Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

ARTICLE INFO
Article ID: 04-13-01-0002
© 2020 Shell Global
Solutions (US) Inc.
doi:10.4271/04-13-01-0002

In-Depth Analysis of
Additive-Treated Gasoline with a
Modified High-Frequency
Reciprocating Rig Technique
Wendy Lang,1 Edward Malisa,1 Joseph Russo,1 Andreas Glawar,1 John Mengwasser,1 William Colucci, 2
Kristine Morel, 2 and Edward Nelson1
1
Shell Global Solutions (US) Inc., USA
2
Afton Chemical Company, USA

Abstract History
Received: 14 Mar 2019
Gasoline fuel lubricity is key to reducing wear and energy losses from friction in engines. The High- Revised: 25 Jun 2019
Frequency Reciprocating Rig (HFRR) test protocol recommended for gasoline fuels has been Accepted: 05 Nov 2019
modified to evaluate the wear and friction properties of additized fuels. Adapted from the American e-Available: 21 Nov 2019
Society for Testing and Materials (ASTM) D6079 test for diesel lubricity and literature-based proce-
dures developed for gasoline fuels, the protocol and hardware used in this study allow for differen- Keywords
tiation of fuels with unique additive chemistries and varying additive treat rates (EPA-approved HFRR, Gasoline, Lubricity,
lowest additive concentration, LAC, or higher). Supplementing HFRR tests, measurements of acoustic Additives, Wear, Friction
emissions corroborate friction coefficient trends using different additized fuels. Anti-wear perfor- reducer, Engine, Acoustic
mance of fuels during engine tests was characterized by roller-follower pin wear and metal concen- emissions
tration in engine oil, further distinguishing LAC from alternate additized fuels. The engine tests and
acoustic emissions measurements support HFRR observations that gasoline fuels with varying Citation
additive chemistries and concentrations can offer enhanced lubricity compared to fuels additized Lang, W., Malisa, E., Russo, J.,
with basic LAC additives. Glawar, A. et al., “In-Depth
Analysis of Additive-Treated
Gasoline with a Modified
High-Frequency
Reciprocating Rig Technique,”
SAE Int. J. Fuels Lubr.
13(1):19–35, 2020,
doi:10.4271/04-13-01-0002.

ISSN: 1946-3952
e-ISSN: 1946-3960

19
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020
20 Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020
1. Introduction
T
he lubricity characteristic of a fuel is key to preventing
material wear under loaded contact conditions within
the engine injection systems by maintaining a protec-
tive film between the two fuel-wetted surfaces [1]. Diesel fuels
have specifications for fuel lubricity because the use of high-
pressure injectors and pumps in these types of engines
requires lubricity to control wear and catastrophic failures.
Traditional gasoline-powered engines have been port fuel
injection engines which operate at relatively lower pressures,
and so the demands on the moving parts in fuel pumps and
injectors have been lower [2, 3, 4, 5]. However, with the
increasing prevalence of gasoline direct injection engines and
their continuing evolution, improved fuel lubricity could
become key to reducing wear and the risk of pump failure
under high-pressure conditions [2, 3, 4, 5, 6]. Fuel lubricity
challenges have existed for several decades, starting in the
1960s with instances of aviation jet fuel pump failure [2, 3,
4,  5]. It was determined that hydrotreatment of jet fuel
removed sulfur and other polar species which otherwise
contribute to fuel lubricity characteristics [2, 3, 4, 5]. In the
1980s, diesel fuel pump performance suffered as sulfur content
in fuels was also reduced by the hydrotreating process of the
fuel [2, 3, 4, 5]. Gasoline fuels have been severely hydrotreated
to reduce the negative effects of sulfur on catalytic converter
life and performance [2, 3, 4, 5]; and, due to their lighter
­distillation cut, have innately diminished natural anti-wear
properties [2, 4, 7].
Whereas wear is a material loss characteristic of relative
motion at a surface, friction impacts lubricity in terms of
energy loss within an engine system [8]. Ramalho and
Miranda reasoned that friction energy is dissipated through
wear particle generation, a rise in temperature through heat
generation, and entropy changes associated with material
transformation at interfaces [8]. Depending on the wear mech-
anism, wear volume and energy dissipated from friction are
considered to be linearly related [8, 9]. However, deviations
from the general correlation can occur under the influence of
a third body (e.g., a lubricant) [8, 9]. In quantifying energy
losses from friction, studies have noted that in passenger cars,
one-third of fuel energy is used to overcome friction in
engines, transmissions, tires, and brakes [10]. Approximately
40-60% of mechanical friction in an engine can be attributed
to pistons, rings, and cylinder walls [11]. Additional penalties
are experienced in bearings, seals, and valve trains, and by
pumping and hydraulic viscous losses [10]. Methods of
lowering friction include advanced surface coatings, modified
surface topographies, and the use of lubricants to provide fluid
and chemical films, as well as corrosion protection [10]. Fuel
additives such as surface modifiers can be used to mitigate
against friction and wear by forming a protective layer on the
metal surfaces [5, 6, 11]. Approximately 25% of incoming fuel
additives impinge upon cylinder walls and are captured by
the thin film of oil exposed during intake and compression
strokes [11]. Since cylinder wall temperatures are typically less
than 175°C, the additive can survive the combustion process
and be  delivered to locations where boundary friction is
present, such as between piston rings and cylinder walls [11].
Engine and vehicle tests offer the capability to assess wear,
friction, and fuel lubricity under realistic operating conditions
with real parts and materials. However, a less resource-inten-
sive and well-controlled alternative is the simple and easy-to-
use HFRR [3]. Fuel and material properties are analyzed under
boundary lubrication conditions with repeated-pass slow-
speed sliding of one specimen against another [12]. Wear is
measured by a wear scar produced over the duration of the
test [12]. Additionally, the friction coefficient is measured as
a ratio of friction force to applied load: the higher the friction
coefficient, the poorer the lubricity characteristics of the lubri-
cant or fuel and the more significant metal-to-metal contact
and wear may be [6, 12]. Initially developed to screen and
evaluate the effect of additives on diesel fuel lubricity, the
HFRR test method for diesel fuels has been standardized per
ASTM D6079 and tests have been found to produce wear
results which correlate well with fuel performance in diesel
fuel pumps [3, 13].
The conventional diesel method (ASTM 6079) was
modified to measure gasoline wear and friction properties by
Wei, Korcek, and Spikes, taking into consideration the higher
volatility of gasoline and extreme sensitivity of gasoline
lubricity to tiny amounts of contaminants [2, 3]. These modi-
fications included (1) a deeper fuel bath fitted with a lid to
reduce the gasoline evaporation and (2) lowering the operating
fuel temperature to 25°C versus 60°C used for testing of diesel
fuel [2, 3]. The sealed sample cup reduced the need to refill
the chamber, preventing exposure of the rubbing contacts
during the test. Also, evaporation would change the composi-
tion of the fuel over the course of the test and affect the results
[2, 3, 6, 14]. Wei et al. successfully utilized the covered-cup
gasoline method when surveying commercial gasolines with
and without additives, studying considerable differences in
wear depending on gasoline composition (bulk fuel, detergent
additives), determining the effect of additive concentration
on both friction and wear, establishing a linear relationship
between wear and gasoline kinematic viscosity, and investi-
gating the effectiveness of using diesel additives in gasoline
to reduce wear [2, 3].
Arkoudeas et al. employed the same HFRR test conditions
to assess the lubricity of 126 samples of commercial gasolines
as dependent on fuel composition (unleaded, super unleaded,
lead replacement petrol), and found a strong correlation
between the friction coefficient and wear scar diameter [7].
In contrast, Lopreato et al. did not observe a correlation
between the friction coefficient and wear when studying the
behavior of ethanol-containing gasoline fuels [4]. Wear was
found to increase with increasing ethanol content until
approximately 18% ethanol in gasoline, beyond which wear
scar values decreased [4].
The effects of ethanol, water, and aromatic content of
gasoline on wear were further studied by Chiampradit et al.
[15] using the modified HFRR method. Ethanol was observed
to not have an effect when blended in gasoline but reduced
the negative effects of water in gasoline on wear. Increasing
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020 21

water content increased wear for E0 fuels, and increasing  FIGURE 1   Lab A HFRR setup with covered gasoline cup
aromatic content decreased wear [15]. sample holder and 200 g load.
Agudelo et al. [6] found that with no water vapor pressure
control during ethanol/gasoline HFRR tests, E20 to E85 fuel
blends displayed minimal variation in wear scar diameter and
coefficient of friction regardless of the addition of anhydrous
(0.2 wt% water) or hydrated (4 wt% water) ethanol to gasoline.
That is, altering ethanol and water content in samples did not
have a significant impact on lubricity [6].
Though the work of Wei et al. [2] and others provide key
insights into evaluating gasoline lubricity with the HFRR, and
the patent literature contains examples of the HFRR use,
applications of the HFRR and comparisons of the HFRR to
other metrics of wear and friction remain somewhat limited
in the literature.
In this study, the HFRR test method for gasoline modified
from ASTM D6079 by Wei et al. was amended to evaluate
wear and friction using gasoline fuels with different additive
packages and additive concentrations. In addition, acoustic
emissions were measured as an alternative technique to assess
wear and friction [16]: hardware modifications were made in
this study enabling sound monitoring during HFRR tests. To
complement the HFRR, wear was alternatively assessed via
© Shell Global Solutions (US) Inc.
Sequence VG/VF engine tests. Though these standard tests
are typically used to evaluate engine oils, studies have demon-
strated the transfer of fuel additives into sump oil [11, 17], and
as such, the engine tests were employed to probe the impact
of fuel additives on engine wear. The engine and acoustic
measurements were used to corroborate wear and friction
results from the modified HFRR tests, and statistical differ-
entiation of fuels additized with a range of additive chemis-
tries and treat rates further demonstrated the robustness of
the modified HFRR as a test method for gasoline.
ASTM D7688, and JPA-5S-50. Specimen properties are listed
in Table 1. The ball was secured in the holder and pressed
against the fixed disk with the entire contact area fully
immersed in fuel during the test. The HFRR specimens were
2. Methodology used once per experiment.
Before each experiment, the specimens and HFRR parts
(sample well, lid, and arm) were successively cleaned and soni-
2.1. Modified HFRR Test cated in different solvents. The Lab A HFRR parts were cleaned
Two PCS HFRR instruments with gasoline conversion kits in toluene, methanol, and acetone (in that order) followed by
were utilized to assess wear and friction at two independent drying with nitrogen gas for 15 min. The Lab B parts were
industrial laboratories: Lab A and Lab B. The objective was to cleaned following the sequence of toluene, acetone, and iso-
assess HFRR test protocols and methods for gasoline and octane, with a heptane rinse before drying. These cleaning
compare wear and friction results for similar samples from procedures were modified from the ASTM D6079 standard
the two labs. The conversion kit hardware included deeper (cleaning balls, disks, and hardware in heptane or 50/50
cup fuel holders to accommodate the larger gasoline sample isooctane/2-propanol, rinsing with acetone, and drying) to
size compared to the standard diesel sample size (15 mL vs improve the removal of surface active species between test
2 mL). The gasoline cups were covered with PTFE lids to
minimize evaporation of test fuel. The Lab A HFRR setup is TABLE 1  HFRR specimens.
enclosed in a transparent plastic box to reduce the effects of
evaporation, minimize temperature changes during opera- Specimen Disk (lower) Ball (upper)
tion, and provide noise control. Figure 1 shows the Lab A Diameter 10 mm 6 mm
HFRR test rig. Each test rig had one operator throughout the Hardness 190-210 Hv30 58-66 Rockwell “C”
tests described below. Surface finish/ <0.02 μm Ra surface <0.05 μm roughness
Specimens used were made of SAE-AMS 6440 steel and roughness finish
certified in accordance with ISO 12156-1, ASTM D6079/ © Shell Global Solutions (US) Inc.
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020
22 Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020
TABLE 2  HFRR test conditions for diesel and
gasoline samples.
Test conditions Diesel [13] Gasoline
Fluid volume (mL) 2 15
Stroke length (μm) 1000 1000
Frequency (Hz) 50 50
Fluid temperature (°C) 60 25
Applied load (g) 200 200
Test duration (min) 75 75
© Shell Global Solutions (US) Inc.
runs [13]. For consistency, a torque wrench was used to tighten
screws when securing specimens within the Lab A HFRR setup.
Prior to transferring the gasoline sample to the Lab A
HFRR cup, the sample was shaken for 15 min and nitrogen
gas used to blow any residues from the cup. A glass pipette
was used to transfer 15 mL of sample to the cup and a visual
inspection conducted to check for residues or particles
(samples with visible residues or particles were discarded). A
small level was used for both HFRR setups to ensure the
crossbar was level and therefore the applied load aligned.
There is no defined standard to test gasoline, but typical test
conditions are listed in Table 2 along with standardized condi-
tions for evaluating diesel per ASTM D6079 [1, 2, 3, 4, 6, 7, 12,
13, 14, 15]. The lower temperature utilized for gasoline testing
mitigates the risk of combustion. The impact of water content
and relative humidity on diesel fuel wear performance is widely
noted; and as such, relative humidity is addressed in standard
procedures (e.g., 30-85% per ASTM D6079 [13], 53% ± 5% per
ISO 12156-1:2018 [18]). In modifying and applying diesel stan-
dards to gasoline tests, many studies have adhered to ASTM
D6079 humidity specifications [1, 2, 3, 4, 7, 15, 19, 20] though
some studies have been conducted without humidity controls
[6]. Given approaches described in the literature and standards,
relative humidity levels at Lab A were maintained in the range
specified by ASTM D6079 and HFRR tests at Lab B were
conducted under ambient conditions. To account for variability
 FIGURE 2   Sound monitoring equipment with the Lab A HFRR gasoline setup.
in not only relative humidity but also other key factors that affect
lubricity (e.g., additive concentration and chemistry, base fuel),
randomized statistical test matrices were designed and carried out.
Whereas ASTM D6079 recommended calibration inter-
vals include stroke-length calibrations every three months
and temperature probe calibrations every 12 months utilizing
reference fluids high and low in lubricity [13], the Lab A
approach was to conduct a daily HFRR instrument calibration
before evaluating fuels.
During a test, the upper specimen is repeatedly passed
over the lower specimen as controlled by an electromagnetic
vibrator. The fuel temperature and friction coefficient were
monitored throughout each test. An aluminum heater block
maintains a constant fluid temperature and a piezoelectric
force transducer measures the friction force generated between
the two specimens. At the end of each test, the wear scar on
the upper specimen was measured using a digital micrometer
under a standard metallurgical microscope with vertical illu-
mination and 100× magnification. Typical wear scars appear
in the form of a circle or an ellipse such that dimensions across
and in the direction of specimen motion (major and minor
axes) can be averaged to give the mean wear scar diameter.
The Lab B HFRR setup is further equipped with a digital
camera and image reader offering digital images of the wear
scar as alternatives to visual inspection by microscopy.
Supplementing the standard 75 min HFRR tests were a
series of shorter experiments to assess wear and the effective-
ness of a protective fuel additive film over time. The tests were
conducted at Lab A by running for a shorter amount of time,
stopping the test, measuring the wear scar, and restarting runs
from the beginning with new specimens. Tests were conducted
for 2, 5, 15, and 75 min runs. Two tests were completed for
each prescribed time period and results averaged.
Additional modifications to the Lab A HFRR setup
included acoustic monitoring elements. Acoustic emission
monitoring over the course of a test was conducted with the
use of a Cole-Parmer Digi-Sense Data Logging Sound Meter
positioned above the HFRR gasoline cup as shown in Figure 2.
© Shell Global Solutions (US) Inc.
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020 23

Although differences in procedure were explored at both Labs TABLE 3  Fuels tested.
A and B, the results of the independent investigations provided Description (treat rate relative Lab/engine
reasonably similar and reliable results. Fuel to LAC) resting
LACi Lowest additive concentration LACα: Lab A
(PIB amine), i = α, β, γ LACβ: Lab B
2.2. Sequence VG/VF Testing LACγ: Engine
Protocol TTi Top Tier™ equivalent additive TTα: Lab A
concentration at ~2× LACi(PIB TTβ: Lab B
Engine tests to assess anti-wear performance were conducted amine)
using standard Sequence VG/VF tests per ASTM D6593 [21].
A1 Additive A at ~4× LAC Engine
The Sequence VG and VF tests were both used to evaluate
engine oils for their ability to minimize sludge formation and A2 Additive A at ~7× LAC Labs A and B,
Engine
varnish deposits in spark-ignition gasoline engines operating
B2 Additive B at ~7× LAC Labs A and B
under conditions designed to accelerate deposit formation.
The Sequence VF test was furthermore used to assess anti-wear B2 E0 Additive B at ~7× LACα in E0 Lab A

© Shell Global Solutions (US) Inc.

performance of additized oils via roller-follower pin wear and B3 Additive B at ~8× LACβ Lab B
metal concentration measurements. The test engine utilized D3 Additive D at ~8× LACα Lab A
was a Ford 4.6L spark-ignition, four-stroke, eight-cylinder Ci, i = 1-36 Non-Lab A unleaded premium US Lab A
engine with electronic port fuel injection. The test oil used was gasoline samples
formulated to meet ILSAC GF-5 specification. The total run Ci, i = 37-39 Non-Lab A unleaded premium Lab A
time of the test was 216 h, with oil samples procured every 24 (AKI = 91) Canadian gasoline
h and on the final drain at the end of the test. Per ASTM samples
D5185-18, the oil samples were analyzed in terms of iron
concentration as an indication of wear using ICP-AES
(Inductively Coupled Plasma Atomic Emission Spectroscopy) additive chemistry varies). Fuels were tested in randomized
[22]. Roller-follower pin wear measurements for both intake test matrices. Wear, friction, and sound results obtained
and exhaust valves of cylinder 8 were also completed at the using the Lab A HFRR instrument were averaged over trip-
end of the test. licate runs. Using the Lab B HFRR instrument, duplicate
runs were conducted using LAC, Top Tier™, and A2 fuels,
and four runs conducted using B2 and B3 fuels; these exper-
2.3. Test Fuels iments were randomized in the test matrix to ensure statis-
tical soundness. Tests for which the same base fuel was
A variety of different gasoline fuels were assessed using
utilized for LAC and other samples are noted as such in
HFRR and/or Sequence VG/VF tests, including fuels
discussion of results.
containing three experimental additive packages and 39
US/Canadian market samples, as listed in Table 3. Fuels
tested were unleaded premium E10 (10% ethanol) gasoline
samples unless otherwise indicated (e.g., E0 to represent 0%
ethanol in gasoline). Market fuels sampled from retail
3. Results and Discussion
stations across the USA and Canada are labeled as Ci (for
Commercial), the letter i corresponding to a distinct fuel. 3.1. Wear and Friction
Experimental fuels are labeled by the additive letter (A, B,
D) and additive concentration level (1, 2, 3). Fuels A, B, and
Coefficient Measurements
D comprised three different additives with unique anti-wear Using the Lab A HFRR instrument, the anti-wear perfor-
and friction reducer chemistries. Three different LAC fuels mance of premium fuels sourced from retail sites in the USA
α, β, and γ containing PIB amines at similar treat rates were was compared. Mean wear scar results at 95% statistical
blended and tested. Top Tier™ equivalent fuels containing significance are shown in Figure 3 for 30 gasoline samples
additives at approximately two times the LAC concentration obtained at retail stations across the USA and fuels A2 and
(i.e., at a typical Top Tier™ treat rate) were also blended and D3. The mean wear scar diameters range from approximately
tested. In testing fuels containing a range of additive 675 μm to 875 μm. These results indicate that the wear protec-
concentrations 1-3, additive concentration levels are char- tion provided to the test specimens was better using A2 than
acterized relative to LAC fuels: concentration level “1” corre- for all other samples tested. (The use of different colors indi-
sponding to approximately four times LAC, concentration cates results that are statistically significantly different.) The
level “2” approximately seven times LAC, and concentration range of wear scar results obtained demonstrate the ability of
level “3” approximately eight times LAC. Concentration HFRR to distinguish among a large survey of gasoline fuels
levels correspond to a consistent treat rate; for example, collected from around the USA at different times and places
fuels compared at an additive concentration level “2” all and with differing base fuel compositions. Performance differ-
contain the same concentration of additive (though the ences could be due to additives used within samples and/or
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

24 Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020

 FIGURE 3   Wear scar using US market unleaded premium gasoline samples. Conducted at Lab A.

© Shell Global Solutions (US) Inc.

due to differences in base fuel properties (e.g., aromatics,
olefins, sulfur, oxygenates, viscosity).
As part of a second survey using the Lab A HFRR instru-
ment, additive B fuels and US and Canadian unleaded
premium gasoline samples were assessed in terms of anti-
wear and friction reducer performance. The LACα, TTα, and
B2 samples were blended using the same base fuel. Wear scar
results for US market fuels along with LAC α , TTα , and B2
fuels are shown in Figure 4. The mean wear scar diameter
was found to range from approximately 600 μm to 840 μm,
similar to the range observed in the survey in Figure 3. Fuels
not shown in the same color (e.g., red, orange, blue) are
significantly different at the 95% confidence level; fuels shown
as cross-hatched with two colors are statistically similar to
other fuels represented by the two colors. LAC α and TTα
(~2 times the additive treat rate of LACα) fuels were found to
be in the same class as US fuels with statistically insignificant
differences between LACα and TTα. However, using an alter-
nate additive at a concentration ~7 times that of LACα, B2
was observed to produce significantly reduced wear (600 μm
scar) compared to the other samples tested in this matrix
(~800 μm scar).

 FIGURE 4   Wear scar using US market unleaded premium gasoline samples and LAC α , TTα , and B2 fuels. Conducted at Lab A.

© Shell Global Solutions (US) Inc.

 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020
Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020 25
The relation between HFRR wear scar diameter and
additive concentration has been proposed to exist in three
characteristic ranges [23]: (1) at low additive concentrations,
there is minimal reduction in wear scar with an increase in
concentration; (2) at effective additive concentrations,
increasing the concentration reduces the wear scar; and (3) at
higher concentrations, increasing the level of additives further
leads to marginal reductions in wear scar. In Figure 4, it is
indeed observed that increasing the treat rate ~2 times from
LACα to TTα using the same additive does not change the wear
scar diameter. A significant reduction in wear is achieved
using B2, which could be due to alternate additive chemistry
and/or the higher additive concentration.
Corresponding friction coefficient results from the same
tests are shown in Figure 5. The friction coefficient values were
averaged over the course of tests. As observed with the wear
results, LACα and TTα fuels fall within the same class as other
premium fuels with an average friction coefficient of approxi-
mately 0.6. The TTα friction coefficient is directionally lower
than that of LACα. The friction coefficient measured for B2 is
nearly half in value and statistically different at a 95% confi-
dence level compared to four out of six US market samples
(market fuels C35 and C36 were observed to have intermediate
friction coefficients statistically indistinguishable from the
other fuels). The directional and statistical differences in
friction coefficients measured further highlight the ability of
the HFRR method in differentiating fuels and additive concen-
trations, with friction trends consistent with those for wear.
Similar differentiation of anti-wear performance and
friction properties was observed using a smaller set of
Canadian unleaded premium gasoline samples. Canadian
market fuels C37-C39 comprise of 10% ethanol while B2
 FIGURE 5   Friction coefficients using US market unleaded premium gasoline samples and LAC α , TTα , and B2 fuels.
Conducted at Lab A.
© Shell Global Solutions (US) Inc.
evaluated in this survey was an E0 fuel. As seen in Figure 6,
wear scar results fell within three statistically different catego-
ries (with 95% confidence) ranging from 475 μm for B2 (with
no ethanol in gasoline) to approximately 840 μm for market
fuels C37 and C38. Furthermore, the mean wear scar diameter
for B2 (E0) is notably smaller than that of B2 (E10) shown in
Figure 4: while B2 (E10) produced a wear scar of 599 μm and
B2 (E0) had a wear scar of 475 μm. Blended using the same
gasoline and containing the same concentration of the same
additive, this difference suggests that 10% ethanol generates
greater wear. A limited number of studies in the literature
have observed varying HFRR results for the effect of ethanol
in gasoline or diesel on wear: ranging from improved lubricity
to no effect to worsened wear [4, 15, 19, 24]. As such, a system-
atic series of studies using HFRR could further elucidate
ethanol effects.
Friction coefficients measured using the same Canadian
market fuels and B2 (E0) are shown in Figure 7. As seen with
corresponding wear scar results, three separate classes were
observed for friction coefficients at a 95% confidence level. B2
(E0) had the lowest friction coefficient of 0.28, consistent with
the smallest observed wear scar diameter. Accompanying
greater wear, the market fuel friction coefficients ranged from
0.71 to 0.83. Within this narrow, higher range of values, the
results were nevertheless statistically differentiated such that
C38 and C39 were significantly dissimilar (with C37  in
between), demonstrating the ability of the HFRR to distin-
guish fuels with respect to friction coefficients.
Having conducted two surveys involving A and B addi-
tive-treated gasoline fuels and market fuels at Lab A, A and
B additive packages were compared directly in a series of tests
conducted using the Lab B HFRR instrument. Wear scar and
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

26 Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020

 FIGURE 6   Wear scar using Canadian market unleaded premium gasoline samples and B2 (E0). Conducted at Lab A.

© Shell Global Solutions (US) Inc.

friction coefficient results using LACβ, TTβ, A2, B2, and B3
fuels are shown in Figures 8 and 9, respectively. Consistent
with observations using the Lab A HFRR instrument in
Figures 4 and 5, both α and β LAC and TT fuels are signifi-
cantly different (with 95% confidence) from superior B2 fuels
both in terms of wear scar and friction coefficients.
No statistical differentiation was made between B2 (~7×
LAC) and B3 (~8× LAC), demonstrating diminishing returns
of increasing additive concentrations above what is presumably
already an effective level. Wear scar values decrease slightly
from 622 μm using B2 to 618 μm using B3, while friction coef-
ficients are similar: 0.32 for B2 and 0.33 for B3. The A2 fuel is
also not statistically significantly different from the B fuels,
though a directional improvement was observed with a wear
scar value of 605 μm while the friction coefficient was 0.34.
Generally, wear scar values observed at Lab B fall within
range of those measured using the Lab A HFRR setup for
LAC, TT, B2, and A2. This is seen in Figure 10a, which
summarizes wear scar results relative to LAC treat rate for
samples containing LAC, TT, A, and B additives tested at both
labs. Figure 10b includes analogous friction results for compa-
rable samples. The friction coefficient for B2 was observed to
be a relatively low average of 0.34; the same value was observed
using the Lab A HFRR. Friction coefficients for the LACβ and

 FIGURE 7   Friction coefficients using Canadian market unleaded premium gasoline samples and B2 (E0). Conducted at Lab A.

© Shell Global Solutions (US) Inc.

 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020 27

 FIGURE 8   Wear scar using unleaded premium LACβ, TTβ, and A and B additive-treated gasoline samples. Conducted at Lab B.

© Shell Global Solutions (US) Inc.

TTβ fuels were measured to be approximately 0.42, whereas
Lab A instrument measurements using LACα and TTα fuels
at the same treat rates were found to be approximately 0.6.
The differences in average friction coefficient values highlight
the differences in additive chemistries when comparing α and
β at the same treat rate. The differences in friction coefficients
could also arise from factors other than additive chemistry
or concentration including the base fuel(s) utilized and modi-
fications to the operating procedure and setup.
Wear scar aspect ratios (calculated as the wear measured
in the X dimension divided by wear measured in the Y direc-
tion) observed at both labs were also comparable. The majority
of market survey samples generated wear scars with aspect
ratios very close to or slightly greater than 1. Samples with the
smallest observed wear scar diameters and better performance
exhibited higher wear scar aspect ratios, as seen in Figure 11.
A and B samples tested at both labs had average wear scar
diameters less than 650 μm with aspect ratios greater than

 FIGURE 9   Friction coefficient using unleaded premium LACβ, TTβ, and A and B additive-treated gasoline samples.
Conducted at Lab B.
© Shell Global Solutions (US) Inc.
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

28 Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020

 FIGURE 10   (a) Wear scar and (b) friction coefficient results using experimental additives at treat rates relative to LAC,
conducted at Lab A (“A”) and Lab B (“B”).

© Shell Global Solutions (US) Inc.

1.10, whereas LAC and TT samples had significantly greater
wear scar dimensions and average aspect ratios of approxi-
mately 1.01-1.02.
Select wear scar images taken at Lab B are shown in
Figure 12. In general, greater wear in the X direction is
expected as the reciprocating motion is in the X direction.
This appears to be more pronounced in samples with smaller-
sized and more elliptical-shaped wear scars, such as for B2
and B3 in Figure 12c and 12d, respectively. In contrast, LAC
and TT wear scars were more circular in outline. The differ-
ences in overall wear scar dimensions and morphology corre-
spond to differences in additive chemistry and/or treat rate.
LAC and TT exhibit similar wear scar characteristics despite
the higher treat rate with TT, as was the case for B2 and B3.
However, altering the experimental additive used from LAC
to B and increasing the treat rate approximately sevenfold led
to significantly less wear and a noticeably different wear scar
aspect ratio.
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

 FIGURE 11   Average wear scar aspect ratios (wear in X dimension/wear in Y dimension) versus average wear scar diameters for
samples containing experimental additives analyzed at Lab A (“A”) and Lab B (“B”).

© Shell Global Solutions (US) Inc.

 FIGURE 12   Wear scar images, wear scar diameters, X/Y aspect ratios, and X and Y measured wear dimensions for samples
analyzed at Lab B under 100× magnification.
© Shell Global Solutions (US) Inc.

29
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

30 Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020

3.2. Friction and Wear
Measurements over Time
The change in friction coefficient over time during the Lab A
HFRR tests was further studied by stopping the test at different
time points: 2, 5, 15, and 75 min. Friction coefficients and wear
scars were measured at the stop of each test and averaged over
duplicate runs. As shown in Figure 13a, the peak in friction
coefficient near the start of tests is reproduced using LACα.
The friction coefficient quickly peaks by the time the test is
stopped at 2 min. Running the test until 5 min, the friction
coefficient begins to fall. By the 15 min point, the friction
coefficient value has fallen from approximately 2.0 to 0.5, the
latter being a relatively stable value observed during the
remainder of the full 75 min run. The friction coefficient
values greater than 1 near the start of the test signify that a
friction force greater than the normal force applied by the
200 g load is overcome to move the ball in contact with the
disk and results in the initiation of a wear scar. Similar
“run-in” behavior was observed using the Lab B HFRR instru-
ment. Figure 13b compares friction coefficient versus time
results for LAC samples tested at Lab A and Lab B. Though
the base fuels, operators, protocols, and hardware were
different, overall trends in friction coefficient behavior were

 FIGURE 13   (a) Friction coefficient measurements over increasing time intervals during LAC α HFRR tests conducted at Lab A
and (b) LAC α and LACβ tests conducted at Lab A and Lab B, respectively.

© Shell Global Solutions (US) Inc.

 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020
Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020 31
 FIGURE 14   Experimental wear scar measurements at increasing time intervals during LAC α HFRR tests conducted at Lab A.
© Shell Global Solutions (US) Inc.
comparable: a peak above 1 shortly after the start of test
followed by a decline to steady state values. This behavior has
furthermore been noted in the literature [14] and could
be attributed to the definition of the specimen surfaces and
disparities at the start of the test. The surfaces in contact
become larger in area so that the net force per unit area
declines as the rate of wear slows. Once the wear scar evolution
declines to a slower value, the friction coefficient stabilizes.
Wear scar measurements taken at 2, 5, 15, and 75 min
points demonstrate the benefits of a protective additive film
with logarithmic wear increasing as logarithmic time
increases. That is, with increasing time but stabilizing friction
coefficients, the rate of wear production decreases. Figure 14
shows the experimentally measured wear scar results at 2, 5,
15, and 75  min accompanying friction measurements in
Figure 13a. The fitted relationship between wear and time is
such that
ln ( wear scar ) = 5.3326 + 0.3159 ln ( time ) Eq. (1)
and nearly all experimental wear scar measurements fall
within the range of error (95% confidence interval) of
predicted wear scar at a given time.
3.3. Sound Measurements
Acoustic emissions during Lab A HFRR tests were recorded
to assess differences between LACα and B2 blended in the
same premium base fuel. As shown in Figure 15, less sound
is produced using B2 (74.8 dBa averaged over the test with a
72.4-77.1 dBa 95% confidence interval) compared to LACα
(82.7 dBa average, 80.3-85.0 dBa 95% confidence interval).
Sound recorded shortly after the start of tests reaches a
maximum before arriving at equilibrium levels for the
majority of the HFRR test. This trend is comparable to that
observed with the friction coefficient measurements over the
course of the same tests, as seen in Figure 16: coefficient values
for LACα and B2 average to 0.74 and 0.32, respectively. While
B2 sound and friction coefficient measurements peak shortly
after the start of test, LACα measurements peak at approxi-
mately 120 seconds and at higher values. Similar behavior and
timing were previously observed in a series of timed tests
using LACα as shown in Figure 13. The higher additive concen-
tration and alternate additive chemistry in the B2 fuel could
lead to more effective and faster film formation, minimizing
sound and friction effects during the run-in period. This is
ultimately beneficial for the remainder of the test as B2 average
sound and friction values trend lower than LACα values.
3.4. Engine Tests
Several studies have demonstrated that as much as 25% of the
fuel additive in the fuel passes through the combustion
chamber of the engine and is absorbed into the sump oil
[11, 17]. Remmert et al. showed that this transfer of additive
was responsible for an increase in engine efficiency [17].
Therefore, a standard engine test was used to investigate the
potential impact of fuel additives on engine wear. Sequence
VG/VF engine tests were carried out using LACγ, A1, and A2
samples blended using the same base fuel (unleaded
Haltermann SVGM2). One test was completed per sample
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

32 Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020

 FIGURE 15   Sound produced during LAC α and B2 HFRR tests conducted at Lab A.

© Shell Global Solutions (US) Inc.

with statistical error (95% confidence) assessed relative to
reference tests from the test lab’s database. Wear was quanti-
fied in terms of roller-follower pin wear from both intake and
exhaust valves of cylinder 8, and Fe levels measured at 24 h
intervals over the course of the 216 h test. Figure 17 shows pin
wear results with A1 and A2 results statistically lower than
the wear using LACγ for both intake and exhaust. Statistically,
A1 and A2 were equivalent (i.e., not significantly different) in
terms of intake and exhaust pin wear. Thus, it appears that
the use of the A additive package at higher treat rates leads to
improved anti-wear performance compared to the LACγ fuel.
Fe levels in oil samples taken periodically during and at
the end of the test (216 h) were analyzed as an additional
measure of wear. Fe concentrations in the end of test oil
samples are compared in Figure 18. Less Fe was detected using
A1 and A2 fuels compared to LACγ using two-sided testing
at 95% confidence. One-sided testing at 95% confidence
enabled complete differentiation of LACγ, A1, and A2. Thus,

 FIGURE 16   Friction coefficient measurements during LAC α and B2 HFRR tests conducted at Lab A.

© Shell Global Solutions (US) Inc.

 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020
Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020 33
 FIGURE 17   Intake and exhaust valve pin wear using base fuel, LACγ, A1, and A2.
© Shell Global Solutions (US) Inc.
when the additive concentration was increased, less wear was
observed in terms of Fe in the engine oil, and directional and/
or statistical differentiation of fuels as observed in the
Sequence VG/VF engine tests corroborate wear results previ-
ously shown using HFRR tests.
4. Conclusions
Based on the existing ASTM D6079 test and hardware and
procedural recommendations in the literature for testing of
the lubricity of gasoline (Wei et al.), the recommended HFRR
test protocol for gasoline was further optimized and used to
effectively differentiate fuels containing a range of additive
packages and concentrations by their wear and friction prop-
erties. Alterations to the standard protocol for diesel lubricity
(ASTM D6079) were used in these investigations and include
a modified cup and lower temperature to reduce the impact
of fuel evaporation on results. Additional modifications made
in these investigations included: daily instrument calibra-
tions with standard reference fuels; thorough cleaning and
sonication of specimens in three to four solvents before
drying with N2 gas; the use of a leveler tool to align the
applied load; consistent use of the procedure by one indi-
vidual per instrument; the use of a variety of tools (micros-
copy and micrometer, spindle reader, digital camera) for
visualization of wear.
Acoustic emission monitoring equipment was also used
to assess sound as further means of corroborating wear and
friction within the HFRR setup. Sequence VG/VF engine tests
supplemented those conducted using the benchtop HFRR
instruments and showed differences in wear behavior of addi-
tives depending on both concentration and chemistry.
Three unique additive packages containing anti-wear and
friction reducer components, LAC and Top TierTM equivalent
fuels, and 39 US and Canadian market unleaded premium
gasoline fuels were tested using HFRR with a subset of fuels
also assessed in terms of acoustic and/or engine tests.
Statistical differentiation of fuels was quantified in terms of
wear and friction. All but three market fuels were found to
be significantly different than fuels additized with A and/or
B packages. Dissimilarities in wear and friction coefficients
of E0 and E10 B fuels were also quantified. The HFRR was
further applied in differentiating fuels containing a range of
additive concentrations, with LAC and Top Tier™ fuels
observed to be statistically less effective in protecting against
wear and friction compared to fuels containing alternative
additives at higher treat rates (≥7× LAC). These observations
were consistently made using two independently operated
HFRR instruments, demonstrating the robustness of the
modified gasoline testing methods.
Acoustic emissions measured in tandem with HFRR tests
confirmed trends observed with friction coefficients when
assessing LAC and B2 (7× LAC) fuels. Relatively high sound
and friction coefficients measured near the start of HFRR
tests could reflect an initial “run-in” period during which
contact surface disparities and friction forces greater than
the applied load are overcome. Surfaces can become smooth
over time and sound and friction coefficient values equili-
brated with the development of a protective additive layer.
Additive chemistry and/or a higher concentration of additive
can produce a more protective layer, reducing wear and
friction such that the average sound level corresponding to
LAC was higher than those of B2 with 95% statistical confidence.
Differentiation of LAC and fuels additized with package
A was confirmed via Sequence VG/VF engine tests with wear
characterized by pin wear and Fe levels in engine oil. LAC and
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020
34 Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020
 FIGURE 18   End of test Fe concentration using base fuel, LACγ, A1, and A2 with (a) two-sided and (b) one-sided 95%
confidence interval.
A fuels with higher additive concentrations (≥4× LAC) were
observed to be significantly dissimilar in terms of pin wear
and Fe concentration. The engine tests thus validated observa-
tions that gasoline fuels with different chemistries and higher
additive concentrations can produce less wear than LAC fuels,
as demonstrated using benchtop HFRR methods.
Contact Information
wendy.lang@shell.com
Acknowledgments
The authors would like to acknowledge Vivek Raj Mohan,
Roger Cracknell, Anne Coleman, and Jennifer Kensler (Shell
© Shell Global Solutions (US) Inc.
Global Solutions) and Joseph Calderone (Afton Chemical
Corporation) for their insights and support.
References
1. Tzanetakis, T., Voice, A.K., and Traver, M.L., “Durability
Study of a High Pressure Common Rail Fuel Injection
System Using Lubricity Additive Dosed Gasoline-Like Fuel,”
SAE Technical Paper 2018-01-0270, 2018, doi:10.4271/2018-
01-0270.
2. Wei, D.P., Spikes, H.A., and Korcek, S., “The Lubricity of
Gasoline,” Tribology Transactions 42(4):813-823, 1999,
doi:10.1080/10402009908982288.
 Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020

Lang et al. / SAE Int. J. Fuels Lubr. / Volume 13, Issue 1, 2020 35

3. Wei, D.P., Korcek, S., and Spikes, H., “Comparison of the
Lubricity of Gasoline and Diesel Fuels,” SAE Technical Paper
962010, 1996, doi:10.4271/962010.
4. Lopreato, L.G.R., de Oliveira, E.J., and Duarte, M.V.E.,
“Gasoline Lubricity: An Exploratory Evaluation,” SAE
Technical Paper 2012-36-0502, 2012, doi:10.4271/2012-36-
0502.
5. Margaroni, D., “Fuel Lubricity,” Industrial Lubrication and
Tribology 50(3):108-118, 1998.
6. Agudelo, J., Delgado, Á., and Benjumea, P., “The Lubricity of
Ethanol-Gasoline Fuel Blends [La lubricidad de
lasmezclasetanol-gasolina],” Rev. Fac. Ing. Univ. Antioquia
59:8, 2011.
7. Arkoudeas, P., Karonis, D., Zannikos, F., and Lois, E.,
“Lubricity Assessment of Gasoline Fuels,” Fuel Processing
Technology 122:107-119, 2014, doi:10.1016/j.
fuproc.2014.01.008.
8. Ramalho, A. and Miranda, J.C., “The Relationship between
Wear and Dissipated Energy in Sliding Systems,” Wear
260(4-5):361-367, 2006, doi:10.1016/j.wear.2005.02.121.
9. Amiri, M. and Khonsari, M.M., “On the Thermodynamics of
Friction and Wear - A Review,” Entropy 12(5):1021-1049,
2010, doi:10.3390/e12051021.
10. Holmberg, K., Andersson, P., and Erdemir, A., “Global
Energy Consumption due to Friction in Passenger Cars,”
Tribology International 47:221-234, 2012, doi:10.1016/j.
triboint.2011.11.022.
11. Hayden, T., Ropes, C.A., and Rawdon, M.G., “The
Performance of Gasoline Friction Modifier Fuel Additive,”
SAE Trans. 110(3):1811-1821, 2001, https://doi.
org/10.4271/2001-01-1961.
12. PCS Instruments, “HFRR Installation & Test
Preparation Manual.”
13. ASTM International, “Test Method for Evaluating Lubricity
of Diesel Fuels by the High-Frequency Reciprocating Rig
(HFRR),”Nov. 2018, doi:10.1520/D6079-18.
14. Gevorgyan, G., Paukner, R., Erichsen, J., Weisse, M. et al.,
“HFRR Test Method with Stainless Steel Specimens for
Gasoline Fuels,” in 59th Ilmenau Scientific Colloquium,
Ilmenau, 2017.
15. Chiampradit, N., Nomura, T., Ichiyanagi, M., and Isobe, Y.,
“Study of the Effect of Gasoline Components on Lubricity,”
International Journal of Automotive Engineering
8(4):6, 2017.
16. Aghdam, A.B. and Khonsari, M.M., “Prediction of Wear in
Reciprocating Dry Sliding via Dissipated Energy and
Temperature Rise,” Tribology Letters 50(3):365-378, 2013,
doi:10.1007/s11249-013-0133-y.
17. Remmert, S.M., Felix-Moore, A., Nattrass, S.R., Buttery, I.
et al., “Demonstration of Fuel Economy Benefit of Friction
Modifier Additives via Fuel-to-Lubricant Transfer in Euro-5
Gasoline Fleet,” SAE Int. J. Fuels Lubr. 6(3):677-690, 2013,
doi:10.4271/2013-01-2611.
18. European Committee for Standardization, “Diesel Fuel -
Assessment of Lubricity Using the High-Frequency
Reciprocating Rig (HFRR) - Part 1: Test Method
(ISO 12156-1:2018),”2018.
19. Oguma, M., Matsuno, M., Kaitsuka, M., and Higurashi, K.,
“Evaluation of Hydrous Ethanol Fuel Lubricity by HFRR,”
SAE Technical Paper 2016-01-2260, 2016, doi:10.4271/2016-
01-2260.
20. Lois, E. and Arkoudeas, P., “Lubricating Aspects of
Automotive Fuels,” in: Carmo, J., ed., New Advances in
Vehicular Technology and Automotive Engineering (London,
UK: InTech, 2012), doi:10.5772/48552.
21. ASTM International, “Test Method for Evaluation of
Automotive Engine Oils for Inhibition of Deposit Formation
in a Spark-Ignition Internal Combustion Engine Fueled with
Gasoline and Operated under Low-Temperature, Light-Duty
Conditions,” Mar. 2019, doi:10.1520/D6593-17.
22. ASTM International, “Test Method for Multielement
Determination of Used and Unused Lubricating Oils and
Base Oils by Inductively Coupled Plasma Atomic Emission
Spectrometry (ICP-AES),” Nov. 2018, doi:10.1520/D5185-18.
23. Fox, M., “A Model for Fuel Additive Lubricity,” in Life Cycle
Tribology: Proceedings of the 31st Leeds-Lyon Symposium on
Tribology, Leeds, Paper XVII, 585-592, 2004.
24. Kuszewski, H., Jaworski, A., and Ustrzycki, A., “Lubricity of
Ethanol-Diesel Blends - Study with the HFRR Method,” Fuel
208:491-498, 2017, doi:10.1016/j.fuel.2017.07.046.

© 2020 Shell Global Solutions (US) Inc. Published by SAE International. No part of this publication may be reproduced, stored in a retrieval system, or transmitted,
in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the copyright holder(s).

Positions and opinions advanced in this work are those of the author(s) and not necessarily those of SAE International. Responsibility for the content of the work lies
solely with the author(s).
Downloaded from SAE International by Columbia Univ, Tuesday, April 14, 2020