See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/257670756

High Pressure Rheology of Environmentally Friendly Vegetable Oils

Article in Tribology Letters · August 2013

DOI: 10.1007/s11249-013-0180-4

CITATIONS READS

17 4,519

5 authors, including:

Sobahan Mia Nobuyoshi Ohno

Khulna University of Engineering and Technology Saga University
47 PUBLICATIONS 215 CITATIONS 141 PUBLICATIONS 757 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Finite Element Analysis of Hybrid Composite Material View project

Jute Fiber Reinforced Epoxy Composites and Hybrid Composites View project

All content following this page was uploaded by Nobuyoshi Ohno on 06 May 2015.

The user has requested enhancement of the downloaded file.

Tribol Lett (2013) 51:273–280
DOI 10.1007/s11249-013-0180-4
ORIGINAL PAPER
High Pressure Rheology of Environmentally Friendly
Vegetable Oils
Toshifumi Mawatari • Ryusei Fukuda •
Hirohito Mori • Sobahan Mia • Nobuyoshi Ohno
Received: 30 October 2012 / Accepted: 26 June 2013 / Published online: 16 July 2013
Ó Springer Science+Business Media New York 2013
Abstract Environment-friendly lubricant is the key
demand in twenty-first century for the issue of global climate
change. Vegetable oils as base oil for lubricants and biodiesel
fuel are environmentally preferable to petroleum. They are
usually excellent boundary lubricants, but their high-pres-
sure behavior is not investigated yet properly. In this
research, first solidification characteristics of rapeseed oil,
soybean oil, sunflower oil, palm oil, coconut oil, olive oil,
camellia oil, mustard oil, castor oil, rapeseed methylester,
and soybean methylester were investigated. Next, a very
useful viscosity–pressure–temperature relation on the basis
of phase diagram was derived for the nine vegetable oil.
Keywords Vegetable oil  Phase diagram  Rheology 
Viscosity  BDF
1 Introduction
So far, a number of studies of vegetable oil have been
developed with respect to environment-friendly lubricants
and the raw materials of biofuels [1–4]. The main
T. Mawatari (&)  R. Fukuda  H. Mori  N. Ohno
Department of Mechanical Engineering, Saga University,
1, Honjo, Saga 840-8502, Japan
e-mail: mawatari@me.saga-u.ac.jp
S. Mia
Department of Mechanical Engineering, Khulna University of
Engineering and Technology, Khulna 920300, Bangladesh
component of vegetable oils has glyceride of fatty acids,
and they have a superior to the performance for boundary
lubrication. However, the limitations of vegetable oils are
their high cost, and thermal and oxidation instability.
Environment-friendly lubricant and biodiesel fuel (BDF)
are the key demand in twenty-first century for the issue of
global climate change. Vegetable oils as base oil for
lubricants and BDF are environmentally preferable to
petroleum. Vegetable oils have a good elastohydrodynamic
traction property [5, 6], but their high-pressure behavior is
not investigated yet properly. In recent year, the common
rail system (CRS) injecting a diesel fuel by extremely high
pressure attracts the attention from the viewpoint of
environmental [7]. However, when diesel fuel is used at
high pressure, a part of the fuel ingredient precipitates it as
wax, and it becomes the problem that flow properties of
fuel decrease. Based upon visual or direct evidence for
solidification phenomena of a variety of vegetable oils at
the high pressure and low temperatures, the present paper
deals with this problem summarizing the results of high-
pressure rheology of environmental-friendly vegetable oils
[8, 9].
2 Sample Oil
Rapeseed oil, soybean oil, sunflower oil, palm oil, coconut
oil, olive oil camellia oil, mustard oil, and castor oil were
tested. All samples were obtained from commercial sources
and used as supplied without further purification. The list
of tested oils and their physical properties are given in
Table 1, where saturated fatty acid wt% is the total of
lauric acid, myristic acid, palmitic acid, and stearic acid in
vegetable oil triglycerides as shown in Table 2.
123
274 Tribol Lett (2013) 51:273–280

Table 1 Physical properties of

Oil name Density, q (g/cm3) Viscosity, m (mm2/s) Saturated fatty acid
vegetable oils
15 °C 40 °C 100 °C wt%

Rapeseed oil 0.922 35.1 8.03 5.7

Soybean oil 0.925 31.9 7.55 14.1
Sunflower oil 0.925 33.0 7.74 10.4
Palm oil 0.916 60.4 7.62 48.7
Coconut oil 0.926 27.6 5.89 77.0
Olive oil 0.917 38.7 8.28 13.1
Camellia oil 0.919 40.1 8.50 10.3
Mustard oil 0.920 44.1 9.41 5.1
Castor oil 0.965 262 19.8 2.1

Table 2 Composition of vegetable oils [10]

Type Saturated fatty acid Unsaturated fatty acid
Fatty acid name Lauric acid Myristic acid Palmitic acid Stearic acid Oleic acid Ricinoleic acid Linoleic acid Linolenic acid

Carbon number C12 C14 C16 C18 C18:1 C18:1 C18:2 C18:3
Rapeseed oil – – 4.0 1.7 58.6 – 21.8 10.8
Soybean oil – – 10.3 3.8 24.3 – 52.7 7.9
Sunflower seed oil – – 6.7 3.7 19.0 – 69.9 0.7
Palm oil – – 44.2 4.5 39.3 – 9.6 0.3
Coconut oil 47.0 18.0 9.0 3.0 7.0 – 2.0 –
Olive oil – – 9.9 3.2 75.0 – 10.4 0.8
Camellia oil – – 8.2 2.1 85 – 4.1 0.6
Mustard oil – – 3.5 1.6 19.7 – 22.2 13.4
Castor oil – – 1.1 1.0 4.1 87.8 4.8 0.5

3 Experimental Results

3.1 Viscoelastic Solid Transition Temperature (TVE0)

and Wax Crystallization Temperature (Twax0)
at Atmospheric Pressure

The experimental setup for the measurement of the visco-

elastic solid transition temperature at atmospheric pressure
TVE0 is shown in Fig. 1. When a minute air bubble is
trapped in a space between a test fluid and a cover glass
plate, its volume can expand as a result of contraction of
the fluid by cooling. Figure 2a represents the experimental
view of castor oil. The photoelastic effect appears under a
dark polarized field at -58 °C. This temperature is a TVE0
Fig. 1 Apparatus for observation of low-temperature behavior
of castor oil containing a little wax as shown in Tables 1
and 2. Figure 2b represents the experimental view of
rapeseed oil. For the high content of wax in rapeseed oil,
the dark field observed throughout the bubble and liquid oil oil, camellia oil, and mustard oil is shown in Table 3. Palm
due to its occurrence of wax crystallization at -26 °C. This oil with the high content of palmitic acid and stearic acid
temperature is a Twax0 of rapeseed oil. Twax0 of rapeseed triglyceride as shown in Table 2 showed the highest wax
oil, soybean oil, sunflower oil, palm oil, coconut oil, olive crystallization temperature at atmospheric pressure Twax0.

123
Tribol Lett (2013) 51:273–280 275

Fig. 2 Experimental view of

TVE0 and Twax0. a Castor oil
TVE0 = -58 °C. b Rapeseed oil
Twax0 = -26 °C

Table 3 Twax0 and pwax of vegetable oils into the test machine, and pressure was applied in the
Oil name Twax0 pwax (GPa) upper plunger by a hydraulic power unit. The density
corresponding to the pressure was determined by mea-
°C 20 °C 50 °C 100 °C
suring the fluid volume in the machine by using a linear
Rapeseed oil -26 0.33 0.51 0.86 gauge. Isothermal compressibility influence was consid-
Soybean oil -7 0.25 0.50 0.73 ered in the experiment.
Sunflower oil -8 0.31 0.41 0.67 One of the basic equations for the solidification of oils is
Palm oil 37 – – 0.42 the equation of volumetric change that is used in the
Coconut oil 7 – 0.34 0.61 strength of materials. The volumetric strain e is defined as
Olive oil -14 0.25 0.43 0.73 the ratio of the decrease in volume to the original volume
Camellia oil -27 0.32 0.52 1.02 [13]:
   
Mustard oil -26 0.21 0.48 0.71 dV o ln q o ln q
e¼ ¼  dp þ  dT
V  op T oT P
1
¼  dp þ 3ddT ð1Þ
K
3.2 Direct Visual Observation of Wax Crystallization
Under High Pressure (pwax) where V is volume, q is density, p is pressure, T is the
temperature, K is tangent bulk modulus, and d is coefficient
The viscometer of the falling ball type originally of thermal expansion.
designed by Saga University as shown in Fig. 3a was The change in density q against pressure p at 20 °C of
also utilized for direct observation of wax crystallization soybean oil and at 10 °C of castor oil is shown in Fig. 6.
under high pressure less than 0.35 GPa [11]. The exper- Differentiating the pressure–density curve, the tangent bulk
iments more than 0.35 GPa used the diamond anvil cell modulus K = (dlnq/dp)-1 is estimated as shown in Fig. 7.
(DAC) [12] as shown in Fig. 3b. The wax crystallization Due to high contents of wax in soybean oil, abrupt change
of rapeseed oil and soybean oil under high pressure is of bulk modulus was found at high pressure. The bulk
shown in Fig. 4. Experiments are done at oil temperature solidification pressure of soybean oil at 20 °C is 0.62 GPa.
20, 50, and 100 °C, and pressure up to 2 GPa. pwax of The wax crystallization pressure of soybean oil as shown in
rapeseed oil, soybean oil, sunflower oil, palm oil, coconut Table 3 results in lower transition pressure compared with
oil, olive oil, camellia oil, and mustard oil is shown in Fig. 6. This corresponds to initial appearance of solid
Table 3. grains. On the other hand, castor oil containing a little wax
as shown in Tables 1 and 2 changes to the viscoelastic
3.3 Viscoelastic Solid Transition Temperature at High solid from the liquid under high pressure. The viscoelastic
Pressure (pVE) and Tangent Bulk Modulus K solid transition point pVE of castor oil is obvious from the
abrupt change of dK/dp in Fig. 7. For castor oil, the vis-
The high-pressure density measurement of the test fluids coelastic transition point is 0.78 GPa at 10 °C. The vis-
was measured in the high-pressure densitometer shown coelastic transition pressure pVE at each temperature of
in Fig. 5. Two milliliters of the test fluid was poured castor oil is listed in Table 4.

123
276 Tribol Lett (2013) 51:273–280

(a)

Load
Diamond
Fig. 5 High-pressure densitometer

Gascket

0.4 Castor oil 10

h Soybean oil 20
0.3
d
g/cm3

Chamber 0.2

0.1
ln

Load -0.1
(b) 0 0.5 1
p GPa
Fig. 3 Apparatus for observation of high-pressure behavior. a High-
pressure viscometer. b Diamond anvil cell (DAC) Fig. 6 Changes of density with pressure

Fig. 4 Wax crystallization of

vegetable oil under high
pressure. a Rapeseed 20 °C,
0.33 GPa. b Soybean 20 °C,
0.23GPa

123
Tribol Lett (2013) 51:273–280 277

3.4 Phase Diagram of BDF (Bio Diesel Fuel)
In recent year, the common rail system (CRS) injecting a
diesel fuel by extremely high pressure (3rd generation
200 MPa CRS) attracts attention from the viewpoint of
environmental [14]. Therefore, we performed the direct
observation of the solidification under the high pressure.
The BDF used in this study are rapeseed methylester
(RME) and soybean methylester (SME). The physical

Table 6 Twax0 and pwax of BDF

Soybean oil 20 Name Twax0 pwax (GPa)
10 Castor oil 10 viscoelastic solid
transition point
pVE=0.78GPa °C 25 °C 50 °C 100 °C

RME -6 0.26 0.53 0.85

K GPa

5
SME 0 0.18 0.39 0.65

bulk solidification
pwaxb=0.62GPa
0
0 0.5 1 (a) 100
p GPa Liquid

Fig. 7 Relationship between tangent bulk modulus K and pressure 50

p of soybean oil and castor oil
Solid

T,
0
Rapeseed oil
RME
Table 4 Viscoelastic solid transition pressure pVE of castor oil
-50
TVE0 PVE (GPa) 0 0.5 1
p, GPa
Oil name °C -5 °C 10 °C 25 °C
(b) 100
Castor oil -58 0.57 0.78 1.1
Liquid
Solid
50
T,

0
Soybean oil
Table 5 Physical properties of BDF SME
Name Density, q (g/cm3) Viscosity, m (mm2/s)
-50
15 °C 40 °C 100 °C 0 0.5 1
p, GPa
RME 0.885 4.57 1.78
SME 0.886 4.19 1.68 Fig. 9 Phase diagram of BDF (biodiesel fuel). a RME (rapeseed
methlester). b SME (soybean methlester)

Fig. 8 Wax crystallization of

BDF under high pressure.
a RME,20 °C, 0.21GPa.
b SME, 20 °C, 0.17GPa

123
278 Tribol Lett (2013) 51:273–280

Table 7 Pressure-viscosity coefficient a (GPa-1) of vegetable oils oil film thickness of the vegetable oils can be correctly
Type 20 °C 40 °C 60 °C 80 °C
calculated when the pressure viscosity coefficient of these
oils is applied to Hamrock–Dowson equation [17]. In
Rapeseed oil 11.0 9.5 9.2 10.0 Fig. 10, viscosity as a function of the pressure and tem-
Soybean oil 11.2 8.8 8.9 9.7 perature is shown for rapeseed oil, soybean oil, and olive
Sunflower oil 11.9 9.2 9.0 9.7 oil each. A very useful viscosity–pressure–temperature
Palm oil – – 9.9 9.3 correlation was derived by Sorab and Vanarsdale [18].
Coconut oil – 13.6 9.5 10.3 The pressure–temperature relation of the absolute vis-
Olive oil 11.8 10.0 9.7 9.6 cosity g (Pa s) is given by:
Camellia oil 11.4 9.4 9.0 9.7        2
g p T0 p
Mustard oil 13.2 9.2 9.4 9.1 ln ¼ A1  1 þ A2  1 þ A3 1
g0 p0 T p0
Castor oil 14.8 12.4 9.5 8.4  2   
 T0  p T0
þ A4  1 þA5 1 1 ð2Þ
T p0 T

properties of BDF are shown in Table 5. The BDF removes
glycerin from the vegetable oil which becomes the raw
materials to lower the viscosity in ester interchange. The
viscosity of RME and SME of Table 5 is smaller than
rapeseed oil and soybean oil of Table 1.
The wax crystallization of RME and SME under high
pressure is shown in Fig. 8. Experiments are done at oil
temperature 25, 50, and 100 °C, and pressure up to
2 GPa. pwax and Twax0 of RME and SME are shown in
Table 6.
The phase diagram of RME and SME is shown in Fig. 9.
The phase diagram of the rapeseed oil and soybean oil of
raw materials is shown in figure for a comparison. The
phase diagram of BDF shifts to the low-pressure side a
little in comparison with vegetable oil of raw materials.
The design pressure of the third generation CRS is
0.20 GPa, and it is necessary to consider a phase diagram
of BDF enough and to design it.
3.5 Viscosity–Pressure–Temperature Relation
A high-pressure falling body viscometer as shown in
Fig. 3a is used to determine high-pressure viscosity up to
0.35 GPa and at temperature from 20 to 80 °C of vege-
table oils. Barus equation [15] was applied to the test
results of the present high-pressure viscosity test, and
pressure-viscosity coefficients of the vegetable oils were
obtained. Table 7 shows these values. Biresaw and
Bantchev [16] derived the pressure-viscosity coefficients
of ten vegetable oils from the elastohydrodynamic lubri-
cation film thickness. With regard to soybean oil, olive
oil, and castor oil, the values at temperature of 40 °C
calculated by them agree well with those obtained in the
high-pressure viscosity test. Namely, this means that the
where g0 is ambient viscosity at 313 K, p0 is 0.1013 MPa,
and T0 is 313 K.
The results of a regression analysis of the viscosity
data are summarized in Table 8. In Fig. 10, the solid
lines are theoretical curves from Eq. (2), which match
closely with the experimental data. High-pressure vis-
cosity of vegetable oil containing wax can be more
clearly from this equation. But the use of this equation is
limited by the pressure ranges without the wax
crystallization.
The viscosity–pressure–temperature relation of castor
oil without the wax crystallization under high pressure is
shown in Fig. 11. A very useful viscosity–pressure–tem-
perature correlation on the basis of free volume and phase
diagram was derived by the authors [13]. The solid-to-
liquid transition relation of castor oil is shown in Table 4.
The equation related to the temperature and pressure of the
viscoelastic solid temperature TVE is represented in the
following formula:
TVE ¼ TVE0 þ A1 lnð1 þ A2 pÞ ð3Þ
where A1 and A2 are parameters that depend on fluid
properties. The parameters obtained for castor oil are as
follows: TVE0 is 215 K, A1 is 106.2 K, and A2 is 1.18
(GPa)-1. The viscosity–pressure–temperature relationsh is
given below [13]:
B1 ðT  TVE ÞðTVE0 =TVE Þ
log10 g ¼ 7  ð4Þ
B2 þ ðT  TVE ÞðTVE0 =TVE Þ
Results of regression analysis of the viscosity data are
B1 = 11.3 and B2 = 50.9 for castor oil. Figure 11 has
shown the viscosity as a function of pressure and tem-
perature for castor oil. Solid lines are the theoretical
curves by Eq. (4), which match closely with the experi-
mental data.

123
Tribol Lett (2013) 51:273–280 279

Fig. 10 Comparison of 103 10 3

predicted and observed values 2 Rapeseed oil Soybean oil
of high-pressure viscosity of 10 10 2
crystallization crystallization
pwax=0.33GPa
vegetable oils 101 10 1 p wax =0.08GPa p wax=0.25GPa

s
pwax=0.14GPa

,Pa s
100 0 10 0

,Pa
0
-1 -1
10 10
100 20 100 20
40 40
10-2 60 10 -2 60
80 80
10-3 10 -3
0 0.1 0.2 0.3 0.4 0 0.1 0.2 0.3 0.4
p,GPa p,GPa

103 103
2
Sunfower seed oil Palm oil
10
crystallization
102
pwax=0.31GPa
101 pwax=0.12GPa
101
s

,Pa s
crystallization
0 pwax=0.28GPa
100
,Pa

10 0

10-1 10-1
100 20 100
10-2 40
60 10-2 60
80
80
10-3 10-3
0 0.1 0.2 0.3 0.4 0 0.1 0.2 0.3 0.4
p,GPa p,GPa

103 103
Coconut oil Olive oil
102 102
crystallization
pwax=0.08GPa pwax=0.25GPa
101 101

s
,Pa s

crystallization
pwax=0.22GPa
0
100 100

10-1 ,Pa 10-1

20
100 40
100
10-2 60 10-2 40
60
80 80
10-3 10-3
0 0.1 0.2 0.3 0.4 0 0.1 0.2 0.3 0.4
p,GPa p,GPa

103 103
Camellia oil Mustard oil
102 102
crystallization crystallization
pwax=0.32GPa pwax=0.33GPa
101 pwax=0.12GPa 101 pwax=0.07GPa
s
,Pa s

pwax=0.21GPa
100 0
,Pa

100 0

10-1 10-1
20 20
100 40 100
10-2 60 10-2 40
60
80 80
10-3 10-3
0 0.1 0.2 0.3 0.4 0 0.1 0.2 0.3 0.4
p,GPa p,GPa

Table 8 Parameters for Eq. (2) Name A1 A2 A3 A4 A5
of vegetable oil 10-3 – 10-7 – 10-4

Rapeseed oil 1.52 11.1 -1.54 13.1 2.44

Soybean oil 1.53 11.3 -1.75 15.7 0.34
Sunflower oil 1.55 10.7 -1.65 10.9 7.03
Palm oil 1.30 14.1 -1.43 -0.15 -12.8
Coconut oil 1.84 18.3 -2.13 71.6 13.8
Olive oil 1.53 13.6 -1.52 26.3 3.76
Camellia oil 1.69 11.1 -2.00 4.24 4.06
Mustard oil 1.40 12.7 -1.43 24.2 -0.10

123
280 Tribol Lett (2013) 51:273–280

6 6. Ohno, N., Shiratake, A., Kuwano, N., Hirano, F.: Behavior of

Castor oil some vegetable oils in EHL contacts. In: Dowson, D et al. (ed.)
Elastohydrodynamics’96: Fundamentals and Application in
4
Lubrication and Traction. pp. 243–251. Elsevier Science B.V.,
0 ISBN 0-444-82809-5 (1997)
2 7. Okamoto, T., Konno, M.: Improvement of low temperature flow
characteristics of bio diesel fuel (solidification pressure and
20
improvement of solidification characteristics by blending DME).
0
40 Trans. Jpn. Soc. Mech. Eng. B74(748), 2711–2717 (2008)
100
60 8. Mia, S., Hayashi, S., Ohno, N.: High pressure tribological
80
-2 behavior of vegetable oils as lubricant. In: Proceedings of the
0 0.5 1 International Conference on Mechanical Engineering, Dhaka,
Bangladesh FL-07, 1–5, 2007
9. Mia, S., Ohno, N.: Prospect of mustard and coconut oil as
Fig. 11 Comparison of predicted and observed values of high- environment friendly lubricant for Bangladesh. In: Proceedings
pressure viscosity of castor oil of International Conference on Environmental Aspects of Ban-
gladesh, Kitakyushu, Japan GE06, 120–121, 2010
10. Nihon yukagaku kyoukai: Yushi Kagaku Benran. ISBN
4 Conclusions 4621030353, Maruzen, Tokyo (1971)
11. Hirano, F., Sakai, T., Kuwano, N., Ohno, N.: Chain matching
Based upon visual or direct evidence for solidification between hydrocarbon and fatty acid as interfacial phenomena.
phenomena of rapeseed oil, soybean oil, sunflower oil, Tribol. Int. 20, 186–204 (1987)
12. Ohno, N., Mia, S., Tateishi, K., Morita, S., Shitara, Y.: Con-
palm oil, coconut oil, olive oil, camellia oil, mustard oil, struction of phase diagram up to 2 GPa and 200 °C for thermo-
and castor oil at the high pressure and low temperatures, a reversible gel-lubricants by diamond anvil cell. Lubr. Sci. 21,
very useful viscosity–pressure–temperature relation was 183–192 (2009)
derived for each vegetable oil. 13. Ohno, N., Hirano, F.: High pressure rheology analysis of traction
oils based on free volume measurements. Lubr. Eng. 57, 16–22
(2001)
14. Yoda, T.: An advanced diesel common rail system for achieving
a better balance between ecology and economy. Denso. Tech.
References Rev. 14, 30–35 (2009)
15. Barus, C.: Isotherms, isopiestics and isometrics relative to vis-
1. Bartz, W.J.: Lubricants and the environment. Tribol. Int. 31, cosity. Am. J. Sci. 45, 87–96 (1893)
35–47 (1998) 16. Biresaw, G., Bantchev, G.B.: Pressure viscosity coefficient of
2. Fox, N.J., Stachowiak, G.W.: Vegetable oil-based lubricants—A vegetable oils. Tribol. Lett. 49, 501–512 (2013)
review of oxidation. Tribol. Int. 40, 1035–1046 (2007) 17. Hamrock, B.J., Dowson, D.: Isothermal elastohydrodynamic
3. Oguz, H., Duzcukoglu, H., Ekinct, S.: The investigation of lubrication of point contacts. III—fully flooded results. Trans.
lubrication properties performance of Euro-diesel and biodiesel. ASME. J. Lubr. Technol. 99, 264–276 (1977)
STLE. Tribol. Trans. 54, 449–456 (2011) 18. Sorab, J., Vanarsdale, W.: A correlation for the pressure and
4. Kaneko, T.: Features of biofuels. J. Jpn. Soc. Tribol. 55, 305–310 temperature dependence of viscosity. STLE. Tribol. Trans. 34,
(2010) 604–610 (1991)
5. Biresaw, G., Bantchev, G.B.: Elastohydrodynamic (EHD) trac-
tion properties of seed oils. STLE. Tribol. Trans. 53, 573–583
(2010)

123

View publication stats