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Basics of Diesel Engines and

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3 ■ ■

Diesel Fuels
Jon Van Gerpen
Department of Biological and Agricultural Engineering, University of Idaho, Moscow, ID

Introduction
The diesel engine has been the engine of choice for heavy-duty applications in agricul-
ture, construction, industrial, and on-highway transport for more than 50 years. Its early
popularity could be attributed to its ability to use the portion of the petroleum crude oil
that had previously been considered a waste product from the refining of gasoline. Later,
the diesel’s durability, high torque capacity, and fuel efficiency ensured its role in the most
demanding applications. Although diesel engines have not been widely used in passenger
cars in the United States (<1%), they have achieved widespread acceptance in Europe with
>50% of the total market (Valdes-Dapena, 2007).
In the United States, on-highway diesel engines now consume greater than 40 billion
gallons of diesel fuel per year and virtually all of this is in trucks (U.S. Energy Information
Administration. www.eia.doe.gov). At the present time, only a small fraction of this fuel
is biodiesel. However, as petroleum becomes more expensive to locate and extract, and
concerns about fuel security and global warming increase, biodiesel is likely to emerge as
one of several potential alternative diesel fuels.
In order to understand the requirements of a diesel fuel and how biodiesel can be consid-
ered a desirable substitute, it is important to understand the basic operating principles of the
diesel engine. This chapter describes these principles, particularly in light of the fuel used and
the ways in which biodiesel provides advantages over conventional petroleum-based fuels.

Diesel Combustion
The operating principles of diesel engines are significantly different from those of the
spark-ignited engines that dominate the U.S. passenger car market. In a spark-ignited
engine, fuel and air that are close to the chemically correct, or stoichiometric, mixture are
inducted into the engine cylinder, compressed, and then ignited by a spark. The power
of the engine is controlled by limiting the quantity of fuel-air mixture that enters the
■ 21 ■
22 ■ J. Van Gerpen

Fig. 3.1. Cross section of a diesel engine combustion chamber.

cylinder using a flow-restricting valve called a throttle. In a diesel engine, also known as a
compression-ignited engine, only air enters the cylinder through the intake system. This air
is compressed to a high temperature and pressure, and then finely atomized fuel is sprayed
into the air at high velocity. When it contacts the high temperature air, the fuel vaporizes
quickly, mixes with the air, and undergoes a series of spontaneous chemical reactions that
result in a self-ignition or autoignition. No spark plug is required, although some diesel
engines are equipped with electrically heated glow plugs to assist with starting the engine
under cold conditions. The power of the engine is controlled by varying the volume of fuel
injected into the cylinder, so there is no need for a throttle.
Fig. 3.1 shows a cross section of the diesel combustion chamber with the fuel injector
positioned between the intake and exhaust valves. Most diesel engines utilize a bowl-
in-piston design where the bulk of the air charge is trapped in a carefully contoured cavity in
the piston. The shape of the cavity is designed to encourage air flow patterns that when com-
bined with the high velocity fuel spray cause rapid and complete mixing of the fuel and air.
The timing of the combustion process must be precisely controlled to provide low
emissions with optimum fuel efficiency. This timing is determined by the fuel injection
timing plus the short time period between the start of fuel injection and the autoignition,
called the ignition delay. When the autoignition occurs, the portion of the fuel that was
already prepared for combustion burns very rapidly during a period known as premixed
combustion. When the fuel that had been prepared during the ignition delay is exhausted,
the remaining fuel burns at a rate determined by the mixing of the fuel and air. This period
is known as mixing-controlled combustion.

Particulate Emissions
The heterogeneous fuel-air mixture in the cylinder during the diesel combustion process
contributes to the formation of soot particles, one of the most difficult challenges for
diesel engine designers. These particles are formed in high temperature regions of the
combustion chamber where the air-fuel ratio is fuel-rich and consists mostly of carbon
 Basics of Diesel Engines and Fuels ■ 23

with small amounts of hydrogen and inorganic compounds. Although the mechanism is
still not understood, biodiesel reduces the amount of soot produced and this appears to be
associated with the bound oxygen in the fuel (McCormick et al., 1997). The particulate
level in the engine exhaust is composed of these soot particles along with high-molecular-
weight hydrocarbons that adsorb to the particles as the gas temperature decreases during
the expansion process and in the exhaust pipe. This hydrocarbon material, called the
soluble organic fraction, usually increases when biodiesel is used, offsetting some of the
decrease in soot (Sharp et al., 2000). Biodiesel’s low volatility apparently causes a small
portion of the fuel to survive the combustion process at light loads, probably as liquid
coating the cylinder walls, where it is then released during the exhaust process.

NOx Emissions
A second difficult challenge for diesel engine designers is the emission of oxides of nitro-
gen (NOx). NOx emissions are associated with high gas temperatures and fuel-lean con-
ditions; in contrast to most other pollutants, they usually increase when biodiesel is used
(Sharp et al., 2000). NOx contributes to photochemical smog formation and is difficult to
control in diesel engines because measures taken to reduce NOx tend to cause increases in
particulate emissions and fuel consumption. The bound oxygen on the biodiesel molecule
may play a role in creating a leaner air-fuel ratio in NOx formation regions thus increas-
ing the availability of oxygen for NOx formation. However, the dominant mechanism
is probably more complex. Tat et al., 2000, have suggested that changes in the physical
properties of biodiesel, such as the speed of sound and bulk modulus, can affect the fuel
injection timing and this can increase NOx. Another possible effect is that biodiesel’s
reduction in combustion-generated solid carbon reduces the amount of radiative heat loss
and thus increases the in-cylinder temperature (Cheng, et al., 2006). Since most NOx
formation follows the temperature sensitive Zeldovich, or thermal pathway (Heywood,
1988), the higher in-cylinder temperatures can increase NOx production.

Autoignition Properties
One of the most important properties of a diesel fuel is its readiness to autoignite at the
temperatures and pressures present in the cylinder when the fuel is injected. The labora-
tory test that is used to measure this tendency is the cetane number (CN) test (ASTM D
613). The test compares the autoignition tendency of the test fuel with a blend of two
reference fuels, cetane (hexadecane) and heptamethylnonane. Fuels with a high CN will
have short ignition delays and a small amount of premixed combustion since little time is
available to prepare the fuel for combustion. Most biodiesel fuels have higher CNs than
petroleum-based diesel fuels. Biodiesel fuels from more saturated feedstocks have higher
CNs than from less saturated feedstocks (Knothe et al., 1997). Biodiesel from soybean
oil is usually reported to have a CN of 48–52, while biodiesel from yellow grease, con-
taining more saturated esters, is normally between 60 and 65 (Van Gerpen, 1996). For
more details, see Chapter 4.1, Basics of the Transesterification Reaction, and the tables in
Appendix A.
24 ■ J. Van Gerpen

Energy Content (Heat of Combustion)

The energy content of the fuel is not controlled during manufacturing. The lower heat-
ing value for diesel fuel can vary depending on the refinery in which it was produced,
the time of year, and the source of the petroleum feedstock because all of these variables
affect the composition of the fuel. Diesel fuels with high percentages of aromatics tend to
have high energy contents per liter even though the aromatics have low heating values per
kilogram. Their high density more than compensates for their lower energy content on a
weight basis. This is of special importance for diesel engines because fuel is metered to the
engine volumetrically. A fuel with lower energy content per liter, such as biodiesel, will
cause the engine to produce less peak power. At part load conditions the engine operator
will still be able to meet the demand for power but a greater volume of fuel will have to
be injected. The fuel injection system may advance the fuel injection timing when the fuel
flow rate increases, and this can cause an increase in the NOx emissions. In addition to the
compressibility effects mentioned earlier, this effect is another reason for the higher NOx
emissions observed with biodiesel (Tat et al., 2007).
Biodiesel fuels do not contain aromatics but they contain methyl esters with different
levels of saturation. Unsaturated esters have lower energy content on a weight basis; but
due to their higher density, they have more energy per unit volume. For example, methyl
stearate has a higher heating value of 40.10 MJ/kg, which is 0.41% higher than that of
methyl oleate (39.93 MJ/kg). However, on a volume basis (at 40°C), methyl stearate
has an energy content of 34.07 MJ/L, which is 0.7% less than that of methyl oleate
(34.32 MJ/L) (Freedman & Bagby, 1989; Weast, 1970–1971). These differences are small
enough that feedstock differences are difficult to detect in actual use.
Biodiesel has lower energy content (lower heating value of 37.2 MJ/kg for soy biodiesel)
than No. 2 diesel fuel (42.6 MJ/kg). On a weight basis, the energy level is 12.5% less. Since
biodiesel is denser than diesel fuel, the energy content is only 8% less on a per gallon basis
(32.9 MJ/L vs. 36.0 MJ/L). Because diesel engines will inject equal volumes of fuel, diesel
engine operators may see a power loss of ~8%. In some cases, the power loss may be less
than this because biodiesel’s higher viscosity can decrease the amount of fuel that leaks past
the plungers in the diesel fuel injection pump, leaving more fuel to be injected.
Tests have shown that the actual efficiency at which the energy in the fuel is con-
verted to power is the same for biodiesel and petroleum-based diesel fuel (Monyem &
Van Gerpen, 2001). Therefore, the brake specific fuel consumption (BSFC), which is
the fuel flow rate divided by the engine’s output power and is the parameter most often
used by engine manufacturers to characterize fuel economy, will be at least 12.5% higher
for biodiesel. The values for heat of combustion of various fatty materials taken from the
literature are given in the tables in Appendix A.

Emissions
Under ideal circumstances, all of the carbon in the diesel fuel will burn to carbon dioxide
and all of the hydrogen will burn to water vapor. In most cases, virtually all of the fuel fol-
lows this path. However, if sulfur is present in the fuel, it will be oxidized to sulfur dioxide
 Basics of Diesel Engines and Fuels ■ 25

and sulfur trioxide. These oxides of sulfur can react with water vapor to form sulfuric acid
and other sulfate compounds. The sulfates can form particles in the exhaust and elevate
the exhaust particulate level. Currently, the U.S. Environmental Protection Agency (EPA)
limits the sulfur level of on-highway diesel fuel to 15 ppm. This virtually eliminates sulfur
as a component of exhaust particulate and allows the use of catalytic after-treatment on
diesel engines. Sulfur is a powerful catalyst poison and, if present in the fuel, limits the
options available for controlling emissions on future engines. Biodiesel from soybean oil
is very low in sulfur. However, biodiesel from some animal fat feedstocks has sulfur levels
that exceed the EPA mandate and require further treatment.
Aromatic hydrocarbons are characterized by stable chemical structures. They are usu-
ally present in diesel fuel at levels between 25%–35%. As mentioned earlier, they are
considered desirable by diesel engine operators because they provide greater energy per
liter of fuel; however, they may contribute to higher emissions of particulate and NOx,
and have lower CN. In the early 1990s, the California Air Resources Board implemented
standards that limited the aromatic content of diesel fuels sold in California to 10%. The
board later allowed the aromatic content to be higher if fuel producers could show that
their fuels produced equivalent or lower emissions than the low aromatic fuel. Biodiesel
contains no aromatic compounds.
Carbon monoxide and unburned hydrocarbon emissions are usually quite low for
diesel engines compared with gasoline engines, and most engine manufacturers have
little difficulty meeting the regulatory requirements for these pollutants. Oxides of
nitrogen (NOx) and particulates are a greater challenge. Emission regulations requiring
dramatic reductions in these pollutants started in 2007 and will be fully implemented
in 2010. Traditionally, engine manufacturers were able to use late injection timing,
cooling of intake air after the turbocharger compressor with air-to-air heat exchangers,
and exhaust gas recirculation to control NOx. Extremely high fuel injection pres-
sures could provide the air-fuel mixing needed to control particulates. With the recent
tightening of emission regulations, it has become clear that these techniques, which
primarily rely on modifying the in-cylinder combustion process, will not be sufficient.
Additional emission reduction measures in the exhaust stream will be described later.
Biodiesel’s emission reduction advantages, as well as its tendency to increase NOx,
may become irrelevant as emissions are virtually eliminated by exhaust after-treatment
equipment.

Low Temperature Operation

Diesel fuel contains small amounts of long chain hydrocarbons, called waxes that crys-
tallize at temperatures within the normal diesel engine operating range. If temperatures
are low enough, these wax crystals will agglomerate, plug fuel filters, and prevent engine
operation. At a low enough temperature, the fuel will actually solidify. This phenomenon
also occurs with biodiesel. The saturated fatty acids produce methyl esters that will start
to crystallize at ~0°C for soybean oil and as high as 13°C–15°C for animal fats and frying
oils (Lee & Hammond, 1995). The most common measure of this tendency to crystallize
26 ■ J. Van Gerpen

is the cloud point (CP). This is the temperature at which the onset of crystallization is
observed visually as cloudiness in the fuel. A more extreme test is the pour point (PP),
which is the lowest temperature at which the fuel can still be poured from a vessel. ASTM
D 2500 and ASTM D 97 are used to determine the CP and PP of the fuels, respectively.
Other tests are used to measure the tendency of the fuel to plug fuel filters.
Additives, known as PP depressants, can be used to inhibit the agglomeration of the wax
crystals, which then lowers the point at which fuel filter plugging occurs. It is also common
to add No. 1 diesel fuel to No. 2 diesel fuel to lower its operating point. No. 1 diesel fuel
has a very low level of waxes and dilutes the waxes in No. 2 diesel fuel, which lowers the
temperature at which they cause the fuel to solidify. Both No. 1 and No. 2 diesel fuels can
be blended with biodiesel to lower its operating temperature. Biodiesel used at the 1%–2%
level as a lubricity additive does not seem to have any measurable effect on the CP. The
allowable operating temperature for B20 blends is higher than that for the original diesel
fuel, but many B20 users have been able to operate in cold climates without problems.

Viscosity
Fuel viscosity is specified in the standard for No. 2 diesel fuel (ASTM D 975) within a
fairly narrow range (1.9 to 4.1 cSt). Hydrocarbon fuels in the diesel boiling range easily
meet this viscosity specification. Most diesel fuel injection systems compress the fuel for
injection using a positive displacement piston pump. In order to develop the high pres-
sures required in modern injection systems, the clearances between the piston and cylin-
der are ~0.0001” (0.0025 cm). Despite this small clearance, a substantial fraction of the
fuel leaks past the plunger during compression. In older engines, this leakage corresponds
to a power loss. In modern common rail injection systems, the system can compensate
for temperature-related viscosity changes, although the calibration will be based on die-
sel fuel. The biodiesel specification in ASTM D 6751 requires B100 to have a viscosity
between 1.9 and 6.0 cSt. The European specification EN 14214, which presumes a nar-
rower range of possible feedstocks, limits the viscosity range to between 1.9 and 5.0 cSt.
The viscosity range for typical biodiesel fuels overlaps the diesel fuel range with some
biodiesels having viscosities above the limit (Tat & Van Gerpen, 1999). If fuel viscosity
is extremely excessive, as is the case with vegetable oils, there will be a degradation of the
spray in the cylinder causing poor atomization, contamination of the lubricating oil, and
the production of black smoke. More details on viscosity are given in Chapter 6.2, Viscos-
ity of Biodiesel, and data appear in the tables of Appendix A.

Corrosion
Many of the parts in the diesel fuel injection system are made of high-carbon steels. They
are prone to corrosion when in contact with water. Water damage is a leading cause of
premature failure of fuel injection systems. Diesel fuel containing excessive water that
enters the injection system can cause irreversible damage in a very short time. Many diesel
engines are equipped with water separators that cause small water droplets to coalesce
 Basics of Diesel Engines and Fuels ■ 27

until they are large enough to drop out of the fuel flow where they can be removed. There
are some reports that these water separators are not effective when used with biodiesel.
Water can be present in fuels as dissolved water and free water. Petroleum-based diesel
fuel can only absorb ~50 ppm of dissolved water, whereas biodiesel can absorb as much
as 1500 ppm (Van Gerpen et al., 1997). While this dissolved water can affect the stability
of the fuel, corrosion is associated with free water. ASTM D 2709 is used to measure the
total amount of free water and sediment in a diesel fuel sample. The method uses a cen-
trifuge to separate the water and the specifications on both diesel fuel and biodiesel limit
the amount of water and sediment to 0.05%.
Some compounds in diesel fuel, especially sulfur compounds, can be corrosive. Since
copper compounds are particularly susceptible to this type of corrosion, copper is used
as an indicator of the tendency of the fuel to cause corrosion. In ASTM D 130, pol-
ished copper strips are soaked in the fuel to characterize the tendency to corrode metals.
Although some tarnish is typically allowed, any evidence of corrosion causes the fuel to
fail the test. Biodiesel generally passes this test easily.

Sediment
Diesel fuel filters are designed to capture particles that are >10 µm in size. Some newer
engines are even equipped with filters that capture particles as small as 2 µm. These filters
should stop foreign materials from entering the fuel injection system. However, when
fuels are exposed to high temperatures and the oxygen in air, they can undergo chemical
changes that form compounds that are insoluble in the fuel. These compounds form var-
nish deposits and sediments that can plug orifices and coat moving parts, causing them to
stick. Several test procedures have been developed that attempt to measure the tendency
of diesel fuels to produce these sediments, such as ASTM D 2274, but none have gained
the acceptance needed to be included in the diesel fuel specification (ASTM D 975).
Because of its high concentration of unsaturated compounds, biodiesel is expected to be
more susceptible to oxidative degradation than petroleum-based diesel fuel. In recogni-
tion of this increased tendency to oxidize, an oxidative stability test is now included in
ASTM D 6751.
Inorganic materials present in the fuel may produce ash that can be abrasive and con-
tribute to wear between the piston and cylinder. ASTM D 482 is used to characterize ash
from diesel fuels. The ASTM specification for biodiesel, D 6751, requires that ASTM D
874 be used. This method measures sulfated ash, which is specified because it is more sen-
sitive to ash from sodium and potassium. These metals originate from the catalyst used in
the biodiesel production process and are likely to be the main sources for ash in biodiesel.
When fuel is exposed to high temperatures in the absence of oxygen, it can pyrolyze to
a carbon-rich residue. While this should not occur in the cylinder of a properly operating
engine, some injection systems have the potential to create a region within the injection
nozzle where this residue can collect and limit the range of motion of moving parts.
Various test procedures such as ASTM D 189, ASTM D 524, and ASTM D 4530 have
been developed as an attempt to predict the tendency of a fuel to form in-cylinder carbon
28 ■ J. Van Gerpen

deposits. Unfortunately, it is very difficult to reproduce in-cylinder conditions in a test; so

the correlation of these procedures to actual engine deposits is limited.
Diesel fuel injection systems have very closely fitting parts that are subjected to high
loads. These parts require lubrication to prevent rapid wear. All diesel injection systems
rely on the fuel itself to provide this lubrication. While the mechanism remains a topic
for debate, it is known that as refiners have reduced the sulfur content of diesel fuel, the
ability of the fuel to provide the necessary lubrication has decreased. The property that
characterizes the ability of the fuel to lubricate is the lubricity. There are two methods
that are commonly used to measure diesel fuel lubricity, the scuffing load ball on cylinder
lubricity evaluator (SLBOCLE: ASTM D 6078–99) and the high frequency reciprocating
rig (HFRR: ASTM D 6079–99) but both procedures have been widely criticized. This is
primarily due to the lack of correlation between the test procedures and the large amount
of test-to-test variability. In spite of the criticism, the HFRR test has been added to the
specification for diesel fuel (ASTM D 975). Biodiesel has excellent lubricity and as little
as 1%–2% biodiesel can raise the lubricity of a poor lubricity fuel to an acceptable level
(Schumacher & Adams, 2002).

Flashpoint
Diesel engine operators are accustomed to treating diesel fuel as if it were nonflammable.
The volatilities of both No. 1 and No. 2 diesel fuel are low enough that the air-vapor
mixture above the fuel is below the flammability limit. The property that characterizes
this behavior is the flashpoint. The flashpoint is the temperature at which the fuel will give
off enough vapor to produce a flammable mixture: 52°C–66°C for diesel fuel and below
–40°C for gasoline. An important advantage of biodiesel is that its very high flashpoint,
>150°C, means that biodiesel presents a very low fire hazard.

New Technologies
Requirements for lower emissions and continued demands for improved fuel economy
have driven the engine industry to technical advances that incorporate state-of-the-art
electronics and manufacturing technology. Electronically controlled cam-actuated unit
injection has pushed the limits for fuel injection pressures to >2000 bar. The rapid mixing
provided by the high spray velocity resulting from this extreme injection pressure pro-
vides low particulate formation and virtually complete soot oxidation while allowing the
retarded injection timing settings needed for reduced NOx.
The introduction of common rail injection systems for light- and medium-duty
engines has allowed new flexibility in programming the injection event. These systems
allow multiple injections within a single engine cycle. A common strategy is to start the
combustion with two brief injections, called the pilot- and pre-injections. These injec-
tions produce an environment in the cylinder so that when the main injection occurs, the
ignition delay will be shorter, the amount of premixed combustion will be less, and the
NOx production will be reduced. These small injections that precede the main injection
 Basics of Diesel Engines and Fuels ■ 29

also reduce engine noise and vibration. Immediately following the main injection, a small
amount of fuel may be injected to assist in oxidizing the soot particles. Then, later in the
expansion process a post-injection provides the elevated exhaust hydrocarbon level needed
by the after-treatment equipment. The high degree of control offered by common rail
injection systems would have been useless without the use of an electronic control unit.
The application of powerful on-board computers to diesel engines initially lagged behind
their use on spark-ignition engines, but current engines have corrected this deficiency.
To improve the engine’s air supply, variable geometry turbochargers have been devel-
oped to extend the engine operating range over which adequate air is provided to keep
particulate emissions low. Air-to-air after coolers are also used to lower intake air tempera-
tures to reduce both NOx and particulate emissions.
With the exception of some oxidation catalysts, diesel engines traditionally did not
use exhaust after-treatment for emission control. The three-way catalyst technology that
is widely used for spark-ignited vehicles is not suitable for use on diesel engines because it
requires a near stoichiometric fuel-air mixture to obtain simultaneous reductions in carbon
monoxide, unburned hydrocarbons, and oxides of nitrogen. Diesels always operate with
excess oxygen; thus, the reducing catalyst required to eliminate NOx cannot operate. The
oxidation catalysts provided on some diesel engines are able to reduce particulate levels by
oxidizing some of the adsorbed hydrocarbons from the soot particles, but they are not effec-
tive at reducing the solid portion of the particulate and they do nothing to reduce NOx.
Recent innovations include catalyzed diesel particulate filters or traps. These devices
force the exhaust to pass through a porous ceramic material that captures the exhaust
particles. The surface of the ceramic is coated with a catalyst that oxidizes the particles as
they are collected. NOx traps and absorbers are also being developed. These devices cata-
lytically convert the NOx to stable compounds that are collected within the catalyst and
then are periodically removed during regeneration cycles. The catalysts used in both the
particulate traps and the NOx absorbers are very sensitive to fuel sulfur, which is a catalyst
poison. As mentioned earlier, to allow this technology to develop, the U.S. EPA mandated
a reduction in fuel sulfur from 500 to 15 ppm in 2006.
In spite of the major changes made to fuel sulfur levels, NOx reducing after-treatment
devices are not currently able to meet the performance and durability targets set by the
EPA. At the time of this writing (2009), most engine manufacturers are expected to equip
their engines with selective catalyst reduction (SCR) to meet NOx regulations in 2010.
SCR injects a solution of urea in water, known as “diesel exhaust fluid (DEF),” into the
exhaust gases. At the high temperatures in the exhaust, the urea breaks down into ammo-
nia and with the aid of a catalyst, the ammonia converts the NOx to nitrogen and water
vapor. Urea is already widely used as an agricultural fertilizer and the infrastructure for
production and distribution already exists in most of the country. Truck drivers will now
need to fill a small urea tank as they refuel with diesel fuel.
Little is known about biodiesel use in advanced technology engines. Although the
addition of exhaust after-treatment systems to control particulate and NOx emissions
may reduce one of the driving forces for biodiesel use, there is no indication that biodiesel
will not be fully compatible with the new engine systems.
30 ■ J. Van Gerpen

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