Tribol Lett (2014) 56:107117
DOI 10.1007/s11249-014-0390-4
ORIGINAL PAPER
Studies of the Kinetics of Lithium Grease Microstructure
Regeneration by Means of Dynamic Oscillatory Rheological
Tests and FTIRATR Spectroscopy
Maciej Paszkowski Sylwia Olsztynska-Janus
Iwona Wilk
Received: 11 May 2014 / Accepted: 5 August 2014 / Published online: 26 August 2014
Springer Science+Business Media New York 2014
Abstract As part of this research, the kinetics of soap
grease thickener microstructure regeneration during 24-h
relaxation after 1-h shearing were studied. A lubricating
grease, based on mineral oil ORLEN OIL SN-400, con-
taining associated molecules of lithium 12-hydroxystearate
was subjected to analysis. Rheological dynamic oscillatory
and FTIRATR (Fourier Transform Infrared Attenuated
Total Reflectance) spectroscopy were used to study the
kinetics of thickener microstructure regeneration. Changes
in the values of storage modulus G0 and loss modulus G00 of
the investigated grease during its relaxation in the linear
viscoelastic range were examined. In addition, the
mechanical stability of the thickener microstructure at a
variable oscillation frequency was tested, and changes in
the cohesive energy of the grease versus the latters
relaxation time were assessed. FTIRATR spectroscopy
was used to study the physicochemical interactions
between the associated molecules of lithium 12-hydroxy-
stearate. Infrared bands were assigned to the vibrations of
the particular functional groups of the grease components,
and the spectral parameters in the absorption spectra in the
range of 7003,700 cm-1 were examined. The studies
carried out using the two investigative methods have
revealed that the intensity of thickener microstructure
regeneration was the highest in the first hour of grease
M. Paszkowski (&)
Institute of Machine Design and Operation, Wroclaw University
of Technology, Ignacego Lukasiewicza 7/9, 50-371 Wroclaw,
Poland
e-mail: maciej.paszkowski@pwr.edu.pl
S. Olsztynska-Janus  I. Wilk
Institute of Biomedical Engineering and Instrumentation,
Wroclaw University of Technology, Plac Grunwaldzki 13,
50-370 Wroclaw, Poland
relaxation after shearing. In this time interval, the largest
changes in the vibrations of the main functional groups of
the grease components were observed. In the next hours,
the kinetics of thickener microstructure regeneration were
substantially lower.
Keywords Grease  Thixotropy  Rheology  Infrared
spectroscopy  FTIRATR
1 Introduction
Lubricating greases are rheologically complex non-Newto-
nian fluids. They are chemically and physically heteroge-
neous two-phase systems. In lubricating greases, the
dispersed phase (called a thickener) is usually made up of
flocculated anisometric particles forming a spatial structure.
The particles are most often molecular associates of metallic
salts of fatty acids. Depending on the kind of metal hydroxide
used in the neutralization of fatty acids, lithium, calcium,
sodium, aluminum, etc., thickeners are obtained. A thickener
endows lubricants with proper consistency and rheological
and tribological properties. Its share usually does not exceed
20 % of the total volume of a lubricant composition. An oil
base (typically a mineral or synthetic oil) is the dispersion
phase for a thickener. As a result of mechanical occlusion
and capillary forces, the oil is trapped in the free spaces of the
thickener network, whereby the latter assumes the charac-
teristic spatial shape [1]. Depending on the size of thickener
particles, lubricating greases can assume the characteristics
of a mechanical or colloidal dispersion system [2]. The
degree of dispersion of the dispersed phase depends on the
way the lubricant is produced and used.
One of the functions of lubricating greases is to reduce
the friction and intensity of wear of tribological node
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surfaces and to protect them against moisture, aggressive
media and mechanical impurities (mainly wear products).
In order for lubricating greases to perform their function,
they should be supplied, in proper amounts and at proper
time intervals, to the space between the interacting sur-
faces. Lubricants are usually fed by centralized lubrication
systems. Their advantage is that the lubrication process can
be fully automated and controlled, whereby its reliability is
increased owing to the elimination of the human factor
from the servicing of the particular friction nodes. Another
important aspect of the use of lubrication systems is
environment protection thanks to a reduction in lubricant
consumption by as much as 90 % relative to hand-feed
lubrication [3]. This is achieved owing to the more precise
(consistent with the demand) lubricant feeding. In order for
a lubrication system to function properly, besides the
proper choice of its structural components, it is equally
important to know the rheological properties of the lubri-
cating grease used and its behavior at each stage of dis-
tribution in this system. The lubricating grease should be
characterized by the lowest possible resistance of flow in
the main conduit, the distributors, and the supply conduits,
and its consistency should ensure the proper protection of
the lubricated surfaces in the receiving (service) point.
In the first seconds, when a portion of lubricant is being
pumped into the main conduit, the lubrication system pis-
ton pump must overcome the lubricants resistance to flow,
due to, among other things, the existence of the so-called
yield stress and, to a lesser degree, to the lubricants ability
to form a boundary layer in the proximity of the material of
which the main conduit is made [4, 5]. The resistance to
flow depends on many factors, such as the instantaneous
condition of the thickener network, its elastic and plastic
deformability, the rate of the flow generated by the pump,
and the physical and chemical activity of the environment
[6, 7]. When the flow limit is exceeded, the structural
viscosity of the lubricant decreases until it reaches a pla-
teau, i.e., a structural viscosity close to the dynamic vis-
cosity of the oil base. Between the successive cycles of
lubricant distribution to the tribological nodes, the micro-
structure of the lubricant is partially regenerated, whereby
its structural viscosity increases. This is caused by physi-
cochemical interactions between the particles in the lubri-
cant volume, the Brownian movements of the particles [8],
and steric effects [2]. The phenomenon of the thermal
decrease in the structural (apparent) viscosity of the
lubricant during it shearing, followed by its increase and
the resolidification of the lubricant when shearing ends, is
called lubricant thixotropy [9]. The intensity of grease
microstructure regeneration depends on, among other
things, the shearing conditions existing prior to the relax-
ation of stresses in the lubricant. The thixotropy of lubri-
cating greases can have a negative effect on, e.g., the
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Tribol Lett (2014) 56:107117
proper functioning of automated lubrication systems,
especially the extensive ones containing large amounts of
lubricant and protecting several hundred friction nodes.
The formation of a coagulation structure may cause
uncontrolled pressure buildup in the main lubrication
conduit in the next cycle of distribution of the lubricant and
an increase in its flow resistances. Consequently, it
becomes impossible to precisely determine the amount of
the lubricating medium reaching the service points, which
may result in their insufficient lubrication or in increased
environmental pollution. Another hazardous consequence
of an increase in the structural viscosity of the lubricating
grease during its relaxation may be the appearance of
dangerous inertial phenomena in the lubrication system.
The phenomena may lead to increased energy consumption
by the piston pump and in extreme cases, to its damage and
the failure of the equipment being lubricated. Considering
the importance of the problem, particularly in the context
of the increasingly widespread automation of machine and
equipment lubrication systems, it was imperative to carry
out experimental studies to explain the phenomenon of
lubricant thixotropy. The current knowledge on the thix-
otropy of lubricating greases is presented in [10].
The present work is the continuation of the research
reported in [11], which has established that there is an
inexplicit relationship between temperature T of lithium
grease, its shear rate c, _ thickener percentage Sc, and
microstructure regeneration during the relaxation of the
grease in the lubrication systems of machines. In the
adopted ranges of input variables: T (from -20 to ?80 C),
c_ (8.148.6 s-1) and Sc (49 %), the largest increase in
structural viscosity was observed for lithium grease with
thickener percentage Sc = 7.5 %, sheared at shear rate
c_ = 8.1 s-1 at temperature T = 28 C. However, the cited
work [11] does not explain the changes in the thickener
microstructure during the grease relaxation stage, in the
response plane point where the increase in structural vis-
cosity was the largest. This is the subject of the present
paper. In order to assess the kinetics of microstructure
regeneration, rheological dynamic oscillatory tests and
FTIRATR (Fourier Transform Infrared Attenuated Total
Reflectance) spectroscopy studies were carried out. The
ATR technique, which enables one to study infrared radi-
ation absorption by recording the radiation reflected from
the sample, was used for structural examinations. This
technique is commonly used to investigate highly absor-
bent materials, which represents a great advantage over the
conventional transmission technique. ATR is highly sen-
sitive, enabling one to detect even the slightest changes in
the biochemical properties of the examined samples, and
any modifications of the molecular interactions. The other
advantages of ATR are only a small amount of the material
is needed for measurements, and spectra are quickly
Tribol Lett (2014) 56:107117
Table 1 Main physicochemical properties and structural composi-
tion of oil ORLEN SN-400
Kinematic viscosity of oil at 40 C (cSt) 81.06
Kinematic viscosity of oil at 100 C (cSt) 9.51
Viscosity index () 93
Density at 20 C (g/cm3) 0.88
Flow temperature (C) -9
Carbon content in aromatic structures (%) 9.75
Carbon content in naphthenic structures (%) 21.14
Carbon content in paraffin structures (%) 69.11
obtained [1214]. Because of the kind of sample, ATR
with one reflection in a diamond crystal was employed.
This crystal has the best properties and is the hardest,
chemically inert, scratch resistant, and is characterized by
good penetration depth. It is used to investigate both
organic and inorganic substances [12]. Therefore, the ATR
technique can be perfectly suitable for the investigation of
lubricants.
2 Materials
A lubricating grease, based on mineral oil SN-400 (OR-
LEN OIL, Poland), thickened with lithium 12-hydroxy-
stearate was subjected to tests. The main physicochemical
properties and structural composition of the base oil are
specified in Table 1. The share of the lithium thickener in
the total volume of the grease amounted to 7.5 % (con-
sistency class 2 according to NLGI [15]). The grease did
not contain any solid additives.
A sample of the lubricating grease was produced in a
semi-technical plant modeling the operating conditions of
an industrial lubricant plant. The thickener was synthesized
in situ in the base oil during the production of the lubricant.
12-hydroxystearic acid was introduced into the reactor
containing base oil amounting to 50 % of the amount
specified in the lubricant composition, and the reactor
heating system was switched on. At a temperature of
8085 C, when the acid completely dissolved while the
agitator was working, lithium hydroxide monohydrate
suspension in water was introduced into the reactor. The
neutralization reaction was conducted for 2 h at a tem-
perature of 9095 C. When the neutralization process
ended, the reactor contents were heated up to a temperature
of 120130 C in order to evaporate water (introduced with
the lithium hydroxide and the water coming from the
neutralization reaction). Then the reactor contents were
gradually heated up to 200 5 C. This temperature was
maintained for 15 min until the soaps completely dissolved
and a solution formed. Subsequently, the rest of the base oil
was introduced. The oil was fed in four portions in order to
109
keep the end temperature of the reactor contents not lower
than about 160 C. Then the produced grease was
dynamically cooled down to a temperature of about 60 C.
Subsequently, it was subjected to homogenization in a
Frym disk colloid mill with a gap set at 0.2 mm.
3 Methods
3.1 Rheological Dynamic Oscillatory Tests
The lithium grease was tested using a Physica Anton-Paar
MCR 101 rotational rheometer. The rheometer operated in
the plateplate configuration with a constant measuring gap
height of 1 mm. A sand blasted plate (PP-40/S) 40 mm in
diameter and with roughness Ra = 2.8 lm was used in
order to reduce lubricant slip at the wall. The rheometer
comprised a P-PTD200 Peltier heating/cooling unit and an
H-PTD200 insulating flange with air circulation inside the
measuring head. The grease sample would be thermostatted
at a constant temperature of 28 C with an accuracy
of 0.01 C. Before each measurement, the sample would
be kept at the constant temperature in the rheometer head
for 5 min after the set temperature stabilized. The mea-
surements would be repeated five times. For the sake of
clarity, no confidence levels were included in the diagrams.
In the first stage of the studies, critical deformation cc was
iteratively determined. Its value constituted the upper limit
of the linear viscoelasticity (LVE) of the tested grease. For
this purpose deformation amplitude, sweep tests in a range
of 0.01100 % at constant oscillation frequency f = 1 Hz
were carried out. The tests were preceded by the 1-h-long
shearing of the grease in steady conditions at a shear rate of
8.1 s-1. Deformation amplitude c, for which storage
modulus G0 amounted to 5 % of its maximum value, was
adopted as the upper limit of LVE [16]. It was necessary to
determine cc in order to shear the grease in the elastic range
in the rheological tests without destroying its microstruc-
ture. In the second stage of the studies, the kinetics of the
regeneration of the lithium thickener microstructure in the
grease, in the LVE range at deformation c \ cc and con-
stant oscillation frequency f = 1 Hz, were evaluated by
means of the Three Interval Thixotropy Test (3ITT). For
this purpose, changes in the values of storage modulus G0
and loss modulus G00 for the fresh grease (the rest interval)
and after shearing it at shear rate gradient c_ = 8.1 s-1 (the
load interval) in steady conditions for 1 h were measured.
The microstructure regeneration investigations lasted for
24 h (the recovery interval). In the next stage of the studies,
the stability of the grease microstructure at the oscillation
frequency changing in a range of 0.1100 rad s-1 and at
constant deformation amplitude c \ cc was assessed. The
tests were carried out after shearing the grease for 1 h in
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Fig. 1 Changes in storage modulus G0 and loss modulus G00 in first (rest) interval and third (recovery) interval of thixotropic test
steady conditions and after 3, 6, 12, and 24 h of its relax-
ation. The RHEOPLUS/32 software (version 3.4) was used
to record rheometric data. Rheological dynamic oscillatory
tests are quite commonly used to assess, among other
things, the mechanical stability of the microstructure of the
thickener in new lubricant mixtures or the effect of a
change in lubricant production parameters on microstruc-
ture stability. The results of such tests are reported in, e.g.,
[1721].
3.2 ATRFTIR Vibrational Spectroscopy
The spectroscopic measurements of the grease were per-
formed using a Nicolet 6700 FTIR spectrometer made by
Thermo Scientific (USA), equipped with ATR accessories
[22]. A sample of the grease was directly placed on the
Heated Diamond Top-Plate of the Golden Gate Mk II ATR
Accessory (Pike, USA). The heated top-plate enabled the
recording of spectra at a constant temperature of 28 C.
After the grease was put on the diamond crystal, the ATR
FTIR spectra of the control sample (before shearing), after
shearing and in the course of 24-h-long relaxation in a
range of 7004,000 cm-1, were obtained. Because of the
rapid processes taking place in the first hour of relaxation,
spectra were recorded precisely at 1-min intervals during
the first hour and then at 15-min intervals until the end of
the 24-h period. The precise spectra recording time was set
by a computer program written for this experiment. The
resolution of 4 cm-1 was selected, and the recorded spectra
were averages of 32 scans. Three measurement series were
carried out in order to check the repeatability of results. All
the measurements were performed at 28 1 C. A system
consisting of a compressor and a dryer was connected to
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Tribol Lett (2014) 56:107117
the spectrophotometer in order to get rid of water vapor and
carbon dioxide. The OMNIC software, available at the
laboratory workstation, was used to record the ATRFTIR
spectra. The OriginPro program (ver. 9.0) was used to
analyze the spectra and to process the diagrams. Second-
order derivatives were calculated to determine the precise
positions of the vibration bands. Similarly as in the pre-
vious papers [23, 24], difference spectra and the main
spectral parameters were measured. In order to make the
difference spectra clearer, they were smoothed with a
37-point Fourier transform algorithm, using the OriginPro
software.
4 Test Results and Discussion
Preliminary rheological tests showed that critical defor-
mation cc of the investigated lithium grease sample
amounted to 0.103 % at phase angle tan d = 0.0518. Thus,
in the first and third intervals of 3ITT, the grease would be
sheared oscillatorily in the linear viscoelastic range at
constant deformation amplitude c = 0.090 %, oscillation
frequency f = 1 Hz, and a time of, respectively, 100 s and
24 h (Fig. 1a). In this way, it was possible to study the
kinetics of the regeneration of the grease microstructure
without destroying the latter. The second interval lasted
1 h, and the grease would be sheared in steady conditions
at shear rate c_ = 8.1 s-1 (Fig. 2).
In the third interval, the microstructure of the lithium
grease would regenerate very slowly. In the course of the
24-h relaxation of the grease, storage modulus G0 would
increase all the time, while loss modulus G00 would slowly
decrease. The highest regeneration kinetics were observed
Tribol Lett (2014) 56:107117
Fig. 2 Destruction of thickener microstructure at shear rate
c_ = 8.1 s-1 in second (load) interval of thixotropic test
during the first hour of grease relaxation (Fig. 1b). Sub-
sequently, the changes in storage modulus G0 were slight.
Then the degree of microstructure regeneration in the
60th minute and after the 24-h relaxation of the grease was
assessed. For this purpose, the following relation was used:
G02  G01
DR  100%;
G00  G01
where G00 an average storage modulus for the first inter-
val of 3ITT, G01 the initial value of the storage modulus
for the third interval of 3ITT (for shearing stress
s [ 0.1 Pa), G02 the end value of the storage modulus for
the third interval of 3ITT.
Fig. 3 Changes in storage modulus G0 (a) and phase angle tan d (b) versus frequency of deformation of lithium grease at particular stages of its
resolidification
111
It emerges from the 3ITT oscillation studies that in the
60th minute of relaxation 24.05 % (G0 = 12,445.83) of the
microstructure of the lithium grease would regenerate. After
the 24-h relaxation, the degree of microstructure regenera-
tion would amount to 34.92 % (G0 = 15,763.37), which
means an increase by 11.87 %. The tested grease was char-
acterized by a strong coagulation structure during stress
relaxation, which showed high mechanical stability in the
elastic range at an oscillation frequency of 0.1100 rad s-1
and deformation amplitude c = 0.090 % (Fig. 3). The
changes in the values of storage modulus G0 and loss mod-
ulus G00 as a function of oscillation frequency in the 3rd, 6th,
12th, and 24th hour of grease relaxation were slight. How-
ever, one can discern a distinct shift in curves as a function of
grease resolidification time. The mechanical stability of the
microstructure was clearly increasing during this time.
Knowing the values of critical deformation amplitude
cc and storage modulus G0LVR in the critical point at the
particular stages of the 24-h resolidification of the grease,
changes in the latters cohesive energy Ecoh (J m-3) were
calculated. Cohesive energy density is used in the quan-
titative assessment of the degree and force of aggregation
of dispersed phase particles in a heterogeneous system. It
is a measure of the totality of the physicochemical
interactions between the particles. The higher the value of
cohesive energy density, the more flocculated the micro-
1 structure [25]. Cohesion energy density is interrelated to
stress in grease through the following relation proposed
by Tadros [26]:
Zcc
Ecoh rc  dc; 2
0
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Fig. 4 Changes in cohesion energy density Ecoh of lithium grease
after shearing at shear rate c_ = 8.1 s-1 versus grease resolidification
time (p = 0.05)
substituting rc = cc G0LVR into Eq. (2) one gets
Zcc
1 functional groups of the molecules contained in the grease
Ecoh cc  G0LVR dc c2c  G0LVR :
2 (Table 2). The second derivative of the original spectrum
0
The above relation is simplified for the case when
G0  G00 .
Figure 4 shows changes in the maximum cohesion
energy of the tested grease as a function of its resolidifi-
cation time for constant oscillation frequency f = 1 Hz.
The tests showed that cohesion energy density continu-
ously increased during the 24-h-long resolidification of the
grease. At the beginning of thickener microstructure,
regeneration energy density amounted to 47.55 J m-3. In
the course of the 24 h of grease resolidification, this value
Fig. 5 FTIRATR spectrum of lithium grease containing floccules of lithium 12-hydroxystearate at temperature of 28 C (a) and its second
derivative (b) in ranges: 3,2002,600 and 1,800700 cm-1
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Tribol Lett (2014) 56:107117
increased by 31.18 J m-3 and ultimately amounted to
78.73 J m-3.
This most probably means that the degree of thickener
microstructure aggregation increased with grease stress
relaxation time. As a result of the migration and combi-
nation of the molecular associates, the lithium thickener
would become increasing cross-linked. When determining
the successive points of the curve, each time (after shearing
and a proper grease resolidification time) a new grease
sample would be placed in the rheometer head. Each of the
measuring points lasted 60 min and was not included in the
total grease resolidification time. The tests would be
repeated five times in each of the seven points.
Structural studies using FTIRATR spectroscopy con-
sisted in the analysis of the changes in absorption in the
grease samples before and immediately after shearing and in
the course of the 24-h relaxation of the grease. All the
measurements were performed at a temperature of 28 C
ensured by the ATR heated diamond top-plate. In the spec-
trum of the lithium grease containing 12-hydroxystearate
floccules (Fig. 5), one can distinguish several bands in the
middle infrared range. At the beginning of the spectral ana-
lysis, the bands in the FTIRATR spectrum of the lithium
grease were assigned to the particular vibrations of the
3
was used for this purpose. The minima in the second deriv-
ative indicate that absorption bands were most probably
present in the original spectrum. First of all, the FTIRATR
spectrum showed very strong absorbance mainly in the range
of 2,7503,050 cm-1. This range is characteristic of the
asymmetrical and symmetrical vibrations of hydrophobic
groups, i.e., methyl and methylene groups (CH3 and CH2)
originating from lithium 12-hydroxystearate molecules. The
CH3 groups absorbed infrared radiation at 2,952 and
2,871 cm-1, while the CH2 groups showed vibration
activity at 2,919 and 2,851 cm-1 [27].
Tribol Lett (2014) 56:107117 113

Table 2 Positions in (cm-1) and proposed assignment of vibrations In the second range (below 1,800 cm-1), the so-called
to lithium grease bands at temperature of 28 C in spectral range of dactyloscopic (fingerprint) range, bands originating from
3,700700 cm-1
the stretching vibrations of the polar groups, i.e., carbonyl
m (cm-1) Vibration assignmenta groups C=O, and from the bending vibrations of the
hydrophobic groups (CH3 and CH2) are mainly observed,
3,677 mas(OH) hydrogen bonding
which is consistent with the literature [28]. At a wave-
3,652 mas(OH) hydrogen bonding
number of 1,740 cm-1, a band possibly originating from
2,952 mas(CH3)
the vibrations of the hydrogen-bonded C=O groups
2,919 mas(CH2)
appeared [29]. Below 1,600 cm-1, two bands in the form
2,871 sh ms(CH3)
of a doublet were observed at wavenumbers: 1,579 and
2,851 mas(CH2)
1,560 cm-1. The bands correspond to the asymmetrical
1,740 mas(C=O) hydrogen bonding
vibrations of the COO- carbonyl group of the stearate
1,579, 1,560 db mas(COO-)
thickener [30, 31]. In turn, the symmetrical mode of the
1,456 ms(COO-) ? bs(CH2)
carbonyl group.
1,376 bs(CH3)n COO- is located at a wavenumber of 1,456 cm-1.
721 q(CH2)n Simultaneously, this band overlaps with the absorption of
a
vibrations: m, stretching; b, in plane bending; c, out-of-plane CH2 group of the hydrocarbon chain. Base oil components
bending; q, in plane bending (rocking); s, symmetrical; as, asym- are also found at a wavenumber 1,376 cm-1. In this region,
metrical; sh, shoulder; db, doublet

Fig. 6 a FTIRATR spectra of lithium grease during 1-h relaxation spectrum at temperature of 28 C. Arrows indicate direction of
at temperature of 28 C in spectral range of 7003,700 cm-1. change. For sake of clarity, spectra have been shifted on scale
b ATRFTIR difference spectra measured relative to first grease

123
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Fig. 7 Absorbance dependences for particular vibration bands of lithium grease functional groups during relaxation (presented values are
averages from three measurements)
one can expect vibrations of the CH hydrophobic groups
originating from the CH3 groups of the hydrocarbon chain
as the base oil component. Scissoring vibrations of the
CH2 groups in the main oil chain, the (CH2)n mode, are
characteristic of the band at a wavenumber of 721 cm-1
[32].
Figure 6a shows exemplary FTIRATR spectra of
grease as a function of relaxation, and next to them
(Fig. 6b) the difference spectra relative to the first spectrum
in order to better illustrate the changes in the lithium grease
123
Tribol Lett (2014) 56:107117
structure. The analysis focused on the spectral parameters
of the bands originating from the vibrations of the fol-
lowing groups: CH2, CH3, and C=O, which under the
applied shearing forces and during the relaxation process
underwent the largest modification. As the relaxation pro-
cess proceeded, a marked decrease in the absorbance
originating from the vibration of mas(CH3) positioned at a
wavenumber of 2,952 cm-1 was observed (Fig. 7). At the
same time, the absorbance of the vibration band for the
CH3 groups at 1,376 cm-1 decreases. The changes have
Tribol Lett (2014) 56:107117
an exponential character for up to 4 h of the relaxation
process. Then they evidently stabilize. In the same time
interval (up to 4 h), the intensity of the vibration of the
OH groups in a range of 3,6803,560 cm-1 increases.
Probably, the number of intermolecular hydrogen bonds
with the OH groups increases during the relaxation of the
grease. The longer the relaxation time, the more bands
there are in this region and the better the regeneration of
the grease structure. The hydrophobic interactions con-
tribute to the formation of new spatial thickener structures,
as evidenced by the accompanying changes in the spectral
parameters of the nonpolar CH3 and CH2 groups.
The observed processes are accompanied by a drop in
the absorbance characteristic for the C=O group vibrations
at 1,740 cm-1. This suggests a reduction in the number of
the C=O groups interacting with the OH groups. Conse-
quently, the OH groups are liberated as a result of shear
stress and can interact with the other fragments of the chain
of lithium 12-hydroxystearate molecules. This leads to
structural changes in the grease. Additionally, the mode of
the COO- carbonyl stretching modes is found as a band at
1,456, 1,579 cm-1 and as a shoulder at 1,560 cm-1
(Fig. 7). These vibrations of the stearate thickener increa-
ses during relaxation. This is probably due to a decline in
the interactions between the carbonyl groups and hydrogen
atoms. As a result, the freedom of the vibrations of the
COO- groups increases. In the range below 1,800 cm-1,
there are also the vibrations of the CH2 groups originating
from the base oil. The band absorbance at 721 cm-1 does
not change in the course of relaxation. The absence of any
modification indicates that the oil chain most inner CH2
groups probably do not change their structure during the
return to equilibrium. It is commonly known that about
30 % of the oil is bound by the molecular attraction forces
acting between the thickener and the oil components.
These are strong bonds. While 70 % of the oil is bound by
the capillary forces and closed in the free spaces of the
thickener network. These are weak bonds. Perhaps the
absorbance of the 721 cm-1 band relates to the 30 % part
of the oil, which is most strongly bound with the thickener,
whereby the absorbance of the CH2 groups does not
change. The absence of any modification indicates that the
chain does not change its structure during the return to
equilibrium. Only the ends of the chains and the interac-
tions between them undergo alterations.
In summary of spectral analysis, modifications in the
vibration bands of the carbonyl groups, C=O (decrease in
absorbance at 1,740 cm-1), and COO- (increase in
absorbance at 1,456, 1,579 and 1,560 cm-1), probably are
related to a change of flocculate chain structure of lithium
12-hydroxystearate and a reduction in the number of
hydrogen bonds between the carbonyl groups and the OH.
Therefore, the intensity of the band at 1,740 cm-1
115
decreases (this band is responsible for vibrations of
hydrogen-bonded C=O groups [29]), and freedom for
vibration derived from COO- group increases during first
hours of relaxation. It is suggested that these modifications
show the breakup of hydrogen bonds formed as a result of
shearing during the early process of the formation of small
aggregates [2]. At the same time, increasing the intensity of
the vibration of OH groups in the range of
3,6803,560 cm-1 indicates the fact that the free OH
group may interact with other fragments of the molecular
chain of lithium 12-hydroxystearate. Then, the amount of
intermolecular hydrogen bonds increases, what can influ-
ence the formation of new spatial thickener structures and
partial reconstruction of the microstructure during the
relaxation process. As a consequence, due to the hydro-
carbon chain, association, absorbance observed in the
range of 3,0002,800 cm-1 decreases. In this region, there
are vibrations of the hydrophobic groups (CH2, CH3)
derived from molecules of lithium 12-hydroxystearate. The
spectral analysis shows that the relaxation time of lithium
grease reconstruction occurs probably partly due to the
thickener microstructure shear force decay. According to
the authors, the structure of the lithium 12-hydroxystearate
evidently changes during relaxation process, and grease
microstructure is probably partly recovered.
5 Conclusions
The tests have shown that mineral oil-based greases
thickened with lithium 12-hydroxystearate exhibit strong
thixotropic properties. As the grease is being sheared, the
cross-linked microstructure of the thickener is destroyed.
During the relaxation of stresses in the grease, the molec-
ular associates try to return to the initial state of equilib-
rium, causing an increase in the structural viscosity of the
grease. This has been confirmed by the analysis of the
rheological and spectral parameters. The tests indicate that
the two measuring methods, i.e., rheometry and vibrational
spectroscopy, perfectly complement each other in the
assessment of the physical and chemical changes taking
place in the microstructure of lithium grease during its
relaxation after shearing.
The rheological three-interval thixotropic tests in the
linear viscoelastic range have shown that as the grease
resolidified, storage modulus G0 increased, while loss
modulus G00 decreased. The largest changes in the thick-
ener microstructure were observed in the first hour of the
relaxation of stresses in the grease. In this time interval,
about 24 % of the microstructure regenerated. After 24 h,
the degree of microstructure regeneration amounted to
nearly 35 %. The largest changes in the grease in the first
hour after its resolidification were corroborated by the tests
123
116
of the mechanical stability of the thickener network at a
variable oscillation frequency and by the cohesive energy
tests. The grease cohesive energy density in the course of
24-h stress relaxation increased by over 30 J m-3 relative
to that for the grease immediately after shearing.
The analysis of the results yielded by Attenuated Total
Reflectance Fourier Transform Infrared spectroscopy
showed that the components of the grease had undergone
conformational changes. The largest changes in relative
absorbance in the microstructure were observed for the
bands originating from the asymmetrical vibrations of the
COO- carbonyl group of the stearate thickener and from
the vibrations of the hydrophobic CH groups of the base
oil: 8 and 14 %, respectively. After the 24-h relaxation, the
absorbance amounted to, respectively, 19 and 23 %.
Smaller changes (in the order of a few per cent) were
observed for the methyl and methylene groups character-
istic for lithium 12-hydroxystearate molecules. This con-
firms the observation that hydrophobic interactions take
part in the formation of new spatial structures of the
thickener. Not all of the spectral parameters underwent
changes. The vibration band for the CH2 groups (the oil
chain most inner groups) at 721 cm-1 remained unchan-
ged. This proves that they did not undergo any structural
modification during the return to equilibrium. The shearing
process does not affect the strong bonds in the oil, pro-
duced by the forces of intermolecular attraction between
the thickener and the oil components. Only the ends of the
chains and the weak interactions between them undergo
modifications.
Acknowledgments Some results of this research were presented at
the 5th World Tribology Congress, Torino, Italy, September 813,
2013. The research was funded by the Institute of Machine Design
and Operation and the Institute of Biomedical Engineering and
Instrumentation, at Wroclaw University of Technology. Wroclaw,
Poland. The Golden Gate Mk II ATR Accessory with Heated Dia-
mond Top-plate (USA), purchased with funds provided as part of the
grant Equipment for the Community Biooptics Laboratory in the
Institute of Biomedical Engineering and Instrumentation at Wroclaw
University of Technology No. 6180/IA/119/2012 by the Ministry of
Science and Higher Education, was used in the studies. The authors
would like to give their heartfelt thanks to Prof. Magorzata Komo-
rowska from the Institute of Biomedical Engineering and Instru-
mentation at Wroclaw University of Technology for the fruitful
discussion and Dr. Anna Zajezierska from the Oil and Gas Institute in
Cracow for preparing the grease sample for the tests.
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