Tribology International 38 (2005) 337–353

www.elsevier.com/locate/triboint

Importance of the triboemission process for tribochemical reaction

Czeslaw K. Kajdas*
Warsaw University of Technology, Institute of Chemistry in Plock and Central Petroleum Laboratory in Warsaw (Poland),
31 Zwirki i Wigury Ave., Warsaw 02 091, Poland

Abstract
Chemical reactions under boundary lubrication conditions are distinct from those of thermochemical ones. Flash temperature is very short
and holding in esteem the mechanically triggered chemistry and thermally triggered chemistry at the contact of asperities caused by the flash
temperature effect, the following question arises. ‘Can this reaction initiation process be considered in terms of overcoming the activation
energy by heat or by another form of energy’? The purpose of this paper is to discuss that question in terms of the hypothesis: The common
denominator of tribochemical reactions is that they might be initiated by low-energy electrons. This is consistent with the negative-ion-
radical action mechanism (NIRAM) approach assuming that tribochemical reactions are initiated by electrons in the energy-range of 1–4 eV.
The hypothesis is also relevant to the next author’s hypothesis saying that the intermediate reactive species of both tribochemical reactions
and some heterogeneous catalytic reactions are produced by the same mechanism, governed by the NIRAM approach. The catalyst effect on a
chemical reaction is to increase its rate. The reaction rate is further increased when the catalyst is under friction (tribocatysis). The primary
objective of this work is to better understand mechanisms of tribochemical reactions and catalytic processes. To initiate thermochemical
reactions, heat should be supplied. The same is due to heterogeneous catalytic reactions, however, the catalyst lowers the reaction activation
energy. Even a very high calculated flash temperature is short lived, thus, it rather cannot initiate tribochemical reactions by heat. The present
author assumes that flash temperature can be expressed in the form of the thermionic emission. Bearing this in mind, it is possible to
hypothesize that heterogeneous catalytic reactions are also initiated by thermal electrons. Accordingly, the tribocatalytic process might be
initiated and/or enhanced by triboelectrons. Important objective of this work is to better understand both tribochemical reactions and
catalytic/tribocatalytic processes. Tribochemistry of simple environment friendly lubricant compounds and examples of water synthesis
catalytic and tribocatalytic processes are presented and discussed.
q 2004 Elsevier Ltd. All rights reserved.

Keywords: Boundary lubrication; Triboemission; Triboelectrons; Exoelectrons tribochemistry; Flash temperature; NIRAM approach; NIRAM-HSAB theory

1. Introduction
To better understand the complexity of tribochemistry, it
is good to start with citation of some statements recently
presented by Ludema [1] ‘The state of tribology is mixed.
Overall tribology is compelling and vital art not a coherent
community. There is great emphasis on, and progress in
several scientific aspects and in routine maintenance aspects
of the field but almost no product engineer has the tools for
estimating product life with useful precision, from first
principles.’ On the other hand, the nature and the effects of
the interactions that take place at boundary friction contact
are associated with various physical processes,
* Fax: C48 22 6595894.
E-mail address: ckajdas@zto.pw.plock.pl
e.g. triboemission, and also control the friction and wear
behavior of the materials involved. Wear of materials, that
can also be considered in terms of the contact surface
enlargement, occurs by many different mechanisms, depend-
ing on the materials, the environment, the operating
conditions, and the geometry of the wearing bodies.
Triboemission process is defined as the emission of electrons,
ions, photons, UV radiation, IR radiation, acoustic emission,
etc. under conditions of tribological damage. Most recent
review paper by Kajdas et al. [2] considers the major issues of
triboemission, particularly electron emission processes. The
surface enlargement during friction creates new surfaces,
which form a bridge between the physics and chemistry of
wear processes, leading to microscopic aspects of a wide
variety of wear mechanisms. During these interactions forces
are transmitted, energy is exchanged, the surface topography

0301-679X/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2004.08.017
338 C.K. Kajdas / Tribology International 38 (2005) 337–353
is altered, and loose wear particles are generated. All these
seemingly random and complex phenomena follow a certain
order and satisfy the laws of nature, as explained by Suh [3].
Not only such variables as sliding velocity, normal load,
material hardness, but also the environment of hydrocarbons
under boundary lubrication conditions [4,5], are correlated
with triboemission charge intensities. According to
Nakayama and Hashimoto [5], triboemission of both
negatively and positively charged particles was measured
during the scratching of various metals, ceramics, and
polymers under boundary lubrication conditions with
saturated hydrocarbons.
Presently, the triboemission process should be considered
along with micro-triboplasma, recently discovered by
Nakayama and Nevshupa [6], because it is mostly composed
of UV photons and exoelectrons. According to the most
recent Nevshupa’s paper [7], mechanoemission is an
ensemble of emission phenomena resulting from mechanical
action between solids. Study of mechanoemission is an
intricate problem since it includes a multitude of mechanical
actions and a multitude of emission phenomena of various
physical natures, which may vary depending on the ambient
conditions and type of materials. Mechanoemission strictly
relates to mechanochemistry defined as a branch of chemistry
dealing with the chemical and physicochemical changes of
substances of all states of aggregation due to the influence of
mechanical energy [8]. Historically, the term mechanochem-
istry was coined by Ostwald for this field of research and the
mechanoemission has been a subject of physics and
chemistry, while studies were focused especially on the
electromagnetic aspects, i.e. emission of electrons, ions and
electromagnetic radiation. Many experimental and theore-
tical studies of the mechanoemission have been done with
disperse systems using milling of materials, peeling out of
adhesive films as well as with plastically deformed and
fractured materials like polymers, ionic and covalent
crystals, etc. According to [7], the following main types of
triboemission phenomena can be distinguished:
(i) emission of gas atoms and molecules including
emission of radicals and molecular clusters,
(ii) emission of electromagnetic radiation,
(iii) emission of electrons,
(iv) emission of ions,
(v) emission of magnetic field,
(vi) emission of electric field including emission of electric
charges and generation of tribocurrents,
(vii) emission of noise, vibration and acoustic emission
(AE),
(viii) emission of heat.
These emission types are shown in Fig. 1. Emission of
gas atoms and molecules at friction results from the
competition gas release and gas adsorption processes.
When at certain sliding conditions, the rate of gas
adsorption exceeds the rate of gas release, total emission
Fig. 1. General scheme of triboemission [7].
rate becomes negative. Such emission of negative rate has
been called ‘anti-emission’.
By physical nature, triboemission phenomena are
classified into two classes: (1) emission of particles
(‘corpuscular’), and (2) emission of energy (Fig. 2). The
particle emission includes neutral particles (atoms, mol-
ecules, radicals and clusters) and charged particles (elec-
trons, negative ions and positive ions). Three main types of
energy emission encompass: electromagnetic energy,
mechanical energy and heat. Mechanical energy includes
mechanical oscillations of various frequency ranges, i.e.
vibration, noise, ultrasonic emission, acoustic emission, etc.
Electromagnetic emission can be classified into static and
dynamic. Static emission includes static electric and
magnetic fields, while dynamic emission includes electro-
magnetic waves of various wavelengths, i.e. radio waves;
IR, visible, UV light; and X-rays.
For many years, mechanoemission has been considered
almost exclusively originating from high energetic ‘inter-
intermediate excited states’ [7], which are formed in the
material of mechanically affected solids due to breaking of
chemical bonds, i.e. due to plastic deformation, fracture,
peeling of adhesive films, etc. [8–10]. The excited states are
formed because the rate of the energy release exceeds the
rate of the energy dissipation. These excited states give rise
to emission of electrons, ions, molecules, etc. The
mentioned triboplasma [6] introduced a new activation
mechanism that does not require initial breaking of
chemical bonds in the mechanically affected solids, as
frictional electrification can occur without breaking bonds,
e.g. due to contact potential difference and thermoelectric
effect [11]. On the other hand, from the standpoint of
mechanoemission, friction is considered simplistically as
plastic deformation and breaking of chemical and adhesive
bonds.
Looking at the frictional contact ‘black box’, it is to
assume that ‘high energy intermediate excited states’ of
mechanoemission should also include ‘flash temperature’.
 C.K. Kajdas / Tribology International 38 (2005) 337–353
Fig. 2. Classification of triboemission phenomena by physical nature [7].
This can be somehow substantiated by Gilman’s statement
emphasizing that mechanochemical effects have often been
attributed to strain energy assisting thermal energy [12].
When covalent bonds are bent/sheared, the energies of their
highest occupied molecular orbitals are raised, whereas the
energies of their lowest unoccupied molecular orbitals are
lowered. Thus, the gap between levels, which determines a
bond’s stability, is decreased [13]. Considering now that
strain becomes large enough to close the gap, the bonding
electrons can move freely, so that a transformation, or
reaction, can proceed athermally [12]. The simplest way
illustrating that phenomenon is based on the NIRAM-HSAB
model and presented below [14].
Work [15] presents a generalized negative-ion-radical-
action-mechanism (NIRAM)-hard and soft acids and bases
(HSAB) theory and provides its possible application for
accounting for some tribochemical processes under bound-
ary lubrication conditions. The approach combines reactiv-
ity of lubricant molecules and tribological solids according
to reactions triggered by mechanical action and reactions
affected by acid–base interaction. Major HSAB interactions
are related to tribochemical reactions, initiated by low-
energy electrons. Fig. 3 depicts a general approach to the
NIRAM-HSAB action mechanism. Specific issue of the
tribomicroplasma discovery is that the plasma emits mostly
electrons, invisible ultraviolet photons and, to a less extent,
infrared photons [6,16].
Considering the (a) triboemission process, (b) ‘flash
temperature’ phenomenon, and (c) tribomicroplasma gen-
eration in a gap around a sliding contact, this paper aims at
339
presenting all these phenomena in terms of electronic
energy. From the view-point of tribochemistry, the micro-
plasma components and the general triboemission and/or
fractoemission processes, it is also necessary to consider an
interaction of negatively charged particles with photons. For
example, it is known that the absorption of a single photon
with an energy, hn, (h is the Planck’s constant and n is
frequency) larger than the electron affinity results either
indirect photoemission from negatively charged clusters or
in a fast thermalization of the energy and a subsequent
delayed emission [17]. Bearing in mind all the discussed
physical facts, possible ‘conversion’ of flash temperature to
thermionic emission might be considered as follows. The
flash temperature conversion is then the interaction of UV
photons with negatively charged particles (clusters) pro-
duced by thermal electrons, leading to generation of
additional low-energy electrons that, according to the
NIRAM approach are responsible for triggering tribochem-
ical reactions. Fig. 4 shows the general approach to
molecular mechanism of tribochemistry schematically
demonstrating possible conversion of a thermally excited
spot to low-energy electrons.
Fig. 3. NIRAM-HSAB lubrication mechanism approach: Sa, tribological
microsurface area; Lm, lubricant molecule; eK, electron emitted under
boundary lubrication sliding conditions [15].
340 C.K. Kajdas / Tribology International 38 (2005) 337–353
Fig. 4. Illustration of the tribochemical reaction triggering by triboemission.
Typical physical phenomena evolving from wearing
processes comprise increased contact temperature and
triboemission. Emitted low-energy electrons can initiate
tribochemical reactions, which govern tribology processes
by forming anti-wear films. The chemical reactions due to
friction include several types of reaction processes.
(i) Genuine tribochemical reactions (initiated only by
mechanical action).
(ii) Reactions of thermochemical processes: oxidation,
polymerization, degradation).
(iii) Heat enhanced tribochemical reactions controlled by
both heat and mechanical action.
(iv) Catalytic processes.
The primary objective of this work is to better understand
mechanisms of tribochemical reactions and catalytic
processes.
2. Triboemission
Triboemission of electrons is a particular case of the
general phenomenon of exoelectron emission (EE), which is
observed when a material surface is disturbed and whose
origin is still unclear. EE has been observed from both
metals and non-metals and there is strong evidence that
oxides or other non-metallic surface layers are needed for
EE to occur. Triboemitted electrons are thought to play a
significant role in tribochemical reactions under boundary
lubrication conditions [2,14,18–20]. Important research in
the field of triboemission was carried out by Nakayama et al.
[21] on using a Faraday-cup type assembly to detect bursts
of electric current—either charged particle emission or
surface-charge variation—from scratching diamonds on
metals and insulators. Kim et al. [22] investigated photon
emission, electron emission intensities, and electron kinetic-
energy from reciprocating scratching of MgO with dia-
mond. The work of Molina et al. [23–25] characterized
triboemission of electrons from diamond-on-alumina,
diamond-on-sapphire, alumina-on-alumina, and diamond-
on-aluminum. The three ceramic-materials consistently
showed burst-type negatively charged triboemission during
contact at constant load and speed, while the aluminum
system produced no significant emission. Decaying emis-
sion after contact ceased also was detected from the three
ceramic systems for durations exceeding the minute-range
[25]. For the cases of diamond-on-alumina and diamond-on-
sapphire, energy spectrometry showed that a large fraction
of the triboemitted negative charges were of low-energy
(e.g. 1–5 eV). This finding was of significant importance
because in the NIRAM approach, it was hypothesized that
the energy level of triboelectrons to initiate tribochemical
reaction should be 1–4 eV [18]. A new high-vacuum
triboemission instrument—that is based on a channel-
electron multiplier (CEM) in the pulse-counting mode—
was designed, constructed and employed for measurements
of charge intensity [23,24]. The new triboemission instru-
ment features a rotating-sliding shaft, which introduces
the mechanical inputs into a high-vacuum chamber.
Detailed descriptions of the triboemission instrument’s
features, operating ranges and measurement and data
acquisition capabilities were presented in the work of
Molina et al. [23–25].
The retarded-energy spectrum of negative charges
triboemitted from diamond-on-sapphire is depicted in
Fig. 5. The spectrum shows that important fractions of
negatively charged particles are emitted in the zero to about
5 eV energy-range, with only decaying fractions extending
to higher-energy triboemission. Similar retarded-energy of
negative charges triboemitted from diamond-on-alumina
was obtained [26]. Higher-energy emission may result from
 C.K. Kajdas / Tribology International 38 (2005) 337–353
Fig. 5. Retarded-energy-spectrum for negatively charged triboemission from diamond-on-sapphire [25].
patches of electrostatic charge on the surface. Dickinson
et al. [27] postulated, although for different material systems
than sapphire or alumina, that electrostatic potential would
increase kinetic-energy of particles immediately after
emission.
Fractoemission from semiconductors was investigated
by Dickinson et al. [28], who used a channel electron
multiplier (CEM) in pulse-counting mode to detect electron
emission outputs from bending fracture of single crystal Si.
Another work [29] studied in-vacuum emission during
cleavage by bending of Si and Ge. They observed burst-type
electron emission starting at the onset of cleavage with
durations ranging from tens of microseconds to 1.8 ms. The
signals were independent of dopant concentrations, of high-
vacuum levels and of temperature. Maxima of integrated
signal intensity were up to three times higher for Si cleavage
than for Ge under the same conditions. All the reported
fractoemission outputs were substantially longer than the
typical fracture durations (e.g. 2–10 ms). A review of
relevant earlier research work on triboemission can be
found in the paper [2].
Research described by Molina et al. [30] was carried out
to compare the negatively charged triboemission process
from semiconductors with the triboemission results from
selected insulators (e.g. alumina and single crystal sapphire)
and one related conductor material (e.g. aluminum). Fig. 6
shows a clear decreasing trend of the triboemission intensity
as contact progresses on the same wear track for diamond-
on-Si and diamond-on-Ge. Such decreasing triboemission
may relate to decreasing semiconductor wear. Clear
evidence for a new finding was presented that no emission
is produced after the contact ceased for these semiconduc-
tors, while post-contact triboemission was previously
detected for an insulator (e.g. alumina) under vacuum.
Creation of new surface by wear and bond cleavage is
essential to triboemission from ceramics, however, clear
mechanism for charged particle triboemission is still
lacking. This paper does not consider that issue. A detailed
341
atomic mechanism explaining triboemission can be difficult
to develop for ceramics, because their surface reconstruc-
tion is a very complex process. Variety of triboemission
phenomena and distinction of their physical nature prescribe
a multitude of detection methods. Despite of the similarity
and interrelation of triboemission mechanisms, various
types of triboemission are subject of various branches of
science. In this connection, developing of a general
classification of detection methods and application-specific
characteristics of triboemission is of high importance.
Selection of the measuring method is a multi criterion
problem, when many parameters like sensitivity, resolution,
reliability, accuracy, medium, geometry, propagation direc-
tion, speed of propagation and others should be taken into
account. Detailed characteristics of various triboemission
types are presented and discussed in [7]; typical emission
rates and range of intensities are given for reference. The
signal-to-noise ratio is estimated qualitatively for typical
measuring methods and shows the difficulty of reducing the
normal noise. The ratio is specific to the detection method
and can vary significantly for various measuring
methods for the same triboemission type. The selected
detector type should be able to operate in the medium,
Fig. 6. Average rates of negatively charged triboemission for first-25 turns
in diamond-on-Si and diamond-on-Ge measurements. Load: 5 N. Speed:
1.9 mm/s [30].
342 C.K. Kajdas / Tribology International 38 (2005) 337–353
where the triboemission propagates, and should be placed
considering the propagation direction. Another important
characteristic of the triboemission is a propagation speed,
which determines the time constant of the data acquisition
system.
3. Tribochemistry
3.1. Thermochemical and tribochemical reactions
Mechanical action at solid surfaces tends to promote
chemical reactions and to produce surface chemistry that
may be entirely different to those observed in static
conditions. Chemical reactions are characterized by chemi-
cal kinetics concerning with their velocity and also the
mechanism by which chemical reactions occur. Chemical
reactions of tribological additives under the boundary
lubrication conditions involve the formation of a film on
the contact surface. These reactions initiated by mechanical
action in the direct contact zone relate to tribochemistry
considering the chemical changes of both solid mating
elements and lubricant molecules due to the influence of
boundary and/or mixed lubrication conditions. According to
[8], tribochemistry is a branch of chemistry dealing with the
chemical and physicochemical changes of solids due to the
influence of mechanical energy. Tribochemical reactions
are distinct from those of thermochemical ones.
The feasibility that chemical reactions in solids can be
initiated by mechanical deformation and/or tribological
contact has been considered for over 100 years [31]. The
spontaneous emission of low-energy electrons (exoelec-
trons) from solid surfaces subjected to plastic deformation,
abrasion, fatigue cracking, or phase transformation is well
known from as early as 1950 [32]. However, the hypothesis
that low-energy electrons, which are spontaneously emitted
from rubbing surfaces, can be the key factor in some
tribochemical reactions, was formally postulated in rela-
tively recent work [18]. Accordingly, a concept of
ionization of lubricant components by low-energy electrons
(1–4 eV), which are emitted from freshly formed surfaces in
the friction of mating surfaces, was proposed. Considering
now, an electron of 4 eV, it is easy to realize that its
attachment to a molecule can split the molecule into two
reactive intermediates:
AB C e/ AKðnegative ionÞ C B% ðfree radicalÞ
These reactive intermediates can react by both anionic and
free radical mechanisms. Accordingly, we do not need to
introduce any heat, e.g. by heating the sample up to over
300 8C, because the molecule receives energy of some
400 kJ/mol to initiate the reaction. That energy level
exceeds well carbon–carbon (C–C) or carbon–oxygen
(C–O) bonding energies. This points out that even few
low-energy electrons are able to initiate tribochemical
reaction, similarly as UV photons. Bearing this is mind, it is
possible to hypothesize that low-energy electrons are not
only initiating tribochemical reactions according to the
NIRAM approach, but also might contribute significantly to
flash temperature.
A relevant application of the NIRAM hypothesis was the
development of the mechanism of vinyl-type tribopolymer-
ization [33,34], the seminal idea for which was early
introduced by Furey [35]. Another example considers
reactive intermediates generated by low-energy electrons
and UV irradiation. Zhao et al. [36] hypothesized that low-
energy electron mediated degradation of PFPE lubricants
under sliding conditions of computer head on hard disk in
UHVC is the dominant mechanism. The hypothesis was
very helpful in better understanding and accounting for all
the major experimental findings. Work by Vurens et al. [37]
demonstrated the negative ion emission from the Demnum
S200 lubricant during irradiation with low-energy electrons
(e.g. of less than 14 eV).
3.2. Flash temperature
To better understand how flash temperature can initiate
the process of tribochemical reactions, flash temperature has
been connected with the thermionic emission process.
Bearing in mind that the duration of ‘flash temperatures’
is very short and holding in esteem both the mechanically
triggered chemistry (mechanochemistry) and the thermally
triggered chemistry at the contact of asperities caused by the
flash temperature effect, it is necessary to ask the question
‘Can this reaction initiation process be considered in terms
of overcoming the activation energy by heat or by another
form of energy?’
In this paper, the author’s answer to that question is
comprised in the following hypothesis: The common point
in question of tribochemical reactions is that they are mostly
initiated by low-energy electrons enhanced by ultraviolet
photons. Additionally, the initiation mechanism of tribo-
chemical reactions will be bridged with heterogeneous
catalytic effects by another hypothesis saying that ‘the
intermediate reactive species of both tribochemical reac-
tions and some heterogeneous catalytic reactions are
produced by the same mechanism’. It should be emphasized
that the flash temperature is short lived and thus, it cannot
initiate chemical reactions by heat. The present author has
suggested that flash temperature, expressed as the maximum
computed friction temperature, can also be expressed in the
form of the thermionic emission. Accordingly, the thermio-
nic emission is assumed to bridge ‘hot spots’ with rubbing
surface spots activated by triboemission of electrons (see
Fig. 4). Therefore, flash temperatures might also be
expressed in the form of electronic energy. This is consistent
with NIRAM assuming that tribochemical reactions are
initiated by low-electrons (exoelectrons).
 C.K. Kajdas / Tribology International 38 (2005) 337–353
3.3. NIRAM approach
The application of the NIRAM approach explains the
role of exoelectrons in some relevant tribochemical
reactions, in particular in tribopolymerization of addition-
type monomers [33,34], which was mentioned in Section
3.1. NIRAM comprises the following major stages [18–20]:
(i) Low-energy electron emission and creation of posi-
tively charged spots, generally on the top of asperities.
(ii) Action of the emitted electrons with the lubricant
molecules causing the formation of negative ions and
radicals on the rubbing surfaces.
(iii) Reaction of negative ions with metal surfaces, and
other reactions such as free radical reactions, forming
an organometallic (or inorganic) film which protects
the rubbing surfaces from wear.
(iv) If the shear strength is high chemical bonds of
organometallic compounds are cleaved resulting in
producing inorganic films and further radicals.
(v) Eventual destruction of protective layer caused by
wear, followed by electron emission and subsequent
formation of a new protective film according to stages
(i)–(iv), as demonstrated in Fig. 7.
In summary, this boundary lubrication model proposes
the formation of protective organometallic and inorganic
layers on rubbing surfaces according to the NIRAM
approach. The initiation reaction process is due to
triboemitted low-energy electrons combined with flash
temperature. The latter might also be considered in
electronic form (thermionic emission).
3.4. Catalysis, tribocatalyses, and tribochemistry
Thermochemical reactions are distinct from tribochem-
ical ones [8]. Similarly, heterogeneous catalytic processes
Fig. 7. Reaction cycle of lubricant components on solid contacts during friction.
343
are distinct from tribocatalytic ones [38]. Most surface
catalytic reactions and the formation of surface intermedi-
ates involve charge transfer, either an electron transfer or a
proton transfer. These processes are often viewed as
modified acid–base reactions [39]. The electron transfer
capability of a catalyst is expressed according to the Lewis
definition. A surface site with a free pair of electrons that
can be transferred to the adsorbate is a Lewis base. A site
capable of receiving a pair of electrons from the adsorbate is
a Lewis acid. Considering now the NIRAM-HSAB concept
[15], it is possible to look for similarities and differences
between tribochemistry and catalysis. There is a link
between tribochemistry and catalysis and/or tribocatalysis
[38]. The first application of that approach for platinum
catalyzed water synthesis from hydrogen and oxygen under
both friction and non-friction conditions was most recently
demonstrated [40].
4. Discussion
4.1. Brief introduction to ecological lubricants
A wide variety of ester oils is used in many applications
including engine oils, gear oil and hydraulic fluids.
Incorporated to mineral oil esters generally improve the
lubricant anti-wear property and/or reduce friction coeffi-
cient. Presently, there is increased interest in developing
environment friendly (ecological) lubricants for a wide
variety of reasons, however, the driving force mostly relates
to more stringent regulations, especially those that require
the use of low-emission lubricants. The same is due to fuels
of new generation that must incorporate lubricity additives.
Apart from fatty acids, esters are good candidates as
lubricity additives for current diesel fuels. Accordingly, one
important trend is to develop ashless anti-wear additives for
344 C.K. Kajdas / Tribology International 38 (2005) 337–353
both lubricants and fuels. Esters are suitable products for
such purpose. In the most recent paper by Furey et al. [41], a
review of developments in environment friendly anti-wear
additives in lubricants from tribopolymerization was
presented. Another group of potential tribological additives
relates also to regular esters, particularly those produced
from natural products.
Usually, it is suggested that the soap formation by the
ester under boundary lubrication conditions is due to the
hydrolysis process of the ester. Over 50 years ago, Bowden
and Moore [42] assumed that esters with reactive metals
such as zinc and cadmium caused chemical attack. Thus, it
has been emphasized that the reaction with the ester was due
to hydrolysis [42,43]. The hydrolysis reaction is known to
be catalyzed by acids or bases. It is, however, difficult to
realize that under typical boundary lubrication conditions
mineral acid or base might be present to catalyze the ester
hydrolysis process. At this point, the following questions
should be addressed. How the boundary friction process can
affect base oils, particularly pure chemicals, for example,
hexadecane in comparison with tribochemistry of car-
boxylic acids and some alcohols. What is the part of
NIRAM in initiating tribochemical reactions and what are
their specific intermediates? Earlier paper [44] presented
new tribochemical findings concerning those questions and
evidenced the findings by detailed surface analytical data of
different mating element wear regions, mostly obtained by
using FTIRMA and SEM/EDS techniques.
4.2. Tribochemistry of simple compounds
Majzner and Kajdas [45], investigating tribochemical
reactions of carboxylic acids under boundary lubrication
conditions found that, apart from regular salt (monodentate
carboxylate group), salts with double bond in a, b position
and chelating symmetric bidentate carboxylate group are
formed. Fig. 8 shows the proposed structure of iron salt with
double bonding. Such compounds were not detected after
reactions took place under static conditions. This also
Fig. 8. Example of chelating bidentate structure formed from caprylic acid
[45].
clearly shows the difference between tribochemical and
thermochemical reactions. Fischer et al. [46] studied
tribochemical and thermochemical reactions of stearic
acid adsorbed on a copper surface. Chemisorbed stearic
acid was found in both monodentate and bidentate sites.
Interestingly, the bidentate surface configuration was
increased after the occurrence of the tribochemical reactions
induced by surface rubbing.
Using a pin-on-disk tribometer, systematic tribological
tests were performed on disks made from steel, aluminum,
brass and bronze. The obtained test results described in [47]
clearly demonstrated that distinct and very similar spectra
were obtained from the wear scar regions for each of the
materials tested. Fig. 9 presents Fourier transform infrared
microscopy (FTIRM) spectra taken from various metal
disks lubricated with hexadecane after 500 m sliding
distance. This finding allows stating that in all these cases
similar tribochemical reactions occurred on different
material surfaces. Interestingly, all major absorption bands
of the spectra presented in Fig. 9 are very similar to the
spectrum taken from the wear scar after a four-ball machine
test lubricated with SN400 base oil, as shown in Fig. 10.
Using a pin-on-disk apparatus, Makowska et al. [49]
investigated tribochemical changes of hexadecane under
boundary lubrication conditions in detail. The research
considered both (i) the chemical transformation of the bulk
lubricant and (ii) the chemistry of products generated in wear
tracks. Gas chromatography/mass spectrometry analysis of
hexadecane after friction tests showed that the following
compounds are formed during the friction process: alde-
hydes, alcohols and carboxylic acids. These tribochemical
processes lead to the formation of homologous compounds
with smaller molecular weights than hexadecane.
Another work [50] was focused on the temperature
influence on tribochemical reactions of hexadecane. The use
of the FTIRM and electron spectroscopy for chemical
analysis (ESCA) techniques to analyze the surface films and
deposits in the contact region allowed to evidence the
formation of three reaction products from hexadecane under
boundary lubrication conditions. These products include: (i)
compounds having Fe–O bonding (salts and chelates),
Fig. 9. FTIRM spectra of hexadecane tribochemical reaction products on
the surface of different materials [47].
 C.K. Kajdas / Tribology International 38 (2005) 337–353 345

Fig. 10. FTIRM spectrum taken from wear scar of a four-ball machine test lubricated with a mineral base oil (SN 400) [48].

(ii) carbonyl compounds and (iii) iron carbide. Fig. 11
presents FTIRM spectrum taken from the wear track
generated at 200 8C. Characteristic infrared absorption
bands around 3500–3000, 1740 and 1600 cmK1 in this
spectrum are different from those obtained at ambient
temperature (see Fig. 12). The observed signals most
probably relate to carbonyl compounds, e.g. esters,
aldehydes, ketones. It appears that thermal oxidation
process proceeding in the bulk lubricant at elevated
temperature is more enhanced and leads to formation of
different oxygen containing compounds. It seems that
absence of bands assigned to –COOFe groups are caused
by relatively thick organic layer. These results show that
tribochemical reactions of both fatty acids and hydro-
carbons are very complex. Interestingly, the tribochemistry
of simple alcohols under boundary lubrication conditions of
a steel-on-aluminum system is also very complex [55].
Specific physicochemical processes lead to significant
changes on the surface and in the bulk oil. The latter
changes lead to the lubricating oil deterioration [51].
Looking at the presented results, it is possible to say that
inert and non-polar compounds, such as hexadecane or base
oil hydrocarbons, under boundary lubrication conditions
can—via tribochemical reactions—produce a mixture of
compounds that just lubricate. These results also provide an
evidence for the hypothesis that two types of oxidative
processes of hexadecane under boundary lubrication
conditions should be considered. The first one at ambient
temperature that is controlled by the mechanical action and
the second one clearly controlled by temperature. This
clearly supports the statement that at present, the basic
mechanisms of boundary lubrication are very poorly
understood mostly due to complexity and perpetual
transient nature of boundary lubrication [52]. More research

Fig. 11. FTIR spectrum of triboreaction products formed during friction process carried out at 200 8C [50].
346 C.K. Kajdas / Tribology International 38 (2005) 337–353

Fig. 12. FTIRM spectrum of triboreaction products formed during friction process carried out at ambient temperature (20 8C) [50].

is needed to clarify the reaction mechanisms, particularly palmitic acid and 1-octanol; C16CC16 denotes the mixture of
the mechanism of surface reactions. Paper by Hsu [53] palmitic acid and 1-hexadecanol. The wear reduction for the
summarizes our understanding of boundary lubrication from system lubricated by plain n-hexadecane equals zero.
a chemical perspective and highlights some research needs Experiments [54] were designed in a way aiming at
to be addressed in the future. checking what might be the effect of a possible breakage of
the ester bond by hydrolysis on the lubricant anti-wear
4.3. Reaction mechanism of esters property. Thus, two series of lubricants were selected. The
first lubricant series included hexadecane with ester
The ester hydrolysis process leads to a cleavage of the additives and the second series of lubricants related to
ester to generate another compounds interacted with water. mixtures of these ester substrates (acid plus alcohol), added
In the case of monoesters, hydrolysis results in formation of to the base fluid (hexadecane) at the same concentrations as
two compounds: alcohol and carboxylic acid. Triester of for the esters. Equimolar ratio (1:1 molar ratio) of the acid to
glycerol with carboxylic acids under hydrolysis yields alcohol was used for all the mixtures applied. If under the
glycerol and three molecules of carboxylic acids. To check testing conditions, the ester hydrolysis actually involves the
the importance of hydrolytic reaction for the soap formation breaking of the ester bond to produce an acid and an alcohol,
mechanism from esters, we tried to find if typical conditions the anti-wear behavior of the esters should correspond to the
under boundary lubrication cause the hydrolysis of esters anti-wear behavior of their substrates. In other words,
dissolved in hexadecane [54]. The lubricants tested included
hexadecane with five ester additives (palmitates) at the Table 1
concentration range 0.03–1.5 wt%. The results provided Relative ball wear reduction for tested additives at various concentrations
clear evidence that under the boundary lubrication conditions [54]
aliphatic esters present in hexadecane do not hydrolyze to Additive Relative ball wear reduction (%)
form the acid/alcohol substrates of the ester. These esters and
Additive concentration in n-hexadecane (wt %)
equimolar mixtures of their substrates were used as additives.
The results clearly show the previously proposed reaction 1 0.1 0.03
mechanism of esters, which was based on the NIRAM PAL-C8 69.2 21.5 6.4
approach. Relative ball wear reduction results for steel C16CC8 77.3 77.1 77.2
PAL-C10 67.5 20.8 6.7
lubricated with the tested lubricants are summarized in C16CC10 81.1 81.2 80.9
Table 1. The PAL stands for palmitate and Cn denotes the PAL-C12 51.4 18.0 8.7
alcohol used to make the ester. Thus, PAL-C8 is octyl C16CC12 90.1 89.9 90.1
palmitate and PAL-C16 is hexadecyl palmitate. The mixtures PAL-C16 78.7 27.8 18.8
of palmitic acid with different alcohols are denoted by C16C C16CC16 96.4 96.4 96.5
PAL-C18 53.8 19.6 10.0
Cn, where C16 stands for palmitic acid and Cn relates to the C16CC18 91.6 91.7 91.8
alcohol. Accordingly, C16CC8 is the equimolar mixture of
 C.K. Kajdas / Tribology International 38 (2005) 337–353
Fig. 13. Influence of the solution concentration of octadecyl palmitate
(series 1) and equimolar mixture of palmitic acid and 1-octadecanol (series
2) in hexadecane on the ball wear [54].
the equimolar acid/alcohol mixture at very low concen-
tration in hexadecane should not provide higher relative
wear reduction than the ester at much higher concentrations.
The wear reduction data presented in Table 1 clearly
demonstrate that the lowest wear reduction is observed for
the lowest concentration of the esters, however, the mixtures
of palmitic acid and different alcohols reduce wear very
dramatically at this concentration. This finding is of
particular importance for the soap formation mechanism
under boundary lubrication conditions. Fig. 13 shows the
ball wear reduction versus the additive concentration in
hexadecane. These results enable to state that the hypothesis
saying ‘during the friction process under boundary lubrica-
tion conditions lubricated by aliphatic esters, the ester
hydrolysis process cannot proceed without an adequate
catalyst’ is well substantiated. Thus, it is possible to
conclude that the soap formation mechanism from esters
under boundary lubrication conditions can be controlled by
the NIRAM approach.
The ester base-promoted hydrolysis process presented in
the most simple way can be expressed by the following
reactions:
RCOOR1 CK OHðstrong baseÞ/ RCOOH C ½R1 OK
/ ½RCOOK C R1 OH
Fig. 14. Ester reactive intermediates generated by electron attachment.
347
that lead to the ester substrates: the carboxylic acid in the
form of anion [RCOOK] and alcohol (R1OH). The strong
base (KOH) is the conjugate base of the water molecule. In
this case, conjugate base is the ion that forms when an acid
loses its proton. Accordingly, [R1OK] and [RCOOK] are
also conjugate bases of their acids. The stronger the acid, the
weaker will be its conjugate base. Thus, we can relate the
strength of a base to the pKa of its conjugate acid. The pKa is
the negative logarithm of the acidity constant, Ka, present-
ing an equilibrium related to the strength of an acid (KaZ
[H3OC][AK]/[HA]). The larger the pKa value of the
conjugate acid, the stronger is the base. For example, the
conjugate base of ethyl alcohol (pKaZ16) is stronger than
the conjugate base derived from acetic acid (pKaZ4.75)
[56]. Taking now into account, the water molecule
interaction with a low-energy electron (exolectron) emitted
under boundary friction conditions, the KOH strong
conjugate base along with hydrogen free radical (H%) are
produced:
HOH C e/ HOK C H%
It can be realized that in this case the hydrolysis process
is initiated by the HOK strong conjugate base, generated
during the water molecule splitting process by the attached
exoelectron. Thus, it is conceivable to consider the
exoelectron-promoted hydrolysis without any catalyst. On
the other hand, it is necessary to bear in mind another, and
even more important process, namely, the exoelectron
interaction with an ester molecule, producing directly two
types of negative ions RCOOK and ROK. The ester reactive
intermediates produced via the dissociative electron attach-
ment, showing two types of C–O bond cleavage, are
presented in Fig. 14.
The first bond cleavage type produces carboxylate anion
(RCOOK) and the free radical R%1. The second bond
cleavage generates the alkoxide anion (ROK) and the
R–%CaO free radical that undergoes further reactions. To
produce free radicals and thereby initiate the free radical
chain reaction process either heat or catalyst is needed.
Therefore, an electron attachment in this case acts as
348 C.K. Kajdas / Tribology International 38 (2005) 337–353
a catalyst. The exoelectron dissociative attachment to an
ester molecule yielding two types of negative ions is clearly
evidenced by the electron attachment mass spectrographic
results [57].
The carboxylate anion RCOOK interacts with a posi-
tively charged friction solid surface site to produce a salt
(soap). This fact supports a mechanism presented below.
The mechanism shows both the salt and chelate type film
formation by carboxylate anion and alkoxide anion. Please
note that the caboxylate anion’s pKa value is lower than that
of the alkoxide value. This means the carboxylate ion is
more acidic species than that of the alkoxide anion or, in
other words, the carboxylate anion is the more stable species
than the alkoxide one. Alkoxide ions (R–CH2–OK) are
known to split off two hydrogen atoms [58]. Recently, it was
found that such ions might form very special film on wear
tracks as elucidated by FTIRM analysis [55].
Fig. 15 depicts the formation mechanism of the tribofilm
elucidated for the ethanol lubricated steel-on-aluminum
friction system. Most recently, some evidence for such
specific film was also presented for fluorinated alcohols
[59]. Therefore, it is conceivable to give the positive answer
to the question previously asked ‘Is the NIRAM approach
responsible for initiating tribochemical reactions of esters’?
One conclusion of an early review on mechanically
initiated chemical reactions in solids [60] was as follows:
Fig. 15. Chemical reactions of the tribofilm formation process under boundary lubrication conditions of steel-on-aluminum lubricated with ethanol; Al in the
third equation is considered as OAlC [55].
‘Although not new, the study of mechanically induced
chemical reactions in solids has received sparse attention
probably because the subject lies uncomfortably between
chemistry and materials science’. That review examined a
number of possible ways in which mechanical energy can
initiate chemical reactions and emphasized that in many
cases chemical reactions are initiated by heat although
examples exist in which electrical charging and ‘direct bond
excitation’ play an important role. The present author
assumes that the direct bond excitation might be caused by
an electron attachment. The new ‘mechanically initiated’
hydrolysis mechanism presented in this paper is precisely
associated with the above approach to tribochemistry. More
detailed and very sophisticated research is needed to find
unanimous evidence for this mechanism and to elucidate the
complexity of the surface tribofilms produced by ester
lubricants or ester anti-wear and/or friction reducing
additives.
4.4. Flash temperature
Flash temperature is the maximum local temperature
generated at some points in a sliding contact. The flash
temperature occurs at areas of real contact due to the
frictional heat dissipated at these areas. The duration of the
flash temperature is often of the order of a microsecond [61].
 C.K. Kajdas / Tribology International 38 (2005) 337–353
Usually, the flash temperature concept is attributed to Blok
[62], followed by Archard [63] and others [64] by
developing solutions for stationary and moving regimes
based on the Peclet number, va/K, where v is the velocity, a,
the contact radius and K, thermal diffusivity. Recently,
Soom et al. [65] found that during the earlier parts of a
sliding interval, all heat input is confined to small volumes
at individual asperities which form ‘hot mounds’ sur-
rounded by much cooler regions where there is little or no
temperature change. They have demonstrated that as the
contact takes place at the tip of the contacting asperities,
local temperatures reach significant values even in the very
small time interval of 3 ms. The maximum temperature
reached at a single asperity contacts corresponds to the flash
temperature. As there may be many asperity contacts of
different size interacting at once, there will be a distribution
of flash temperatures. From the analysis, they found that the
high flash temperatures occur even while the overall
temperature rise of the surface may be orders lower [65].
This information leads to a linkage of triboemission with
flash temperature. At this point, it is necessary to come back
to the general question ‘Can the tribochemical reaction
initiation process be considered in terms of overcoming the
activation energy by heat or by low-energy electrons?’
Now we need to come back to the present author’s
suggestion that flash temperature, expressed as the maxi-
mum computed friction temperature, can also be considered
in terms of the thermionic emission. Accordingly, the
thermionic emission is assumed to bridge ‘hot spots’ with
rubbing surface spots activated by triboemission of
electrons, as depicted in Fig. 4. Accordingly, flash
temperatures might also be expressed in the form of
electronic energy. Most recently, that assumption was
confirmed by examining of thermionic emission due to
frictionally generated heat. The emission of electrons from a
surface due to heating was investigated theoretically for
sliding contacts. Vick et al. [66] showed that high local
temperatures generated by friction of the contacts between
rubbing surfaces can really activate the emission of
electrons. A thermal model previously developed by Vick
and Furey [67,68] for sliding contact was used to predict the
temperature rise over the surface and the Richardson–
Dushman equation for thermionic emission was then used to
estimate the corresponding current density from the surface.
The computed results demonstrate that high local tempera-
tures generated by friction of the contacts between rubbing
surfaces can activate the emission of electrons. Thus, similar
to the typical TSEE, thermionic emission due to frictionally
generated temperatures in sliding contact could have a
number of important consequences including activation of
tribochemical reactions according to the NIRAM approach
and enhancement of surface activity as demonstrated in
Fig. 4.
Looking at other evidences for the importance of low-
energy electrons in triggering tribochemical reactions, the
recent discovery of microplasma generation in a gap around
349
a sliding contact [6] should be also taken into account.
Specific issue of this discovery is that the plasma emits
mostly invisible ultraviolet photons and, to a lesser extent,
infrared photons. From the view-point of the microplasma
components and the general triboemission and/or fractoe-
mission processes, it is necessary to consider an interaction
of negatively charged particles with photons. It is known
that the absorption of a single photon with an energy, hn,
larger than the electron affinity results either in direct
photoemission from negatively charged clusters or in a fast
thermalization of the energy and a subsequent delayed
emission [17]. Bearing in mind all these physical facts, it is
proposed to understand the flash temperature effect as the
thermionic emission process that can also initiate tribo-
chemical reactions.
Accordingly, flash temperatures might also be expressed
in the form of electronic energy. This is consistent with the
NIRAM approach assuming that tribochemical reactions are
initiated by low-energy electrons. All the above information
shows the existence of specific physical and chemical
phenomena that are responsible for the initiation process of
tribochemical reactions that differ from thermochemical
ones.
4.5. Catalysis and tribocatalysis
Catalysis is the phenomenon of a catalyst action and the
catalyst is a substance that increases the rate at which a
chemical system approaches equilibrium, without being
consumed in the process [69]. The primary effect of a
catalyst on a chemical reaction is to increase its rate, and this
must mean to increase its rate coefficient. The reaction rate
is further increased when the catalyst is under friction
(tribocatalysis). To initiate thermochemical reactions heat
should be supplied. The same is due to heterogeneous
catalytic reactions, however, the catalyst lowers the reaction
activation energy. For example, the activation energy of
uncatalyzed reaction: 2N2 O/2N 2 CO 2 equals to
245 kJ/mol and for the gold catalyzed reaction the activation
energy is lowered by a half (121 kJ/mol) [69]. It is to note
that the lowering of the activation energy is a fundamental
principle of catalysis and that it applies to all forms of
catalysis. For catalytic process to occur, there has to be a
chemical interaction between catalyst and the reactant–
product system, however this interaction should not change
the chemical nature of the catalyst except of the surface.
Accordingly, specific surface active sites are of particular
importance. Usually, to initiate a heterogeneous catalytic
process, some heat to overcome the activation energy
barrier must be delivered. Regularly, it requires to elevate
the system temperature to over 200 8C. Even a very high
calculated flash temperature is short lived, thus, it rather
cannot initiate tribochemical reactions by heat. It is assumed
that flash temperature can be expressed in the form of the
thermionic emission. Bearing this in mind, it is possible to
350 C.K. Kajdas / Tribology International 38 (2005) 337–353

Fig. 16. First sequences of the water synthesis process during Pt pin sliding on Pt disk: interaction of hydrogen and oxygen molecules with the catalyst under
static conditions and the electron emission phenomenon plus formation of the oxygen negative-ion-radical reactive species associated with friction [40].

say that heterogeneous catalytic reactions are also initiated
by thermal electrons.
The present author’s hypothesis says that ‘the inter-
mediate reactive species of both tribochemical reactions
and some heterogeneous catalytic reactions are produced
by the same mechanism’. Numerous chemical reactions
relating to catalytic processes can proceed with the same
velocity at significantly reduced temperatures in compari-
son to the thermal reference procedure [8]. This situation
is very similar to the non-catalytic thermochemical
reactions and their tribochemical analogues. Therefore,
from the view-point of the reaction mechanism both
catalytic processes and typical tribochemical reactions
might relate to the same driving force—governed by the
affect of low-energy electrons. Heterogeneous catalytic
processes can be initiated by thermally emitted electrons.
Tribocatalytic process is the typical catalytic reaction
enhanced by the action of triboelectrons produced in the
test system. This hypothesis can be evidenced by our most
recent experimental data described by Kajdas et al. [40]
and Hiratsuka et al. [70]. Based on the hypothesis,
the mechanical action and separately only pure heat action
on the platinum catalyzed water synthesis process were
investigated. UHV experiments have been performed to
generate adequate results for comparison of the effect of
mechanically treated platinum catalyst with the thermally
treated catalyst. On the basis of the obtained results, a
new reaction mechanism was proposed [40]. This specific
mechanism is based on the fact that most of the hydrogen
absorbed in platinum exists in the atomic form. On the
other hand, it was taken into account that under friction
conditions low-energy electrons are emitted. To provide
more evidence for the proposed mechanism, further
research is planned to combine with measurement of
triboelectrons. Figs. 16 and 17 present the proposed action
mechanism of the tribocatalytic process. The following
reaction mechanism is proposed for the process. As
Fig. 16 demonstrates the first phase relates to static
adsorption/chemisorption/diffusion processes of oxygen
and hydrogen. After the friction process onset, low-energy
electrons are emitted. One oxygen molecule attaches one
electron and the oxygen negative-ion-radical reactive

Fig. 17. Sequence of the tribocatalyzed water synthesis process during Pt pin sliding on Pt disk [40].
 C.K. Kajdas / Tribology International 38 (2005) 337–353
Fig. 18. Effect of temperature on the exoelectron emission rate (log I) and
the formation rate of ethylene oxide C2H4O [71].
species is produced. According to Fig. 17, the negatively
charged end of the oxygen molecule interacts with the
positively charged platinum surface spot left by the
emitted electron and thereby the oxygen is chemisorbed.
The other oxygen atom (free radical) looks for hydrogen
atom (free radical) but not for hydrogen molecules (H2)
that are available in the chamber. Hydrogen in the form of
free radical is desorbed from the wear track on platinum
disk and interacts with the oxygen free radical forms
hydroxyl group. Further reaction to form water are
depicted in Fig. 17.
Fig. 16 shows that in the first dynamic stage hydrogen
radicals (H%) and electrons (e) are evolved. The emitted
electron can easily interact with oxygen molecule (O2) to
produce radical-negative-ion (%O–OK). Then, as Fig. 17
shows, the generated radical-anion reactive species look for an
adequate positively charged site on the platinum surface
Fig. 19. Initiation of catalytic and tribochemical processes [38].
351
where hydrogen radicals are available. Such interaction
results in the formation of platinum bonded peroxy-hydrox-
ide. Peroxides are known to be very unstable due to the weak
oxygen–oxygen bonding. Decomposition of the peroxide
leads to generation of hydroxy-radical (HO%) just in the place
where hydrogen free radicals (H%) are evolved. Recombina-
tion of the two radical types produces water molecules.
Actually, it is well known and acknowledged that
heterogenous catalytic reactions take place at centres
where the electron exchange in the catalyst–substrate
system is favored and that electron emission arises from
centers at the surface where electrons are weakly bound. At
this point, that thermally stimulated electron emission
(TSEE, thermionic emission) occurs in the same range of
temperatures which is typical for heterogeneous catalysis
(see Fig. 18).
Taking into account the fact that thermionic emission
has been observed during catalytic reactions, catalysis and
thermionic emission seem to be somehow correlated.
Another reproducible relation was found between catalytic
activity and thermionic emission capacity in different
groups of material such as (i) Pt/SiO2 with different Pt
contents, and (ii) ZnS/Cu with different copper contents
[72]. The catalytic oxidation of hydrogen and carbon
monoxide at NiO, ZnO and platinum black was found
with the occurrence of electron emission. It was also
demonstrated that highly hydrated oxides, e.g. alumina,
magnesia show a strong gas evolution accompanied by
electron emission [73]. Finally, considering all the
discussed results, it is suggested that some heterogeneous
catalytic processes proceed according to the NIRAM-
HSAB approach similarly to tribochemical reactions.
However, typical pure tribochemical reactions are
initiated by triboelectrons and heterogeneous catalytic
processes can be initiated by thermally emitted electrons.
352 C.K. Kajdas / Tribology International 38 (2005) 337–353
On the other hand, a tribocatalytic process can be taken
up as the catalytic process enhanced by the action of low-
energy electrons emitted from the friction contact as
depicted in Fig. 19.
5. Conclusions
(1) Tribochemical reactions under boundary lubrication
conditions are distinct from those of thermochemical
ones.
(2) Tribochemical reactions are mostly stimulated by
triboelectrons (exoelectrons).
(3) Flash temperature is short lived, therefore, it cannot
initiate chemical reactions by heat.
(4) On examples of heterogeneous catalysis, links between
tribochemistry and catalysis/tribocatalysis have been
demonstrated (see Fig. 18).
(5) New general approach to better understanding tribo-
chemistry and tribocatalysis is proposed. The approach
is well evidenced by the most recent research results on
the reaction initiation processes of both catalytic and
tribocatalytic reactions of water synthesis [40].
(6) To provide more evidence for the proposed mechanism,
further research is planned to be combined with
measurement of triboelectrons.
(7) Finally, it seems to be justifiable to conclude that the
most recent specific and sophisticated research on
tribochemistry/tribocatalysis clearly demonstrates the
importance of low-energy electrons in boundary
lubrication.
Acknowledgements
The author wishes to express his sincere thanks to
Professor Ken Ludema for his generous help, fruitful
discussions, and suggestions while writing this paper.
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