lubricants

Article
Lube Oil Wear Reduction via Organic Tribofilms
Nurul Athirah Ismail and Samira Bagheri * ID

Nanotechnology & Catalysis Research Centre (NANOCAT), IPS Building, University of Malaya,
50603 Kuala Lumpur, Malaysia; tira.athirahismail@gmail.com
* Correspondence: samira_bagheri@um.edu.my; Tel.: +60-176-153-692

Received: 20 July 2017; Accepted: 4 August 2017; Published: 9 August 2017

Abstract: Effective tribofilms are desirable to protect mechanical systems. In the research,
the reduction in wear and friction were investigated through the use of organic additives.
Graphene-based organic additives were prepared by surface modification of graphene using organic
moiety that will provide tribochemical reaction with rubbing metal surface. The role of surface
protective additives becomes vital when operating conditions become severe and moving components
operate in a boundary lubrication regime. After protecting film is slowly removed by rubbing, it can
regenerate through the tribochemical reaction of the additives at the contact. Many researchers
demonstrated that organic additives physically or chemically adsorbed on rubbing metal surfaces
to form monolayers, with their shear strength deriving primarily from the weak van der Waal
interactions between opposing hydrocarbon chains at the interfaces. Experiments were conducted on
a base oil where 0.01 wt % of the additive was used. Tribological evaluation was conducted using
four-ball tester under room temperature and the morphology of the worn surfaces were characterized
using Field emission scanning electron microscopy (FESEM). Experimental results showed a 16%
reduction in friction and 30% reduction in wear when compared to the base oil containing no additive.

Keywords: organic; tribofilms; additive; lube oil; wear; tribochemical

1. Introduction
Fuel economy is one of the major factors that speeds up research in the formulation of lubricant
and lubricant additives. To put it simply, the reduction in fuel consumption is named fuel economy.
An increase in combustion efficiency and friction reduction in the transmission and engine can lead to
fuel economy [1]. An increase in transportation activities has consumed significant portions of our
energy resources. And most of the energy produced is used to overcome friction in moving mechanical
systems [2]. Friction can result in both advantageous and disadvantageous ways. When driving
and braking cars on the road, we depend on friction. However, in the context of lubrication
and tribology, friction and wear is an unwanted phenomenon that occurs when close contact of
surfaces occurs in relative motion [3]. Friction and wear are the two major causes for energy and
material losses in mechanical processes [4]. To improve the effective functioning of mechanical
components or two surfaces in contact, better lubricant along with chemical additives is required.
In military combat operations, extreme tribological environment is required [5]. For the protection
of mechanical components, from friction and wear in aerospace, automotive, military and various
industrial applications, an efficient lubricant is demanded. Moreover, the technology of protecting
machines entirely depends on the quality of lubricants. The addition of nanomaterials as additives in
base lubricant oil is a rapidly progressing field of research, because nanomaterials are different from
traditional bulk materials due to their extremely small size and high specific surface area [6]. Different
researchers have tried a variety of nanomaterials dispersed base oils to improve the wear and friction
reduction [7,8].

Lubricants 2017, 5, 30; doi:10.3390/lubricants5030030 www.mdpi.com/journal/lubricants

Lubricants 2017, 5, 30 2 of 12

Low wear and friction can be generated by the material with low shear strength, S and high
surface hardness, H. To have a low shear strength, the layers of the materials must be very thin.
Therefore, low friction can be achieved if thin layers of materials with hard surfaces and low shear
strength are used [9]. The layers of the material must be very thin, in order not to increase the contact
area, Ac [10]. Materials that can fulfil these requirements are commonly found in inorganic compounds.
Therefore, in this study, graphene or graphene oxide is used as the base material in preparing the
solid organic tribofilms for reduction of friction and also wear. An ideal sheet of graphene consists of
a 2D honeycomb structure of carbon atoms in a single layer [11]. It was confirmed that graphene has
extremely high rigidity and breaking strength. The values calculated corresponds to Young’s modulus
of E = 1.0 TPa and intrinsic strength of 130 GPa, proving that graphene is one of the strongest material
ever determined [12]. Graphene has been tested and proved to be one of the strongest materials ever
measured [13]. Graphene being two-dimensional material, offers unique friction and wear properties
that is not typically seen in conventional materials. Its high chemical inertness, extreme strength and
easy shear capability on its densely packed and atomically smooth surface are the major favourable
attributes for its impressive tribological behaviour. Because of its high load-bearing limit, high chemical
steadiness, low surface energy, strong intramolecular and weak intermolecular bonding, nanocarbon
materials have gained incredible attention by tribology scientists. Graphene had also been the focus of
enthusiasm in studies because of its excellent properties and unique structure.
Only a few reviews on graphene in tribology and mechanical applications have been reported so
far [14]. Also, a few scientists have revealed that graphite [15] and some of the graphite derivatives [16]
together have the desirable properties mentioned earlier. The tribological properties of graphite
nanosheets as an oil additive has been explored by Lin et.al. [17]. In between layers of graphite, there
is weak interatomic interaction, van der Waals forces and low shear stress [18]. The properties of
graphite as an additive for lube oil has been investigated and found that to have some improvement
in the reduction of friction and wear when graphite or graphite derivatives were introduced into
the oil at optimum concentration [19]. Philip et al. have studied effect of graphite and carbon
nanofibers as additives on the performance efficiency of gear pump driven hydraulic circuit using
ethanol solution. They claim that both graphite and carbon nanofibers dispersions in ethanol within
a concentration range of 195–1500 ppm can maintain hydraulic circuits with increase pump efficiency
without modifying the viscosity of the ethanol [20]. Zhang et al. has reported 17% and 14% reduction in
frictional coefficient and wear, respectively, with oleic acid-modified graphene as lubricant additive [21].
Ou et al. studied tribological properties of reduced graphene oxide (RGO) sheets on silicon substrate
synthesized via covalent assembly [22]. They attributed the wear and friction reduction of RGO to
its self-lubricating property. Similarly, Lee et al. have demonstrated the generality of the tribological
results on thinnest graphene sheets, which indicates that this may be a universal characteristic of
nanoscale friction for atomically thin materials weakly bound to substrates using frictional force
microscopy [13].
From an application point of view, nanolubricants are technologically important because of their
usage in various industries. Even though reports were already present on nanolubricants, they suffer
from low efficiency. Hence, it is always essential to improve the efficiency of lubricants. Studies show
that the graphene platelets are a failure as oil additive at higher temperatures, and this could be due to
the damaging of the protective film formed by the graphene at higher temperatures, and also due to
a significant increase in agglomerations within the lubricant [17]. Therefore, the application thus far is
considerable restricted. Nevertheless, the issue with dispersion stability can be resolved by utilising
some chemical and physical methods. The solution to this would be the addition of a dispersant or
modification that will reduce the agglomeration and improve the dispersive ability in the lubricant [14].
Therefore, in this study, organic moiety was introduced on the surface of GO which act as the base for
solid inorganic additive in order to provide the organic tribofilms and at the same time improve their
dispersion in base oil.
Lubricants 2017, 5, 30 3 of 12

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2. Experimental Methods
2. Experimental Methods
2.1. Materials
2.1. Materials
Graphene oxide, 1-bromodecane, 1-bromooctane, 1-bromodecane, 1-bromododecane and
Graphene
sodium azide (NaN oxide, 1-bromodecane, 1-bromooctane, 1-bromodecane, 1-bromododecane and
3 ) were purchased from Sigma-Aldrich (Germany). Tetrahydrofuran (THF),
sodium azide (NaN3) were purchased from Sigma-Aldrich (Germany). Tetrahydrofuran (THF),
dichloromethane (DCM), diethyl ether, dimethyl formamide (DMF), dimethyl sulphoxide (DMSO), and
dichloromethane (DCM), diethyl ether, dimethyl formamide (DMF), dimethyl sulphoxide (DMSO),
trimethylamine (Et3 N) were purchased from Friendemann Schmidt. Sodium hydride (NaH), dimethyl
and trimethylamine (Et3N) were purchased from Friendemann Schmidt. Sodium hydride (NaH),
malonate, lithium aluminium hydride (LiAlH4 ), magnesium
dimethyl malonate, lithium aluminium hydride
sulphate (MgSO ), chloroform and thionyl
(LiAlH4), magnesium sulphate4 (MgSO4), chloroform
chloride
and (SOCl 2 ) were
thionyl purchased
chloride (SOCl2) from
wereMerck. Dichloromethane
purchased (DCM), sodium ascorbate
from Merck. Dichloromethane and copper
(DCM), sodium
sulphate pentahydrate
ascorbate and copper (CuSO 4 ·5Hpentahydrate
sulphate 2 O) were purchased from
(CuSO4·5H Fischer
2O) were Scientific
purchased andFischer
from propargyl bromide
Scientific
was purchased
and propargylfrom Sigmawas
bromide Aldrich.
purchased from Sigma Aldrich.

2.2. Materials Preparation

2.2. Materials Preparation

Three Three major

major stepssteps
werewere involved
involved in preparation
in preparation ofof materialsasasshown
materials shownin inFigure
Figure 1.1. For
For the first
first step,
step, alkyne-functionalized
alkyne-functionalized GO, GOfGO, wasGO f was synthesized. Firstly, DiPPOH (dimethyl malonate and
synthesized. Firstly, DiPPOH (dimethyl malonate and propargyl
propargyl
bromide) bromide) was
was prepared prepared
by using by usingmalonate
dimethyl dimethyl and
malonate and propargyl
propargyl bromide bromide as the starting
as the starting materials.
materials. In an ice bath, dimethyl malonate was added to a sodium hydride suspension (60 wt % in
In an ice bath, dimethyl malonate was added to a sodium hydride suspension (60 wt % in mineral oil)
mineral oil) in dry THF followed by propargyl bromide (80 wt % in toluene). The mixture was left
in drystirred
THF followed by propargyl bromide (80 wt % in toluene). The mixture was left stirred overnight
overnight and then extracted using water and followed by dichloromethane. The combined
and then extracted
organic phaseusingwas water and followed
concentrated usingby dichloromethane.
a rotary evaporator, The combined organic phase
leaving dimethyl 2,2- was
concentrated
di(propynyl)malonate, DiMDiPM as the product. The DiMDiPM was then stirred in anhydrous THF.as the
using a rotary evaporator, leaving dimethyl 2,2-di(propynyl)malonate, DiMDiPM
product.
LiAlHThe DiMDiPM
4 was added towas then stirred
the stirred solutionin and
anhydrous THF.
the mixture LiAlH
left 4 was
stirred added to Water
for overnight. the stirred
and 10%solution
and the
NaOHmixture leftwas
solution stirred
addedforcarefully
overnight. Water
to stop and 10%
the reaction NaOH
[23]. solution
The mixture was
was added
filtered and carefully to stop
the filtrate
was dried
the reaction using
[23]. The MgSO
mixture4. Concentrate
was filteredthe andproduct usingwas
the filtrate a rotary
dried evaporator
using MgSO to 4have the 2,2- the
. Concentrate
dipropargyl-1,3-propanediol,
product using a rotary evaporator DiPPOH.
to have the 2,2-dipropargyl-1,3-propanediol, DiPPOH.

Figure 1. The overview on materials preparation.

Figure 1. The overview on materials preparation.

Graphene oxide
Graphene waswas
oxide stirred in chloroform.
stirred InIn
in chloroform. anan
iceice
bath
baththionyl
thionylchloride
chlorideand
and trimethylamine
trimethylamine was
added dropwise
was into the mixture
added dropwise into the [24,25].
mixtureThe mixture
[24,25]. The was thenwas
mixture stirred
thenfor 2 h and
stirred for further
2 h andconcentrated
further
usingconcentrated using a rotary
a rotary evaporator evaporator
to produce to produce
chlorinated GO.chlorinated GO. In
In anhydrous anhydrous
THF, NaH was THF, NaH followed
added was
by the chlorinated GO and DiPPOH prepared. The mixture was stirred overnight then concentrated
using a rotary evaporator to produce alkyne-functionalized graphene oxide, GOf .
Lubricants 2017, 5, 30 4 of 12

The second step required is to prepare azide-functionalized alkyl. 1-bromohexane and anhydrous
sodium azide added into DMF and the reaction mixture was stirred at 80 ◦ C under reflux for
overnight [26]. The mixture was then extracted using water and diethyl ether. The combined organic
phases were added with MgSO4 to remove water. The mixture was filtered and the filtrate was
concentrated by rotary evaporator to give 1-azidohexane as the product. The 1-bromohexane was
replaced by 1-bromooctane, 1-bromodecane and 1-bromododecane with same procedure to give the
product of 1-azidooctane, 1-azidodecane, and 1-azidododecane respectively.
The final step in the preparation of materials is the cycloaddition reaction between the
azide and alkyne group. The prepared alkyne-functionalized graphene oxide and four different
azide-functionalized alkyls followed by sodium ascorbate were added to the mixture of water and
DMSO (20:10) and sonicated for 1 h. CuSO4 ·5H2 O was added and then sonicated for 2 h. The mixture
was stirred overnight and then wash with water and ethanol [27–29]. The product dried overnight and
give reduced-functionalized graphene oxide, rGOf as the final product.

2.3. Materials Characterization

Fourier-Transform Infrared (FTIR) spectra are obtained using a Perkin-Elmer FTIR
spectrophotometer within the wave number in the range of 4000–400 cm−1 . Samples are finely ground
with potassium bromide, KBr and then compressed into pellet form. PANalytical diffractometer used
to obtain the pattern of X-ray diffraction (XRD) of the sample with a 2θ angle ranging from 5 to 50◦
and scan rate of 10◦ /min. Thermal Gravimetric Analysis (TGA) with thermal analyzer under an inert
atmosphere in the range of 50 to 800 ◦ C was performed at a heating rate of 10 ◦ C/min.

2.4. Tribological Characterization

Group II 500 N petroleum-based oil was used in the preparation of lubricant oil. The prepared
additives material were added in the base oil at 0.01 wt %, and transferred into a blending flask.
The flask was immersed in the Thermo-6D ultrasonic bath. An RW20IKA mechanical stirrer
(IKA, Wilmington, NC, USA) was used with 2 blade propellers, and was inserted into the mixture
flask. The mixture was stirred at a rate of 300 rpm at 60 ◦ C under 40 kHz ultrasonic frequency for an
hour to confirm the complete mixing and dispersion of both components.
The four-ball tester were used to determine the tribological behavior of the synthesised materials.
The main measurement of four-ball tester was to determine the wear preventive properties, extreme
pressure properties and the friction behaviour of lubricant oil. This experiment used the Ducom
Four-ball Instrument, while the balls were AISI 52-100 steel balls (USA) with a diameter of 12.7 mm and
64–66 Rc hardness. ASTM D2783 standard method was followed for the tribological characterizations
using the aforementioned four-ball instrument. The test conditions for this standard include room
temperature at a speed of 1200 rpm, load 400 N and test duration of 60 min.
At the end of four-ball test, the ball bearings were collected and washed with acetone, then dried
in an oven for an hour at 70 ◦ C. The wear scar on the three stationary ball bearings surface were
analysed using scanning electron microscopy (SEM) spectroscopy. The metallograph were analysed
and expressed as wear scar diameter WSD). The SEM images of the wear scar on steel ball were
obtained using Phenom ProX desktop SEM operates (Nanoscience Instruments, Phoenix, AZ, USA)
at 15 kV.

3. Results and Discussion

3.1. Materials Characterization

Figure 2a shows the spectrum for the synthesised alkyne functionalities, DiPPOH. Few peaks
can be observed that can prove the success of DiPPOH synthesised. The synthesised DiPPOH is very
crucial in order to provide the alkyne functionalities to the graphene oxide (GO). The absorption peaks
at 3282 cm−1 , 2117 and 646 cm−1 corresponding to the presence of C≡C terminal stretching, C≡C
Lubricants 2017, 5, 30 5 of 12
Lubricants 2017, 5, 30 5 of 12

stretching andbe
alkanes can C≡ C bending
seen respectively
at 2958 and [30].
2888 cm−1. At Absorption
around peaks
1024 to 1295 cmindicating the
−1, numbers C–H stretching
of absorption peaks of
alkanes can be seen at 2958 and 2888 cm −1 . At around 1024 to 1295 cm−1 , numbers of absorption peaks
were observed, indicating the presence of C–O stretching of alcohol. The functional groups observed
were observed,ofindicating
in spectrum the presence
DiPPOH proved ofsynthesis
that the C–O stretching of alcohol.
of DiPPOH The functional groups observed
was a success.
in spectrum of DiPPOH proved that the synthesis of DiPPOH was a success.

Figure The
2. 2.
Figure TheFTIR
FTIRspectra
spectraofof(a)
(a)synthesized
synthesized DiPPOH and(b)
DiPPOH and (b)GO
GOand
andGO
GOf. f
.

Figure
Figure 2b2b showsthe
shows thecomparison
comparison of of GO
GOand andGO GO f spectrum.
f spectrum. FewFewnewnewpeaks in GO
peaks inf spectrum
GOf spectrum can
canbebeobserved
observed that cancan
that prove thethe
prove success of alkyne-functionalized
success of alkyne-functionalized GO when compared
GO when with GO.
compared with TheGO.
Theabsorption peaks at 3282, 21122112
and 676 andcm676corresponding
cm−1 corresponding to the presence
to theofpresence
C≡C terminal stretching,
−1
absorption peaks at 3282, of C≡ C terminal
C≡C stretching
stretching, C≡C and C≡C bending
stretching and Crespectively.
≡C bending The intensity of C–H
respectively. Thestretching
intensityatof2930
C–H cm−1 increased at
stretching
in GO −f,1 thus proving that the GO have been attached by the organic moiety synthesized, DiPPOH
2930 cm increased in GOf , thus proving that the GO have been attached by the organic moiety
[27].
synthesized, DiPPOH [27].
The intensities of the vibration peak of O–H groups at 3418 cm−1 reducing proved that the O–H
The intensities of the vibration peak of O–H groups at 3418 cm−1 reducing proved that the O–H
groups had been replaced by other functionalities. This may be due to the covalent functionalization
groups had been replaced by other functionalities. This may be due to the covalent functionalization
that covalently attached the alkyne-functionalized molecule at the –OH groups on the surface of GO
that covalently attached the alkyne-functionalized molecule at the –OH groups on the surface of
thus reducing their –OH group’s intensity. Lastly, the intensities of C–O stretching for ester was
GOincreased
thus reducing their –OH group’s intensity. Lastly, the intensities of C–O stretching for ester
at 1041 cm−1 proving that, the covalent attachment of the alkyne functionalities was a
increased at 1041 cm−1 proving that, the covalent attachment of the alkyne functionalities was
wassuccess.
a success.Four main functionalities group can be observed in all four FTIR spectra of azide-functionalized
Four(a)
alkyl; main functionalities
azidohexane; group can (c)
(b) azidooctane; be observed
azidodecane; in all
(d)four FTIR spectrashown
azidododecane, of azide-functionalized
in Figure 3a. In
alkyl; (a) azidohexane;
all four (b) azidooctane; (c)
different azide-functionalized azidodecane;
alkyls, similar peaks (d) azidododecane,
can be observed. shown
The peakin Figure
at 2900 3a.cmIn−1all
four different
indicated theazide-functionalized
alkane stretching. Thealkyls,peak atsimilar
2100 cm peaks canmajor
−1 are the be observed.
peaks thatThe peak at
indicated the2900 cm−1
success
indicated the alkane
of the azidation stretching.
reaction, whichThe peak atto2100
is related cm−1stretching.
the azide are the major peaks that
The presence of indicated
azide group theissuccess
very
of the azidation
crucial in order reaction,
to make which
sure isthatrelated to the azide stretching.
the cycloaddition reaction in The clickpresence
couplingofbetween
azide groupazideisand very
alkyne
crucial can take
in order place.sure
to make Peaks atthe
that 1455 and 1257 cmreaction
cycloaddition −1 represents the presence of methyl group alkane
in click coupling between azide and alkyne
canbending
take place. and Peaks
aliphatic amineand
at 1455 stretching −1 represents
1257 cmrespectively [26].the presence of methyl group alkane bending
Figure 3b showed the FTIR spectrum
and aliphatic amine stretching respectively [26]. of GO and four different rGOf. All the four final products,
rGO f; rGO3b
Figure f_C6, rGOf_C8,
showed therGO f_C10,
FTIR and rGOof
spectrum f_C12
GOhave andalmost similar peaks.
four different rGOfFour
. Allmain oxygen-
the four final
containing functionalities group of GO can be observed in the FTIR spectrum
products, rGOf ; rGOf _C6, rGOf _C8, rGOf _C10, and rGOf _C12 have almost similar peaks. Four main presented in Figure 3b.
The peaks at 1725 functionalities
oxygen-containing and 1624 cm−1 were indicated
group of GOtocan thebe stretching
observed of C=O
in theand the spectrum
FTIR stretching of aromatic in
presented
C=C respectively. The presence of peaks at 1051 and 3418 cm −1 related to the stretching of C–O groups
Figure 3b. The peaks at 1725 and 1624 cm−1 were indicated to the stretching of C=O and the stretching
and O–H groups respectively.
of aromatic C=C respectively. The presence of peaks at 1051 and 3418 cm−1 related to the stretching of
C–O groups and O–H groups respectively.
Lubricants 2017,
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2017, 3030 6 of612
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Lubricants 2017, 5, 30 6 of 12

Figure 3. 3.The
Figure TheFTIR
FTIRspectra
spectraof
ofsynthesized
synthesized (a) azide-functionalized
azide-functionalizedalkyl
alkyland
and(b)
(b)GO
GO and
and rGO
rGO f. f .

Figure 3. The FTIR spectra of synthesized (a) azide-functionalized alkyl and (b) GO and rGOf.
For For
allall four
four differentrGO
different rGO,f,one onecrucial
crucialpeak peak can can be be seen
seen at at 2358
2358 cm cm−indicating
−1
1 indicating thethe
stretching
stretching of of
f
C–N,For proving
all thedifferent
four success rGOof azide-alkyne
f, one crucial coupling
peak can reaction
be seen on
at the GO
2358 cm sheets [27,31].the
−1 indicating The intensities
stretching of of
C–N, proving the success of azide-alkyne coupling reaction on the GO sheets [27,31]. The intensities
of
C–N, theproving
peaks the indicating
success of theazide-alkyne
presence ofcoupling oxygen-containing
reaction on the functionalities
GO sheets [27,31]. showed Thea intensities
dramatic
the peaks indicating the presence of oxygen-containing functionalities showed a dramatic reduction
reduction
of the peaks fromindicating
GO to rGOthe f. The intensities
presence of of the peak indicatedfunctionalities
oxygen-containing to O–H of carboxylic showed acid a groups
dramatic at
from GO to−1rGOf . The intensities of the peak indicated to O–H of carboxylic acid groups at 3418 cm−1
3418
reductioncm from was GO reduced
to rGOin broadness
f. The intensities due to esterification.
of the peak indicatedThis to O–H may be due toacid
of carboxylic the groups
covalent at
was reduced in broadness due to esterification. This may be due to the covalent functionalization that
functionalization
3418 cm−1 was reduced that covalently
in broadnessattacheddue the alkyne-functionalized
to esterification. This molecule may be at due the to
–OHthegroups
covalenton
covalently
the
attached the
surface of GO,
alkyne-functionalized
thus reducing their –OH
molecule at the –OH groups onthe
group’s intensity. However,
thepeaksurface of GO, thus
at groups
1725 cm −1
functionalization that covalently attached the alkyne-functionalized molecule at the –OH
−1 indicated the stretching of C=O
on
reducing
indicated
the surfacetheir –OH group’s
theofstretching intensity.
GO, thusofreducing
C=O remains However,
their the –OH samethe peak
from GO
group’s at 1725 cm
to rGOHowever,
intensity. f. These observations
the peak atproved 1725 cm that−1
remains
C=O the
stretch same
of from
esters GO
remains to rGO .
throughout
f These the observations
functionalization
indicated the stretching of C=O remains the same from GO to rGOf. These observations proved that proved that
process. C=O
The stretch of esters
functionalization remains
of GO
throughout
introduces
C=O stretch theof functionalization
new absorption
esters remainspeaks, process.
throughoutapparently The
the functionalization
arising from the
functionalization of GO
azidoalkyl
process. The introduces
into the new absorption
products.
functionalization For
of GO
peaks,
example, apparently
introduces thenew arising
doublet from
at 2918 and
absorption the
peaks, azidoalkyl
2850 cm is indicated
apparently−1 into the products.
arisingtofrom For
the stretching example,
the azidoalkyl the
of asymmetric doublet
into the C-H at 2918
of alkanes
products. Forand
2850 cm is− 1 indicated to2918
the stretching of−1asymmetric C-H
in azidoalkyl.
example, the Absorption
doublet at peakandon all cm
2850 four different
is indicated rGO to at of
f the 1451alkanes in
of azidoalkyl.
cm related
stretching −1 Absorption
to the presence
asymmetric C-H of C-H
of alkanes peak
onbend
allazidoalkyl.
four different rGOf that
atpeak
1451 cmbeen−1 related to the presence of C-H bend of
in of alkane, proving
Absorption it has
on all four successfully
different rGO attached
f at 1451 on GO.
cm−1 related toalkane, proving
the presence that it
of C-H
hasbend
been ofsuccessfully
The changes
alkane, inattached
proving thethat iton
structurehasGO. of the
been samples can
successfully be further
attached on GO. studied by performing the XRD
measurement.
The Thechanges
changes The XRD
inin the patterns
thestructure
structure for
ofofGO theand
the rGOf iscan
samples
samples shown
can in Figure
be further
be further 4a. Forbyby
studied
studied GO, a broad peak
performing
performing at
thethe
XRD 2θ
XRD
=measurement.
10.0° can be The
measurement. observed,
TheXRD referring
XRD patterns
patterns for to aGO
for GOd-spacing
and
andrGO off is
rGO 0.860
f shown
is nm.
shown The
in peak
Figure
in Figure of
4a. GO
For
4a. was
GO,
For not
a
GO, observed
broad
a peak
broad in
at
peakall
2θ at
the
= four
10.0° ◦ different
can be final
observed, products,
referring rGO
to a . rGO
d-spacing shows of a new
0.860 nm.
2θ = 10.0 can be observed, referring to a d-spacing of 0.860 nm. The peak of GO was not observed in
f f diffraction
The peak peak
of GOat 2θ
was= 19.9°,
not referring
observed into a
all
alld-spacing
the
thefour of 0.818
fourdifferent
different finalnm.
final Reduction
products,
products, rGO rGO in
f. rGOthe f d-spacing
shows a new after functionalization,
diffraction peak at 2θ indicated
f . rGOf shows a new diffraction peak at 2θ = 19.9 , referring
that
◦ upon
= 19.9°, referring to a
to functionalization,
d-spacing
a d-spacing of of
0.818 thenm.
0.818 structure
nm.Reduction of theinsamples
Reduction inthe was changed
thed-spacing
d-spacing after
afterdue to the amorphization
functionalization,
functionalization, indicatedof the
indicated material
that upon
that upon
by introducing
functionalization, the organic
the moiety
structure of into
the the
samples interlayer
was spacing
changed
functionalization, the structure of the samples was changed due to the amorphization of the material dueof GO.
to the amorphization of the material
byby introducing
introducing thetheorganic
organicmoiety
moietyinto intothe the interlayer
interlayer spacing
spacing of ofGO.
GO.

Figure 4. The (a) XRD patterns of GO and rGOf and (b) Thermal gravimetric analysis (TGA) diagram
Figure
of The
GO4.and
Figure 4. (a)(a)fXRD
rGO
The . XRDpatterns
patternsof
ofGO
GO and
and rGO and (b)
rGOf and (b)Thermal
Thermalgravimetric
gravimetricanalysis
analysis (TGA)
(TGA) diagram
diagram
of of
GO and
GO and rGO
rGOf . f.
Lubricants 2017, 5, 30 7 of 12
Lubricants 2017, 5, 30 7 of 12

TGA
TGA diagram
diagram ofof GO
GO and
and four
four different
different rGO
rGOff are
areshown
shownin inFigure
Figure4b.
4b.Firstly,
Firstly, the
the loss
loss occurred
occurred at at
the
the temperature
temperature belowbelow 125125 °C,
◦ C, primarily
primarily duedue toto the
the loss
loss of
of water
water molecules.
molecules. Mass
Mass loss
loss below
below 125125 °C◦C
indicated
indicated that
that the
the content
content ofof adsorbed
adsorbed water
water for
for rGO
rGOff was
waslower
lower when
when compared
compared to to GO.
GO. ItIt shows
shows that
that
rGO has lower water content than GO. This can prove that the hydroxyl
rGOf has lower water content than GO. This can prove that the hydroxyl groups in the rGOf have
f groups in the rGO f have
been
been
reducedreduced by covalent
by covalent functionalization
functionalization of the organic
of the organic moiety moiety on the of
on the surface surface of GOSecondly,
GO [27,32]. [27,32].
Secondly, the unstable oxygen-containing functional groups will be thermally
the unstable oxygen-containing functional groups will be thermally decomposed at a temperature decomposed at of
a
temperature
◦
225 C [32,33]. of Weight
225 °C [32,33]. Weight
loss of rGO loss of rGOf at 225 °C was very low compared to weight loss
◦
f at 225 C was very low compared to weight loss of GO. It proved
of GO. It proved that upon functionalization
that upon functionalization of GO, the oxygen-containing of GO, the oxygen-containing
functional groups werefunctional groupsduring
also reduced were
also reduced during the
the click-coupling reaction. click-coupling reaction.
To
To study
study thethe morphology
morphology of of the
the rGO
rGOff,, FESEM
FESEM waswas carried
carried out,
out, and
and the
the images
images are are shown
shown in in
Figure 5. All the four different rGO f have almost similar SEM images. Fluffy aggregates
Figure 5. All the four different rGOf have almost similar SEM images. Fluffy aggregates on rGOf can on rGO f can
be
be clearly
clearly observed
observed duedue toto the
the presence
presence of of organic
organic moiety
moiety on
on their
their surfaces
surfaces [27].
[27]. The
The FESEM
FESEM imageimage of of
rGO
rGOffshows
showsthat
thatfunctionalization
functionalization waswas successfully
successfully done by by
done decorating organic
decorating molecules
organic molecules on theon GO.
the GO.

Figure 5.
Figure The FESEM
5. The FESEM images
images including
including EDXEDX spectra
spectra of
of four different rGOf with
with magnification
magnification of
of
50,000×,(a)
50,000×, (a)rGO
rGOf_C6,
f _C6,(b)
(b)rGO
rGO f _C8,
f_C8, (c)(c)rGO
rGO f _C10
f_C10 and
and (d)rGO
(d) rGO f _C12.
f_C12.

The
The EDX
EDX analysis
analysis proved
proved the
the appearance
appearance of of element
element nitrogen,
nitrogen, N in the rGOff.. ItIt proved
proved that
that the
the
rGO
rGOff has
hasbeen
beendecorated
decoratedwith
withaatriazole
triazolering
ringthat
thatresults
resultsfrom
from the
the reaction
reaction between
between alkyne
alkyne and
and azide
azide
functionalities.
functionalities. Previous
Previousresults
resultsof
ofFTIR
FTIR that
that has
has been
been discussed
discussed earlier
earlier proved
proved that
that the
the N
N detected
detected
were
were groups of azide. Besides
Besides that,
that, there
there is
is no
no trace
trace of
of the
the Cu
Cu element
element inin the
the rGO
rGOff,,proving
proving that
that there
there
are
are no
no residues
residues of Cu that was used as the catalyst in the click coupling reaction left.

3.2. Dispersibility
3.2. Dispersibility Test
Test
Simplest qualitative
Simplest qualitative test
test was
was carried
carried out
out to
to determine
determine whether
whether the the reduced
reduced functionalized
functionalizedGO, GO,
rGO has better dispersibility in oil than GO. The dispersibility of GO and four different
rGOff has better dispersibility in oil than GO. The dispersibility of GO and four different rGOff in oil rGO in oil
was observed.
was observed. Upon
Upon preparation
preparation of of the
the dispersibility
dispersibility test,
test, GO
GO and and all
all four
four different
different rGOff separately
separately
dispersed in
dispersed in base
base oil
oil subjected
subjected toto the
the same
same sonication
sonication time.
time. After
After sonication,
sonication,itit can
can bebe seen
seen that
that GO
GO
cannot be uniformly dispersed in base oil, but for the
cannot be uniformly dispersed in base oil, but for the rGOf, it canrGO f , it can easily disperse in the base
easily disperse in the base oil. After oil.
After
one one month
month of observation,
of observation, it can itbecan be observed
observed thatGO
that the theinGO
base in oil
base oil sedimented
sedimented to thetobottom
the bottom
and
while the rGOf is still uniformly dispersed in base oil. Comparisons between GO and the four
Lubricants 2017, 5, 30 8 of 12

Lubricants 2017, 5, 30 8 of 12
and while the rGOf is still uniformly dispersed in base oil. Comparisons between GO and the four
different
different rGO
rGOff before
beforeand
andafter
after11month
monthare
areshown
shownin
inFigure
Figure6.
6.ItItproved
provedthat
thatupon
uponfunctionalization,
functionalization,
the dispersibility of the rGO in the base oil improved.
the dispersibility of the rGOf in the base oil improved.
f

(a)

(b)
Figure
Figure 6.
6. The
The GO
GO and
and four
four different
different rGO
rGOff dispersed
dispersed in
in base
base oil
oil (a);
(a); after
after 11 month
month (b).
(b).

3.3. Tribological Characterization

3.3. Tribological Characterization
The coefficient of friction, CoF data were collected after a four-ball friction test. The variation of
The coefficient of friction, CoF data were collected after a four-ball friction test. The variation of
CoF with different rGOf in the base oil was measured by applying 400 N load.
CoF with different rGOf in the base oil was measured by applying 400 N load.
Figure 7 presents the CoF as a function of time for base oil, base oil with GO and also base oil
Figure 7 presents the CoF as a function of time for base oil, base oil with GO and also base oil with
with four different rGOf. The experiments were repeated three times with fixed load to check the
four different rGOf . The experiments were repeated three times with fixed load to check the stability
stability of the CoF value. From the results where the variation of mean and standard variation values
of the CoF value. From the results where the variation of mean and standard variation values was
was calculated, it can be noted that the lubricant yielded consistent CoF value over multiple runs
calculated, it can be noted that the lubricant −3yielded consistent CoF value over multiple runs with the
with the maximum deviation of 7.662 × 10 . The results of CoF at concentration of 0.01 wt % are
maximum deviation of 7.662 × 10−3 . The results of CoF at concentration of 0.01 wt % are summarised
summarised in Table 1.
in Table 1.
Lubricants 2017, 5, 30 9 of 12
Lubricants 2017, 5, 30 9 of 12

Figure 7. The coefficient of friction (CoF) of base oil with GO and four different
different rGO
rGOff.

Table 1. Average Coefficient

Coefficientof
ofFriction,
Friction,CoF
CoFand
anddifference
differenceininpercentage
percentageforfor
allall
thethe
prepared samples.
prepared samples.

Sample
Sample
Average Coefficient of Friction, CoF Difference
Average Coefficient of Friction, CoF
Difference (%)
(%)
Base oil 0.077 Benchmark
Base oil 0.077 Benchmark
Base
Baseoil
oil with GO
with GO 0.078
0.078 +0.779
+0.779
Base
Baseoil
oil with rGOf f_C6
with rGO _C6 0.065
0.065 −14.86
−14.86
Base
Baseoil
oil with rGOf f_C8
with rGO _C8 0.065
0.065 −15.39
−15.39
Base oil with rGO
Base oil with rGOf_C10
f _C10 0.065
0.065 − 15.78
−15.78
Base oil with rGO _C12 0.065 −15.51
Base oil with rGOf f_C12 0.065 −15.51

As shown in Table 1, the CoF of base base oil was increased when added with GO. It can be due to
the agglomeration of GO in the base oil that makes the oil not stable and all the GO sediment and do
not provide lubrication [17]. Besides Besides that,
that, when
when the GO in the base oil agglomerate, it will result in
rough contact surface
surface that will results
results in increase
increase of CoF.
CoF. It
It is
is also
also clear that all these synthesised
synthesised rGO rGOff
causes a reduction in the CoF of the additive-added lubricant when compared to base oil without any
rGOff . It
It can
can be
be due
due to
tothe
thetribochemical
tribochemical reaction
reaction that
that occurs
occurs between
between the organic moiety that has been
attached on GO.
The polar groups on the rGOff which results from the attachment of organic moiety on GO were
assumed to tribochemically react with the positively charged metal surfaces reducing the friction
through the formation of organic tribofilmstribofilms [34].
[34].
In relation
relationwith
withaverage
averageCoFCoF obtained
obtained previously, the the
previously, addition of rGO
addition in base
of frGO oil also
f in base oilhas
alsoa direct
has a
impact on theironwear
direct impact theirscar diameter
wear (WSD). (WSD).
scar diameter From the SEMthe
From metallographs of wear surfaces
SEM metallographs on the steel
of wear surfaces on
balls used
the steel in four-ball
balls test, the test,
used in four-ball average wear scar
the average diameter
wear (WSD) were
scar diameter (WSD) measured and theand
were measured results
the
were
resultsshown in Figure
were shown in 8. The measurements
Figure 8. The measurements were repeated three times
were repeated three to check
times to the
checkstability of the
the stability
calculated WSD. WSD.
of the calculated From theFrom results, it can be
the results, noted
it can be that
notedthe lubricant
that yielded
the lubricant consistent
yielded WSD value
consistent WSD
and
valuetheand uncertainty level was
the uncertainty levelbelow ±5%.±5%.
was below WearWear
scar diameter (WSD)
scar diameter of the
(WSD) ofsteel ball ball
the steel waswasset as
setthe
as
benchmark to calculate the reduction in WSD after the addition of four different
the benchmark to calculate the reduction in WSD after the addition of four different rGOff 0.01 wt %. rGO at 0.01 wt %.
Lubricants 2017, 5, 30 10 of 12
Lubricants 2017, 5, 30 10 of 12

Figure 8. SEM metallographs

metallographs ofofwear
wearsurfaces
surfaceswith
withGO GOand
andfour
four different
different rGOrGO
f atf at 0.01
0.01 wtwt % base
% in in base
oil
oil
(a) (a)
basebase
oil;oil;
(b) (b)
GO;GO; (c) rGO
(c) rGO f_C6;
f _C6; (d)(d)
rGOrGO f_C8;
f _C8; (e) (e)
rGOrGO f_C10
f _C10 andand
(f) (f)
rGOrGO f_C12.
f _C12.

When
When compared
compared to to the
the WSD
WSD ofof base
base oil,
oil, all
all the
the four
four different rGOf were
different rGO effectively reduced the
f were effectively reduced the
WSD
WSD when they were added into the base oil. However, similar to the CoF value, thethe
when they were added into the base oil. However, similar to the CoF value, WSDWSDforfor base
base oil
oil that was added with GO also slightly increased. The smallest WSD can be observed
that was added with GO also slightly increased. The smallest WSD can be observed with the used of with the used
of
rGOrGO f_C10 that gave the highest reduction of WSD, which is about 30%. For rGOf_C6, rGOf_C8 and
f _C10 that gave the highest reduction of WSD, which is about 30%. For rGOf _C6, rGOf _C8 and
rGO f_C12, their reductions of WSD were 23%, 27% and 29% respectively. The trend in reduction of
rGOf _C12, their reductions of WSD were 23%, 27% and 29% respectively. The trend in reduction of
WSD
WSD for for all
all the
the prepared
prepared samples
samples were
were similar
similar to
to the
the trend
trend in
in reduction
reduction ofof CoF.
CoF. Significant
Significant reduction
reduction
of
of WSD for all the prepared samples can be observed when compared to the WSD of
WSD for all the prepared samples can be observed when compared to the WSD of base
base oil
oil without
without
any addition of rGO f and also base oil that was added with GO.
any addition of rGO and also base oil that was added with GO.
f

4.
4. Conclusions
Conclusions
The
The functionalization
functionalization of of solid
solid material
material byby attachment
attachment ofof organic
organic moiety
moiety waswas proved
proved toto effectively
effectively
improve their tribological properties by formation of organic tribofilm. The tribology
improve their tribological properties by formation of organic tribofilm. The tribology tests confirmedtests confirmed
aa good
goodreduction
reduction in friction
in friction and can
and wear wear can be accomplished
be accomplished with
with base oil base oilwith
formulated formulated with
functionalized
functionalized
graphene oxide.graphene
Their good oxide. Their
friction good friction
properties properties
also tribute to goodalso tributeproperties.
anti-wear to good anti-wear
Different
properties. Different rGO
rGOf with variations f with
in their variations
alkyl in their
chain gives alkylvalues
different chain gives
of CoFdifferent
and WSD. values
The of CoF and
highest WSD.
reduction
The highest
in both CoFreduction
and WSDincan bothbeCoFseenand WSD
with thecan
usebeofseen
C10 with the use
attached on of
rGOC10 attached on rGOf. The
f . The highest recorded
highest recorded reduction of CoF and WSD were 16% and
reduction of CoF and WSD were 16% and 30% respectively. The outcomes apparently30% respectively. The confirmed
outcomes
apparently confirmed that graphene sheets attached with organic moiety in oil create
that graphene sheets attached with organic moiety in oil create protective films with ease to avoid protective films
with ease tosurfaces
the rubbing avoid thefromrubbing
coming surfaces from
into direct coming
contact into
and, bydirect contact and,
that, completely by that,the
enhances completely
tribology
enhances the tribology
behaviour of the oil. behaviour of the oil.

Acknowledgments: The Theauthors

authorsare
arepleased
pleasedtoto
acknowledge
acknowledge thethe
University of Malaya
University and and
of Malaya Nanotechnology and
Nanotechnology
and Catalysis
Catalysis Research
Research Centre
Centre (NANOCAT).
(NANOCAT). This
This work
work waswas financially
financially supportedbybythe
supported theUniversity
University of
of Malaya
Malaya
Grand Challenge
Grand Challenge Grant
Grant (Grant
(Grant No. GC001A-14AET) and
No. GC001A-14AET) and University
University ofof Malaya
Malaya Postgraduate
Postgraduate Research
Research Grant
Grant
(Grant No. PG058-2015B).
(Grant No. PG058-2015B).
Author Contributions: Nurul Athirah Ismail and Samira Bagheri contributed equally to this manuscript.
Author Contributions: Nurul Athirah Ismail and Samira Bagheri contributed equally to this manuscript.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
Lubricants 2017, 5, 30 11 of 12

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