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cn

Tribol Lett (2010) 40:149154

DOI 10.1007/s11249-010-9650-0

ORIGINAL PAPER

Synthesis, Characterization, and Tribological Behavior

of Neopentyl Polyol Ester-Based and Mixed Oil-Based
Titanium Complex Grease
Jiguo Chen

Received: 26 September 2009 / Accepted: 22 June 2010 / Published online: 6 July 2010
Springer Science+Business Media, LLC 2010

Abstract Four types of titanium complex grease were

synthesized using a 3-l reaction vessel, and their friction
and wear behavior were evaluated using a four-ball tester
in the presence of two base oils: neopentyl polyol ester and
a mixture oil of neopentyl polyol ester, 650SN, and
epoxidized soy bean oil (4.5:2.5:1), with two compositions:
benzoic acid/stearic acid and sebacic acid/stearic acid. The
results indicate that mixed oil-based titanium complex
grease has excellent tribological properties. Moreover,
compositions affect the physical characteristics of titanium
complex grease but have little effect on the frictionreduction, antiwear, and load-carrying capability of the
same types of oil-based titanium complex grease. In
addition, base oils also affect the tribological property of
titanium complex grease. Based on scanning electron
microscopy and x-ray photoelectron spectrometer of the
worn surfaces of steel balls lubricated with the different
types of grease, synergistic boundary lubrication was proposed to illustrate the friction-reduction and antiwear
properties of titanium complex grease.
Keywords Titanium complex grease
Friction and wear

Load-carrying capacity
Scanning electron microscope
(SEM)
X-ray photoelectron spectroscope (XPS)

additives on lubricating grease have been conducted in the

past few years. However, these studies are generally limited to lithium grease, calcium grease, aluminum grease,
and other types of grease [110].
As one of the most used type of lubricating grease,
titanium complex grease is a high-performance grease with
a high drop point, oxidation resistance, extreme pressure
property, antiwear property, long life, and excellent physicalchemical properties at elevated temperatures [11],
making it suitable for the various tribological applications
of steel plants, power plants, packaging, and fertilizer
industries [12]. Kumar et al. [13, 14] report that the wear
scar diameters of rapeseed oil, diisodecyl adipate, diisooctyl azelate, and polyol ester-based titanium complex
grease are 0.6, 1.0, 0.85, and 0.7 mm, respectively,
whereas the friction coefficients are not mentioned. In
addition, little data are currently available on the tribological behavior and lubricating mechanism of the titanium
complex grease of different components.
Thus, the tribological behavior and lubricating mechanism of four types of titanium complex grease were investigated in detail, and their physical characteristics were also
characterized in this study. The results can provide guidance
to the tribological application of the titanium complex grease
of different components in industrial application.

1 Introduction
2 Experimental Details
A number of studies on thermorheological behavior, tribological performance, application, and effects of different

2.1 Synthesis of Titanium Complex Grease

J. Chen (&)
School of Mechatronics Engineering, Harbin Institute of
Technology, Harbin 150001, Peoples Republic of China
e-mail: ch781001@yahoo.com.cn

All materials and additives used in this article were commercial products and were used without further purification; all reagents used in the synthesis were of analytical
grade. The base oils used in the experiments were mixed

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oil and neopentyl polyol ester with a viscosity of

150 mm2 s-1 at 40 C and a flash point [250 C. The
mixed oil was composed of neopentyl polyol ester, 650SN
with kinematic viscosity of 120135 mm2 s-1 at 40 C and
a flash point [255 C, and epoxidized soy bean oil
(4.5:2.5:1, absolute weight) with a flash point [255 C,
iodine values of 60.0 mg I2 g-1, and acid value \0.35. 2,
6-di-tertiary butyl paracresol (BHT) was used as antioxidant of the different types of lubricating grease.
The process was performed in a 3-l reaction vessel using
a mechanical stirrer. The synthetic details and procedure
are as follows: Stearic acid, benzoic acid or sebacic acid,
titanium (IV) isopropoxide (1:1:1 equivalent ratio), and
base oil were mixed at 80 C. Once the saponification
reaction was completed, the mixture was slowly heated to
200210 C after adding water. Afterward, 3060 wt% of
the total base oil was added into the mixture to help it cool
down, as well as 1 wt% BHT. The mixture was then
allowed to cool to ambient temperature and homogenize by
a three-roller mill. The whole synthetic process occurred
over a period of 8 h on the average. Therefore, the resulting
grease consisted of 17 wt% titanium complex soap, 1 wt%
antioxidant, and 82 wt% base oil.
2.2 Characterization
The dropping point and penetration of the different types of
titanium complex grease were measured according to
national standards GB/T 3498 (similar to ASTM D2265)
and GB/T 269 (similar to ASTM D217), respectively. The
average values of at least three times tests were reported.
Meanwhile, tribological properties were examined at
ambient temperature on an SQ-III four-ball tester (Xiamen,
China). The friction and wear tests were conducted at a
rotating speed of 1450 rpm and loads of 200, 300, 400, and
500 N for 60 min. The maximum non-seizure loads were
evaluated. The PB values were recorded at room temperature for 10 s. The balls tested were made of GCr15 bearing
steel (AISI 52100) with an HRC 5961. The wear scar
diameters on the steel balls were measured using an optical
microscope to a resolution of 0.005 mm. The friction
coefficients were measured and recorded with a strain
gauge equipped with a four-ball tester. For comparison, the
tribological properties and physical characteristics of
650SN-based and mixture-based (the mixture of 650SN
and neopentyl polyol ester, 1:1.8, absolute weight) titanium
complex grease were also investigated.
The morphologies of the wear scars were observed by an
S-570 scanning electron microscope (SEM, Hitachi, Japan).
The chemical states of the elements on the wear scars were
determined using a PHI-5700 multifunctional x-ray photoelectron spectroscope (XPS) to explore the possible tribochemical changes involved in the tribological process. The

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Tribol Lett (2010) 40:149154

XPS analysis regions were about 2 nm to 0.8 mm, and the

exciting source was Mg Ka radiation. The binding energies
of the target elements were determined at a pass energy of
29.35 eV with a resolution of 0.3 eV, and the binding
energy of carbon (C1s: 284.6 eV) was used as reference.
Before each test, all specimens were cleaned using ultrasonic
bath in petroleum ether and dried at room temperature.

3 Results and Discussion

3.1 Physical Characteristics of Titanium Complex
Grease
The results of the dropping point and penetration of the
different types of titanium complex grease show that neopentyl polyol ester-based titanium complex grease has a
No. 4 (NLGI grade) consistency; the corresponding dropping point of benzoic acid/stearic acid titanium complex
grease is 144 C, and that of sebacic acid/stearic acid
titanium complex grease is 154 C. However, 650SNbased, mixture-based (the mixture of 650SN and neopentyl
polyol ester, 1:1.8), and mixed oil-based (the mixture of
neopentyl polyol ester, 650SN and epoxidized soy bean oil,
4.5:2.5:1) titanium complex grease has a No. 2 (NLGI
grade) consistency, while the dropping point of mixturebased (the mixture of 650SN and neopentyl polyol ester,
1:1.8) sebacic acid/stearic acid titanium complex grease is
277 C, but that of 650SN-based benzoic acid/stearic acid
titanium complex grease is 268 C. Moreover, the dropping point of mixed oil-based (the mixture of neopentyl
polyol ester, 650SN and epoxidized soy bean oil, 4.5:2.5:1)
benzoic acid/stearic acid titanium complex grease is
266 C, while that of mixed oil-based (4.5:2.5:1) sebacic
acid/stearic acid titanium complex grease is 280 C.
Therefore, when the consistency concentration is 17%, the
synthetic capability of neopentyl polyol ester-based titanium complex grease is better than that of other types of
oil-based titanium complex grease, and the reactive degree
of benzoic acid/stearic acid and sebacic acid/stearic acid
titanium complex grease is above 80%. Furthermore, the
results also show the dropping point of sebacic acid/stearic
acid titanium complex grease is higher than that of benzoic
acid/stearic acid titanium complex grease, i.e., compositions affect the dropping point of different types of titanium
complex grease.
3.2 Tribological Behavior
Figure 1 shows friction coefficient as a function of test
duration lubricated by different types of titanium complex
grease at 400 N for 60 min. The friction coefficient of
650SN-based titanium complex grease is much lower than


Tribol Lett (2010) 40:149154

Fig. 1 Friction coefficient as a function of test duration lubricated by

different types of titanium complex grease at 400 N for 60 min

that of other types of oil-based titanium complex grease,

and this becomes slightly different with an increase in time.
In addition, with the exception of 650SN-based titanium
complex grease, the friction coefficients of other types of
oil-based titanium complex grease are basically similar.
The mean friction coefficient in 60 min is shown in Fig. 2.
The friction coefficients of benzoic acid/stearic acid and
sebacic acid/stearic acid titanium complex grease have
minor differences, indicating that compositions have little
effect on the friction coefficients of the same types of oilbased titanium complex grease.
Figure 3 shows the wear scar diameter lubricated by
different types of titanium complex grease at 400 N for
60 min. Indeed, the wear scar diameters lubricated by
mixed oil-based (4.5:2.5:1) titanium complex grease are
2225% lower than those lubricated by neopentyl polyol
ester-based titanium complex grease. At the same time, the
wear scar diameter lubricated by mixed oil-based

Fig. 2 Mean friction coefficient lubricated by different types of

titanium complex grease at 400 N for 60 min

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Fig. 3 Mean wear scar diameter lubricated by different types of

titanium complex grease at 400 N for 60 min

(4.5:2.5:1) benzoic acid/stearic acid titanium complex

grease is reduced by 31.5% as compared to that of 650SNbased benzoic acid/stearic acid titanium complex grease,
and the wear scar diameter lubricated by mixed oil-based
(4.5:2.5:1) sebacic acid/stearic acid titanium complex
grease is reduced by 11.2% as compared to that of mixturebased (the mixture of 650SN and neopentyl polyol ester,
1:1.8) sebacic acid/stearic acid titanium complex grease.
These prove that 12.5 wt% epoxidized soy bean oil is
important in the antiwear property of mixed oil-based
(4.5:2.5:1) titanium complex grease. These wear scar
diameters results are consistent with those of Kumar et al.
[11, 14]. In addition, the minor differences of these results
indicate that compositions have little effect on the antiwear
capacity of the same types of oil-based titanium complex
grease.
Figure 4 shows friction coefficient and wear scar
diameter as a function of applied load lubricated by different types of titanium complex grease. The friction
coefficient and wear scar diameter of the different types of
titanium complex grease varied in a similar manner with
increasing load and had minor differences, indicating that
friction systems can be lubricated effectively even up to
loads of 200500 N. The minor differences in these results
also indicate that compositions have little effect on the
antiwear and friction-reduction capacity of the same types
of oil-based titanium complex grease at 400 N.
Table 1 gives the load-carrying capacity lubricated by
different types of oil-based titanium complex grease. The
results show that the PB values of mixed oil-based
(4.5:2.5:1) titanium complex grease are equal to 1100 N.
These values are higher than those of other types of oilbased titanium complex grease, indicating a 37.5%
increase. This is because 12.5 wt% epoxidized soy bean oil
provides a high load-carrying capacity under boundary

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Tribol Lett (2010) 40:149154

Fig. 4 Friction coefficient and

wear scar diameter as a function
of applied load lubricated by
different types of titanium
complex grease: a Friction
coefficient, b Wear scar
diameter. BS benzoic acid/
stearic acid, SS sebacic acid/
stearic acid, NPE neopentyl
polyol ester, MBO mixed base
oil, SN 650SN

Table 1 Load-carrying capacity lubricated by different types of oil-based titanium complex grease
Benzoic acid/stearic acid

PB(N)

Sebacic acid/stearic acid

650SN

Neopentyl polyol ester

Mixed oil (4.5:2.5:1)

650SN and NPE (1:1.8)

Neopentyl polyol ester

Mixed oil (4.5:2.5:1)

800

800

1100

800

800

1100

lubrication. At the same time, the results also show that

compositions have no effect on the load-carrying capacity
of the same types of oil-based titanium complex grease.
3.3 Surface Analysis
In order to understand the lubrication mechanism of different types of titanium complex grease, the morphologies
and spectra of typical elements on wear scar are investigated by SEM and XPS. Figure 5 shows the SEM morphologies of the wear scar of steel balls lubricated with
different types of titanium complex grease at 400 N for
60 min. The worn surface of the steel ball lubricated by
different types of oil-based titanium complex grease is
characterized by slightly adhesion wear (Fig. 5a, c, e, g),
while that lubricated by mixed oil-based (4.5:2.5:1) titanium complex grease is smooth and shows signs of fine
scratch (Fig. 5eh). Moreover, the wear scar diameters
lubricated by mixed oil-based (4.5:2.5:1) titanium complex
grease (Fig. 5e, g) are smaller than those lubricated by
neopentyl polyol ester-based titanium complex grease
(Fig. 5a, c). Those results agree with the above-mentioned
wear scar diameters (Fig. 3).
Figure 6 shows the XPS spectra of typical elements on
the wear scar of steel balls lubricated by different types of
titanium complex grease at 400 N for 60 min [5, 15]. The
corresponding relative atomic concentrations on the wear
scar are shown in Table 2. The C1s relative atomic concentration (Table 2) shows a decreased tendency after
sputtering for C=O, which can be ascribed to the adsorbed
titanium complex grease, and this can be confirmed by the
detailed scan of the C1s region at a peak of approximately
286.2 eV (Fig. 6a). The binding energy of approximately

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399.9 eV (Fig. 6c) is attributed to the N of the contaminated source. There is an indication of above 1.5% N1s on
) lubricated by neopentyl polyol
the worn surfaces (5060 A
ester-based titanium complex grease after 2 min sputtering,
while the relative atomic concentration of N is 0% under
the lubrication of mixed oil-based (4.5:2.5:1) titanium
complex grease. In this case, a relatively high wear scar
diameter under the lubrication of neopentyl polyol esterbased titanium complex grease can be partly ascribed to the
contamination in the tribo-layer. However, different antiwear performances are observed, which can mainly be
attributed to the different base oils. In addition, peaks at
709.5, 710.9, and 711.4 eV (Fig. 6b) in the Fe2p region are
attributed to FeO, Fe2O3, and FeOOH, respectively, and the
relative atomic concentration of Fe increases after sputtering. This indicates that a lubrication film containing the
different types of titanium complex grease is formed,
which can effectively reduce the friction coefficient. The
Ti2p at a binding energy of 458.7 eV corresponds to titanium dioxide (Fig. 6e, f). At the same time, an increased
tendency of the relative atomic concentration can be found
for Ti2p after sputtering. Titanium chemical sediment is
also argued to be present during the tribological process,
and titanium dioxide on the worn surface can result in
better antiwear performance. Moreover, the O1s at binding
energies of 529.9 and 530.4 eV (Fig. 6d) corresponds to
TiO2 and Fe2O3, respectively.
Based on the above analysis, we found that a lubrication
film is formed during the friction process under the lubrication of titanium complex grease. The lubricant layer
consists of absorbed organic materials coming from the
titanium complex grease itself. In addition, the atomic
concentration of Ti is increased after sputtering. This might


Tribol Lett (2010) 40:149154

Fig. 5 SEM morphologies of the wear scar of steel balls lubricated

with different types of titanium complex grease at 400 N for 60 min:
a Benzoic acid/stearic acid (neopentyl polyol ester-based oil 9100),
b Benzoic acid/stearic acid (neopentyl polyol ester-based oil 9500),
c Sebacic acid/stearic acid (neopentyl polyol ester-based oil 9100),

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d Sebacic acid/stearic acid (neopentyl polyol ester-based oil 9500),

e Benzoic acid/stearic acid (mixed base oil 9100), f Benzoic acid/
stearic acid (mixed base oil 9500), g Sebacic acid/stearic acid (mixed
base oil 9100), and h Sebacic acid/stearic acid (mixed base
oil 9500)

Fig. 6 XPS spectra of the typical elements on the wear scar of steel balls lubricated by different types of titanium complex grease at 400 N for
60 min: a C1s, b Fe2p, c N1s, d O1s, e Ti2p, and f Ti2p. BS benzoic acid/stearic acid, SS sebacic acid/stearic acid

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Table 2 Relative atomic concentration on wear scar

Composition

Benzoic acid/stearic acid

Based oil

Neopentyl polyol ester

Mixed oil (4.5:2.5:1)

Sebacic acid/stearic acid

Neopentyl polyol ester

Mixed oil (4.5:2.5:1)

Sputter times t(s)

C1s

O1s

61.61

30.97

1.59

4.32

1.51

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28.33

47.05

10.41

12.48

1.73

81.21

14.82

1.37

0.67

1.92

120

66.45

23.41

8.35

1.79

0.00

72.66

21.28

1.54

2.56

1.96

120

47.23

36.66

6.41

8.14

1.55

69.27

25.22

1.95

2.28

1.28

120

28.65

50.51

12.20

8.64

0.00

indicate that the tribochemcial reaction of titanium oxide

occurs on the worn steel surface at tribological conditions
to form TiO2, which can deposit on the rubbing surface
firmly and enhance the antiwear capability of titanium
complex grease.

4 Conclusions
From the above experimental results, we draw the following conclusions:
(a)

The antiwear property and load-carrying capability of

mixed oil-based (4.5:2.5:1) titanium complex grease
are better than those of neopentyl polyol ester-based
titanium complex grease. Furthermore, compositions
affect the physical characteristics of titanium complex
grease, but have little effect on tribological properties
of the same types of oil-based titanium complex
grease. In addition, different base oils have an impact
on the friction-reduction and antiwear properties of
titanium complex grease.
(b) XPS analyses indicate that a tribochemical titanium
sediment is formed, and lubrication films are thick
under the lubrication of mixed oil-based titanium
complex grease. The synergistic boundary lubrication
film contributes to the significantly improved tribological performance of mixed oil-based titanium
complex grease.
Acknowledgments The author thanks Professor Jianjun Qu of the
School of Mechatronics Engineering, and Harbin Institute of Technology for supplying the four-ball tester.

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