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SAE TECHNICAL
PAPER SERIES 2000-01-1918

Understanding Diesel Lubricity

R. H. Barbour, D. J. Rickeard and N. G. Elliott
Esso Research Centre

Reprinted From: Diesel and Gasoline Performance and Additives

(SP–1551)

and
International Spring Fuels & Lubricants
Meeting & Exposition
Paris, France
June 19-22, 2000

400 Commonwealth Drive, Warrendale, PA 15096-0001 U.S.A. Tel: (724) 776-4841 Fax: (724) 776-5760
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Understanding Diesel Lubricity
R. H. Barbour, D. J. Rickeard and N. G. Elliott
Copyright © 2000 CEC and SAE International.
ABSTRACT
Diesel fuel injection pumps are lubricated primarily by the
fuel itself. Traditionally, fuel viscosity was used as a rough
indicator of a fuel's ability to provide wear protection, but
since the advent of low sulphur diesel, even some fuels of
higher viscosity have been found capable of producing
wear. This paper provides further insights into the main
contributors to diesel fuel lubricity, their source and the
impact of refinery processing. The most effective way to
monitor lubricity is also considered. We have found that
diesel lubricity is largely provided by trace levels of
naturally occurring polar compounds which form a
protective layer on the metal surface. Typical sulphur
compounds do not confer this wear protection
themselves rather it is the nitrogen and oxygen
containing hetero-compounds that are most important. A
complex mixture of polar compounds is found in diesel
and some are more active than others. The process of
hydrotreating to reduce sulphur levels also destroys
some of these natural lubricants. Other refinery
processes also influence the concentration of the lubricity
agents in the final fuel blend. Lubricity additives have
been developed to compensate for the deterioration in
natural lubricity observed in low S diesels. The interaction
between natural polars and lubricity additive has been
investigated and the findings may explain why some poor
lubricity fuels are more responsive to lubricity additive
than other. Difficulties are encountered when using
knowledge of refinery streams to predict the lubricity of a
diesel blend. The most effective way to monitor lubricity
performance is by making measurements on the finished
fuels. Vehicle tests have shown that the High Frequency
Reciprocating Rig is a good indicator of diesel lubricity
performance.
INTRODUCTION
Interest in diesel fuel lubricity has escalated since the
early 90s. It was at this time that ultra low sulphur
(<20ppm) Swedish Class 1 and 2 fuels were
commercialised and coincident with this there was an
increased incidence of drivability problems and pump
failures. These problems were soon linked with excessive
wear on critical components of fuel injection pumps. On
some occasions pump failure occurred after less than
1
2000-01-1918
Esso Research Centre
8,000km.1 Rotary distribution pumps which are solely
dependent on the fuel for lubrication, were the worst
affected. Similar problems were observed with extreme
fuels in the USA.
Low sulphur diesel fuels (<500ppm) have now been
introduced in all regions and ultra low sulphur fuels
(<50ppm) are starting to make an impact in Europe and
the US. Such fuels are considered to be necessary to
enable the introduction of advanced exhaust after
treatment technology. Consequently, fuel lubricity issues
continue to be of interest.
There have been a great many investigations into the
lubricity properties of diesel fuels from a variety of
perspectives. For example, vehicle tests have been
conducted2 to 4 to reproduce the problem, bench tests
have been developed5 to 11 to mimic the problem and
monitor fuel lubricity, fuel matrices have been evaluated12
to 18 and model compound studies conducted19 to 22 to
investigate compositional effects and additive technology
has been developed1, 23 as the likely solution.
This paper helps to consolidate some of the findings from
earlier work, and in addition provides a deeper
understanding of the mechanisms governing diesel fuel
lubricity. It also looks to explain some refinery effects and
to seek ways to improve lubricity from a base fuel
perspective.
DEVELOPING CONFIDENCE IN BENCH TEST
MEASUREMENTS
Vehicle testing is costly, inherently variable and time
consuming. Consequently, many field problems are
reproduced in simplified bench tests. These tests can
provide valuable data in a timely and cost effective
manner but they also need to be treated with some
caution. Vehicle tests need to be conducted in order to
gain confidence in the bench test measurements and to
validate leads generated from bench testing.
The High Frequency Reciprocating Rig (HFRR), initially
developed at the Imperial College London, has shown
much promise and is now widely used to monitor fuel
quality. A specification of 460um maximum wear scar has
been agreed in Europe and the test protocol has been
accepted by CEN as ISO reference - ISO 12156-1:1997.
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Vehicle and pump rig data developed primarily by ESSO2
and Shell3 demonstrated that there was a good
correlation between wear in rotary pumps and HFRR
wear scar diameter. Figure 1 below shows a plot of the
HFRR wear scar diameter in microns versus pump wear
as defined by the Bosch rating system. This system is
based on a combination of visual wear rating and
measured wear loss. It measures both sliding and
vibration wear on several critical components. Low values
are indicative of good performance with a pass being < 4.
Figure 1. Correlation of injection pump vs bench
test wear
In the ESSO test programme a high S fuel (nominally
0.2%) was seen to give adequate protection against wear
while the pump components from a vehicles run on a low
S fuel (nominally 500ppm) showed excessive wear. It
also showed that lubricity additive could return the
lubricity performance of the LSADO to the same level as
the high S ADO.
There are many different types of diesel fuel injection
systems present on current vehicles. Due to the ever
increasing requirement for reduced engine emissions
new systems such as Common Rail and Electronic Unit
Injectors are being developed and introduced rapidly.
These systems provide even higher fuel injection
pressures for improved fuel air mixing, improved
combustion and hence reduced exhaust emissions.
These developments however, are relatively recent and
the most common systems in use remain in-line and
rotary pump applications. In-line pumps have been
traditionally fitted to heavy-duty vehicles where durability
is critical. In these systems the critical highly loaded
moving parts - the cam and follower assembly - are
lubricated by engine oil. Conversely rotary pumps are
entirely lubricated by the diesel fuel and because of their
lower manufacturing costs have in the main been fitted to
light-duty applications. More than one type of rotary or
distributor pump design exists, and different designs
respond differently to fuel quality.
With the wide array of pump types and critical
components one would not expect a single bench test to
directly correlate with each and every one, but like the
HFRR, it should show directional effects and highlight
problem fuels.
2
UNDERSTANDING THE UNDERLYING EFFECTS
This initial investigation was conducted in order to identify
the key ingredients in high sulphur diesel that give it good
lubricity properties. From early experience it had been
suggested that the S compounds removed during
hydrotreatment were responsible. This was somewhat
influenced by the known anti-wear properties of S based
additives in lubricating oils.
The study reported here involved the fractionation of a
high sulphur diesel fuel by a two-stage process using
column chromatography and NOT distillation. Where
distillation fractionates diesel by boiling point, column
chromatography fractionates diesel by polarity. Non-polar
molecules do not interact with the stationary phase and
therefore pass through the column at a faster rate than
polar molecules. Solvents of increasing polarity are used
to elute / transport the more polar compounds through
the column in order of polarity. The most polar
compounds are collected in the final fraction.
This series of non-polar to polar fractions was required to
investigate the effect of diesel constituents in the two
main lubrication regimes, boundary and hydrodynamic.
These regimes are dependent upon the speed of the
moving surfaces and the applied load. In hydrodynamic
lubrication a fluid layer separates the moving surfaces
and it is the fluid viscosity that determines the level of
protection provided. In boundary lubrication the moving
surfaces are in contact and the protection is provided by
a molecularly thin layer adsorbed on the surfaces. In this
regime the level of protection is dependent upon the
properties and coverage of this layer.
A typical good lubricity high sulphur ADO (1000ppm S)
was selected for this investigation. It was initially
fractionated using silica as the stationary phase. The fuel
was added directly to a column packed with an equal
volume of silica. As the fuel gradually passed on to and
through the column a faction was collected without the
use of any eluent. When the fuel had fully eluted onto the
silica the eluents were applied in order. As the THF was
added a dark band started to move down the column. A
separate collecting vessel was introduced as the dark
eluent exited the column. The clear and dark THF
fractions were analysed separately. Table 1 shows the
eluents in order, the amount collected in each fraction in
a weight and % basis and some initial characterisation
(IP391) of the fractions. The IP391 test broadly quantifies
the amount of 1, 2 and 3+ ring aromatic compounds in
diesel samples. Being a chromatographic technique,
IP391 is founded upon the increasing polarity of
compounds with an increasing number of rings.
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Table 1. Silica fractionation of Fawley ADO

IP391 (mass %) HFRR

Fraction Eluent Wt (g) Wt % fuel 1RAs 2RAs 3+RAs µm
1 No eluent 172.6 19.2 0 0 0 561
2 Pentane 407.9 45.3 4 0 0 520
3 Pentane 202.3 22.5 21 8 0 522
4 THF (clear) 37.6 4.2 28 19 2 462
5 THF (dark) 64.2 7.1 8 40 13
Total 884.6 98.3

This table shows that the majority of the fuel was
collected in the first three fractions. The final fraction
constituted about 7% of the fuel.
The increasing level of 2 and 3+ring aromatics
compounds throughout the fractionation is a clear
indication of the increasing polarity of each subsequent
fraction.
The lubricity performance of these fractions was
evaluated using the HFRR. The fractions were tested
neat (except fraction 5 because of its limited availability)
and in a series of blends. These blends were prepared by
sequentially adding each fraction in the same order (non-
polar to polar) and ratio as collected in order to gradually
reconstitute the starting ADO. The HFRR results are
plotted in Figure 2 against the cumulative amount
collected at each stage of the fractionation, to give some
idea of the volume fraction at each stage.
Furthermore, the subsequent fractions were no better
except for a minor improvement for the penultimate
fraction. As the final fraction as only available in limited
quantities it was not tested neat. The fractions were then
blended together in the same ratio as collected in order to
gradually reconstitute the Fawley ADO. Figure 2 shows
that the lubricity only improved to the same level as the
starting ADO when the final fraction (fraction 5) had been
added. Thus, the key agents were concentrated in this
final fraction.
The final fraction was then blended into the penultimate
blend (fractions 1 to 4) in increasing amounts up to its
natural level. HFRR results for these blends produced the
non-linear treat curve shown in Figure 3. Small amounts
(up to ca. 1%) of the polars had no effect. Only
when a critical concentration was reached was an
improvement observed. Higher concentrations, above ca
2 to 4%, had no additional effect. Thus, the starting
Fawley ADO contained a large surplus of the natural
lubricity agents.

Figure 2. Lubricity performance of fractions and

blends from silica column
chromatography
Figure 3. Treat rate curve for silica fraction 5.
The first (no eluent) fraction gave an HFRR wear scar
diameter (WSD) of 561 µm versus 280 µm for the starting
ADO. This was a clear indication that the key agents
were no longer present in this initial fraction.

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Table 2. Biosil fractionation of Fawley polar fraction
Fraction Eluent
BF1 Hexane
BF2 Hex/Dichloromethane (94/6)
BF3 Hex/Dichloromethane (50/50)
BF4 Dichloromethane/MeOH (90/10)
Total
In the second stage, 30g of the active silica fraction
(fraction 5) was further fractionated using a Biosil (Silicic
acid) stationary phase.24, 25 This was done in order to
concentrate the active agents even further. Table 2
provides a summary of the eluents employed and the
amount collected in each fraction on a weight and %
basis. The % values are given both in terms of the
starting fraction and as a percentage of the total fuel.
The first two fractions contained the largest amounts,
while the latter two fractions were much smaller and only
represented trace levels of the original fuel. The lubricity
performance of these fractions was evaluated using the
HFRR. As these fraction were only available in limited
quantities they were not tested neat but in a sequential
blend approach as before. The silica fractions were
blended together first and then the Biosil fractions were
added in sequence. The results are plotted in Figure 4
below.
Figure 4. Lubricity performance of Biosil fractions.
Biosil fractions sequentially added to
combined silica fractions
This plot only shows the region of interest. As in the
previous study (Figure 2) the lubricity performance of the
blend of silica fractions (fractions 1 to 4) was poor. This
poor performance continued even after the addition of
Biosil fractions 1, 2 and 3. The performance only showed
an improvement after the addition of the final Biosil
fraction. Thus, a significant portion of the silica polar
fraction had no effect on lubricity. The final Biosil fraction
4
Wt (g) Wt % of polars Wt % of fuel
12.4 41.1 2.92
15.3 50.8 3.61
1.1 3.6 0.26
0.47 1.6 0.11
29.2
contained the majority of the key agents and only
constituted a minor portion of the fuel.
In a supporting HFRR study Biosil fractions 1 to 3 were
blended separately into silica fraction 1 (the poor lubricity
'no eluent' fraction) at 3%, a concentration much higher
than their natural occurrence. The blends containing
Biosil fractions 1 and 2 had poor lubricity (HFRR WSD of
590 µm and 573µm respectively), while the blend
containing biosil fraction 3 had good lubricity (HFRR
WSD of 272µm). Thus, this penultimate Biosil fraction
also contained a small amount of the good actors but not
enough to reach the critical threshold when added at its
natural concentration.
This work shows that the key lubricity agents were
concentrated largely in the final biosil fraction with a small
amount still 'contaminating' the penultimate fraction.
A range of different fuels and streams were fractionated
in a similar manner. The polar fractions varied in amount
and performance. Even Swedish Class 1 fuel contained
some polars but clearly not enough to reach the critical
threshold. When these polars were back-blended at a
higher concentration an improved response was
observed as shown in Figure 3.
Viscosity results for the blends exemplified in Figure 3
were shown to have a constant viscosity (KV40 = 3.1cSt)
along the entire treat curve (see Figure 5 below). At no
stage was the viscosity perturbed.
Thus, trace levels of polars compounds have the
largest effect on fuel lubricity.
Figure 5. Treat rate curve for silica fraction 5.
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The effect of viscosity was probed in more detail using a
series of hydrocarbon fluids. Many of these samples
were the initial (no eluent) fractions from silica column
chromatography of different fuels and streams. All of
these samples were free (or virtually free) of polars and
thus dependent upon bulk viscosity to provide protection.
The results for these samples, plotted in Figure 6,
showed that HFRR lubricity is impacted by viscosity
but the effect is small. A viscosity of ca. 6cSt, well
above the diesel specification limit, was required to meet
the 460µm maximum wear scar target. The viscosity
effect was largely linear but some unexplained underlying
effects appear to exist. When the viscosity range was
extended outwith the diesel range some non-linearity
was observed. Moving lower (into mogas) gave a sharp
deterioration while moving higher into light lube oils the
curve started to plateau as the test limit was reached.
Figure 6. Impact of viscosity on HFRR lubricity
(Results for diesel fuel fractions and
hydrocarbon samples)
When low and high viscosity samples, containing virtually
no polars, were treated with typical lubricity additive the
viscosity effect translated through the treat curve and as a
consequence less additive was required in the high
viscosity sample to meet the 460µm target (see Figure 7).
Figure 7. Lubricity performance of low and high
viscosity samples treated with lubricity
additive
5
HOW DO POLARS IMPROVE LUBRICITY?
The active polar fraction from silica chromatography was
investigated in two complementary experiments. In the
first, Sum Frequency Generation (SFG)26 was used to
quantify the concentration of polar compounds on a
metal-like substrate at different bulk concentrations. The
solid substrate consisted of a 300 angstrom iron layer
grown on a sapphire prism using sputtering deposition,
which then becomes oxidised by reaction with air.
The polar THF fraction from Fawley ADO was blended
into a paraffinic base fuel (hexadecane) so that the polar
compounds, aromatic in nature, were readily identifiable.
The blends prepared for this study were also evaluated
using the HFRR. The SFG and HFRR results are both
plotted in Figure 8 below.
This graph shows that the SFG signal intensity increases
with the bulk concentration showing that more
compounds are adsorbing on the surface. At a level of
around 8% the signal plateaus. This is believed to be the
point at which the surface is fully covered or saturated
with compounds. It can also be seen from this graph that
the concentration for surface saturation coincides with
the concentration for optimum lubricity.
Figure 8. Analysis of adsorbed compounds using
SFG
Figure 9. Analysis of adsorbed compounds using
FTIR
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Further evidence was obtained for the surface-active and the oxygen content was measured by neutron
nature of the polar fractions from adsorption studies activation. The values reported in Table 3 below are in
using Fe2O3 powder. In this study an extremely high ratio ppm.
of powder to fuel was employed to provide a large surface
These data show that the potent silica fraction contains
area for adsorption. The diesel was mixed with the
all the N containing compounds, the majority of the 3+
powder and then after a period of time the filtrate was
ring polyaromatics and the O compounds but only ca.
extracted by ultra-centrifugation. FTIR spectra were
50% of the S compounds. Thus, the poor lubricity
obtained for the original diesel and for the resulting
fractions still contain a significant portion of the S
filtrate. A difference spectrum was obtained by
compounds, but none of the N compounds.
subtracting the fuel from the filtrate. This represents the
compounds that are missing from the filtrate which were Biosil fractions were characterised in a similar manner
assumed to be adsorbed on the metal surface. This (see Table 4 below).
spectrum was compared with the spectrum of the polar
The most potent fraction (fraction 4) contains high
fraction from silica column chromatography. This
levels of hetero-compounds. The N compounds are
comparison is shown in Figure 9. From this we can see
concentrated in this fraction and also the penultimate
that the distinctive peaks in the 'polars' trace match the
fraction which also showed some ability to enhance
absorbances in the filtrate-fuel difference spectrum.
lubricity, while the S compounds are spread throughout
These peaks are characteristic of aromatic compounds.
active and inactive earlier fractions as are the O
Both studies support the proposal that that the polar compounds.
fraction contains compounds that adsorb on a metal
The modified IP 391 method did not detect any aromatic
surface, thus providing a protective layer.
compounds in Biosil fractions 3 and 4. A likely
When the SFG test cell was flushed with neat interpretation for this is that these fractions do contain a
hexadecane the absorbances corresponding to the mixture of aromatics compounds but they are so polar
adsorbed compounds diminished and eventually that they strongly adsorb to the HPLC column and are not
disappeared. When a similar study was conducted with removed/transported by the relatively non polar eluent n-
ester lubricity additive in hexadecane the absorbances hexane.
remained after the hexadecane flush. This showed that
The key agents are the most polar compounds
the natural lubricity agents were not strongly adsorbed to
present in the diesel. These compounds are only
the surface while typical lubricity additive molecules
present in trace levels and they are surface active.
were.
The active fractions are rich in N, O and S.
WHAT COMPOUND CLASSES ARE PRESENT IN
WHAT TYPES OF COMPOUNDS ARE
THE ACTIVE FRACTIONS?
CONTAINED IN THE ACTIVE FRACTIONS?
Diesel fuels contain a myriad of different compounds.
GC traces for the active silica and biosil fractions show
The majority are purely hydrocarbon but there is still, in
the presence of a complex mixture of compounds. A few
some fuels, a sizeable minority of S, N and O hetero-
were characterised by mass spectrometry using libraries
compounds. Because of the complexity of this system,
of fragmentation patterns for known compounds. Typical
no-one has been able to fully characterise a diesel fuel to
diesel compounds like substituted quinolines, indoles and
the stage that each compound is itemised, even with the
carbazoles were identified as well as more novel
most advanced analytical techniques.
compounds like benzocinnolines, benzanthracenones
General compositional data were obtained first to obtain and benzpyrenones. However, these compounds only
some insights into the chemical classes present, and constituted a very minor portion of the sample and thus
then more in-depth analyses (e.g. advanced mass should not be used to obtain a misguided view of the
spectrometry) were used to characterise a few of the sample composition. It is likely that these samples
individual compounds. contain a broad range of different compounds, some of
which will have complex hydrocarbon frameworks with
Table 3 below shows characterisation data for fractions
mixtures of heteroatoms and functional groups. These
from silica column chromatography. IP391
will not be readily characterised as they are unlikely to be
measurements were made according to a modified
in reference libraries due to difficulties in obtaining
method, which is more suited to the polar fractions of
reference samples.
most interest (see Appendix 1 for details). Sulphur and
nitrogen contents were measured by an ANTEK method

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Table 3. Compositional analysis of silica fractions

Table 4. Compositional analysis of biosil fractions

WHAT TYPES OF COMPOUNDS IMPROVE Further studies showed that compounds with > 1
LUBRICITY? heteroatom tended to be more active than those with only
one. The precise nature of the heteroatom was also
This question cannot be addressed using refinery important, e.g. exocyclic N compounds were more active
samples, since even the most complex and specific than heterocyclic N compounds and particular
fractionation processes cannot separate the fuel into combinations and geometries were more active than
individual molecules. Study is best done through the use others. Table 6 below shows a subset of the data to
of model compounds. However, this can also be exemplify these general structure activity relationships.
subjective since the compounds selected may not be the
most representative.
Due to the complexity of the system there are a great
many different structural features that could be
investigated. Only a few were considered in our activities.
To avoid any confusion the test compounds were
generally evaluated in a fluid that was void of other polar
compounds, e.g. Isopar M or an ultra low S diesel. Such
fluids generally had poor solvency properties and special
care need to be taken to fully dissolve the most polar
candidates.
Firstly, typical aromatic hydrocarbons only had a marginal
effect on the lubricity of Isopar M (see Table 5 below).
This level of performance is still worse than typical poor
lubricity low S diesels. Figure 10. Comparison of S, N and O model
compounds
Typical S compounds like benzothiophene (and
dibenzothiophene) had little or no impact on lubricity. Some polycyclic hetero-compounds were active at
However, its O (2,3 Benzofuran) and N (Indole) extremely low concentrations. For example, at a
analogues did show some activity with the N being more concentration of 50ppm in an ultra low S diesel, 5- methyl
active than O (see Figure 10). benzimidazole gave a WSD of 389µm (vs 560µm for the
base fuel).

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Table 5. HFRR performance of typical aromatic hydrocarbons
Compound
Mixed xylenes
Naphthalene
Phenanthrene
Pyrene
Compounds were dissolved in Isopar M which gave a WSD of 820µm
Table 6. HFRR performance of N hetero-compounds
Compound
Quinoline
1-Amino naphthalene
Quinazoline
3-Amino quinoline
1,8-Diamino naphtalene
This work only starts to scratch the surface of the
possible structure active relationships (SARs) involved,
but is probably sufficient for this discussion. Many other
workers have reported more detailed SARs.19-22 Let it
suffice to say they are many and complex.
In summary, there is NO single class or type of
compound that provides the natural lubricity
performance. The protection is provided by a complex
mixture of polar compounds, most are active to some
extent however large or small. The nature of the
compounds involved is both crude and refinery
processing dependent. Even with the most advanced
techniques available today it is not possible to fully
itemise each compound involved.
Because hydrodesulphurisation is not a selective process
it removes N and O as well as S. The removal of N and O
from hetero-compounds destroys their ability to perform
as lubricity agents. Thus, low S fuels have lower levels of
active N and O compounds and thus worse lubricity.
DO NATURAL LUBRICITY AGENTS COMPETE
WITH LUBRICITY ADDITIVE?
Because a fuel needs a critical threshold of polar
compounds in order to have a good lubricity performance
(Figure 3) poor lubricity fuels can still contain measurable
levels of the key agents, but just not enough. When such
poor lubricity fuels are treated with additive there may be
a synergistic or antagonistic interaction between the
remaining natural lubricity agents and the additive.
µm)
HFRR WSD (µ
1% 3%
716 745
609 660
666
653
Heteroatom details µm) @ 500ppm
HFRR WSD (µ
1 heterocyclic N 539
1 exocyclic N 544
2 heterocyclic Ns 499
1 hetero N and 1 exo N 341
2 exocyclic Ns 306
A study was conducted to gain some insight into the
interactions involved. Swedish Class 1 fuel was blended
with increasing amounts of a polar fraction from silica
column chromatography and the resultant blends were
evaluated both unadditised and treated with 200ppm of a
typical ester lubricity additive. The results, plotted in
Figure 11 below, show that fuels containing higher levels
of natural polars require less lubricity additive. Thus, it
appears that the natural and synthetic lubricity agents
complement each other. Because of this, it is likely that
additive requirements will increase as S levels are
reduced further below 500ppm, if as expected there is a
coincident reduction in the level of the active lubricity
agents.
REFINERY INSIGHTS
A survey of typical distillate streams (virgin and cracked)
showed that before hydrotreatment most streams have
good lubricity performance (see Figure 12 below). After
hydrotreatment for 500ppm fuel the higher boiling
streams retained much of their performance while a
noticeable deterioration was observed for the lighter
boiling streams (see arrow on Figure 12 at 360 C).
Because higher boiling streams contain a higher level of
hetero-compounds to start with they can still retain a
threshold amount after moderate hydrotreatment. An
analysis of research samples showed that high-boiling
samples will eventually show a deterioration but only after
extremely severe hydrotreating conditions as shown in
Figure 13. This effect is clearly founded upon the non-
linear treat curve shown in Figure 3.
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had a much larger surplus of polars and could withstand

higher levels of dilution than the after sample (see Figure
14).

Figure 11. Interaction of diesel polars and lubricity

additive

Figure 14. Dilution Study - Impact of hydrotreatment

on the lubricity performance of heavy
refinery streams

It is therefore difficult to use lubricity measurements of

refinery streams to predict the lubricity performance of
finished blends because of the non-linearity of these
effects. Thus, the most straightforward way to monitor
lubricity is through the final blend and not the component
streams.
Undercutting or tailing a high boiling refinery stream has
a similar effect to hydrotreating. The off-cut contains a
Figure 12. Lubricity performance of refinery streams higher concentration of polar hetero-compounds and
before and after hydrotreatment for thus the under-cut has a reduced concentration.
500ppm S ADO
Trends in refinery processing, S reduction, lowering the
FBPt, saturation of aromatics, will all cause lubricity to
deteriorate and increase the dependency on lubricity
additives.

CONCLUSIONS

• The largest contribution to diesel fuel lubricity comes

from trace amounts of surface-active polar
compounds.
! These act by forming a protective layer on the
metal surface, thus improving boundary
lubrication
! The active molecules do not persist on the
Figure 13. Heavy streams hydrotreated to ultra low S surface and need to be continually replenished
levels
! The most active polar materials naturally
When a high boiling stream retains a good lubricity occurring in diesel fuel are hetero-compounds
performance after hydrotreatment this does not mean containing N and / or O
that it's lubricity potential has remained untouched. A ! Structure activity relationships are not fully
dilution study was conducted in which a poor lubricity understood. However, the most active
stream was blended into samples taken before and after compounds tend to have > 1 heteroatom,
hydrotreatment. This showed that while both samples with the heteroatoms in an exposed
had acceptable lubricity performance the 'before' sample (exocyclic) configuration.

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! Diesel fuels contain a complex mixture of hetero-
compounds which cannot be fully characterised /
itemised even with the most advanced analytical
techniques.
• Natural polar species are concentrated in the heavier
fraction of diesel fuel
• Fuel viscosity only has a small effect on lubricity
! The viscosity effect can be confounded by the
increased concentration of N and O hetero-
compounds in higher viscosity streams.
! In the absence of polar compounds, the
European HFRR specification cannot be met
• The improvement in lubricity as a function of the
concentration of polars is non-linear.
! A minimum threshold amount is required to
achieve an improvement. At higher treat rates the
lubricity performance reaches a plateau.
! This non-linearity underpins the impact of
refinery processing on the lubricity of refinery
streams
• Both undercutting and hydrotreating deteriorate
lubricity by removing the natural lubricity agents
! The deterioration in lubricity is only observed for
neat streams when the level of polars is reduced
below the critical threshold.
! The deterioration in lubricity is NOT due to the
removal of the typical S compounds as they have
little or no effect on lubricity. Some are even pro-
wear.
• Blend lubricity is dependent upon the nature and
amount of the blend components
! HFRR measurements for neat streams are not a
reliable indicator of their performance in blends
due to the non-linear behaviour of polar
compounds.
• Refinery streams for LSADO can still retain an
adequate concentration of natural lubricity agents as
long as they only undergo mild hydrotreatment i.e.
originate from sweet crudes.
• Natural lubricity agents complement
additives
! Lubricity additive requirements can be reduced
by maximising the amount of natural lubricity
agents
! Future fuels with lower S contents will require
higher additive treat rates than used today
ACKNOWLEDGEMENTS
The authors would like to thank their colleagues in the
Analytical Department (D.J. Abbott), at Corporate
Research (H.S. Pink, M.S. Yeganeh, C.S. Hsu, P.J.
Berlowitz) and in Process Research (G.E. Markley) for
their support with this programme.
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APPENDIX 1 - MODIFIED IP 391 METHOD

The standard IP391 method is conducted by High

Performance Liquid Chromatography (HPLC) and is
calibrated using a standard of xylene, methyl
naphthalene, and phenanthrene in cyclohexane. Current
studies on polar fractions have shown that this method
does not give comparable results to mass spectrometry
and super critical fluid chromatography (SFC). This was
improved using a modified standard containing
mesitylene, indane, methyl naphthalene, biphenyl, and
phenanthrene dissolved in n-hexane. The samples are
run in the normal manner and where samples show an
absence of saturates, which is usually the case for the
polar fractions, the results are normalised to 100%.

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