Applied Sciences: Molecular Science of Lubricant Additives

applied
sciences
Review
Molecular Science of Lubricant Additives †
Ichiro Minami
Division of Machine Elements, Luleå University of Technology, 97187 Luleå, Sweden; ichiro.minami@ltu.se
† Dedicated to the late Professor Keiji Yamamoto in memory of his contributions to organo-silicon chemistry.
Academic Editor: Jun Kubota

Received: 8 March 2017; Accepted: 21 April 2017; Published: 28 April 2017
Abstract: This review aims at introducing an engineering field of lubrication to researchers who
are not familiar with tribology, thereby emphasizing the importance of lubricant chemistry in
applied science. It provides initial guidance regarding additive chemistry in lubrication systems
for researchers with different backgrounds. The readers will be introduced to molecular sciences
underlying lubrication engineering. Currently, lubricant chemistry, especially “additive technology”,
looks like a very complicated field. It seems that scientific information is not always shared by
researchers. The cause of this is that lubrication engineering is based on empirical methods and
focuses on market requirements. In this regard, engineering knowhow is held by individuals and
is not being disclosed to scientific communities. Under these circumstances, a bird’s-eye view of
lubricant chemistry in scientific words is necessary. The novelty of this review is to concisely explain
the whole picture of additive technology in chemical terms. The roles and functions of additives
as the leading actors in lubrication systems are highlighted within the scope of molecular science.
First, I give an overview of the fundamental lubrication model and the role of lubricants in machine
operations. The existing additives are categorized by the role and work mechanism in lubrication
system. Examples of additives are shown with representative molecular structure. The second
half of this review explains the scientific background of the lubrication engineering. It includes
interactions of different components in lubrication systems. Finally, this review predicts the technical
trends in lubricant chemistry and requirements in molecular science. This review does not aim to be
a comprehensive chart or present manufacturing knowhow in lubrication engineering. References
were carefully selected and cited to extract “the most common opinion” in lubricant chemistry and
therefore many engineering articles were omitted for conciseness.
Keywords: tribology; tribo-chemistry; lubrication mechanism; lubricant formulation; molecular design
1. Introduction
1.1. Tribology and Lubrication Engineering

Tribology, defined as “the science of interacting surfaces in relative motion” [1], was coined
in 1966 [2] by combination of “tribos” (“rubbing” in Greek) [1] + “logy”. This term is becoming
popular as we can find the term in dictionaries, not only in science and engineering fields but also
in general culture. Although this name is relatively young compared to other engineering fields,
empirical knowhow had been known from ancient days back to 2000 BC [3]. Now we can find various
tribological phenomena in our daily life; dental care, shaving, wiping, cooking, etc. Needless to
say, we enjoy modern civilized life using many machines; house equipment, vehicles, IT devices,
industrial manufacturing, transportations, etc. We need tribology every time in everywhere. Thanks to
lubrication engineering, we usually use these devices without being aware of tribology. However, we
experience occasionally that the breakdown of a machine and this mostly happens due to failures of
moving elements. This indicates the importance of lubrication engineering in prolonging the lifetime
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Appl. Sci. 2017, 7, 445 2 of 33
of machines. Lubrication also plays a significant role in improving energy efficiency. Moreover,
lubrication engineering can contribute to comfortable machine operation by reducing unpleasant
vibrations and noises that were developed from the moving contacts. Therefore, lubrication engineering
does work hard in the background to support our civilized activities. Here, most readers of Applied
Sciences would agree with the importance of lubrication engineering but might have little interest
in it as research subject, probably because lubrication is a mature technology and hence is not a
subject in applied sciences. Actually, lubrication engineering, especially lubricants, are still being
developed by mostly trial and error procedures. So far, this has worked well for industrial applications.
From now on, industrial R&D has to pay attention to more energy efficiency with sustainability.
Since conventional procedures consume time and energy, a smart method should be considered.
In this regard, the author believes that the application of fundamental sciences in the right methods
brings successful R&D. Although many lubricants are manufactured by a combination of different
substances, the understanding of the chemistry in lubricants seems rather underestimated. Actually,
chemical information of lubricants is provided without detail and precise description, mainly due to
the complexity of contents and the business matter. Although many tribologists state the importance
of chemistry in tribology, they sometimes disregard “chemistry” because it looks like “a black box.”
This article surveys the chemistry of lubricant additives from viewpoint of fundamental chemistry,
with the hope that it leads to a better understanding of tribological phenomena with molecular science.
The author wishes the readers to be good supporters of tribology, especially those who are not familiar
with machine elements. It would be an unexpected pleasure of the author if this article motivates
a reader to undertake a tribology project with scientific aims.
1.2. The Functions of Lubricants

Lubricants are those substances that intervene between rubbing surfaces, thereby preventing any
negative influences upon moving. The three major functions of lubricants are below.
• Controlling friction—This is the primary role of lubricants. Reducing friction and preventing
wear and seizure (or failure) are necessary in most applications. Well-controlled, high friction is
required for clutches, breaks, etc. Since this is the central objective of the lubricant, we discuss
the phenomena with a lubrication model (Stribeck curve, see Figure 1). Optimized performances
with minimized side effects could be achieved by proper selection of lubricants for specific
machine elements. As modern machines are required to work in a more energy efficient way,
the roles of lubricants are increasing. The importance of additives is emphasized (see Section 2.1
tribo-improvers).
• Cooling the contact—Heat generated by rubbing motion can have many negative influences
on surface materials, such as transformation of microstructure or thermal failure. Ageing of
lubricants is accelerated at higher temperatures. Heat accumulation could be prevented by
circulating a liquid lubricant. The heat capacity of a lubricant is the controlling factor for this
function. This function is mainly supported by the properties of base fluids. Some additives
contribute to the heat conductivity of primary (see Section 2.5.2) or secondary (see Section 2.3.5)
base fluids.
• Cleaning the contact—Wear particles, external dusts, or deposits by aged lubricants could appear
during machine operation. These contaminants negatively influence lubrication performances.
Circulating a lubricant can wash out these nuisances physically. Advanced lubricants contain
some substances to help the cleaning process (see Sections 2.3.2 and 2.3.3).
Lubricants can appear as a liquid, as a semi-solid (greases), or as a solid (including particles

and coatings) form. Since cleaning and cooling functions need fluidity, greases and solid lubricants
could be applied to machine elements where heat and contamination are not serious factors. Because
of the three functions and the benefit of handling, liquid lubricants are most ubiquitous in many
practical applications. Therefore, various additives have been developed and are being applied in
Appl. Sci. 2017, 7, 445 3 of 33
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liquid lubricants. In this regard, this review mainly focuses on additives in liquid lubricants. Of course,
lubricants. In this regard, this review mainly focuses on additives in liquid lubricants. Of course, the
the demands of greases and solid lubricants are also substantial mainly for task-specific purposes.
demands of greases and solid lubricants are also substantial mainly for task‐specific purposes.
Fluid between sphere/flat tribo-contact
L
R2
V
λ < 0.7 mixed
Friction coefficient
 R1
λ>2
Hm
boundary lubrication
lubrication hydrodynamic
lubrication Nomenclature
V Velocity
L Load
R1,R2 Surface roughness
 Viscosity
Hm Minimum film thickness
Hersey number (η･V･L-1) λ = 2·Hm/(R1+R2)
Note: Hm (Minimum thickness of liquid film developed from base fluid between the surfaces, clearance of the
surfaces) could be calculated from the operating parameters (load and velocity) and material parameters
(elastic modulus and pressure-viscosity relations). For detail, see [5].

Figure 1. The Stribeck curve and lubrication regime.
Figure 1. The Stribeck curve and lubrication regime.
1.3. The Stribeck Lubrication Model
1.3. The Stribeck Lubrication Model
There are many types of machine elements with different configurations that work under
There are many types of machine elements with different configurations that work under different
different operating parameters. Lubrication systems are individually designed in most cases. Despite
operating parameters. Lubrication systems are individually designed in most cases. Despite this,
this, we have a versatile model for simulation and explanation of the lubrication performances, the
we have a versatile
Stribeck model
curve [4]. The for simulation
model concept and explanation
is the dependence of of
thefriction
lubrication performances,
coefficient the Stribeck
on the operating
curveparameters (load and velocity), the material properties (surface roughness and elastic modulus), and
[4]. The model concept is the dependence of friction coefficient on the operating parameters
(loadthe lubricant properties (viscosity and pressure‐viscosity relations). As Figure 1 depicts, the friction
and velocity), the material properties (surface roughness and elastic modulus), and the lubricant
properties (viscosity
coefficient and pressure-viscosity
of a lubrication relations).
system varies with As Figure
the Hersey number 1 depicts,
calculated thefrom
friction coefficient
viscosity, load, of a
and velocity.
lubrication systemWhen
variesa with
liquid (lubricating
the Hersey numberoil) is applied to tribo‐contact,
calculated from viscosity, it develops
load, and a liquid
velocity.film
When
between the surfaces. The thickness of liquid film H (or clearance between the surfaces supported
a liquid (lubricating oil) is applied to tribo-contact, it develops a liquid film between the surfaces.
m
by the liquid)

The thickness depends
of liquid filmboth
Hm on
(or the properties
clearance of the the
between solid and the supported
surfaces liquid materials
by the[5]. A viscous
liquid) depends
liquid tends to provide a thicker liquid film at the contact, while a low viscous liquid tends to
both on the properties of the solid and the liquid materials [5]. A viscous liquid tends to provide
provide a thinner film between surfaces. If the thickness of the liquid film is greater than the surface
a thicker liquid film at the contact, while a low viscous liquid tends to provide a thinner film between
roughness R1 and R1 (more precisely λ > 2), the surfaces could be completely separated by the liquid.
surfaces. If the thickness of the liquid film is greater than the surface roughness R1 and R1 (more
Therefore, the surfaces can move without contact between solids and this results in low friction. This
precisely λ > 2),regime
lubrication the surfaces couldas be“hydrodynamic
is defined completely separated by the
lubrication”. liquid.
Ideally, Therefore,
machine the surfaces
elements are
can move without contact between solids and this results in low friction. This lubrication regime is
designed to operate in this regime since low friction as well as negligible wear could be achieved.
defined
When as the
“hydrodynamic lubrication”.
Hersey number becomes Ideally,
smaller, machine elements
the lubrication are to
regime shifts designed to operate
the boundary in this
regime.
Asperities on the surfaces come to interfere with each other. As a result, friction becomes higher and
regime since low friction as well as negligible wear could be achieved. When the Hersey number
substantial wear occurs. This regime is defined as boundary lubrication. The properties of surfaces
becomes smaller, the lubrication regime shifts to the boundary regime. Asperities on the surfaces
comeare important with
to interfere to achieve lubrication
each other. As a performances
result, friction in becomes
this lubrication
higherregime. Mixed lubrication
and substantial wear occurs.
regime is an intermediate regime between hydrodynamic lubrication and boundary lubrication.
This regime is defined as boundary lubrication. The properties of surfaces are important to achieve
Although the phenomena in the real world are more complicated, this simplified model helps us to
lubrication performances in this lubrication regime. Mixed lubrication regime is an intermediate
understand the role of each substance in lubrication systems. Today, the Stribeck model is a
regime between hydrodynamic lubrication and boundary lubrication. Although the phenomena
consensus model to predict the lubrication performance.
in the real world are more complicated, this simplified model helps us to understand the role of
each substance in lubrication systems. Today, the Stribeck model is a consensus model to predict the
lubrication performance.
Relative importance of three functions varies with individual application. For example,
metalworking fluids have to wash out cutting dusts from the contact and have to cool the tool
surface simultaneously. High water based fluids are frequently used in metalworking applications.
Although the lubricity is inferior to that of petroleum-based fluids, water-based fluids have strong
advantages in cleaning and cooling functions together with cost effectiveness. Of course, the lubricity
Appl. Sci. 2017, 7, 445 4 of 33
of metalworking fluid is necessary to prevent tool wear, for example, but cooling and cleaning are
a technical priority in most cases. On the other hand, friction reduction is the major concern for bearing
applications. This is why greases are mostly used in bearing lubrication where cooling and cleaning
functions are of secondary importance. The differences in requirements of lubricants for different
applications could be understood more clearly if we look at the Stribeck curve [4]. Bearings should
be operated under hydrodynamic (precisely under elasto-hydrodynamic) conditions where wear of
material and heat generation are trivial. On the other hand, metalworking processes are “heavily”
influenced by boundary conditions.
When we look at the Stribeck curve carefully, friction increases as Hersey number increases
under a hydrodynamic lubrication regime. This means that if the operating conditions are constant,
friction increases as viscosity of the fluid increases. Since viscosity is defined as “a measure of the
resistance to flow” [6], increased friction by viscosity could be understood as “internal friction in fluids”.
Anyhow, viscosity of fluids has to be controlled t a proper level; that is as low as possible for achieving
hydrodynamic lubrication. Additive technology for controlling viscosity is discussed in Section 2.2.1.
Although machine elements are designed to work under a hydrodynamic regime at steady
state, they experience boundary regimes at least during start-stop operations where the velocity is
0. Therefore, lubricants should support all lubrication regimes, from hydrodynamic to boundary
lubrications, and hence different functions are required. This is the main reason for the complexity
of the lubricant in which different additives are required in a lubricating fluid. Thanks to successful
research by both experiments and simulations, the Stribeck curve well represents the phenomena under
(elasto-)hydrodynamic regimes. In general, we can use lower viscosity lubricants for fast-running
machines in comparison with slow-running machines. Similarly, heavy-load machines need higher
viscosity lubricants, compared to light-load machines.
Wear of tribo-material happens under boundary and mixed lubrication regimes where direct
surface-surface contact occurs. This leads to changes in surface roughness and a possible shift in
lubrication regimes as a consequence. However, the Stribeck curve is based on the assumption that the
material parameter (surface roughness in this case) is constant. It should be noted that the Stribeck
curve does not fully support for boundary and mixed lubrication regimes. Nonetheless, it indicates
inferior lubrication performances under boundary and mixed lubrication regimes compared to those
under hydrodynamic lubrication.
1.4. Tribo-Chemical Reactions

Mechano-chemical reactions have a long history from the alchemist ages [7–10]. Since then,
various chemical reactions have been empirically examined under mechanical stresses such as
agitation in pestle-mortar or collision of solids. In addition to scientific approaches [11,12], industrial
applications of mechano-chemical reaction could be found in preparation of materials [13,14] and
waste treatments [15,16]. The term, “tribolysis” was first published in 1928 [17]. It seems to indicate
“tribo-chemical reaction” but this article is describing alterations of petroleum products by mechanical
agitation (traditional tool for mechano-chemical reactions) compared with photolysis and thermolysis
of these substances.
Tribo-chemical reactions could be categorized as a part of mechano-chemical reactions. t should be
defined precisely as “conversion of molecules to others under the influence of rubbing”. Additionally,
this review focuses on this phenomenon “especially under lubricated conditions”. In this regard,
chemical reactions of lubricants, both base fluids and additives, are of interest. It is generally agreed
that tribo-chemical reactions are complicated phenomena. There are two major causes of the complexity.
One is the problem with the analytes. Lubricants are mixture of various compounds, including base
fluids and different additives. In most cases, their principle structure is hydrocarbons and hence clear
identification of each substance is difficult. When we focus on the reaction mechanism of an additive
of interest, the problem of the detection limit with instrumental analysis usually arises. Concentration
of additive could be as low as in the range of mmol·kg−1 . Specific analytical tools, such as surface
Appl. Sci. 2017, 7, 445 5 of 33
sensitive analysis, combined with a model lubricant (e.g., a solution of single additive in a solvent)
could be a solution for the analyte problem. Actually, many articles are being published on the
mechanism of tribo-improvers (see Section 2.1) with this procedure.
On the other hand, much progress in understanding of the energy for reaction is necessary.
Chemical reaction is an arrangement of atoms within or between molecule(s), and is accompanied
with breaking and making chemical bonds. This process needs energy to occur; tribo-chemical reaction
is a conversion of mechanical energy into chemical energy in one sense. From this point, possible
driving forces (sources of energy for chemical reactions) for tribo-chemical reactions are summarized
in Figure 2. Six possible driving forces are considered for the initiation process of tribo-chemical
reactions [18].
• Heat induces various chemical reactions. It was estimated that rubbing surface could reach as
high as 250–450 ◦ C [19]. Friction generates heat and this is considered as the major cause of
tribo-chemical reactions.
• Nascent surfaces could be exposed by wear of solid surfaces under mixed and boundary
conditions. Similarly, a mechanical stress to crystalline materials can sometimes cause lattice
defects. These produce a chemically active site on the rubbing surfaces [20]. The chemical activity
of transition metals is induced by vacant d-atomic orbital.
• Exo-electrons could be emitted from rubbing surfaces. Those electrons have low energy to promote
chemical reactions but can produce radical intermediates for further chemical reactions [21].
• Elevated pressure up to Giga-Pascal (>104 bar) could be generated at tribo-contact [22]. Since
chemical reactions are initiated by a collision of molecules, compression of reactant raises the
probability of the collision. Chemical reactions at high pressure under static conditions are well
known [23].
• Orientation of molecules may occur if they were flown through a narrow area [24]. This means
the reacting functional groups are close to each other and increases the probability of reaction.
This, together with elevated pressure, contributes to the entropy factor of the reaction.
• Shearing can dissociate chemical bonds in a molecule directly. It is a well-known phenomenon
that molecular mass of polymers can decrease under shearing conditions. The formation of radical
species by the dissociation of a carbon–carbon bond had been reported [25]. Typical shear rate at
tribological contact is in the range of 105 –107 s−1 [19].
Appl. Sci. 2017, 7, 445 6 of 33
exo-electrons Orientation Elevated

(electrochemical of molecules pressure
reactions) (entropy factor) (entropy factor)
+e→ • → →
L
V
Friction heat Nascent surface Shearing

(enthalpy factor) (catalysis of metal) (mechanical
bond dissociation)
→ M → • → •
•
: hydrocarbon CxHy, • : carbon radical

Revised from figure 13 in ref. 18
: functional group M : metal with d-orbital

Figure 2. Possible driving forces for chemical reactions at tribo‐contact.
Figure 2. Possible driving forces for chemical reactions at tribo-contact.
1.5. Components in Liquid Lubricants
So‐called lubricant formulation is a process of mixing substances to prepare a lubricant. The
substances should be properly selected to meet the requirements of machine operation. The
components in liquid lubricants are classified in two groups—base fluids and additives. Base oils are
the major contents of lubricating fluids. It has been empirically known from ancient times that
viscous fluids provide lubrication performances. It was found, about a hundred years ago, that
Appl. Sci. 2017, 7, 445 6 of 33
A tribo-chemical reaction can beneficially or detrimentally influence to the lubrication

performance. There is a consensus in the tribology community that tribo-chemical reactions concern
mainly boundary lubrication conditions. However, from the viewpoint of a reaction mechanism, they
can occur under (elasto-)hydrodynamic conditions as well; elevated pressure, heat by compression,
and shearing are three examples.
1.5. Components in Liquid Lubricants

So-called lubricant formulation is a process of mixing substances to prepare a lubricant.
The substances should be properly selected to meet the requirements of machine operation.
The components in liquid lubricants are classified in two groups—base fluids and additives. Base
oils are the major contents of lubricating fluids. It has been empirically known from ancient times
that viscous fluids provide lubrication performances. It was found, about a hundred years ago, that
certain substances can improve lubrication performances if dissolved in base fluids [26]. Then many
engineering knowledge was accumulated and additive technology for lubricant became a common
technique later on. Today, lubricating fluids are manufactured from base oils and 5–20 mass% of
different additives depending on the practical requirement (Graphic abstract). Base fluids are viscous
liquids having proper viscosity for the application. API defines the category of base oil, as summarized
in Table 1. API Groups I–III are made from crude oil through distillation and refinery processes [27].
They are so-called mineral oils and they constitute the majority of base fluids today because of
their availability at a reasonable cost. In brief, mineral oils are composed of various hydrocarbons
(normal and branched alkanes, cycloalkanes, aromatics, heterocyclic compounds, etc.). It seems
difficult to show the chemical contents in mineral oils, because they vary with production area and
refinery processes. Therefore, viscosity represents the properties of base oil. Conventionally, kinematic
viscosity at 40 ◦ C and at 100 ◦ C is considered for lubricants. The refinery processes have two major
purposes; they are purification and modification of molecular structure. Typically, organic sulfides
and unsaturated hydrocarbons were extracted by solvents to produce Group I, or decomposed by a
catalytic hydrogenation to produce Group II. The importance of these processes for additive technology
is that these impurities often show antagonism to many types of lubricant additives. On the other hand,
a catalytic isomerization of hydrocarbon molecules produces Group III oils. The differences between
Groups I-II and Group III oils are their rheological properties.
Here we introduce the key properties of base fluids; viscosity index: dependency of viscosity
by temperature. Viscosity of hydrocarbons drops as temperature increases. Viscosity index (VI)
represents the rate of changes by temperature [28]. “High” viscosity index is defined as fewer changes
in viscosity by temperature change, as illustrated in Figure 3. Both fluid A and B pose similar viscosity
at 40 ◦ C, while those at 100 ◦ C are different. Needless to say, higher VI is desirable because many
lubrication systems generate friction heat during machine operations. When considerable viscosity
drop happens during machine operation, it causes a shift of the lubrication regime to boundary (see
Figure 1). As a consequence, it raises the risk of high friction and wear. We also discuss this issue
in Section 2.2.1. VI could be calculated according to ASTM D2270, for those fluids of VI < 100. It is
recommended to use software on computers, since currently base fluids with VI > 100 are commonly
used [29].
Besides mineral oils being the major resources of base fluids, natural triglycerides (TG, also
known as vegetable oils, plant oils, or animal tallow) were the only resources of lubricants before the
petroleum age. Although they were used before petroleum products, TGs are currently classified in
Group V because of the fewer demands compared to mineral oils. Technically, those additives for
mineral oils do not always work well for TGs. One reason for this is that additives are manufactured by
petroleum industries. Therefore, industries are interested in improving the performances of petroleum
products. The relevant scientific discussions are given in Section 4.4.
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Appl. Sci. 2017, 7, 445 7 of 33
Appl. Sci. 2017, 7, 445 7 of 33
Appl. Sci. 2017, 7, 445 7 of 33
Table 1. API base oil category and examples.
Appl. Sci. 2017, 7, 445 Table 1. API Table 1. API base oil category and examples.
base oil category
Contents and examples.
Table 1. API base oil category and examples. 7 of 33
Category Classification Contents Viscosity Index Remarks
Category Classification Saturates, Mass% Aromatics, Mass% Sulfur, ppm Examples Viscosity Index Remarks
Saturates, Mass% Aromatics, Mass% Contents
Sulfur, ppm Examples
Category Classification Contents Viscosity Index Remarks
Category Classification Contents
Saturates, Mass% Aromatics, Mass% Sulfur, ppm Examples Viscosity Index Remarks
Category Group I Classification
Solvent‐refined mineral oil Saturates,
65–85 Mass% Aromatics, Mass%
15–35 Sulfur,
Contents
300–3000 ppm Examples Viscosity
80–119 Index Remarks
Extraction of impurities by solvents
Category Classification
Saturates, Mass% Aromatics, Mass% Sulfur, ppmppm Examples Viscosity Index Remarks
Group I Solvent‐refined mineral oil 65–85 Saturates, Mass% Aromatics, Mass%
15–35 Sulfur,
300–3000 Examples
80–119 Extraction of impurities by solvents
Group I Solvent‐refined mineral oil 65–85 15–35 300–3000 80–119 Extraction of impurities by solvents
Group I Solvent‐refined mineral oil 65–85 15–35 300–3000 80–119 Extraction of impurities by solvents
Group I Solvent-refined mineral oil
Group I 65–85
Solvent‐refined mineral oil 15–35
65–85 15–35 300–3000
300–3000

80–119 80–119 Extraction of impurities by solvents
Extraction of impurities by solvents
Decomposition of organic sulfides by
Group II Hydro‐processed mineral oil ≧93 <7 5–300 80–119 Decomposition of organic sulfides by
Group II Hydro‐processed mineral oil ≧93 <7 5–300 80–119 catalytic hydrogenolysis
catalytic hydrogenolysis
Group II Hydro‐processed mineral oil
Group II Hydro‐processed mineral oil ≧93 ≧93 <7 <7 <7 5–300
5–300 80–119 Decomposition of organic sulfides by
80–119 Decomposition of organic sulfides by
Group II Hydro-processed
Group II mineral oil
Hydro‐processed mineral oil =93 ≧93 <7 5–300
5–300 80–119
80–119 catalytic hydrogenolysis

Group III Hydro‐cracken mineral oil ≧95 <5 0–30 ≧120 Isomerization of hydrcarbons
Group III Hydro‐cracken mineral oil
Group III ≧95
Hydro‐cracken mineral oil ≧95 <5 <5 0–30 0–30 ≧120 ≧120 Isomerization of hydrcarbons
Isomerization of hydrcarbons
Group III Hydro-cracken mineral
Group III oil
Hydro‐cracken mineral oil =95 ≧95 <5 <5 0–30
0–30 =≧120
120 Isomerization of hydrcarbons
Isomerization of hydrcarbons
Group III Hydro‐cracken mineral oil ≧95 <5 0–30 ≧120 Isomerization of hydrcarbons
Synthetic hydrocarbons,so‐called
Group IV Oligomers of 1‐alkene ‐ ‐ ‐ ‐ Synthetic hydrocarbons,so‐called
Group IV
Group IV Oligomers of 1‐alkene ‐ ‐ ‐ ‐ Synthetic hydrocarbons,so-called
PAO(poly alpha‐olefin) in the market
Group IV Oligomers of Oligomers of 1‐alkene
1-alkene - ‐ - ‐ -‐ ‐ - PAO(poly alpha‐olefin) in the market
Group IV Oligomers of 1‐alkene ‐ ‐ ‐ ‐ PAO(poly alpha-olefin) in the market
Group IV Oligomers of 1‐alkene ‐ ‐ ‐ ‐ PAO(poly alpha‐olefin) in the market
Group V All fluids not included in groups I–IV ‐ ‐ ‐
‐
Non‐PAO synthetics, plant oils, and
Non-PAO synthetics, plant oils, and
Group V All Group V All fluids not included in groups I–IV
fluids not included in groups I–IV - ‐ - ‐ -‐ ‐
- some low quality mineral oils
Group V All fluids not included in groups I–IV ‐ ‐ ‐

‐ some low quality mineral oils
some low quality mineral oils
Group V All fluids not included in groups I–IV ‐ ‐ ‐ ‐ Non‐PAO synthetics, plant oils, and
Group V All fluids not included in groups I–IV ‐ ‐ ‐ ‐ some low quality mineral oils

because many lubrication systems generate friction heat during machine operations. When
considerable viscosity drop happens during machine operation, it causes a shift of the lubrication
regime to boundary (see Figure 1). As a consequence, it raises the risk of high friction and wear. We
also discuss this issue in Section 2.2.1. VI could be calculated according to ASTM D2270, for those
Appl. Sci. 2017, 7, 445 8 of 33
fluids of VI < 100. It is recommended to use software on computers, since currently base fluids with
VI > 100 are commonly used [29].
200
Viscosity, mm2 s-1 150 Fluid A exhibits higher VI than fluid B

VM mitigates the viscosity drop by temperature
100
50 Fluid B + VM
Fluid A
Fluid B
0
20 40 60 80 100 120
Temperature, °C
Figure 3. Temperature-viscosity relation and viscosity index.

Figure 3. Temperature‐viscosity relation and viscosity index.
Besides mineral
In addition to MOsoils and
being the there
TGs, major isresources
growing of base fluids,
demand natural
for base fluidstriglycerides (TG, also
prepared artificially,
known as vegetable oils, plant oils, or animal tallow) were the only resources of lubricants before the
so-called synthetic fluids (SF). Huge types of SFs have been introduced and are being developed
petroleum age. Although they were used before petroleum products, TGs are currently classified in
for lubricants. Among them, synthetic hydrocarbons prepared by the oligomerization of 1-aklens
Group V because of the fewer demands compared to mineral oils. Technically, those additives for
form an individual category, Group IV. They are called “poly-alpha-olefin (PAO)” as a market code.
mineral oils do not always work well for TGs. One reason for this is that additives are manufactured
This pseudo-chemical naming is an example that makes chemists confused.
by petroleum industries.
Other synthetic Therefore,
hydrocarbons, industries
synthetic are
esters, andinterested
poly-ethersin improving
are also being the performances
used of
as base fluids.
petroleum products. The relevant scientific discussions are given in Section 4.4.
The importance of SF is, in contrast to MOs and TGs, the possibility of molecular design for various
In addition
purposes to MOs
[30]. Similar and
to the TGs,
issue there
with is conventional
TGs, growing demand for for
additive base
MOs fluids prepared
cannot always artificially,
be applied
so‐called synthetic fluids (SF). Huge types of SFs have been introduced and are being developed for
to SFs, as discussed in Section 4.4.
lubricants. Among them, synthetic hydrocarbons prepared by the oligomerization of 1‐aklens form
Although the concept of molecular design can create molecules with required properties as
an individual category, Group IV. They are called “poly‐alpha‐olefin (PAO)” as a market code. This
lubricants, it is difficult to support all requirements for a lubrication system with base fluid alone in
pseudo‐chemical naming is an example that makes chemists confused.
a cost effective manner. Here we shall recognize the importance of task-specific lubricant additives.
TheyOther synthetic
are defined hydrocarbons,
as those substances synthetic esters, the
that improve and poly‐ethers
total performancesare also being to
if added used
baseas fluids
base
fluids. The importance of SF is, in contrast to MOs and TGs, the possibility of molecular design for
properly. The performances include both tribological and material related ones. The former contribute
various purposes [30]. Similar to the issue with TGs, conventional additive for MOs cannot always
to reducing friction and preventing wear and seizure during machine operation. The latter mainly
be applied to SFs, as discussed in Section 4.4.
contribute to the lifetime of the lubricant and/or tribo-materials. The method of improvements is
idealAlthough
to enhance the
theconcept of molecular
advantages design
of base fluids can a create
with molecules
synergistic effect.with
In therequired properties
real world, additivesas
lubricants, it is difficult to support all requirements for a lubrication system with base fluid alone in
make up for the shortages in specific properties of base fluids in most cases. Additives as liquid forms
a cost effective manner. Here we shall recognize the importance of task‐specific lubricant additives.
have advantages of handling in liquid lubricants. Solid additives, either as solution or as suspension,
They are
are also defined as
commonly those
used. substances
Greases couldthat improve
be used the cases.
in some total performances if added to base fluids
properly. The performances include both tribological and material related ones. The former contribute
The application of lubricant additive is relatively recent in the long history of lubrication
to reducing friction and preventing wear and seizure during machine operation. The latter mainly
engineering. To the best of the author’s knowledge, the first publication of the phenomena in a scientific
contribute
journal wasto nearly
the lifetime of the
100 years agolubricant and/or to
[31]. According tribo‐materials.
the publication, The method additives
lubricant of improvements
have been is
practiced in the market since the 1950s [26]. Since then, lubricant additives have been developed
by engineering knowhow. This might be the main reason why the descriptions in this field are
less-scientific; confusing terminology, unclear chemical structure, complexity of contents, etc.
1.6. Category of Lubricant Additives

Many types of lubricant additives can be found in the market. In most cases, they are being sold
according to their main roles in lubrication systems, such as anti-wear or anti-oxidation agents, and
friction modifiers. It would be instructive to classify those substances according to their working
functions, the means of action (how does it work), and their working site.
Appl. Sci. 2017, 7, 445 9 of 33
1.6.1. Working Function Category

This is an upgraded categorization of existing methods, grouping “substances by their role” into
large groups. All additives belong to one of the following groups.
• Tribo-improvers (tribology-improving additives) directly contribute to improve the tribological

performances of the lubricant. In short, they are responsible for the primary role of lubricants (see
Section 1.2). Friction modifiers (FM), anti-wear agents (AW), extreme pressure additives (EP) are
representative ones. They stand at a central position in the technology of lubricant additives.
• Rheo-improvers (rheology-improving additives) concern the fluidity of the base oil. Viscosity
modifiers (VM) are the main additives in this group. Pour point depressants (PPD) make the base
oil applicable in a chilly environment. They indirectly contribute to the lubrication performances,
mainly in hydrodynamic regime.
• Maintainers help to keep the substances (both lubricant and materials of machine elements)
in good condition through preventing the degradation of substances participating in the
lubrication system. They mainly contribute to prolonging the lifetime of the lubrication system and
partly contribute to the lubrication performances in some cases. Antioxidants (AO) play a decisive
role in preventing the ageing process of lubricants. Detergents and dispersants can mitigate the
negative influences of contaminants on lubrication. Corrosion inhibitors (rust preventives) can
protect the tribo-materials from corrosion. Air bubbles may be incorporated in lubricants during
machine operation. They cause lubricant starvation at the contact and promote the autoxidation
processes. Anti-foam agents (foam breaking agents, defoamers) can break bubbles. Water is
a ubiquitous contaminant in most applications. It drops the viscosity of the lubricant and causes
ageing of both lubricants and materials. Demulsifiers (emulsion breaking agents) are beneficial
for separating contaminated water in a lubricant.
• Auxiliaries are sometimes incorporated with specific purpose in addition to above additives.
1.6.2. Working Site Category

From another viewpoint, the working site of each additive can be characterized, as below.
This category focuses on the action mechanism (the way the additive works) at a molecular scale rather
than practical performances.
• Interface agents work at the interfaces between different phases. Lubricated contacts involve solid
(tribological material)—liquid (lubricant) interfaces. Examples are tribo-improvers as the main
actors in this category. Corrosion inhibitors deactivate the surfaces to be attacked by corrosive
matters. A lubricant may intake air bubbles while circulating, and thereby develops various
forms. The interaction of foam decomposing additives at the border between gas–liquid phases
can destroy the bubbles.
• Bulk agents concern the properties and/or stability of liquid as uni-phase matter. Rheo-improvers
are representative examples of this group. Antioxidants (except metal deactivators), and other
auxiliaries are in this group.
1.6.3. Working Mechanism Category

This gives more insight into the action mechanism, how a molecule behaves and/or changes
while working. It also connects to the level of energy to activate the functions.
• Chemical additives are those additives that undergo chemical reaction(s) while working.
A chemical reaction is defined as a rearrangement of electrons that bind atoms in a molecule.
Chemical changes at interfacial phenomena in tribology are mostly irreversible, although there is
a certain possibility of reversible reactions in the liquid phase. The initiation of chemical reaction
needs much more energy than physical phenomena. Examples are anti-wear agents that provide
This gives more insight
more into the into
action
the mechanism, how a molecule behaves behaves
and/or changes
various forms. The interaction of foam decomposing additives at the border between gas–liquid
This gives insight action mechanism, how a molecule and/or changes
phases can destroy the bubbles.
This gives more insight into the action mechanism, how a molecule behaves and/or changes
 Bulk agents concern the properties and/or stability of liquid as uni‐phase matter. Rheo‐improvers
 while working. It also connects to the level of energy to activate the functions.
Chemical additives are those
 Chemical additives are additives that undergo
those additives chemical
that undergo reaction(s)
are representative examples of this group. Antioxidants (except metal deactivators), and other
chemical while working.
reaction(s)
while working.
 auxiliaries are in this group.
Chemical additives are those additives that undergo chemical reaction(s) while working.
Appl. Sci. 2017, 7, 445A chemical reaction is defined as a rearrangement of electrons that bind atoms in a molecule.
Chemical changes at interfacial phenomena in tribology are mostly irreversible, although there 10 of 33
Chemical changes at interfacial phenomena in tribology are mostly irreversible, although there
is a certain possibility
certain of reversible
possibility reactions
of reversible in the liquid
reactions in a
the phase.
liquid The
is a initiation
phase. of chemical
The changes
initiation of chemical
This gives more insight into the action mechanism, how molecule behaves and/or
reaction needs
is a
reaction much
certain needs more
much energy
possibility of
more than
energy physical
reversible than phenomena.
reactions
physical in the Examples
liquid
phenomena.
are
phase. anti‐wear
The
Examples agents
initiation
are of chemical
anti‐wear agents
boundary film on rubbing
reaction needs
surfaces
much more
through
energy
tribo-chemical
than physical
reactions. Antioxidants
that provide boundary film on rubbing surfaces through tribo‐chemical reactions. Antioxidants
phenomena. Examples are
also belong
anti‐wear
to
agents
group.that provide boundary film on rubbing surfaces through tribo‐chemical reactions. Antioxidants
Chemical additives are those additives that undergo chemical reaction(s) while working.
this also belong to this group.
also belong to this group.
• Physical Physical additives are those substances that work without any chemical changes. Examples are
 additives are those substances that work without any chemical changes. Examples are
Physical additives are those substances that work without any chemical changes. Examples are
 is a certain possibility of reversible reactions in the liquid phase. The initiation of chemical
nano‐particle additives such as tribo‐improvers and viscosity modifiers. Physical changes need
nano-particle additives such as tribo-improvers and viscosity modifiers. Physical changes need
reaction needs much more energy than physical phenomena. Examples are anti‐wear agents
less activation
less activation less energy
activation than
than chemical
chemical
energy changes changes
changes
than chemical and
andare usually
areand usually reversible
energy reversible
are usually processes.
processes.
reversible They They
processes. last
They last
last
longer than the chemical ones.
less activation energy
longer than the chemical ones. than chemical changes and are usually reversible processes. They last

The above
The categories are independent
above categories of each of
are independent other.
each The function
other. category category
The function is a universal
is a universal
The above categories
above are independent
categories of each
are chemical
energy than independent other. The
of each
changes and
function
other.
are usually
category
criterion mainly for engineering applications and overviewing the technology. Phase and scientific
The less The function
reversible
is a universal criterion
processes. category
activation They last is a universal
mainly for engineering applications and overviewing the technology. Phase and scientific categories
categories focus on investigation of mechanism and developing new technologies through molecular
design. Table 2 depicts an interactive character of these categories for individual lubricant additives.
focus on investigation of mechanism
categories are and developing new The technologies through
The above independent of each other. function category molecular design.
is a universal
Table 2 depicts criterion mainly for engineering applications and overviewing the technology. Phase and scientific
an interactive character of these categories for individual lubricant additives.
Table 2. Relations of different classification of additives.
Table 2. Relations of differentWorking Site
classification of additives.
Working Working Working Site
Mechanism
Working
Mechanism InterfaceInterface Working Site Bulk Bulk
Working Working Site
Working Site
Working Mechanism
Mechanism Interface Bulk
chemically
chemically
Interface
Mechanism Interface Bulk Bulk
chemically
chemically
chemically

physically
physically
physically
physically
physically
2. Individual Lubricant Additives and Their Working Mechanism
2. Individual Lubricant Additives and Their Working
This chapter introduces individual Mechanism
additive categories related to the role in lubrication.
Although the description follows conventional ways to introduce lubricants [32–34], this chapter
ThisThis
chapterchapter
This introduces
chapter
introduces individual
introduces
individual additive
individual
additive categories
additive
categories related
categories
related to theto role
the in
related
primarily focuses on how molecules behave for lubrication performances. Representative molecular
role in role
lubrication.
to lubrication.
the in Although
lubrication.
Although the
Although description
This chapter
the follows
introduces
description conventional
individual
follows ways
conventional to ways
introduce
additive categories
to lubricants
related
introduce [32–34],
to
lubricants
structure and the process of action are given briefly to help the readers’ understanding and further the this
role chapter
[32–34], in lubrication.
this chapter
the description follows conventional ways to introduce lubricants [32–34], this chapter primarily
scientific
Although investigations.
the description The science of
follows lubricant additives,
conventional ways especially their action
to introduce
primarily focuses on how molecules behave for lubrication performances. Representative molecular mechanism,
lubricants is
[32–34], this chapter
focuses on howunder discussion in the tribology community and is still under investigation by different researchers.
molecules behave for lubrication performances. Representative molecular structure
structure and the process of action are given briefly to help the readers’ understanding and further
and the process Here the author
of action are tried
givento show the consensus
briefly mechanism,
to help additives,
the readers’as the “greatest common
understanding measure”
and further scientific
scientific investigations. The science
The of lubricant especially their action
scientific investigations. science
extracted from carefully selected articles.
mechanism,
of lubricant additives, especially their action mechanism, is
is
investigations. The science of lubricant additives, especially their
under discussion in the tribology community and is still under investigation by different researchers.
scientific action mechanism,
investigations. The science of lubricant additives, especially their action mechanism, is under is
discussion in
Here the the
Here tribology
author
the tried
author community
to show to the
tried andthe is still
consensus
show under mechanism,
mechanism,
consensus investigation as by
as the “greatest different
the common
“greatest researchers.
measure”
common Here
measure”
the author tried
Here to show
the the
author consensus
tried to mechanism,
show
the as
consensus the “greatest
mechanism, common
as the measure”
“greatest extracted
common from
measure”
carefully selected articles.
2.1. Tribo-Improvers
Those additives contribute to the primary purpose of a lubricant and many R&D activities have
been and are being performed intensively. Therefore, this review puts special emphasis on this
category. There is a consensus among tribologists and lubrication engineers that tribo-improvers
could be conveniently classified into FMs, AWs, and EPs. Generally, FMs effectively work for
“relatively light-load” mixed lubrication while AWs prevent wear for “harder” mixed lubrication,
depicted as a simple Stribeck curve in Figure 4. It is empirically known that their effects overlap
each other. That is, friction reduction by FM is usually associated with wear reduction to some
extent. Similarly, AW primary prevents wear and sometimes reduces friction, but not always.
In consequence, the demarcation between FM and AW is not clear. This can be understood by
their working mechanism below.
could be conveniently classified into FMs, AWs, and EPs. Generally, FMs effectively work for
“relatively light‐load” mixed lubrication while AWs prevent wear for “harder” mixed lubrication,
depicted as a simple Stribeck curve in Figure 4. It is empirically known that their effects overlap each
other. That is, friction reduction by FM is usually associated with wear reduction to some extent.
Similarly, AW primary prevents wear and sometimes reduces friction, but not always. In consequence,
the 2017,
Appl. Sci. demarcation
7, 445 between FM and AW is not clear. This can be understood by their working 11 of 33
mechanism below.
higher
Supposed to Base
FM fluid
Supposed to
Wear rate
AW
AW FM
lower
lower Friction coefficient higher

Figure 4. Overlap effects of tribo-improvers.
Figure 4. Overlap effects of tribo‐improvers.
2.1.1.2.1.1. Friction Modifiers (FM)
Friction Modifiers (FM)
Historically, carboxylic acids with a straight hydrocarbon chin (higher fatty acids) were the first
Historically, carboxylic acids with a straight hydrocarbon chin (higher fatty acids) were the first
recognized “lubricity improving substances” when they were dissolved in mineral oils [35]. They
recognized “lubricity improving substances” when they were dissolved in mineral oils [35]. They have
have been well‐studied from both a scientific and engineering perspective in the past 70 years. The
been well-studied from both a scientific and engineering perspective in the past 70 years. The benefit
benefit of carboxylic acids in scientific research is the availability of pure compounds as commercially
of carboxylic acids in although
available reagents, scientifictheir
research is the
practical availability
applications of pure
are trivial compounds
[36]. However, an as analogous
commercially
available reagents, although their practical applications are trivial [36]. However,
molecular structure could be found in various practical additives, indicating the importance of good an analogous
molecular structure could be found in various practical additives,
understanding in the working mechanism from a scientific viewpoint. indicating the importance of good
understanding
Figure in5 the working
explains mechanism
the effective from mechanism
working a scientific of
viewpoint.
carboxylic acids (octadecanoic acid,
n‐C17H35COOH is the most frequently employed in fundamental research) for steel as a tribo‐material.
Figure 5 explains the effective working mechanism of carboxylic acids (octadecanoic acid,
n-C17Engineering surfaces are usually covered with contaminants or oxide layers, which can be removed
H35 COOH is the most frequently employed in fundamental research) for steel as a tribo-material.
by
Engineeringrubbing. This are
surfaces exposes
usuallyactive surfaces
covered withthat interact with
contaminants the FM
or oxide molecule.
layers, whichFurther
can berubbing
removed by
provides the energy to the molecule for surface reactions. It produces organic salt (salt of carboxylic
rubbing. This exposes active surfaces that interact with the FM molecule. Further rubbing provides the
acid), and results in chemisorption (adsorption with chemical bond between adsorbent and
energy to the molecule for surface reactions. It produces organic salt (salt of carboxylic acid), and results
adsorbant). Chemisorption possesses a strong interaction with the surface compared to that of
in chemisorption (adsorption with chemical bond between adsorbent and adsorbant). Chemisorption
physisorption [37], and hence it is beneficial for protecting the film against rubbing [38]. The alkyl
possesses a strong interaction
group in the molecule has with the surface
significant role in compared
lubrication. toDirect
that ofasperities,
physisorptioncontact [37], and
upon hence it is
rubbing
beneficial
could for
be protecting thethe
mitigated by film againstFM
adsorbed rubbing [38]. The
molecules. The Van
alkylder
group
Waals in attraction
the molecule force has significant
could be
role in lubrication. Direct asperities, contact upon rubbing could be mitigated by the adsorbed
generated between oriented molecules. It strengthens the robustness of the film to support the load
applied to the contact [35]. In fact, alkyl chains having >12 methylene (‐CH
FM molecules. The Van der Waals attraction force could be generated between 2‐ unit) are beneficial for
oriented molecules.
boundary lubrication [39]. This model has been proved under dynamic conditions (so‐called “in lubro”)
It strengthens the robustness of the film to support the load applied to the contact [35]. In fact, alkyl
chains using optical interferometry [40] or liquid cell scanning probe microscope [41].
having >12 methylene (-CH2 - unit) are beneficial for boundary lubrication [39]. This model
has been proved under dynamic conditions (so-called “in lubro”) using optical interferometry [40] or
liquid cell scanning probe microscope [41].
Although the interaction of the acid moiety with the surface is a chemical process, the hydrocarbon
group (commonly straight hydrocarbons having 15–17 carbons), a major part of the molecule,
is supposed to be unreacted. However, common spectroscopy cannot provide clear evidence of
additive molecules that are mainly composed of the hydrocarbon moiety. It should be noted that
the concentration of FM is usually around 10 mmol·kg−1 in hydrocarbons as base fluids and hence
it is difficult to identify additive molecules as highly diluted solutions. Nonetheless, clear evidence
of chemisorption was obtained by surface mass spectroscopy using deuterium-labeled molecules
as model FM [42]. This is frequently misunderstood by tribologists as “those FMs physisorp on
surfaces”, probably because the alkyl group is unreacted. A term “quasi-physical adsorption” might
be convenient to distinguish those FMs from “tribo-chemical types” explained below.
Some lubricant additives take advantage of tribo-chemical reactions. Figure 6 illustrates the
working mechanism of organic salts of molybdate. The first step is the interaction of additive molecules
Appl. Sci. 2017, 7, 445 12 of 33
with the rubbing surface, which is an analogous mechanism in Figure 5. The difference appears in the
next step. When the tribo-process provides enough energy to the molecule, the molecule decomposes
to inorganic salts. Since the reaction is associated with the dissociation of many chemical bonds,
it needs relatively higher energy than the chemisorption process. The inorganic salts (molybdenum
disulfide as the example in Figure 6) are usually more robust than organic salts to heat and mechanical
shearing. Contrary to the chemisorption mechanism, the organic moieties in an additive molecule
were decomposed during the tribo-film formation. In this regard, the main role of the organic moiety is
to dissolve the precursor of inorganic salt in base fluids (mostly hydrocarbons). Some contributions of
carbon-deposit to the tribological properties have been also suggested for the tribo-chemically derived
film [43].
Appl. Sci. 2017, 7, 445 12 of 33

Figure 5. Working mechanism of adsorption type tribo‐improvers.
Figure 5. Working mechanism of adsorption type tribo-improvers.
Appl. Sci. 2017, 7, 445 13 of 33
Although the interaction of the acid moiety with the surface is a chemical process, the hydrocarbon
group (commonly straight hydrocarbons having 15–17 carbons), a major part of the molecule, is
supposed to be unreacted. However, common spectroscopy cannot provide clear evidence of
additive molecules that are mainly composed of the hydrocarbon moiety. It should be noted that the
concentration of FM is usually around 10 mmol∙kg−1 in hydrocarbons as base fluids and hence it is
difficult to identify additive molecules as highly diluted solutions. Nonetheless, clear evidence of
chemisorption was obtained by surface mass spectroscopy using deuterium‐labeled molecules as
model FM [42]. This is frequently misunderstood by tribologists as “those FMs physisorp on
surfaces”, probably because the alkyl group is unreacted. A term “quasi‐physical adsorption” might
be convenient to distinguish those FMs from “tribo‐chemical types” explained below.
Some lubricant additives take advantage of tribo‐chemical reactions. Figure 6 illustrates the
working mechanism of organic salts of molybdate. The first step is the interaction of additive
molecules with the rubbing surface, which is an analogous mechanism in Figure 5. The difference
appears in the next step. When the tribo‐process provides enough energy to the molecule, the molecule
decomposes to inorganic salts. Since the reaction is associated with the dissociation of many
chemical bonds, it needs relatively higher energy than the chemisorption process. The inorganic
salts (molybdenum disulfide as the example in Figure 6) are usually more robust than organic salts
to heat and mechanical shearing. Contrary to the chemisorption mechanism, the organic moieties in
an additive molecule were decomposed during the tribo‐film formation. In this regard, the main role
of the organic moiety is to dissolve the precursor of inorganic salt in base fluids (mostly
hydrocarbons). Some contributions of carbon‐deposit to the tribological properties have been also
suggested for the tribo‐chemically derived film [43].
Molybdenum disulfides are well‐known solid lubricants [44]. Certain oil‐soluble molybdenum
Figure 6. Working mechanism of tribo‐chemical reaction type tribo‐improvers.
Figure 6. Working mechanism of tribo-chemical reaction type tribo-improvers.
salts are practical FMs [45–47] as precursors of molybdenum disulfide.
Inorganic particles, tribo‐improvers
Some task‐specific such as soft metals
have or been
carbon allotropes, For
developed. can example,
physically interact
the with the
importance of
rubbing surfaces and
“anti‐shudder agent” thereby improve
is sometimes the tribological
pointed properties [48–52].
out for driveline They could
systems. It prevents be used
stick‐slip due not
to
only for FMs but also AWs or EPs depending on their properties. Their stable dispersion has to be
higher static friction than dynamic friction, which results in the vibration of material being in the
prepared for liquid lubricants. The details are omitted because this review pays much attention to
same direction as the motion. This belongs to FM and analogous substances to FMs are employed.
molecular structure.
2.1.2. Anti‐Wear Agents (AW)
Appl. Sci. 2017, 7, 445 13 of 33
Molybdenum disulfides are well-known solid lubricants [44]. Certain oil-soluble molybdenum
salts are practical FMs [45–47] as precursors of molybdenum disulfide.
Inorganic particles, such as soft metals or carbon allotropes, can physically interact with the
rubbing surfaces and thereby improve the tribological properties [48–52]. They could be used not
only for FMs but also AWs or EPs depending on their properties. Their stable dispersion has to be
prepared for liquid lubricants. The details are omitted because this review pays much attention to
molecular structure.
Some task-specific tribo-improvers have been developed. For example, the importance of
“anti-shudder agent” is sometimes pointed out for driveline systems. It prevents stick-slip due
to higher static friction than dynamic friction, which results in the vibration of material being in the
same direction as the motion. This belongs to FM and analogous substances to FMs are employed.
2.1.2. Anti-Wear Agents (AW)

Wear is a change of shape on surfaces through eliminating a small portion of the material from the
triboogical contact. It happens under relatively hard mixed lubrication conditions where adsorption
type FMs cannot support the lubrication performances. As discussed in the mechanism of reaction-type
FMs, inorganic salts generated by tribo-chemical reactions are suitable. The differences between AWs
and reaction-type FMs are not the chemical process of tribo-film formation but the physical properties
of the tribo-film provided at the tribo-contact. In general, hard materials are more robust to wear
compared to soft material. Inorganic phosphates on steel surfaces are well known as the protecting
film [53]. Zinc bis(dialkyldithiophosphates) (ZnDTPs) are the most widely used AWs in practical
lubricants so far [54]. Intensive studies on working mechanism of ZnDPTs by surface analysis have
revealed the formation of inorganic compounds composed of phosphorus, sulfur, and zinc [55].
The process of boundary film formation has been studied experimentally [56–59] and in-silico [60].
Co-existence of other tribo-improvers such as molybdenum carbamates displays improvements in
lubrication performances [61–64]. Organic esters of phosphoric and phosphonic acids also display AW
properties for steel surfaces [19].
2.1.3. Extreme Pressure Additives (EP)

Formerly, these were so-called as load carrying agents. When the tribological conditions become
severe, at higher load and/or higher temperature, welding of the material may occur. EP can prevent
such failure of materials upon rubbing contact. Their functions are unique compared to FMs and AWs.
EPs first react with the surface, which is analogous to AWs. However, the product does not protect
the surface but mildly removes the atoms on the uppermost surfaces (Figure 7). The reaction of an EP
molecule (dialkyl disulfide in this case) with the atom−α on the surface is associated with migration
of a bonded-electron from the material, as depicted by a red arrow. It weakens the interaction of the
atom−α with other atoms in the material resulting facile migration of atom−α from the material.
The wear process releases the mechanical energy at the contact point, otherwise the accumulated
energy can induce serious damages to the tribo-materials. The function is so-called “controlled wear
mechanism”. This is closely related to the mechanism of “corrosive wear” or “chemical wear” where
certain chemical substances promote the wear of material. Contrary to the other wear processes
such as abrasive and adhesive wear, corrosive wear produces relatively smooth surfaces (less surface
roughness). Chemically aggressive substances can induce corrosive wear. Similarly, EPs are relatively
reactive with surfaces are compared to substances for FMs and AWs [65].
It is empirically known that EPs can help the running process in an efficient way. This could be
understood by the smooth removing of the initial asperity on the surfaces. In some cases, EPs can
provide “rescue tasks” when the machine elements are under fatal conditions with severe wear. EPs are
expected to lower the contact stress through the corrosive wear. This can make the lubrication regime
milder. However, the effect should not last.
otherwise the accumulated energy can induce serious damages to the tribo‐materials. The function is
so‐called “controlled wear mechanism”. This is closely related to the mechanism of “corrosive wear”
or “chemical wear” where certain chemical substances promote the wear of material. Contrary to the
other wear processes such as abrasive and adhesive wear, corrosive wear produces relatively
smooth surfaces (less surface roughness). Chemically aggressive substances can induce corrosive 14 of 33
Appl. Sci. 2017, 7, 445
wear. Similarly, EPs are relatively reactive with surfaces are compared to substances for FMs and
AWs [65].
Wear of weakly bound α through breaking

●− α bonds releases mechanical energy
S
CnH2n+1− S S−CnH2n+1 S S S
α
α α
rubbing rubbing
Transferring one electron from ●−● bond

and one electron from S−S bond forms a
new ●−S bond
The arrow mark shows the origin and the destination of the transferring electron

Figure 7. Working mechanism of EP (controlled wear).
Figure 7. Working mechanism of EP (controlled wear).
It is empirically known that EPs can help the running process in an efficient way. This could be
Contrary to the extensive academic researches on FMs and AWs, scientific approaches to EP
understood by the smooth removing of the initial asperity on the surfaces. In some cases, EPs can
provide “rescue tasks” when the machine elements are under fatal conditions with severe wear. EPs
functions are still fewer, mainly due to the difficulties of analysis. Evaluation of EP such as ASTM
D2783are expected to lower the contact stress through the corrosive wear. This can make the lubrication
results in welded surfaces with relatively poor repeatability.
regime milder. However, the effect should not last.
In summary, all tribo-improvers work on the surface under dynamic processes. In other words,
Contrary to the extensive academic researches on FMs and AWs, scientific approaches to EP
the mechanical energy continuously stresses the rubbing contact. It damages the surface more or
functions are still fewer, mainly due to the difficulties of analysis. Evaluation of EP such as ASTM
less, resulting in wear, for example. Here, the importance of recovering the tribo-film has arisen,
D2783 results in welded surfaces with relatively poor repeatability.
as pointed out in Figure 8. As discussed supra, the function of all tribo-improvers start with the
In summary, all tribo‐improvers work on the surface under dynamic processes. In other words,
interaction to the rubbing surface. Then the intermediate material (the transition state) is converted to
the mechanical energy continuously stresses the rubbing contact. It damages the surface more or less,
the tribo-film through adsorption or tribo-chemical reaction, according to the lubrication conditions.
resulting in wear, for example. Here, the importance of recovering the tribo‐film has arisen, as pointed
When the machine works under high wear rate conditions, the regeneration process should be done
out in Figure 8. As discussed supra, the function of all tribo‐improvers start with the interaction to
the An
quickly. rubbing
increasesurface. Then the
in affinity intermediate
of the additive tomaterial (the transition
tribo-materials, state) is in
or an increase converted to under
reactivity the the
tribo‐film through adsorption or tribo‐chemical reaction, according to the lubrication
tribological conditions is the usual method of lubricant chemistry. An increase in robustness of the conditions.
When the machine works under high wear rate conditions, the regeneration process should be done
tribo-film is challenging. Multi-functional tribo-improvers are possible by a proper combination of
quickly. An increase in affinity of the additive to tribo‐materials, or an increase in reactivity under
each moiety in FM, AW,
Appl. Sci. 2017, 7, 445 and EP molecules (Figure 9). 15 of 33
the tribological conditions is the usual method of lubricant chemistry. An increase in robustness of
the tribo‐film is challenging. Multi‐functional tribo‐improvers are possible by a proper combination
of each moiety in FM, AW, and EP molecules (Figure 9).

Figure 8. The importance of dynamic process for tribo‐improvers.
Figure 8. The importance of dynamic process for tribo-improvers.
EP AW FM
EP AW FM

Appl. Sci. 2017, 7, 445 15 of 33
Figure 8. The importance of dynamic process for tribo‐improvers.
EP AW FM
EP AW FM
severe Tribological conditions mild
Reaction Reaction Adsorption
EP AW FM
Figure 9. Multi-functional tribo-improver (model).
Figure 9. Multi‐functional tribo‐improver (model).
2.2. Rheo-Improvers (Rheological Properties Improvers)

2.2. Rheo‐Improvers (Rheological Properties Improvers)
Viscosity is the primary property of base fluids for liquid lubricants, as discussed in Section 1.1.
Viscosity is the primary property of base fluids for liquid lubricants, as discussed in Section 1.1.
Those
Those substances
substances that
that are responsible
are forfor
responsible fluidity of base
fluidity oil are
of base oil rheological property
are rheological improvers.
property They
improvers.
contribute
They to the lubrication
contribute performance
to the lubrication by modifying
performance the bulk properties
by modifying the bulk ofproperties
the liquid, of
mainly under
the liquid,
hydrodynamic conditions. From the viewpoint of functions, rheo-improvers could be categorized as
mainly under hydrodynamic conditions. From the viewpoint of functions, rheo‐improvers could be
“indirect” tribo-improvers between mixed and hydrodynamic lubrication regimes.
categorized as “indirect” tribo‐improvers between mixed and hydrodynamic lubrication regimes.
2.2.1. Viscosity Modifiers (VM)

2.2.1. Viscosity Modifiers (VM)
Formerly, VM were called viscosity index improvers (VII). The retired name indicates the role of
Formerly, VM were called viscosity index improvers (VII). The retired name indicates the role
the additive more directly. VI (see Figure 2 and Section 1.5) is an engineering parameter to qualify the
of the additive more directly. VI (see Figure 2 and Section 1.5) is an engineering parameter to qualify
lubricants
the in practice.
lubricants The bulk
in practice. properties
The bulk are dependent
properties on theon
are dependent structure of the base
the structure fluids.
of the base In fact,
fluids.
the manufacturing process of the API Group III includes the isomerization of hydrocarbons.
In fact, the manufacturing process of the API Group III includes the isomerization of hydrocarbons. Structural
features of features
Structural VM are polymers [66].
of VM are The molecule
polymers canmolecule
[66]. The be compactly packed
can be at lower
compactly temperatures,
packed at lower
while it expands at
Appl. Sci. 2017, 7, 445 higher temperatures (Figure 10). It is expected that molecules with
temperatures, while it expands at higher temperatures (Figure 10). It is expected that molecules with large volume
16 of 33
possess resistance to flow, thereby displaying high viscosity [33]. Applicable temperature
large volume possess resistance to flow, thereby displaying high viscosity [33]. Applicable range of
temperature range of lubricants was made wider by improving VMs. A
lubricants was made wider by improving VMs. A technical challenge for advanced VMs is stabilitytechnical challenge for
advanced VMs is stability under shearing (see Figure 3 and Section 1.4) [67].
under shearing (see Figure 3 and Section 1.4) [67].
Base fluid molecule

Principle chain of VM molecule
low Temperature high

Figure 10. Working mechanism of viscosity modifier.
2.2.2. Pour Point Depressant (PPD)
Lubricants may freeze if while machine pauses at low temperatures. This causes lubrication
failure and leads to serious damages to machine elements. A pre‐heating system can prevent the
problem, but it consumes considerable time and energy. PPDs are beneficial for machineries under
cold climates. PPDs are typically branched hydrocarbons [68]. Each branched alkyl group can
Appl. Sci. 2017, 7, 445 16 of 33
low Temperature high
Lubricants may freeze if while machine pauses at low temperatures. This causes lubrication
failure and leads to serious
Lubricants damages
may freeze if while tomachine
machine elements.
pauses A pre-heating
at low temperatures. This system can prevent the
causes lubrication
problem, but itand
failure consumes considerable
leads to serious damages time and energy.
to machine PPDs
elements. are beneficial
A pre‐heating forcan
system machineries
prevent the under
problem, but it consumes considerable time and energy. PPDs are beneficial for machineries under
cold climates. PPDs are typically branched hydrocarbons [68]. Each branched alkyl group can interact
with oil cold climates.
molecules, PPDs are
thereby typically branched
preventing hydrocarbons
the crystallization [68].
of the oilEach branched
molecules alkyl group
together. can of the
Because
interact with oil molecules, thereby preventing the crystallization of the oil molecules together.
branching structure, the PPD molecule can keep free volume around the molecule that this makes the
Because of the branching structure, the PPD molecule can keep free volume around the molecule
partial structure mobile (Figure 11).
that this makes the partial structure mobile (Figure 11).
Base fluid molecule

Alkyl chain of PPD molecule (flexible)
Mobility around
flexible PPD
Solidified, Fluid
Without PPD
chilly Temperature normally

Figure 11. Working mechanism of pour point depressant.
Figure 11. Working mechanism of pour point depressant.
Both VM and PPD are macro‐molecules (polymers) compared to the molecular mass of base oil
Both VM and
molecule. PPD are
However, the macro-molecules (polymers)
functions of VM and compared
PPD are different. The to thefunction
main molecular mass
of VM is to of base
oil molecule. However, the functions of VM and PPD are different. The
suppress mobility at higher temperature thereby increasing the viscosity. main function of VM is to
On the at
suppress mobility other hand,
higher branched structure
temperature is beneficial
thereby increasing for the
PPDs because the molecule has to be
viscosity.
responsible for mobility at lower temperatures. The functions of both additives involve a physical
On the other hand, branched structure is beneficial for PPDs because the molecule has to be
effect and the changes are reversible by temperature change unless the molecule decomposes.
responsible for mobility at lower temperatures. The functions of both additives involve a physical
effect and the changes are reversible by temperature change unless the molecule decomposes.
2.3. Maintainers
Tribology is an entropy-increasing process that generates heat and worn particles as mechanical
energies are lost. It is usually accompanied with retarding of lubricants and tribo-materials, resulting
in inferior lubrication performances called “lubricant ageing”. Maintainers mitigate any negative
influences on the lubrication performance. In most cases, the ageing processes are accelerated by
internal and external contaminants accumulated in the system while the machine works. The function
of maintainers is either pro-active or post-active.
2.3.1. Antioxidants (AO)

Autoxidation is the oxidative degradation of organic compounds that occurs spontaneously
under aerobic conditions without any active treatments such as reagents, catalysts, or driving forces.
Most organic materials experience this reaction as ageing processes, and lubricants are no exceptions.
Therefore, they have been well studied both from engineering and scientific approaches [69–73].
The consensus reaction pathway is the radical chain reaction mechanism, which is initiated by the
hemolytic dissociation of a C–H bond by heat or ultraviolet irradiation. Figure 12 explains the possible
mechanism of radical formation under tribo-chemical conditions.
• Thermal dissociation of a carbon–hydrogen bond to yield hydrogen radical and carbon radical.
The function of maintainers is either pro‐active or post‐active.
2.3.1. Antioxidants (AO)
Autoxidation is the oxidative degradation of organic compounds that occurs spontaneously
under aerobic conditions without any active treatments such as reagents, catalysts, or driving forces.
Most organic materials experience this reaction as ageing processes, and lubricants are no exceptions.
Appl. Sci. 2017, 7, 445 17 of 33
Therefore, they have been well studied both from engineering and scientific approaches [69–73].
The consensus reaction pathway is the radical chain reaction mechanism, which is initiated by the
hemolytic dissociation of a C–H bond by heat or ultraviolet irradiation. Figure 12 explains the
• Shearpossible mechanism of radical formation under tribo‐chemical conditions.
stress can dissociate a carbon–carbon bond though direct mechanical
forces, yielding two
carbon radical intermediates. Polymers can decompose through this mechanism.
 Thermal dissociation of a carbon–hydrogen bond to yield hydrogen radical and carbon radical.
• Wear  of Shear stress can dissociate a carbon–carbon bond though direct mechanical forces, yielding two
tribo-materials exposes nascent surfaces that may catalyze the dissociation of
a carbon–hydrogen bond.
carbon radical intermediates. Polymers can decompose through this mechanism.
 Wear of tribo‐materials exposes nascent surfaces that may catalyze the dissociation of a
carbon–hydrogen bond.
X CH2 X CH2
CH CH
CH HC
H
H C C
H2 H2
X CH2 X CH2 X CH2

CH Shearing CH C
H
H2C CH H2C
C H C C
H2 H2 H2
X CH2 X CH2
CH CH
M M
CH HC
H
H C C
H2 H2
H C Depicts hydrogen radical and carbon radical, respectively
L
Vacant d orbital Deactivation L coordinates to the vacant d orbital, thereby blocks the site
on metal atom
Where M is transition metals such as Fe, Ni, Cu, L is Lewis acid
M M
Figure 12. Initiation step of autoxidation (generation of radical intermediates).
Figure 12. Initiation step of autoxidation (generation of radical intermediates).
Among the three initiation mechanisms, causes by shearing and nascent surfaces are unique in
Among the three
lubrication initiation
systems mechanisms,
(see Section causes
1.4). The carbon by shearing
radicals and
are ready to nascent
react surfaces
with oxygen are unique
to yield
in lubrication systems (see Section 1.4). The carbon radicals are ready to react with oxygen to yield
peroxy‐radical species that further react with another hydrocarbon molecule (Figure 13).
The reaction results in regeneration of the carbon radical intermediate and oxidized molecule.
peroxy-radical species that further react with another hydrocarbon molecule (Figure 13). The reaction
This regeneration step is the characteristic to the radical chain reaction mechanism. Theoretically,
results in regeneration of the carbon radical intermediate and oxidized molecule. This regeneration step
the autoxidation can proceed again and again until the depletion of the hydrocarbon once the carbon
is the characteristic to the radical chain reaction mechanism. Theoretically, the autoxidation can proceed
again and again until the depletion of the hydrocarbon once the carbon radical species were generated.
It should be noted that the radical intermediates can react with oxygen, even while the machine stops.
Therefore, the radical intermediates should be deactivated as soon as they were generated.
The radical scavengers can deactivate the active intermediates, thereby breaking the chain reaction.
Phenol derivatives are commonly used for this role [74–76]. Even with these reagents, a small portion
of radical species can react with oxygen and yield peroxide. In other words, the function of the radical
scavengers is not always perfect in preventing the autoxidation reaction. Organic peroxides possess
strong oxidative attack to other organic molecules and metallic materials. Aromatic amines [77,78],
alkyl sulfides [79], and ZnDTP [80] are frequently employed to decompose peroxy radicals or peroxides.
Peroxide decomposers are post-active AO that deactivate the active intermediates after the reaction
with oxygen. On the other hand, radical scavengers and metal deactivators are proactive AO that
suppress the reaction prior to the oxidation step.
It is empirically known that certain metal catalyzes the autoxidation of hydrocarbons. The wear
process produces nascent surfaces that display catalytic activities. The surface reactions become
significant when tiny wear particles are dispersed in the lubricant, because they have large surface
area. Metal deactivators can interact with metal surfaces and block the active sites on the surfaces.
From the mechanistic viewpoint, metal deactivators work at a solid-liquid interface and the others
work in the liquid phase.
Appl. Sci. 2017, 7, 445 18 of 33
radical
Appl. Sci. 2017, 7, 445species were generated. It should be noted that the radical intermediates can react with 18 of 33
oxygen, even while the machine stops. Therefore, the radical intermediates should be deactivated as
soon as they were generated.
OH OOH O O
H H H H H H H
C C C and/or C
C C C C C C C OH
H
H
H
Peroxide H
H
H H H H
decomposer Peroxides Organic oxides
Post-active AO
H
H H
C
C C
H Regeneration step of
H H
Radical species after
The oxidation
O2
(catalyst)
Metal
(inactive) Metal
Metal R
deactivator H H H H
C C
C C
H C C
H H Radical H
Carbon radical scavenger H H
Proactive AO
Heat or shearing
R R Red arrow depicts initiation step (Fig. 12)

R R
Blue arrow depicts anti-oxidation
Hydrocarbon
R R
Figure 13. Oxidation of lubricants and working mechanism of AO (in ellipse).
Figure 13. Oxidation of lubricants and working mechanism of AO (in ellipse).
The radical scavengers can deactivate the active intermediates, thereby breaking the chain
reaction. Phenol derivatives are commonly used for this role [74–76]. Even with these reagents,
Different types of AOs are frequently used together in a lubricant [81]. Since tribological processes
a small portion of radical species can react with oxygen and yield peroxide. In other words, the
usually induce
function different causes
of the radical of autoxidation,
scavengers different
is not always AO
perfect in complement
preventing each other
the autoxidation to prevent the
reaction.
ageing processes happening simultaneously.
Organic peroxides possess strong oxidative attack to other organic molecules and metallic materials.
Aromatic amines [77,78], alkyl sulfides [79], and ZnDTP [80] are frequently employed to decompose
peroxy radicals or peroxides. Peroxide decomposers are post‐active AO that deactivate the active
2.3.2. Detergent
intermediates after the reaction with oxygen. On the other hand, radical scavengers and metal
Several tribo-improvers contain nitrogen, phosphorus, or sulfur atoms in the molecule. Oxidation
deactivators are proactive AO that suppress the reaction prior to the oxidation step.
of these compounds It is empirically known that certain metal catalyzes the autoxidation of hydrocarbons. The wear
results in mineral acids and their derivatives. These acidic compounds can attack
process produces nascent surfaces that display catalytic activities. The surface reactions become
tribo-materials and/or further promote the ageing of the lubricant. Detergents neutralize or deactivate
significant when tiny wear particles are dispersed in the lubricant, because they have large surface
these aggressive chemicals (Figure 14) [82]. Fine particles of calcium carbonate could be dispersed
area. Metal deactivators can interact with metal surfaces and block the active sites on the surfaces.
in hydrocarbons with the aid of surfactant. This releases the alkali salt upon formation
From the mechanistic viewpoint, metal deactivators work at a solid‐liquid interface and the others
Appl. Sci. 2017, 7, 445 19 of 33 of acidic
compounds. work in the liquid phase.
Because of the structural features, they are called “over-based type detergent”. The base
acidic compounds. Because of the structural features, they are called “over‐based type detergent”.
Different types of AOs are frequently used together in a lubricant [81]. Since tribological
number and mean particle size are the measure of the quality for these additives.
The base number and mean particle size are the measure of the quality for these additives.
processes usually induce different causes of autoxidation, different AO complement each other to
prevent the ageing processes happening simultaneously.
reservoir
Lubricant
2.3.2. Detergent
Several Circulation contain nitrogen, phosphorus, or sulfur atoms in the molecule.
tribo‐improvers
Fuel & air
ICE
Oxidation of these compounds results in mineral acids and their derivatives. These acidic compounds
can attack tribo‐materials and/or further promote the ageing of the lubricant. Detergents neutralize
SO
or deactivate these aggressive chemicals (Figure 14) [82]. Fine particles of calcium carbonate could be
SO3
3
SO 3
dispersed in hydrocarbons with the aid of surfactant. This releases the alkali salt upon formation of
SO
Exhaust gas 3
3
SO
SO3
SO
Sulfuric, phosphoric acids

(oxidation of AW)
Nitric acid (oxidation of N2)
CaCO3
Over-based detergent
Neutralization

Figure 14. Working mechanism of detergent (example diesel engine oils).
2.3.3. Dispersant
An internal combustion engine often yields soot. When it disperses in the lubricant, abrasive
wear, damaged seals, or depleted tribo‐improvers may occur [83]. When the ageing proceeds further,
organic oxides are converted to polymers. This yields insoluble matters or deposits. In contrast to
wear particles of metallic materials, these oligomers and polymers are gel‐like and are not easily
filtered off. A dispersant molecule can interact with these organic contaminants and disperse in the
liquid phase (Figure 15) [84]. The primary function of dispersants is surfactant, which is analogous
to detergent. However, the dispersant molecule has more polar groups in order to capture organic
CaCO3
Over-based detergent
Neutralization

Appl. Sci. 2017, 7, 445 19 of 33
2.3.3. Dispersant
2.3.3. Dispersant
wear, damaged seals, or depleted tribo‐improvers may occur [83]. When the ageing proceeds further,
wear, damaged seals, or depleted tribo-improvers may occur [83]. When the ageing proceeds further,
organic oxides are converted to polymers. This yields insoluble matters or deposits. In contrast to
organic oxides are converted to polymers. This yields insoluble matters or deposits. In contrast to wear
wear particles
particles of metallic
of metallic materials,
materials, these oligomers
these oligomers and polymers
and polymers are and
are gel-like gel‐like
are notand are filtered
easily not easily
off.
filtered off. A dispersant molecule can interact with these organic contaminants and disperse in the
A dispersant molecule can interact with these organic contaminants and disperse in the liquid phase
liquid phase (Figure 15) [84]. The primary function of dispersants is surfactant, which is analogous
(Figure 15) [84]. The primary function of dispersants is surfactant, which is analogous to detergent.
to detergent. However, the dispersant molecule has more polar groups in order to capture organic
However, the dispersant molecule has more polar groups in order to capture organic contaminants
contaminants sufficiently and to keep it dispersed in the liquid phase.
sufficiently and to keep it dispersed in the liquid phase.
reservoir
Lubricant
R
Circulation
Fuel & air O
ICE O N
HN
O HN
Exhaust gas H
N
N
R O
where R = CnH2n+1
Contaminated soot
Multiple interactions
Dispersant molecules
capture the contaminants

Figure 15. Working mechanism of dispersant (example diesel engine oils).
Figure 15. Working mechanism of dispersant (example diesel engine oils).
2.3.4. Corrosion Inhibitor, Rust Preventive

Corrosion and rust are defined as an oxidative degradation of metallic materials through
electrochemical processes. The Galvanic corrosion process is the representative corrosion process in
lubrication systems. The mechanism in brief is as follows. Metal surfaces are usually covered with an
oxide layer. The tribological process wears the oxide off and exposes metal surfaces. The electrical
potential between metal and metal oxide is different. When a conductive liquid exists between the
surfaces, Galvanic cell is formed. The metal atom liberates electrons and forms metal ion by increasing
the oxidation number (this process is the oxidation of metal). The electron liberated from the metal
reduces an oxygen molecule in the system (Figure 16). Base fluids (hydrocarbons) are insulators but
some additives can increase the electrical conductivity of the lubricant. Another cause of corrosion is
the ionization of metal by acidic compounds that occur without oxygen. Both corrosion mechanisms
can take place under static conditions while the machine is pausing. Corrosion inhibitors provide
a protecting layer on metal surfaces [85]. The protection layers could be either organic (adsorption type,
providing organic layers) or inorganic (reaction type, providing passive layers), which are analogous
to FMs (see Section 2.1.1). In contrast to FMs, those protecting films from corrosion do not need
mechanical robustness.
insulators but some additives can increase the electrical conductivity of the lubricant. Another cause
of corrosion is the ionization of metal by acidic compounds that occur without oxygen. Both corrosion
mechanisms can take place under static conditions while the machine is pausing. Corrosion
inhibitors provide a protecting layer on metal surfaces [85]. The protection layers could be either
organic (adsorption type, providing organic layers) or inorganic (reaction type, providing passive
Appl. Sci. 2017, 7, 445 20 of 33
layers), which are analogous to FMs (see Section 2.1.1). In contrast to FMs, those protecting films
from corrosion do not need mechanical robustness.
Liquid phase Worn surface

(1/2) O2+ H2O 2OH− Metal2+
Non-rubbed surface
Uppermost surface
2e−
Metal + [base]−H
Solid phase Metal [Metal]+[base]− + H+
Galvanic corrosion Ionization with acids
Oxidants or acids
Surface film keeps corrosion-promoting

substances away from the surfaces
Organic Inorganic
(adsorption of molecule) (formation of passive layer)

FigureFigure 16. Corrosion of metal and the working mechanism of corrosion inhibitor.
16. Corrosion of metal and the working mechanism of corrosion inhibitor.
2.3.5. Anti‐Foam Agent (Defoamer)
2.3.5. Anti-Foam Agent (Defoamer)
Lubricants can intake air during work and circulation. This develops an air bubble in the
Lubricants can intake air during work and circulation. This develops an air bubble in the
lubricants, and results in drop of viscosity [86]. In addition to the physical changes, the autoxidation
lubricants, and oils
of base results in drop of
is facilitated viscosity
because the [86]. In addition
probability to the physical
of oil–oxygen contact is changes,
increased the autoxidation
through an of
extended area of the gas‐liquid interface. In this regard, non‐visible tiny bubbles
base oils is facilitated because the probability of oil–oxygen contact is increased through an extended are problematic.
area of theAnti‐form agents interface.
gas-liquid are composed of surfactant‐like
In this molecules
regard, non-visible that
tiny can interact
bubbles are between gas‐liquid
problematic. Anti-form
interfaces. The function is to merge tiny bubbles into a large one, thereby helping to release the
agents are composed of surfactant-like molecules that can interact between gas-liquid interfaces.
molecule from the liquid phase (Figure 17) [87].
The function is to merge tiny bubbles into a large one, thereby helping to release the molecule from the
liquid phase (Figure
Appl. Sci. 2017, 7, 445 17) [87]. 21 of 33
Gas
Gas
Liquid Liquid
Anti-foam agent
molecule
The surfactant promotes the coalescing of tiny bubbles into large ones.
As a result, large bubbles can rise to the surface and pop.

Figure 17. Working mechanism of anti‐foam agent (defoamer).
Figure 17. Working mechanism of anti-foam agent (defoamer).
2.3.6. Demulsifiers (Emulsion Breaking Agents)
Water is a ubiquitous contaminant for almost all lubricants. It causes many problems in lubrication
systems including
systems including viscosity
viscosity drop,
drop, corrosion
corrosion of metallic
of metallic materials,
materials, hydrolysis
hydrolysis of additives,
of additives, etc.
etc. Therefore,
Therefore, lubrication systems are better if they have water release systems from the lubricant. It is
lubrication systems are better if they have water release systems from the lubricant. It is reasonable
reasonable to drain contaminated water from the lubricant (density less than 1) while the lubricant is
to drain contaminated water from the lubricant (density less than 1) while the lubricant is settling in
settling in a reservoir. As discussed supra, and summarized in Table 2, many additives work at the
interface. These additives have surfactant nature more or less. Therefore, water can diffuse in the
lubricant in the form of water‐in‐oil emulsion with the aid of those additives. Demulsifiers break
water‐in‐oil emulsion by deactivating the surfactant type additives as illustrated in Figure 18.
The role of anti‐foam agents and demulsifiers is to release contamination, gas or liquid
Figure 17. Working mechanism of anti‐foam agent (defoamer).
systems
Appl. including
Sci. 2017, 7, 445viscosity drop, corrosion of metallic materials, hydrolysis of additives, etc.
21 of 33
Therefore, lubrication systems are better if they have water release systems from the lubricant. It is
reasonable to drain contaminated water from the lubricant (density less than 1) while the lubricant is
a reservoir. As discussed supra, and summarized in Table 2, many additives work at the interface.
settling in a reservoir. As discussed supra, and summarized in Table 2, many additives work at the
These additives have surfactant nature more or less. Therefore, water can diffuse in the lubricant in the
interface. These additives have surfactant nature more or less. Therefore, water can diffuse in the
form of water-in-oil emulsion with the aid of those additives. Demulsifiers break water-in-oil emulsion
lubricant in the form of water‐in‐oil emulsion with the aid of those additives. Demulsifiers break
by deactivating the surfactant type additives as illustrated in Figure 18.
water‐in‐oil emulsion by deactivating the surfactant type additives as illustrated in Figure 18.
The role of anti-foam agents and demulsifiers is to release contamination, gas or liquid respectively,
The role of anti‐foam agents and demulsifiers is to release contamination, gas or liquid
from the lubricants. However, they work in the opposite way; anti-foam agents activate the gas-liquid
respectively, from the lubricants. However, they work in the opposite way; anti‐foam agents activate
interface, while demulsifiers deactivate the water-oil interface.
the gas‐liquid interface, while demulsifiers deactivate the water‐oil interface.
oil oil
water
water
Interface-type
additive
Demulsifier
Deformer interacts with interface-type additive thereby
destabilizes the water-in-oil emulsion.

Figure 18. Working mechanism of Demulsifier.
Figure 18. Working mechanism of Demulsifier.
2.4. Multi-Functional Additives

Some additives have inter-category functions, i.e., display more than two roles out of three
(tribo-improving, rheo-improving, and maintaining, see graphic abstract and Table 2) functions.
ZnDTPs are well-known and the most widely used additives in lubricants that act as FM, AW, AO, and
corrosion inhibitors, depending on the structure of the alkyl group [88,89]. This means that ZnDTPs
take the role as both tribo-improvers and maintainers. Other examples in practices are: over-based
calcium sulfonates as detergent and AW [90], and functionalized poly(methacrylate) as VM and
AW [91].
2.5. Auxiliaries
Not the all but some specific lubricant may include certain substances that are not categorized as
the major groups.
2.5.1. Antibiotics
High water content fluids could be used for some hydraulic fluids or metal working fluids. These
fluids occasionally experience biological decay during storage. Antibiotics can prevent ageing.
2.5.2. Conductivity Improver

These additives are not very common but required for certain applications. The conductivity is
one of the bulk liquid properties. Hydrocarbons, most commonly used as base oils, possess relatively
poor thermal conductivity. Although this property is of importance for the cooling effect, other
advantages with hydrocarbons are usually considered. Dispersion of inorganic particles may increase
the conductivity [92].
2.5. Auxiliaries
2.5. Auxiliaries
Not the all but some specific lubricant may include certain substances that are not categorized
Not the all but some specific lubricant may include certain substances that are not categorized
as the major groups.
as the major groups.
2.5.1. Antibiotics
2.5.1. Antibiotics
Appl. Sci. 2017, 7, 445 High water

High content
water fluids
content could
fluids be used
could for for
be used some hydraulic
some fluids
hydraulic or metal
fluids working
or metal fluids.
working fluids.
22 of 33
These fluids occasionally experience biological decay during storage. Antibiotics can prevent ageing.
These fluids occasionally experience biological decay during storage. Antibiotics can prevent ageing.
2.5.3. Colorings These additives are not very common but required for certain applications. The conductivity is
These additives are not very common but required for certain applications. The conductivity is
one one
of the bulk
of the liquid
bulk properties.
liquid Hydrocarbons,
properties. most
Hydrocarbons, commonly
most used
commonly as base
used oils, oils,
as base possess
possess
This ingredient is relatively poor thermal conductivity. Although this property is of importance for the cooling effect,
notrelatively poor thermal conductivity. Although this property is of importance for the cooling effect,
necessary for lubrication performances but is sometimes beneficial for
lubricant maintenance.other advantages with hydrocarbons are usually considered. Dispersion of inorganic particles may
Specific coloring can prevent mistakes by mixing wrong lubricant when
other advantages with hydrocarbons are usually considered. Dispersion of inorganic particles may
increase the conductivity [92].
increase the conductivity [92].
replacement or replenishment is taken. In some applications, leakage could be found easily by coloring
of the liquid. 2.5.3. Colorings
2.5.3. Colorings
This ingredient
This is not
ingredient necessary
is not for for
necessary lubrication performances
lubrication but but
performances is sometimes beneficial
is sometimes for for
beneficial
3. Evaluation of Tribo-Improvers
lubricant maintenance.
lubricant Specific
maintenance. coloring
Specific can can
coloring prevent mistakes
prevent by mixing
mistakes wrong
by mixing lubricant
wrong when
lubricant when
replacement or replenishment
replacement is taken.
or replenishment In some
is taken. applications,
In some leakage
applications, could
leakage be found
could easily
be found by by
easily
Even if a researcher develops an excellent additive, it would be never commercialized directly.
coloring of the liquid.
coloring of the liquid.
The R&D processes of lubricants has been undertaken step-by-step as briefly shown in Table 3. Among
3. Evaluation of Tribo‐Improvers
3. Evaluation of Tribo‐Improvers
three additive categories, rheo-improvers and maintainers are analogous substances for other industrial
materials. Development and
The R&D
The
primary
processes
R&D
evaluation
of
processes lubricants ofhas
has
of lubricants
these
been additives
undertaken
been
couldas
step‐by‐step
undertaken
follow
step‐by‐step briefly theshown
shown
as briefly
procedure
in Table for
3. 3.
in Table
those materials. On theAmong
other
Among hand,
three
three tribo-improvers
additive categories,
additive categories, are unique
rheo‐improvers tomaintainers
and and
rheo‐improvers lubricants.
maintainers are are This section
analogous substances
analogous focuses
for for
substances
other industrial materials. Development and primary evaluation of these additives could follow the
other industrial materials. Development and primary evaluation of these additives could follow the
on tribo-improvers.
procedure for for
procedure those materials.
those On On
materials. the the
other hand,
other tribo‐improvers
hand, are are
tribo‐improvers unique to lubricants.
unique This
to lubricants. This
section focuses on tribo‐improvers.
section focuses on tribo‐improvers.
Table 3. Research phase and tribo-testing.
Table 3. Research phase and tribo‐testing.
Table 3. Research phase and tribo‐testing.
Test Test Test
Sample Sample
Sample Test Test Test Test Cost of
Test Cost of
Cost of
R&D Phase R&D Phase
Focus R&D Phase Focus
Focus TestLubricant
Equipment Outcome
Outcome Periods
Outcome
Category Category
LubricantCategory Lubricant Equipment
Equipment Periods Evaluation
Periods Evaluation
Evaluation
Incubate‐
Incubate‐ Specific
Specific Universal
Universal The The role
The role
Incubate-break Specific role
Possibilitybreak
break Possibility
Possibility Universal
components tribo-tester
components tribo‐tester
tribo‐tester component
component
through through Laboratory components
through component
Laboratory
Laboratory
test Tribo‐tester
Tribo‐tester
test test Tribo-tester according to Technical
Improve Applicability Prototype according to
according to Technical
Technical
Improve
Improve Applicability
Applicability Prototype
industrial standards
Prototype benefit
industrial
industrial benefit
benefit
standards
standards
Engineering
Optimize Feasibility Bench test Machine component
Machine Engineering
Machine benefit
Engineering
Optimize Feasibility Full
Optimize Feasibility Bench test
Bench test component
Full Full component benefit benefit
formulated Industrial
Verity & tune Verity&
Productivity Field
Verity& test formulated
Real machine
formulated Industrial
Industrial
Productivity Field test
Productivity Field test Real machine benefit
Real machine
tune tune benefit
benefit
Because of variety of machine elements—their configurations, operating conditions, and

environment—lubricants should be formulated for each machine element. The performances of
these lubricants are evaluated using the practical machine under real conditions and environments.
This so-called field test is a time- and cost-intense procedure and is usually employed just before the
introduction of the product into the market. Prior to the field test, lubricants have to pass the laboratory
tests that are classified as “bench tests”. This tests lubricants using the real machine elements (part
of whole machine) under simulated operating conditions and environments in the laboratory. These
tests should focus on optimizing, verifying or tuning of the machine. Therefore, fully formulated
lubricants are employed for evaluation. Since these phases test long-term durability and safety of the
machine, requirements for lubricants are close to practical qualities. The first two phases in R&D are
carried out using laboratory equipment in a time- and cost-effective manner. Standard tests regulated
by the authorized organizations such as ASTM are usually employed in these early research stages.
Each standard test clearly defines the equipment and the procedure and mainly focuses on the quality
control of industrial materials. Another advantage of the standard tests is that equipment and related
parts including consumables are commercially available in most cases. Therefore, these tests are also
employed for evaluation of prototype lubricants in an “improving” phase.
It should be noted that the standard tests define the minimum requirements as industrial
products for individual applications. These procedures are supposed to evaluate fully formulated
lubricants. Therefore, these procedures may involve over-loaded conditions for lubricant additives
under an incubate-breakthrough phase.
Contrary to well-established methods and apparatuses for chemical analysis such as
spectroscopies, there is no consensus as to a universal tribo-testing procedure for tribo-improvers in
laboratories. Simple tribo-testers (not a part of machine element) are beneficial in an incubating phase.
Factors to be considered in conducting a tribo-test of lubricants are described below.
Appl. Sci. 2017, 7, 445 23 of 33
• Configuration of tribo-contact: a point contact generates high contact stress while line and square
contact generate low contact stress. A careful setup of the test specimen is needed to ensure the
alignment of contact. This influences the repeatability of the test considerably. Ball-on-flat type
point contact provides a comparatively easy setup.
• Type of relative motion: Reciprocation sliding, unidirectional sliding, rolling, and a combination
of rolling and sliding are most commonly employed.
• Tribo-materials: Various materials are used in different machine elements. Simple tribo-tests are
beneficial for evaluating the compatibility of tribo-improvers with specific materials in machine
elements. Surface roughness of the materials should be considered.
• Operating conditions: Load, velocity, and temperature of lubricant should be controlled in
a proper way.
• Testing environment: Should be kept away from contaminants as much as possible to obtain the
results with good repeatability. Humidity of room air can influence the tribological properties.
In summary, there are countless test conditions that combine the above factors. Under these
circumstances, simple comparison of the results, i.e., friction coefficient or wear rate, between different
groups does not always make sense. Performances of tribo-improvers should be evaluated by
comparing the base fluid (without the tribo-improver, see Figure 4).
4. Discussion as Multi-Component Systems
4.1. Formulation of a Lubricant

Based on the understandings of each component for lubricants, this section discusses the
combination of additives to achieve lubrication performances. Manufacturing a lubricant, so-called
“formulation”, requires high-level engineering knowledge; what base oil(s) and additives should be
chosen? What is the concentration of each component?—The contents in lubricants are in a black
box in most cases. It seems an implicit agreement that everybody can produce a fake-lubricant if
the detailed contents in a lubricant were disclosed. That might indeed be possible but this is not a
good reason to attempt this. Here is a simple question; can you serve a high-quality dinner by merely
following the recipe of a three-star Michelin restaurant? Note that lubricants cannot be formulated by
simple mixing of base fluids and additives. The reason for non-disclosure of lubricant contents might
be an economical matter. Everybody can calculate the total cost of the raw materials in a lubricant and
then might feel that the product price is too expensive, without considering the cost for the quality.
The cost discussion is not in the scope of this review and the following sections highlight the science of
additive technology.
4.2. The Quality of Each Ingredient

The total performances of formulated lubricant are often influenced by the quality of each
component. In chemistry, quality of substance is nearly equal to the purity. In this regard, it is a
tacit knowledge that even a small amount of impurities sometimes play a decisive role, especially
in tribological performances. This phenomenon could be understood by a competitive interaction
of impurities against the tribo-improvers with tribological surfaces. Actually, many lubricants are
made of industrial grade chemicals that are usually less pure compared to reagent grade. Laboratory
tribo-tests are a reasonable way to check the quality of the ingredients of lubricants.
4.3. The Interaction of Ingredients

Because of the nature of multiple components in a lubricant, an interaction between each
component (either as additive or as base oil) occurs inherently. The interaction can result in a positive,
negative, or neutral effect on lubrication performances including lifetime of usage. A positive effect
is a synergistic effect; improved performance by combination compared to one component alone.
tribological performances. This phenomenon could be understood by a competitive interaction of
impurities against the tribo‐improvers with tribological surfaces. Actually, many lubricants are
made of industrial grade chemicals that are usually less pure compared to reagent grade. Laboratory
tribo‐tests are a reasonable way to check the quality of the ingredients of lubricants.
4.3. The Interaction of Ingredients
Appl. Sci. 2017, 7, 445 24 of 33
Because of the nature of multiple components in a lubricant, an interaction between each
component (either as additive or as base oil) occurs inherently. The interaction can result in a positive,
Creating new function(s) that were not provided by each ingredient is also within this category. The
negative, or neutral effect on lubrication performances including lifetime of usage. A positive effect
oppositeis case
a synergistic effect; improved
is an antagonistic performance
effect. In the neutralby combination
case, eachcompared
ingredient to works
one component alone. even
independently,
Creating new function(s) that were not provided by each ingredient is also within this category. The
though they interact with each other in a molecular level.
opposite case is an antagonistic effect. In the neutral case, each ingredient works independently,
Antagonism of ingredients is frequently observed in preparation and evaluation of prototype
even though they interact with each other in a molecular level.
lubricants. A simple example is shown in Figure 19; each tribo-improver A or B prevented wear by
Antagonism of ingredients is frequently observed in preparation and evaluation of prototype
a laboratory test, while mixing them both displayed higher wear than the base oil alone. Antagonism
lubricants. A simple example is shown in Figure 19; each tribo‐improver A or B prevented wear by
a laboratory test, while mixing them both displayed higher wear than the base oil alone. Antagonism
should be notified if A + B displays much more wear than B (not base oil), in this example. A reaction
should be notified if A + B displays much more wear than B (not base oil), in this example. A reaction
of A with B was suggested in this case [93]. Depletion of tribo-improvers by dispersants [94,95] is
of A with B was suggested in this case [93]. Depletion of tribo‐improvers by dispersants [94,95] is
categorized as antagonism in a broad sense.
categorized as antagonism in a broad sense.
1.2
Wear volume, ×10-2 mm3
1.0
0.8
0.6
0.4
0.2
0.0
Base oil Additive A Additive B Additives A&B
Sample
Figure 19. Antagonism of two additives.
Figure 19. Antagonism of two additives.
The term “synergism” seems to be often used in the literature, aiming to show the result is
The term “synergism” seems to be often used in the literature, aiming to show the result is
positive. Here we introduce a clear definition for lubricant chemistry. In molecular science, the molarity
of a
positive. substance
Here (unit as mol∙kg
we introduce −1) is important. Therefore, the lubrication performance should be
a clear definition for lubricant chemistry. In molecular science, the
molarity of a substance (unit as mol·kg−1 ) is important. Therefore, the lubrication performance should
Appl. Sci. 2017, 7, 445 25 of 33
be compared using samples with the same molarity of the additive. In short, “synergism” should be
stated ascompared
an improvement by combination,
using samples with the same if the total
molarity molarity of In short, “synergism”
of the additive. the combined ingredients is exactly
should be
same as the single component. Improvement by simply mixing could be the effect of the totalis amount
stated as an improvement by combination, if the total molarity of the combined ingredients
exactly same as the single component. Improvement by simply mixing could be the effect of the total
of ingredients (better performances by higher concentration of ingredients), as concisely illustrated
amount of ingredients (better performances by higher concentration of ingredients), as concisely
in Figure 20. In this regard, mass concentration is the most common unit in lubrication engineering.
illustrated in Figure 20. In this regard, mass concentration is the most common unit in lubrication
Therefore, it is better to reconsider the published results.
engineering. Therefore, it is better to reconsider the published results.
The same molarity

worse
0.3
Normalized wear rate
Lubrication performances
0.2
0.2
0.1
Synergism
Could be effect of
Concentration
0.1
better
0.0
BF BF + AW-A BF + AW-B BF + AW-A&B BF + AW-A&B
(keep molarity) (simply mixed)
Sample
AW-B AW-A
BF (base fluid)
(anti-wear additive) (anti-wear additive)
Figure 20. Synergism model (example of AW).
Figure 20. Synergism model (example of AW).
It is uncertain in terms of engineering knowledge whether a combination of tribo‐improvers,
e.g., FM and AW, can provide better lubrication performances. This could be classified into
3 phenomena, as illustrated in Figure 21.
 Synergy is defined as the combination improves BOTH friction and wear compared to each
ingredient alone.
Normal
Lubric
0.1
Synergism
Could be effect of
Concentration
0.1
better
0.0
Appl. Sci. 2017, 7, 445 BF BF + AW-A BF + AW-B BF + AW-A&B BF + AW-A&B 25 of 33
(keep molarity) (simply mixed)
Sample
AW-B AW-A
BF (base fluid)
It is uncertain in terms of engineering knowledge whether a combination
(anti-wear additive) of tribo-improvers,
e.g.,
(anti-wear additive)
FM and AW, can provide better lubrication performances. This could

Figure 20. Synergism model (example of AW). be classified into 3 phenomena,
as illustrated in Figure 21.
It is uncertain in terms of engineering knowledge whether a combination of tribo‐improvers,
• Synergy is defined
e.g., FM and AW, ascan
theprovide
combination improvesperformances.
better lubrication BOTH friction This and wear
could compared
be classified to each
into
3 phenomena, as illustrated in Figure 21.
ingredient alone.
• 
Enhanced performance
Synergy is defined of
as one while scarifying
the combination theBOTH
improves other friction
seems and
to have
wear an improved
compared effect but
to each
ingredient alone.
should not be defined as synergism.
 Enhanced performance of one while scarifying the other seems to have an improved effect but
• Antagonism is any other phenomena except the above two.
should not be defined as synergism.
 Antagonism is any other phenomena except the above two.
BF + FM
higher
BF
worse
Enhanced FM by
scarifying AW
Lubrication performances
Wear rate
BF + AW
Enhanced AW by
AW + FM
scarifying FM
Synergy
better
lower
lower Friction coefficient higher
better Lubrication performances worse

Figure 21. Synergy chart (example of FM and AW).
Figure 21. Synergy chart (example of FM and AW).
As is common knowledge, different AOs (radical scavengers, peroxide decomposers, and metal
Appl. Sci. 2017, 7, 445 26 of 33
deactivators) are dissolved in a lubricant [83]. From a mechanistic viewpoint, these AOs are on
standby for As is common knowledge, different AOs (radical scavengers, peroxide decomposers, and metal
different causes of autoxidation (Figures 12 and 13). Therefore, this is understood by the
deactivators)
complemented effect.are dissolved in a lubricant [83]. From a mechanistic viewpoint, these AOs are on
standby for different causes of autoxidation (Figures 12 and 13). Therefore, this is understood by the
The interaction of different additives highly concerns the formulation process of a lubricant.
complemented effect.
It occasionally happens that the lubrication performances can differ by the order of a mixing process.
The interaction of different additives highly concerns the formulation process of a lubricant.
Although this involves high-level engineering knowledge in formulating a lubricant, the phenomena
It occasionally happens that the lubrication performances can differ by the order of a mixing process.
could be explained by the interaction of additives, as illustrated in Figure 22. As discussed supra
Although this involves high‐level engineering knowledge in formulating a lubricant, the phenomena
(Table 2), a lubricant
could be explained contains
by the different surfactant-type
interaction molecules
of additives, as illustrated in that work
Figure at interfaces.
22. As Because of
discussed supra
(Table 2), a lubricant contains different surfactant‐type molecules that work at interfaces. Because of
the “interface activating nature”, these molecules aggregate themselves or incorporate other additives.
the “interface activating nature”, these molecules aggregate themselves or incorporate other additives.
Base fluid Additive-A Additive-B

Figure 22. Possible variation of performance by formulation process.
Figure 22. Possible variation of performance by formulation process.
4.4. Additive Technology for Synthetic Fluids
Historically, additive technology in lubrication engineering arose in the early period of the
petroleum age. Mass production of mineral oils, together with naphtha and fuels from crude oils,
provided considerable benefits in the market. Liquids with proper viscosity for lubrication had
become available at reasonable costs. However, neat mineral oils (without additives) usually display
Appl. Sci. 2017, 7, 445 26 of 33
4.4. Additive Technology for Synthetic Fluids

Historically, additive technology in lubrication engineering arose in the early period of the
petroleum age. Mass production of mineral oils, together with naphtha and fuels from crude oils,
provided considerable benefits in the market. Liquids with proper viscosity for lubrication had
become available at reasonable costs. However, neat mineral oils (without additives) usually display
poor lubrication performances, especially in reducing friction and wear, in comparison with natural
triglycerides (plant oils and animal tallow that had been the resources of lubricants since the ancient
days until the petroleum age). After the advantage of additives had been recognized, the demands of
additive technology sprang up. It was proved in many applications that additive technology enables
machine operation with enhanced reliability, improved energy efficiency, and prolonged lifetime, etc.
It should be emphasized that the improvements in lubricant performance motivated an advanced
design of machine elements. This further promoted the improvement of lubricant performances. Today
and in the future, additive technology is and will be indispensable in lubrication systems.
The majority of base oils in the lubricant industry had been and is still Group I oils. Therefore,
additive technology has been focused on improvement of Group I oils. Demands of quality lubricants
from users are promoting the shift of base fluids to Group II or III from Group I. Then the problem
with the solubility of additives in these base fluids arose. The same problem happens with Group IV.
Although Groups I−IV are composed of hydrocarbons, Group I oils contain a considerable amount of
cycloalkanes (naphthenic) and aromatics that are responsible for good solvency. Solvency-improving
fluids are usually blended in these poor solvents (Group II–IV oils).
Solvency could be understood by the affinity of a solute to the solvent. If a compound does
not dissolve in the base oil, formulation of a liquid lubricant is impossible. On the other hand, high
solubility of a solute in the solvent is not desirable. A proper solubility, especially for tribo-improvers,
is required in formulating a lubricant. Figure 23 depicts a model of solubility−adsorptivity relation on
lubrication performance, in consideration with an adsorption isotherm. From the working mechanism
of tribo-improvers (Figures 5–7), it is possible to ascertain that they start by adsorption on rubbing
surfaces. Assume that there is a threshold of surface coverage at C by which adsorption enables the
tribo-improver to work. When additive-A and additive-B were compared at the same concentration
of XA, the former displays expected performances while the later displays none, due to insufficient
amount of molecules on the surface. A higher concentration of XB is needed for additive-B to perform.
However, using an additive at high concentration rises the risk of disadvantages by the interaction with
other additives. Therefore, additives should have proper solvency to the base fluids. The solubility in
the base fluid is the second key factor in choosing additives after the primary lubrication function.
Esters and polyethers belong to Group V oils and are receiving growing demands as fast
biodegradable fluids [96]. Contrary to Groups I−IV oils, they contain oxygen atoms in their molecule.
Here we discuss the difference between hydrocarbon and oxygen-containing molecules (esters and
polyethers) in terms of polarity. Polarity is a result of unequaled sharing of the bonding electron pair,
due to the differences in electron negativity of the atoms that form the covalent bond. The electron
negativity of hydrogen, carbon, and oxygen are 2.2, 2.5, and 3.5, respectively. Hydrocarbons are being
constructed with the combination of a carbon–carbon bond and carbon–hydrogen bonds. Since the
differences in the electron negativity of the atoms of these bonds are low (0 for C–C bond, 0.3 for
C–H bond), hydrocarbons display “non-polar” properties. On the other hand, esters and polyethers
have carbon–oxygen bonds (the difference in the electron negativity is 1.0), together with C–C and
C–H bonds. Some substances involve hydrogen–oxygen bond(s) in which the difference in the electron
negativity is 1.3. These oxygen involving bonds make the molecule polar. Furthermore, the chemical
structure should be considered for the polarity of the molecule, which is omitted here for simplicity.
Generally, polar liquids are good solvents and hence esters and polyethers can dissolve common
additives for Groups I oils up to high concentrations. This is an analogous problem to that of additive-B
in Figure 23. By and large, polar molecules display an affinity to steel surfaces. This induces adsorption
of polar fluids on tribo-surfaces. Here, competitive adsorption of a base fluid against a tribo-improver
Appl. Sci. 2017, 7, 445 27 of 33
on rubbing surfaces. Assume that there is a threshold of surface coverage at C by which adsorption
enables the tribo‐improver to work. When additive‐A and additive‐B were compared at the same
concentration of XA, the former displays expected performances while the later displays none, due
Appl. Sci. 2017, 7, 445 27 of 33
to insufficient amount of molecules on the surface. A higher concentration of XB is needed for
additive‐B to perform. However, using an additive at high concentration rises the risk of disadvantages
occurs.by the interaction with other additives. Therefore, additives should have proper solvency to the base
When the base fluid molecules adsorb on the surface and block the surface from being
fluids. The solubility in the base fluid is the second key factor in choosing additives after the primary
interacted with the additive, additive effects will not result.
lubrication function.
Solubility low proper high
Base fluid
Liquid phase Tribo-improver
Tribo-contact
Interface
Lubrication poor optimum fair
Surface coverage (normalized)
1.00
0.80
C additive-B
additive-A
0.60
0.40
0.20
0.00
0.00X 0.10 0.20 0.30 0.40 0.50 X0.60 0.70 0.80 0.90 1.00
A b
Appl. Sci. 2017, 7, 445 Concentration (normalized) 28 of 33
Figure 23. Solubility of a tribo‐improver and lubrication performance.
Figure 23. Solubility of a tribo-improver and lubrication performance.
at reasonable concentrations, while conventional AW needs a much higher concentration to work in
polyether. Conventional AWs usually work in hydrocarbon oils at a concentration of 10 mmol∙kg
Esters and polyethers belong to Group V oils and are receiving growing demands as fast −1
It was anticipated that increased polarity in an additive molecule can enhance the
biodegradable fluids [96]. Contrary to Groups I−IV oils, they contain oxygen atoms in their molecule.
(310 ppm of phosphorus content) or below. adsorption
Here we discuss the difference between hydrocarbon and oxygen‐containing molecules (esters and
activity from solution in a polar solvent. Examples have enhanced polarity by chemical modification
The relation between chemical structure and physical properties for synthetic esters has been
of polyethers) in terms of polarity. Polarity is a result of unequaled sharing of the bonding electron pair,
phosphates
reviewed suchNon‐polarity
in [98]. as AW for polar synthetic
index fluids, as shown
was introduced in Figure
therein 24 [97]. This prevented
as an engineering parameter. wear
The
at due to the differences in electron negativity of the atoms that form the covalent bond. The electron
reasonable concentrations, while conventional AW needs a much higher concentration to work in
performance of model AW for polar synthetic fluids were evaluated and analyzed regarding
negativity of hydrogen, carbon, and oxygen are 2.2, 2.5, and 3.5, respectively. Hydrocarbons are −1
polyether. Conventional AWs usually work in hydrocarbon oils at a concentration of 10 mmol·kg
polarity index as minor revision of non‐polarity index. As shown in Figure 25, performance of the
being constructed with the combination of a carbon–carbon bond and carbon–hydrogen bonds.
(310 ppm of phosphorus content) or below.
anti‐wear properties decreases as the polarity of the base fluid increases [99].
Since the differences in the electron negativity of the atoms of these bonds are low (0 for C–C bond,
0.3 for C–H bond), hydrocarbons display “non‐polar” properties. On the other hand, esters and
polyethers have carbon–oxygen bonds (the difference in the electron negativity is 1.0), together with
C–C and C–H bonds. Some substances involve hydrogen–oxygen bond(s) in which the difference in
the electron negativity is 1.3. These oxygen involving bonds make the molecule polar. Furthermore,
the chemical structure should be considered for the polarity of the molecule, which is omitted here
for simplicity.
Generally, polar liquids are good solvents and hence esters and polyethers can dissolve
common additives for Groups I oils up to high concentrations. This is an analogous problem to that
of additive‐B in Figure 23. By and large, polar molecules display an affinity to steel surfaces. This
induces adsorption of polar fluids on tribo‐surfaces. Here, competitive adsorption of a base fluid
against a tribo‐improver occurs. When the base fluid molecules adsorb on the surface and block the
surface from being interacted with the additive, additive effects will not result.
It was anticipated that increased polarity in an additive molecule can enhance the adsorption
activity from solution in a polar solvent. Examples have enhanced polarity by chemical modification
of phosphates such as AW for polar synthetic fluids, as shown in Figure 24 [97]. This prevented wear

Figure 24. Performances of different AW in synthetic fluid (polyether).
Appl. Sci. 2017, 7, 445 28 of 33
The relation between chemical structure and physical properties for synthetic esters has
been reviewed in [98]. Non-polarity index was introduced therein as an engineering parameter.
The performance of model AW for polar synthetic fluids were evaluated and analyzed regarding
polarity index as minor revision of non-polarity index. As shown in Figure 25, performance of the
anti-wear properties decreases as the polarity of the base fluid increases [99].

Figure 25. AW performances for different synthetic fluids (ester).
Figure 25. AW performances for different synthetic fluids (ester).
4.5. Tribo‐Improvers for Non‐Ferrous Materials
4.5. Tribo-Improvers for Non-Ferrous Materials
Most tribo‐improvers are developed for lubrication of steels. When it comes to other materials,
Most tribo-improvers are developed for lubrication of steels. When it comes to other materials,
affinity of each additive to the material is different from that of steel. Therefore, the kinetics in the
affinity of each additive to the material is different from that of steel. Therefore, the kinetics in the
adsorption step
adsorption step (Figure
(Figure 6)
6) would
would bebe influenced.
influenced. The
The processes
processes of
of tribo-chemical
tribo‐chemical reaction
reaction and
and the
the
property of the tribo‐film could be different from those with steel. Various materials including
property of the tribo-film could be different from those with steel. Various materials including coatings
are being developed for tribological purposes. Molecular structure of tribo-improvers should be tuned
for the materials.
4.6. Additive Technology for Environmentally Acceptable Lubricants

Because of the concern for reducing the impacts on the global environment, demands of EAL
(environmentally acceptable/adapted lubricants) are increasing. The biodegradability is one of the key
factors in choosing base fluids for EAL [96]. Synthetic esters, natural triglycerides, polyethers, and
certain synthetic hydrocarbons are candidates of the base fluids in EALs. Significant investigation
in additive technology is needed, especially in the solubility of additives, as discussed in the
previous section. Besides the problem of solubility and adsorption for synthetic fluids, toxicity
and bioaccumulation tendency of additives are also a concern. Although the contents are minor
portions, it has been pointed out that certain ingredients in industrial products should be or might be
better if replaced by safer substances [100]. “Greener” candidates have been proposed for 10 specific
cases therein. Among them, antimicrobials, small amines, boron alternatives, corrosion inhibitors,
alkanolamides, and surfactants relate to lubricant chemistry.
5. Summary
Even though they constitute the minor contents in a lubricant, additives are responsible for various
functions in lubricating a machine element. The functions include not only tribological properties but
also the material properties and maintenance. Many machines are in use under various lubrication
conditions. Therefore, the required functions of each lubricant are different. This leads to a vast
variety of commercial lubricants. Publications in lubrication engineering and lubricant chemistries
Appl. Sci. 2017, 7, 445 29 of 33
are mostly focused on individual engineering phenomena. Unfortunately, scientific viewpoints have
thus far underestimated such lubricant technology. This review helps the readers to survey the
additive technology for lubricants. The main role and functions of individual additive category were
introduced with an emphasis on molecular science. Similarity and dissimilarity in functions and
molecular structure were discussed by comparing different additive categories.
The continuous developments in machine elements require advanced lubricants more and more.
The improvement in efficiency, reliability, and lifetime together with environmental acceptability
are core concerns. These technological requirements should be solved by additive technology.
The availability of synthetic fluids and new tribo-materials open the opportunities for designing
advanced machine elements. This requires a much bigger lineup of task-specific lubricants. This
would constitute a paradigm shift from empirical knowhow to a smart technology in research and
development of advanced lubricants. Here we wish to propose the algorithm of molecular science in
the R&D of lubricant chemistry. Lubricant chemistry is an ever-improving science.
Acknowledgments: A part of this work is supported by Maritime Technologies II Research Programme in the
framework of the ERA-NET MARTEC II project CA 266111 ArTEco ‘Arctic Thruster Ecosystem’ and “Austrian
COMET-Program” in the frame of K2 XTribology (project No. 849109) within the “Excellence Centre of Tribology”
(AC2 T research GmbH).
Conflicts of Interest: The author declares no conflict of interest.
Nomenclature
Abbreviation Description
AO Antioxidant
API The American petroleum Institute, http://www.api.org/
ASTM The American Society for Testing and Materials, http://www.astm.org/
AW Anti-wear, anti-wear additive
BF Base fluid (base oil)
EP Experme pressure, extreme pressure additive
FM Friction modifying, fricition modifier
ICE Internal conbustion engine
MO Mineral oil
PPD Pour pont depressant
SF Synthetic fluids
STLE The Society of Tribologists and lubricationEngineers, http://www.stle.org/
TG Triglyceride
VI Viscosity index
VM Viscosity modifying, Viscosity modifier
ZnDTP Zinc bis(dialkyldhitiophosphate)
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© 2017 by the author. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Applied Sciences: Molecular Science of Lubricant Additives

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Keywords: tribology; tribo-chemistry; lubrication mechanism; lubricant formulation; molecular design

1.1. Tribology and Lubrication Engineering

Appl. Sci. 2017, 7, 445; doi:10.3390/app7050445 www.mdpi.com/journal/applsci

1.2. The Functions of Lubricants

Lubricants can appear as a liquid, as a semi-solid (greases), or as a solid (including particles

Fluid between sphere/flat tribo-contact

Hersey number (η･V･L-1) λ = 2·Hm/(R1+R2)

by the liquid)

1.4. Tribo-Chemical Reactions

exo-electrons Orientation Elevated

Friction heat Nascent surface Shearing

: hydrocarbon CxHy, • : carbon radical

A tribo-chemical reaction can beneficially or detrimentally influence to the lubrication

1.5. Components in Liquid Lubricants

Viscosity, mm2 s-1 150 Fluid A exhibits higher VI than fluid B

Figure 3. Temperature-viscosity relation and viscosity index.

1.6. Category of Lubricant Additives

1.6.1. Working Function Category

• Tribo-improvers (tribology-improving additives) directly contribute to improve the tribological

1.6.2. Working Site Category

1.6.3. Working Mechanism Category

lower Friction coefficient higher

2.1.2. Anti-Wear Agents (AW)

2.1.3. Extreme Pressure Additives (EP)

Wear of weakly bound α through breaking

Transferring one electron from ●−● bond

severe Tribological conditions mild

Reaction Reaction Adsorption

2.2. Rheo-Improvers (Rheological Properties Improvers)

2.2.1. Viscosity Modifiers (VM)

Base fluid molecule

low Temperature high

Base fluid molecule

chilly Temperature normally

2.3.1. Antioxidants (AO)

X CH2 X CH2 X CH2

H C Depicts hydrogen radical and carbon radical, respectively

R R Red arrow depicts initiation step (Fig. 12)

Sulfuric, phosphoric acids

2.3.4. Corrosion Inhibitor, Rust Preventive

Liquid phase Worn surface

Galvanic corrosion Ionization with acids

Surface film keeps corrosion-promoting

2.4. Multi-Functional Additives

2.5.2. Conductivity Improver

Appl. Sci. 2017, 7, 445 High water

Because of variety of machine elements—their configurations, operating conditions, and

4. Discussion as Multi-Component Systems

4.1. Formulation of a Lubricant

4.2. The Quality of Each Ingredient

4.3. The Interaction of Ingredients

The same molarity

FM and AW, can provide better lubrication performances. This could

lower Friction coefficient higher

better Lubrication performances worse

Base fluid Additive-A Additive-B

4.4. Additive Technology for Synthetic Fluids

Appl. Sci. 2017, 7, 445 Concentration (normalized) 28 of 33

4.6. Additive Technology for Environmentally Acceptable Lubricants

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