The viscosities of three biodiesel fuels at temperatures up to 300 8C

R.E. Tate, K.C. Watts

*
, C.A.W. Allen, K.I. Wilkie
Department of Biological Engineering, Dalhousie University, P.O. Box 1000, Halifax, NS, Canada B3J 2X4
Received 12 April 2005; received in revised form 29 September 2005; accepted 25 October 2005
Available online 18 November 2005
Abstract
In order to obtain the kinematic viscosities of biodiesel fuels at temperatures up to 300 8C, a modied Saybolt viscometer was designed. The
viscometer was used to measure the efux times for 60 ml of methyl esters of canola and soy, and ethyl esters of sh-oil. The Modied Saybolt
Viscometer was calibrated using a standard oil and can be used to measure the kinematic viscosity to within 0.056 mm
2
/s with 2% repeatability.
Using the measured densities over the same temperature range, the dynamic viscosities were obtained.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Viscosity; Temperature
1. Introduction
Viscosity is one of the most important fuel properties. The
effects of viscosity can be seen in the quality of atomization
and combustion as well as engine wear. The higher viscosity
of biodiesel fuel compared to diesel makes it an excellent
lubricity additive [1,2]. On the other hand, the high viscosities
of biodiesel fuels are reportedly responsible for premature
injector fouling [1] leading to poorer atomization.
These issues need to be addressed if biodiesel fuel is to
become the alternative to petroleum diesel. Biodiesel fuels are
the fatty acid methyl or ethyl esters derived from vegetable or
animal fats and oils. Fatty acid composition has a signicant
effect on the viscosities of fats and oils, and in turn biodiesel
fuels. The fatty acid compositions of fats and oils are feedstock
dependent and are also affected by factors such as climatic
conditions, soil type, plant health, and plant maturity upon
harvest [3]. Biodiesel fatty acid compositions and fuel proper-
ties can vary signicantly from one supplier to the next, even
if it is fromthe same type of plant/animal (i.e. soy bean oil). The
quality of fuel atomization is signicantly affected by viscosity.
Since viscosity can vary signicantly between different
biodiesel fuels, there exists a need to measure the temperature
dependant viscosities of biodiesel fuels and verify prediction
models used to predict the temperature dependant viscosity
based on the fatty acid composition of the fuel.
The objective of this paper is to report on the experimentally
determined effect of temperature on the viscosity of three
commercially available biodiesel fuels. This is part of a larger
research project to determine the temperature and pressure
dependence of physical properties that affect biodiesel fuel
atomization and combustion (viscosity, surface tension,
density and droplet size) and verify the prediction models
proposed by Allen et al. [4,5] and Yuan et al. [6] over the
temperature range of 20 to 300 8C, a temperature just below the
boiling point of the lightest oil fraction.
2. Experimental methods
The three biodiesel fuels selected were available commer-
cially in either their pure or their blended forms. For this work
100% methyl esters of canola (Milligan Bio-Tech, SK) and soy
(West Central Soy, IA) and ethyl esters of sh-oil (Wilsons
Fuels, NS) were obtained. These are referred to CME, SME
and FEE in this paper. The properties of the fuels are given in
Table 2 of the companion paper The densities of the three
biodiesel fuels at temperatures up to 300C (d.o.i.: 10.1016/
i.fuel.2005.10.024).
2.1. Apparatus
Saybolt viscometry was selected because of the adaptability
of operation to elevated temperatures. This type of viscometer
Fuel 85 (2006) 10101015
www.fuelrst.com
0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.10.015
* Corresponding author. Tel.: C1 902 494 3232; fax: C1 902 423 2423.
E-mail address: chris.watts@dal.ca (K.C. Watts).
operates under the same principles as other capillary
viscometers; the efux time for a known volume of the fuel
through a calibrated orice is related to kinematic viscosity.
The Saybolt viscometer design [7] was modied to allow
for remote operation at temperatures ranging from room
temperature to the boiling point of the most volatile oil
fraction. An insulated, three part chamber was designed to
house the Modied Saybolt system (Fig. 1). In the lower
chamber was a receiving ask made of 3/8 in. stainless steel
tubing and a 50.8 mm diameter steel sphere. Small holes were
drilled at two heights on opposite sides of the tubing (Fig. 1)
and were compression sealed with Lexan discs. Two lights,
rated at 14-volts, and two photodiodes made up the level
detection system. When the liquid level reached the holes
the liquid impeded the amount of light transmitted to the diode
and a distinct decrease in the signal voltage from the diode
was observed. The receiving ask was heated to the test
temperature with a 125 W rope heater.
Standard Saybolt and Furol tips, 1.765 and 3.150 mm,
respectively, were too large in diameter to yield meaningful
results at elevated temperatures where viscosities are
inherently low. Based on the predicted kinematic viscosity of
0.77 mm
2
/s and the dynamic viscosity of 0.50 mPa s at 300 8C
for 100% soybean oil methyl esters by Yuan et al. [6], an orice
diameter of 1.016 mm was selected. The efux time for water
was measured as 105 Modied Saybolt Seconds (MSS) at
20 8C and 91 MSS at 98 8C. These efux times correspond to
kinematic viscosities of 1.004 and 0.295 mm
2
/s and dynamic
viscosities of 1.00 and 0.281 mPa s [7]. The selected orice
diameter was deemed adequate for the expected measurement
range.
The oil in the reservoir was heated with two 250 W band
heaters controlled by an external onoff temperature controller
purchased from Watlow. Three type K thermocouples were
used to monitor and control the oil, chamber, and receiving
ask temperatures. Type K wire thermocouples, calibrated to
480 8C, were used for the control of the sample temperature
and monitoring the receiving ask temperature. A type K
thermocouple probe, calibrated to 980 8C, was used for
monitoring the sample temperature. The oil was continuously
stirred during the heating process to ensure a uniform oil
temperature. The nal modication necessary was the remote
actuation of the reservoir stop. A solenoid actuated by a solid-
state relay was used to control the stop.
2.2. Methodology
The experimental procedure was based on ASTM D88 [8],
with the exception of the procedures that were automated. Prior
to each fuel change, reservoir and receiving ask were cleaned
with toluene and dried with acetone. As a precaution, a 100 mm
wire mesh was used to lter the uid as it was poured into the
reservoir. The apparatus was assembled and a continuously
heated ow of nitrogen was started to prevent oxidation of the
oil during heating.
Once the reservoir was lled and the chamber reassembled,
operation of the Modied Saybolt viscometer was controlled
via a program developed under LabWindows CVI. A PCI-
MIO-16E-4 National Instruments data acquisition board was
used for the acquisition of the temperature and light sensor
signals. The sample and chamber temperatures were continu-
ously monitored. When a stable test temperature was attained
an indicator light on the computer monitor was lit. The solid-
state relay and solenoid were then manually activated releasing
the reservoir plug. The light detecting diode signals were
scanned simultaneously and continuously for a predetermined
time greater than the estimated efux time. At the completion
of this time, the solenoid was deactivated and the reservoir plug
closed.
Analysis of the collected data within the program required
the user to select four points with the cursor beginning with
the start time of the low level sensor signal change and ending
with the stop time of the high level sensor signal change. Each
sensors data array was searched to nd the index points
selected. The voltage and time data within these indices were
used to determine the maximum slope of each sensor signal
and corresponding time at which it occurred. The difference
between these two times is equivalent to the efux time of
60 ml of the sample uid in MSS.
Each experiment took between 5 and 30 min, depending
on the test temperature. Three samples of each fuel were tested
at 20 8C intervals between 20 and 300 8C. Fig. 1. Modied saybolt viscometer [10].
R.E. Tate et al. / Fuel 85 (2006) 10101015 1011
2.3. Calibration and repeatability
In order to determine the relationship between MSS and
kinematic viscosity, calibrations were performed using
distilled water, Cannon viscosity oil standard No.1 and each
of the biodiesel fuel samples at the specic temperatures for
which the kinematic viscosity was known. By using three
samples of each of the uids repeatability of the Modied
Saybolt viscometer was determined.
2.4. Kinematic viscosity
Capillary ow of a Newtonian uid is governed by the
Poiseuille equation:
dP
dl
Z
8Qm
pr
4
(1)
Since the Modied Saybolt Universal viscometer is a
modied capillary viscometer, kinematic viscosity is deter-
mined by measuring the time for 60 ml of uid to ow through
a short capillary tube. Since the ow rate, tube length, tube
diameter, and pressure are known, Eq. (1) becomes:
m
rt
Z
ghpr
4
8Vl
ZC
1
(2)
The average head h is considered xed for a specic
instrument as the variation is over the same range for all
liquids. Flow through the short capillary tube is turbulent and
thus the velocity distribution is not established. A correction
factor, C
2
/t, is needed. Therefore, the relationship between
MSS and kinematic viscosity, including corrections for
entrance and exit effects due to the short tube length, is
n ZC
1
MSS C
C
2
MSS
(3)
3. Results and discussion
3.1. Calibration
The results of the calibration and accuracy and repeatability
analysis are shown in Fig. 2 and Tables 1 and 2. Regression
analysis yielded C
1
Z0.028 and C
2
ZK199 with an R
2
of
0.994. The repeatability of the Modied Saybolt viscometer
was found to be 2%. The errors associated with the Modied
Saybolt Viscometer were less than 0.056 mm
2
/s, on average.
3.2. Kinematic viscosity
Figs. 35 show the relationships between the kinematic
viscosity and temperature of CME, SME, and FEE, respect-
ively. When the ratio of temperature to a liquids critical
temperature, T
r
, is less than 0.7, kinematic viscosity is often
represented by the Andrade equation. A modied form of
the Andrade equation, as proposed by Tat and Van Gerpen [9],
was used
lnn ZAC
B
T
C
C
T
2
(4)
where n is the kinematic viscosity, T is the absolute
temperature, and A, B, and C are constants specic to the uid.
Results of the regressions using Eq. (4) are shown in
Table 3. With the lowest R
2
value greater than 0.95, Eq. (4)
provides a good t and representation of the data.
Fig. 6 compares this experimental data for SME to that of
Tat and Van Gerpen [9], who regressed their data to Eq. (4)
with an R
2
Z0.999, and the predicted viscosities from Yuan
Table 1
Modied saybolt viscometer repeatability results for the oil standard and
biodiesel fuel samples
Fluid type Tempera-
ture (8C)
Measured
kinematic
viscosity
(mm
2
/s)
Average
kinematic
viscosity
(mm
2
/s)
Absolute
error
(mm
2
/s)
Percent
error (%)
Canon oil
Standard
No. 1
20 1.298 1.255 0.042 3.368
1.255 0.000 0.007
1.213 0.042 3.375
25 1.335 1.316 0.019 1.467
1.368 0.052 3.971
1.244 0.072 5.438
40 1.017 1.087 0.070 6.399
1.095 0.009 0.792
1.148 0.061 5.607
Fish-oil
EE
40 3.999 3.978 0.022 0.543
3.928 0.050 1.257
4.006 0.028 0.714
Soy ME 40 3.989 3.982 0.007 0.171
3.969 0.014 0.342
3.989 0.007 0.171
Canola
ME
40 4.608 4.647 0.038 0.827
4.654 0.008 0.166
4.677 0.031 0.661
Average 0.032 1.96
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
80 90 100 110 120 130 140 150 160 170 180 190 200 210
MSS
K
i
n
e
m
a
t
i
c

V
i
s
c
o
s
i
t
y

(
m
m
2
/
s
)
Fig. 2. Modied saybolt viscometer calibration results. $ CME, ,SME, 6
FEE, CCanon oil standard no. 1, Bdistilled water, calibration curve.
R.E. Tate et al. / Fuel 85 (2006) 10101015 1012
et al. [6] at low temperature. Tat and Van Gerpen [9] measured
the viscosity of soy methyl esters (NOPEC Corporation, FL)
over the range of 20 to 100 8C using a Precision Scientic
Kinematic Viscosity Bath and following procedures outlined in
Table 2
Modied Saybolt viscometer error analysis results for the oil standard and
biodiesel fuel samples
Fluid type Temperature
(8C)
Measured
kinematic
viscosity
(mm
2
/s)
Standard
kinematic
viscosity
(mm
2
/s)
a
Absolute
error
(mm
2
/s)
Distilled
water
20 0.971 1.004 0.033
25 0.862 0.893 0.030
30 0.745 0.801 0.056
35 0.661 0.723 0.063
40 0.537 0.685 0.147
45 0.564 0.602 0.038
50 0.513 0.553 0.040
55 0.408 0.511 0.103
60 0.491 0.474 0.017
65 0.513 0.433 0.069
70 0.486 0.413 0.073
75 0.409 0.388 0.022
80 0.397 0.365 0.032
85 0.387 0.345 0.043
90 0.393 0.326 0.067
95 0.342 0.309 0.033
Average 0.054
Canon oil
Standard No.
1
20 1.087 1.067 0.110
25 1.316 1.269 0.047
40 1.255 0.365 0.049
Average 0.068
Fish-oil EE 40 3.978 3.982
Soy ME 40 3.982 4.200
Canola ME 40 4.647 4.473
Overall
average
0.056
a
Data were obtained from [7] for distilled water and from the suppliers data
sheets for the oil standard and fuel samples. N.B: Due to uncertainties in the
manufacturers reported viscosity, the standard error for the fuel samples was
not determined.
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
Temperature (C)
K
i
n
e
m
a
t
i
c

V
i
s
c
o
s
i
t
y

(
m
m
2
/
s
)
Fig. 4. Kinematic viscosity of 100% soy methyl ester.
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
Temperature (C)
K
i
n
e
m
a
t
i
c

V
i
s
c
o
s
i
t
y

(
m
m
2
/
s
)
Fig. 5. Kinematic viscosity of 100% sh-oil ethyl ester.
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
Temperature (C)
K
i
n
e
m
a
t
i
c

V
i
s
c
o
s
i
t
y

(
m
m
2
/
s
)
Fig. 3. Kinematic viscosity of 100% canola methyl ester.
Table 3
Viscosity correlation constants for three biodiesel fuels over the temperature
range of 20300 8C
Fuel type A B C R
2
100% Canola
methyl ester
K0.341 K498 338,301 0.986
100% Soy
methyl ester
0.076 K1078 469,741 0.951
100% Fish-oil
ethyl ester
K0.453 K739 415,238 0.968
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
0 20 40 60 80 100
Temperature (C)
K
i
n
e
m
a
t
i
c

V
i
s
c
o
s
i
t
y

(
m
m
2
/
s
)
Fig. 6. Comparison of experimental and predicted kinematic viscosities of
100% soy methyl ester up to 100 8C. !SME, $Tat and Van Gerpen [8], ,
Yuan et al. [6].
R.E. Tate et al. / Fuel 85 (2006) 10101015 1013
ASTM D 445 [10]. Yuan et al. [6] predicted the viscosity of soy
methyl esters based on chemical composition and structure of
the oil up to the critical point of the fuel. The results from this
study and the extrapolated results of Tat and Van Gerpen [9]
are shown in Fig. 7 and compared to our experimental data.
There is very good agreement between the experimental
results found in this work and those of Tat and Van Gerpen [9]
where the maximum absolute error was 0.61 mm
2
/s at 40 8C.
Yuan et al. [6] over estimated the kinematic viscosity by an
average of 0.70 mm
2
/s when T!80 8C and under estimated the
kinematic viscosity by an average of 0.58 mm
2
/s when TO80 8C.
3.3. Dynamic viscosity
Using the measured densities from Tate [11], the dynamic
viscosities of each of the biodiesel fuels were calculated (Fig. 8
and Table 4).
4. Conclusions
1 A modied Saybolt Viscometer was shown to give the
efux time of 60 ml of biodiesel fuels up to the boiling point
of the lightest oil fraction to within 0.056 mm
2
/s and 2%
repeatability.
2 The viscosities of three commercial biodiesel fuels, canola
methyl esters, soy methyl esters, and sh oil ethyl esters,
decreased with temperature, experimentally and as pre-
dicted by a modied Andrade equation.
3 The predicted and low temperature experimental values in
the literature for kinematic viscosities of soy methyl esters
compare very well with the experimental viscosities
obtained in this work.
Acknowledgements
The authors acknowledge the support of the Natural Science
and Engineering Research Council (NSERC) by way of an
operating grant to K.C. Watts.
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
Temperature (C)
K
i
n
e
m
a
t
i
c

V
i
s
c
o
s
i
t
y

(
m
m
2
/
s
)
Fig. 7. Comparison of experimental and predicted kinematic viscosities of
100% soy methyl ester up to 300 8C. !SME, $Tat and Van Gerpen [8], ,
Yuan et al. [6].
0
1
2
3
4
5
6
0 50 100 150 200 250 300
Temperature (C)
D
y
n
a
m
i
c

V
i
s
c
o
s
i
t
y

(
m
P
a
-
s
)
Fig. 8. Dynamic viscosities of three biodiesel fuels from 20 to 300 8C. $CME,
,SME, 6 FEE.
Table 4
Kinematic and dynamic viscosities predicted from the correlations of three biodiesel fuels over the temperature range of 20300 8C
Temperature (8C) Kinematic viscosity (mm
2
/s) Dynamic viscosity (mPa s)
Canola ME Soy ME Fish-oil EE Canola ME Soy ME Fish-oil EE
20 6.665 6.455 6.411 5.751 5.518 5.372
40 4.566 4.153 4.143 3.828 3.447 3.369
60 3.361 2.923 2.915 2.736 2.354 2.298
80 2.615 2.203 2.190 2.065 1.720 1.672
100 2.126 1.752 1.731 1.627 1.324 1.279
120 1.788 1.452 1.424 1.325 1.061 1.017
140 1.546 1.245 1.210 1.108 0.879 0.834
160 1.367 1.095 1.056 0.946 0.746 0.701
180 1.231 0.985 0.940 0.822 0.647 0.601
200 1.125 0.901 0.852 0.724 0.569 0.524
220 1.041 0.837 0.783 0.644 0.508 0.462
240 0.974 0.786 0.729 0.579 0.458 0.412
260 0.919 0.746 0.685 0.524 0.416 0.370
280 0.873 0.713 0.649 0.476 0.380 0.335
300 0.835 0.687 0.620 0.435 0.349 0.304
R.E. Tate et al. / Fuel 85 (2006) 10101015 1014
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R.E. Tate et al. / Fuel 85 (2006) 10101015 1015