Surface and Coatings Technology 180 – 181 (2004) 76–84

Historical developments and new trends in tribological and solid lubricant

coatings
C. Donneta,*, A. Erdemirb
a
Universite´ Jean Monnet, Laboratoire Traitement du Signal et Instrumentation UMR 5516, Bat. F, 10 rue Barroin, 42000 Saint-Etienne, France
b
Argonne National Laboratory, Energy Technology Division, Argonne, IL, USA

Abstract

In recent years, several new solid lubricant and modern lubrication concepts have been developed to achieve better lubricity
and longer wear life in demanding tribological applications. Most of the traditional solid lubricants were prepared in the form of
metal, ceramic and polymer-matrix composites. They have been used successfully in various engineering applications. Recent
progress in thin-film deposition technologies has led to the synthesis of new generations of adaptative, self-lubricating coatings
with composite or multilayered architectures, by using duplexymultiplex surface treatments. These modern self-lubricating coatings
progressively make their way into the commercial marketplace and meet the ever-increasing performance demands of more severe
applications. The present paper reviews our recent understanding of the lubrication mechanisms of both traditional and new solid
lubricants, with particular emphasis on solid lubricant methods and practices.
䊚 2003 Elsevier B.V. All rights reserved.

Keywords: Solid lubricants; Tribological coatings; Friction; Wear

1. Introduction wear resistance to extend the lifetime of the components.

When service conditions in tribological applications
become severe, solid lubricants may be the only choice
for controlling friction and wear. According to Holmberg
et al. w1x, a general design appraisal of the tribological
requirements on a coated-surface contact can be formu-
lated as follows:
● The initial coefficient of friction (CF), the steady-
state CF, and the friction instability must not exceed
certain design values.
● The wear of the contacting surfaces, including the
coated one, must not exceed certain design values.
● The lifetime of the system must, with a specified
probability, be longer than the required lifetime. The
lifetime limit of the system may be defined as the
time when even one of the earlier requirements is not
maintained.
The concomitant decrease of both friction and wear
is not systematically required. In some applications,
such as coated tools, the challenge is to increase the
*Corresponding author. Tel.: q33-4-77-91-58-02; fax: q22-3-77-
91-57-81.
E-mail address: christophe.donnet@univ-st-etienne.fr (C. Donnet).
In other applications, a strong reduction of the friction
in the 10y2 range is paramount to save energy. In spite
of considerable research developments, through more
than 2000 published papers from the past 25 years, there
exists no single solid lubricant that can provide both
low friction and wear over broad use conditions, tem-
peratures and environments. Solid lubricants exhibit the
following major shortcomings. Except for soft metals,
most solid lubricants are poor thermal conductors, hence
they cannot carry away heat from sliding interfaces.
Depending on the test environment and contact condi-
tions, their friction coefficients may be high or fluctuate
significantly. There wear lives are finite and their replen-
ishment is more difficult than that of liquid lubricants.
Oxidation and aging-related degradation may occur over
time and present some problems, for example, with
transition-metal dichalcogenides. Upon exposure to high
temperatures or oxidative environments, they may
undergo irreversible structural-chemistry changes that in
turn lead to loss of lubricity and the generation of some
abrasive, non-lubricious by-products. The deposition
procedure may be complex.
Recently, Erdemir presented an up-to-date review on
solid lubricants and self-lubricating films w2x, including

0257-8972/04/$ - see front matter 䊚 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.10.022
 C. Donnet, A. Erdemir / Surface and Coatings Technology 180 – 181 (2004) 76–84
Fig. 1. Historical development of tribological coatings and solid lubricant films.
a classification of traditional and emerging solid lubri-
cants. In this paper, major emphasis is placed on the
various historical approaches that have been used to
optimize solid lubricant films, and, more generally,
tribological coatings. This historical description, though
not exhaustive, will include the research of specific
material compositions (Part 2), the development of the
deposition processes (Part 3) and the development of
successive generations of films (Part 4). Fig. 1 presents
a general view of the impressive research production
over the past 25 years on this subject. Each part will
summarize the major results and practices, on the basis
of few selected examples from published works. The
objective is to propose a guideline to identify the major
milestones in the development of tribological and solid
lubricant coatings, as schematically illustrated in Fig. 1.
2. Specific material compositions for solid lubricants
2.1. Basic materials
Historically, the important development in the for-
mulation and use of solid lubricants is first due to the
natural ability of various materials to exhibit rather low
friction and low wear under specific conditions. Basic
solid lubricants are generally classified in two categories,
i.e. soft and hard coatings, depending on whether the
hardness value is lower or higher than f10 GPa w1,3x.
This classification, even though arbitrary, for hard coat-
ings is the result of their rather higher wear resistance
when compared with softer ones; for thin soft coatings,
wear and lifetime are particularly critical. Hard coatings
77
include oxides, carbides, nitrides, borides, and some
carbon-based compositions (diamond, low hydrogenated
diamond-like carbon wDLCx). Soft coatings include pol-
ymers, soft metals, halides and sulfates of alkaline earth
metals, some carbon-based compositions (highly hydro-
genated DLC) and the well-known lamellar solids,
including transition-metal dichalcogenides and graphite.
Most of these basic materials have been extensively
studied and some of them present properties that are
attractive when the materials are used under specific
conditions (see excellent reviews in w2,4–6x). For exam-
ple, most oxides become highly lubricious and can
provide fairly low friction at elevated temperatures;
Erdemir proposed a crystal–chemical model to classify
lubricious oxides on the basis of lubrication performance
and operational limits w7x. Efforts to optimize new basic
compositions and structures are still in progress. Recent-
ly, Cs-based oxides were reported to be very promising
for lubricating Si-based ceramic components at high
temperatures. At 600 8C, 0.02–0.1 friction coefficients
have been reported for Cs2O-lubricated Si3N4 ceramics
w8x. During sliding at high temperature, a mixed oxide
layer consisting of Cs2O and SiO2 was found and
believed to be responsible for low friction.
2.2. Modern practice
As described in the Part 4, the combination of basic
solid lubricants to build various film structures (nano-
composites, superlattice, gradient, etc.) has been the
subject of intense research for the past decade. However,
these developments did not prevent the emergence of
78 C. Donnet, A. Erdemir / Surface and Coatings Technology 180 – 181 (2004) 76–84
new ‘single’ structures or original concepts in solid
lubrication. Let us focus on three emerging directions.
2.2.1. Research of new ternary and quaternary (or
more) phases
The versatility of most vacuum deposition techniques
such as plasma vapor deposition (PVD), chemical vapor
deposition (CVD), and ion-beam-assisted deposition
(IBAD) allows the producion of rather complex com-
positions, generally consisting in multicomponent phas-
es. The objective is to improve the wear resistance under
severe conditions, rather than decreasing friction. The
pioneers are probably Knotek et al. w9x with the optim-
ization of (Ti, Al, V) C, N compositions, which allowed
significant improvement in the wear life of tools. This
was probably the beginning of numerous attempts to
deposit complex multicomponent compositions, as
recently reviewed by Jehn w10x. From the initial binary
hard materials, titanium and chromium nitride and car-
bide have been improved by alloying these binary
structures with metal andyor metalloid components. The
nature and amount of alloying elements strongly influ-
ence friction and wear behavior. Such investigations
were extended to a large number of elements, including
Zr, Hf, V, Nb, Cr, Mo, W, Al and Si, with various
chemical combinations. For example, it has been shown
that the lattice structure of binary nitrides remains
unchanged and can contain large amounts of ‘third’
elements, like Al in Ti–Al–N or AlN dispersed in the
fcc CrN w11x. In contrast to this behavior, two- or
multiphase coatings, such as nc-TiNya-Si3 N4 in Ti–Si–
N films w12,13x, can be found. In many other cases,
ternary coatings can show amorphous phases, e.g. the
(W, Si, N) system w14x. The other well-investigated
systems are Ti–B–N w15x, Cr–B–N w16x, and Ti–Al–
B–N w17x, on which an excellent up-to-date review has
been recently published w17x. From this complex chem-
ical research, it is now possible to tailor various struc-
tures, including multilayered, gradient, superlattice,
nanostructured and adaptative coatings with extreme
tribological properties, as depicted in Part 4.
2.2.2. Research on new compositions: the example of
CNx coatings
It is not usual for a material to find large scale
applications only a few years after its discovery. But
this has been the case for carbon nitride films, which
are already used as protective coatings on hard disks
and recorder heads w18x. The wear rates of carbon
nitride coated disks can be 10 times lower than those of
disks coated with a commercial DLC film of the same
thickness w19x. A flurry of attempts to produce the
elusive C3N4 material that is theoretically harder than
diamond has been reported. Most of the films deposited
are, in fact, amorphous CNx, with x f0.1–0.3. Primarily
because of a large variation in their microstructure and
chemical stoichiometry, amorphous CNx films produced
by various research groups exhibit large variations in
mechanical properties and tribological performance (see
Ref. w20x for a summary on CNx films). Reported
friction values range from 0.05 to )0.5 in air, and
friction tends to increase as the film’s nitrogen content
is increased. In a dry environment or vacuum, much
higher friction coefficients were observed. Such a large
scatter in friction has been attributed to the difference
in N content, C–N bondings, carbon hybridization ratios,
and deposition methods and conditions. Noteworthy,
however, is the extreme surface smoothing of the coating
that takes place during sliding wear with root mean
square surface roughness of -0.5 nm, and this has a
large impact on applications that involve gliding and
sliding contacts. Normally, most hard materials are very
brittle, but CNx films are very elastic, which seems to
be a contradiction. In a recent paper w21x, Hultman et
al. presents evidence that CNx may exhibit a fullerene-
like structure, which would give this material an elastic
behavior consistent with a resilient character. The
observed structure consists of sp2-coordinated basal
planes that are buckled by the incorporation of pentagons
and cross-linked at sp3-hybridized C sites, both of which
are caused by structural incorporation of nitrogen. Car-
bon nitride, thus, deforms elastically due to bending of
the structural units.
2.2.3. Solid lubricants dispersed in oils
How the use of coatings affects the friction and wear
behavior of an oil-lubricated contact is neither simple
nor obvious. Published results on the benefit of coatings
in a lubricated contact have been controversial w22,23x,
consistent with the complexity of such systems due to
the several tribological mechanisms that are simultane-
ously involved. Certain solids (such as HBN and boric
acid) have been mixed with oils and greases in powder
form to achieve improved lubrication under extreme
pressure and temperature conditions w24,25x. In bound-
ary-lubricated steel contacts, a boundary film is contin-
uously formed by tribochemical reactions that occur
among the steel surface and sulfur- or phosphorus-based
additives dispersed in the oil. Some of these additives
contribute to a reduction of friction, particularly when
they contain Mo (in dithiomolybdate), with evidence of
the formation of nanocrystalline MoS2 inside the contact
during friction, as shown by Martin et al. w26x. The
demonstration of such complex mechanisms indicates
that some basic solid lubricant mechanisms may be
activated by tribochemistry in liquid-lubricated contacts.
Recently, Rapoport et al. w27x demonstrated how inor-
ganic fullerenelike supramolecules of metal dichalcogen-
ide MX2 (MsMo, W and XsS, Se), which form
nanoparticles in the 10–100-nm range and are used as
additives in oil, provided substantial friction and wear
reduction when compared with additives like platelets
 C. Donnet, A. Erdemir / Surface and Coatings Technology 180 – 181 (2004) 76–84
of pure dichalcogenide. Recently, carbon and WS2 were
prepared in the form of hollow nanotubes and were
shown to provide high mechanical strength and very
low friction coefficients under certain sliding conditions
w28,29x. Research and development on coupling solid
lubrication concepts and tools with additive knowledge
merits much greater research for next-generation
lubricants.
3. Vacuum technology for the deposition of solid
lubricants
3.1. Basic considerations
Solid lubricants can be applied to a tribological
surface in various forms. The oldest and simplest method
is to sprinkle, rub, or burnish the fine powders of solid
lubricant on surfaces to be lubricated. Fine powders of
certain solid lubricants were also used to lubricate
sliding bearing surfaces with great success w30x. Certain
solid lubricants have been blended in an aerosol carrier
and sprayed directly onto the surfaces to be lubricated.
Powders of solid lubricants can be strongly bonded to a
surface by appropriate adhesives and epoxy resins to
provide longer wear life w31x. They can also be dispersed
or impregnated into a composite structure. However, in
most modern applications, thin films of solid lubricants
are preferred over powders or bonded forms. They are
typically deposited on surfaces by advanced vacuum
deposition processes, such as sputtering, ion plating,
IBAD or plasma enhanced chemical vapor deposition
(PECVD), to achieve strong bonding, dense microstruc-
ture, uniform thickness and long wear life. In the context
of the present paper, it is not possible to review the
impressive scientific production related to the vacuum
deposition process. Basic considerations can be found
in Ref. w1x. For further information, it is useful to refer
to the relevant journals and up-to-date conference pro-
ceedings. However, in spite of the refinements in depo-
sition procedures, lifetimes of most solid lubricants are
still limited because of the finite lubricant film thickness.
To increase their durability, a self-replenishment or
resupply mechanism is needed but very difficult.
3.2. Modern developments
3.2.1. Multiplex and hybrid processes
One-way to extend the composition and architecture
of tribological coatings is to combine various deposition
processes to achieve specific properties unachievable by
using one process only. Such approaches have been
termed hybrid, duplex or multiplex coatings, as widely
illustrated by Matthews et al. (see Ref. w32x). This
concept can be achieved with just two differing layers:
for example, an electroless coating that improves abra-
sive wear performance and enhances corrosive resistance
79
can be used as a load-supporting layer for hard coatings
w33,34x. Because many wear-resistant hard coatings are
relatively brittle, they can be successfully applied only
to hard and stiff substrate materials such as hardened
steel, cemented carbide or structural ceramics. On softer
substrates, it is necessary to include the concept of
pretreating the substrate surface to produce a hardened
outer layer, which can then support the coating more
effectively for load accommodation w35,36x. The concept
of duplex treatment is achieved when, for example,
nitriding and PVD coating are performed in sequence
within one coating system. Such developments are still
in progress.
3.2.2. Low-temperature processes
The deposition of tribological coatings and solid
lubricants may require deposition temperatures that
range from room temperature to more than 1000 8C.
The heat resistance of the substrate materials may
strongly limit the number of possible coatingysubstrate
combinations. For some methods, including CVD, high
deposition temperatures can cause undesired phase tran-
sitions, softening or shape changes. This is the case for
Al, Cu and Mg alloys with deposition temperatures in
the first 100 8C, for most steels, with deposition tem-
peratures of 100–500 8C, whereas ceramic materials
usually support higher temperatures, typically up to 1000
8C. PVD and CVD processes may induce significant
temperature increase during deposition, ranging between
f100 and 1000 8C (CVD). Thus, all types of PVD and
CVD coatings can be applied to most ceramic materials
and cemented carbides. Some heat-resistant steels, such
as high-speed steel (HSS), can be treated by all types
of PVD and some low-temperature CVD processes.
Progress in PVD or CVD coating of low-alloy steel,
copper-based, light-metal-based alloys remains very lim-
ited. Electrochemical plating, chemical (electroless)
plating and, in a certain way, thermal spraying allow
film deposition at much lower temperatures, but the
versatility of the latter techniques is lower than that of
vacuum techniques. However, the emerging need to
deposit solid lubricant films on temperature-sensitive
materials, such as polymers, is strongly restrained by
using vacuum technology. The development of less
conventional processes, such as sol–gel techniques, is
encouraged.
3.2.3. Large-scale manufacturing
Most of the published work related to tribological
coatings has been performed by using deposition pro-
cesses at laboratory scale, that is, with treated plane
surfaces in the 1–10 cm2 range. The transfer of such a
technology toward higher dimensions andyor more com-
plex shapes remains one of the most difficult technolog-
ical and economical challenges. This is particularly true
for industrial manufacturing of complex structures that
80 C. Donnet, A. Erdemir / Surface and Coatings Technology 180 – 181 (2004) 76–84
include gradient, superlattice and nanostructured films
(Part 4). In large-scale manufacturing, the distribution
and deposition rate must be very well defined, so the
thickness and property variation tolerance should be
minimized. Most of the properties evaluated at the
laboratory scale may diverge when the deposition scale
is larger. Moreover, in many cases, complicated instal-
lations, including shielding and shuttering, are not appli-
cable. Finally, the coating supplier must be watchful of
the reproducibility of the process vs. time. Some papers
present deposition runs performed on industrial vacuum
devices. A combined cathodic arcyunbalanced magne-
tron deposition system with four vertical targets is
detailed in Ref. w37x. These linear cathodes, in combi-
nation with up to three-fold substrate rotation, must be
used to achieve homogeneous rate distribution over the
whole height of the vacuum chamber, with a distance
of 1 m between two opposing targets and an outer
diameter of the rotating substrate table of 750 mm. The
magnets and the polarization of the electromagnetic
coils are arranged in a close magnetic field configuration
to achieve high plasma density and the possibility to
control the temperature at as low as 200 8C under
specific conditions. Evidence of industrial production of
nanolayered TiAlCrNyTiAlYN coatings is shown and
the process has been proved stable and reproducible.
Deposition of gradient TiyTiC(H)ya-C:H films that
exhibit friction in the 10y2 range with high wear
resistance under high-vacuum conditions has been per-
formed in an industrial duplex reactor that combines
magnetron sputtering for Ti deposition and PECVD for
deposition of hydrogenated DLC w38x. Due to confiden-
tial requirements, less work in that field is published
and most data are kept within companies for their own
use.
3.2.4. Combination of deposition with surface
structuring
Precise patterning of coatings is a rather new concept
that will probably progress in the near future. Plasma,
chemical or laser techniques as widely performed by
the microelectronic industry for many years, can be used
to achieve a specific geometrical design on a surface.
Laser treatment has advantages related to its versatility
and fast adaptability. Excimer lasers have been used to
induce patterns on DLC films w39x, but emerging fem-
tosecond laser facilities will probably introduce new
perspectives in that field. Indeed, the ultrashort laser
pulses (in the 100-fs range, with power density as high
as 1013 W cmy2) can ablate all kinds of materials
without any collateral effects (negligible thermal affect-
ed zone), contrary to nanosecond pulses w40x. Lifetime
increases upto a factor of 10 have been achieved by
patterning of TiN w41x and TiCN w42x films with a
femtosecond laser. Recently, laser patterning of wear-
resistant DLC with two configurations, either by coating
already patterned substrates (indirect processing), or by
direct laser processing of deposited DLC films has been
studied w43x. Pore depths that yield to positive tribolog-
ical improvements ()10 mm) are larger than film
thickness (-5 mm). The authors indicate that debris
particles were trapped in the surface pore obtained by
indirect laser processing, thus preventing the breakdown
of the tribological system. According to Voevodin et al.
w44x, the three-dimensional design considerably
improved the tribological characteristics of hard coatings
by permitting solid lubricant replenishment inside the
friction contacts. Such patterning may also have a
positive effect both by carrying away heat from sliding
interfaces and by trapping abrasive wear debris. In Ref.
w44x, a functionally-gradient Ti–TiC–TiCyDLC coatings
with an upper layer of tough nanocrystallineyamorphous
composite was used for load support, crack prevention
and stress equalization. This coating was processed by
laser irradiation to form grooved tracks along wear
paths, which were then filled with MoS2 to provide a
solid lubricant reservoir in the lateral dimension of the
coating. The three-dimensional coating was tested in
long-duration sliding tests at fixed and cycling humidity.
The coating exhibited environmental adaptation, with
friction coefficients of 0.15 in humid air and 0.02 in
dry nitrogen. The wear life was increased by at least
one order of magnitude when compared with that for a
hard-gradient coating with a top layer of MoS2 without
three-dimensional laser processing. Coating patterning
probably will be a major axis of development in coatings
technology in the next decade.
4. Structure of tribological and solid lubricant
coatings
4.1. Generation I: single-component coatings
In spite of the enormous efforts to develop new
coatings and coating systems, only a few and mostly
‘simple-structured’ films prevailed on the market and
continue to be favorites. Most commercial PVD and
CVD coatings consist of one single layer, often contain-
ing one (or two) single phase(s). Probably, in many
cases, the needed storage dump and higher tool produc-
tion costs if complex systems are applied explains the
persistence of this first generation of tribological coat-
ings in many industrial operations. The commercially
successful coatings include TiC, TiN, CrN, CrC, Al2O3,
TiAlN, TiCN, DLC, W2C, WCyC, MoS2, diamond, soft
metals and some polymers. To fulfill the functional
demands, an adhesion interlayer may be necessary. In
the previous section (Part 2), the development of hard
coatings has been particularly highlighted. Let us briefly
focus on the particularities of some of the other coatings.
Well-known solid lubricants (graphite, HBN and tran-
sition-metal dichalcogenides) owe their lubricity to a
 C. Donnet, A. Erdemir / Surface and Coatings Technology 180 – 181 (2004) 76–84
unique layered structure, but the detailed mechanisms
are not exactly the same from one lamellar solid to
another; water vapor is necessary to lower the friction
of graphite but rapidly inhibits the lubricating properties
of MoS2. The latter one is widely used in vacuum
lubrication and considerable data have been accumulat-
ed, leading to deep knowledge of its lubricating mech-
anisms w20,45x, including the evidence of superlow
friction in the solid state w46,47x. Soft metallic lubricants
have crystal structures with multiple slip planes and do
not work-harden appreciably during sliding contact.
Dislocations and point defects generated during shear
deformation are rapidly nullified by the frictional heat
produced during sliding contact. Reported friction coef-
ficients of soft metals range from 0.1 to 0.4, depending
on the metal and test conditions w2x. Film-to-substrate
adhesion is extremely critical for achieving long wear
life or durability, especially on the surfaces of ceramic
tribomaterials w48x. Considerable works have been
devoted to carbonaceous materials, including DLC films.
These amorphous structures, which contain both sp2 and
sp3 hybridizations, have hydrogen content that ranges
between -1 and f50 at.%, from which most of the
structure’s properties are derived w49x. Among solid
lubricants, they probably exhibit the widest range of
friction and wear behavior. The reader can refer to
specific references related to the tribological behavior
of DLC films w20,50x. Diamond films are extremely
hard and offer several outstanding properties, such as
high mechanical strength, chemical inertness and very
attractive friction properties. At present, several CVD
techniques are available to produce high-quality dia-
mond films with micro- and nanocrystalline structures
on various substrates. The high-quality diamond coatings
produced by CVD exhibit most of the desired mechan-
ical and tribological properties of natural diamond w20x.
Recently, nanocrystalline diamond (NCD) films with a
very smooth surface finish have also been deposited by
microwave CVD in the near absence of hydrogen w51x.
When polished or NCD coatings are used in sliding-
contact experiments, very low friction coefficients are
attained w52x. Polymers in various forms are used widely
in tribology. They are light-weight, relatively inexpen-
sive, and easy to fabricate. They can easily be blended
with other solids to make self-lubricating composite
structures. Certain polymers (polytetrafluoroethylene
wPTFEx, polyimide, nylon, ultra-high-molecular-weight
polyethylene wUHMWPEx, etc.) are self-lubricating
when used in both bulk and thin-film form, or as binders
for other solid lubricants w53x. Except when they contain
self-lubricating inorganic filler w54x, they generally can-
not be used at temperatures higher than 250 8C. One of
the most popular polymers is probably UHMWPE,
which is used widely in total joint replacements, even
if improvement of its wear resistance against harder
counterfaces is required to enhance the wear life of
81
protheses w55x. Other solid lubricants include boron-
containing materials: hexagonal boron nitride and boric
acid, which can be formed in situ by reaction between
B2O3 and water during friction, as reviewed in Ref. w2x.
(Oxy-)thiomolybdates of Cs or Zn and a few other
alkali metals, certain complex oxides and oxide-fluorides
w2,7x and sulfate-based coatings (CaSO4, BaSO4 and
SrSO4) w56x were shown to be rather lubricious at
elevated temperatures (300–600 8C). Under those con-
ditions, the candidates that achieve low friction and high
wear resistance are rather limited and this is consistent
with the use of ‘simple’ coating structures, because more
complex ones (such as multilayer, superlattice) may be
altered by the combination of friction and high temper-
ature during operation.
4.2. Generation II: multiplayer and multicomponent
Multicomponent coatings are made up of two or more
constituents in the form of grains, particles or fibers.
Multilayered coatings are composed of a periodically
repeated structure of lamellae of two or more materials,
with thicknesses up to a few tens of a micrometer (if
the thickness of each lamellae is in the nanometer range,
these films are generally classified as superlattice, as
reviewed in Part 4.3). Generally, multilayered coatings
are distinguished from sandwich layers, which include
several superimposed films that achieve complementary
properties. This second generation of tribological coat-
ings is generally constituted by a combination of basic
materials described in the previous section (Part 4.1).
Details on the diversity of structure available can be
found in Ref. w1,57x. The advantage of combining
several structures and compositions within one coating
include achievement of various individual physical prop-
erties (i.e. diffusion barrierqlow friction), reduction of
the mismatch in mechanical and chemical properties
between the substrate and the coating (mainly to
enhance adhesion), control of the residual strain and
therefore the stress within the coatings, the ability to
stop cracks during operation under severe conditions,
and enhancement of hardness andyor toughness by
allowing layers or phases to slide over each other when
they deflect under load. The versatility of vacuum
technology (as depicted in Part 3) and the emergence
of multiplexyhybrid processes has led to considerable
developments of this generation of coatings, which has
been recently found as major industrial applications. A
large up-to-date overview that presents various examples
and applications of multilayered and multicomponent
coatings is presented in w10x.
4.3. Generation III: gradient, superlattice and nano-
structured coatings
Control of the structure and composition of coatings
at the nanoscale is an exciting scientific subject com-
82 C. Donnet, A. Erdemir / Surface and Coatings Technology 180 – 181 (2004) 76–84
bined with an industrial challenge. This control can be
achieved mainly through three structural configurations.
The first configuration is the functionally graded coat-
ings, which are regarded as the logical progression from
multilayered coatings. Grading the composition by a
drastic control of the deposition process has been
achieved to combine a relatively hard TiAlN phase with
a softer MoS2 phase with an increase in the latter phase
toward the top surface w58x. One other benefit of grading
the composition is that it improves adhesion of DLC-
based coatings that contain metal additions. Such
improvements have been obtained by Ti and TiC(H)
graded underlayers to increase the wear resistance of
DLC films w38,59x. Second, nanostructured coatings
include nanocrystallized films (with grain sizes in the
nanometer range) and nanocomposite films, as a logical
progression of multicomponent films toward the nano-
scale. Nanocomposites include structures that combine
amorphous phases with crystallized ones, as widely
emphasized by Veprek w61x. Third, superlattice corre-
sponds to the multilayer concept extrapolated to a
thickness of individual layers in the 5–50-nm range.
The major function of these structures is to significantly
enhance hardness, fracture toughness and adhesion of
the coatings, and thus to improve their wear resistance.
In recent years, the literature and the theoretical under-
standing of this new generation of films have been
grown, in particular with regard to compositionally
modulated superlattice films w60x, and nanocrystallized
w61x and nanocomposite w62x coatings. On the macro-
scopic scale, the concept associated with this generation
of coatings is maximization of hardness (H) while
ensuring an adequately low elastic modulus (E), to
provide an appropriate ‘elastic stain to failure,’ as
determined by the HyE ratio w63x. On the nanometer
scale, the mechanism corresponds to a higher resistance
to dislocation movement by precluding the formation of
stable ones. This is achieved by decreasing the grain
size, in accordance with the well-known Hall–Petch
relationship, or by controlling the presence of interfaces
between nanocrystallized (nc) metal nitrideymetal w64x,
or between amorphous and nanocrystallized phases as
with nc-MnNya-Si3N4 (where M is Ti, W, V or other
transition metal) w61x. The most recent developments to
extend the use of nanometer-scale coatings are probably
devoted to their stability at high temperature, to avoid
phase transformation, grain growth and diffusion pro-
cesses. This seems to be possible if the layer materials
are thermodynamically stable with respect to each other
and are stable to form low-energy coherent interfaces
w65x.
4.4. Generation IV: smart (adaptative or chameleon)
coatings
This recent innovation corresponds to coatings being
able to change their properties to meet the requirements
of the operating conditions during their solicitation,
generally under severe conditions, and being able to
change during the lifetime. Smart coatings imply a deep
knowledge of the film structure and composition
dependence vs. temperature, contact pressure and envi-
ronment. The most recently developed cutting-tool coat-
ings, based, for example, on TiAlN with the addition of
yttrium or chromium, may produce a stable oxide during
cutting at high temperature and enhance the wear resis-
tance w58x. Another example of such behavior, recently
published by Voevodin et al. w66,67x and related to a
composite coating produced within the W–C–S system,
consisted of 1–2-nm WC and 5–10-nm WS2 grains
embedded in an amorphous DLC matrix. The WCy
DLDyWS2 nanocomposite exhibited self-adaptation to
operations that occur in aerospace systems. This adap-
tation was found in crystallization and reorientation of
initially nanocrystalline and randomly oriented WS2
grains, graphitization of the initially amorphous DLC
matrix, reversible regulation of the composition of the
transfer film between WS2 and graphite with environ-
mental cycling from dry to humid air and possible
DLCyWS2 synergistic effect, providing friction reduc-
tion in oxidizing environments. Friction lower than 0.05
was recorded during a space simulation test of 2 million
cycle, and recovery of low friction in tests that simulate
ambientyspace environmental cycling was demonstrated.
Another challenge for smart solid lubricants is achieve-
ment of lubrication in the widest range of temperature.
No single material is known to be lubricious from
ambient temperature to 800 8C. Thus, the way to produce
a lubricant coating that can operate over a broad tem-
perature range is to combine low- and high-temperature
lubricants into a composite or layered structure, such as
CaF2 and WS2, which interact during friction to form
CaSO4 w68x. A similar concept has been demonstrated
by combining transition metal dichalcogenide (MoS2 or
WS2) with oxides (ZnO or PbO) to form PbMO2 or
ZnWO4, which are lubricious at high temperature
w69,70x. The future challenge of smart coatings is prob-
ably to achieve the design lubricative properties with
reversibility under multiple cycles of temperature or
environmental variation.
5. Conclusion and future trends
In recent years, there have been numerous exciting
developments in the fields of tribological and solid
lubricant coatings. These novel coatings have much to
offer for increasingly stringent application conditions of
future tribosystems. Each and every one of these coat-
ings is rather unique and designed or formulated to
work under certain application conditions. Regardless of
the type, unfortunately there exists no such coating that
can work under any type of application conditions.
Depending on the test environment, temperature and
 C. Donnet, A. Erdemir / Surface and Coatings Technology 180 – 181 (2004) 76–84
sliding conditions, the performance and durability of
tribological and solid lubricant coatings vary a great
deal. To overcome such variations in performance and
durability, researchers have been exploring novel coating
architectures having multi-layers, micro surface textur-
ing, nano-structures andyor composites. Such exotic
coatings appear to work better than their traditional
counterparts in both the machining and sliding contact
applications. Some of the nano-composite coatings are
superhard and depending on their compositions, some
of them are able to provide better performance and
durability over broad application conditions.
For tribological and solid lubricant coatings, strong
adhesion between coatings and substrates is critically
important for long service life. Modern deposition tech-
niques equipped with hybrid processing capability are
quite able to impart strong adhesion between coatings
and their substrates. There is no doubt that search for
newer and better tribological and solid lubricant coatings
will continue in coming years, since the application
conditions of future mechanical systems will undoubt-
edly be much more demanding than the current ones.
One of most exciting trend nowadays is on the devel-
opment of coatings for dry andyor near dry machining
applications. With the knowledge base and technical
resources available now, there should be no doubt that
such coatings will become available in the near future.
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