength is many times more inferior.
2.2 Polycrystals
b
d , (2.30)
D
2.2 Polycrystals 49
Fig. 2.8 Arrangement a and spacing between dislocations b for symmetric (100) small-angle
boundaries
It is necessary to have at lease two sets of dislocations with the orthogonal Burgers
vectors for two asymmetric small-angle boundaries (Fig. 2.9). The effect of dislo-
cations on the structure of crystals intensifies as the angle d grows (Fig. 2.9). The
boundaries this type of dislocations produce relate to the small-angle boundaries.
In addition to the mentioned small-angle intergrain boundaries, the solid bodies
manifest the small-angle twisting boundaries which contain also at least two sets
50 2 Crystalline Materials: Surfaces of Solid Bodies
helical dislocations. The mixed boundaries comprise the dislocation grids with three
Burgers vectors.
Some crystallographic planes pass through the intergrain boundary and continue
to adjacent grains. It means that some atoms in these planes are in perfect position
in respect to the atoms in adjacent crystallites even on the intergrain boundaries.
These nodes of lattices are called the nodes of coincidence; they form the lattice of
coincidence positions. The parameter is introduced as the measure of density of
coincidence positions in the polycrystal:
Vc. p.
= , (2.31)
Vc
where Vc. p. the volume of the lattice elementary cell with coincidence positions;
Vc the volume of the crystal elementary cell.
The small-angle boundaries can be characterized by the value of the parameter
close to 1. For instance, for the large-angle boundaries, it is > 1; it is = 5
when the angle of rotation is 37 .
The energy of intergrain boundaries is the sum of energies of separate disloca-
tions; the sum depends on the orientation of adjacent grains.
The zero on the graph abscissa axis (Fig. 2.10) corresponds to the absence of
boundaries. Even slight disorientation of two adjacent grains (10 ) induces the energy
leap almost to the maximum. Then the energy reduces somewhat just up to the angle
range about 70 and remains constant afterwards [2].
It is noted above that the excessive energy of the intergrain boundaries prede-
termines the crystal drive to minimize the dimensions and the energy as a result.
2.2 Polycrystals 51
Fig. 2.10 Dependence of energy of boundaries between grains of silicon iron on angle of dis-
orientation of grains
The broken surface chemical bonds alter the coordination of the sphere of surface
atoms and re-hybridize their valence orbitals. It results in new surface electron states,
the effective charges of surface atoms, the order of their arrangement and the inter-
atomic distances change. The latter results in the crystal without extra deformation
or distortion of its phonon spectrum. That is why the surface is rarely treated as the
geometrical plane. The substance layer adjacent to the surface (the surface layer)
is three-dimensional phase which has a number of physical properties different the
volumetric characteristics of the condensed body.
Nevertheless, to make further calculations easier, let us apply the model homo-
geneous surface. It may look simple but it yields often good correlation with the
experiment. Let us imagine the physical properties, the arrangement of atoms, and
the distribution of their effective charges over the homogeneous surface change only
normal to the surface. Thus, problem from three-dimensional turns into the one-
dimensional.
The atoms of the surface layer even in perfect crystals are in principally new
conditions from the solid body atoms. While the atom within the crystalline lattice is
surrounded regularly by adjacent atoms from all sides, the surface atom has the rele-
vant surrounding only from one side. It generates the force which affects the surface
atom in the direction of the crystalline lattice interior (Fig. 2.11a). The combination
of these forces causes surface tensioning particularly vividly manifested by fluids. It
is exactly due to the surface tensioning the free falling drop becomes a ball having
the least surface area.
The surface tensioning of solid bodies causes the deformation of surface layers. It
reduces the crystalline lattice period versus the period in the crystalline space deeper
regions (Fig. 2.11).
Figure 2.11a, b, leads to the conclusion that atoms in surface layers have free
(uncompensated) chemical bonds. The electrons of these atoms possess a natural
tendency to produce new links. While there are no foreign atoms on the surface, the
surface electrons have only one opportunity to couple, it is to bond to adjacent surface
atoms. It leads, in the simplest case, to pairing of the atoms and the resulting pairs
were called dimers. The atoms of each dimer approach mutually and concurrently
Fig. 2.11 Forces affecting atom within (a) and on surface of crystal (b), deformation of crystal
surface layers (c)
2.3 Solid Body Surface 53
move away from the adjacent surface atoms, the latter, in their turn, form mutually
their own dimers. This process is accompanied by changes in the original crystalline
lattice.
The crystalline lattice of surface layers (even that of the perfect crystal) is strongly
distorted and it corresponds to a high concentration of dislocations accumulating on
the surface. The solid body surface has in fact the excessive energy compared with
deeper layers of the crystal. His energy is proportional to the surface area. Among
the works dealing with the surface energy calculation, the results of Gilman are note-
worthy (J. GilmanAmerican physicist and chemist) [14] because the calculation
is relatively simple and the results feature good correlation with the experimental
results. The Gilman equation for the crystal surface energy is the following:
Ea02
Usur = , (2.32)
2 y0
where y0 the spacing between adjacent atomic planes; a0 the radius of action of
cohesive forces; Ethe elasticity modulus.
The difference between the surface crystalline structure and the volumetric crystal
structure corresponds to the same large difference in the electron structure.
Due to the crystalline lattice periodic structure, the electron density follows the
Fourier harmonic law (J. FourierFrench mathematician and physicist):
1
e = Fhkl exp 2i h x + k y + l z , (2.33)
h,k,l
1 e (r )
= Z e2 + dr + ex , (2.35)
|r R| |r r |
R
54 2 Crystalline Materials: Surfaces of Solid Bodies
Fig. 2.12 Perfect crystal energy picture: a potential electron energy change; b wave function
describing electron state
where Z ion charge; Rradius-vector characterizing the atom position in the crys-
talline space; ex exchange potential.
The exchange potential is the characteristic of the quantum nature of exchange
interactions fortifying the interatomic and intermolecular bonds by increasing the
electron density between positively charged nuclei. The exchange interactions have
the non-Coulomb nature and depend on the type of wave functions describing how
the electrons behave in quantum systems.
The electron density profile for the mail state in the gel model possesses the planar
translation invariance, see Fig. 2.13. but the density e (z) variance has two particular
features: first, electrons spill out into the region z > 0 (vacuum) and produce
a surface electrostatic dipole; second, the function e (z) oscillates when its value
approaches the value compensating the volumetric charge. These are called Friedel
oscillations after their discoverer French mineralogist Ch. Friedel. The wavelength
of these oscillations is the following:
1
, Fr = 3 2 e ,
3
Fr = (2.36)
Fr
The Friedel oscillations originate because electrons in metals can move freely
when their energy is close to the Fermi energy producing almost monochromatic
waves; here interference over the metal boundary causes oscillations. The electrons
having the constant wave vector with the value between 0 and Fr try to screen off
the distribution of the positive ground charge which contains a step at z = 0. The
Friedel oscillations contribute significantly to formation of the surface dipole layer
playing a sizeable role in surface processes [17].
2.3 Solid Body Surface 55
W A = (13 + 23 ) 12 , (2.37)
W A = 12 (1 + cos ) . (2.38)
Adsorption means the absorption of the condensed body (adsorbent) by the sur-
face layer from the substances in the gaseous or fluid phase. The desorption or
reverse adsorption is possible when the adsorbents are regenerated by eliminating
the absorbed substances (adsorbates). The volumetric adsorbate can be calculated
using the Freundlich formula (H. FreundlichGerman physicist and chemist):
Vad = ad Pad
n
, (2.39)
where Vad the volumetric adsorbate; ad the constant depending on the nature
of adsorbate and adsorbent; Pad the adsorbate pressure; n varies from 0.1 it 0.9
(it tends to increase as the temperature grows).
The main thermodynamic equation describing adsorption is the Gibbs equation:
G Gb = , (2.40)
chem T
where the tensioning coefficient at the phase interface; chem the adsorbate
chemical potential.
The Gibbs equation serves as the original to derive particular equations of adsorp-
tion. Usually the adsorbent surface is always coated by adsorbate particles; the longer
the particles stay on the surface, the thicker becomes the coat. It is due to the forces of
interactions between the adsorbent surface and the adsorbate particles. The surface
energy reduces in the process of adsorption. It proves that adsorption is an energy
gainful process with the ensuing consequences.
2.3 Solid Body Surface 57
There are physical or simple adsorption and chemosorption when chemical bonds
appear between molecules of substances and the sorbent. The force of attraction
should accompany the physical adsorption to bond particles to the solid body surface.
Van der Waals forces play this role (see para 1.1), their mechanism is the polarization
effect.
Electrons in the solid body are kept spaced due to the Coulomb and quantum
exchange interaction based on the Pauli principle. These forces and polarization effect
in the positively charged region around the electron called the hole with exactly the
same charge as the electron but with the opposite sign. Moving through the crystal,
the electron trails the tail of holes. When the electron quits the solid body, it leaves
a hole on the solid body surface as the polarization charge. Similar processes evolve
when atoms approach to the solid body surface. The example of interactions between
hydrogen atoms and the metal surface (Fig. 2.14) gives the idea how the symmetric
antihydrogen appears in the metal. In case of the multielectron atom the pattern
of interactions is more complicated: quantum mechanical ion exchange interaction
adds to the purely Van-der-Waals mechanism of adsorption.
The electrons are kept spaced due to the exchange components of the surface
forces. At the qualitative level, the electron to create its own exchange correlation
hole [16] with a single unaffected by other electrons. The electron moves through the
crystalline space and rails the shell of holes called figuratively the polarization coat
in [16]. The graphic presentation serves to describe vividly how the atom interacts
with the solid body surface representing it as the line of constant charge density
reflecting objectively the polarization processes.
The electron density configuration in Fig. 2.15a, corresponds to the case when
a single atom is on the electron gel surface. The electron densities in the atom
and on the solid body displace. The contour map is more demonstrative showing the
difference between charge planes in the atom-surface system and the superposition
of charge planes of the free atom and the pure surface (Fig. 2.15b). The surface
region with the deficit of electrons is well seen which can be represented as the
corresponding mirrored antiatom.
The localization of valent electrons of the atom adsorbate on the atom side
facing the adsorbent surface does not mean that bonds appear in the chemical sense.
Bonds appear due to the same cause why the energy of valent electrons reduces
because their own holes surround them. The energy of this interaction keeps atoms
58 2 Crystalline Materials: Surfaces of Solid Bodies
Fig. 2.15 Constant charge density line calculated for xenon adsorption on gel, a full charge density;
b changes in charge density induced by adsorption. Full line corresponds to excess of electrons,
dotted lines correspond the deficit of electrons
on the surface with the help of the mechanism of physical adsorption. This energy
amounts to
e (r )ex (r )
Wad = dr dr , (2.41)
|r r |
Fig. 2.17 Constant charge density line during adsorption of atoms Li, Si, Cl on gel, a full charge;
b targeted charge. Lines: designations see Fig. 2.15
in gel) and the regions of the minimal electron densities they induce when forming
the polarization coat.
The difference of electron densities appearing during chemosorption permits to
introduce the notion of the binder (the maximum electron density) and the antibinder
(the minimum density) levels which represent the system of sorbed atoms or mole-
cules called the surface cluster or surface molecule [16].
To describe molecular adsorption, the orientation of adsorbate particles should
be known in respect to the substrate. The matter of their spatial arrangement during
adsorption is omitted just because of the symmetric molecules. But these molecular
structures are capable to polarize and often acquire the charge density asymmetric
distribution. The macromolecules and molecules of lubricating materials have the
dominating chain structures. The chain structure position on the solid body surface
is characterized by two coordinates x, y and two angles , (Fig. 2.18).
Fig. 2.19 Orientation of chain molecules with active center on metallic specimen surface: a mole-
cule experiences torque; b nonelastic collision occurs; c absolutely elastic impact
are much lower than their volumetric values. Hence, the energy of activation of the
surface diffusion makes up just a part of the energy of activation of the volumetric dif-
fusion. The surface diffusion process proper is usually considered as the sequence of
elementary acts shown schematically in Fig. 2.21. When substances under the effect
of thermodynamic forces, the atoms detach from the second atomic plane, move
along smooth terraces, slide off the lattice step and get trapped in the vacancies.
Groups of bonded atoms or some regions of the surface layer as a whole can move
during surface diffusion. Usually the surface diffusion is considered as the process
altering the adsorbate concentration from the non-equilibrium to the equilibrium
distribution when there are corresponding concentration gradients.
In the general case, the solid body surface has a laminar structure (Fig. 2.22).
The topmost are the films consisting of the atoms and molecules adsorbed from
the environment. This film is differently thick: it is thicker where the defects of the
crystalline structure accumulate (the adsorption centers). The mechanical working
of the engineering materials (forging, extrusion, etc.) activates the surface layers
additionally.
The solid body surface is not absolutely smooth, at least due to the dislocations
creating dislocation steps. This type of surface deviations from the perfect state are
Fig. 2.22 Scheme of solid body surface: 1 films of adsorbed molecules, 2 surface layer proper, 3, 4
layers modified by mechanical treatment of structure, 5 solid body crystalline structure proper
62 2 Crystalline Materials: Surfaces of Solid Bodies
Fig. 2.23 Arrangement of atoms of one same substance at phase boundary: a disagreement between
lattice parameters; b latent boundary
2.4 Phase Boundaries 63
Fig. 2.24 Semicoherent boundary (nm): a scheme, b microscopic photograph of boundary between
Pt and NiO (letters indicate ruptures of crystallographic planes) [6]
As crystals grow, the disagreement between the structure parameters over phase
boundary augments and the elastic energy increases at the phase boundary. The
energy is gainful to compensate the disagreement by producing boundary disloca-
tions which relieve mechanical stresses. This type of boundaries is termed partially
coherent type (Fig. 2.24).
If both phases possess absolutely different structures, the coherence is fully lost
and the incoherent phase boundary (Fig. 2.25). Like in the case of the intergrain
boundaries, some energy can appear at the phase boundary and preferable lattice
configurations. The phase boundaries in composites are, as a rule, in the nonequilib-
rium state (Fig. 2.25).
The insufficient knowledge of the structure phase boundaries inhibits the descrip-
tion of their properties at the atomic level [6]. The phenomenological description is
usually used combing the interface properties with the physical parameters of inter-
actions between phases which can be determined experimentally. One of them is
the surface tensioning which is associated with excessive surface free energy and
determines the equilibrium type of the interface surfaces in mixed phases.
Let us consider the fluid drop shape in equilibrium on the solid body surface
(Fig. 2.26). The surface tensioning act along the contact line as the forces conditioning
the drop configuration based on the criterion of the minimum energy. The equilibrium
in vertical direction takes place if
64 2 Crystalline Materials: Surfaces of Solid Bodies
Fig. 2.25 Incoherent boundary: a schematic view; b high resolution electronic microscope image
sg = s f + f g cos . (2.42)
This equation (the Dupret equation) enables to estimate the wetting angle .
The drop spread over the solid body surface (2.42) is a particular case of the
equilibrium of three phases (Fig. 2.27). In the general case, the Herring equation is
true (C. HerringAmerican physicist theoretician):
2.4 Phase Boundaries 65
23 13
=
(1 + 2 3 ) sin 1 + (3 1 ) cos 1 (1 + 1 3 ) sin 2 + (1 2 ) cos 2
12
= , (2.43)
(1 + 1 2 ) sin 3 + (1 3 ) cos 3
where i = i (ln hkl ) determines the dependence of the interphase energy on the
adsorbate phase orientation in respect to the selected crystallographic directions of
the adsorbent crystalline lattice. The subline indexes correspond to Fig. 2.27.
The surface energy of boundaries of some crystallographic phases turns out very
low, for instance, that of the coherent twin boundaries. If the energy of all three bound-
aries is independent of their orientation in space, the Herring equation is simplified
to the Young equation:
12 23 31
= = . (2.44)
sin 3 sin 1 sin 2
References
Abstract The main regularities of elastic vibration in crystals are discussed. There
are given elements of quantum model of elastic vibrations propagation in crystals. The
basic laws of dislocations motion and diffusive flows in solids as well as regularities
of influence this processes on solids microstructure and mechanical properties are
represented.
So, the world of crystals, like other types of solid bodies, is not stiff, frozen. Its
particular arrangement changes under the effect of external force factors. Regretfully,
these changes are least reflected in publications and are rarely considered when
constructing structural and theoretical models for solutions of engineering problem.
The external effect on the solid body generates a response in the form of perturbations
of the crystalline space. The simplest type of these perturbations is the propagation
of elastic oscillations in the substances. Because the crystalline space is anisotropic
by nature, the oscillations appearing in the crystal depend on its structure parameters.
Let us consider how the elastic oscillations propagate in the simplest lattice of the
cubic type [1].
To displace the elementary crystal volume (Fig. 3.1) in the direction of axis x, the
equation of the second Newton law is true:
2u x Xx Xy Xz
= + + , (3.1)
t 2 x y z
where si j = ci1
j constant elastic flexibility constants; cij elastic rigidity
constants.
Equation (3.1) is the following for the cubic crystal with the account of (3.23.3):
2u ex x e yy ezz ex y ezx
2 = c11 + c12 + + c44 + . (3.4)
t x x x y z
3.1 Elastic Waves in Crystals 69
u
ex x = x x = ; e yy = yy = ; ezz = zz = ,
x y z
u
ex y = yx + x y = + ,
y x
(3.5)
e yz = zy + yz = + ,
z y
u
ezx = zx + x z = + ,
z x
The relevant equation for displacements and are obtained from Eq. (3.7a) by
circular permutation of values, for instance:
2 2 2 2 2u 2
2 = c11 2 + c44 + (c12 + c44 )
+ + ,
t x y2 z 2 x y xz
2 2
2 2 2 u 2
2 = c11 2 + c44 + + (c12 + c44 ) + .
t x y2 z 2 x y xz
(3.7b)
2 = c11 2 . (3.10)
70 3 Dynamic Microprocesses in Solid Bodies
Hence, the speed of elastic wave propagation through the crystal in the direction
(100) is equal to
c11
cel = frg =
1
. (3.11)
The transverse wave or the displacement wave is characterized by the wave vector
directed along the cube ridge coinciding with the axis x. It displaces the particle in
the direction of axis y:
2
cel = c0 exp [i( y t)] . (3.12)
Similarly for the transverse wave in the direction (100) of the crystal:
c44
3
cel = . (3.13)
Similar expressions can be obtained too for motion of particles along axis z.
Let us consider the propagation of elastic oscillations in planes xy along the cubic
lattice diagonal, i.e., in the direction (110). The dislocation of particles along the
axis z is
= 0 exp i x x + y y t . (3.14)
It is apparent from Eq. (3.15) that the result is independent of the wave direction
in the plane xy.
Let us consider other waves propagating in the plane xy.
u = u 0 exp i x x + y y t ,
(3.16)
= 0 exp i x x + y y t .
1 1
1)2 = (c11 + c12 + 2c44 ) 2 , 2)2 = (c11 c12 ) 2 . (3.19)
2 2
The first root describes the longitudinal wave motion, the second the transverse
wave motion. To determine the direction of displacement of particles, let us substitute
the first root into (3.17):
1 1 1
(c11 + c12 + 2c44 ) 2 u = (c11 + c44 ) 2 u + (c12 + 2c44 ) 2 , (3.20)
2 2 2
and obtain that u = . Hence, the particles dislocate along directions (110) parallel
to the vector . Let us substitute the second root into Eq. (3.17) and obtain u = ,
i.e., the direction of particles coincides with direction (110) perpendicular to .
Hence, the wave vector of definite value and directions in the cubic lattice
has three types of own oscillations; their directions are neither strictly parallel nor
perpendicular to . Thus, in accordance with relations (3.11) and (3.13), the speed
of propagation of elastic oscillations in the solid body is the following:
1/2
elastic characteristics
cel = . (3.21)
medium density
M= . (3.22)
c
The Mach number characterizes the medium compressibility, i.e., its density vari-
ations
/ under the effect of comprehensive compression. With the account of
the laws of thermodynamics and the equation Bernoulli equation for perfect fluid
flow [2]:
M2 . (3.23)
It follows from relation (3.23) that the medium compressibility augments as the
Mach number grows.
72 3 Dynamic Microprocesses in Solid Bodies
The energy of oscillations of the crystalline lattice or the energy of elastic waves
is a quantum magnitude. The quantum energy of the elastic wave is called phonon
similarly to the photon as the quantum of electromagnetic wave. The sound (elastic)
waves in crystals are the propagation of phonons. The thermal oscillations of atoms
in the crystals can be considered the thermal excitation of phonons similarly to the
thermal excitation of photons which the emission of the absolutely black body.
According to the assumption of M. Plank which is in the base of the matter
quantum theory, the energy of each type of oscillations of the electromagnetic field
is the proportional value h, or the energy of one photon. The energy n of photons
oscillating with the frequency f is equal to:
w = nh f ,
or (3.24)
w = n f n ,
ds = in + G
r.l , (3.25)
where G r.l the reverse lattice vector; in and ds wave vectors of the incident
and dissipated X-ray phonon.
During dissipation the crystal in general experiences the recoil with the impulse
G r.l . The summary wave vector of interacting waves persists in the periodic lattice,
but only with possible addition of the vector G r.l . The true impulse of the whole
3.2 Quantum Crystalline Lattice Oscillations 73
system is strictly constant. If the photon undergoes nonelastic dissipation when the
phonon with the wave vector , then the rule of its selection is the following:
ds + = in + G
r.l . (3.26)
ds = in + + G
r.l , (3.27)
c pht
pht = ,
nr f
c (3.28)
pht = ,
nr f
p pht =
pht .
where pht the photon wave vector pht the wavelength; c the speed of light;
p pht the photon impulse.
The photon interacting with the beam of phonons in the crystal can dissipate due
to the fact that the field of elastic deformations alters the local concentration of atoms
[in accordance with (3.25)], and, hence, the crystal refraction index. Thus, the elastic
wave modulates the medium optical properties. Vice versa, the electromagnetic field
of the flow of photons alters the crystal elasticity.
If the photon undergoes dissipation in the crystal , it can result [in accordance with
relations (3.26) and (3.27)] in the appearance or absorption of the phonon. Assume
that, during the photon dissipation, a phonon appears with the wave vector phn and
the frequency phn . This process is shown schematically in Fig. 3.2.
In accordance with the energy preservation:
Due to different speeds of sound and light, only a small portion of the energy of
the incident photon can be transferred to the phonon . For the phonon with the wave
vector phn comparable with the wave vector of the photon pht it can be shown that
pht = pnt , pht = pht . Then, it follows from (3.26) that
2c pht nr f
phn = sin (/2) . (3.33)
c
Diffusion is the most important natural dynamic process influencing the integrity
of physicist and mechanical characteristics of the solid body [1, 3, 14, 15]. The
diffusion in the material results in the leveling of the chemical potential . The diffusion
levels the concentration of each phase component by the volume of the single-phase
material at constant temperature and when there no external diffusion forces. In
case the temperature is not constant and external forces are in effect, the spatial
inhomogeneous equilibrium distribution of each component of forces sets in the
material. In the general case, the mass transfer by diffusion is described by the
differential equation in particular derivatives of the second order which is most often
the following:
dCm (x, t)
= div(D gradCm ) qm Cm + F, (3.34)
dt
3.3 Diffusion in Crystals 75
m = D gradC A t = D C A t,
C
m = D A t. (3.35)
x
The sign minus indicates that the diffusion flow moves towards the concentration
reduction, that is why the isolated system tends to disappearance of the concentration
gradients. Usually, Eq. (3.35) is used with the specific substance quantity referred to
the cross section area unity per unit of times. This physical value has acquired the
name of the density of flow of the diffusing substance J . Then the Fick equation
becomes the following;
J = D C, (3.36)
or
C
J = D .
x
The flow density J determines the substance diffusion rate. If the system has the
temperature gradient T and the pressure gradient P, Eq. (3.36) is the following:
T P
J = D C + DT + DP , (3.37)
T P
C 2C
= D 2. (3.38)
t x
76 3 Dynamic Microprocesses in Solid Bodies
Fig. 3.3 Changes in concentration of two semifinite rods of diffusing substance at two different
diffusion rates
In the general case, the coefficient of diffusion D is not constant and depends
on the concentration, the spatial and time coordinates. Hence, relation (3.38) can be
re-written in the following way:
C
= [D(C)C] ,
t (3.39)
C C
= D(C) .
t x x
The general view of the solutions of Eq. (3.39) for the medium which can be
represented as two detached semi-infinite rods (Fig. 3.3) is the following:
x
2 Dt
C2 C1 2 C2 C1 x
C (x, t) C1 = e d = 1 + erf .
2 2 2 Dt
(3.40)
The solutions of the Fick equation of the second order are treated in [5].
The value L D = 2 Dt included into Eq. (3.40) is termed the diffusion length
in the theory of diffusion.
Different references
describe the value L differently, for
instance, L D = 2Dt in [5], L D = 6Dt in [4]. Generally, the diffusion length
or the diffusion path is proportional to Dt and it is the distance to which particles
can travel during diffusion . For further discussion, let us assume
L D Dt (3.41)
P = . (3.42)
3.3 Diffusion in Crystals 77
The diffusion flow J results from displacement of particles by the force P. When
the displacement rate is , ( C) particles passes per unit of time through unit of
area of the transverse cross section;
J f = C. (3.43)
= B P, (3.44)
where B is the mobility of particles which, in accordance with the Einstein equation
[1, 4] is equal to
D
B = . (3.45)
kT
Substitution of (3.42), (3.44) into (3.45) in formula (3.43) yields:
D
J = C. (3.46)
kT
With the account of (3.46) and (3.37) the equation of the first Fick law becomes
the following:
C
Jgen = J + J = D C + . (3.47)
kT
The Fick laws establish the bonds between the observable diffusion flow and
the concentration gradient and show that nature tends to even distribution of con-
centrations through the whole volume of the substances. Yet, the thermodynamic
equilibrium in the substance at constant temperature and pressure is determined by
the minimum free energy and Gibbs G [6], moreover, this requirement to the
homogeneous distribution of concentrations is not obligatory.
For the system of n-components:
n
G = Wint + pV T S + i Ni , (3.49)
i=1
78 3 Dynamic Microprocesses in Solid Bodies
where i the chemical potential; Ni the number of particles of the i-th compo-
nent; ppressure; T temperature; V volume; Sentropy; Wint the internal
energy in the diffusion system.
For the mixture of components, the diffusion flow Ji of each in the thermodynamic
interpretation of open systems [7] is recorded in the following way:
T
Ji = L ik , (3.50)
T
k
The values L ik and Dik are symmetric tensors of the second rank; the non-diagonal
components L ik are equal to zero in Eq. (3.52).
For the two component system, Eq. (3.52) can be represented as follows:
1 C1
L 11 = D1 ,
x x (3.53)
2 C2
L 22 = D2 .
x x
L ii = Bi Ci , (3.54)
or
i
Di = Bi , (3.55)
(ln Ci )
Relation (3.55) reflects the dependence of the diffusion coefficient on the chemical
potential gradient.
It follows from Eqs. (3.513.52) that the diffusion coefficient is the tensor deter-
mined by the crystalline structure parameters. If the crystalline lattice is symmetric
cubic, the diffusion coefficient is isotropic, i.e., Di tensor can be replaced with scalar
value, it is true for 70 % of metals. For crystals with a low degree of symmetry,
and the diffusion coefficients depend usually on the direction and it can be fixed
mathematically by substituting tensors Di j in the matrix form [4]:
3.3 Diffusion in Crystals 79
D1 0 0 D11 0 0 D11 0 0
Dcube = 0 D1 0 ; Dhex = 0 D11 0 ; Drhomb = 0 D22 0
0 0 D1 0 0 D33 0 0 D33
One more interpretation of the tensor Di j components is shown in [5]. The diago-
nal tensor elements determine the direct processes and non-diagonal the intersecting
processes . Thermodiffusion and the Dufour effect are the intersecting processes in
the theory of diffusion (L. DufourSwiss physicist); according to this effect the
heat flow stirred by diffusion of non-reacting gases appears due to appearance of the
gradient of substance concentration. The thermal flow J Q , appears during constant
pressure because the gradient of concentration and temperature is equal to:
J Q = h f T T D C, (3.56)
where h f the heat conductivity coefficient; the diffusant density; the dif-
fusant chemical potential; D the Dufour coefficient.
In addition to the thermal flow, this system acquires the substance flow:
J M = C(1 C) DT T D C, (3.57)
Fig. 3.4 Mechanisms of diffusion in solid bodies: a exchange, b circular, c internodal, d vacational
Here d designates the diffusing atom jump length, td = 1/ f r is the time interval
between consecutive jumps.
The Arrenius law is the main equation of heat-activated diffusion:
WD
D = D0 exp , (3.61)
kT
Wd = Uv + E a . (3.62)
The Arrenius law serves here to describe predominantly the temperature depen-
dence of diffusion processes in condensed bodies. According to the ideas developed
by M. Eyring (the American physicist and chemist) [5, 8], the values in formula
(3.61) can be represented in the following way:
kT
S
D0 = d 2 e k , (3.63)
h
where
Sthe change of entropy of the diffusing substance; hthe Plank constant.
The physical sense of the value d is much identical to d , but it is also bound
by the substance structure. For crystalline bodies, it is the lattice constant, for the
amorphous and fluid bodies they are the mean spacing between molecules and the
value of the elementary jump, respectively.
3.3 Diffusion in Crystals 81
With the account of (3.60) and (3.61), let us represent the Arrenius equation in
the following way:
Wd
D = 0 d exp
2
. (3.64)
kT
The effect of the crystal structure. For different types of crystalline lattices,
the values Wd differ slightly, though d and 0 can vary within a broad range. Rep-
resentation of the diffusion coefficient in solid bodies with the help of the rates of
the Eyring reactions yields its exponential dependence on the activation temperature
and energy. Diffusion in the unordered substitution alloys cannot be described with a
single exponent because various potential barriers are to be overcome in lattice nodes
with differently configured atoms. If the diffusion evolves through vacations or with
the help of the circular mechanism (Fig. 3.4b), the diffusion coefficients of different
mechanisms differ too. Due to this fact the substance results directed towards the
larger partial diffusion coefficient:
JR
= (D1 D2 ) C, (3.65)
dJ j
Jy+dy = Jy + ,
dy
C C
Jy = Dbr , Jx = DV , (3.67)
y y
C 2C 2DV C
= Dbr 2 + . (3.68)
t y x
It follows from expression (3.68) that the diffusion coefficients do not depend
on the localization of boundaries. With some assumptions, the following can be
obtained [4]:
y 2 x
C (x, y, t) = C0 1 erf . (3.69)
4
DV t Dbr DV1 2 DV t
The motion of dislocations is the most essential dynamic process affecting the crys-
talline structure in space [4, 9]. The dislocations moves over the surfaces called the
sliding surfaces and lead to the crystal plastic deformation. The sliding surface cor-
responds to the axis of dislocation and its Burgers vector. In the particular case, the
dislocation axis lies in one plane which contains the Burgers vector.
The reason why the term the surface and the sliding plane are selected becomes
understandable when considering how the dislocations behave in the real crystal.
The dislocations in the crystal can slip along their sliding surfaces; their motion
resembles to some extent the distribution of elastic perturbations in a long spiral
spring or water ripples. As long as the dislocation travels in one direction, the upper
half of the material displaces in respect to the lone one by the value and in the Burgers
vector direction. In other words, the sliding of dislocations indicates the slipping
of one crystal part in respect to the other (Fig. 3.7a).
Crystal deformation. The vector n is directed normal to the plane of sliding of
dislocations :
n = Sb , (3.70)
where Sdislocation
length element; bBurgers vector.
b)
The helical dislocations ( S// have no definite sliding and it can be variable mak-
ing the sliding possible in the transverse direction (Fig. 3.7a). The plane of sliding
of prismatic dislocations contain the line of dislocations , correspondingly the pris-
matic dislocations are stationary. The boundary and mixed dislocations can issue
from original sliding planes (ascend) due to absorption or creation of point defects
(Fig. 3.7b). The absorbed vacancies vanish from the crystal volume; hence, the dislo-
cations serve as the sink for vacancies. The dislocations in the reverse process act
as sources of vacancies. Creation and removal of point defects changes the crystal
volume.
The sliding motion of dislocations is considered conservative because it does
not produce nor absorbs point defects or alters the crystal volume. This motion of
dislocations is called climbing. The material transfer in the process of climbing is
84 3 Dynamic Microprocesses in Solid Bodies
Fig. 3.7 Variants of motion of dislocations: a scheme of unidirectional sliding crystal parts due to
motion of helical dislocations; b helical dislocation slides in two directions (111) and (111)
= d blmd , (3.71)
The combination of the equations of equilibrium and compatibility (see Sect. 2.1)
for the dislocations moving with the velocity in the direction of axis x does not lead
to relation (2.16) like in the stationary case; it rather leads to the following equation:
1
where x = (x t) 1 , = 1 c2 , cthe velocity of propagation of
2 2
b y
u x = u y = 0; u z = ar ctg , (3.75)
2 x
and
G s by
zx = x z =
2 (x t)2 + 2 y 2
. (3.76)
G s b (x t)
yz = zy =
2 (x t)2 + 2 y 2
U
W = , (3.77)
and, respectively
m0
m D = ,
86 3 Dynamic Microprocesses in Solid Bodies
U
where m 0 = 2 .
c
The value m 0 is the equivalent mass at rest of a single dislocation length which,
by the order of magnitude, is equal to:
m 0 = b2 , (3.79)
Gs b
max = , (3.80)
2 d
where dthe crystalline lattice period.
For displacement of two crystallographic planes to the distance x equal to 1/4
of the interatomic distance, the stress in the crystal should be increased to the
maximum values max . When x = b, the stress of displacement falls to zero since
this position corresponds to the crystal new equilibrium state. This dependence can
be described by the following harmonic law.
2 x
= max sin . (3.81)
b
The value max corresponds to the theoretical crystal strength in shear. How-
ever, the limit shear stress registered by testing metals and alloys is many orders of
magnitude less than max . The contradiction is due to the fact that the atoms in the
materials under load move stagewise rather than simultaneously. This type of motion
is comparable with the caterpillar motion. This mechanism in crystals corresponds
to the motion of dislocations . When the dislocation with the Burgers vector b moves
through the crystal with the thickness l, it induces the dislocation of crystal parts (the
shear deformation) by the value
b
= . (3.82)
l
The summarization of the drift of many dislocations can be recorded as (3.71).
Expression (3.71) is easily transformed into the type describing the deformation at
various moments of time:
= d b, (3.83)
Let us consider the dislocation sliding in a single crystal volume under the effect of
the external force and free of internal stresses. According to (3.71), the deformation
increment by displacement d caused by the sliding of the dislocation element
with the length dl to the distance d Sd , perpendicular to the direction of motion of
dislocations, is defined by the following expression:
d = b dl d Sd . (3.84)
d A1 = d . (3.85)
As a result, the force P affects the dislocation induced by the field of elastic
stresses in the crystal which sets the dislocation in motion. The work fulfilled by this
force per unit of the dislocation length is the following:
d A2 = P d Sd dl. (3.86)
The values dA1 and dA2 are equal, then, with the account of (3.86), the following
can be recorded:
b d Sd dl = P d Sd dl,
or
P = b. (3.87)
If the mechanical stress acts in the crystal, the force per unit of the dislocation
with the Burgers vector b and the linear element S (2.8) is determined by the following
formula [4]:
P = b S. (3.88)
In order to displace the dislocation (Fig. 3.8) the force should be applied creat-
ing the critical displacement stress to its sliding plane (3.87). The critical stress or
Peierls stress p (R. PeierlsBritish physicist) can be calculated with the following
formula [4]:
2G s 2 d
p = exp , (3.89)
1 b (1 )
Fig. 3.8 Phases of motion of dislocation over its plane: a < p , b motion start, c crystal shear
P12 = 1 b2 S2 , (3.90)
The crystalline space of the solid body decelerates the motion of dislocations.
This effect acquired the name of locking dislocations. There are several variants of
locking (or friction by another terminology) [9].
The chemical locking occurs under the effect of defects in the crystalline lattice
packing concentrating in the layer several atoms thick. The solubility of chemical
elements in this phase differ from their solubility in the main crystalline lattice, so
the alloying element atoms can accumulate on the packing defects and multiply them.
As a result, the boundary dislocations are locked and so do the helical dislocations to
a lesser extent. For the dislocations to resume motion, additional mechanical stress
should be applied with the depended on the concentration of the dissolved element.
The chemical locking of the motion of dislocations is observed predominantly among
the crystals with the face centered lattice.
The elastic locking is typical for the crystals with the substitution atoms differ-
ing in size from the matrix atoms. The local fields of elastic deformation appear and
interact with the elastic fields of dislocations striving to reduce the lattice distortions.
The alien atoms occupy the most gainful energy positions near the dislocations. The
energy from interactions amounts to fractions of electron-volts, while the interac-
tion between helical dislocations and substitution atoms is still weaker. An extra
stress is needed to resume motion of the dislocations locked elastically; the stress is
proportional to the parameter of dimensional incompatibility of atoms
:
1 dd
= , (3.91)
d dC
where dthe crystalline lattice constant; Cthe concentration of impurities.
The mechanism of elastic locking of motion of dislocations is actuated when the
Cottrell atmosphere forms around dislocations (Sect. 2.1) and acts as the peculiar
anchor. The anchor moves together with dislocations. and has either to tow the
atmosphere or get detached.
The electrostatic locking occurs in the dislocations with the stretched negatively
charged nucleus which interacts with the additional charge appearing adjacent to
3.4 Motion of Dislocations 89
the dissolved atom; the atom has the valence different from that of the solvent.
The free electrons are screened off by a highly effective braking mechanism, but in
this case its effectiveness is poor because the atomic levels can change noticeably
in case of such defects. Another mechanism of electrostatic locking is a peculiar
manifestation of the Schottky barrier observed when the Cottrell atmosphere forms
around the positively charged nucleus of vacancy dislocations. The potential barrier
on the surface of dislocations for the main charge carriers; the barrier is several
Debaye screening lengths L D . for instance, for aluminum L D is equal to 0.05 nm [10].
The locking mechanism orders the field of stresses of dislocations [11]. It is
exactly the case when the lack of precipitated atoms due to the dislocation stresses can
result in the structures of the near order around dislocations. The dislocation creates
spontaneously around itself the energy barrier (self locks), as a result, yield spots
can appear on the crystal deformation curves, while the sold substitution solutions
demonstrate the hardening effect proportional to the squared concentration of the
dissolved element.
Creep. The measured values of the critical displacement stresses in crystals are
usually smaller than those calculated according to (3.80). It is primarily to the neglect
of the factor of thermal deformation activation. The mechanical stress, at which dis-
locations can overcome obstacles, relieves due to the thermal activation. Dislocations
travel among obstacles and stop in front of them for some induction period for the
system to accumulate the thermal activation energy needed to overcome the obstacle.
With these considerations in mind, Eq. (3.80) can be represented as:
W ( )
= 0 exp , (3.92)
kT
where
W the activation energy needed to overcome obstacles under the effect
of stresses . "
4b 2 WL p
W ( ) = ,
2 (3.93)
1
WL = G s b .2
2
where p the Peierls stress calculated with formula (3.89).
Combination of Eqs. (3.92) and (3.93) yields the expression friction the critical
stress at the temperature T and the deformation rate :
2
= p AT ln
2
, (3.94)
0
where A4 constant.
The critical displacement stress at T = 0K corresponds to the Peierls stress and
it reduces as the temperature grows and becomes proportional to T 2 .
90 3 Dynamic Microprocesses in Solid Bodies
The speed of motion of the vacancies among the dislocations, hence, irrespective
of the mechanism of motion of dislocations, the velocity of sliding dislocations
depends on their distribution in the crystal is the following:
b
= , (3.95)
BT
LD
= n , (3.96)
d
where L D the distance to which the dislocation moves in the sliding plane; d the
distance to which the dislocation climbs in the direction perpendicular to this plane.
The motion of dislocations determines the property of solid bodies such as creep
the numerical characteristic of which K creep is approximately equal to (3.80).
Substitution of (3.80) with the value from (3.72) yields the following equation of
the mean creep rate:
4 2 2
creep = . (3.97)
BT G s
The dynamic processes in crystals influence significantly the physical, chemical and
mechanical characteristics of crystalline solid bodies. The processes of diffusion
alter the chemical composition of the solid body inevitably the material mechanical
properties, including the appearance of point defects due to the origination of con-
centrators of stresses in bonds (relation 2.7). The spatial and elastic waves appearing
in the solid body under the effect of external forces alter the crystalline structure. But
originating and moving dislocations alter the crystal properties most. It is apparent
that the metric of microprocesses is not a still image; it is a changing structure of the
complex world.
These phenomena are studied by a special sphere of physics of solids; it is the
solid body dynamics. This sphere comprises the classic and quantum mechanics of
collective movements of atoms in the perfect crystal, the dynamics of defects in
the crystalline lattice, the theory of interactions crystal with various physical fields,
such as thermal flows, electromagnetic and other types of emission, description of the
physical mechanisms of strength and plasticity of solid bodies [12]. The dynamics of
crystalline lattice perturbations in the solid body treat various oscillations subdivided
3.5 Dependence of the Crystalline Lattice Parameters on Dynamic Factors 91
into acoustic, optical and electromagnetic polarization oscillations. Each of the listed
oscillatory process has its own frequency and dispersion relations making up most
essential characteristics of the frequency spectrum.
The dynamic processes in solid bodies result in the microparameters included
into various calculation relation as constants characterizing those or those properties
materials which do not belong to them. It leads to the mismatch between the theo-
retical conclusions and the relevant experimental findings. The methods of physical
and chemical analysis of solid body surfaces serve to validate the microparameters
of substances a using fine physical experimentation [13]. Famous German tribologist
H. Czichos shows the scheme of these studies (Fig. 3.9).
The scheme of in Fig. 3.9 reflects the principle of these methods which imply
the exposure the surface of the material in question to a definite type of emission of
X-rays, electrons, ions and others. The task of the primary emission is to excise atomic
levels in the elements in question which, in their turn, emit the excessive energy. The
typical emission provides the information about the nature of the emitting atom,
their chemical environment and the specific structural features of the surface under
study. A number of authors [14, 15] point at the necessity to take into account the
effect of thermal fields on the structures of substances, as well as bonds modifying
these structures under the thermal factor effect together with the macrocharacter-
istcs of materials involved in friction. The description of temperature effect on shear
stresses in metals and allow as an example of the successful theoretical model com-
bining the crystal parameters with the effective dynamic factors [9]. The analysis
of the experimental of dependencies of displacement stresses on the temperature of
the monocrystal Mg and Li-F (Fig. 3.10) permits to assume the following simple
dependence for their description:
G s = G 0s eBT T , (3.98)
G s b2 kT
= . (3.99)
2 d D
In accordance with equation (3.60) the parameter d of which can be assumed
equal approximately by the order of magnitude to the crystalline lattice period d, and
= d /t, expression (3.99) is simplified as follows:
Gs 2
b = kT,
2
from which it is easy to find that
"
2 kT
b= . (3.100)
Gs
Using empirical relation (3.98), let us represent formula (3.100) in the following
way: "
2 k 1/2 BT T
b (T ) = T e 2 . (3.101)
G 0s
This equation establishes the regularities of the temperature effect on the Burgers
vector. Formula (3.101) splits into two factors, the firs being constant for this crystal,
3.5 Dependence of the Crystalline Lattice Parameters on Dynamic Factors 93
while the second representing a simple enough function with only one variable T . The
simple mathematical dependence b(T ) permits to apply such relations to validation
of calculation of the mechanical, physical and chemical characteristics of solid bodies
exposed to external mechanical effects.
References
1. Ch. Kittel, Introduction into Solid Body Physics (Mir, Moscow, 1978), p. 791
2. A.M. Prokhorov (ed.), Physical Encyclopedia, vol. 3 (Sov. Encyclopedia, Moscow, 1992),
pp. 672672c
3. D.N. Lyubimov, V.A. Ryzhikov, Processes in Friction: Manual (South Russia State Engineering
University, Novochherkask, 2006), p. 147 (Phys. Chem.)
4. G. Gottstein, Physical and Chemical Principles of Science of Materials (Binom, Moscow,
2009), p. 375
5. D.N. Lyubimov, K.N. Dolgopolov, Difusive Processes in Friction (IP Bouryhin V.M., Shakhty,
2010), p. 148
6. L.D. Landau, E.M. Livshits, Statistical Physics, Part 1, (Nauka, Moscow, 1976), p. 421
7. F. Glensdorf, I. Prigozhin, Thermodynamic Theory of Structure: Stability and Fluctuation (Mir,
Moscow, 1973), p. 280
8. D.N. Lyubimov, K.N. Dolgopolov, Modern Tribology (Selected Chapters) (IP Bouryhin V.M.,
Shakhty, 2010), p. 181
9. R. Kana, (ed.), Physical Science of Metals, vol. 3 (Mir, Moscow, 1968), p. 483
10. V.F. Kiselev, S.N. Kozlov, A.V. Zoteyev, Fundamentals of Solid Body Surface Physics (INBU,
Moscow, 1999), p. 284
11. G.S. Pisarenko, (ed.), Strength of Materials (Vyshcha Shkola, Kiev, 1986), p. 775
12. A.M. Prokhorov, (ed.), Physical Encyclopedia, vol. 1 (Sov. Encyclopedia, Moscow, 1988),
p. 638
13. Kh.X. Chikhos, System Analysis in Tribonics (Mir, Moscow, 1982), p. 348
14. V.I. Kostetsky, Surface Strength of Materials in Friction (Tekhnika, Kiev, 1976), p. 283
15. V.I. Kolesnikov, Thermophysical in Processes in Metal-Polymer Triobosystems (Nauka,
Moscow, 2003), p. 279
Chapter 4
Friction Microdynamics
Abstract Basic notions about physical and chemical interaction of solids surface
and microprocesses initiating and accompanying this interaction are propounded.
Analysis of phenomena arising as a result of tribosurface activation is given. The
probability of Lorentz relativistic effects of local time deceleration in friction contact
is discussed. The quantity order of this effect is estimated.
American physicist P. Bridgman, Nobel Prize winner, reckons, each new theory
supposes that at last it is exactly there is the happy theory which is to prove the
right answer. Following this reckoning and the above-mentioned apparatus of
solid body mathematical physics, let us try to describe the changes occurring in the
solid body structure under the effect of friction forces and the effect of observable
changes on friction forces. Let us try to preserve the style in which the contents are
presented in the preceding chapters.
The friction forces are fundamentally different by their physical nature from the
forces of characterizing or universal gravitation. The main difference is that they
depend significantly on the configuration of contacting bodies and the velocity of
their relative displacement [1]. There are tangential forces of resistance acting along
the boundaries of interface between solid bodies [2].
The solid bodies touch with parts of their surfaces making up the real contact area
AF which is smaller than the nominal contact area. The value A F and the kinetics
of its appearance are governed by the tribological properties of materials in tribounit
and the geometry of the contact surface. The analytic expressions for calculation of
AF are quite complex, that is why simple relations are usually used in practice, such
as the equations proposed by British tribologists F. Bowden and D. Tabor [3]:
N
AF = ,
Y
(4.1)
N
AF = ,
HB
where N load; Y yield limit of softer material; HBhardness of softer material
in the interface.
The friction force FFr is proportional to the contact real area [2, 4]:
Expression (4.2) was named the single term friction law. In the general case, the
friction force is the function of many variables: normal load N , sliding velocity ,
contact temperature T , contact time T0 in the environment, and other parameters of
external friction. In practice, the specific friction force Fn is used often equal to the
relation between FFr and the nominal contact area AN and still more often he friction
coefficient f which the relation between the friction force and the nominal load:
FFr
Fn = ,
AN
(4.3)
FFr
f = .
N
If the tangential force is applied to the statically loaded contact between solid bod-
ies, a small relative dislocation 0.11 m appears virtually instantly in the direction
of the force in effect. These displacements preceding sliding are reversible in some
cases or irreversible in others. It means that large-scale elastic plastic processes are
already underway before the contact sliding begins.
The friction at the sliding start is traditionally likened to the result of mechanical
interactions between micron-sized asperities on the interfaced bodies. In other words,
the friction as the force of resistance is due to the dissipative processes of engagement-
disengagement of microasperities and can be represented as the sum of friction forces
over micron-sized spots. This statement has acquired the name of the friction additive
law [5]. The schemes of elementary processes during engagement-disengagement of
microasperities in the contact are shown in Fig. 4.1 [3].
The processes of formation and separation of microcontacts comprise the follow-
ing sequence of main stages: elastic and plastic deformation of asperities, sloughing,
4.1 Friction Effect on Solid Body Surface 97
Fig. 4.1 Scheme of single event in friction process: a elastic deformation, plastic deformation,
ploughing; b adhesive bonding; c is the shear of adhesive bonds, restoration of elastic deformation [3]
and adhesive bonding shear. In accordance with this friction additive law the follow-
ing can be recorded [5]:
FFr = F1 + F2 + F3 + F4 , (4.4)
where A FFr the actual area of the dynamic friction contact; ACFr the actual area of
the static contact calculated with formula (4.3); the coefficient characterizing
the interface stress-strain state; f the friction coefficient.
As a rule, the coefficient varies within 3.327, still, the experimental data are
available proving that, at the friction coefficient f 0, 0.4, the value can be
considered close to 1 [3]. Hence, expression (4.5) can be written in the following
simplified form:
A FFr = ACFr 1 + f 2 . (4.6)
98 4 Friction Microdynamics
The real contact area expands in friction due to the changes in distribution of
mechanical stresses over the friction surface. Solution of contact problems in the
theory of elasticity [3] proves that the maximum deformation of the friction piece
evolves in the layer under the asperity. In the first approximation, the deformable
layer thickness is equal to 11.5 of the contact spot diameter. When the material
slides and rubs, strain stresses appear behind the microasperity and attenuate at a
distance 510 contact spot diameters. While statically the micron-sized asperities
on the tribosurface rest on the counterbody surface forming stationary contact spots.
The sheer force initially passes the re-distribution contact spots and makes the solid
bodies approach inducing the preliminary dislocation.
Statically during plastic deformation the stress-strain state in the contact between
solid bodies in the actual contact zone corresponds to the state result from indentation
of the ball indenter into the counterbody. Plastic deformation
appears in the surface
layer of the solid body with the layer thickness h 3.1 R (Rthe indenter radius).
When micron asperities move, the surface of the viscoplastic counterbody fails to
restore the original shape; therefore the counterbody response does not coincide with
the normal to the vector of normal load N . According to the Hertz theory, maximum
compressive stresses appear on the contact surface, while the maximum one way
directed tangential stresses appear somewhat deeper [3]. For instance, when two
cylinders have the contact width R, this depth is equal approximately to 0.8R. The
sign-variable tangential stress factor in rolling is an essential factor which appears in
counterbody closer to the tribosurface than the maximum one way directed tangential
stress.
When the contact between solid bodies is exposed to friction, the zone of maxi-
mum stresses in the counterbody shifts towards the tribosurface. It is shown in Fig. 4.2
in which the field of distribution of mechanical stresses is calculated for the cylinder
and plane interface [3].
The analysis of distribution fields of mechanical stresses in Fig. 4.2 evidences that
the maximum stresses in friction displace towards the tribosurface and may appear on
Fig. 4.2 Scheme of evolution of tangential stresses (in MPa) in cylinderplane contact: a in static;
b in friction. R Indenter width; traced zoneregion of maximum mechanical stresses
4.1 Friction Effect on Solid Body Surface 99
it. The mechanical stresses distort the crystalline lattice of the solid body surface layer
originating dislocations. Thus, the region of the maximum mechanical stresses in the
interface is the zone where the dislocations concentrate. The dislocation under the
effect of friction approach to the solid body surface; it is identical if the dislocations
appear on the surface. It is noted above [relations (2.23) and (2.24)] that the growing
number of dislocations augments the plasticity and reduces the yield range Y of
materials. It expands the contact real area in accordance with the Bowden-Tabor
formula (4.1).
I.V. Kraguelskii, the soviet school of tribology founder, and associates studied
the plastic flow of copper and steel specimens and established that the distribution
of the yield limit in the surface layer is ambiguous. Two layers are identified with
regularities of deformation processes which the authors called surface subsurface
layers [6]. It is shown that the copper surface layer extends to the depth 0.51 m
and is characterized by the exceptionally high density of dislocations close to limit.
The gradient of the yield limit is also exceptionally steep an amounts on the average
to 200 MPa/m. The subsurface layer is 50100 m thick and it is characterized
by the sparser dislocations and smoother yield limit gradient amounting tentatively
to 3 MPa/m. The surface layer of steel specimens at the identical depth had much
smaller yield stresses and the yield limit gradient had the opposite sign versus he cop-
per counterbodies. The contact discreteness dictates strong initial friction moments
and strong fluctuation and stresses in the subsurface layer of the specimens. It
results in the plastic flow, inhomogeneous work hardening of the metal. The plastic
zone depth is determined by the dimension of the real contact spots and by the spot
boundary conditions (the magnitude of tangential stresses on the tribosurface or in
the lubricating material layer) [6].
The tribosurface of solid bodies has always a vividly pronounced defective struc-
ture which contains virtually all crystalline structure imperfections (Sect. 2.3). When
the deep dislocations, the situation is aggravated intensifying the tribosurface
activity. Active regions appear in the surface and subsurface layers. They feature
a strongly heterogeneous structure composition making them considerably differ-
ent from the structure and the composition of the original material. The extremely
high surface concentration of dislocations mentioned above results in the fact that
the plastic deformation during interactions can reach tens of percent and more in
the actual contact area, while its rate amounts to 102 103 s1 . So much intensive
plastic shear strain results in the energy dissipation and deformation generating heat
inducing a considerable internal heating of the surface layer [7].
When tribocontact appears, the superactive tribosurfaces approach to so intimate
spacing that forces of adhesion come into action. Because the actual contact area
grows and juvenile surfaces appear, these forces augment many times compared
with the similar forces in the static contact bringing the surfaces still closer. The
force of friction perform the work which, in accordance with formula (4.3), is equal
to
A Fr = f N t, (4.7)
In accordance with the findings disclosed by B.I. Kostetskii in [8], virtually all
friction work is open for heat generation Q (over 90 % of the value A Fr (4.7)).
According to [9], the thermal flow through a single asperity (the contact spot) rough-
ness is determined by the formula:
qfc = E eq fa H , (4.8)
1
q= E. (4.9)
2
Equate the right terms in (4.8) and (4.9). Since by definition = FAFrF , and the
value A F can be found with the Bowden and Tabor formula (4.1), then:
= f Y . (4.10)
2Y (1 + ) G s
H = . (4.11)
E eq a
2Y (1 + ) G 0s BT T
H = e . (4.12)
E eq a
The diffusion flow generated by friction in accordance with (3.39) and (3.49)
decomposes into three components [14]:
J = Jc + Jm + J , (4.16)
where J is the total diffusion flow; Jc , Jm , J are the diffusive flows realign to the
gradients of concentration, temperature and electric potential, respectively.
After substitution into expression (4.16) the values of particular diffusion flows
it can explicitly be rewritten in the following way:
C c c
J = D + QT + F z eff , (4.17)
z kT 2 kT 2
where C the speed of light; Fthe Faraday number; z eff the effective value of
the transferred charge; Cthe diffusant concentration.
The diffusion flow value is much affected the substances structure in which the
mass transfer takes place. In accordance with the universal principle of energy expe-
diency, it is namely the structure that governs the physical and chemical mechanism
of mass transfer by diffusion. It is established in [15, 16] that the diffusion in friction
follows mainly the vacational and internodal mechanisms.
High intensity of diffusion flows makes the diffusion one of the most essential
phenomena accompanying friction and which determines the tribocouple friction
characteristics. The mass transfer influence friction and wear in a variety of ways
which are worth considering. Let us begin with the thermodynamic influence of
diffusion on friction processes.
Thermodynamics of tribosystem. The tribounit is the tribosystem configured in
a definite way. The system in the general case is a consistency of elements combined
together into a definite integrity and unity. The integrity (unity) of the object is the
capability of the latter to stand apart from the environment. The most significant
attribute implicitly included into the notion system is the structure governing its
integrity. The structure is an internal type of the system consistency determining
the unity of stable mutual links between the systems elements. L.I. Bershadskii
defined the tribosystem as the dynamic and dissipative system in which the energy
degradation is embodied and micromechanical motion occurs [17, 18]. Its carriers
are microvolumes and triboexcited materials and interphase boundaries opened to
friction activated flow of substance, heat, electricity, sound et cetera.
The apparatus of thermodynamics of inequilibrium systems are used more and
more frequently in recent decades to describe the tribocouples of various designs and
applications [19]. The reason is that the tribounit as the mechanical system is in the
state of constant energy pumping up by friction forces. Because the tribosystem
has no endless energy capacity, the tribocouple emits the accumulated energy in
some way after it achieves some critical value. The processes of energy emission
4.2 Diffusive Triboprocesses in Friction 103
The second principle of thermodynamics for the open systems is recorded in the
following way [21]:
dS = (dS)1 + (dS)2 , (4.20)
where (dS)1 is the entropy changes under the effect of processes within the system
(dS)2 and due to the exchanges with the environment.
The values in Eq. (4.20) are the following: (dS)1 is more than and (dS)2 less
than zero. It means that due to the exchange with the environment the entropy in
the open thermodynamic system, the entropy can become negative. It proves that the
degradation of the thermodynamic system can transform into the complex behavior
of its evolution [19, 22].
The stationary states in the open thermodynamics systems can be similar to the
equilibrium states mentioned above which are described by Onsager dissipative func-
tions (L. OnsagerAmerican physicist):
1
0 = L i,k i k ,
2
(4.21)
1
0 = Ri,k Ji Jk ,
2
1 dS
s = . (4.22)
V dt
This rate in the open systems is described with bilinear expressions in respect to
the flow of thermodynamic forces included into phenomenological equation (4.18):
dS
= Ji i + Jjj. (4.23)
dt
i j
Thus, the rate of entropy variations in the open thermodynamic system is deter-
mined by the interaction between energy flows. The forces due to the interactions
affect both flows. These effects obtained the name of intersecting processes exem-
plified by the Dufor diffusion considered above. The intersecting processes imply
the non-equilibrium transfer processes during which the flows Ji and Jk are due to
the thermodynamic forces k and i at i = k, respectively. The equality L ik = L ki
corresponds to the intersecting processes.
The tribocouple is a classic example of the open thermodynamic system. First,
the tribocouple has all attributes of the notion system because all most important
tribounit characteristics, for instance, friction resistance belongs to the tribounit as a
whole rather than to its parts. The friction resistance implies the collective qualitative
4.2 Diffusive Triboprocesses in Friction 105
tribounit characteristics or the capability to achieve the state with extremely weak
friction forces while simultaneously preserving the conditions of tribostrength or the
tribounits ability to resist the destructive friction processes. Second, a combined
effect of the mechanical, physical and chemical processes within a tribounit turn it
into an integral system.
The main channels of energy dissipation in the tribosystem are transfer of matter
and heat. In accordance with the earlier described bonding, the transfer phenomena
and the gradients of respective physical amounts, thermodynamic forces c and m
in the main energy dissipation channels of the tribosystem can be recorded in the
following way [23]:
C
c = ,
C
T
T = , (4.24)
T
where C is the matter concentration; T is the temperature.
The corresponding thermodynamic flows can be represented in the following way:
Jc = L c c = m,
JT = L T T = Q, (4.25)
tive gradient of mechanical behavior which is at the base of the present-day high
friction resistance of tribosystems [25, 26]. The third body appearance with the tri-
bobonds means that the friction coefficient and the wear reduce. The direct contact
between solid bodies is replaced with more favorable interaction between tribo-
surfaces through third bodies. The wear resistance as an essential characteristic of
materials is determined in many respects by the structure and duration of the third
body [2]. The tribology knows the following relation [27, 28]:
hm
I = kS , (4.26)
t
where I is the wear of materials; k S is the coefficient of filling of the tribocontact by
the third body; t is the duration of the third body; h m is the third body thickness.
The coefficient k S can be determined in the following way:
AF
kS = , (4.27)
A T.B
F
where AF is the tribocontact actual area; AT.B.F is the third body actual area.
The analysis of relation (4.26) and (4.27) leads to interesting conclusions. The
thicker the third body the sooner it and the friction parts wear away. At the same time,
the larder contact area the third body covers and the longer it exists the more favorable
conditions appear for the tribocouple to operate and the longer the steady friction
lasts the later the irreversible degradation processes begin. Thus, the tribosystem is
capable to undergo evolution with the most favorable conditions being the third body
appearance when the diffusion processes evolve to the maximum intensity.
The third body evolution proceeds though the phase of nucleation [12]. It is
shown in [29] that the third body appears initially in the tribosurface regions with the
strongest adhesion, for instance, over the boundaries between intergrain crystallites
(Sect. 2.4) (Fig. 4.3).
When the third body forms, the adsorbed atom (adatoms) jump from one adsorp-
tion center on the tribosurface to the other with the frequency exp(W/kT).
The atom stays in the bonded state in adsorption center.
The speed Jc of nucleation of the third body is determined by the surface diffusion
intensity:
Jc = c D D Nc n(t), (4.28)
where Deff is the diffusion effective coefficient taking into account the variety of
forms and mechanisms of this process; i , Ji are the flows of diffusing particles; h m
is the third body thickness.
It follows from relations (4.284.31) that the kinetics of formation of the third
body, hence, the variations of friction characteristics of tribocouples are determined
in many respects by the diffusion processes. It is established in [16] how the bonds
and the diffusion activation energy WD relate to the friction coefficient (Fig. 4.4).
Hydrogen-related wear. The hydrogen transfer in metals by diffusion plays a par-
ticular role tribology [30]. On the one hand, the kinetics of hydrogen penetration into
the crystalline lattice produces its effect because it is the lightest element of the peri-
odic system of chemical elements being highly motile. On the other hand, damages in
the structure of tribomaterials favor its penetration. The elastic and plastic tribodefor-
mation affects the intensity of interactions between tribomaterials and environment
Fig. 4.3 Nuclei of third bodies over boundaries between grains of crystallites: a appearance of
polymeric film; b concentration of lubricating particles over boundaries between grains of austenite
steel [29, 30]
108 4 Friction Microdynamics
augmenting the concentration of the particles adsorbed from the environment and
affecting the crystalline structure defects. The mechanical and thermal phenomena
in friction accelerate the release of hydrogen from lubricating and tribomaterials
into the tribocontact area. Thus, the external medium enters into the interaction with
transferred dislocations activated by the surface metallic layer intensifying both phys-
ical and chemical softening and adsorptive and diffusive hydrogenation processes.
The Cottrell atmosphere mentioned in Chap. 2 in which hydrogen dominates appears
leading to local overstresses in the tribomaterial resulting in the propagation of micro-
cracks.
It is assumed in [31] in respect of the hydrogen diffusion flow in the metal that
it consists of the electroactive and electropassive components. The electroactive
component is the directed motion of the ionized hydrogen (plasma, in fact) through
the regular metal crystalline structure. The electropassive components are produced
by the atomic hydrogen penetrating into the metal through its crystalline structure
defects. The most likely hydrogen in steels is the solid solution of protons interacting
with the electron cloud. The hydrogen can be in metals in the molecular form or as
hydrates and methane in hydride producing metals.
In accordance with the Fick law, the hydrogen diffusion flow is directed in response
to the environment temperature and nature. The effect of the temperature field on the
hydrogen concentration distribution is theoretically estimated in [31]. Equation (3.39)
is the following in the one-dimensional approximation
C c T W
D0 + = J0 e kT , (4.32)
x kT 2 x
Q
where z = xl ; y = CC0 ; = kT W
;p = W ; = CC0l ; = (l) (0); lthe
specimen thickness.
All physical values with the index 0 correspond to the tribosurface. The diffusion
flow J (x) can be represented in the following way:
(1 p)
J (x) = exp d x. (4.34)
x
0
D0 c0 e p (0)
J0 = (1 exp( p )) ,
l I (l)
exp[(1 p) ]
Jl = exp(1 p) 1 . (4.35)
(1 p)
The hydrogen diffusion flow follows the Arrhenius law (3.63). The mathematical
analysis of Eq. (4.35) permits to assume that there are maxima of hydrogen concen-
tration profiles in the metal [31]. Their appearance can induce secondary hydrogen
diffusion flows mentioned in [9, 14].
The motion of the secondary hydrogen diffusion can be directed towards the pos-
itive temperature gradient seemingly in contradiction to the heat and mass transfer
laws. This fact is treated in the monograph [31] as a variant of solution of diffu-
sion equations ant it was not scrupulously analyzed from the physical viewpoint.
Nevertheless, it is apparent that the negative temperature decelerates the secondary
diffusive flows. It is possible if the diffusive flow constants Jc in Eq. (4.16) excel the
similar flow values JT in the same formula.
As it follows from the Fick law in Eq. (4.17), the diffusion coefficient character-
izing the flow JT is equal to
c Q
DT = D 2 . (4.36)
kT
The distribution of hydrogen tribocouples determines the resulting flow J made
by differently directed flows Jc and JT having different signs:
c Q T C
J = Jc JT = D . (4.37)
kT x
2 x
where x is the diffusion layer thickness of the secondary flows; T is the tempera-
ture difference in the diffusion layer; C is the difference of hydrogen concentrations
in the diffusion layer.
The value x is actually the diffusion length which enables to rewrite formula
(4.38) in the following way:
D c Q
J = T C . (4.39)
2t kT 2
The above results give grounds to assert that formulas (4.374.39) provide a
satisfactory description of the processes of hydrogenation of metallic materials in
friction. The calculations and experiments have manifested that the amount of the
hydrogen diffusion grows as the function of load and test time, the hydrogen maxi-
mum concentration zone shifts deeper into the specimen. It is due to the mechanical
and thermal activation of materials in friction adding defects in the crystalline struc-
ture (particularly due to dislocations) thus accelerating considerably the diffusive
processes. Diffusive bonds as dislocations move are unambiguous and it is appar-
ent that this factor affects the kinetics of triboprocesses. Russian tribologist S.A.
Polyakov assumed that it was the main diffusion and dislocation mechanism of evo-
lution of tribosystems [24].
where jik = eilm lkS mS is the tensor of the flow density of dislocations; ik , lk
s
S
is the tensor of the density of dislocations; mS is the velocity of dislocations.
Equation (4.40) has the form of the continuum equation with the distinction that
the tensor of density of dislocations serves instead of the environment density [24].
This equation takes into account both the sliding and climbing of dislocations (see
3.8). Equation (4.40) discloses the physical sense of FrankReed-Herring dislocation
sources which have different velocity parameters and dislocation structure. Let us
consider the regularities of appearance of the dislocation structure in friction.
Tribosurface role. Large clusters of dislocations are needed to activate mechan-
ically the tribosurface. They appear at definite (critical) values of the load and speed
factor. B.V. Deryagin demonstrated that the clusters of dislocation would surface on
the solid body and induce its mechanoactivation accompanied by the exoelectronic
emission. This initial stage is believed corresponding to the friction with limited or
low-active lubrication. In these conditions the electron work depends on the normal
load and has different values during elastic deformation of the surface layer, when
unsaturated plastic deformation processes evolve intensifying the density disloca-
tions, and dynamic equilibrium is reached during saturated the plastic deformation
with nucleation and annihilation of dislocations [33].
For description of the kinetics of the dislocation displacement combination let
us see the following equation containing the velocity parameters in the implicit
form [24]:
D
= D + 1D 2D D D D 2
, (4.41)
t
112 4 Friction Microdynamics
Eq. (4.41) can be ignored. The physical sense of the coefficients D , 1 and 2
D D
can be analyzed using the diffusion and dislocation principles in Eq. (4.40). Let us
consider the stationary form of Eq. (4.41) satisfying the condition tD = 0. It yields
the expression for the density of dislocations:
1
D = D 1D 2D . (4.42)
D = 0D e mS , (4.43)
n
= 0D . (4.44)
hn
The physical sense of the parameter 1D in (4.42) corresponds to the ratio between
the sliding velocity c and the free run l of dislocations. The value c depends
substantially on the concentration of point defects in the material. The higher con-
centration accelerates the motion of steps on dislocations overcoming obstacles by
diffusion [34]. The tribosurface is virtually unlimited source and drain of vacancies
as defects most easily appearing in metals. Thus, the velocity c and the concen-
tration of vacancies grows as a function of approach to the tribosurface. With the
account of the above-said
c [Cv (x)]
1 = , (4.45)
l
where Cv is the concentration of vacancies; x is the coordinate normal to the surface.
The physical sense of 2 is studied by revealing the causes why the dislocations
leave the sliding zone. The cause can by the climbing of boundary dislocations. The
rate and the distance of climbing h n are found in the following way:
4.3 Motion of Dislocations in Friction 113
8C0 D C
n = ,
bb C0
(4.46)
2C
hn = ,
D bb
where (d/d)cl is the relative changes of the crystalline lattice constants when
dislocations climb; (d/d)x is the similar value at the depth x from the tribosurface.
The deviation of the theoretical dependence (4.48) from the experimental one
(Fig. 4.6) does not exceed a few percent.
Tribosurface damage. The coefficient D in Eq. (4.41) can be replaced with
expression D DD assuming that the density D grows due to the intensified
0
114 4 Friction Microdynamics
functioning of the source of dislocations. New dislocations appear when the points
of fixing of the dislocation loop come nearer (Fig. 2.8). For this case it is advisable
to group the coefficients D /0D , 1D and 2D into one coefficient k1 . If we ignore
the D D
2 and integrate the obtained equation, the result is the following:
D = 0D exp k1 t, (4.49)
W (P + p) V + We
C = C0 exp , (4.51)
kT
where W is the energy of formation of vacancies; P and p are external pressure and
internal stress in the crystal; V are changes in the crystal volume when the vacancies
appear according to relation (2.1); We is the energy relating to the additional work
of formation of vacancies.
4.3 Motion of Dislocations in Friction 115
Equation (4.50) with the account of (4.51) can be rewritten in the following way:
1 cr 1 W (P + p) V + We
t p = ln exp . (4.52)
k1 0D C0 kT
If the dislocation structures formed with the help of the mechanism described
with Eq. (4.47), it can result in the polygonal cellular structure. When the dislocations
climb, their walls can rupture due to the bending causing the microcracking [10]. The
stresses in the walls are sufficiently strong and have the order of magnitude 103 G s ,
where G s is the shear modulus. The osmotic force facilitates the rupture of the bent
wall; it appears when vacancies oversaturate and reach the value 1.6 N/m per unit
of the dislocation length. This mechanism of cracking can be called the dislocation
diffusion mechanism because the material loses quicker the continuum under the
effect of the dislocation dipole due to the wall rupture.
The dislocations accelerate as their density reduces (Sect. 3.4), the c D1 . It
would seem that the propagation of dislocations in sliding would result a new stage
of hardening of the surface layer. But it is easy to show that even when the sliding
velocity of dislocations increases to the value at which they detach from the Cottrell
atmosphere (about 103 cm/s), their concentration reduces due to the climbing which
quite effectively compensates the propagation of dislocations.
Let us write Eq. (4.40) in the expanded form and assume D = 0 and separate the
dislocations into two types: those climbing from the density n and those sliding c :
D c c n n
= . (4.53)
t l S l n
Reduce Eq. (4.53) to the stationary form assuming D /t = 0. Then express the
total density of dislocations tot. through n = tot. 0D and assuming approxi-
mately h n /l = 1, record:
c
cym = 0D + c . (4.54)
n
Because c is larger than n , then nc > 1 and acquires the value from 103 to 5.
Introduce the relation h /l into formula (4.54) where h is the distance the dislo-
cation has to cover to annihilate on the surface. The expression is the following:
c h
tot. = 0D + c , (4.55)
n l
4 2 2
= . (4.56)
G 2s b
D
= b. (4.57)
kT
Let us use the Hook equation = G s and transform (4.57) in the following
way:
D
= bG s . (4.58)
kT
Substitute the velocity of dislocations (4.58) into (4.56) to obtain the following:
4 2 2 D
= . (4.59)
G s kT
4.4 Relativistic Effects in Friction 117
d 4 2 2 D
= dt. (4.60)
G s kT
Ws
= 0 exp . (4.61)
kT
This equation characterizes the process of shear deformation of the tribopart
surface layer as the thermoactivated process with the activation energy Ws equal to:
4 2 2
Ws = Dt. (4.62)
Gs
Substitute expression (3.43) of the diffusion length L D into formula (4.62), then
4 2 2 2
Ws = L D. (4.63)
Gs
Ws = F D L D . (4.64)
4 2 2
FD = L D. (4.65)
Gs
The dependence FD (x D ) into formula (4.65) proves that the mechanical force
affecting the dislocations has a quasielastic nature. The stress is a relation between
the load N and the real contact area A F which, from the Bowden and Tabor equation
is equal to N /Y , then = Y . In this case, (4.65) is written in the following way:
4 2 Y2
FD = L D. (4.66)
Gs
kT
FD = . (4.67)
D
By equating the right terms of Eqs. (4.66) and (4.67) and taking into account
formula (3.43), the following is obtained:
118 4 Friction Microdynamics
kT 4 2 Y2
= Dt,
D Gs
or
4 2 Y2 3
= D t. (4.68)
G s kT
4 2 Y2 b3 1
= t 2,
kT G s
or
4 2 Y2 b3
= f rq . (4.70)
kT G s
Let us use the numerical values listed in [24] and relations (3.22) and (3.74),
calculate the Mach number M for some tribomaterials:
8 2 Y3 b2 f rq
M= = . (4.71)
c kT G 2s Gs
The M value is of the order of magnitude 0.1 for silver; hence, the order of
magnitude of the value used in Eqs. (3.76)(3.80) to increase the accuracy of
calculation of the motion of dislocations, is equal to 0.99.
Lorentz transformations. The correctness of application of amendment in
tribological calculation elates to the solution of the following problems:
1. Would expressions (3.75, 3.76) be the Lorentz transformations (H. Lorentz
Austrian physicist, author of the classic electron theory who developed the elec-
trodynamics of the moving media) with all resulting conclusions regarding the
motion of dislocations in tribomaterials?
2. The resemblance of Eqs. (3.75, 3.76) to the Lorentz transformations is formal.
Hence the question is if equations (3.77, 3.78) are truly devoid of the physical
sense or the STR effects appear in the tribosystem?
To answer let us consider the classic conclusion about the Lorentz transformations
which begins with the analysis of transformation of the Galileo coordinates [36]:
4.4 Relativistic Effects in Friction 119
x = x t x = x + t
or . (4.72)
t = t t = t
x = x + t,
t = x + t, (4.73)
= 1; = ; = 0; = 1, (4.74)
but in this case, relations x /t and x/t are unequal. If the x/t is the speed of light,
then it seems different in different counting systems contradiction to the structure
main postulates STR.
Einstein tries to find the solution when
x x
= = c ,
t t
x x + t xt + c +
= = x = , (4.75)
t x + t t + c +
c +
c = .
c +
If, by analogy with (3.76), the parameter is introduced into these equations, the
mathematical identity between (4.77) and (3.78) is apparent. The canonic Lorentz
transformations are obtained due to the identical speed of light in the vacuum in
120 4 Friction Microdynamics
accordance with the arbitrary counting system [20]. The rate of propagation of elastic
oscillations c during motion of dislocations is devoid of the fundamental property
of the seed of light constancy. Hence, the transformations of coordinates (3.76) are
including disregarding this fundamental experimental fact. It should be established
if the conclusions from the Lorentz transformations are applicable to the solid body
microdynamics.
German physicist G. Minkowsky, one of the founders of the STR, commented in
1908 the result obtained by Lorentz stated, According to Lorentz each moving body
should contract in the direction of its motion; if the speed ofmotion is equal to , then
the contraction should be proportional to the multiplier 1/ 1 c2 . This hypothesis
2
seems fantastic because the contraction of bodies should not be considered the result
of ephyr resistance or any such phenomena, it can be just considered as the gift from
above or as the phenomenon accompanying the motion proper.
Whence the following conclusion. The Lorentz transformations are incompatible
with the classic ideas of the space-time. According to Lorentz, the solid body with
the length l , stating in the system of coordinates k , acquires a new length moving
in respect to the k with the velocity in the system k:
2
l = l 1 . (4.78)
c2
Relation (4.78) is called the Lorentz length contraction. Absolutely hard rows
serve in the classic physics to measure distances by marking the standard length
on the rods. This length stays constant when the rod occupies a new position and
remains in it in time. Namely these postulates of the common sense are rejected
by the Lorentz transformations. Analyzing the length changes (4.78), we conclude
that it is necessary to admit its full dependence on the measured body velocity.
Entertain wrote, while the size of the ball (hence, that of any other solid body
of any shape) does not change in response
to motion along axes y and z, the size
along axis x contracts in respect to 1/ 1 c2 stronger as the grows. All moving
2
objects observed in the system at rest flatten at = c into flat shapes. This argument
becomes senseless for the velocities above the speed of light [37].
Relativism ideology. The metric of the relativistic space relates closely to the
notions time and simultaneity. Einstein said, We see that no absolute values
should be attributed to the notion of simultaneity. Two events observed concurrently
from one of the coordinate system are already not perceived as concurrent when
analyzed from the system moving in respect to the given system. He continues, If
the point A in the space where the clock is placed, the observer in the point A can
determine the time of events immediately close to A by watching the position of the
clock arms concurrently with these events. If there is clock in another point in the
space, then the events can be determined by the observer staying immediately close
to the B. but it is impossible to compare the event A with the event B unless further
assumptions are made; we have determined only the A-time and the B-time not
4.4 Relativistic Effects in Friction 121
the common A and B time. The latter can be done by introducing the definition
that the time the light needs to proceed from A to B the light needs to pass
from A to B is the time needed for the light to pass from A to B [37].
If two events in the coordinate system k occur in one and the same spot treated
with the time interval t , then these two events are separated in the system k with
the time interval t:
t
t = . (4.79)
1 c2
2
Fig. 4.7 Curved space-time metric under gravitation of massive bodies [38]
of the bodies and that of the sun equals to = 1.75 . This deviation was registered
during the solar eclipse of 1919 (Fig. 4.8) [39].
The external similarity between the curved space and the energy of the crystalline
space is amazing (Fig. 2.12).
American physicist and theoretician and Nobel Prize winner R. Feunman wrote,
the nature tells us that time is similar to space. The time becomes the space: they
should be measured by the same units Russian physicist theoretician O. Arsenov
tells of the mutual correspondence between the fundamental length of the physi-
cal space (the Plank length is 1.6 1033 cm) and the time quantum [40]. Einstein
asserted in general that the pas, present and future are just an illusion, though obses-
sive [37]. In other words, the STR ejects the universality of the present moment of
time and states that the simultaneity is relative and the time directions are identical.
Feunmans proof of this statement is his hypothesis stating that the antiparticle or
positron is a usual electron moving back in time for a moment. The signs of electric
charges of these particles indicate exactly the directions in time to trace the path
through Minkovskii space-time. This assumption served grounds for the mathemat-
ical apparatus which Feunman developed for the spatial time interrelation of the
quantum mechanics for which he was awarded the Nobel Prize highlighting for
the fundamental contribution into the development of the quantum electrodynamics
that had profound consequences for physics of elementary particles [41].
Relativist assessment of phenomena in tribophysics. Like the Einsteinian
space-time, the crystalline structure is different from the Newton homogeneous and
isotropic space by the assigned directions and particular points creating the power
fields which influence the motion of material particles in the solid body volume.
Chapters II and III sow that the motion of material objects in the solid body (diffu-
sive flows, vacancies and dislocations) obey both the crystal metric and act on the
4.4 Relativistic Effects in Friction 123
crystalline lattice with power fields deforming it. It is apparent the electromagnetic
quantum nature of the forces acting within and on the surface of solid bodies is
not identical to the gravitation which governs the metric of the universal space and
time. The forces of gravitation are present in the crystals, but because the subjects
of motion and the structural components of the crystalline space are so negligible,
they are small versus the forces of cohesion and they are justifiably ignored in all
calculations.
If the analogy between the SRO objects and the motion of dislocations in friction
are true, then it is justifiable to introduce relativistic amendments into calculations
of the micromechanisms of friction, wear and lubrication and to take into account
the relativistic effects when constructing the models explaining some phenomena
observed during friction. For instance, the extremely high degree of mechanoacti-
vation of tribosurfaces [8] resulting, in particular, in the appearance of self excited
states which can be explained by the tribosurface absorption of the energy of dis-
locations possessing excessive energy. According to Einstein, if the body releases
energy E than its mass drops as E/c2 . It is immaterial if the energy borrowed from
the body transforms into other types so we proceed to a more general conclusion:
the body mass is the measure of the energy the body contains [37]. This statement
provides ground for relativistic verification of formula (3.81), determining the mass
of the dislocation at rest of the singular length.
So, the time flow of the experimentation differs from the local time during which
the moving objects exist and which retards according to the STR (4.79). The time is
included into many physical laws and it is quite natural that the time dimensionality
effects as the evolution of various processes. This effect is most often insignificant
and it is justifiable to ignore this effect in the description of processes. However, there
is a category of physical phenomena when it is expedient to take the phenomenon into
account. It can be assumed that this effect intensifies the extraordinary physical and
chemical activity of the tribosurface. The super excited state of the substance from the
external observer view last longer due to the delayed local time, like mu-mesons. That
is why the tribochemical reactions manage to complete a new chemical compounds
manage to appear which would be unlikely to appear otherwise [8, 11].
The reasons are apparently equivalent to the direction of the present, future and
past time leading to the paradoxes contradicting to the causal principle. That is why
the physics employ the notion time arrow. The direction of entropy grows points at
exactly this state as the next event in the pair of adjacent events not the preceding one.
Many contemporary physicists believe that the entropy is the time arrow turning the
time into a simple sequence of states. American physicist, the Nobel Prize winner,
L. Cooper elucidates this statement in the following way [42], The idea that the
system changes during any physical process from the more ordered to less ordered
state provides us with the time direction that was missing before. The equation of
motion in the Newtonian mechanics is reversible. One way direction of motion of
planets around their orbits is in no way better than the opposite Yet I is clear that
the identified direction exists among other more complex events: it is easier to park
the car than to leave the parking, it is easier to smash glass than to fix it, it is easier to
scatter the cubes ten to assemble them, it is easier to kill tan to revive a human being.
124 4 Friction Microdynamics
If the system is ordered, its entropy is small; there are many ways to upset its order.
If the system is fully disordered (the entropy is great), it is had to find at least one
way to restore it into the original ordered state. It is easy to break the vase into tiny
fragments: any out of thousands of combinations on the rug represents the broken
vase But to restore the vase from fragments, each fragment is to be placed into its
own exact position; still it had bearing in mind the random motion of thousands of
fragments to place them into the necessary position. The assigned time direction is
explained in this way because it is hard to transfer the physical system he assigned
only possible state.
The fundamental theory of thermodynamics of open systems envisages the
possibility of reducing the entropy which we cursorily touched in Sect. (4.2). Equa-
tions (4.20)(4.23) confirm that it is possible to avoid the entropy growth by exchang-
ing the energy of the thermodynamic system with the environment. The entropy is
reduced more considerably during mass transfer processes. The more intensive the
mass transfer the less the entropy grows, and, following the logic of L. Cooper, the
more apparent the relativistic possibility of time retardation.
These abstract reasons at the first look were confirmed when S. Hawking
(S. HawkingBritish physicist) developed the thermodynamics black holes. When
the black hole interacts with the outer space, the entropy growth is zeroed in it and
around [43] virtually corresponding to the stop of time. It explains the observed fact
of the abnormal motion slowing of duct clouds around the assumed black holes.
O. Arsenov writes in this respect that the noose on the black hole cannot be tightened
into a single point. The thing is that the frozen star has so great field of gravitation
that the time nearby practically stops [40].
Thus, the regularities of time retardation during friction interaction between solid
bodies is determined b two fundamental theories: the special theory of relativity and
the thermodynamics of open systems. Te region within which these effects should be
most evident ate surface layers involved in friction. The tribologist would set them
into a particular category obeying specific laws due to the particular conditions of
their existence [3].
In fact, the dislocations accelerate in friction as much as they approach to the
tribosurface (see Sect. 4.3). It means that the Mach number of the dislocations and the
effect of the relativistic amendment effect (3.78) on the space-time parameters of
their motion intensifies. Correspondingly does the effect of friction of the relativistic
special effects, like the metric changes, time retardation and others. The surface
layers of solid bodies involved in friction exchange the energy actively with the
environment, so they become a classic example of the open thermodynamic systems
in which it is most probable to reduce the entropy growth. Based on the above said
let us consider the specific features of the processes evolving in the tribocontact.
4.4 Relativistic Effects in Friction 125
References
B.I. Kosteskii was the first to perform a profound physical analysis and advanced a
correct model of mechanoactivation of solid bodies [1]. The heat of friction deter-
mines the thermal activation of materials of tribocouples, which is accompanied by
nucleation, and exit of dislocations to the tribosurface. When dislocations saturate the
surface layers of tribopieces, the potential barriers, hence, energy of activation reduce
either in respect to the physical and chemical processes evolving in the materials.
The climbing of dislocations is believed the most typical surface structural tribo-
process [2]. It results from the phenomena in the Kottrell atmosphere. This process
leads to the growth of dislocation loops, which create fascinating structures like the
vacation disks on the tribosurface. Figure 5.1 shows the photographs of the disks on
the polycrystal tribosurface made with the scanning electron microscope.
The energy reduction of the barriers for sliding and climbing of dislocations
resulting from mechanothermal activation of the surface layer on the tribosurface
is similar to the weakening of bonds between structural elements of tribomaterial.
Acceleration of dislocations when approaching to the tribosurface proves indirectly
the changes in properties of the surface layer (4.3) indicating sparser dislocation
density. The metals with polycrystalline structure manifest the so-called metallurgi-
cal effects due the activating triboeffects [3]. They lead to the change of grain size of
crystallites, relaxation of stresses in friction, growth of the surface of the intercrys-
tallite boundaries, increase of the adhesion component of the force of friction. The
grains appear reducing the metal resistance to shear deformation.
Figure 5.2 shows the findings of the study of the effect of intergrain boundaries
on the copper friction characteristics. The polycrystalline copper indenter moved
in the direction perpendicular to the boundaries between grains on copper bicrystal
consisting of a pair of grains with the crystallographic orientation (111) and (210).
Since the crystallographic plane (210) possesses larger energy surface than the plane
(111), the friction coefficient grows in leaps when crossing the boundary through
the grain section. The discovered effect appears when the indenter moves in both
directions. The boundaries between grains of crystallites are characterized by the
specific friction coefficient value.
5.1 Mechanoactivation of Surfaces of Tribocouples 129
Fig. 5.2 Friction coefficient change during indenter transit through boundaries between copper
grains with crystalline orientation: a from grain (210) to grain (111), b in reverse direction [3]
= 0.01qhq
W = 0.01E eq f a H (T ),
or, from (4.12): (5.1)
W 0.02 f Y (1 + ) G 0s eAT .
where, in accordance with the designation in formulas (4.9)(4.12): qhq is the heat
quantity passing through the contact spot; E eq is the thermal equivalent of the
mechanical work; f is the friction coefficient; a is the temperature conductivity;
H is the contact spot microhardness; is the Poisson coefficient; G 0s is the mod-
ulus of displacement at T = 0 K; BT is the empirical constant from relation 3.100;
T is the temperature.
Formula (5.1) has a rather simple mathematical form convenient for practical use
because all physical values in it are listed in the commonly accessible tables as well
as the experimental parameters having precise physical sense.
The energy accumulation process W is accompanied with formation of a spec-
tral structure on the tribosurface consisting of the crystalline structure surface defects
emerging on the surface. According to the terminology introduced by B.I. Kosteskii
it is named the ultradispersed microstructure, while the process of its forma-
tion is called the structural activation surface. The value of the stored energy
depends on the bonging energy released because of formation of the ultradispersed
microstructure. The division of the activation tribosurface into the structural and ther-
mal is conditional. The ultradispersed microstructure formation is determined by the
kinetics nucleation and movement of the crystalline structure defects towards the
tribosurface and relates to tribothermal activation of the tribomaterial. It is exactly
why B.I. Kosteskii introduced the term structural thermal tribosurface activation
into tribology.
130 5 Plasma Triboprocesses
5.2 Triboplasma
The friction heat sources act as the actual contact spots called hot spots [4]. The
tribomaterial transition from the initial steady state into the triboplasma is similar to
the changes in substances during heating. As the temperature grows, the solid body
melts and then evaporates. If the temperature continues to grow, quite a large gas
atom ionizes. A new high-energy state or plasma appears with approximately equal
numbers of positive ions and electrons determining its quasineutrality.
Plasma physics. The term plasma is used in physics to designate the substance
quaternary aggregate state [5]. Plasma in nature has a variety of forms (Fig. 5.3). The
ionosphere exists at the altitude 70500 km; it has the concentration of particles about
1012 m3 , its thermal energy is 0.2 eV. The solar wind is the terrestrial plasma stream
with the parameters n 106 107 m3 and thermal energy kT 10 eV. The solar
crown surrounds the sun and it has plasma density n 1014 m3 and the thermal
energy 100 eV. The density of electrons in the white dwarf star is approximately
1035 m3 , the thermal energy is above 200 eV, etc. the intensive research in the sphere
of plasma physics originated in the considerable degree from the thermonuclear
synthesis problem to solve which it is necessary to create and arrest the hot (almost
stellar) plasma.
The plasma electrons and ions move together and interact through long-range
coulomb forces which diminish in accordance with he inversely squared distance
between particles. The displacement of charged particles induces electric currents
and the Lorentz forces affect magnetic fields thus the particles additionally. Various
collective processes of motion appear in the high-energy capacity system, which can
be exemplified by the wave phenomena [6].
The screening of the applied electric potential is one of the fundamental plasma
properties. If a probe with applied potential is introduced into the plasma, its
components are attracted or repulsed in response to the potential sign. Thus, the
plasma strives to screen off the electrostatic perturbation the potential sign induces.
The screening typical length can be estimated. Assume that the ion density in the
5.2 Triboplasma 131
Fig. 5.3 Various plasma types on nkT diagram [5]: n mean density of plasma particles, R D
Debye radius, W f Fermi energy
or E = ,
(5.3)
(0 , E) = 0 2 = ch ,
e2 n 0
ch = e(n e n 0 ) = , (5.4)
kTe
2 = ,
R 2D
1 1
kTe 2 1 kTe 2
RD = = 7.45 10 3
. (5.5)
n e e2 ne e
where T is the plasma temperature; n is the mean density of particles in plasma [8].
If the initial gas volume in which plasma forms exceeds 4/3 R 3D this plasma is
considered quasilinear, if V pl < 4/3 R 3D , then the plasma is a set of independent
charged particles. The number of electrons in the Debye sphere is equal to
3
kT 2 1
n R 3D = n 2. (5.8)
e2 e
Relation (5.8) in the theory of plasma obtained the name of the parameter of
perfection. If the plasma density grows while the temperature remains constant, the
parameter of perfection reduces.
The collective motion of charged particles reflects another fundamental plasma
property. The coherent motion of charged particles relates to the appearance of waves.
If the wave phase velocity ph exceeds slightly the thermal velocity T of particles,
then the wave propagates through plasma without attenuation or amplification. When
the values ph and T are comparable, the energy exchange between waves plasma
particles is probable. L.D. Landau discovered the specific mechanism of wave atten-
uation. Landau implied by attenuation the interaction between waves and particles,
which does require collision of plasma particles.
Triboplasma specific features. The state of the matter named triboplasma
is postulated in [4, 9, 10]. Nonetheless, the triboplasma is the fact discovered
experimentally rather than a hypothetical something. Its existence is proven by
the mechanical emission of charged particles from the tribosurface affecting the
electromagnetic fields (the field effect) in the tribocouple and thus its parameters
[11], the abnormal intensification of the chemical activity of tribomaterials [4] and
many others. The triboplasma implies in general the energy clots, which transform
the substance surface layer into the tribocontact. The triboplasma is unstable like
other plasma types and it has short life time about 108 s. Many mechanisms of
tribochemical transformations are written off to origination and evolution. For
instance, the processes of tribocoordination are described in this way; these processes
5.2 Triboplasma 133
lead to the appearance of lubricating structures like surfing films [10, 12]. The tri-
boplasma duration and the tribounit closedness to analytic instruments impede the
triboplasma research.
An effort to study the substance plasma state by measuring diffusion constants
with radioactive indicators is made in [13]. To this end, the distribution of radioac-
tive elements was investigated in time through the specimen volume. The obtained
diffusion coefficients were compared with the values established by measuring the
ion conductivity. It is found that the results obtained with both methods correlate
well thin the experiment accuracy range.
The method is advanced in [14] to determine the diffusion layer thickness on
the tribosurface with the unique method of X-ray spectral fluorescent analysis [15].
The measurement results served to find the diffusion coefficient with the help of
relation (3.43).
Triboplasma model. Let us assume that the diffusion coefficient De on the surface
layer of the abradable solid body can be determined experimentally. Assume that the
Debye length calculated with formula (5.7) governs the triboplasma parameters. It is
apparent that friction is unable to ionize the substance completely as if it occurs on
the stars or during the nuclear explosion. Hence, the triboplasma should be referred
to the so-called imperfect plasma for which Eq. (5.8) is he following [16, 17]:
n R 3D = 1. (5.9)
L
1
De = f (x)d x, (5.10)
L
0
where L is the tribolayer of the tribocouplethe diffusion length; f (x) is the function
of the change of the diffusion coefficient.
The substance active states originating in friction are characterized by the maxi-
mum diffusion coefficient D0 rendering the states unsteady. They attenuate quickly
and return to the solid body unexcited state. Hence, the friction should be accompa-
nied by the value D0 abrupt drop, the function f (x) is the following:
134 5 Plasma Triboprocesses
The substitution of the value f (x) from formula (5.11) into (5.10) yields
D0
De = (1 e D L ). (5.12)
D L
D0 here first corresponds to the value D in the actual contact spots, second, it is
the diffusion coefficient corresponding to the triboplasma; D is the logarithmic
attenuation decrement of the diffusion coefficient.
1 D0
D = ln , (5.13)
Ld DT
D0
De ln = D0 D T . (5.14)
DT
Since the plasma diffusion coefficient D0 is much times larger than the value DT
(D0 DT ), then (5.14) can be rewritten as
D0 D0
ln = ,
DT De
or (5.15)
D0
DT = D0 exp .
De
D0 W
= . (5.16)
De kT
Then, using the Eyring formula (3.65) in which the structural triboplasma factor
d is substituted with the Debye radius R D , while the exponent in relation (4.13) can
be expanded into the Maclaurin series due to the smallness of difference (W Q)
only the second expansion term m can be taken. After transformations, expression
[17, 18] yields
R 2D
D0 = (Q W ), (5.17)
h
R 2D
D0 = Q . (5.18)
h
Let us return to relation of perfection parameter (5.9) from which the following
follows
1
R 2D = . (5.19)
n RD
Let us substitute the value R 2D from (5.19) into formula (5.18) and obtain the
following:
Q
D0 = , (5.20)
n h RD
Q
RD = . (5.21)
h n D0
By combining the constants into a separate factor, rewrite the relation for D0 :
2e Q
D0 = . (5.22)
h k nT
2e
Let us designate the constant h k made up by the fundamental physical con-
stants with a1:
2e
a1 = , (5.23)
h k
then
Q
D0 = a1 . (5.24)
nT
136 5 Plasma Triboprocesses
Following the logic of the performed transformations, let us introduce one more
constant and designate it through a2:
2e
a2 = a1 k = k. (5.26)
h
After that relation (5.25) can be written as
i
De = a2 T. (5.27)
n
The value i is equal to the relation QW , which characterizes the degree of substance
ionization and shows how much the substance triboplasma energy is more than that
of the substance in the steady state. It assumed in [19] that the physical values i and
the performance of the tribochemical reactions are close; a quire essential parameter
but extremely hard to estimate. The performance of the tribochemical reactions (x )
determines the portion of energy of the mechanical effect (friction) expended in the
tribosystem to initiate chemical reactions. It is reported in [10] that the performance
factor ranges from 0.01 to 0.05. The calculation of the value i for metal-polymer
tribocouples yielded the magnitude 103 allowing assuming that the values i and
x are close. Thus, it can be conclude that the kinetics of tribochemical reactions
are determined by relaxation processes in the triboplasma; the application of the
energy diffusion approach apparatus to the description of triboprocesses make the
calculation simple and accurate and check the parameters hardly accountable so far.
Relation (5.27) establishes the law of proportionality of the diffusion coefficient
and the square root in response to the temperature what is typical for the substances
in the gaseous state, that the triboplasma has the properties to gases. It enables
to simplify consideration of relaxation processes by applying the apparatus of the
kinetic plasma theory and the wave physics.
Triboplasma parameters. The mentioned approach enables to resolve the para-
dox of modern tribology. It is based on the tribosurface ability to emit photons and
charged particles (electrons and protons) with the energy 15 eV remaining incon-
siderably heated. Though the tribocouple maximum temperature does not exceed
400500 C, much higher temperature localizes on contact spots existing shortly
and moving with the collinear velocity [20]. The emission with spot of electron
energy of 1 eV is equivalent to the temperature reduction by 1.1 104 K [5].
An effort is made [17] to assess the triboplasma temperature. The substitution of
the value R D from (5.7) and Eq. (4.8) into formula (5.18) yields
(kT )2 + A a f H W kT 4 e2 n h De = 0. (5.28)
5.2 Triboplasma 137
k B T = q D0 , (5.29)
B D0
= . (5.30)
q kT
q c
B = 0.5 , (5.31)
m
where c is the free run length; is the mean velocity of particles.
For plasma in expression (5.31), let us substitute c with R D :
q RD
B = 0.5 . (5.32)
m
The relation RD is a fragment of time t p during which the substance particles are
with the Debye radius zone; it is similar to being in the plasma state. The comparison
of Eqs. (5.30) and (5.31) yields
D0 0.5t p
= ,
kT m
or (5.33)
2D0 tp
= .
kT m
To determine the time t p let us use the relation of the diffusion length, which for
the triboplasma transforms into
138 5 Plasma Triboprocesses
RD = 2D0 t. (5.34)
0.5
tp = 2
, (5.35)
D0 n 3
tp 0.5
t p = = . (5.36)
2
D0 n 3
0.25kT
m= 2
, (5.37)
D0 n 3
m 0.25kT
m = = . (5.38)
2
D0 n 3
r , t) + n (
n(
r , t) = 0,
r , t) (
(5.40)
t
5.2 Triboplasma 139
J
= n ,
(5.41)
r , t)
(
n (
r , t) = D (
r , t) n (
r , t) . (5.42)
1
Dn (
r) .
r , t) = n (
(5.44)
tp
The solution of (5.44) for the cylindrically shaped plasma with the radius r and
the constant D is the following:
2.4x t
n = n 0 I0 exp , (5.45)
r tp
where I0 is the Bassel function of the zero order (F. BasselGerman astronomer).
The particle containment time:
r2
tp = . (5.46)
5.8D
Relation (5.46) between the particle containment time, the diffusion coefficient
and the plasma flow radius r is actually general. The digital factor only changes
insignificantly in response to the plasma geometry.
The balance between energy and plasma corresponds to the equation derived
in [5]:
3 3 Vi
nkT + nkT
+ J Q = Q p
i j . (5.47)
t 2 2 i, j x j
where
is the velocity of particles in the diffusion flow; i j is the tensor of the
diffusion flow density.
The first term in the right part of equation (5.47) is the heat Q generated per unit
of time due to the collision of particles; the second term is the work of pressure p,
the third term is the heating of the plasma substance by the internal friction forces.
140 5 Plasma Triboprocesses
The left part of the first term contains the derivative of the thermal energy in time
(the power) and its generation per volumetric unit, and the second part describes
the energy losses by convection, the third part corresponds to the energy due to the
plasma heat conductivity p . Hence, the thermal flow relates to the heat conductivity
trough the known relation [23]:
When the convection losses are negligibly small in plasma, the heat generation in
the right part of the Eq. (5.47) equal zero:
3
nkT p (kT ) = 0,
t 2
3 p
If n = const, then kT = (kT ) . (5.49)
t 2 n
The value p /n is the temperature conductivity coefficient a (4.8). Hence, the
solution at a = const is the following:
2.4 t
T = T0 I0 x exp , (5.50)
r tE
r
tE = .
3.87a
The parameter t E is called the energy of particle containment time and is an
essential characteristic of mutual collisions of particles in the plasma flow.
The magnetohydrodynamic description of the plasma processes yields particularly
good results when the number of collisions between particles is large and when their
free run is short [5], i.e. in the case of the utmost suitable triboplasma description.
Assume ei designates the frequency of collisions between electrons and ions,
Te designates the thermal velocity of electrons, then
l
ei T e , (5.51)
2 R
where l is the free run length of the plasma particles; R is the radius of the power
typical portion.
If the Ohm law is adapted to the plasma hydrodynamics, then in accordance
with [22], the following relation can be written:
1
E
+
B
pi = J
, (5.52)
en
where E
and B
are the electric field intensity and the vector of the magnetic induction
of the field, respectively; pi is the gradient of pressure of the flow J
; is the plasma
5.2 Triboplasma 141
viscosity = m e ei e2 n 1
e ; e is the electron charge; n is the density of electrons;
where B,
E
are the vectors of induction and intensity of the magnetic and electric
the indexes e and
fields, respectively; e
B is the singular vector coinciding with B,
i relate to electron and ion, respectively; r L is the Larmor electron radius; k is the
Boltzmann constant.
While the first term in the right part of Eq. (5.53) an be ignored, the diffusion
coefficient of plasma particles D is in accordance with Fick law equal to
Ti
D = r L2 ei 1 + . (5.54)
Te
Yet, the first term of equation (5.53) is not always negligible little. For instance,
when the plasma is configured horizontally due to the different conductivity, the
separation of charges because of the drift is not fully eliminated by displacement of
charges along magnetic power lines, so the
electric
field E due to induction processes.
n k (
r
k t) ,
r , t) = n k exp i(
(5.55)
and the frequency k . Respectively, the total number of particles n per volume unit
is the following:
r , t) = n 0 (
n(
r , t) + n k (
r , t). (5.56)
k
r
k t) ,
k k
142 5 Plasma Triboprocesses
n
+ n
= 0. (5.57)
t
The frequency k is a complex value expressed by the relation
k = kr + ik . (5.58)
where kr is the real part of the complex frequency k ; k is the imaginary part k .
With the account of (5.565.58) can write:
n 0 n k
+ + n 0 k + n k k = 0. (5.59)
t t
k k k,k
The averaging of Eq. (5.60) in time with the account of the complex nature of the
parametrically included frequency yields
k |n k |2 + n 0 Re(n k k ) + n 0 Im(n k k ) = 0,
kr |n k |2 + n 0 Im(n k k ) n 0 Re(n k k ) = 0. (5.61)
n 0
= ( n 0 ) = 0, (5.63)
t
and the flow of outgoing particles
J = Dn 0 = Re (n k k ) exp (2k t). (5.64)
k
5.2 Triboplasma 143
n 0 Im(n k k )
Introduce the parameter k : k = .
n 0 (Re(n k k ))
Then Eq. (5.64) becomes
k |n k |2 exp(2k t)
k
D |n 0 | =
2
,
1 + k
|n k |2
D= k . (5.65)
k
|n 0 |2 (1 + k )
The diffusion coefficient D is added into the Eq. (5.65) based on the analysis of
fluctuation losses.
Let us consider the case when the electric field E k of fluctuations of plasma
frequency has the electrostatic nature, hence, it can be expressed through the potential
gradient k in the plane wave approximation
E k = k . (5.66)
This field makes the plasma particles drift with the velocity k :
E
k B
i
e
B k
k = = . (5.67)
B2 B
where e
B is the singular vector with direction coinciding the magnetic field intensity.
This expression and the equation after it describe the fluctuation component of the
plasma particles normal to their flow. The substitution of (5.67) into first Eq. (5.60)
yields
e
B
k
n k = n 0 . (5.68)
B k
n 0 = pl n 0 x
, (5.69)
where x
is the singular vector, coinciding with the abscissa axis.
Then relation (5.68) can be transformed in the following way
n k pl y ek
= k = k , (5.70)
n0 B k k kTe
144 5 Plasma Triboprocesses
where k y is the y-projection of the wave vector; k pl is the value inverse to the change
in plasma density.
The value
kTe
k = y pl (5.71)
eB
is called the drift frequency.
If the complex frequency k = rk + ik is represented in the following way
k Ak exp (ik ) [5], the drift velocity of the particles is
kT n
k = i
l
B
e k
Ak exp(ik ). (5.72)
eB n 0
Then from (5.64) the equation of diffusion coefficient can obtained in the following
way in the following way:
2
kTe y n k
D= Ak sin k . (5.73)
eB pl n0
k
The coefficient of abnormal diffusion in the tribocouple surface layer grows in time
due to the fluctuation losses. In the final account, the term k > 0 begins to dominate
in equation and (5.64) and has the maximum growth tempo. Yet, the amplitude |n k |
of wave oscillations of particles due to the non-linear effects the plasma tends to
the limit value, which is by order of magnitude, is ( pl /x )n0 . Bearing this in mind,
relation (5.65) transforms into
k
D= . (5.74)
x2
of B and they are proportional to B2 , while the fluctuation losses are B1 . As the
magnetic field intensifies, the fluctuation losses decline gradually.
The anisotropy of diffusion coefficients leads to the appearance of the self-
coordinated electric field in plasma mentioned above. It is not always identical to the
electrostatic field and induces eddy currents. The latter accelerates the leveling of
the concentration of charged particles. The ambipolar diffusion is the joint transfer
of ions and electrons when their concentration is similar towards reduction of their
concentration. The diffusion in plasma is rarely ambipolar. The deviations occur due
to the spatial anisotropy and the diffusion coefficient of the diffusion flow compo-
nents. In the general case, the rule of equal divergence (the scalar field) of diffusion
flow of ions and electrons [18].
The gas plasma contains also the triboplasma in which the particles perform
longitudinal oscillations of definite frequency called Langmuir waves, in addition
to chaotic thermal motion of particles [5] (J. LangmuirAmerican physicist, the
Nobel Prize winner). The Langmuir waves propagate with the frequency p called
the plasma frequency:
4 ne2
p = , (5.76)
me
where n is the density of charged particles; e is the electron charge; m e is the electron
mass.
The separation of the value n from formula (5.76) and its substitution into
Eq. (5.27) yield
4 e2 i
De = a2 T. (5.77)
m p
i
De = a3 T, (5.79)
p
respectively:
i T
p = a3 . (5.80)
De
Thus, the equations of diffusive mass transfer together with the equations of mag-
netic hydrodynamics have yielded the relations permitting to assess the theoretically
the most essential triboplasma parameters, such as temperature, Debye radius, dif-
146 5 Plasma Triboprocesses
fusion coefficients and plasma frequency. Together with experimental data, these
equations provide an adequate physical model of the substance state.
The preceding section manifests that the triboplasma is a complex dynamic system of
mobile electrically compensated positive and negative charge. This physical system
is an unsteady fluctuation structure in which gradients of densities and temperatures
appear inducing various flows making the physical system to transform into the
steady state. It is identical for plasma to relax from the transformation and restore
the original aggregate state.
Therefore, let us substitute fluctuation Eqs. (5.58) and (5.57) into the equation of
continuity:
n
+ n + n = 0. (5.81)
t
Then let us linearize [22]:
n 0
i n + dr + i n 0 dr = 0, (5.82)
r
where i is the imaginary unity; is the wave vector; dr is the drift velocity of plasma
particles; is the effective (averaged) frequency.
Equation (5.82) is recorded in the approximation coincidence vector of the drift
velocity of the with the external magnetic field power lines. The magnetic field
separates the triboplasma, so in further description, it is necessary to switch over
from considering the plasma as a homogeneous electrically balanced substance to
its ion-electron structure. Since the density of electrons describes the Boltzmann
distribution, then
n e e
= . (5.83)
n0 kTe
d e
ne m e = pe en . (5.84)
dt
Expression (5.84) can be rewritten in the complex form [24]:
i n e m e e = i( pe + en 0 ), (5.85)
where e is the electron charge; pe is the pulse of electrons in the perturbed state; e
is the drift velocity of electrons in the perturbed state.
5.3 Wave Processes in Triboplasma 147
If relation (5.83) is true in respect of ions, then, using the condition of quasilin-
n e n u
earity [24] = , the dispersion equation can be obtained:
n0 n0
2
e iT Te 5 e 2
1 + + qi = 0, (5.86)
/ Ti 3 3
(kTe ) dn e
e = ,
eBn e dr
d (ln Ti )
qi = ,
d (ln n i )
form. The cold plasma (triboplasma) may manifest five branches of oscillations in
the magnetic field [25]. During propagation of oscillations, there are one Langmuir
mode along the magnetic field and four transverse wave modes coexisting in different
frequency bands. The Alfvn waves in the low frequency band with the following
law of dispersion:
a
a = a 1 ,
cfr
H
a = , (5.88)
4 n i m i
eH
cfr = ,
m i c
where a is the Alfvn velocity; H is the magnetic field intensity; c is the speed of
light; cfr is the cyclotron frequency.
The Alfvn waves curve the magnetic field power lines. The external magnetic
field restores this distortion. In addition to the slow Alfvn waves, there can be fast
or magnetic sound waves.
Another example of the waves appearing in plasma during interactions with exter-
nal electromagnetic fields is electrostatic waves. The dispersion relation for this type
of plasma waves is often recorded through the dielectric permeability tensor compo-
nents:
x2 x x + 2x z x z + z2 zz = 0, (5.89)
where i , i are the resulting frequency of the wave vectors between interacting
waves.
5.3 Wave Processes in Triboplasma 149
Fluctuations and density of plasma charges produce the electric field inducing
the current tending to restore plasma neutrality. Due to the inertia of charged plasma
particles, they slip into the equilibrium position corresponding to the minimum
potential energy which, in the final account, results in the collective oscillations with
some frequency p . These oscillations can be represented as individual quasipar-
ticles with the energy p . For instance, the electron passes through plasma and
loses the energy in portions multiple of the energy and the plasmon p rather than
continuously [8, 28].
The theory of dispersion of surface plasmons is intricate but the gel-model of the
surface enables to obtain a simple relation to calculate the frequency of plasmons:
150 5 Plasma Triboprocesses
p
pl = (1 + 0.5qd + ) (5.91)
2
where pl is the plasmon frequency; q d are the dipole moments of the plasmon
localization region.
E
1 B
= , (5.92)
x c t
where E is the electric field intensity; B is the magnetic induction; c is the speed of
light.
The motion of triboplasma particles in electromagnetic fields can be considered as
the drift or the directed displacement of charged particles under the effect of various
inducing causes superposed on the main motion. For instance, the directed motion of
triboplasma particles under the effect of electromagnetic fields is imposed on their
thermal motion. The drift velocity is calculated the following formula:
c F
H
D = , (5.93)
q H2
where F is the force affecting the charged particle; q is the particle charge; H is the
external magnetic field intensity.
Correspondingly, the drift flow is
nc F
H
jdr = , (5.94)
H2
where n is the density of charged particles.
The particles can drift in the inhomogeneous magnetic field along and across the
field directions. The transverse magnetic field inhomogeneity implying the condensa-
tion and discharge of the power lines results in the Larmor orbit rotation (precession)
(J. LarmorBritish physicist) of similarly charged particles less in the weaker field
region than in the stronger field region [7]. It is equal to repulsion of the Larmor
5.4 Effect of External Electromagnetic Fields on Triboplasma 151
circumference center across the power lines towards the reducing magnetic field.
Actually, the force appears proportional to the magnetic field intensity gradient H
.
Correspondingly the drift velocity of is equal to:
r L H
dr = , (5.95)
H
where r L is the Larmor radius; is the normal component of the velocity of particles
(across the magnetic field power lines).
When particles move with the velocity along the curved magnetic field power
line with the curvature radius R, the drift appears with the direction determined by
the centrifugal inertial force m2 /R. The drift velocity is equal to
2
dr = , (5.96)
R L
ldr L
= , (5.98)
2
where ldr is the drift length.
The multiplier of Eq. (5.97) is
2
1
2
sin B = sin B d B = . (5.99)
0
Substitute relations (5.98) and (5.99) into formula (5.97) to obtain the expression
to calculate the Lorentz force;
qldr B L
FLor = . (5.100)
152 5 Plasma Triboprocesses
The product q ldr is the dipole moment pd , and then relation (5.88) can be
rewritten in the following way:
pd B L
FLor = . (5.101)
The dipole moment relates to the electric field intensity through the relation:
p
d = E, (5.102)
L EB
FLor = . (5.103)
The total force of the electromagnetic field affecting the macroscopic system with
the mass m is equal to [5]:
m EB
FLor = L . (5.104)
Thus, the combine electric and magnetic field effect on the particle produces the
ponderomotive force calculated with formula (5.106). This force induces the directed
displacement triboplasma making the mass transfer factor many times stronger.
This motion can be described with the magnetic hydrodynamics apparatus [22].
It is assumed that the typical distances and durations for the moving triboplasma are
much larger than the similar values (run length and time) than individual particles.
For this case, the Maxwell equation (J. MaxwellBritish physicist, founder of the
classic electrodynamics, one of the founders of statistical physics) can be written in
the following way:
div H
= 0,
5.4 Effect of External Electromagnetic Fields on Triboplasma 153
H
= rot
H
. (5.107)
t
Equation (5.107) are added with the equation of continuity:
+ div () = 0, (5.108)
t
where is the density of moving macroobjects.
The collective interaction of plasma components can be described with the mag-
netic hydrodynamics apparatus, which treats plasma as the fluid for which the Euler
equations are true:
Vfl
1 fV
+ Vfl Vfl = P + F , (5.109)
t
4
j = rot H,
c
Then (5.110) can be rewritten in the following way:
1
f FV = rot H
H
. (5.111)
4
Respectively, Euler equation ( 5.109) is rewritten as
V 1 1
+ (V ) V = P + r ot H
H
. (5.112)
t 4
ik
(V ) = , (5.113)
t xk
154 5 Plasma Triboprocesses
Unlike the canonic form of ik , this tensor in (5.114) is supplemented with the
tensor of stresses.
The energy reservation law in the classic hydrodynamics is expressed by the
following equation:
2
+ Wint = divW,
t 2 (5.115)
E = + Q ,
2
Here Wint , Q = Wint + /P are the internal and thermal energy as the function
of the fluid mass unity.
If the macrovolumes of the plasma conductive fluid are moved the ponderomotive
force, then, if the magnetic field exists, the fluid energy density should be supple-
mented with the term H 2 /8 and the energy density flow (the above mentioned
Umov-Poynting vector). Than the energy preservation, law magnetic hydrodynam-
ics is rewritten in the following way:
2 H2
+ Wint + = divW, (5.116)
t 2 8
1
E = + Q + H [ H ] .
2 4
1 E
r ot H
. (5.117)
c t
Because the rate of displacement of the model fluid is much slower than the speed
of light, then
ldr
1, (5.118)
c t
5.4 Effect of External Electromagnetic Fields on Triboplasma 155
Whence
H 2 c2 ,
H
= (H ) H (V ) H H div, (5.119)
t
1 V
div = .
t
Then:
H d H H
+ V = V. (5.120)
t dt
It follows from Eq. (5.120) that the magnetic field was as if frozen the relax-
ing triboplasma ad each power line shifts together with particles in this plasma or
quasifluid. Therefore, it is with while mentioning the relevant case of the tribo-
plasma synonym or magmaplasma. The value H/ characterizing the process its
displacement changes in every space point proportionally to the stretching of the
corresponding fluid line. The fluid line in hydrodynamics implies the ideal straight
line along which the particle of theses fluid displace.
Whence it can be assumed that the triboplasma moves without intersecting the
magnetic power lines. It is worthwhile to mention the following: the triboplasma
microvolume exist a short time corresponding to the contact sot life and which can
be considered as a highly polarized fluid favorable for friction between contact spots.
The theoretical model of the extreme state of the tribocouple surface layer or the
triboplasma discussed in the preceding sections permits to learn its temperature,
values of charges of particles and their mass. The advanced triboplasma energy dif-
fusion model answers the problem of the triboplasma components but it does not
permit to trek the kinetics of processes governing its evolution: to determine the life
of triboplasma particle, the duration of the recombination processes, the mechanism
of interactions between the triboplasma and the tribosurface material. The deficit of
experimental data does not permit to formulate a valid theory of dissipative tribo-
processes accompanying the surface tribochemical transformations and appearance
of third bodies. The closedness of the triboplasma by tribocouples, their short life
make nearly impossible to apply common analytical methods. The researcher can
judge about the triboplasma nature only by traces left by the triboprocesses. That
is the tribologists work like paleontologists restoring the ancient pangolin appear-
ance by the imprints of fangs on the rock. At present, it is a challenging problem
to develop a method of tribomonitoring of physical and chemical transformations in
triboplasma straight when friction is underway.
156 5 Plasma Triboprocesses
Fig. 5.6 Frequency spectra of electromagnetic oscillations of polymeric specimen. a before friction,
b during friction. Friction couple polyamide-6steel
electric field applied to tribocontact. Apparently, the positive potential applied to the
metallic counterbody amplifies the diffusion into the polymeric tribocounterpart [14].
It concerns, in the first place, the charged particles or triboplasma components. When
the direction of the external electric field changes, the diffusion is strongly weakened.
The electromagnetic spectra in Fig. 5.7 reflect it as the magnification of the amplitude
A of high frequency harmonics. The regularities of harmonics amplification A
in friction are shown in Fig. 5.7 in dependence of the direction and magnitude of the
external electric field in the tribocontact.
It is noted in [19] that calculation of the plasma frequency p with formula (5.80)
yields the numerical value p = 1060 MHz. During the experiment (Fig. 5.6) new
harmonics were registered in friction in the range 3040 MHz. It is good correlation
and another proof of the monochromatic approximation correctness in triboplasma
description.
This method has drawbacks due to the instability contact phenomena on the tri-
bosurface. Contact between elements of the tribocouple means fast recombination
processes strongly affecting the physical and chemical parameters of tribomaterials
and the kinetics of plasma processes. A tribometer was designed to study triboplasma
and eliminate these drawbacks (Fig. 5.8) [36].
Fig. 5.8 Scheme of experimental stand to study triboplasma: a experimental, b scheme of plasma
trap: 1 tribosurface, 2 plasma trap, 3 triboplasma particle, H
and E
magnetic and electric field
intensities, respectively; c torricellian dependence of current power i on load F
The stand is tribotester of shaft-insert pairs. The shaft is made from polytetrafluo-
rethylene block (PTFE). The counterbody is from steel 45. The tribocouple is placed
under the vacuum cap connected to the fore vacuum pump (Fig. 5.8a).
The tribosurface and the counterbody have the slots or plasma traps to catch the tri-
boplasma particles carried away by friction. The slots contain the sensitive electrodes
of the registering means of the spectral analyzer isolated from the counterbody metal.
Constant current source supplies potentials with different signs to the counterbody;
a magnetic field is created around the counterbody. The external electromagnetic
field generated in the tribocouple maintains the triboplasma substance in the active
state [5] (Fig. 5.8b). Additionally, electromagnetic oscillations of different frequency
within the range 010 GHz are applied to the tribocouple from the external generator.
The characteristic signals from the plasma trap are delivered to the spectral analyzer
which a set of individual harmonics by frequencies.
The counterbody is made of two parts to investigate the load variations. Both
parts are pressed to the tribocouple with a calibrated spring. The friction moment is
fixed by power changes of the electric motor so that the current changes in its coils
(similarly to the friction tester Timken (Barond Co., USA)). Figure 5.8c shows how
the current power i depends on the force N of clamping of the counterbody to
the shaft. It is obvious that the dependence of i on N is linear proving that the
measurement is valid. The friction parameters were checked at the sliding velocity
1 m/s and the load 10 N, each point was checked during 30 min.
The closeness of the problems to be solved makes the tribometer like the one with
the schematic diagram in Fig. 5.8 with the common tokomak plant used in nuclear
5.5 The Experimental Methods of Triboplasma Study 159
physics to generate and maintain the high temperature plasma (Fig. 5.9). That is why
the tribometer is called Tribocollahedron.
The tribocollahedron checks the nominal contact area at initial stage of friction
interactions in triboplasma based on the difference in measurement o triboprocesses
[10]. The triboplasma components get inevitably into the plasma traps provided on
the counterbody; electric and magnetic fields and the analyzer are connected to the
traps.
Since triboplasma is the electrically active substance state, the external electro-
magnetic field affects the substance and reveals those harmonics of the spectrum,
which relate directly to the triboplasma. This power field effects register the spec-
trum harmonics in the frequency band 10100 MHz and 11.5 GHz. The findings in
[5] show that megahertz frequencies in plasma are due to ion oscillations, the super
high frequency band belongs to electrons. The profiles of obtained electromagnetic
spectra reveal two vividly pronounced peaks both in the Megahertz and gigahertz
regions, which, in accordance with the theory of oscillations, evidence that there are
two types of oscillators in both frequency bands. These oscillators are apparently
electrons and differently charged ions (Fig. 5.10a).
The resonance phenomenon should be observed under the external force effect
every time when the external effect frequency coincides with one of those harmonic
oscillations belonging to the system proper [37]. Since both combined systems can
oscillate with normal frequency, so the resonance occurs with one of two frequencies.
This fact permits to verify the Eigen frequency of detected harmonics by imposing
the induced electromagnetic oscillations on the tribosystem (Fig. 5.10b, c).
The results of harmonics measurement in Fig. 5.10 reveal that the following Eigen
frequencies correspond to the oscillators in the megahertz region: the oscillator gen-
erating the first harmonics resonate at 40 MHz, the second can resonate at 20 and
60 MHz. The harmonics resonate in the gigahertz band at 1.2 and 1.5 GHz. The
harmonics are numbered from low to high frequencies.
160 5 Plasma Triboprocesses
(a)
The identified oscillators have different charged states well manifested under the
effect of electric and magnetic fields (Fig. 5.11).
The research is still underway and the curves in Fig. 5.11 and it is so far hard to
judge which harmonics relate to positively or negatively charged oscillators but can
be definitely determined how the changes in intensivity (amplitude) of harmonics
respond the friction resistance characteristics of the tribocouple.
The method we have selected to register the friction parameters the growing
current power i impairs the friction resistance characteristics of the tribocouple
because the current growth in the tribometer coils causes the amplitude of elec-
tromagnetic spectral harmonics to augment. The measurement results are shown
in Fig. 5.12.
It is established that in the megahertz spectral band the amplitude rise of the
first harmonic corresponds to the current power i and friction coefficient drop, i
demonstrate the inverse effect: its amplitude declines as the current power grows. The
first harmonic in the gigahertz band relates to the current power changes in a more
complex way: initially it demonstrates growth coinciding with the i reduction, then
this dependence becomes implicit. The second harmonic behaves within this band
like its megahertz counterpart.
5.5 The Experimental Methods of Triboplasma Study 161
(a) (b)
Fig. 5.11 Dependence amplitudes of harmonics on directions of electric and magnetic fields:
a and b in megahertz and gigahertz spectral bands in dependence on b in megahertz and gigahertz
spectral bands in directions; c and d, b in megahertz and gigahertz spectral bands in dependence on
magnetic field directions. 1 and 2 harmonics at direct field direction (plus on metallic counterbody;
NS magnetic field), 1 and 2 at inverse electric field polarity and inverted magnetic poles
Fig. 5.12 Dependence of amplitude of harmonics and friction resistance characteristics of tribo-
couple: a megahertz band; b gigahertz band (indexes 1 and 2 correspond to numbers of harmonics)
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Chapter 6
Wave Tribochemistry of Post-Plasma States
Summarizing the above said, note that virtually each triboprocess has a correspond-
ing wave, starting with Friedel waves in gel-models of surface states ending with
Alfvn waves in triboplasma. The processes of propagation of elastic deformation in
crystals evolve as undulations. The dislocations move in friction under the effect of
quasielastic force (4.66) and in accordance with the laws of classic mechanics and
generate waves with the frequency
2 Y
d = , (6.1)
GM
The idea that the triboplasma is the physical system consisting of many charged
oscillators permits to construct a rather correct theoretical model of its internal evo-
lution. The model is applicable to solution of these problems in which the triboplasma
corresponds to a definite wave process having the frequency p and the energy
W [1]. In accordance with the laws of wave mechanics, to describe the changes
taking place in a given physical system, let us introduce those values which remain
constant or very little in the given system state but they would acquire any value.
These values in the theoretical physics came to be called the adiabatic invariants I
[2]. The following relation can serve as this value: I = Wp .
The condition of these expressions in accordance with the adiabatic invariant is
the following:
dI d W
= = 0. (6.2)
dt dt p
ln W + C1 = ln p + C2 , (6.3)
W = p A5 exp C3 , (6.4)
whence
W
S= . (6.5)
B7 p
In accordance with the least work principle and based on relation (6.5), when tak-
ing into account the small dissipation energy corresponding to the contact spot con-
ditions, the triboplasma evolves towards the value p . Similar results are obtained
when studying how the ionization and substance relaxation time depends on the tri-
bocouple surface, which, using the Hamiltonian equation [3] can be written in the
following way:
T
dq d qd p
Tt = dt = dH
= , (6.6)
dp
dH
0
1 2 1 2
(x, t) = 20 cos t sin t, (6.8)
2 2
where 0 is the amplitude of oscillations; 1 , 2 is the frequency of harmonics; t is
the time characterized by the frequency w = 1 2 with the period T = 2/w .
The representation of plasma oscillations as the wobbling described by the func-
tion (x, t) agrees with the measured charge densities of the thermonuclear plasma
shown in the monograph [4] (Fig. 6.1) because the value (x, t) characterizes the
density of charges in particular.
Thus, the wobbling frequency w is at the same time is the plasma frequency that
can be calculated with the known formula [4]:
168 6 Wave Tribochemistry of Post-Plasma States
Fig. 6.1 Image of contours of equal charge densities in thermonuclear plasma [4]
4q 2 N
w2 = 2p = , (6.9)
Mp
h pl
where t = is the actual plasma relaxation time.
Hence,
2C
p =
t
or, in accordance with (5.80), it is the following:
i T 2C
a3 = .
De t
Then:
De
i =2 C . (6.12)
a3 T t
De
i = a4 C . (6.14)
T t
The parameter i (the degree of substance ionization) reflects the kinetics of trans-
formation of the tribomaterial aggregate state.
Relation (6.14) determines the optimum triboplasma characteristic ensuring the
process of post-plasma tribochemical reactions. Their evaluation with formula (6.14)
permits to establish the relations between the most essential parameters governing
chemical transformations: the transferred substance mass depends in accordance with
formula (3.37) on the diffusion coefficient, the relaxation time t and corresponding
plasma temperature T . The temperature affects both time t and the diffusion coeffi-
cient De . It can be assumed that there is some optimal value I at which the evolution
170 6 Wave Tribochemistry of Post-Plasma States
of post-plasma states leads to the appearance of third bodies with the relevant low
friction coefficients ad low wear levels. It follows from (6.14) that the I compa-
rable before with the efficiency of tribochemical reactions that the latter grow the
shorter the substance stays in the triboplasma state. In other words, the efficiency
of tribosystems rows as soon as the triboplasma transforms into steadier substance
state.
Let us consider the triboplasma on the solid body surface from the quantum stand-
point. Let us represent the triboplasma as the planar wave propagating in the semiin-
finite space. It is shown in [7, 8] that the frequency oscillations of plasmons reduces
after interaction with the solid body surface: s2 = 0.52p the solid body-evacuated
medium interface solid body-rarefied medium and 2s = 0.5(2p1 + 2p2 )the
condensed media designated with indexes 1 and 2. The frequency of oscillations
reduces because the plasma part of its energy is lost during interaction with the tribo-
surface. In the particular case, the frequency of surface oscillations s coincides with
the frequency Friedel oscillations (2.36), the surface chemical activity can augment
substantially due to the resonance effects.
Like any plasma, the triboplasma is a non-equilibrium system. The chemical reaction
in it evolves differently from the traditional chemistry canons [9]. The average energy
of molecules reagents and their products amount to 0.150 eV, therefore, the role
of nonelastic collision increases sharply in the plasma chemical system. The typical
durations of the physical and chemical processes come close to make impossible to
treat them independent. So it is better to consider multichannel alternatives of evo-
lution of tribosystems taking into account the interaction between channels and the
environment effect on the reacting subsystems [10]. We observed the same hierarchy
when analyzing Eq. (6.14) noting the interaction between three channels: diffusion,
temperature and time. This interaction creates optimal conditions by the criterion
of initiation of tribochemical reactions in order to distribute the charge densities
(q max), (Fig. 6.2).
The kinetics of plasma chemical reactions is described using the Pauli equation
taking into account the quantum structure of the energy of atoms and molecules [11]:
Ni
= i pi j p ji N (t) ch.r
i
Ni (t) + Ri (t), (6.15)
t
i
ith energy state; Ri is the speed of excitation of the energy level; i is the frequency
of collisions between particles.
In the general case, the coefficient of the rate of chemical reactions depends on
the section of the reaction, its energy and the function of distribution of reacting
particles by energy [10]. In order to initiate appearance of chemical compounds due
to the recombination phenomena in the triboplasma, the kinetic energy of plasma
components should be reduced in order to increase the plasma section of chemical
reactions. The latter is identical to the areas of denser electrons shown in Fig. 6.2 and
determined for plasma by wave equations (6.10) and (6.14).
The nonelastic collision between plasma components leads to the appearance of
complex ions and radicals; the dynamics of their appearance is described by the
kinetic equation [5]:
d
N (t , t) = k N 2 (t , t) km N (t , t)N (t),
dt
N (t , t) = N0 ,
t dS (6.16)
N (t , t) dt
0 dt
N (t) = ,
S(t)
where N (t , t)the surface density of ions and radicals at the moment of time t;
Sthe chemical compound appearing on the surface within the moment of time t ;
N0 the initial density of ions and radicals at the moment of time t = 0; N (t)the
observed concentration of ions, radicals and clusters.
The plasma ions and radicals vanish combining into molecules. This process is
limited by the rate of delivery of plasma components to the tribosurface active centers.
Two delivery mechanisms are most likely:
the diffusion which in Eq. (6.16) is characterized by the constant k D proportional
to the coefficient of diffusion De ;
the mechanical agitation of reacting substances taking place when the tribosurfaces
slip and cause the recombination of ions and radicals detached from different sur-
faces. The constant km proportional to the shear deformation takes this process
into account.
t
Wa (t) = Na0 (t)Wa (t) + Va ( )a (t )Wa (t )d , (6.17)
0
where Wa the adhesion energy; Na0 the initial density of adhesive bonds; a (t)
the function of distribution of the adhesive bonds; Va ( )is density of formation of
the adhesive bonds; Wa (t)is average the energy of the adhesive bonds.
172 6 Wave Tribochemistry of Post-Plasma States
where 1 and 2 are constants of reaction intensities; f 1 (x) and f 2 (x) are functions
taking into account the tribocouple design; A6 , A7 , B8 , B9 are the empirical constants.
The constants of rates of tribochemical reactions are determined from the
Arrhenius equation:
Wch
ch.r = 0 e kT , (6.20)
W1 = 1 Na s ,
(6.21)
W2 = 2 (1 2 Na )s ,
where 1 and 2 are the tribocontact geometrical parameters; s is the sliding velocity.
With the account of (6.19), (6.21), system (6.18) is reduced to the following linear
equation:
d2 N d Na
2
+ 2A + B Na = B Na |t , (6.22)
d d
1
where 2A = ,
+ W1 + W2 1 f 1 (x)A6
6.2 Post-Plasmatic States and Wave Processes Due Tribochemical Synthesis 173
W2
B= .
+ bW1 W2 1 W1 A7 1 f 1 (x)A6 1
d Na
If the condition A2 > 0, Na (0) = Na0 , d 0 = bW2 Na2 is fulfilled, the
=
solution of Eq. (6.22) is the following:
t t
Na ( ) = Na [ +c1 e 1 + c2 e 2 , (6.23)
where t11 = A6 + A26 B8 , t21 = A7 A27 B9 ,
t1 (N Na0 ) + t1 t2 W1 Na0 b t2 (N Na0 ) + t1 t2 W2 Na0 b
c1 = , c2 = ,
t2 t1 t2 t1
N = Na |t .
The changes in time of the mean energy of adhesive bonds depend on the nature of
tribochemical processes. The kinetics of generation and interaction of active centers
play a governing role.
For instance, when substance on the tribosurface is in the post-plasma state, the
dynamic equilibrium is typical between ionization of particles (appearance of active
centers) and their recombination (interaction) of the centers. The transition of the
triboplasma to the steady state is accompanied by the equilibrium disorder and dislo-
cation shift towards recombination processes. The dynamic equilibrium between ion-
ization and recombination at the post-plasma stage of evolution of materials ensures
a long enough stage of tribosystem evolution.
The chemosorption of reactive triboplasma agents precedes the tribochemical
interaction between surface layers. The analytical expression for the chemosorption
can be written in the following way [5]:
dC Wch
= k0 C(1 S) exp , (6.24)
dt kT
dC 2C
= D 2 . (6.25)
dt x
174 6 Wave Tribochemistry of Post-Plasma States
Wd 2C Wch
D0 e kT = k0 C(1 S)e kT , (6.27)
x2
where Wd is the energy of activation of diffusion processes.
The activation energies Wd and Wch have close absolute values [5, 13]; hence,
relation (6.27) can be rewritten as
or (6.28)
2C k0 (1S)
x2
+ D0 C = 0.
Equations (6.28) and (6.29) describe analytically the experimental data called in
[14] the friction oscillations of metal ion concentration in friction in the selective
transfer mode (ST) (Fig. 6.3).
Equations (6.28) and (6.29) are not limited by the selective transfer phenomenon;
they are rather general proving the universality of the effect of friction oscillations
of the concentration of chemisorbed substance in friction.
The solution of differential Eq. (6.28) can be written in the following way:
C0 cos (x L D ) = 0,
Substitution of (6.31) into the formula to find the diffusion length L D yields:
x = . (6.32)
8De t
k0 kT pl (1S)
Wd t = 1.26.
The chemisorbed substance enters into the chemical reaction; its kinetics is
described in the general form by the equation [5]:
dC Wch
= k0 C exp
n
, (6.35)
dt kT
C n1 = 1 S, (6.36)
k0 kT pl C n1
t = 1.26 (6.37)
Wd
k0 W pl C n1
t = 1.89,
Wd
or (6.39)
W pl C 1n
= 1.6 .
Wd k0 t
It follows from these equations that the relation between the triboplasma energy
and the diffusion activation energy (actually the energy of cohesive bonds) is constant
for the given friction conditions. Relation (6.39) is useful for the next theoretical
constructions.
2
+ x2 = 0,
x2
2
+ y2 = 0,
y2
(6.42)
2
+ z2 = 0,
z 2
2
+ 2 = 0.
t 2
= exp i (t r ) , (6.43)
providing:
2
2 = x2 + y2 + z2 = c2 . (6.44)
Let us use wave functions (6.45) to consider the essence of the realistic amend-
ments verifying the theoretical calculation of tribophysics. Let us assume the sta-
tionary wave functions of particles have all coordinates x, y, z the same but depends
on the time and equals . The second system of coordinates, x , y , z , t , moves in
respect to the first one in the direction of abscissa axis with the velocity . Then
the coordinates x , t relate to some space point through Lorentz x, t transformations
(4.77). The Lorentz transformations for the velocity is directed in the negative
direction of the axis x, time t relates to t with formulas (4.77), hence, the wave
function (6.45) is written in the following way [19]:
i i W0 t W0
exp W t = exp , (6.46)
c2
2
where W = Wint + 2m p
is the energy excess or deficit versus the energy at rest
W0 = mc2 .
In the general case, W p should include the kinetic atom energy and its energy
bonds
or excitation. It can be called the internal energy with the amplitude
exp i W p x px [19].
The dispersion equation considered above for particular cases of description of
waves in plasma are used together with Eq. (6.40) those from the wave physics.
The dispersion relations imply the integral solutions of the response functions
describing the response of the equilibrium stationary physical system to the external
effect. The dispersion relation reflects the analytical properties of the response func-
tions in the complex plane frequency registering it as the (the energy) dependence
setting a number of its limits. To derive a dispersion relation, it is unnecessary to
know the structure or the physical system dynamics. Such relations are based on the
general principle of causality: no physical event can affect the event in the past. In
wave physics the dispersion relation is the frequency dependence included into wave
Eqs. (6.43) and (6.45), from the wave vector , i.e., = ( ). Actually, Eq. (6.46)
belongs to the dispersion relations.
The key notion when analyzing the dispersion of waves are the phase and group
velocities of waves ph and g which coincide only at = c when ph = g = c.
These values in the anisotropic media differ both by magnitude and direction.
The KleinGordon equation is of definite interest because it is relativistic invariant
(O. Klein and W. GordonSwedish and German physicists) which describes the free
scalar physical field that in one-dimensional approximation is the following [2]:
d 2 A(x) m 2
= 0 2
A(x). (6.52)
dx2 (S D)2
The solutions of differential equation (6.52) differ strongly at > 0 and < 0 .
In the first case, Eq. (6.52) describes the sinusoidal wave and is the following:
d 2 A(x)
= 2 A (x) , (6.53)
dx2
2
where 2 = m
(S D)2
02 is the wave number.
The expression for 2 is a relation for the sinusoidal wave. The general solution
of wave equation (6.53) is the following:
where A8 and B10 are the constants determined from the boundary conditions.
Exponential wave appear in the tribosystem at the frequencies < 0 . Let us
introduce the positive constant 2 :
m 2
2 = 0 2
. (6.55)
(S D)2
d 2 A(x)
= 2 A(x) . (6.56)
dx2
The general solution of Eq. (6.56) is a superposition of two exponential functions:
A (x) = Ae x + Be x , (6.57)
The constant , which characterizes the reduction of the amplitude per length
unit, is called the absorption coefficient:
The value 1 is called the penetration depth. There is a similarity between the
values and the wave number for sinusoidal waves; the like similarity is observed
between the penetration depth and the wavelength . Expressions (6.53) and (6.55)
are a full dispersion relation for tribosystem elements.
6.3 Apparatus of Wave Mechanics for Description of Tribocouple Micromechanics 181
Let consider the instances of application of the wave physics apparatus to treat-
ing plasma and post-plasma processes in tribosystems. Let us consider the substance
transition into the triboplasma, then the post-plasma processes, and finally restoration
of the initial state. Let us equate the wave function describing one of the substance
aggregate states and to the wave function corresponding to the state into which sub-
stance transits the initial steady state.
Assume that the dislocations describe the behavior by some wave function 1 ;
it is represented by the plane waves with the frequency disl existing within the
interval of time 0 to t1 . Under the effect of friction forces, the substance surface turns
into the triboplasma; its existence is described too by the plane wave with the wave
function 2 and the frequency p within the interval of time t1 to t2 :
1 = 01 exp(idisl t1 ) ,
(6.60)
2 = 02 exp i p t2 ,
considering only real numbers of the obtained equation, the following can be
recorded:
X 1 cos disl t = X 2 cos p t
or
(6.61)
X1
cos disl t = cos p t.
X2
where X 1 and X 2 are the real parts of the amplitudes of wave functions 1 = 2 .
182 6 Wave Tribochemistry of Post-Plasma States
It is noted above that only an insignificant part of the friction energy turns the
tribocouple surface into the triboplasma corresponding to the condition X 1
X 2 .
Hence, the relation between the amplitudes X 1 / X 2 is rather large. It follows from
relation (6.61) that cos disl t is small. Therefore:
disl t ,
2
or (6.62)
disl .
2t
In accordance with relation (6.1):
2 Y
= ,
GM 2t
whence (6.63)
GM
t= .
4Y
The value cos p t is close to unity, p t 0, or, in accordance with (5.80) and
(6.63):
GMT
a3i 0.
De
Since the values a3, G, M, T differ from zero at the moment of time t, i = 0. In
other words, t corresponds to the particular moment of time (the singularity point),
after which the tribosurface substance leaves he initial steady state without transiting
yet in the plasma state. The substance begins to turn into plasma at the moment of
time t = t + dt.
The spontaneous concentration of the wave energy within a small space region
is the wave collapse. The latter appears in the plasma and sound waves and make
the process probable in friction. The plasma collapse is accompanied by the appear-
ance of the cake-like cavern or the reduced density in which the oscillating electrical
field gets locked with its maximum being in the center. The system becomes like
a black hole [18]. The triboplasma wave collapse alters significantly the tribo-
couple parameters. To assess its probability and aftermath is one of the challenging
tribophysical problems.
References 183
References
U0 (1 cos n)
U () = ,
2
(7.1)
U ()
p () = p0 exp ,
kT
Fig. 7.1 Dependence of surface potential S p and absorption on number of adsorbed particles and
scheme of orientation of their electric moments [2]
shows the curve how the tribosurface potential S p depends on the number of adsorbed
multipoles together with the scheme of their orientation.
The above reasons have significant limits determined by the complex structure of
the electromagnetic field on the tribosurface. Therefore, it is virtually impossible to
calculate the full surface potential energy with the account of the surface topology
excepting several simplest cases. The kinetics of appearance of molecular layers fol-
lows the quantum adsorption mechanisms treated in Chap. 2 based on the interaction
between adsorbate electron shells and the solid body gel-surface. Interaction between
atoms and molecules in the surface layer alters the surface structure and topology
created by the power field on this surface. The example in [3] shows the interaction
between the golden monocrystal and the common salt monocrystal surfaces where
interatomic forces begin to generate clusters on the golden surface consisting of
chlorine and sodium atoms. The forces of boning but the surface of gold and chlo-
rine and sodium atoms are different. After the electron structure change due to the
clusterization, the interaction between gold and chlorine atoms becomes dominating
when the chemical bonding takes place as a result of overlapping of gold d-orbitals
and p-orbitals with four chlorine atoms on the cluster surface (Fig. 7.2) [3].
The activation of the solid body surface by friction forces and transition of the
material into the triboplasma state expand opportunities of exclusively various chem-
ical transformations. Paper [4] shows that the frictionexcited surface acquires the
active enter or the mesoregions of abnormally intensive adsorption, the centers are
analogs of the cluster depicted in Fig. 7.2. The energy model of active centers is
treated in works [4, 5]. The adhesive center appears in the spots where dislocations
188 7 Antifriction Micromechanisms
Fig. 7.2 Contour map of binder orbitals of AuCl in AuNaCl (001) system. Full (dotted) lines
correspond to positive (negative) wave functions
emerge on the tribosurface and serves the region of intensive transfer of the material
producing the lubricating layer.
The motility of molecules in the lubricating layer stays longer the higher the
temperature, the lower the degree of saturation of the monomolecular layer on the
tribosurface and the fewer the hysteric obstacles to the molecules movement. These
obstacles may be, first, the micron-sized asperities on the tribosurface, and, second,
the adsorbed molecules. The motility maxima can be inhibited by chemical reactions
in the monomolecular layer resulting in complex molecules and their cluster.
The adsorption of the molecular structure on the tribosurface corresponds to the
boundary friction conditions in the tribosystem. The boundary lubricating film is
thin compared with its linear dimensions. It can be assumed that the rate of the
displacement of the lubricating fluid particles normal to the tribosurface is negligibly
slow versus the velocity along the surface. The pressure is constant throughout
the film thickness, the dependence of its material viscosity on temperature and it can
generally be represented in the following way:
= 0 exp [ (T T0 )] . (7.2)
If the lubricating layer is assumed the incompressible fluid, then the relation
between viscosity and pressure in the isothermal:
(P) = 0 e P (7.3)
where 0 is the lubricating fluid viscosity at the air pressure and normal temperature;
is the viscosity piezo coefficient; P is pressure.
The hydrodynamic elastic lubricating film bears the load on the micron asperities
of the tribosurface. The friction force is determined in the general case by the viscous
friction of the film and the contact spot friction.
7.1 Lubricating Layer Formation 189
1/2
f fr = 3r S0 , (7.4)
where r is the relation between the radial clearance and the shaft radius; S0 is the
Zommerfeld number.
Pr2
S0 = , (7.5)
where f 0fr is the friction coefficient at rest; Dr is the radial clearance; h min is the
film thickness corresponding to the Stribeck minimum curve.
German tribologist R. Stribeck studied sliding and rolling bearings and obtained
the results in Fig. 7.3 that the friction coefficient f fr depended on the lubricating layer
thickness in the following way:
x= , (7.7)
P
where is the sliding velocity.
According to Stribeck, the abscissas to the left of x1 correspond to the zone of
boundary contact friction with the characteristics described by relation (7.6); the
abscissas to the right of x3 correspond to the hydrodynamic or rheodynamic friction;
mixed friction dominates within the interval x1 x2 ; the Vogelpohl relations can
describe it.
The boundary friction mechanisms and parameters are determined by the following
main factors:
the physical nature of tribomaterials, the condition and properties of tribosurfaces;
the structure, physical and chemical characteristics of the lubricating material;
the regularities of the adsorption of lubricating molecule, the physical and mechan-
ical characteristics of the layer of adsorbed molecules;
the pressure, the lubricating layer effective thickness, the sliding velocity, the tem-
perature and other parameters of the tribounit;
the tribochemical transformations of the lubricating tribomaterial molecules, the
changes in the boundary layer structure in friction: redistribution of the lubricating
material over the profile of micron asperities, the adsorption of polar molecules on
the tribosurface, the thermal disintegration of molecules, catalytic processes and
chemical reactions, oxidation, in the first place.
Thus, the boundary friction during adsorption and appearance of lubricating mate-
rial polarized molecules and active oriented film structures they produce on the
tribosurface are not stationary processes. The analysis of the lubricating layer back-
ground after its molecules contact the tribosurfaces until the layer degenerates
permits to trace the chain of events modifying the triboprocess radically during
their evolution. During the run-in stage, boundary layers nucleate, then the third
body appears and govern the steady friction; any damage of the third body lands
to degradation and fracture of boundary layers [2]. Famous Russian tribologist
A.A. Polyakov treated the process of evolution of lubricating layers as manifesta-
tion synergic processes representing them by the dissipative structure. According to
Polyakov, the dissipative structure implies the space or space-time structure existing
and circulating indefinitely long in time provided there is constant energy and matter
supply. The dissipative structure is an open, reversible unending structure appear-
ing in a relatively homogenous environment [4]. D.N. Garkunov and A.A. Polyakov
admitted the fact of space-time mechanism of evolution of lubricating layers as an
essential argument in favor of the relativistic effects in friction. The dissipative struc-
ture consists of intersecting reacting flows. For instance, a substance arrives into the
system activated by friction and with excessive free energy and leaves it after the
energy is expended. A.A. Polyakov believes that the dissipative structure results from
kinetic transitions from conservative movement of dislocations to their climbing cor-
responding to the conditions, which lead to the relativistic dislocations.
follows Eq. (6.15), and then chemical transformations proceed further as described
in Sect. 6.2 when the dynamic equilibrium between ionization and recombination
of ionized triboplasma particles evolves. The relations between tribochemical trans-
formations of tribomaterials with plasma and post-plasma processes governs the
kinetics of tribochemical reactions. They quickly reach the maximum intensity after
the induction period is over, the reactions evolve in steady friction, and their tribo-
chemical intensity falls as quickly to zero as soon as friction ceases (Fig. 7.4).
The variety and specific features of products characterize the tribochemical reac-
tions since the tribosystem is the open thermodynamic system in which entropy can
reduce, German physicist and chemist G. Heinicke asserts [8] that chemical trans-
formations can evolve in friction contact with positive entropy changes, for instance:
Unique tribochemical reactions of oxidation of noble metals can take place that
are unlikely under usual conditions:
3 1 3
Au + CO2 Au2 O3 + C.
4 2 4
There is a class of chemical transformations, which govern the specific tribo-
chemical feature of the selective transfer [8, 9]. It is found that the d-elements in the
tribocontact zone or with the electron d-shell vacant (iron, cobalt, nickel, copper) or it
is just filled (zinc, cadmium, hafnium) reduces the friction coefficient and tribocouple
wear (Fig. 7.5).
One the explanation of this phenomenon is that many d-elements are typical
acceptor electrons forming easily complexes with organic and inorganic ligands. The
processes of transitions of electrons and formation of complex compounds belong to
the category of plasma chemical transformation of tribomaterials. The chemical and
active components of lubricating materials, surfactants, are chemisorbed by active
surface centers. It can lead to the surfing film as one of the most effective factors of
wear and friction reduction. The theory of complex compounds can help understand
the mechanism how the surfing film appears.
192 7 Antifriction Micromechanisms
M + L M L, (7.8)
where M is the metal central atom (ion); L is the ligand; ML is the complex.
The term ligand serves to designate groups of atoms or molecules surrounding
the central (complex forming) atom. The fields enervate by the ligand perturb the
energy and the wave function of the central atom and provide the complex with its
specific chemical properties. Various types of links are effective in complex com-
pounds: from inclusion of molecules into the crystal lattice to covalent or coordination
links. The coordination links are most often covalent because they are implemented
by combining the electron pair between two atoms. The term coordination means
that the combined electrons belonged originally to one of the atoms. That is why the
synonym of complex compounds is the term coordination compound.
The mathematical apparatus of the theory of perturbations [12] serves to describe
the chemical properties of complex compounds; this theory is the base of the theory of
fields of ligands [1]. Its author is British physicist J. Van Vlech, Nobel Prize winner,
who fulfilled in the 1930s the spectroscopic study of ions of transitional metals into
crystals. The transitional elements differ from the elements in the main subgroups
of the periodic system because they produce many stable compounds with electron
shells partly left vacant. These shells, as it is noted in Sect. 7.2, are d-orbitals and
free atoms, in the first approximation. The triangular, octahedral or more intricate
7.3 Complex Compound of Tribomaterials 193
complexes can form in the transitional elements [11]. Though the coordination links
are most often the property of transitional metals, there is not any prohibition limiting
the bonding among other elements.
The preceding chemical models of the properties of complex compounds explained
the fact by electrostatic interaction between ions of metals and ligands. The com-
bination of fields generated by ligand charges is called the ligand field. This model
explained how complex molecular configuration appeared. The electrostatic theory
was substantially modified to answer the problem of stability of complex compounds
and the effect of the ligand fields on the d-electrons of the central ion [13]. It is
apparent that the energy of d-electrons is determined by two main perturbations:
the electron repulsion and the effect of fields of ligands. The complex compounds
among which the ligand field dominates are called the strong field complexes. The
complexes in which the determination of d-electron levels the electron repulsion
plays main role are named the weak field complexes [1].
The complex formation sis described using the quantum mechanics models of
chemical interaction making up the theory of nucleus and valence. Based on the
content of Sect. 7.2, let us treat the model of transitional states founded by German
physicist F. London in 19291930.
The model of the transitional state is based on the assumption that complex
compounds pass through the stage of the so-called activated complex or through the
non-equilibrium or quasimolecular state. The non-equilibrium activated complex
does not comply with the minimal potential energy. However, estimates with the
methods of statistical physics and probability manifest that the components of the
chemical reaction of generation of complexes are very likely to undergo the activated
complex stage. The process is shown schematically in Fig. 7.6.
The changes in the concentration of substances participating in the reaction
X, Y, Z during chemical interaction are plotted along the abscissa axis called the
reaction coordinate. The ordinate axis corresponds to the variations of the poten-
tial system energy as a result chemical transformations. It follows from Fig. 7.6 that
the activated complex is a less gainful energy state versus the initial state of reagents
and even in worsened state of reaction products which are in the so-called saddle
point [1]. The following formula [1] represents the rate of complex XY generation
during interaction between ions, atoms or radical X with the molecule or ligand YZ:
d
[X Y ] = ch.r [X ] [Y Z ] , (7.9)
dt
where ch.r. is the constant of the rate of reactions calculated with relation (6.20).
In accordance with the Arrenius law, to implement the chemical reaction, the
reagents X, Y, Z should overcome the energy (potential) barrier with the activation
energy Wx (6.20). However, it possible to bypass this barrier. Transformations of
chemical elements follow the laws of quantum mechanics the regularities of which
appear in the so-called tunnel effect. The effect determines the wave function
omitting the zeroing in the points where the full energy of particles W is less than the
potential barrier. This behavior of free particles
is described in quantum mechanics by
W
the wave function proportional to ex p i t , and, when the particles pass through
W U
the potential barrier, the wave function reduces to ex p i t , where U is
the potential barrier value. Due to his fact, even if U > W , the probability of the
particles to be beyond the potential barrier is ||2 > 0 and that is what the tunnel
effect means.
F. London explained the nature of this barrier in the quantum mechanics terms.
During the above reaction, two electrons with opposite spins initially link the atoms Y
and Z with simple bonds, in other words, while the atom X has an unpaired electron.
When the X to the YZ system, the interaction between these three electrons weakens
the YZ bond and atoms Y and Z tend to depart. Hence, the approach of the atom X
to the system YZ increases its potential energy, which is compensated just partly by
new bonds XY. In the final account, the X reaches the point where the attraction of
XY becomes dominating. Then the Z leaves the system reducing its potential energy
(Fig. 7.6). The appearance of the above-described relativistic effects (6.46) boosts
the tunnel effect probability accelerating the complex generation.
Quantum mechanics calculation of the energy of the states of chemical bonds in
the complex compounds is performed with the valence routines based on the electron
wave function found by the main state with the expression [1]:
where H is the Hamiltonian function included into Schrdinger equation (6.41).
If Eq. (7.11) is used to plot successfully the energy surface, it does not mean
that the absolute speed of chemical reaction can be calculated, because they involve
substances with a broad spectral energy range of thermal excitation. Therefore, the
statistical physics should b used in calculation taking into account hat that the reactive
substances are in equilibrium with activated complex.
The mechanism of generation of complexes. During generation of complexes,
compounds have different geometrical configurations depending on the ligand field
type. The ligand field effect on the electron (most often) shell and the central ion
leads to the fission of their energy spectra (Fig. 7.7).
The fission parameter
depends on the ligand and metal ion nature. The ligand
field parameters are determined by the central ion perturbation the external electron
ligand shells. That is why it is justifiable to expect that the factors affecting the value
are comparable with metal ion and its charge. The drawback of this model is that
the treated interactions possess the electrostatic nature and the model ignores the
quantum exchange forces affecting the redistribution of electrons among the energy
levels and formation of covalent bonds. These forces should affect the value
, which,
in the final account, depends on the total intensity of ligand fields, irrespective of
their nature. The analysis of Orgel diagram (L. OrgelBritish physicist) confirms it
for most common octahedral complexes (Fig. 7.8).
The Orgel diagram shows how the relative energy of low- and high-spin config-
urations of electron shells depends on the parameter
. The energy is counted from
the energy zero; the mean values are selected of five out of d-orbitals surrounding the
central ion. When the values of the
configuration of the complex compound are
small, the configuration with free spins (the high-spin) configuration is considerably
more stable than the low-spin. As the
grows, the difference between energies of
configurations diminishes and when the value
is critical, both configurations have
the same energy. When
continues to grow, the low-spin configuration becomes
still more stable than configuration with free spins. Thus, irrespective of distinct
division of the central atoms by the number of coupled electrons, the theory ligand
fields ignore the difference between types of bonds because the orbitals of the close
energy and symmetry participate in the bonding.
Russian tribologist A.S. Kuzharov established [14] that in friction the complex
compound form following the mechanism similar to that in the theory of the acti-
vated complex. The role of the activated complex in the Kuzharov model is played by
the super-excited plasma and post-plasma state of the substance on the tribosurface.
The tribochemical complex compounds are synthesized directly from the substance
active long-living post-plasma states resulting from relaxation in triboplasma. The
tribocontact particles in microvolumes making up the triboplasma interact with tribo-
surfaces and the lubricating material [9]. The microasperities comprising the contact
spots on interfaced tribosurfaces intensify the relaxation processes in the post-plasma
producing coordination compounds on rubbing surfaces. This process is illustrated
in work [9] and in Fig. 7.9. Two complexes being at the apexes of asperities on the
actual contact spot approach with the velocity . The surface is activated in the actual
contact spot producing the triboplasma with the encircle center. The microasperities
leave the direct interface; the triboplasma relaxes and produces in volume new mole-
cular products. The new LCuL complex attaches to the surface by donor-acceptor
interaction and yields a complex compound and pure metal fragments.
The activated complex state corresponds to the ideas of A.A. Polyakov who wrote,
nature contains the equilibrium structures results from competition between order
and disorder and the dissipative structures generated by energy flow remote from the
equilibrium [15]. Polyakov believes that the dissipative structure means that the
tribocouple as reached the mode of self-organization corresponding to the tribounit
structural complication. Referring these structures to the systems of the space-time
type, famous Italian physicist D. Carrierri wrote, The main difference of the closed
in the internal equilibrium state from the system open to the flows of substance and
energy is how it behaves in time. In the equilibrium state, the system stays in
respect to the time revolution. This symmetry gets immediately disordered if the
effect of external flows moves the system away enough from the equilibrium so that
this new state is apparently more ordered [4]. Carrieri believes thus that after the
transit to dissipative structures is accomplished, the space-time continuum changes
and so does the course of time [16].
The tribosynthesis of complex compounds relates to the activated complex with
the dissipative structure living microsecond fractions and needing the energy to be
continuously pumped up by friction forces. The tribocontact between rough surfaces
and tribocouple materials lasts 104 103 s [16], still, the abnormal intensity of
the reaction of tribochemical synthesis of coordination compounds is emphasized by
many tribologists [8, 9, 14]. One of the models of tribochemical processes attributes
the high activity of reagents to the appearance of inverse population of transitional
states [17]. The inverse population is the substance non-equilibrium state when the
population of upper among a pair of energy levels with one type of atoms, ions or
molecules in the composition exceeds the population of the lower level. It is little
likely; the structural thermal substance activation by friction would the order of
population of atomic shells from smaller to larger energies. Moreover, the inversely
populated media spontaneously emits coherent electromagnetic waves. This fact was
registered experimentally. Versus this model, the hypothesis about the intensification
of tribochemical activity due to the relativistic contribution to the tunnel transition
probability X + YZ XY + Z (Fig. 7.6) is more justifiable.
In addition to formation of complexes from reaction capable substance fragments
on the tribosurface of the lubricating medium, friction initiates also more compli-
cated chemical processes. The central atom of the complex can be substituted with
the counterbody metal. This process of ovecomplication was registered during fric-
tion between the epoxy composite and salycylaldodecylamine copper on the zinc
counterbody using the IR-spectroscopy and X-ray spectral analysis (Fig. 7.10).
The phenomena of ovecomplication are noted within the band 12001800 cm1
as the dislocation with the maximum absorption bands at 2030cm1 within the
long wave spectrum portion. The ovecomplication is confirmed by the coincidence
between the tribosurface copper specimen R-spectra (3) and the models specimen (4),
containing the salycylaldodecylamine zinc complex. The copper substituted with zinc
in the original complex appears on the counterbody as isolated fragments.
The X-ray spectral analysis manifested that copper deposits most on the zinc
counterbody tribosurface during first minutes of friction and it corresponds to the
uppermost local loads and temperature, or the most intensive tribochemical transfor-
mations. Afterwards, the substituted copper surface concentration stabilizes proven
by the constant intensity of the characteristic X-ray emission.
The energy of complex formation reactions. The intensity of tribochemical
interaction is determined by the mechanical energy supply into the tribocontact. It is
worthwhile to estimate the energy consumption efficiency during complex formation
tribochemical reaction. The estimate criterion is the substance quantity gained or
lost due to the friction energy absorption by the tribosurface. Like radiation, sound
and photo chemical reactions, it advisable to introduce the notion of tribochemical
output or the value formally independent of the friction interaction parameters.
198 7 Antifriction Micromechanisms
Fig. 7.10 Findings of spectral study of friction interaction between epoxy composite filled
is the copper complex and zinc counterbody. a IR-spectra: 1 original epoxy resin (ER);
2 ER + copper complex; 3 ditto after friction; 4 ER + zinc complex. b dependence of intensiv-
ity of characteristic copper X-ray emission (CuK ) on zinc counterbody on friction duration
Fig. 7.11 Auger electron spectra of epoxy composite specimen: a before and b after friction on
zinc counterbody, relative units
with ultrasound. It is repeated in the work in question [9] that the triboplasma and
post-plasma friction effects accelerate the tribochemical reactions 3008000 times.
Structure of tribochemical complexes. Chemical transformations are studied
in [18] during friction of the epoxy composite on the galvanized steel by Auger
spectroscopy. Figure 7.11 shows the spectra with the absorption bands typical for
zinc oxide (A), the zinc counterbody surface with the chemisorbed oxygen layer
(B) and the original zinc (C). During friction of the epoxy indenter against the zinc
counterbody, the component B augments in response to the reduction of the A
spectrum component. The B kinetics in the Auger electron spectrum corresponds
to the formation of complex compounds.
The structure of these compounds is established in [15]:
Fig. 7.12 Photographs of zinc counterbody tribosurface: a in usual light; b in polarized light
Fig. 7.13 Photographs of nuclei of third bodies (nanoclusters) during selective transfer [19]
The practical independence of the complex formation rate on the lubricating mate-
rial temperature and zero activation energies corresponding to the formal Arrhenius
law application to the description of interaction between ligands and the metallic
counterbody, prove that the energy needed for the chemical reaction is imparted to
substances during dynamic contacting between tribosurfaces. The tribocoordination
accelerates as energy that is more mechanical is supplied up to some limit value
depending on the ligand concentration. It agrees with the known tribochemical rela-
tion between the tribochemical reaction rate and the initiating mechanical energy [8].
It is shown in Sect. 4.2 that the dynamic evolution complicates the tribosystem,
reduces the entropy factor and forms third bodies. They appear due to the physical
and chemical processes in the tribocontact, the complex formation laying a par-
ticular role [20]. The film of complex compounds demonstrates high lubricity and
202 7 Antifriction Micromechanisms
easy sliding of tribounits like the surfboard sliding. This effect has a prototype in
fundamental physics under the surfing effect term or limited gravitation wave velocity
during interaction between gravitation and electromagnetic fields [21].
Physics and chemistry of complex compounds. The tribosurface is free of oxide
films in the selective transfer mode (ST), while the dislocations of atoms of these
active centers exit to the surface and possess additional bonds. Almost all metals are
acceptors of electrons, while the majority of additives or products of tribodestruction
of tribomaterials are donors of electrons. They act as ligands favoring the formation
of complex compounds. It is a typical attribute of ST formation of chemical bonds
between the lubricating material ligands and metal atoms on tribosurfaces [15].
G.D. Gromyko investigated the lubricity complex compounds [22]. He discovered
the positive effect o oxidation processes on the lubricating function of complexes
and explained it by the growing thermodynamic stability of the appearing complex
compounds. The effect of the oxidation processes on the surface kinetics of the chem-
ical reactions is well known [6]. The surface reactions often involve the intermediate
structures, which are insignificant at the chemosorption stage, but the affect the chem-
ical reaction rate and can favor the appearance of intermediate reactive groups. The
surface chemical reactions evolve predominantly (or exceptionally) in one group of
active centers [3]. The metals with stable oxides have typically the oxygen contain-
ing ligands. These complexes agglomerate near the intergrain boundaries being the
active centers with high adhesive energy. If the lubricating medium is free of products
of oxidation of hydrocarbon, the metal organic compounds appear in which the metal
bonds to the hydrocarbon through the carbon atom. These compounds are unstable
and disintegrate at rather low temperatures.
The authors of [18, 23] perfumed one of the fundamental experimental research
of the tribostructure based on complex compounds and linked the processes of their
formation to oxidation reactions. They studied the friction of epoxy compounds on the
zinc counterbody. The compositions of the epoxy specimens contained the mercupral
(the copper tetraethyl tiuramdisulfide complex) together with its ligand and catalysts
or inhibitors of oxidation processes. The inhibitors of oxidation reactions were KBr
and Vaseline oil, the catalyst was KMnO4 . The triboengineering tests manifested that
introduction of the additives suppressing the oxidation processes in the tribocontact
improves the tribocouple friction resistance. It is particularly apparent when the
Vaseline oil is used because it possesses its own lubricity when it is used together
with the ligand (Fig. 7.15a). Even a sight amount of the KMnO4 oxidant increases
the friction coefficient and intensifies polymeric material wear (Fig. 7.15b).
The measurements of the tribological parameters couple in question are due to
the effect of additives on the kinetics of third body appearance. This process and
relevant tribochemical transformations were studied with X-ray and Auger electron
spectroscopy [7, 24]. The X-ray electron spectrum permits to judge about the sur-
face qualitative and quantities elementary composition and the valence state of the
elements in question (Zn, Cu, S). The radiation transition of the elements in question
into the p-shell (zinc Zn2p, copper Cu2p, sulfur S2p) permits to judge about their
valence state by changes in the typical changes of spectral lines and the relevant type
of the appearing chemical bonds. The most informative are the long wave zinc L
7.4 Tribocoordination or Surfing Effect 203
Fig. 7.15 Dependence of wear I (1, 2) and friction coefficient f (1 and 2 ) on concentration of
introduced oil (a) and oxidants (b)
and M-spectra (ZnL3 M45 M45 ) taken from the metallic counterbody surface. These
lines are produced by transition of electrons to their external shells close to the atom
boundary so that the spectral lines become extremely sensitive to changes in the
chemical environment. The spectral factorization into characteristic components
provides information about the type of chemical compounds and heir concentration
on the surface [25].
The conclusion from the results of the X-ray electron analysis of the copper
and sulfur spectra is that the ratio of their concentrations on the tribosurface changes
constantly and they do not corresponds to the ratio between molecules in the complex.
The complex compound appearing in friction has the copper univalent unlike the
bivalent copper in the mercupal. It is the experimental proof of ovecomplication,
which, in this case, is caused by copper substitution in the complex and a proof also
that the bonds of mercupral molecules rupture.
The Auger spectrums of the electrons leaving the film with the thickness equal
to the length of the free run of electrons have the energy about 992 eV. When the
specimen turns, the angle changes between the direction in the analysis and the
direction normal to the specimen (Fig. 7.16) permitting the spectral analysis of film
layers located at different depth.
The free run length of zinc electrons according to [23] is under 1.3 nm. Taking into
account that there is polymeric transfer layer on the zinc counterbody tribosurface,
the free electrons run to a longer distance than in metals; it can be assumed that the
total analysis does not exceed 3 nm.
The Auger spectra of transfer films depend little on the composition of the poly-
meric specimen material (Fig. 7.17). In most cases, two components can be identified
in the spectra: A corresponds to the zinc oxide, B correspond to the zinc oxida-
tion intermediate stage. Sometimes the spectrum contains the third component C
corresponding to the Zn metallic state.
The structure of the zinc counterbody surface layer before friction can assume the
following: the top layerzinc oxide, the layer beneath is the oxidation intermediate
stage and then follow the zinc proper. The total thickness of the system in question
does not exceed 1.3 nm. The thickness of each sublayer of the proportional area of
the relevant spectral components changes weakly over the specimen surface. The
tribosurface layer corresponding to the relevant oxidation intermediate stage does
not always carry the zinc oxide layer. It is established by changing the angle of
installation of specimens as shown in Fig. 7.17. The spectra registered at = 30
show that the deeper layers contribute to the Auger spectrum, while the surface layers
contribute at = 80 . The spectral component B intensifies when the counterbody
is at = 80 , corresponding to the zinc oxidation intermediate stage. It means that
this layer lies on the zinc oxide surface layer. If it is taken into account, the zinc in
7.4 Tribocoordination or Surfing Effect 205
the complex compound has exactly the oxidation intermediate stage, the component
B proves that a zinc complex compound is under formation.
Numerous experiments have permitted to establish the following regularity: the
antifriction characteristics when the Auger spectral band of absorption widens char-
acterizing the zinc oxidation intermediate stage and proving that the metal complex
concentration augments. When the complex compound layer doubles, the friction
coefficient reduces four times to the value typical for hydrodynamic friction (0.06).
It is shown in [26] that the metal complexes appear both on the metallic tribocouple
surface and on the polymeric surface, including on that made from most chemically
inert fluoroplast-4. The copper positively effect is observed on the triboengineering
characteristics of materials containing PTFE fibers. This effect is apparently due to
the appearance of copper coordination compounds together with products of copper
destruction of macromolecules in the friction zone according to the following scheme:
Surfing film. The complexes adsorbed on the tribosurface are associated with
stable structures named the surfing films. The complex molecules are held in the
surfing films by intermolecular forces demonstrating an extremely high organization
of coordination saturated particles called the supermolecule [27]. The surfing film
is a protective adsorbed based on the associated complex compounds. The latter result
from the chemical compound of free metal atoms in the spots where dislocations
exit to the tribosurface with lubricating material ligands [28]. The surfing film per-
forms the functions of mass exchange between the third body and the environment
and possesses the property of self-restoration. Being destroyed under the effect of
friction forces and reappearing again, it remains stable withstanding the processes
of tribodestruction and oxidation. If the grease consisted only of the surfing films,
it would be eternal needing no replacement. Regretfully, it is impossible so far to
make the material with surfing films in advance so that the films would be supplied
externally into the tribocouple. In practice the oil soluble complex compound and
the materials capable to produce complexes in the lubricating medium, are used as
additives to lubricating materials.
Let us consider the mechanisms of formation of surfing films. It is noted above
that the ST creates favorable conditions for producing coordination compounds,
because the dislocations exit to the tribosurface. The dislocations bear considerable
energy providing grounds for development of the dislocation theory of seizure of
metals. However, a paradoxical reaction of chemosorption of lubricating transfer
layers occurs during the ST; this effect was named the surfing effect.
The chemical and active components of the lubricating material or ligands appear
in the spots where the dislocations exit to the tribosurface of metal complexes. When
the coordination bonds appear, the bonds between metal atoms and crystalline lattice
atoms weaken or rupture. The bonds between the metal and the complex atoms
transform into the chemisorbed state. The complex compound molecule becomes
able to diffuse over the tribosurface combining with other molecules into the film
islands schematically shown in Fig. 7.19a. The processes of film appearance and
tribodestruction mentioned above evolve with approximately the same rate dictating
the dynamic stability of the surfing structure. The analysis of images made with
the scanning tunnel microscope (STM) [29] show that the surfing films possess the
quasicrystalline structure different from the tribosurface structure on which they
appear. Figure 7.19b, shows the photograph of the counterbody surface after friction
of the epoxy specimen containing mercupral.
The surfing film has the structure of the ordered grid of atoms with atom spacing
1.9 nm.
The surfing films are similar to those appearing in friction in the ST mode. They
produce collective adsorption function plastifying the metal on the tribosurface usu-
ally inhibited during common friction by oxide layers. Therefore, the friction pro-
duces denser (doubled or several times higher) concentration of vacancies sharply
localizing he charge carriers charge and determining the variety of chemosorption
mechanisms. The chemosorption accelerates as the temperature and pressure grow
resulting in a higher reliability of tribocouple within the range of working tempera-
tures reducing the wear rate and boosting life of lubricating materials.
7.4 Tribocoordination or Surfing Effect 207
Fig. 7.19 Surfing film portion: a scheme of formation; b STM-photograph of surfing film formed
by copper complex [30]
The range of velocities and loads during ST remains the most essential and still
outstanding problem because this range governs the appearance of dissipative struc-
tures, which reduce the friction and wear parameters by several orders of magnitude.
The servovit film dissipative structure evolves following the vacancy dislocation
mechanism usually producing the surfing structure. The surfing film results from
reaction (7.8) implying the activity of ligands initiated by the atoms on the tribosur-
face with free bonds. The ligand can interact with several atoms in the lattice at once
making the total interaction very strong. It favors clustering adding to the process
special volumetric and surface characteristics that are absent among other forms
of existence of solid bodies. The processes of clustering of complex compounds
relate to the interaction between triboplasma ions and motion of dislocations. The
more dislocations surface, the stronger precipitation of ions, the more intensive is
the clustering and so are the processes of formation of surfing films.
The clustering of complex compounds is possible only when the tribosurface is
free of oxide films. The complex would rather appear on the juvenile surface than
the oxide. The chemical structure of the new complexes lacks the component of
interatomic bonds, irrespective the considerable oxygen content. When there are no
hydrocarbon ligands, oxygen plays their role, which produces bridges binding lig-
ands to the tribocouple metal [31]. The oxygen in the surfing film combines with
metals without oxidizing them because extremely strong covalent bonds are pro-
duced confirmed by the Auger spectroscopy results shown in [23]. The oxide films
208 7 Antifriction Micromechanisms
Most of the additives based on the coordination compounds of metals are referred
to the metal cladding additives because the lubricating behavior is based on the
interaction between the metallic quasimetallic films in the interface. The doping
of lubricating oils with metallic organic complex compounds produces a positive
effect [33]. The results of numerous works in the sphere of chemmotology prove
that the lubricating compositions containing metallic organic or complex com-
pounds possess much better triboengineering properties than the base lubricating.
The following cladding amine complexes of transitional metals are advisable for
the base lubricating oils: [M(L)x Am] [33], where M is the transitional metal cation;
LH2 NRNH2 , H2 N(RNH)n H, Hp N(CH2 CH2 OH)3p ; RCH2 or (CH2 )8 ; A
Cl , SO2
4 , CH2 COO , n = 1. . .4; p = 0, 1, 2; x = 2, 3; m = 2, 4.
The introduction of 10 % of this complex into Lithol-24 reduces the linear wear
of metallic bearings almost to zero and the friction coefficient drop lower than
0.06. Similar effects are observed when the complex with nitrogen-, oxygen- and
sulfur-ligands (RR R N)y MXz are introduced in the base lubricating oil, where
R = C6 C30 , R , R = H or C1 C30 ; M = Sn, Cu, Cd, X = Cl, J, Br, y = 16,
z = 24.
The additives were developed in the USA based on the so-called binuclear com-
plexes of unlike metals or blended complexes of these metals M1 M2 (A)x m(B Ry ),
where M1 and M2 are Cb, Cu, Ag, Zn, Hg, Ni, Co, Fe, Pb etc.; are chloride, bro-
mide, azide, thyocyanate, sulfate, carbonate, etc.; BR are oxides, sulfides, selenides,
tellurides, saturated, unsaturated, cyclic or aromatic hydrocarbon radicals contain-
ing from 4 to 20 carbon atoms. The example of the wear resistance additive is the
following copper complex of the acetylsalicylic acid (Fig. 7.21):
The effect of this additive on the antifriction characteristics of the low-temperature
grease CIATIM 201 is shown in Fig. 7.21 [33].
The chelates of metals have manifested their effective antifriction property many
times. When this complex of free ligands is added with the above chelates, the results
become the best because then the constant metal complex concentration is maintained
210 7 Antifriction Micromechanisms
Fig. 7.22 Dependence of friction coefficient on working time (h) of tribocouples steel 40 Kh
cast iron SCh-15 for lubricating materials: 1 CIATIM 201, 2 CIATIM 201 + 5 % copper salt (II)
acetylsalicylic acid c
in the friction zone. The lubricating compositions of the base oil with additives of
2-oxybenzaldodiecylamine (a) as the ligand and its chelate compounds (b) exemplify
the improved lubricating:
The mixed powdered d-element and the complex former are often added to the
lubricating material. In this case, the metallic complex forms directly in the friction
zone due to the tribochemical transformations.
Chelates of metals containing the molybdenum as the central atom are particularly
effective. They are added into the basic grease in the concentration just 0.52 % by
volume. Molybdenum dithiocarbonates resulting from tribodisintegration of molyb-
denum disulfide possess excellent lubricating properties, for instance, molybdenum
disulfide tridithiocarbonate MoS2 (SCNR2 )3 , where R is the radical.
The antioxidizing additive based on the mixture of copper and molybdenum
dithiocarbonates manifests good results.
7.5 Additives Based on Complex Compounds 211
Due to the book-limited content, it is impossible to list just the main additives
from among their numerous varieties based on the metallic complexes. It is worth-
while to highlight that many of them, in addition to their main purpose, are effective
additive to polymeric self-lubricating compositions. One of the best home plastics
for triboengineering purposes is KGM-3 containing the mercupral as the antifriction
additive [34]. Complex compounds of metals yield a stable antifriction effect in all
types of tribocouples. It is because surfing films and buffer layers [33, 35] appear
containing tribopolymers.
References
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21. A.G. Polnarev, D. Bascaran, Surfing effect in the intersection of electromagnetic and gravita-
tional waves. Phys. Rev. D. 77(10), 3343 (2008)
22. G.D. Gromyko, The effect of oxydation processes on severe boundary friction, in Theory of
Friction, Wear and Lubrication, vol. 3, pp. 124125, Tashkent, 1975
23. A.T. Kozakov, D.N. Lyubimov, A.V. Nikolskii et al., Effect of third body structure on frictional
characteristics of epoxy compositemetal couple. J. Frict. Wear 13(6), 10321038 (1992)
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2010), p. 148
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bodies. Rostov-on-Don: YUFU, p. 406, 2009
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study of triboengineering properties of modified materials based on PTFE fibers, in Special
Purpose Antifrictional Plastic (NPI, Novocherkassk, 1987), pp. 110117
27. Sh.M. Len, Supermolecular ChemistryScale and Prospects, in Nobel Lecture. Chemistry,
vol. 2 (Moscow) (1987)
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issue 4, pp. 1115, Mashinostroyenie, 1989
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ISBN 978-953-307-351-4
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32. V.F. Kiselev, S.N. Kozlov, A.V. Zoteyev, Fundamentals of Solid Body Surface Physics (INBU,
Moscow, 1999), p. 284
33. A.S. Kouzsharov, N.Y. Onischuk, Metal cladding lubricatng materials, in Durability of Rubbin
Parts of Machins, issue 3, (Mashinostroyenie, Moscow, 1988), pp. 96144
34. D.N. Lyubimov, Role of diffusion processes in wear and friction of metal-polymer tribocouples.
Candidate of Science Disseration. Gomel, p. 22, 1990
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Afterword
P (cont.) Submicroroughness, 61
Polychromatic approximation, 155 Subsurface layer, 99
Polygonal cellular, 113, 115 Surface diffusion, 55, 6061, 106
Polymeric chain (linear, ramified and reticular Surface energy, 2122, 31, 33, 47, 53, 55, 56,
structures, homogeneous- and hetero- 65, 186187
geneous), 2526, 56 Surface layer, 33, 5153, 56, 58, 61, 9899,
Polymers (tribopolymer), 15, 25, 2526, 33, 110, 111, 113117, 124128, 130,
200, 211 132133, 144, 149, 155, 173, 187, 204,
Ponderomotive force, 152 208
Positron, 122 Surface tensioning, 52, 55, 6364
Potential barrier, 21, 81, 89, 100, 127, 194, 208 Surfing films, 133, 191, 202, 206209
Potential energy, 2, 4, 14, 30, 33, 150, 186,
193194
Primary emission, 91 T
Principle of the positive gradient of mechani- Temperature conductivity, 100, 129, 140
cal behavior, 105 Term, 3
Theory of perturbations, 192
Thermal activation surface, 89, 111, 116,
Q 127128, 129
Quantum number (main, orbital, magnetic), Thermal expansion coefficient, 12, 1718
67, 9 Thermodiffusion coefficient, 75, 79
Quantum object, 56 Thermodynamic, 5, 51, 56, 71, 101, 102105,
Quantum state, 4, 5, 29 124
Third body, 105106, 176, 190, 202, 206
Transfer phenomena, 102103, 105
R Transitional metals, 15, 17, 19, 192, 209
Real contact area, 96, 98, 100, 117 Transitional state model, 193197
Relativistic (triborelativistic) effects, 120121, Tribochemical output, 197
127, 130, 190, 194 Tribocollahedron, 159
Rigidity coefficient, 71 Tribocoordination, 132
Triboplasma, 127
Triboplasma temperature, 136
S Triboplasma wave collapse, 182
Schrdinger equation, 57, 9, 30, 177, 195 Triborelativistic effects, 127
Secondary hydrogen diffusion, 108, 109110 Tribosystem, 102107, 111, 118, 136, 156,
Section of the reaction, 171 159, 170, 173, 176, 179180, 185, 191,
Shear modulus, 42, 71, 84, 115 198, 201
Sliding plane, 8387, 90, 208 Tribounit, 102
Small-angle boundary, 4850 Tunnel effect, 194, 208
Solar crown, 130 Typical emission, 91
Solar wind, 130
Spatial groups, 23
Specific friction force, 96 U
Spin, 7, 9, 12, 28, 194195 Ultradispersed microstructure, 129, 133
Steady states determined, 8 Umov-Poynting vector, 152, 154
Strength, 12, 13, 19, 45, 86, 90, 104, 116 Uncertainty principle, 56, 167
Stronger, 12
Structural activation surface, 129
Structure type (body-centered cubic (BCC), V
face-centered cubic (FCC), hexagonal Vacancy, 39, 89, 207
densely packed (HDP)), 23 Vector of main translations, 22
Sublimation, 17, 33 Vector of state, 5
Index 219
Vector of the magnetic induction, 140 Wave vector, 7, 8, 28, 54, 69, 71, 7274, 143,
Viscosity, 21, 28, 141, 188189 146, 148, 178, 179
Voids, 38, 4647 Wear resistance, 106, 161, 209
Volume modulus of elasticity, 29 Work, 166
Volumetric diffusion, 61, 8182
Y
W Youngs modules of elasticity, 15
Wave equation, 176 Yield strength, 45
Wave number, 31, 180