Tribol Lett (2008) 29:155–161
DOI 10.1007/s11249-007-9292-z
ORIGINAL PAPER
MoS2 Films Formed by In-contact Decomposition
of Water-soluble Tetraalkylammonium Thiomolybdates
Fernando Chiñas-Castillo Æ Javier Lara-Romero Æ
Gabriel Alonso-Núñez Æ Juan de Dios Oscar Barceinas-Sánchez Æ
Sergio Jiménez-Sandoval
Received: 25 June 2007 / Accepted: 19 December 2007 / Published online: 8 January 2008
Ó Springer Science+Business Media, LLC 2008
Abstract Synthesis and tribological evaluation of three
tetraalkylammonium thiomolybdate (R4N)2MoS4 (R =
methyl, propyl, or ammonia) aqueous-based lubricant
additives on a ball-on-disk tribometer was carried out for a
steel–aluminum contact. Tests were performed at the same
conditions of load, entrainment speed, sliding distance,
temperature, and concentration of MoS2 to compare the
activity (lubrication effect) of the thiomolybdates prepared.
A friction reduction is observed for the three salts com-
pared to pure water; however, significant differences in
friction coefficient are observed depending on the alkyl
group. SEM/EDAX and Raman analysis of the wear tracks
reveal the in-contact formation of a MoS2-lubricating film,
rich in molybdenum and sulfur.
Keywords Tribological
Additive
Water-soluble

Friction
Wear
Film forming
F. Chiñas-Castillo (&)
Mechanical Engineering Department, Instituto Tecnológico de
Oaxaca, Oaxaca, Oaxaca, Mexico
e-mail: fernando-chinas@mail.com
J. Lara-Romero
Chemical Engineering Department, Universidad Michoacana de
San Nicolás de Hidalgo, Morelia, Michoacan, Mexico
G. Alonso-Núñez
Materials Department Chemistry, CIMAV, Chihuahua,
Chihuahua, Mexico
J. D. O. Barceinas-Sánchez
Research Department, CIATEQ, A.C., Queretaro, Queretaro,
Mexico
S. Jiménez-Sandoval
Materials Department, CINVESTAV, Queretaro, Queretaro,
Mexico
1 Background
Lubricant additives, such as friction modifiers and mild
antiwear agents, are added to lubricants for the purpose of
minimizing surface asperity contact that may occur in a
given machine element. Dichalcogenides (i.e., graphite,
molybdenum disulfide), esters, and fatty acids are repre-
sentative additives typically used for these purposes. Their
molecules have a polar head and a lubricant-soluble tail,
and when an additive-containing lubricant enters into the
contact, the polar head anchors on metal surfaces forming a
low-shear tribological film that prevents surface asperity
contact and facilitates sliding motion [1]. As long as the
mechanical contact is not heavily loaded, these molecules
provide a cushioning effect that reduces surface interac-
tions and thus reduce friction. However, as load and
metallic contact increase, the strength of the additive and
the chemical reaction process must increase. This leads to
the use of sulfur–phosphorus-based EP additives, which
form organometallic salts on the loaded surfaces that serve
as sacrificial films to protect against aggressive surface
damage. Frictional heating on continuously modified sur-
faces boosts chemical reactions and interactions between
lubricating additives and the corresponding surfaces in the
contact zone. Characteristics of the lubricating films
formed in the contact depend on tribological mating pairs,
chemical nature of the additive, and operating conditions.
Considerable asperity contact is present in the boundary
lubrication regime where the contacting surfaces are no
longer separated by the lubricant. Under these conditions,
friction characteristics of the mating pairs are entirely
determined by the properties of the solids, and any lubri-
cating film formed at the interface and the friction
coefficient is essentially independent of fluid viscosity. The
average film thickness formed in this regime is thinner than
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the elastically deformed surface roughness. Continuous
asperities, interactions initially cause elastic deformation,
then plastic deformation, and finally, mechanical fracture.
Organomolybdenum compounds and other organome-
tallic salts have been studied for many years because of their
beneficial properties as friction modifiers and used effec-
tively either as a powder, a protective coating, or a lubricant
additive in machine elements such as gears, bearings, and
metalworking applications [2–6]. Molybdenum is well
known for its lamella-layered structure and low-shear
strength that provide excellent friction reduction character-
istics in high-pressure contacts. Paraffin oil-soluble
suspensions of sulfur-containing molybdenum and nano-
particles of MoS2 dispersed in mineral oil have also been
used as lubricant additives and evaluated under boundary
lubrication conditions and ultrahigh vacuum [7–9]. The most
extensively studied class of organomolybdenum compound
is the molybdenum dithiocarbamate (MoDTC) and molyb-
denum dialkyldithiophosphate (MoDTP) either individually
or in synergistic combination with ZDDP, zinc dialkyldi-
thiophosphate (ZDTP), or alkylated diphenylamines to
reduce friction and wear by forming a protective film
composed of MoS2 or enhance its antioxidant performance
[10–15].
Although most studies for these organomolybdenum
additives have been conducted to evaluate their performance
when dispersed in oil media, in recent years there has also
been a growing interest on evaluating their tribological
behavior on water-based fluids for metalworking applica-
tions. Experimental work carried out by Sulek and
Wasilewski has shown that aqueous solutions of lauryl sul-
fates present good antiseizure performance [16]. Maejima
and coworkers explored the lubricating characteristics of
water solutions of (NH)2MoS4 for aluminum surfaces and
reported a lubricity improvement and better wear resistance
[17]. Other studies have also found that inorganic salts (e.g.,
sulfates, phosphates, and chlorides) and organometallic
compounds have good tribological performance on friction,
wear, and seizure for metalworking and EP applications [18,
19]. Polymers have also been used as partially soluble
additives in water-based systems in synergistic combination
with fullerene, as they enhance the antiwear and antifriction
characteristics of the base fluid [20–22]. All these previous
studies show some evidence that a protective film is formed
on the interacting surfaces, which is responsible for the
friction and wear reduction observed.
Recent studies carried out by Georges et al. [23] on the
mechanism of water-based lubricants indicate that lamella
nanostructures at the mechanical contact interface provide
efficient lubrication under severe contact conditions.
This paper presents some results on tetraalkylammonium
thiomolybdates as water-soluble lubricant additives working
under boundary conditions for steel–aluminum surfaces.
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Tribol Lett (2008) 29:155–161
2 Experimental Procedure
2.1 Synthesis of Tetraalkylammonium Thiomolybdates
The tetraalkylammonium thiomolybdate salts used in the
tests were prepared in a two-step synthesis following the
method reported by Alonso et al. [24–26]. In the first step,
a water-soluble ammonium thiomolybdate (NH4)2MoS4 is
prepared from ammonium heptamolybdate (NH4)6Mo7O40
in an ammonia/water solution with H2S flow at room
temperature according to the following chemical reaction:
ðNH4 Þ6 Mo7 O40 þ NH4 OH=H2 O þ flow of H2 S
! ðNH4 Þ2 MoS4
After this, the second step involves a rapid substitution of
[NH4]+1 ions from (NH4)2MoS4 by tetraalkyl ammonium
radicals [R4N]+1, where R = methyl or propyl groups
according to the following chemical reaction:
ðNH4 Þ2 MoS4 þ 2R4 NBr ! ðR4 NÞ2 MoS4 # þ2NH4 Br
The resultant precipitate is the tetraalkylammonium
thiomolybdate salt (where R = methyl, propyl, or ammonium)
called tetramethylammonium thiomolybdate [(Met)4N)]2
MoS4, tetrapropylammonium thiomolybdate [(Pro)4N)]2
MoS4, or tetraammonium ammonium thiomolybdate which
are also soluble in water.
The procedure described for the synthesis of the thio-
molybdate salts yields approximately 80%. The resulting
structures have been analyzed by UV–vis, infrared, Raman,
and TGA-DTA by Alonso et al. [26–28].
2.2 Substrate Materials
The materials used as specimens in the pin-on-disk tribom-
eter were selected considering the importance of steel–
aluminum mating pairs in metalworking applications. The
upper specimen was a 6-mm diameter pin made of stainless
steel 440C, while the lower specimen was a 50-mm diame-
ter 9 6-mm thick disk made of aluminum alloy 6063,
respectively. Surface roughness for the specimens was
approximately 25 and 140 nm rms, while their Brinell
hardness values were approximately 97 and 25 HB for steel
pin and aluminum disk, respectively. The disks were mirror
polished using a liquid suspension containing 0.3-lm Al2O3
abrasive particles. Specimens were thoroughly cleaned in an
ultrasonic bath in boiling toluene, completely rinsed in
acetone, and finally dried, previous to the tribological tests.
2.3 Friction Tests
Tribological friction tests were carried out on a commercial
pin-on-disk tribometer (Micro Photonics-Tribometer). In
Tribol Lett (2008) 29:155–161 157

equipped with a 20-mW He–Ne laser emitting at 632.8 nm,

a holographic notch filter made by Kaiser Optical Systems,
Inc. (model supertNotch-Plus), a 2569 q1024-pixel CCD
used as detector, a computer-controlled XY stage with a
spatial resolution of 0.1 lm, two interchangeable gratings
(600 and 1,800 g mm-1), and a confocal microscope with
10, 50, and 1009 objectives. All measurements were car-
ried out at room temperature with no special sample
preparation.
Worn disk tracks were also examined using a thin window
energy dispersive X-ray spectrometer (EDX) housed in a
JEOL JSM5800 LV scanning electron microscope (SEM).
EDX spectra were obtained at beam energy of 10 keV, beam
current 2.0 nA, and detector take-off angle of 25°.

Fig. 1 Pin-on-disk tribometer

this rig, a steel pin loaded against an aluminum disk forms
the mechanical contact. The pin is firmly secured to a
stationary holder for the pin-on-disk configuration, and the
disk is attached to a horizontal chuck driven by a variable-
speed electric motor and completely submerged in the test
fluid. A linear voltage displacement transducer attached to
the pin holder continuously monitors and records friction
force of the tribocontact.
A picture of the test rig is shown in Fig. 1.
All tests were performed at a constant temperature of
30 °C and 60 ± 5% relative humidity. A dead weight of
3 Results and Discussion
3.1 Friction Tests
Figure 2 shows the friction coefficient as a function of time
of steel–aluminum mating pairs three times with distilled
water as lubricant and for the tetraalkylammonium thio-
molybdate salts synthesized and used as a lubricant
additive at a constant molybdenum concentration for every
0.7

10 N was used in all the tests carried out. Under these (R4N)2MoS4 / water
conditions, the maximum Hertzian pressure is 0.877 GPa
that generates a circular contact area of 0.017 mm2. During 0.6
the tests, the aluminum specimen rotates at a constant
sliding speed of 1 mm/s for a period of 1 h, running a total (a)
distance of 3.6 m in each test. The test conditions selected 0.5
are proper of boundary lubrication regime.
Friction coefficient, µ

The wear rate was obtained from an LVDT sensor on the

pin. The lubricant solution was prepared by adding the 0.4
amount of salt necessary to have a constant 0.3 wt%
molybdenum concentration in three times distilled water
and vigorously mixed for 10 min for each additive solution 0.3
evaluated (methyl, propyl, and ammonium salt).

0.2
2.4 Surface Analysis (b)

Wear tracks on the flat and ball wear scars were examined 0.1 (c)
optically and further analyzed using several surface ana- (d)
lytical techniques at the end of the pin-on-disk sliding tests.
The morphological and chemical characterization of the 0.0
sliding surfaces after the tribological tests was carried out 0 1000 2000 3000 4000 5000

with a Scanning electron microscope (SEM) and laser Time / seconds

Raman spectrometer. Raman spectroscopy was performed Fig. 2 Friction coefficient versus time for (a) water, (b) propyl, (c)
using a LabRam model of Dilor micro-Raman system methyl, and (d) ammonium

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Table 1 Friction coefficient and wear rate for each lubricant 50

evaluated
Friction coefficient Wear rate (mm/s) (R4N)2MoS4 / Water
Water 0.53 ± 0.001 0.0112
Propyl 0.17 ± 0.001 0.00166
40 (a)
Methyl 0.1 ± 0.001 0.00187
Ammonium 0.08 ± 0.001 0.00184

Wear Track Depth / µm

30
solution prepared. The friction coefficient for the speci-
mens lubricated with water is initially 0.2 but increases
with distance and stabilizes at a value of *0.53.
A significant friction reduction was observed when
specimens where lubricated with the synthesized thiosalts, 20
recording friction coefficient values in the range of 0.08–
0.17. The lowest steady-state friction coefficient was 0.08
corresponding to the specimens lubricated with ammonium
thiosalt (see Table 1). 10
These results suggest the formation of a protective (b) , (c)
lubricating film at the contact interface. High temperature (d)
causes the thiomolybdate salts to be transformed to
molybdenum disulfide [24]. This is achieved by a chemical
0
reaction via thermal decomposition caused by the severe 0 1000 2000 3000 4000 5000
rubbing contact conditions present at the interface.
Time / seconds

Fig. 3 Wear rate versus time for (a) water, (b) propyl, (c) methyl,
3.2 Wear Mechanism and (d) ammonium

A linearly dependent penetration of the pin on the alumi-
num specimen as time passes is observed in Fig. 3. In this
graph, wear rate is represented by the slope. Table 1 pre-
sents wear rate values registered after testing the additives
prepared and the control fluid (three times distilled water).
A wear reduction of approximately one decimal point is
reached using the thiomolybdate salts as additives.
After the pin-on-disk surfaces were rubbed for 1 h in the
thiosalt solution at a constant load of 10 N, the worn speci-
mens were characterized and analyzed by SEM, EDX, and
Raman.
Representative SEM micrographs of wear track on disk
specimens lubricated with water, propyl, methyl, and ammo-
nium produced from sliding at 30 °C are shown in Fig. 4a–d.
Some representative SEM micrographs of wear track on
disk specimens lubricated with water, propyl, methyl, and
ammonium thiomolybdates produced from sliding at 30 °C
can be seen in Fig. 5a–d.
The wear track of the disk specimen lubricated with
distilled water at 30 °C presented numerous parallel
plowing grooves in the sliding direction in Fig. 5a. These
surface features indicate dominance of abrasive wear.

Fig. 4 SEM images of the

contact track for (a) water, (b)
propyl, (c) methyl, and (d)
ammonium. Image
magnification 279

Fig. 5 SEM images of the

contact track for (a) water, (b)
propyl, (c) methyl, and (d)
ammonium. Image
magnification 5,0009

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Figure 5b–d reveals different surface features on the all cases, an atomic ratio of approximately two is observed,
wear track produced after being lubricated by the molyb- suggesting the formation of MoS2, which is responsible for
denum thiosalts. The smooth regions and tiny cracks the friction and wear rate reduction noticed during the tri-
observed in these figures indicate in this case that adhesion bological tests.
and localized microcracking were the prevailing wear Figure 6 shows the characteristic distribution of alumi-
mechanisms. This may be attributed to the effect of high num, molybdenum, sulfur, and oxygen in a section of the
sulfide content and the formation of a mixed hard-brittle contact track of the aluminum specimen. This analysis
phase of the tribofilm. Microcracking resulted in regions of confirms the presence of sulfur and molybdenum especially
partial delamination of tribofilm and indicates that both in zones where no aluminum debris was detected.
adhesion and cohesive shearing of the film control the wear An EDX analysis was carried out on aluminum speci-
process. However, it appears that the chemical reactions of mens lubricated with tetraalkylammonium thiomolybdates
the additive and the freshly-exposed surfaces replenished to determine the chemical composition of the laminated
the film expeditiously. debris formed on the track and inside the small crevices
observed. The analysis indicated that laminated debris is
composed primarily of molybdenum disulfide, which is
3.3 Chemical Analysis also present inside the cracks (see Figs. 7, 8).
Raman spectroscopy was carried out on wear particles at
The EDX analysis carried out rendered the atomic percent- different parts of the wear track. The spectra taken on the
ages of molybdenum and sulfur present on the wear track of samples analyzed were compared with those obtained from
the aluminum specimens. Table 2 shows the molybdenum- a standard reference (Fig. 9).
to-sulfur relation found on the wear track of the disk speci- Raman spectroscopy of the wear track revealed very
mens lubricated with the molybdenum thiosalts prepared. In sharp peaks at approximately 402 and 376 cm-1 corre-
sponding to the E12g and A1g vibrational modes of
2H-MoS2 [29].
The Raman analysis of the friction formed tribofilm
Table 2 Atomic percentages of elements detected in the contact zone
proved that the platelets observed in SEM micrographs are
%C %O % Mo %S Mo/S ratio in fact MoS2 sheets. The changing positions of the peaks
provide additional information about the microstructure.
Water 8.20 3.25 0 0 0
Plate-like layers of MoS2 can align themselves parallel to
Propyl 71.54 7.18 1.92 4.21 2.19
the direction of relative motion under high stresses; so they
Methyl 29.96 15.43 2.08 4.42 2.12
can slide over one another with relative ease and thus
Ammonium 8.43 37.11 8.72 19.08 2.18
impart low friction.

Fig. 6 Mapping of aluminum,

molybdenum, sulfur, and
oxygen in a section of the
contact track

Fig. 7 SEM micrograph of

aluminum specimen lubricated
with tetralkylammonium
thiomolybdates (a) 1209, (b)
10,0009

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Fig. 8 EDX analysis of an

aluminum specimen lubricated (a) (b)
10 10
with tetralkylammonium EDAX / Ammonia Al EDAX / Ammonia
thiomolybdates (a) on film, (b)
on substrate Film Substrate
8 8

6 6

Intensity
Intensity
S
Mo

4 4
Al

2 2 S
Mo
O
C O
C
0 0
0 2 4 6 0 2 4 6
Energy, eV Energy, eV

The thiomolybdate salts prepared in the present paper

are stable at temperatures lower than 150 °C. In the ball-
700 Raman on-disk tribometer, contact surface temperatures are higher
He-Ne Laser / 632.8 nm than 150 °C, and this causes the thiomolybdate salt to
thermally decompose forming an in-contact solid molyb-
600 MoS2 denum disulfide.
The use of tetraalkylammonium thiomolybdenum salts
402 (precursors of MoS2) as water-soluble lubricating additives
500 offers an important reduction in friction and wear for high-
pressure contacts. The authors believe that oxygen and carbon
content present in the tribofilm is responsible for the main
400
differences on the friction coefficient values observed among
the (methyl, propyl, and ammonium) ammonium thiomo-
Intensity

lybdates tested, but this assumption requires a deeper analysis.

300
At present some tests are being conducted to elucidate
how the hydrocarbon chain influences the hydrolysis pro-
cess, and the findings will be presented in a future
communication.
200
376

4 Conclusions
100

This paper presents a tribological study on tetralkylam-

monium thiomolybdates. The effectiveness of these
0 additives to reduce friction and wear in aqueous solution
during sliding at a temperature of 30 °C was evaluated on a
200 250 300 350 400 450 500 pin-on-disk tribometer. From the results of this study, the
Raman Shift / cm
-1 following main conclusions can be drawn:

Fig. 9 Raman spectra on the wear track of aluminum specimen 1. Tetralkylammonium thiomolybdates exhibit good friction
lubricated with molybdenum thiosalt and wear reduction properties in water-based systems.

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2. The surface examination of the rubbing zone indicated
that an in-contact non-homogeneous tribofilm contain-
ing molybdenum disulfide is formed on the rubbing
surfaces during the sliding process. Tetraalkylammo-
nium thiomolybdates are transformed to molybdenum
disulfide by high-temperature triboreduction in the
contact influencing friction and wear.
3. From the thiomolybdates evaluated in this study, the
tetraammonium ammonium thiomolybdate performs
better than the rest in both friction and wear.
Acknowledgments The authors wish to express their sincere thanks
to the National Council for Science and Technology (CONACyT—
Projects 46871 and 43634) for the financial support to carry out the
present work.
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