lubricants

Article
Tribological Performance of MoS2 Coatings
in Various Environments
Thomas Gradt 1, * and Thomas Schneider 2
1 Federal Institute for Materials Research and Testing (BAM), 12205 Berlin, Germany
2 AiF Projekt GmbH, 13156 Berlin, Germany; t.schneider@aif-projekt-gmbh.de
* Correspondence: thomas.gradt@bam.de; Tel.: +49-30-8104-3531

Academic Editor: Ga Zhang

Received: 29 February 2016; Accepted: 29 August 2016; Published: 7 September 2016

Abstract: Molybdenum disulfide (MoS2 ) is a well-known solid lubricant for tribosystems running
in vacuum or dry gases. Problems arise due to its sensitivity to humidity, which is a drawback for
its application under ambient conditions. However, by using a physical vapor deposition (PVD)
process, deposition parameters can be optimized not only to gain a coatings structure with favorable
frictional properties but also to minimize the sensitivity to attack by water molecules. Therefore,
an improved tribological behavior even under moist conditions can be achieved. MoS2 coatings
are also candidates for being applied at cryogenic temperatures. They already have proven their
suitability, e.g., for sliding support elements between superconducting magnets of the nuclear
fusion-experiment Wendelstein 7-X. However, these coatings were exclusively produced for this
particular application and the utilization for more common tribosystems may be precluded due to
cost considerations. In view of a wider range of applications, pure and Cr containing PVD-MoS2
coatings with an optimized structure were tested under varying environments including hydrogen
gas and cryogenic temperatures. Results of the most promising variant are presented in this paper.

Keywords: solid lubrication; MoS2 ; extreme environments; hydrogen; cryogenic environment

1. Introduction—Lubricating Properties of MoS2

For vacuum and inert gaseous environment, molybdenum disulfide (MoS2 ) is a well suited and
widely applied solid lubricant [1]. In vacuum, solid lubricants of this type show minimum friction
coefficients as low as 0.03, and, under certain conditions, even lower. However, a major drawback for
the application of MoS2 is its sensitivity to the presence of water vapor. In normal humid air, friction
coefficients between 0.15 and 0.30, accompanied by high wear, are observed.
For low temperature environment some authors report a minimum temperature of 88 K for
special liquid lubricants [2]. However, commercially available oils and greases are only applicable
at temperatures above 173 K. Furthermore, the cryogenic liquids themselves are not able to build
up hydrodynamic lubrication [3]. Therefore, for components such as bearings, liners, moving seals,
and valves, dry sliding, dry rolling or non-contacting systems must be employed.
There are some special applications that require smooth sliding surfaces in vacuum environment
at cryogenic temperatures. One example is the support structure of large superconducting magnets for
nuclear fusion devices [4]. These magnets are cooled by liquid helium, which has a boiling temperature
of 4.2 K. During cool down and ramping up of the magnetic field, the superconducting coils experience
large forces due to thermal shrinkage of the materials and an increasing electrical current in the
magnetic field. This results in a very slow tangential movement of several mm at the supports of the
individual coils. Because frictional heat and mechanical shocks are able to initiate a normal conducting
zone, a lubricant must be employed that guarantees low friction sliding without stick-slip at these

Lubricants 2016, 4, 32; doi:10.3390/lubricants4030032 www.mdpi.com/journal/lubricants

Lubricants 2016, 4, 32 2 of 13
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supports.atTests
stick-slip thesehave shown
supports. thathave
Tests onlyshown
MoS2 that coatings
only without any additions
MoS2 coatings without any are able to meet
additions are such
able
requirements [5].
to meet such requirements [5].
Similar to
Similar tographite,
graphite,MoS MoS 2 crystallizes in a lamellar structure. The Mo atoms form hexagonal planes
2 crystallizes in a lamellar structure. The Mo atoms form hexagonal
with covalently bonded S atoms
planes with covalently bonded S atoms at both at both sides. The spacing
sides. The between the Mo and
spacing between theSatoms
Mo andisSatoms0.154 nm, is
between the Satoms to the nearest
0.154 nm, between the Satoms to the nearest MoS 2 plane 0.308 nm. Between the planes only weak
MoS2plane 0.308 nm. Between the planes only weak Van- Van-der-Waals
forces are acting,
der-Waals forces resulting
are acting,inresulting
easy shearing
in easy tangential
shearingtotangential
the planes, towhich is responsible
the planes, which is for the good
responsible
lubricating properties. Molecular dynamic simulations show that
for the good lubricating properties. Molecular dynamic simulations show that during sliding during sliding a tribofilm is formed a
with basalisorientation
tribofilm formed with of basal
the lattice planes of
orientation [6].
theThese
latticemodel
planes calculations also show
[6]. These model that, withalso
calculations perfectly
show
aligned
that, withlayers, a minimum
perfectly alignedfriction
layers,coefficient
a minimum of 0.006 is possible,
friction dueof
coefficient to 0.006
the repulsive Coulomb
is possible, due to forces
the
between the sulfur atoms.
repulsive Coulomb forces between the sulfur atoms.
MoS22 is
MoS is applied
applied by by burnishing,
burnishing, physical
physical or or chemical
chemical vapor
vapor deposition
deposition (PVD,
(PVD, CVD),
CVD), or or with
with
binders as anti-friction (AF) coatings. It can also serve as friction reducing
binders as anti-friction (AF) coatings. It can also serve as friction reducing component in polymer component in polymer
composites [1].
composites [1].
Anti-friction (AF)
Anti-friction (AF) coatings
coatings consist
consist of of one
one oror more
more solid
solid lubricants
lubricants and,
and, inin most
most cases,
cases, anan organic
organic
binder. Some variants, in particular those containing MoS
binder. Some variants, in particular those containing MoS2 or2 polytetrafluoroethylene (PTFE), or polytetrafluoroethylene (PTFE),
are
are suitable
suitable for lowfor low temperature
temperature operation.
operation.
Many AF
Many AF coatings
coatings need need aa certain
certain running
running in in for
for achieving
achieving the the desired
desired properties.
properties. One One extreme
extreme
case is shown in Figure 1. It is a sprayed MoS coating with polycarbamide
case is shown in Figure 1. It is a sprayed 2MoS2 coating with polycarbamide binder, which was binder, which was specially
designeddesigned
specially for spacefor applications [7]. Figure
space applications [7].1a shows
Figure 1aashows
scanning electronelectron
a scanning microscopy (SEM) (SEM)
microscopy image
of the virgin coating, which consists of only loosely adhered particles.
image of the virgin coating, which consists of only loosely adhered particles. During loading and During loading and sliding
the particles
sliding are compacted
the particles are compactedand get and a preferred order,order,
get a preferred resulting in a very
resulting smooth
in a very filmfilm
smooth (Figure 1b).
(Figure
In Figure 2, the friction coefficients of this coating against 100Cr6 steel balls
1b). In Figure 2, the friction coefficients of this coating against 100Cr6 steel balls (AISI 52100) are (AISI 52100) are shown for
several cryogenic environments [8]. It can be seen that it provides effective
shown for several cryogenic environments [8]. It can be seen that it provides effective lubrication in lubrication in all of the
investigated
all media. In media.
of the investigated cryogenic environment,
In cryogenic friction is considerable
environment, lower than at
friction is considerable roomthan
lower temperature.
at room
temperature. The lowest friction coefficient is 0.02 at 77 K in vacuum. In most cases, higher loads give
The lowest friction coefficient is 0.02 at 77 K in vacuum. In most cases, higher loads and velocities and
lower friction,
velocities whichfriction,
give lower is a common whichfeature of MoS2feature
is a common coatings.
of MoS2 coatings.

(a) (b)
Figure
Figure 1.
1. AF
AF coating
coating with
with polycarbamide
polycarbamide binder
binder [7]:
[7]: (a)
(a) virgin
virgin coating;
coating; and
and (b)
(b) after
after sliding
sliding in
in liquid
liquid
helium (LHe).
helium (LHe).

By using a PVD process, deposition parameters can be optimized to gain coatings with a more
By using a PVD process, deposition parameters can be optimized to gain coatings with a more
textured structure orienting the (002) basal planes parallel to the substrate surface [9]. A similar
textured structure orienting the (002) basal planes parallel to the substrate surface [9]. A similar concept
concept has been used by Koch et al. [5] for coatings developed for support elements in the
has been used by Koch et al. [5] for coatings developed for support elements in the superconducting
superconducting magnet system of the WENDELSTEIN W7-X fusion experiment. They are able to
magnet system of the WENDELSTEIN W7-X fusion experiment. They are able to withstand extreme
withstand extreme operational conditions such as temperatures as low as 5 K in combination with
operational conditions such as temperatures as low as 5 K in combination with high vacuum. Other
high vacuum. Other authors report friction coefficients between 0.015 and 0.06 in liquid nitrogen
authors report friction coefficients between 0.015 and 0.06 in liquid nitrogen (LN ) and minimum wear
(LN2) and minimum wear on both sliding surfaces for Ti containing PVD-MoS22 coatings [10,11].
on both sliding surfaces for Ti containing PVD-MoS2 coatings [10,11].
Lubricants 2016, 4, 32 3 of 13

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Figure 2. Coefficient of friction of a MoS2-AF coating with polycarbamide binder in air and cryogenic
Figure 2. 2.
Figure Coefficient
Coefficient of friction
of friction of of a MoS
a MoS 2-AF 2
-AF coating
coating with polycarbamide
with polycarbamide binder in airbinder in air and
and cryogenic
media [8].
cryogenic
mediamedia
[8]. [8].

A general
A generalfeature of MoS
feature 2 coatings is that the friction coefficient decreases with increasing load,
of MoS 2 coatings is that the friction coefficient decreases with increasing load,
whichA general
makes themfeature of MoS
suitable
which makes them suitable for for coatings
2 high-loaded is that the friction
high-loadedfrictionfriction contacts.
coefficient
Thefriction
contacts. The
decreases
friction curve
curve
with
of aofPVD
increasing
a PVD coating
coating
load,
for for
which
such an makes them
application suitable for
in cryogenics high-loaded
is isshown friction contacts. The friction curve of a PVD coating for
such an application in cryogenics shownininFigure
Figure 3. Thisisisthe
3. This thetype
typeofof coating
coating whichwhich is used
is used for for
such
the an application
narrow
the narrowsupportsupport
in cryogenics
elements
elements in in isthe
the shown
WENDELSTEIN in Figure 3.
WENDELSTEIN 7-X
This is the
magnet
7-X magnet
type of
system.
system.
coating
It was
It was
which
chosen
chosen
is used
because
because it
for
it
the narrow
provides
provides support
low low elements
friction
friction without
without in the WENDELSTEIN
stick-slipeffects
stick-slip effectsand 7-X
and needs magnet
needs nearly system.
nearlynonorunning-in
running-inIt was
[12]. chosen
Only
[12]. because
the firstit
the first
Only
provides
cycle cycle low
deviates friction
deviates
noticeably without
noticeablyfromfrom stick-slip
the the
following. effects
following. and needs
During
During nearly
the next
the next few no
fewcycles running-in
cyclesa stable
a stable [12]. Only
frictional behavior
frictional the first
behavior
cycle deviates
is noticeably
established with from
friction the following.
coefficients in During
the range the next
between few
0.03 cycles
and
is established with friction coefficients in the range between 0.03 and 0.06. Only very small static a
0.06.stable
Only frictional
very small behavior
static is
frictionwith
established peaksfriction
occur and no stick-slip
coefficients in effects
the rangearebetween
visible. Static
0.03 and
and dynamic
0.06. Onlyfriction
very have
small almost
static the
friction
friction peaks occur and no stick-slip effects are visible. Static and dynamic friction have almost the
peakssame
same occur
values.
values.
and No
no coating
No coating
failure occurred
stick-slip
failureeffects
occurred
within the
are within
visible. the
test duration,
Static and dynamic
test duration,
whichfriction
was several
which was several have hundred
almost
hundred
cycles
thecycles
same
for
values. this
No particular
coating application.
failure occurred A further
within result
the of
test this test
duration,was that
which the
wasroughness
several of the
hundred substrate
cycles has
for this
for this
onlyparticular
negligible application.
influence onAthe further
steadyresultstate of this test
friction was that
coefficient. the roughness
Other authors report of the
an substrate
optimum has
particular
only negligibleapplication. A further
influenceofonRathe result
steady of
statethis test was that the roughness of the substrate has only
substrate roughness = 0.1 to 0.15 µmfriction
[10]. The coefficient.
sample with Other authors report
a roughness of Rz = an 2 µmoptimum
is
negligibleroughness
substrate influence on ofthe steady
Rthat
a = range.
0.1 to state0.15friction
µm [10].coefficient. Other authors
The sample report an optimum
with a roughness of Rz = substrate
2 µm is
approximately within
roughness of Rwithin
approximately a = 0.1 that
to 0.15 µm [10]. The sample with a roughness of Rz = 2 µm is approximately
range.
within that range.
0,25
Rz = 2 mic
0,25 0,2 Rz = 6-8 mic
Rz = 2 mic
0,20,15
friction coefficient ?

0,1 Rz = 6-8 mic

0,15
friction coefficient ?

0,05
0,1
0
0,05
-0,05
0-0,1
-0,05
-0,15
-0,1-0,2
-0,15
-0,25
-0,2
Figure 3. First friction
-0,25 cycles of a sputtered MoS2 coating against Al-bronze in LHe environment; two
samples with different substrate roughness; load: 250 N; average sliding velocity: 0.2 mm·s−1 (negative
values
Figure indicate
3. First the reciprocating
friction cycles of a motion) [12].MoS2 coating against Al-bronze in LHe environment;
sputtered
Figure 3. First friction cycles of a sputtered MoS2 coating against Al-bronze in LHe environment; two
two samples with different substrate roughness; load: 250 N; average sliding velocity: 0.2 mm·s−1
samples with different
Because substrate
the application of roughness; load:
MoS2 coatings in250 N; average
normal humidsliding velocity:
air is still 0.2 mm·s
a problem −1 (negative
a test program
(negative values indicate the reciprocating motion) [12].
for further
values optimization
indicate by a variation
the reciprocating motion)of deposition parameters for pure MoS2 and doping by Cr
[12].
atoms was conducted. The results of the best variants are shown in the following.
Because the
Because the application
application of
of MoS
MoS22 coatings
coatingsin
innormal
normalhumid
humidair airisisstill a problem
still a test
a problem program
a test for
program
further optimization by a variation of deposition parameters for pure MoS and doping
for further optimization by a variation of deposition parameters for pure2 MoS2 and doping by Cr by Cr atoms
was conducted.
atoms The results
was conducted. of the best
The results variants
of the are shown
best variants in the following.
are shown in the following.
Lubricants 2016, 4, 32 4 of 13
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2. Materials
2. Materialsand
andMethods
Methods

2.1. Test Rig for Tribological

TribologicalMeasurements
Measurementsat
atTemperatures
Temperaturesbelow
below120
120KK
Tribological investigations at cryogenic temperatures require special devices (cryotribometers)
in respect of of cooling
cooling system,
system,thermal
thermalinsulation,
insulation,and andinstrumentation.
instrumentation.Figure Figure 4 shows
4 shows anan example
example of
an an
of apparatus
apparatus forfor
pin-on-disc
pin-on-disc tests in liquid
tests helium
in liquid helium(LHe)(LHe)[13].[13].
The The
liquid coolant
liquid is filled
coolant directly
is filled into
directly
the sample
into chamber
the sample chamber and theandfriction couple
the friction is immersed
couple is immersed completely into the
completely intoliquid cryogen
the liquid (bath
cryogen
cryostat
(bath operation).
cryostat Therefore,
operation). the environmental
Therefore, the environmental temperature
temperature is equal to the
is equal boiling
to the boilingtemperature
temperature Tb
of the coolant (LN
Tb of the coolant (LN2 : Tb = 77.3 K; LH2 : Tb = 20.4 K; LHe: Tb = 4.2 K). The advantage of this methoda
2: T b = 77.3 K; LH 2 : T b = 20.4 K; LHe: T b = 4.2 K). The advantage of this method is
very
is effective
a very cooling
effective coolingof the
of sample.
the sample. The Thefrictional heatheat
frictional is not is only removed
not only removedby heat conduction
by heat conductionand
convection,
and but also
convection, but by alsoevaporation
by evaporationof theof liquid. The cryostat
the liquid. shown shown
The cryostat in Figurein 4Figure
also allows
4 alsocooling
allows
independently
cooling of the boiling
independently temperature
of the boiling of the coolant.
temperature In this case,
of the coolant. the
In this coolant
case, flows through
the coolant a heat
flows through
exchanger
a and the
heat exchanger and sample is surrounded
the sample is surrounded by vacuum
by vacuumor contact gas. With
or contact additional
gas. With additionalheating, it is
heating,
possible
it to adjust
is possible to adjustthe thetemperature
temperature between
between 4.24.2K K(with
(withLHe-cooling)
LHe-cooling) and and room
room temperature
independently from from the the pressure
pressure in in the
thesample
samplechamber.
chamber.The Thesample
samplechamber
chambercan canbebeevacuated
evacuatedtotoa
residual
a residualpressure
pressureininthe theorder
orderof 10−5−5mbar
of 10 mbarand andtherefore,
therefore,the the cryotribometer
cryotribometer isis alsoalso suitable for
friction tests in high vacuum.

Figure 4.
Figure 4. Cryotribometer CT3, suitable
Cryotribometer CT3, suitable for
for cryogenic,
cryogenic, vacuum
vacuum and
and H
H22 environment.
environment.

2.2. Materials
2.2. Materials and
and Sample
Sample Preparation
Preparation
The disc-shaped
The disc-shaped specimens
specimens were coated by
were coated by an
an unbalanced
unbalanced magnetron sputter process
magnetron sputter process on
on aa PVD
PVD
coating plant H-O-T TT 300 at the Chair of Engineering Design, Friedrich-Alexander-Universität
coating plant H-O-T TT 300 at the Chair of Engineering Design, Friedrich-Alexander-Universität
Erlangen-Nürnberg [14].
Erlangen-Nürnberg [14]. Samples
Samples were held
were in front
held in front of the target
of the without
target additional
without rotation,
additional thus
rotation,
enabling
thus enablingan adjustment
an adjustmentof aofwell defined
a well definedtarget/substrate
target/substrate distance.
distance.Coating
Coatingthickness
thickness was kept
was kept
constant at 1.8 µm ± 0.3 µm, adapting deposition time accordingly. To avoid unintended
constant at 1.8 µm ± 0.3 µm, adapting deposition time accordingly. To avoid unintended annealing annealing
effects during
effects during deposition,
deposition, the substrate material
the substrate material consisted
consisted of secondary hardened
of secondary hardened high
high speed
speed steel
steel
1.3343 (S 6-5-2), which is tempering-resistant up to 450
◦ °C; hardness remained at approximately
1.3343 (S 6-5-2), which is tempering-resistant up to 450 C; hardness remained at approximately 62 HRC. 62
HRC.Five different coatings were tested, three variants of pure MoS and two Cr containing types
2
(MoSFive different coatings were tested, three variants of pure MoS2 and two Cr containing types
2 :Cr). One coating denoted as “standard” (STD) was identified by a preceding extensive variation
(MoS2:Cr). One coating denoted as “standard” (STD) was identified by a preceding extensive
Lubricants 2016, 4, 32 5 of 13

of deposition parameters, resulting in different mechanical and tribological properties. The methods
and Lubricants
results of2016, 4, 32 tests are reported in detail in Reference [14].
these 5 of 13

Before the deposition, the substrates were polished and ultrasonically cleaned in acetone and
variation of deposition parameters, resulting in different mechanical and tribological properties. The
isopropyl alcohol. Additionally, they were prepared by an argon-ion etching process at 2.3 Pa,
methods and results of these tests are reported in detail in Reference [14].
applyingBefore
a 600 V thepulsed DC bias
deposition, the to the substrates
substrates for half and
were polished an hour. Argon also
ultrasonically served
cleaned as working
in acetone and gas
for sputtering.
isopropyl alcohol. Additionally, they were prepared by an argon-ion etching process at 2.3 Pa,
The deposition
applying parameters
a 600 V pulsed forto
DC bias the
thestandard
substratescoating
for halfwere a cathode
an hour. Argonvoltage of 800
also served V, a deposition
as working gas
temperature ◦
of 150 C, an argon pressure of 0.51 Pa and flow rate of 80 sccm, a distance of 90 mm
for sputtering.
between Thethe deposition
sputter cathode and the
parameters sample
for the andcoating
standard a resulting
werecathode
a cathodecurrent
voltageofof 2.09 A.a This
800 V, type was
deposition
temperature
further developed of in
150 °C, an
order to argon
produce pressure of 0.51
coatings withPa and flow
higher rate of
intrinsic 80 sccm,
stress. The aresults
distance of 90two
of the mmmost
between the sputter cathode and the sample and a resulting cathode current
promising variants are shown in the following. Both types, denoted as HS and LS, had higher intrinsic of 2.09 A. This type was
stresses than the standard coating (200 MPa), but to a different degree (HS: 370 MPa, LS: 300two
further developed in order to produce coatings with higher intrinsic stress. The results of the MPa).
mostvariants
For both promising thevariants
cathodeare shownwas
voltage in the
700following.
V and theBoth types, denoted
temperature 50 ◦ C.as
ForHS and
the LSLS, hadthe
type, higher
cathode
intrinsic stresses than the standard coating (200 MPa), but to a different degree (HS: 370 MPa, LS: 300
distance was reduced to 65 mm and the Ar flow rate increased to 115 sccm.
MPa). For both variants the cathode voltage was 700 V and the temperature 50 °C. For the LS type,
Additionally two coatings were doped with chromium at a high (120 A) and low (70 A) Cr cathode
the cathode distance was reduced to 65 mm and the Ar flow rate increased to 115 sccm.
current, respectively, resulting in chromium contents of 10 and 5 at%. In the figures, these variants are
Additionally two coatings were doped with chromium at a high (120 A) and low (70 A) Cr
referred to as CH and CL.
cathode current, respectively, resulting in chromium contents of 10 and 5 at%. In the figures, these
The tribological tests
variants are referred to as were
CHcarried
and CL.out in ball-on-disc configuration. Hardened 100Cr6 steel balls
(AISI 52100)
The with a diameter
tribological of 4 mm
tests were served
carried asball-on-disc
out in counter bodies. If not otherwise
configuration. Hardened indicated in the
100Cr6 steel figure
balls
captions,
(AISI the applied
52100) with aload was 10
diameter of 4Nmm(maximum
served asHertzian contact
counter bodies. pressure:
If not 1860.6
otherwise MPa) in
indicated andthethe sliding
figure
captions,
velocity was 0.1the ms −1 .
applied load was 10 N (maximum Hertzian contact pressure: 1860.6 MPa) and the
sliding
The tests were carried ms
velocity was 0.1 . high vacuum, in vacuum with H2 O vapor at a pressure of 1.4 × 103 Pa,
out−1in
in gaseousThe tests wereatcarried
hydrogen normal outandin high
low vacuum,
pressurein (1vacuum
× 104 Pa) withasH 2O vapor at a pressure of 1.4 × 103
well as in liquid hydrogen.
Pa, in gaseous hydrogen at normal and low pressure (1 ×
The wear coefficients were determined by stylus profilometry, measuring 10 4 Pa) as well as in liquid
thehydrogen.
wear track at four
The wear coefficients were ◦ determined by stylus profilometry, measuring the wear track at four
different positions (shifted by 90 ). The coefficient of friction (COF) was averaged for a sliding distance
different positions (shifted by 90°). The coefficient of friction (COF) was averaged for a sliding
of approximately 1000 m, excluding the running-in phase. In order to test the wear life, the tests were
distance of approximately 1000 m, excluding the running-in phase. In order to test the wear life, the
run until coating failure was detected (failure criterion: COF > 0.25).
tests were run until coating failure was detected (failure criterion: COF > 0.25).
3. Results
3. Results
3.1. Vacuum Environment
3.1. Vacuum Environment
Under vacuum
Under vacuum conditions all variants
conditions showed
all variants friction
showed coefficients
friction below below
coefficients 0.1 and0.1wearandcoefficients
wear
in the range ofin1the 3 × 10
to range − 7 3 ·N − 1 − 1
·m3·N−1. ·mAs
coefficients of 1 tomm
3 × 10 −7 mm an an
−1. As example,
example,Figure
Figure 55 shows
showsa afriction
friction
plotplot
for for
a PVD-MoS
a PVD-MoS2 coating
2 coating in in
high
highvacuum.
vacuum.The The coating
coating is is similar
similartotothe
theone
one used
used in in
thethe Wendelstein
Wendelstein 7-X 7-X
fusion experiment
fusion experiment [5].[5].
The Thepeaks
peakstotonegative
negativedirection
direction are are caused
causedby bytest
teststops
stopsandand restarts.
restarts. It can
It can be be
seenseen
thatthat
the the
friction coefficient
friction coefficient is is
around
around0.06 0.06and
andthe the wear life
lifemore
morethanthan350,000
350,000 cycles.
cycles.

Figure
Figure 5. Coefficient
5. Coefficient of friction
of friction ofofa aPVD-MoS
PVD-MoS2 coating
coating [5]
[5] under
underhigh
highvacuum
vacuum conditions
conditions(residual
(residual
2
105−5 mbar); counterbody: 10-mm 100Cr6 ball, load: 40 N; sliding velocity: 0.5 ms−1.
pressure: 2 × −
pressure: 2 × 10 mbar); counterbody: 10-mm 100Cr6 ball, load: 40 N; sliding velocity: 0.5 ms−1 .
Lubricants 2016, 4, 32 6 of 13
Lubricants 2016, 4, 32 6 of 13

3.2. Air
3.2. Air Environment
Environmentwith
with50%
50%Humidity
Humidity
As expected,
As expected, in in normal
normal air with a water vapor vapor partial
partial pressure
pressure of of1.4
1.4××1010 3 Pa,
3 Pa, corresponding
corresponding to
Lubricants 2016, 4, 32 6 of 13
50%
to 50%relative
relativehumidity,
humidity, thetheCOFCOF increased
increased to to
values
values between
between 0.10.1andand0.250.25and thethe
and wear
wearcoefficient
coefficientup
to to −5 −
103.2. 5 3·N3−1·N
mm ·m−−11,·m −1 , which
which is Humidity
more thanthan oneone order ofofmagnitude
up 10 AirmmEnvironment with 50% is more order magnitudehigher higher thanthan under vacuumvacuum
conditions.AAtypical
conditions. typical example
example of the
of the friction
friction development
development is shown is shown
in Figure in 6.Figure 6. However,
However, best variantsbest
As expected, in normal air with a3 water
−6 mm
vapor
−1 · m −1−1
partial pressure of 1.4 × 103 Pa, corresponding to
variants
showed showed
values in values
the orderin the
of order
10 of 10 · −6 mm
N 3·N
, ·m −1, which is comparable to the wear of diamond-
which is comparable
50% relative humidity, the COF increased to values between 0.1 and 0.25 and the wear coefficient up to the wear of diamond-like
like carbon
carbon 10−5 (DLC)
to (DLC) mm 3·Ncoatings,
coatings,
−1·m−1developed
, whichdeveloped
is for
more for
operation
than operation
oneunder
order under
high high
humidity
of magnitude humidity
[15].
higher [15].
As Asunder
expected,
expected,
than coatings
coatings
vacuum that
that were
were appropriate
appropriate
conditions. Afor forexample
ambient
typical ambient ofair
theconditions
air conditions haddegree
had a development
friction high a highof isdegree
(002)
shown ofin(002)
basal plane
Figurebasal plane orientation.
orientation.
6. However, This
best was
This variants
wasbydetected
detected X-ray
showed by X-ray
diffraction
values diffraction
(XRD),
in the orderwhich (XRD),
of 10 −6 was
mm3·N which
−1·m−1,was
carried out
which carried
for isthe out forwith
coating
comparable tothe coating
thethe
wearbest with the best
performance
of diamond-
performance
in like carbon in humid environment.
humid environment.(DLC) The result is The
coatings, developed for
shown resultin is
operationshown
Figure 7. in
under Figure 7. Therefore,
high humidity
Therefore, [15].
by means of As byameans
expected, of aadapted
suitable
coatings
suitable
that were
adapted
PVD-process appropriate
PVD-process
MoS MoS
coatings for2ambient
coatings
without air conditions
without
further had acan
further
dopants high bedegree
dopants of (002)
can
developed be basal
developed
that areplane
able orientation.
that
to are able to
sufficiently
2
This
sufficientlywas detected
withstand by X-ray
adverse diffraction
conditions (XRD),
such which
as highwas carried
humidity.
withstand adverse conditions such as high humidity. The results of the corresponding test program out for
The the
resultscoating
of with
the the best
corresponding
performance in humid environment. The result is shown in Figure 7. Therefore, by means of a suitable
test the
and program
effect and
of the the effect of the
deposition deposition
parameters areparameters
reported inare reported
detail in detail[14].
in Reference in Reference [14].
adapted PVD-process MoS2 coatings without further dopants can be developed that are able to
sufficiently withstand adverse conditions such as high humidity. The results of the corresponding
test program and the effect of the deposition parameters are reported in detail in Reference [14].

Figure 6. Example of the friction increase of a MoS2 coating in air with 50% relative humidity.
Figure 6. Example of the friction increase of a MoS coating in air with 50% relative humidity.
Figure 6. Example of the friction increase of a MoS22 coating in air with 50% relative humidity.

FigureFigure 7. X-ray
7. X-ray diffraction
diffraction (XRD)
(XRD) patterns:Dominating
patterns: Dominating (002)
(002)orientation
orientationof of
thethe
coating
coatingwithwith
highest
highest
Figuredurability
7. X-ray under moist
diffraction conditions.
(XRD) Pattern
patterns: of the uncoated
Dominating sample
(002) for comparison
orientation of the
durability under moist conditions. Pattern of the uncoated sample for comparison [14]. Reproduced[14]. Reproduced
coating with highest
with
durability permission
underfrom from
moist “Surface
conditions. and Coatings Technology”;
Pattern ofTechnology”; published
the uncoatedpublished
sample for by Elsevier, 2013.
with permission “Surface and Coatings bycomparison [14]. Reproduced
Elsevier, 2013.
with permission from “Surface and Coatings Technology”; published by Elsevier, 2013.
Figure 8a shows a high resolution transmission electron microscopy (HR-TEM) image of a
Figure
coating8a shows
with a high
higher resolution
internal stress. Ittransmission electron
still has a highly microscopy
ordered (HR-TEM)
layered structure image
which of a coating
is visible in
Figure 8a shows a high resolution transmission electron microscopy (HR-TEM) image of a
with higher internal stress. It still has a highly ordered layered structure which is visible in the
coating with higher internal stress. It still has a highly ordered layered structure which is visible in
Lubricants 2016, 4, 32 7 of 13
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Lubricants 2016, 4, 32 7 of 13
upper region.
the upper The selected
region. areaarea
The selected diffraction (SAED)
diffraction image
(SAED) of Figure
image 8b8b
of Figure clearly shows
clearly showsreflexes
reflexesofofthe
the
(002) upper
planes. region.
the (002) planes. The selected area diffraction (SAED) image of Figure 8b clearly shows reflexes of
the (002) planes.

(a) (b)
(a) (b)
Figure 8. (a) High resolution transmission electron microscopy (HR-TEM) and (b) selected area
Figure
Figure8. 8.(a)(a)High resolution
Highimages
resolution transmission
transmission electron microscopy(HR-TEM)
electron microscopy (HR-TEM)and
and(b)
(b)selected
selected area
area
diffraction (SAED) of a MoS 2 coating with higher internal stress.
diffraction (SAED) images of a MoS 2 coating with higher internal
diffraction (SAED) images of a MoS2 coating with higher internal stress.stress.

3.3. Low Pressure Water Vapor Environment

3.3.3.3.
LowLow Pressure
Pressure Water
WaterVapor
VaporEnvironment
Environment
In order to test the influence of water vapor without the presence of oxygen, only H2O gas was
In In
filled intoorder
order the to test
tovacuum
test the
the influence
influence
chamber ofofwater
until water vapor
vapor
a pressure without the
without the presence
corresponding to 100% of
presence ofoxygen,
rH oxygen, only
onlyHIn
was reached. H2O Ogas was
gas
2Figure was
9,
filled
filled into
it can into
be the the vacuum
seenvacuum chamber
that, for chamber
a MoS2:Cruntiluntil
variant a pressure
a pressure
with 5 at% corresponding
corresponding to 100% rH
Cr, the frictiontocoefficient was reached.
100% rH stabilized
was reached. In Figure
0.17,9, 9,
In Figure
at about
it can
it can
which bebeseen
is seen that,
that, fora aMoS
for
considerably MoS2 :Cr
higher 2:Crvariant
variant
than with
in inert 5 at%
at% Cr,
Cr,the
environment the friction
butfriction coefficient
still lowcoefficient
for solidstabilized at at
stabilized
lubricants.about
about
This 0.17,
0.17,
test
which
which is is considerably
considerably higher
higher than
than inin inert
inert environment
environment
clearly shows that oxidation to MoO3 is not the only acting wear mechanism. but
but still
still low
low for
for solid
solid lubricants.
lubricants. This
Thistest
test
clearly shows that oxidation to MoO 3 is not the only acting wear mechanism.
clearly shows that oxidation to MoO3 is not the only acting wear mechanism.

Figure 9. Friction of a MoS2:Cr coating (5 at% Cr) in low pressure water vapor at room temperature.
Figure Friction
9. 9.
Figure ofofa aMoS
Friction 2 :Cr
MoS 2:Crcoating
coating (5
(5 at%
at% Cr) in low
Cr) in low pressure
pressurewater
watervapor
vaporatatroom
room temperature.
temperature.
Figure 10 shows the friction and wear data for all five variants in water vapor. The friction
Figure
Figure
coefficients10of10 shows
shows
the pure thefriction
the
LS friction
and andwear
and
HS coatings wear data
aredata
about for
for alland
all
0.13 five0.17,
five variants
variants in
in water
water
respectively, forvapor.
the CrThe
vapor. Thefriction
friction
containing
coefficients
coefficients
variants. For of
of the the pure LS
pure LS and
all optimized and HS coatings
HS coatings
coatings, the wearare about 0.13
arecoefficients
about 0.13areand
and 0.17,
in0.17, respectively,
respectively,
the order of 10 mm
−6 for the
for·N
3 Cr
the·m
−1 containing
Cr .containing
−1 For the
variants.For
variants.
standard Forallalloptimized
coating optimized coatings,
coatings,
both, friction the
and wearthewear
wear
are coefficients
coefficients
cosiderably areare
in the
higher. in order
Thisthe of 10
order
proves
−6 mm3·N−1·m−1. For the
10−6 mm
of lower
the 3 ·N−1 ·to
sensitivity m−1 .
standard
humidity coating both,
of thesecoating friction and wear are cosiderably higher. This proves the lower
variants.both, friction and wear are cosiderably higher. This proves the lower sensitivity to
For the standard
humidity of these variants.
sensitivity to humidity of these variants.
 Lubricants 2016, 4, 32 8 of 13
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Lubricants 2016, 4, 32 8 of 13

Figure 10. Friction and wear coefficients of optimized MoS coatings vs. 100Cr6 in low pressure H2 O
Figure 10. Friction and wear coefficients of optimized MoS22coatings vs. 100Cr6 in low pressure H2O
vapor;Figure
load:10.
10Friction
N, sliding
andvelocity: 0.1 ms−1 .
wear coefficients
vapor; load: 10 N, sliding velocity: 0.1 ms−1.of optimized MoS2 coatings vs. 100Cr6 in low pressure H2O
vapor; load: 10 N, sliding velocity: 0.1 ms−1.
3.4.Hydrogen
3.4. HydrogenEnvironment
Environment
3.4. Hydrogen Environment
Testsiningaseous
Tests gaseoushydrogen
hydrogen were
were performed
performed at 100 mbar and bar1environmental
bar environmental pressure.
Tests in gaseous hydrogen were performedatat100 100mbar
mbar and
and 11 bar environmental pressure.
pressure. All All
All variants
variants showed showed
a low a low
COF, COF, comparable
comparable to or to
even or even
lower lower
than thethan the
vacuum vacuum
values. values.
Figure 11Figure
showes 11
variants showed a low COF, comparable to or even lower than the vacuum values. Figure 11 showes
ashowes
friction aplot
friction
a friction for plot
plotthe forreference
the reference
forreference
the coationg coationg
coationgin in
H2Hgas inatH
2 gas
gas
at121bar. at 1 bar. was
bar.Friction
Friction Friction
was was
verystable
very very
stable stable
with
with with
a COF
a COF ofa 0.03
of 0.03 COF
of 0.03
and the and
andwear the wear
life with
the wear life with
340,000
life with 340,000
cycles
340,000 cycles
was
cycles was was satisfactory.
satisfactory.
satisfactory.
Results
Results werewere
Results
were similar
similar forfor
similar
for thethe
the CrCr
Cr alloyed types
alloyedtypes
alloyed (Figure
types(Figure 12),again
(Figure 12),
12), againshowing
again showing
showing friction
friction and
andand
friction wear wear
wear
comparable
comparable totovacuum
comparable vacuum
to vacuum conditions.
conditions.
conditions. The
TheThe wear
wear
wear life
life
life was
was
was longest
longest
longest in H
in in22 gas
H H gas
2 at
gas atbar.
1After
at1 1bar. bar. After
about
After about
100
about h, or100
100 h, orh,
or 430,000
430,000 cycles,
cycles, the
the test
test was
was stopped
stopped without
without showing
showing
430,000 cycles, the test was stopped without showing coating failure. coating failure.
coating failure.

Figure 11. Friction

Figure of aofMoS
11. Friction 2 coating
a MoS2 coating(STD)
(STD) vs. 100Cr6
100Cr6ininHH 2 gas
2 gas at room
at room temperature.
temperature.

Figure 11. Friction of a MoS2 coating (STD) vs. 100Cr6 in H2 gas at room temperature.
Lubricants 2016, 4,
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32 99 of
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Lubricants 2016, 4, 32 9 of 13

Figure 12. Friction of MoS2 :Cr (type CL) vs. 100Cr6 in H2 gas at room temperature.
Figure 12. Friction of MoS2:Cr (type CL) vs. 100Cr6 in H2 gas at room temperature.
Figure 12. Friction of MoS2:Cr (type CL) vs. 100Cr6 in H2 gas at room temperature.
Figure 13 shows a comparison of the friction and wear behavior between high and low pressure
hydrogenFigure 13 shows aenvironment
comparison for of the friction and wear behavior between high
lowand low pressure
hydrogenand andvacuum
vacuum environment the
for four
the variants. Between
four variants. vacuum
Between and
vacuum pressure
and lowhydrogen,
pressure
hydrogen and vacuum environment for the four variants. Between vacuum and low pressure
the differences are small. Only the pure coatings with optimized structure
hydrogen, the differences are small. Only the pure coatings with optimized structure showed higher showed higher wear.
hydrogen, the differences are small. Only the pure coatings with optimized structure showed higher
In hydrogen
wear. gas at normal
In hydrogen pressurepressure
gas at normal all variants showed showed
all variants higher wear with
higher the with
wear exception of the standard
the exception of the
wear. In hydrogen gas at normal pressure all variants showed higher wear with the exception of the
coating,
standardwhich showed
coating, which a similar
showedwear rate and
a similar wear distinctively lower friction
rate and distinctively thanfriction
lower in vacuum. In vacuum.
than in addition,
standard coating, which showed a similar wear rate and distinctively lower friction than in vacuum.
the friction of
InInaddition, thethe pure of
friction variant
the purewith lowerwith
variant intrinsic
lowerstress wasstress
intrinsic as lowwasasas forlowtheasstandard variant.
for the standard
addition, the friction of the pure variant with lower intrinsic stress was as low as for the standard
However,
variant. these results are based on only two tests for each condition. Therefore,
variant. However, these results are based on only two tests for each condition. Therefore, only the the
However, these results are based on only two tests for each condition. only
Therefore,the general
only
tendency
general to low friction
generaltendency
tendency to
to low
lowand wear in
friction
friction and
andhydrogen
wear in
wear inenvironment is verified. The
hydrogenenvironment
hydrogen environment pressure
is isverified.
verified. dependence
TheThe pressure
pressure is
less clear andisis
dependence
dependence needs
less to beand
lessclear
clear proved
and needs
needsbyto
tofurther tests.
be proved
be proved bybyfurther
furthertests.
tests.

Figure13.
Figure 13.Friction
Frictionand
andwear
wear coefficients
coefficients of
of optimized
optimizedMoS MoS2 2coatings
coatingsvs.vs.100Cr6
100Cr6 in in
vacuum
vacuumandand
H2 H2
Figure 13. Friction
environment; load:and
10 wear
N, coefficients
sliding velocity: of
0.1 optimized
ms −1; STD:
− 1 MoS 2 coatings
reference coating; vs.
MoS 100Cr6 in
2:Cr: CL:
environment; load: 10 N, sliding velocity: 0.1 ms ; STD: reference coating; MoS2 :Cr: CL: 5 at% Cr; vacuum
5 at% Cr; and
CH: H2
environment;
10 at% Cr; load:
pure 10 N,
coatings sliding
with velocity:
higher 0.1
internal ms −1; STD:
stress: LS: reference
300 MPa; coating;
HS: 370
CH: 10 at% Cr; pure coatings with higher internal stress: LS: 300 MPa; HS: 370 MPa. MPa.MoS 2:Cr: CL: 5 at% Cr; CH:

10 at% Cr; pure coatings with higher internal stress: LS: 300 MPa; HS: 370 MPa.
Lubricants 2016, 4, 32 10 of 13
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32 10
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13
3.5. Cryogenic Environment
3.5. Cryogenic Environment
A relatively
3.5. Cryogenic long endurance was measured for MoS2:Cr (5 at% Cr) at 77 K in liquid nitrogen
Environment
A relatively
(Figure long endurance
14). In contrast, was measured
in liquid helium, which isforalsoMoSan2:Cr (5environment,
inert at% Cr) at 77the K in liquid
COF nitrogen
increased to
A relatively long endurance was measured for MoS2 :Cr (5 at% Cr) at 77 K in liquid nitrogen
(Figure
0.2 after14).
onlyIn3000
contrast,
cyclesin liquid15).
(Figure helium, which isthe
In addition, also an fluctuation
large inert environment,
indicatedthe COF increased
coating failure. to
(Figure 14). In contrast, in liquid helium, which is also an inert environment, the COF increased to 0.2
0.2 after only 3000
Additional cycles (Figure
experiments were15). In addition,
conducted the large
in liquid fluctuation
hydrogen (LH2)indicated
at 20 K. In coating failure.
this environment,
after only 3000 cycles (Figure 15). In addition, the large fluctuation indicated coating failure.
Additional
for most samples, experiments
the COF was were conducted
initially as lowinasliquid hydrogen 0.05,
approximately (LH2)while
at 20 the
K. In this environment,
Cr-containing types
Additional experiments were conducted in liquid hydrogen (LH2 ) at 20 K. In this environment,
yielded 0.06. However, as can be seen in the friction curve of Figure 16, wear life was short. Thetypes
for most samples, the COF was initially as low as approximately 0.05, while the Cr-containing COF
for most samples, the COF was initially as low as approximately 0.05, while the Cr-containing types
yieldedto0.06.
began riseHowever, as can be
steeply beyond 0.1seen
afterinonly
the friction
1000 and curve of Figure
3000 16, wear
cycles for life wasAshort.
all variants. The COF
maximum in
yielded 0.06. However, as can be seen in the friction curve of Figure 16, wear life was short. The COF
began to rise
durability wassteeply
achieved beyond
at 40000.1 afterbefore
cycles only 1000 andwas
the test 3000 cyclesatfor
aborted COFall >variants. A maximum
0.25. Again, in
the variants
began to rise steeply beyond 0.1 after only 1000 and 3000 cycles for all variants. A maximum in
durability
with was achieved
optimized structureatshowed
4000 cycles before the test
no improvement in was aborted to
comparison at the
COFstandard
> 0.25. Again, the variants
coating.
durability was achieved at 4000 cycles before the test was aborted at COF > 0.25. Again, the variants
with optimized structure showed no improvement in comparison to the standard coating.
with optimized structure showed no improvement in comparison to the standard coating.

Figure 14. Friction of MoS2:Cr (5 at% Cr) vs. 100Cr6 in LN2, load: 10 N, sliding velocity: 0.1 ms−11.
Figure 14. Friction of MoS2 :Cr (5 at% Cr) vs. 100Cr6 in LN2 , load: 10 N, sliding velocity: 0.1 ms− .
Figure 14. Friction of MoS2:Cr (5 at% Cr) vs. 100Cr6 in LN2, load: 10 N, sliding velocity: 0.1 ms−1.

Figure 15. Friction of MoS2 :Cr (5 at% Cr) vs. 100Cr6 in LHe, load: 10 N, sliding velocity: 0.1 ms−−11 .
Figure 15. Friction of MoS2:Cr (5 at% Cr) vs. 100Cr6 in LHe, load: 10 N, sliding velocity: 0.1 ms .
Figure 15. Friction of MoS2:Cr (5 at% Cr) vs. 100Cr6 in LHe, load: 10 N, sliding velocity: 0.1 ms−1.
Lubricants 2016, 4, 32 11 of 13
Lubricants 2016, 4, 32 11 of 13

Figure 16.
Figure 16. Friction
FrictionofofMoS 2:Cr
MoS (5 at% Cr) vs. 100Cr6 in liquid hydrogen (LH2), load: 10 N, sliding
2 :Cr (5 at% Cr) vs. 100Cr6 in liquid hydrogen (LH2 ), load: 10 N,
velocity:
sliding 0.1 ms 0.1
velocity:−1 . ms .− 1

4. Discussion
4. Discussion
The results
The results forfor the
the optimized
optimized variants
variants show show thatthat already
already pure pure MoS coatings with
MoS2 coatings with increased
increased
2
internal stress have a higher durability in humid environment. Doping with Cr does not result result
internal stress have a higher durability in humid environment. Doping with Cr does not in lower in
lower friction
friction and theand wear theis wear is not influenced
not influenced significantly.
significantly. The reason Theforreason
the lower for the lower sensitivity
sensitivity to humidity to
humidity of the coatings with optimized structure may be the lower
of the coatings with optimized structure may be the lower number of MoS2 crystallite edges at the number of MoS 2 crystallite edges

at the surface,
surface, whichwhich are postulated
are postulated to be favorite
to be favorite areas areas for water
for water adsorption
adsorption [1]. Water
[1]. Water molecules
molecules at theat
the crystallite
crystallite edges edges
may may be responsible
be responsible for blocking
for blocking crystallite
crystallite alignmentalignment and shearing
and shearing of the MoSof the-planes.
MoS2-
2
planes. This mechanism is active only at the surface and crystallite
This mechanism is active only at the surface and crystallite edges and may be an explanation for edges and may be an explanation
for the
the factfact
thatthat Cr-atoms
Cr-atoms in the
in the bulkbulk materials
materials dodo notnot have
have a positiveinfluence.
a positive influence.Because,
Because,even evenfor for the
the
best variants,
best variants, numerous
numerous active active sites
sites are
are present
present at at the
the surface,
surface, aa lowlow friction
friction coefficient
coefficient similar
similar to to the
the
vacuum value cannot
vacuum value cannot be achieved. be achieved.
In contrast
In contrast to to HH2O,O, low
low pressure
pressure H H2 environment
environment at at room
room temperature
temperature enhances enhances the the friction
friction
2 2
properties of MoS 2. For all variants, friction is considerably lower than in humid environment.
properties of MoS2 . For all variants, friction is considerably lower than in humid environment.
Dependingon
Depending on the
the coating
coating type,
type, wear
wear is is unchanged
unchanged or or up
up to
to one
one order
order of of magnitude
magnitude lower. lower. In In normal
normal
pressure hydrogen,
pressure hydrogen,all all new
new variants
variants showshow aa slightly
slightly higher
higher friction
friction andand aa wear
wear rate
rate similar
similar to to humid
humid
environment. However, the wear life is also long in hydrogen gas at
environment. However, the wear life is also long in hydrogen gas at 1 bar. Because, for such coatings,1 bar. Because, for such coatings,
most of
most of the
the film
film thickness
thickness is is removed
removed duringduring running
running in, in, wear
wear rate
rate isis not
not directly
directly related
related to to the
the wear
wear
life. Contrary
life. Contrary to to humid
humid environment,
environment, in inhydrogen,
hydrogen,aaremaining
remainingthin thinlayer
layerseems
seemstotobebestable stablefor fora
long time.
a long time.
The differences
The differences in in the
the tribological
tribological behavior
behavior of of all
all tested
tested variants
variants between
between the the different
different
environments show that oxidation is not the only mechanism responsible
environments show that oxidation is not the only mechanism responsible for increasing friction for increasing friction and
wear of MoS 2. H2O molecules seem to impede the alignment and shearing of the MoS2 layers resulting
and wear of MoS2 . H2 O molecules seem to impede the alignment and shearing of the MoS2 layers
in higherinfriction.
resulting higher In contrast,
friction. H2 may H
In contrast, act mayas termination of reactive
act as termination edges of
of reactive the MoS
edges of the2 planes, which
MoS2 planes,
2
is a mechanism similar to hydrogen in carbon coatings [15]. As a
which is a mechanism similar to hydrogen in carbon coatings [15]. As a second effect, H2 may trap second effect, H 2 may trap residual

oxygen in
residual the environment.
oxygen in the environment.
There is no straight forward
There is no straight forward explanation
explanationfor forthe
the very
very short
short wear
wear lifelife of
of all
all tested
tested coatings
coatings in in LHe
LHe
and LH 2; in particular, because at 77 K in liquid nitrogen, more than 100,000 friction cycles with a
and LH2 ; in particular, because at 77 K in liquid nitrogen, more than 100,000 friction cycles with a COF
COF
not not higher
higher than 0.03 thanare 0.03 are still possible.
still possible. However, However, in earlier
in earlier tests with othertestsMoS with variants,
other MoS 2 variants,
deviations in
2
the tribological behavior between 77 and 4.2 K were also detected [16]. One reason for earlyreason
deviations in the tribological behavior between 77 and 4.2 K were also detected [16]. One failureforin
earlyand
LHe failure
LH2 in may LHe and LH2expansion
be thermal may be thermal mismatch expansion
between mismatch
the coatingbetween the coating
and the substrate. The and the
stress
substrate.
caused The effect
by this stress increases
caused bywith this decreasing
effect increases with decreasing
temperature. temperature.
For a verification Foreffect,
of this a verification
tests with of
this effect, tests with coatings with different
coatings with different internal stresses are planned. internal stresses are planned.
Lubricants 2016, 4, 32 12 of 13

5. Conclusions
Under humid environmental conditions, MoS2 usually exhibits high friction and short wear life.
Improvements can be achieved by optimizing the deposition process in order to an orientation of the
(002) basal plane parallel to the substrate surface or by doping with metal atoms, e.g., Cr.
Gaseous H environment at room temperature enhances the tribological properties of MoS2
coatings. Friction and wear are low and comparable to the vacuum values under different hydrogen
gas pressures at room temperature.
Early coating failure is observed in liquid hydrogen with a boiling temperature of 20 K. However,
in liquid nitrogen at 77 K, friction is low and wear life is satisfactory. In liquid hydrogen as well as in
liquid helium (4.2 K), friction is only low at the very beginning of sliding. After a few friction cycles,
all variants showed early failure. Thus, in this extreme temperature range, thermal mismatch seems to
dominate the tribological behavior and should be accounted for in future.
The initially low COF could motivate more elaborate testing in the future on this topic as well as on
wear reduction. Operating components such as pumps and valves reliably in (liquid) hydrogen could
become more important as hydrogen gains momentum as medium for energy storage and conversion.

Acknowledgments: This work is funded by the German Research Foundation (DFG) as a part of the project
Tribological Optimization of Molybdenum Disulfide PVD-Coatings for Varying Environmental Conditions (GR 1002/8-1,
ME 1029/17-1, SZ 258/1-1). The coatings were provided Bernd Vierneusel, researcher at the Chair of Engineering
Design, Friedrich-Alexander-Universität Erlangen-Nürnberg. The HR-TEM and SAED images were contributed
by Werner Österle of BAM, Division 5.1, Materialography, Fractography and Ageing of Engineering Materials.
Author Contributions: Thomas Schneider designed and carried out the experiments in vacuum, inert,
and hydrogen environment. Thomas Gradt wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
The following abbreviations are used in this manuscript:
COF Coefficient of friction
LN2 Liquid nitrogen
LH2 Liquid hydrogen
LHe Liquid helium
PVD Physical vapor deposition
CVD Chemical vapor deposition
HR-TEM High resolution transmission electron microscope
SAED Selected area electron diffraction
RT Room temperature
STD reference or standard coating
HS coating variant with an internal stress of 370 MPa
LS coating variant with an internal stress of 300 MPa
CH MoS2 :Cr coating with 10 at% Cr
CL MoS2 :Cr coating with 5 at% Cr

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