Tribology Online, 6, 1 (2011) 55-63.

ISSN 1881-2198
DOI 10.2474/trol.6.55

Article

Mechanochemical Friction of Third-Body as an Exergetic Collision

Rodrigo Bulnes*
Department of Mechanical Engineering, Technical University Federico Santa Maria
Avenida Espana 1680, Valparaiso, Chile
*
Corresponding author: rodrigo.bulnes@postgrado.usm.cl
( Manuscript received 14 September 2009; accepted 27 March 2010; published 31 January 2011 )
( Presented at the World Tribology Congress 2009, Kyoto, 6-11 September, 2009 )

Approximation of a third body proposes that a tribo-contact is conformed by two first bodies (that is to say;
elements of a machine), and by an interface -or third body- of different composition, where velocity between
the first two bodies accommodates tribo-chemically. In other words, the third body interface is a
mecanochemical concept which has the ability to transmit mechanical power in speed. Correspondingly,
thermodynamical activity of this third body friction, is of irreversible non-equilibrium, being more coherent to
establish an exergetic analysis in order to conclude to a holistic and more advanced formulation for the so
badly named Friction Coefficient. Concepts of Irreversible Non-Equilibrium Thermodynamics allow to
establish a new formulation for third-body boundary friction. Microscopic analysis of tribo-fluctuations is
applied to a generic contact to clarify the bond between friction and dissipation. The resulting
mechanochemical formula for the 3rd-bodys boundary friction, falls in the scope of the Physics of the
CHAOS and the phenomena of auto-organization of surfaces.
Keywords: mechanochemistry, kinetics, Gibbs Free Energy and fluctuation-dissipation

1. Introduction
To describe the dynamics of rugosities among bodies
that graze and slide, it is necessary to involve multiple
precision levels phenomena going from the simple
elastic deformation of rugosities, to the most complex
influence that wear particles trapped in the Abbotts
volume would have upon the Load-Carrying Capacity
of surfaces. This simple argument suggests that friction
among bodies () is a phenomenon directly affected by
all kinds of considerations of the Non-Equilibrium
Irreversible Thermodynamics1). However, every effect
originating from those considerations, should be
validated employing time-length escalation.
An example of the previous argument situates in the
third-body tribology2) (debris, contaminant particles,
absorbed films, interface viscosity, tribomutations,
rugosities of the continuous-discrete contact, vacancies
movement, dislocations, metallurgical defects, etc...).
The third-bodies define a combination of effects that
belong to both the scale of the Mechanical Engineer
(adhesive- and Hertzians pressure distribution theories),
an of the Materials Engineer (metallurgical and
superficial composition matter changes. In practice the
third-bodies
are
generated
almost
instantly,
transforming the contact of two bodies in one of
Copyright 2011 Japanese Society of Tribologists

3rd.-body, or of mechanochemical mixed contact). A

coherent thermodynamic description friction -at least for
the scale of both Engineers-, would require
synchronization of the effects that provide generic and
permanent non-equilibrium irreversible conditions...
Another example phenomenological underlies in
the friction heat, but considering it as heat irreversibly
accumulated in the surfaces3). The heat accumulated
suggests the entropy flow existence in the immeasurable
friction interface, that is to say, that there is always a
positive internal tribo-entropy, but to microscopic
scale (phenomenon that necessarily is not presented in
linear, relaxed, static equilibrium conditions). Thus, the
thermodynamic analysis of irreversible non-equilibrium
of the friction emerges coherently supported in the
generic characteristics of operation of any tribological
system, especially in the pseudo-lubricated condition
(tribo-damage mechanics and lubrication failures).
In virtue of a consisting expression for the entropy
rate of a roughness location, this paper explores the
physical implications that provide the thermodynamic
fluctuations
of
generic
mechanochemical
micro-gradients that inhabit the immeasurable friction
interface (tribochemistry activated by mechanical means;
roughness dynamics, textures, tribomutations, etc.). A
conclusion suggests that the best roughness coefficient

55

Rodrigo Bulnes

endures as a collision of dissipated exergy, that is to say,

that possesses physical units. Thus defined, this
friction number reaffirms the notion of third-body in
tribology, and fits well to the Tribology in-situ
program4), and sends to surface auto-organization
concepts5), nicely shown in the selective transfer
zero-wear phenomenon (STP)6).
2. Theoretical and experimental background
The approximation of third tribological body is a
clear mechanical explanation about the chemical and
metallurgical aspects of friction, wear and lubrication of
materials (this approximation applies to the
immeasurable and dynamically unstable friction
interface in mixed boundary lubrication or without
lubrication). It is proponed that a rubbing contact is
formed by two first bodies (elements of the machine),
and by an interface -or third body -, of a different
composition, where the speed of the first two bodies
accommodates. This accommodation is basically
made up of chemical reactions and metallurgical flows
(movements of vacancies, dislocations, composition
changes, etc.) The third-body suggests that the friction
coefficient is a key factor for understanding the
tribochemical aspects of the contact. That is to say, the
third-body leads to a mechanochemical concept for
friction, in as much as the attribute accommodates
tribo-mechanochemically to transmit mechanical power
at speed...
The third-body is translates in stationary rubbing
(with determinist or constant friction coefficient), when
it is assumed that tribo-interface is a thermodynamically
stable system. In this case, it would be enough to apply
the First Law of Thermodynamics to conclude that
friction is a kind of harm thermodynamically
dominated via the heat of stationary friction, as proposed
by the Bloks theory7), his derived relaxation8,9), the
approximation of the temperature integral10) and
others11). However, the Garkunovs STP-phenomenon
under dry friction, impels us to reflex about the nature of
the stationary rubbing itself... Zero wear phenomenon
indicates an especial thermodynamic condition in which
existing zero wear (with circulation of matter and energy
among non-lubricated surfaces), the friction coefficient
remains at a very low value (of hydrodynamic order).
This only circulation or selective transference of species
among surfaces, clearly defines a characteristic which is
proper of dissipative systems, and structures far from
equilibrium12), that is to say, the tribo-interfaces STP
behaves as a self-organized system5), this does not
necessarily means that friction is thermally dominated
The friction process leads to genuine dissipative
potentials, and it is neither necessary to resort to the
notion of force (of rubbing) to clarify this.
It is possible to go further in the dissipative nature of
the friction coefficient applying certain conditions of
Irreversible Non-Equilibrium Thermodynamics to the

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immeasurable tribo-interface. On one hand, on

tribo-interface, there are dissipative processes of
energetic exchange provided and self-reproduced by the
gradient impositions (e.g. micro-fluctuations in
temperature, speed, concentration, flow of vacancies,
dislocation movements, third-bodys dynamics, etc.).
On the other hand, and in virtue of the activation of
those micro gradients by friction, the tribo-system
remains far from thermodynamic equilibrium, including
friction coefficient. The fluctuating nature of is widely
known among tribologists, no mind if the tribo-system
supports or not a thermodynamic stability in accordance
with the First Law.
Using a ball-on-disk apparatus, Santner13) registers
great friction fluctuations, even when load, speed,
temperature and even relative humidity of the essay are
constantly maintained. On the other hand,
experimentally at nanometric scale, Gourdon et. al.14)
confirm the persistent fluctuation of the friction force,
assuring that it modifies its value even when
maintaining all those (all external) parameters constant;
and also the real contact area constant too, friction
oscillates. According to Gourdon et al., the surface shear
stress among rugosities presents time-spatial alterations
due to the existence of superficial chemical
inhomogeneities, that is, at last, friction fluctuations are
due to a certain type of fundamental tribo-chemical
activity grasped (internal) to the oxide layers and
pollutants that is always possible to find settle on the
surfaces (the idea of a surface of rubbing composed by
thermodynamic micro-states -these micro-states
understood as variables that obey to diverse
thermodynamic potentials manifested as sliding
rubbing-, would be very justified to the light of this type
of experimental cross-checks. If it is thought that
surfaces are formed by thermodynamic micro-states that
activate the moment they interact (rub) with the other
thermodynamic micro-states that conform the other
surface, then a different perspective opens -different to
the purely mechanical-, to refer to this thermodynamic
process that will result of the rubbing among these
micro-states: the friction coefficient).
In this paper, it is suggested that permanent internal
micro-fluctuations of mass and energy, (tribomutations
according to Duboka Arseni15)), dissipate a fluctuating
friction, and do it by convoluting with the memory
effect that provides a delay time anchored in the
proper kinetic reaction to which those tribomutations
force (certainly, this is a non-equilibrium mechanism...).
That is to say, the friction coefficient turns out to be a
delayed portion of the exergy internally dissipated by
the tribo-interface, being this an aspect proper of
absolutely irreversible thermodynamic systems16,17). It is
demonstrated here that the observed trajectory for the
friction coefficient (), comes from the collision
between two movements difficult to be observed...
and synchronized: 1. Gibbs Free Energy of reactions,
(G0) and 2. fluctuations of its proper kinetics of
Tribology Online, Vol. 6, No. 1 (2011) / 56

Mechanochemical Friction of Third-Body as an Exergetic Collision

reaction coming from internal tribomutations ( ( g t ) ).

Most of all, a little variation in that internal dynamic
dramatically alters the resulting convolution, that is to
say, the collision .
3. Development of the third-body mechanochemical
friction
Evident thermodynamic activity provided by
tribomutations, well justifies the hypothetic existence of
a generic internal rate of an always positive entropy
production at the level of the immeasurable
tribo-interface (friction is a robust irreversible
phenomenon). That is to say, it is very possible that this
internal tribo-rate of the interface is sustained on
indirect factors, especially third-tribologicals body,
and metallurgic flows at the friction sub-surface (the
typical direct factors are temperature, pressure and
speed of the tribo-system). This internal rate of always
positive production of tribo-entropy, clearly puts the
friction coefficient farther from its orthodox purely
adhesive definition18), thermo-reologic8), and/or as a
measure of the rubbing force (Da Vinci, Amontons and
Coulomb), among others (the tribo-rate of internal
entropy production will, sooner or later, complicate any
calculation for the estimated average value of the
oscillating coefficient of friction that is a
non-deterministic quantity).
In agreement with the previous argument, it is very
reasonable to suppose that the irregular behavior of the
friction coefficient has its origin in the time/gradient
complex mechanism that inhabits in the internal part
of the immeasurable tribo-interface, as the central
hypothesis
of
irreversible
Non-Equilibrium
Thermodynamics suggests when it raises the existence
of internal kinetic -coordenates. In this sense, the
variables or internal inhabitants , have
thermodynamic representation (e.g. the fluctuation g,
with g: micro-Gibbs Free Energy), but it is also
possible to interpret them metallurgical (fluctuations of
tribo-mutations, flow of vacancies, dislocations,
changes in composition, etc.), and/or they can be
considered as a generic mechanochemical activity
coming from the third-body. In any way these internal
conditions are interpreted, it is certain that the
condition of order of the Thermodynamic state of the
tribo-interface, will never be constant; the eventual
order will be dynamic, because it must accommodate
to the external conditions (relative humidity, contact
pressure, speed and others), and internal (metallurgic
flows, tribomutations, etc.). In synthesis, the
immeasurable tribo-interface is a thermodynamically
open system (see Fig. 1), and of feedback control
(third-body circulation, mass and energy between the
surfaces, etc.). In other words, the material
tribo-interface has memory, and consequently, a
constitutive relation for the friction coefficient, being
unnecessary, as demonstrated here, to resort to the
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molecular structure of the material components to refer

to the fluctuating behavior of the dissipation process ...
The fundamental equation of the Thermodynamics
was applied to a generic friction place, but considering a
time differential dt sensitive to the internal fluctuations
; that is to say, and in accordance with the hypothesis
of the thermodynamic local equilibrium, a differential dt
that allowed to incorporate the possible time/gradient
third-body mechanism in the definition of a
tribo-entropy rate , with internal rate int) of
irreversible entropy production.
An expression of the

type16,17) A was obtained, where the

friction coefficient denotes a dissipated

thermodynamic process, is the thermodynamic force
of stationary action (macro-temperature), denotes

density, T an effective temperature, the

average fluctuating and dominant internal kinetic
process (the internal variable also denotes the
advancement degree of a reaction of physicochemical
nature), and A the internal affinity of the tribo-system
(for example: concentration of species that however

Fig. 1. Schematic representation of the

immeasurable tribo-interface as an open
thermodynamic
system
of
feedback-control16). An exergetic friction
coefficient (with physical units), considers
the existence of a complex internal
time/gradient mechanism that
inhabits
in
the
immeasurable
tribo-interface (the coordinates
definition of a purely mechanical friction
coefficient only considers the existence of
directly external influence on the
tribo-interface)
fluctuate, the reciprocal thermic gradients that fluctuate,
dislocations, vacancies, tribomutations, etc.). The
expression for suggests that the friction coefficient
has physical units (inclusive at stationary temperature
; aspect coherent with the treatment of Exergy that is
given to the friction here). The friction coefficient
corresponds with the extensive specific calorific power
variable divided by the square of the effective
Tribology Online, Vol. 6, No. 1 (2011) / 57

Rodrigo Bulnes

temperature [W/kgK2] (lets notice Unit [kg] gives

accounts of wear).
The expression for the rate of entropy internal

rises
from
the
production
int A ,
T

physical-chemistry time/gradient-activity between

and A . As shown below: a linear relation between
-fluctuations and the -dissipation, to the
-stationary temperature, is made, invoking the
Fluctuation-Dissipation Theorem (FDT)1):

R ( )
(t )d and

0
t

0 (t[ ])

R( )
(t )
(t )d , with ( A).

0
t

(1)

dissipates -friction via R (but from the dynamics

provided by ). In other words, is associated to an

average rate of tribo-chemical micro- reactions that - at
a -stationary temperature-, (quasi) steadily dissipate
the
-process,
after
the
rates
compete
thermodinamically and internally in the tribo-interface19).
Competence is given between submicroscopic Free
Energies, thinking they re create from flows of
vacancies, movement of dislocations, internal friction,
tribo-mutations, absorbed particles, wear particles, etc.
Each of these phenomena provide its own
submicroscopic flow of Free Energy, but the most
evident are the -fluctuations coming from the
competence between rates (that yield the response
function R).

It will be demonstrated that a linear solution for

-based on the Gibbs Free Energy-, adapts well to
certain observed trajectories for the friction
coefficient in isothermal conditions5). This solution
considers that at stationary temperature , the
tribo-interface internal processes suffer small but
persistent physicochemical fluctuations in conditions of
quasi-static equilibrium. This is equivalent to suppose
that the process fluctuates around its thermostatic
quasi-equilibrium, always providing irreversibility or
internal entropy (by its own microscopic definition).
The linear approximation N P A , where N and
P are phenomenological coefficients independent from
time, requires that A( , ) b g , where
denotes external coordenates (e.g. pressure, speed, etc.),
b is a new phenomenological coefficient, and g is
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P ( g )

Equations (1) bind to each other (t denotes (macro)

time and denotes (micro) kinetic-time). Tribologically,
these equations indicate that the immeasurable
tribo-interface -at -stationary temperature-, steadily

micro-Gibbs Free Energy internally generated by the

friction system
(does not seem this energy is
susceptible of direct measurement. However, FDT
indicates the power spectrum that would cause the
dance of thermodynamical micro-fluctuations to
tribo-contact level, must be measured, as it is possible to
associate those power spectra to characteristic times t[]
of processes () that react more internally... The
respective autocorrelation analises could perfectly point
out the emergency of the fractal dimensions associated
to these times t[ ] ~ t/ ). This affinity A ~ -g
indicates the degree of advancement of the direct kinetic
reaction.
Finally it goes to an equation of the type1):
(2)

where P 1 N b . From this eq. (2) the

phenomenological micro-response (R) of the
tribo-interface, at a stationary temperature , is extracted
(so we have the terms that vary explicitly with the time,
~~G 0
assuming
that
:

d
- Pgt
; that is to say,
~ -Pgdt (t)G ~ e

0

G 0

~(Pe

-Pgt

)( G0 )~

dR
d

R
t

~Pe

-Pgt

, see eq.

(1)2). It is a hypothesis of this work that Gibbs Free

macro-energy G0, already out of the exponential
scale, behaves as external variable. Thus, exothermic
macro-dissipation of Free Energy (G0), fluctuates

internally ( R ) to stationary temperature ,

R
Pgt
R (t[ ]) G01e Pgt
Pe
t

(3)

where the phenomenological coefficient P denotes the

behavioral conduct change of some local physical
property of the tribo-system (e.g. a local vibration, a
local physicochemical fluctuation linked to a time of
relax (1/), local desorption, endothermic, exothermic,
etc.).
Making some replacements (eq. (3) into eq. (1)1), the
response of the friction coefficient as a genuinely
mechanochemical friction of exergetic-linear order
range, can be obtained17).

(t[ ]) 0 G01 (e Pgt 1)

(4)

Here t[] = Pgt is the thermodynamic equivalent of

the kinetic time (t / ) g t .

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Mechanochemical Friction of Third-Body as an Exergetic Collision

phenomenon is

especially exergetic because the

fluctuations of Gibbs micro-Free Energy ( Pgt g t )

could perfectly be non-linear (from this we named them
micro-Exergy!). On the other hand, if we notice that

gt

denote different scalings linked to

G0 as well as e
one only amount denominated friction, then the eq. (4)
already poses the existence of a collision phenomenon
gt

to describe the attribute

between scales G0 vs. e
(this point will be developed in the next section,
when implications of inverse kinetic reaction A ~ g
are explored).
Analysis follows with a viscoelastic analogy related
to stationary macro-temperature . It poses an
H-function complimentary to R that in the dominium of
time16)

(t[ ]) Pg , where (t[ ])

H (t[ ])

(t[]), is the Diracs impulse function. In other words,

and contradicting Continuum Media Mechanics, also
appears
animated
by
an
energetic-pulsing
phenomenon manifested in terms of an in-situ attribute
of the tribo-interface ( ~ ( 0 ), ( 1 ), ( 2 ),... ); that
is, the time (t[]) = 0 = 0 can be associated to quick
local changes in the way of dissipation of Gibbs Free
micro-Exergy. Successive pulses indicate quick, intense
and successive unfoldings of Exergy, in exothermic or
endothermic conditions (states), depending exclusively
on the laws of thermal, chemical and mechanical
stability (but not exclusively of the stationary
temperature...).
This mechanism would force a
permanent and spontaneous (exothermic) -or induced
(endothermic)- adjustment among: the local temperature,
the friction coefficient (now mechanochemically in-situ
defined), and Gibbss Free micro-Exergy dissipated by
the immeasurable tribo-interface. This is demonstrated
by the partial integration of certain equation16,17):

H (t[ ])
(t )d
t
0
t

H (t[ ] 0)

(5)

The integral expression to the right side of the eq.

(5) would correspond to the fluctuating thermodynamic
micro-force -linked to g-, that forces to an irregular
behavior of (by itself, eq. (5) demonstrates the
mechanochemical nature of , inclusive under
conditions of isothermic or stationary friction). At last
instance, the third-body would be thermodinamically
unstably due to a permanent incompatibility between

the state/process variables g . Nevertheless,

in the isothermal-relax equilibrium the integral of
fluctuations of the eq. (5) disappears, and emerges a
generic in-situ instantaneous relation of the type
(considers a more consistent aspect of external

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macro-fluctuation instead of ): ~ G0 ,
where is the average friction coefficient and, as
it has been explained, G0 (for t[] > 0) is the Gibbs
Free macro-Energy of the tribo-system, but different
from Gibbs Free micro-Exergy of microscopic and
internal reactions that we have denoted for g and
appearing linked to pulsations 0, 1, 2, etc. According
to the integral expression of the eq. (5), internal
phenomena effectively lead to an exponential scaling of
in-situ dissipated energy (for t[] > 0 ).
Clearly the eq. (5) and previous, indicate that under
the appearance of a thermically dominated friction,
actually exists an exergetic dissipation of Gibbs Free
micro-Exergy that appropiates the behaviour observed
for the then badly named friction coefficient
(there is a delay time () involved with all this
description of dissipated potencies by friction). That
is to say -and inclusive in the range of thermo-linear
description of the rubbing phenomenon-, at stationary
temperature exists a double in-situ dissipation of
power linked to material rubbing..: one of them is the
purely mechanical, classical and orthodox power
( P mec FN V , where FN: normal load and V: sliding
speed), and the other is the purely physicochemical
power (G0 and g). However, the imbricated existence
of a real dance of fluctuations of Gibbs Free
micro-Exergy dissipated by the third-body (0, 1, 2,
etc.), separates the factible and simultaneous
observation of these two powers, but G0 and g appear
as responsible for the wear (they would also be
responsible for the tribological failures in general...).
3.1.Mechanochemical friction of third body as a collision
phenomenon
A first linear link between the friction coefficient
of mechanochemically defined (eq. (4)), and the generic
Gibbs Free Energy dissipated by the immeasurable
tribo-interface, has been deducted (besides, a non-lineal
extension of (t[]) is also possible recurring to kinetics
reactions dissipated in the sliding speed20)). In that sense,
a remarkable quality of this Mechanochemical
Friction Theory is that when it is used to calculate the
Load Carrying Capacity of surfaces, they appear natural
and spontaneously -in the speed-normal load plan of the
transmitted power-, the 05 most enigmatic forms of
failure of the Tribology (scuffing, pitting, micro-pitting,
tooth-fracture and extreme-wear20-23)).
It will be demonstrated that it is possible to relate
this deduction with the self-organization of metal
surfaces phenomena5). In all this way of understanding
friction, the friction coefficient will arise as a
collision between Gibbs Free macro-Energy and the
kinetic reaction aroused and incubated by the always
positive internal tribo-rate of entropy production.
Literally speaking, manifests conforms to a collision
between time scales.
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Rodrigo Bulnes

The + sign that accompanies the external factor

G01 (eq. (4)), comes from considering the
dominant presence of a kinetic of direct-dissipated
exothermic reaction by the internal regime-scale of
fluctuations ( A~g e Pgt ); that is to say, the
previous equation (4) has the following two
spontaneous solutions (or the case of perfect
equilibrium between adsorption and desorption we
have : (t[]) = 0, with G0 = 0):

(t[ ]) 0 G01 (e Pgt 1)

0e Pgt , G0 0 (exoth. ads.)

Pgt
0 (1 e ), G0 0 (endoth. des.)

(6)

For the opposite case, dominant presence of a kinetic

of inverse-dissipated reaction by the internal regime of
fluctuations ( A~g e Pgt ), appears a sign - that
accompanies to the factor G 01 . The new internal
dominant scale (kinetic), modifies the equation (4), the
same as the two external solutions that should be
considered as non-spontaneous solutions (especially
exothermic desorption of reagents; physical
adsorption is always Exothermic, but chemical
adsorption may also be endothermic (several authors)):

(t[ ]) 0 G01 (e Pgt 1)

e Pgt , G0 0 (endoth. ads.)
0
Pgt
0 (1 e ), G0 0 (exoth.des.)

(7)

The following Figure 2, shows the trajectories that

this current third-body mechanochemical friction throws,
in conformity with the predictions of the equations (6)
and (7). It should be noticed that, eventually, the
mechanochemical solution for the endothermic
adsorption (see eq. (7)) might be interpreted as a
desorption of reagents in products (the spontaneous
thing is that there is exothermic adsorption of reagents
in products). That is to say, the inverse reaction
reagents products being endothermic, might perfectly
drops to an externally forced desorption -as it is
interpreted in curve 1 of Fig. 2 in Polyakov5)-, faced to a
sudden imposition of contact load (that for the effects of
the present analysis is an influence or external variable
):
In accordance with the ideas here raised, it is
theoretically demonstrated that to establish a
mechanochemical it is necessary to consider the
effect that provides the collision between the time scales

G0 > = < 0 and e

g t

or e

gt

. However, such a

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Fig. 2. Representation of the curves predicted by

the mechanochemical friction for a hypothetical
homogenous tribo-interface (compare them with
Polyakov5)). The curves come from understanding
the friction coefficient as a collision between
scales of energies present in the immeasurable
tribo-interface. A scale is an issue of Gibbs Free
macro-Energy (G0), and the other is dissipation

gt

of micro-kinetics of internal fluctuations ( e ,

etc. internal fluctuations may be of first, second,
etc., degrees, it is even factible to study
intermediate degrees (fractals)). In other words
fluctuations of internal reaction kinetics, may
clearly
become
non-linear
(absolutely
irreversible), being more exact to think in internal
pulsations
of
exergy.
Thus,
the
mechanochemical is s certainly exergy
dissipated in virtue of a collision between time
scales: the external which is G0 and the internal
which are kinetic pulsations. It can properly be
said that -mechanochemical is a dissipated
exergy which is supported for the collision
between
both
scales.
The
endothermic
non-spontaneous adsorption, can be understood as
simple
imposed
desorption
and
the
non-spontaneous exothermic desorption would
turn to maintain a very low friction coefficient, so
low that it quickly tends to a negative value...
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Mechanochemical Friction of Third-Body as an Exergetic Collision

description of raises an important problem, as Fig. 2

scarcely recreates ideally homogeneous conditions.
Nevertheless, the tribocontact is certainly heterogeneous,
so that a formulation nearer to this aspect of reality is
raised by the following non-linear equation for the
mechanochemical (deduction of equations (8) and (9)
are fully explained in Bulnes21-23)):

( g t ) 2 ~ 0

(8)

where is a parameter and ( g t ) denotes an operator

(it could be estochastic). The previous equation has the
form of Logic-Map of the Physics of CHAOS:

t 1 ( g t ) t (1 t )

(9)

where ( / ( g t )) is an external parameter. The

following Figure 3 shows the results of iterating the eq.

(9) for two hypothetical cases: the operator ( g t ) ,

linked to exergetic fluctuations (which are internal),
influences dramatically the dynamics observed for .
This operator is dominant if compared with the effect
provided bye border external conditions (0 and ).
Prediction of these results has an evidently
qualitative character, but the holistic description that
raises this mechanochemical of the third tribologicals
body, is generic enough to allow the incorporation of
effects coming from the coherent states, catalysis,
synergy, structures and dissipative phenomena, etc..., all
of them linked to the self-organization of surfaces5,24). In
other words, this mechanochemical definition of the
friction clearly adapts well to topics like selective
transference (zero-wear Garkunovs phenomenon),
energy dissipation mechanisms (Exergy), dissipation vs.
friction (and wear) correlation, Wear Thermodynamics
(predictions), CHAOS and complexity to different
scales, thermodynamically external forces (radiation,
electrical flow, magnetic flow, load, speed, etc.),
lubrication failures, tribological harm, etc.
Theoretically, this mechanochemical friction should
be fixed (for physical measure). That is, the purely
mechanical aspect is directly measured from the friction
force. However, the chemical aspect must be made,
composed or structured, based on rates of
tribo-chemical reactions, a chapter of Tribology which
is closer to the triboscopy in-situ (the paper points out
that immediatly arises a delay-time () between the
coupling of mechanochemical and tribochemical
processes). Thus, phenomenological coefficients N, P
and b are variable attributes of the interface, that is,
that can be transformed in quantities strongly dependent
from the undirectional time provided by int. However,
this paper only states the need to consider the
Japanese Society of Tribologists (http://www.tribology.jp/)

Fig. 3. Result obtained from iteration of the

equation (9) from t = 0, 1, 2, 3... Hypothetically,
from
the
thermodynamic,
metallurgic,
physicochemical, etc. point of view, the
immeasurable tribo-interface is an heterogeneous
system, so much so that the observed friction may
acquire a cyclical behavior (less heterogeneous
(a), with parameter = 3,5), and even chaotic
(more heterogeneous (b), with parameter = 4,0).
According to the here raised, the microscopic

kinetic-operator ( g t ) , is the subjacent-dominant

phenomenon of the observed trajectory for
(coherently, a coefficient of initial friction 0 =
0.1 and the parameter = 1.0, behave as external
coordinates; behaves as a thermomechanical
factor, eventually associated to the thermal
resilience of the surfaces19)).
immeasurable tribo-interface as a heterogeneous system
that dissipates an essentially unstable -process because
of the practical incompatibility (and theoretical)
synthesized in the expression ~ G0 . The word
incompatible as a synonymous of surfaces composed
of
micro-thermodynamic
states
in-situ,
non-homogeneous among themselves.
Tribology Online, Vol. 6, No. 1 (2011) / 61

Rodrigo Bulnes

Fig. 4. Two Gibbs Free macro-EnergiesG0,

slightly varied between them (continuous
lines and dotted lines. E: units of energy)
Finally, and for corroborating the nature of the
collision of the mechanochemical , the Figures 4 and 5,
show the resulting collision () between a unique
Gibbs Free macro-Energy of reaction (G0) (Fig. 4),
opposite to a light quantitative change between two
fluctuation dynamics of Gibbs Free micro-Exergy

internal of kinetic reactions ( g t ) (Fig. 5, upper). Again,

the -observed movement (Fig 5, below) comes,
fundamentally, from an internal non-observed

movement ( g t ):

Fig. 5. The consistent variations of Gibbs Free

4. Conclusions

micro-Exergies of kinetics reactions ( g ) , are

expressed in % (upper). These two dynamic

The present holistic description of friction suggests

that the friction coefficient arises from the transition
among the incubated Free micro-Exergy of the internal

reaction kinetics ( ( g t ) ), and the Free macro-Energy of

the external reaction (G0). Literally speaking, the
-mechanochemical of third-body dissipated behaves as
a collision among time scales. One of the scales is
manifested to macro-measurement level G0 , whereas
the other belongs to the probabilities space-state linked to

internal kinetics ( ( g t ) ). These ideas are coherent with

the physical checking that it is friction with the
environment which eliminates probability waves
underlying in the sub-atomic world, etc. That is to say,
external dissipation of the process () converts reality
-or own values G0 -, the probabilistic states that

tribo-entropy internal dissipation linked to ( g t )

acquires. This process of tribo-convertion towards
reality, could technically lead to the concept of
decoherence25).
5. References
[1] Woods, L. C., The Thermodynamics of Fluid
Japanese Society of Tribologists (http://www.tribology.jp/)

fluctuations of ( g ) , have the same average

value; one is sinusoidal-stationary, and the other
is irregular (dotted line). Clearly non-observed
kinetics of these fluctuations, are the ones
affecting
the
observed
collision

( g t ) 0 G01 (e g t 1) (below)

[2]
[3]
[4]
[5]

Systems, Clarendon Press, Oxford; Oxford

University Press, New York, 1975.
Godet, M., The Third-Body Approach: a
Mechanical View of Wear, Wear, 100, 1984,
437-452.
Fronius,
S.,
Maschinenelemente
Antriebselemente, VEB Verlag Technik, Berlin,
1971. (in German)
Spikes, H., In-Situ Methods for Tribology
Research, Tribology Letters, 14, 1, 2003, 1.
Polyakov, A., Process of Self-Organization in
Metals, A. A. Blagonravov Engineering Institute,
Russian Academy of Sciences, Moscow, 29, 2,
1993,
19-27.
(Traslated
from
Fiziko-Khimicheskaya Mekhanika Materialov).
Tribology Online, Vol. 6, No. 1 (2011) / 62

Mechanochemical Friction of Third-Body as an Exergetic Collision

[6] Garkunov, D. Kragelsky, I. and Polyakov, A.,

Selective Transfer in Friction Components,
Transport, Moscow, 1969, 104. (in Russian)
[7] Blok, H., Theoretical Study of Temperature Rise
at Surface of Actual Contact Under Oiliness
Lubricating Conditions, Proc. of the Gen. Disc. of
Lub. Inst., London, 2, 1937, 222-235.
[8] Escobar, E., The Additive EP-Condition and the
Critical Scuffing Limit for Rolling-Sliding, Trans.
ASME, Journal of Tribology (JOT), 118, 1996,
125-130.
[9] Escobar, E. and Escobar, C., Rheological 3-D
Modeling of Scuffing for the EP-Additive
Condition, Journal of American Standard Testing
Material (ASTM) International (JAI), 2, 2,
February, 2005, JAI12828.
[10] Winter, H., Michaelis, K. and Collenberg, H.,
Kontaktzeit-Methode zur Berechnung der Fre
btragfhigkeit
von
Stirnradgetrieben,
antriebstechnik, 31, 2, 1992, 57-65. (in German)
[11] Persson, B., Theory and Simulation of Sliding
Friction, Phys. Rev. Let., 71, 8, 23 August, 1993,
1212-1215.
[12] Nicolis, G. and Prigogine, I., Self-Organization in
Non-Equilibrium Systems, John Wiley and Sons,
New York, USA, 1977.
[13] Santner, E., Reibkraftschwankungen- Quelle,
Informationsquelle, Probleme, Tribologie Fachtagung, Gttingen, Germany, 1999. (in
German)
[14] Gourdon, D., Burnham, N., Fritz, M., Hhner, G.
and
Spencer
N.,
Nanotribology
and
Macrotribology: the Relative Roles of Mechanics
and Chemistry in Energy Dissipation Processes,
http://www.snf.ch, 2001.
[15] Duboka, . and Arseni, ., Tribo-Mutations in
Tribo-Mechanical Systems, 2nd International
Conference
on
Tribology,
Proceedings,
Thessaloniki, Greece, Balkantrib, 1996, 703-710.

Japanese Society of Tribologists (http://www.tribology.jp/)

[16] Bulnes, R., Thermodynamical Facts of the

Tribo-Interphase, Linked with the Additive
EP-Reaction, Dipl.-Ing. Thesis, University La
Serena, Chile, 1996. (in Spanish)
[17] Sariego, P. and Bulnes, R., The Friction
Coefficient as a Exergetical Reaction (The
Mechanochemical
Friction),
Latinamerican
Review of Physics (RIF), 4, 1, 2008, 35-42. (in
Spanish)
[18] Bowden, F. and Tabor, D., The Friction and
Lubrication of Solids, Oxford University Press,
Oxford, 1950.
[19] Zhang, F. and Lee, J., Friction-Induced Oscillatory
Behaviour of One-Dimensional Detonations, Proc.
R. Soc. Lond. A, 446, 1994, 87-105.
[20] Bulnes, R., Theoretical Friction and Surface
Damage: Scuffing, Pitting, Micro-Pitting and
Tooth-Fracture Limits, Session IV-special design
considerations, Preliminary Program. American
Gear Manufacturers Association (AGMA), 2004a.
[21] Bulnes, R., Theoretical Friction and Surface
Damage: Scuffing, Pitting, Micro-Pitting and
Tooth Fracture Limits, Binational Congress
CONAMET/SAM, La Serena-Chile, 2004b. (in
Spanish)
[22] Bulnes, R., The Friction Coefficient as a
Thermodynamic Reaction, Journal Remetallica,
Nr.11, Engineering Faculty, Metallurgical
Department, University of Santiago de Chile
(USACH), 2004c, 31-40. (in Spanish)
[23] Bulnes, R., Copyright Nr. 139.301, 2004d.
[24] Abdel-Aal, H., Complexity, Synergy and
Emergence in Tribosystems: Toward an Alternative
Theory for Damage in Sliding Contacts, Int. J.
Materials and Product Technology, 38, 1, 2010.
[25] Zeh, H., The Physical Basis of the Direction of
Time, 5th Edn., Springer, Berlin, Heidelberg,
2007.

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