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Friction and Wear of Low-Phosphorus Engine Oils with Additional Molybdenum

and Boron Compounds, Measured on a Reciprocating Lubricant Tester

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Friction and Wear of Low-Phosphorus Engine Oils

with Additional Molybdenum and Boron Compounds,
Measured on a Reciprocating Lubricant Tester
a a a b c
Peggy Lin , Gary Barber , Qian Zou , Alan H. Anderson Jr. , Simon Tung & Angelo
c
Quintana
a
Oakland University, Rochester, MI
b
Petroleum Department, R.T. Vanderbilt Company, Inc.
c
Chemical & Environmental Sciences Lab., General Motors R&D Center

Available online: 15 Oct 2008

To cite this article: Peggy Lin, Gary Barber, Qian Zou, Alan H. Anderson Jr., Simon Tung & Angelo Quintana (2008): Friction
and Wear of Low-Phosphorus Engine Oils with Additional Molybdenum and Boron Compounds, Measured on a Reciprocating
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 Tribology Transactions, 51: 659-672, 2008
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ISSN: 1040-2004 print / 1547-397X online

DOI: 10.1080/10402000802304330

Friction and Wear of Low-Phosphorus Engine Oils with

Additional Molybdenum and Boron Compounds, Measured
on a Reciprocating Lubricant Tester
PEGGY LIN,1 GARY BARBER,1 QIAN ZOU,1 ALAN H. ANDERSON JR.,2 SIMON TUNG3 and ANGELO QUINTANA3
1
Oakland University
Rochester, MI
2
Petroleum Department
R.T. Vanderbilt Company, Inc.
3
Chemical & Environmental Sciences Lab.
General Motors R&D Center
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Previous research has already extensively characterized the
effects of a variety of engine oils on engine performance. How-
ever, low-phosphorus engine oils, which are of growing impor-
tance due to the reduction of automotive emissions, have not
been studied much. This paper sets forth the results of an initial
investigation involving the effects of low-phosphorus engine oils
on the friction and wear characteristics of typical engine cylinder
kit components from a 3.8-liter, four-cylinder engine. For these
tests, sections of molybdenum-coated piston rings were oscil-
lated against segments of production cast iron cylinder bores.
The oils were evaluated under two sets of conditions; i.e., the
frequency of 20 Hz and a load of 60 N and a frequency of
40 Hz and a load of 120 N. The friction coefficients were con-
tinuously recorded, and the wear depths on the cylinder bore
segments were measured at the conclusion of each experiment.
The oils consisted of low-phosphorus prototype oil (LPPO)
containing 0.05 wt% phosphorus, which is half the amount of
ZDDP in GF–3 oils, and the LPPO treated with six different
supplemental antiwear, anti-friction additives. The remaining
additives in the LPPO were present in the amount required
for full GF–3 formulation. The supplemental additives were se-
lected to lower friction and replace and/or enhance antioxidant
and antiwear properties lost due to lower zinc dithiophosphate
(ZDDP) content. The results of low phosphorus concentration
oils were compared to the results obtained with formulated IL-
SAC GF-3 engine oil. The oils that contained organomolybde-
num ester showed the greatest benefit in friction reduction in
the two different operating conditions. SEM/EDS/XPS surface
analyses on the surfaces run with oils containing organomolyb-
denum ester showed evidence of molybdenum compound for-
mation on the cylinder bore surface. In addition, antiwear film
Manuscript received November 3, 2005
Final manuscript approved April 23, 2008
Review led by Elaine Yamaguchi
formation mechanisms due to surface interaction among the
ZnDTP, organomolybdenum compounds, and metal oxides are
discussed.
KEY WORDS
Friction; Wear; Oil Additives; Piston Ring; Cylinder Bore
INTRODUCTION
Environmental concerns have led to today’s stringent legisla-
tion and regulations aimed at increasing the fuel economy and
lowering emissions of passenger cars and trucks. One approach
to meet improved fuel economy requirements is the use of low-
friction surfaces on engine hardware such as piston liners and
piston rings. Another more economical option for automobile
manufacturing companies is to develop lubricants that can provide
friction reduction, especially under the mixed/boundary lubricat-
ing conditions that are encountered at piston ring and cylinder
bore interfaces. In the area of emission control, much work has
been done to improve the catalytic converters that remove pol-
lutants such as CO and NOx from the vehicle exhaust. From this
work on emission control systems, it was found that phosphorus-
containing antiwear additives, in particular zinc dithiophosphate
(ZDDP), deactivate the catalyst in catalytic converters. Thus, the
development of energy-conserving engine oils with low phospho-
rus content is an important strategy in meeting future fuel econ-
omy and emission control requirements.
Several researchers (Ariga (1); Tung and Emley (2); Tung and
Gao (3); Tung and Tseregounis (4); Gangopadhyay (5); Nakada
(6)) have investigated the tribological characteristics of energy-
conserving lubricants using bench tests and then correlated the
data with engine test results. These studies indicated that it was
important to study the lubricants in bench tests using real en-
gine components. One element that has received much attention
is molybdenum. In the case of energy-conserving lubricants, the

659
 660 P. LIN ET AL.

use of oil-soluble organomolybdenum compounds that form low- TABLE 1—LIST OF TEST OILS
friction tribological films is a well-known approach to reduce en- Additive Element
gine friction (Mitchell (7); Fish and Jinsheng (8)). Sample Concentration Content
Recently there has been significant interest in research related Identity Composition∗ (mass %) (wt %)
to low-phosphorus engine oils. Gao, et al. (9) used a reciprocat-
Baseline GF-3, 5W-30 reference oil with 100 0.10 P
ing ball-on-flat rig to study the tribological performance of SAE
ZDDP
5W-20 oil blended with phosphorus ranging in concentration from
1 Low-phosphorus prototype oil 100 0.05 P
0.02 to 0.1 wt%. A low concentration of phosphorus was found to (LPPO), 5W-30 with 1/2
produce high wear and the coefficient of friction increased with ZDDP of reference
phosphorus concentration at temperatures above 80◦ C. The high 2 LPPO plus 96.60 0.05 P
wear produced by low-phosphorus oils has led to research on ad- Organomolybdenum-ester 0.89 0.07 Mo
ditives that can be combined with low-phosphorus oils to pro- Zinc diamyldithiocarbamate 1.00 0.06 Zn
vide adequate wear protection, Gao et al. used a ball-on-flat high- (ZnDTC)
frequency reciprocating rig to study the tribological performance Alkylated diphenylamine 1.50
of an SAE 5W-20 oil containing 80 ppm Mo and 0.05 wt% P (Gao, 3 LPPO plus 99.11 0.05 P
Organomolybdenum-ester 0.89 0.07 Mo
et al. (10), (11)). They found that the wear produced using the
4 LPPO plus 99.00 0.05 P
0.05 wt% phosphorus plus Mo oil was considerably less than an
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Organoborate-ester 1.00 0.01 B

oil with 0.1 wt% phosphorus with no Mo.
5 LPPO plus 99.05 0.05 P
Due to the high cost of running fired engines, it is common in the Organomolybdenum-ester 0.45 0.035 Mo
automotive industry to test new additive packages in a bench-top Organoborate-ester 0.50 0.005 B
simulator first. Then, only promising additive packages are tested 6 LPPO plus 96.60 0.05 P
in fired engines. In the present research, an evaluation of low- Organomolybdenum-ester 0.40 0.035 Mo
phosphorus engine oils formulated with an organomolybdenum Organoborate-ester 0.50 0.005 B
compound and antiwear additives was made using a bench-test Zinc diamyldithiocarbamate 1.00 0.06 Zn
device, which makes use of production piston rings and cylin- (ZnDTC)
der bore specimens. The testing was performed using a high- Alkylated diphenylamine 1.50
7 LPPO plus 98.11 0.05 P
frequency reciprocating bench wear test machine in which sections
Organomolybdenum-ester 0.89 0.07 Mo
of molybdenum-coated piston rings were oscillated against seg-
Organoborate-ester 1.00 0.01 B
ments of production cast iron cylinder bores. Specifically, eight
engine oils were used in the study. An SAE 5W-30, ILSAC GF- ∗ All oils contain 0.2 mass% sulfur.
3-grade engine oil was tested as the reference oil and compared
to low-phosphorus prototype oil (LPPO), which was experimen- is installed in a holder and reciprocates against the counter cast
tally formulated oil with a GF-3 package of the same viscosity iron cylinder liner segment. The cylinder liner segment is fixed in
grade containing only 0.05 wt% phosphorus. The rest of the ad- the bottom of the oil tray, which is filled with engine oil. The piston
ditives in the LPPO were present in the amount required for the ring section can oscillate against the cylinder specimen at a high
full GF-3 formulation. The other six oils (Oil Samples 2-7, Ta- frequency to simulate the ring movement along the engine cylin-
ble 1) consisted of the LPPO formulated with supplemental addi- der. A heater block is used to control the operating temperature
tives as summarized in Table 1. These are organomolybdenum- underneath the oil tray. A normal load is applied to the piston ring
ester (friction reducer and antioxidant with molybdenum con- section. A piezoelectric transducer attached to the heater block
tent of 0.89 mass percent); organoborate-ester (anti-wear addi- measures the friction force.
tive with boron content of 1 mass percent); zinc diamyldithio- Experimental samples are cut from engine components as
carbamate (anti-wear additive and antioxidant with zinc content shown in Fig. 2. The tests were run for 7 h and the friction co-
of 1 mass percent) and alkylated diphenylamine (ashless antiox- efficient and bore wear depth were measured for a variety of test
idant). All oils had a sulfur content of 0.2 mass percent. Al- lubricants under the same test conditions. In Table 2, the test-
though antioxidancy is not part of the study, ZDDPs are also ing conditions used to simulate the lubricating conditions in an
very effective antioxidants that play a major role in control- operating engine are listed. The oil volume in the oil tray is ap-
ling oil oxidation and engine deposits. Thus, it should be noted proximately 6 mL, which is just enough to cover the surface of the
that all the additives with the exception of the organoborate- cylinder bore. The oils listed in Table 1 were tested in the order in
ester are effective antioxidants that function together to extend which they are listed.
the life of engine oils and prevent engine deposits (Gatto and Both friction and wear were studied for all of the test lubri-
Devlin (12); Karol, et al. (13)). cants. During testing, the friction was highest at end-of-stroke
(sliding velocity = 0.0) due to boundary lubrication and lowest
EXPERIMENTAL DETAILS at mid-stroke where mixed lubrication (maximum velocity) oc-
Tribological characteristics were evaluated using a modified curs. In this study, the friction data reported are the average co-
high-frequency reciprocating friction and wear machine, as shown efficient of friction over the entire stroke. The ring wear during
in Fig. 1 (Tung and Gao (3)). A section of a Mo-sprayed piston ring testing was found to be negligible. The gray cast iron cylinder bore
 Friction and Wear of Low-Phosphorus Engine Oils 661
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Fig. 1—Setup: Cameron–Plint high-frequency friction and wear machine.

samples with an arithmetic average surface roughness of 0.23 µm
and stainless steel molybdenum-sprayed piston ring samples were
cleaned using acetone before and after each test. Figure 2 shows
the cylinder bore and piston ring segment samples before sliding,
and Fig. 3 shows the cylinder bore sample after sliding. Surface
analyses were conducted to analyze the wear scars of the cylin-
der bore segments using a Taylor Hobson Talysurf Analyzer. All
cylinder bore wear scars were measured in the longitudinal direc-
tion as indicated in Fig. 3 using a stylus profilometer. First, the
geometry of the wear profile was removed by filtering, and then
a regression method was used to construct a best fit line from
the unworn portion to the left of the wear scar to the unworn
portion of the right of the wear scar; see Fig. 3. The wear was
then measured relative to the best fit line. Wear was measured
at the three locations shown on Fig. 3 and averaged. In general,
the wear was slightly higher in the center at location 2. The pis-
ton ring diameter is purposely adjusted to be slightly less than
the bore diameter. Thus, the higher wear at location 2 is expected
due to higher contact pressure as compared to locations 1 and
3. Good repeatability was found for the friction results with less
than 1.2% deviation. However, a higher average deviation of wear
measurements was found with deviations between 2.3% and 48%.
The surfaces of the samples were observed using a scanning elec-
tron microscope. The surface topographical parameters with wear
depth were measured using a stylus surface profilometer. The sur-
faces of the cylinder bores and piston rings were also analyzed
using scanning electron microscopy (SEM), energy dispersive X-
ray spectroscopy (EDS), and X-ray photoelectron spectroscopy
(XPS). For samples that were examined by XPS depth profiling,
the depth profile etch rates were calibrated as 10.4 nm/min using
a Ta2 O5 thin-film standard. However, because different materi-
als etch at different rates, this calibration can only be used for
relative comparisons. The wear scar and a “no-wear” area were
examined on each specimen. Before analyses, the samples were
cleaned in hexane and allowed to air dry. The samples that were
examined by SEM and EDS were cleaned using hexane and ul-
trasonically cleaned for 1 min before analyses and allowed to air
dry.

TABLE 2—DIFFERENT SETS OF TEST CONDITIONS

Set up First Set Second Set

Normal load 60 N 120 N

Oscillating frequency 20 Hz 40 Hz
Sliding stroke 8.9 mm 8.9 mm
Maximum sliding velocity 559.2 mm/s 1118.4 mm/s
Temperature 135◦ C 135◦ C
Amount of lubricant ∼6 mL ∼6 mL
Fig. 2—Experimental samples before test: (a) cylinder segment, (b) pis- Test duration 7h 7h
ton ring.
 662 P. LIN ET AL.

friction coefficients of Samples 2 and 3 gave significantly lower

friction results as compared to the GF-3 baseline oil and the LPPO
(Sample 1), which showed the highest coefficient of friction. After
surface break-in (the first hour of sliding) all the oils containing
friction modifiers showed reduced coefficients of friction as shown
in Fig. 4. The run-in friction coefficient for most of the tested en-
gine oils was lower than the friction coefficients in the beginning of
the sliding process, except for the baseline test lubricant and Sam-
Fig. 3—Piston ring and cylinder bore samples after test: measurement ple 1. In the latter cases, the average friction coefficient remained
of the wear depth on the cylinder bore is in longitudinal direction
relatively constant throughout the test.
using a stylus profilometer.
Table 3 shows the average stabilized friction coefficient results.
The standard deviation was calculated based on the averaged indi-
vidual values in duplicate tests for each lubricant. It is obvious that
RESULTS AND DISCUSSION the oil containing the organomolybdenum ester alone (Sample 3)
has the lowest stabilized coefficient of friction. Sample 2 (LPPO
Frequency of 20 Hz with a Load of 60 N
with all of the additives) also showed very low friction.
Friction Characteristics Figure 5 is a bar chart of the average stabilized coefficients of
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Lubricant formulations affect both friction and wear charac- friction, again indicating that Samples 2 and 3 had significantly
teristics. Figures 4 and 5 show the variation of friction coefficient lower coefficients of friction than the other samples tested. These
with all eight engine oil formulations at the first set of test con- results suggest that the formulation balance of ingredients is crit-
ditions (20 Hz and 60 N). It can be observed in Fig. 4 that the ical to performance. Again, Sample 1 and the baseline oil (GF-3

Fig. 4—Average friction coefficient curve at a frequency of 20 Hz and load of 60 N.

 Friction and Wear of Low-Phosphorus Engine Oils 663

TABLE 3—AVERAGE STABILIZED COEFFICIENT OF FRICTION WITH STAN- TABLE 4—AVERAGE BORE WEAR DEPTH (µM) FOR THE MATRIX OF OILS
DARD DEVIATION FOR A FREQUENCY OF 20 HZ WITH A LOAD OF 60 N WITH STANDARD DEVIATIONS FOR A FREQUENCY OF 20 HZ AND LOAD OF
Sample Name Baseline 1 2 3 4 5 6 7 60 N

Friction coefficient 0.09 0.11 0.06 0.04 0.08 0.08 0.09 0.08
Sample Name Baseline 1 2 3 4 5 6 7
Standard deviation 0.007 0.003 0.012 0.007 0.003 0.007 0.006 0.003 Wear Depth (µm) 0.36 0.41 0.84 0.23 0.16 0.08 0.21 1.80
Standard 0.09 0.16 0.26 0.19 0.07 0.00 0.09 0.15
Deviation (µm)

reference oil) showed much higher coefficients of friction com-

pared with the other oils. This shows that Mo is an effective friction
reducer, while these borate esters do not appear to be effective in samples that had a lower wear profile than the GF-3 reference oil
reducing friction under these conditions. were Samples 3, 4, and 6.

Wear of Mo-Sprayed Piston Ring Run Against Cast Iron Frequency of 40 Hz with a Load of 120 N
Cylinder Bore Friction Characteristics
The wear test results are shown in Table 4. The cylinder bore Figure 6 shows the variation of friction coefficient with all
Downloaded by [Oakland University] at 11:52 15 March 2012

wear depth for a frequency of 20 Hz and a load of 60 N ob-
tained with Sample 3 was 0.23 µm, while that obtained with the
GF-3 reference oil was about 0.36 µm. The wear depth obtained
with Sample 5 (Table 4) was 0.08 µm, which was the lowest wear
depth of all samples tested. Sample 2, which had the second low-
est friction coefficient under these conditions, had the highest
wear depth (0.84 µm). This shows that a reduced coefficient of
friction does not necessarily translate into a lower wear depth
profile.
The lubricant with the low level of phosphorus concentration
plus both boron ester and molybdenum additives (Sample 5) had
the lowest wear depth profile of all samples tested. The only other
eight engine oil formulations under lubricated conditions for a
frequency of 40 Hz with a load of 120 N. As was the case at the
lower speed/load condition, it can be observed in Fig. 7 that Sam-
ple 3 gave significantly reduced coefficient of friction results as
compared to the GF–3 baseline oil and the low-phosphorus pro-
totype oil (Sample 1), which showed the highest coefficients of
friction. After surface break-in (the first hour of sliding) all the
oils containing friction modifiers showed reduced coefficients of
friction as shown in Fig. 6. The run-in friction coefficients for most
of the tested engine oils were lower than the friction coefficients
in the beginning of the sliding process, except for the baseline test
lubricant and Sample 1.

Fig. 5—Stabilized friction characteristics of tested lubricants at a frequency of 20 Hz and load of 60 N with standard deviation.
 664 P. LIN ET AL.
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Fig. 6—Average friction coefficient curve at a frequency of 40 Hz and a load of 120 N.

Fig. 7—Stabilized friction characteristics of tested lubricants at a frequency of 40 Hz and a load of 120 N with standard deviations.
 Friction and Wear of Low-Phosphorus Engine Oils 665
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Fig. 8—(a) Bore wear depth of the SAE 5W-30, GF-3 reference engine oil. (b) Bore wear depth of oil Sample 3 containing only organomolybdenum ester
at a frequency of 40 Hz and a load of 120 N.

Table 5 shows the average stabilized friction coefficient results,
which were calculated from averaged individual values in dupli-
cate tests for each lubricant. It is obvious that the oils contain-
ing the organomolybdenum ester (Sample 3 and Sample 2) have
the lowest stabilized coefficient of friction. All of the lubricant
samples containing friction modifiers gave lower coefficients of
friction than the GF-3 reference oil and the low-phosphorus pro-
totype oil. Sample 1 showed the highest coefficient of friction in
both sets of tested conditions. Figures 5 and 7 both show graph-
ical comparisons of the averaged coefficients of friction after 3 h
of sliding. In both cases, Samples 2 and 3 had significantly lower
coefficients of friction than the other samples tested. In particu-
lar, Samples 2 and 3 had lower friction coefficients than Sample 5.
This may be due to the presence of the boron in Sample 5. This
again shows that the molybdenum compound has better friction
reduction capabilities than the boron compound. Again, Sample 1
and the baseline oil showed much higher coefficients of friction
than the other oils.
Wear of Mo-Sprayed Piston Ring Run Against Cast Iron
Cylinder Bore
Sample surface tracings to determine wear are shown in Fig. 8.
Table 6 shows the results of average bore wear depth for the du-
plicate test specimens at a frequency of 40 Hz and load of 120 N.
The prototype engine oil (Sample 1) produces the lowest bore
wear depth of 0.08 µm. Sample 4 was only slightly higher with
0.10 µm. All other samples gave greater wear depth profiles than
the GF-3 reference oil, and Sample 3 gave the second highest wear
depth, 2.08 µm. Sample 5 with the low level of phosphorus plus
both boron ester and molybdenum additives had the lowest wear
of any sample at 20 Hz and 60 N load. However, under the more
severe conditions of 40 Hz and 120 N, the wear was more than

TABLE 6—BORE WEAR DEPTH FOR THE MATRIX OF OILS WITH STANDARD
TABLE 5—AVERAGE STABILIZED COEFFICIENT OF FRICTION WITH STAN-
DEVIATIONS FOR A FREQUENCY OF 40 HZ AND A LOAD OF 120 N
DARD DEVIATION FOR A FREQUENCY OF 40 HZ WITH A LOAD OF 120
N Sample Name Baseline 1 2 3 4 5 6 7
Sample Name Baseline 1 2 3 4 5 6 7
Wear depth (µm) 0.38 0.08 1.28 2.08 0.10 0.47 0.91 3.70
Friction coefficient 0.09 0.10 0.05 0.05 0.08 0.06 0.06 0.06 Standard 0.05 0.03 0.23 0.48 0.04 0.02 0.30 0.10
Standard deviation 0.005 0.004 0.002 0.002 0.000 0.006 0.004 0.001 deviation (µm)
 666 P. LIN ET AL.
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Fig. 9—Average wear depth at a frequency of 40 Hz and a load of 120 N with standard deviation.

with the GF-3 reference oil. Perhaps the shear strength of the
surface films formed with this oil was suitable at the less severe
test conditions but was too low for adequate wear protection at
the more severe test conditions. Figure 9 graphically depicts these
results along with the standard deviations. The results show that,
while ZnDTP may promote formation of good antiwear films, it is
not necessarily a good friction modifier. Other investigations have
shown lubricants containing ZnDTP to have higher friction than
lubricants without ZnDTP (Tung and Gao (14)).
It should be noted that Sample 4 produced the highest coef-
ficient of friction of all the samples containing friction modifiers
at the high speed/high load condition (Fig. 7). On the other hand,
boron at both test conditions does not appear to be nearly as ef-
fective as molybdenum in reducing friction. It is clear from these
two sets of bench test results, however, that low-phosphorus con-
centration engine oils can be formulated to reduce significantly
the coefficient of friction but not necessarily to provide adequate
wear protection at the same time.

EDS/SEM SURFACE ANALYSIS OF PISTON RINGS AND

CYLINDER BORES
In bench testing, the surface characteristics of the bore sam-
ples can be changed due to surface interaction. Figure 10 provides
typical micrographs of the unworn and worn sections of both the
cylinder bore and piston ring for Sample 2. Figure 11 shows the
SEM/EDS of the GF-3 reference oil lubricated cylinder bore after
testing. Since this was a GF-3 oil, the phosphorus concentration
was higher than that of any of the other lubricants. The EDS plots
show phosphorus, sulfur, oxygen, and calcium deposited on the
surface. It can be seen that the sulfur, phosphorus, and oxygen
have higher concentrations in the graphite inclusion.
Fig. 10—(a) Micrograph of cylinder bore sample 2. (b) Micrograph of
Figures 12 and 13 show SEM/EDS of the cylinder bore and piston ring sample with worn and unworn section. (The arrow
piston ring test specimens for Sample 3, which contains the shows the piston ring against cylinder bore sliding direction.)
 Friction and Wear of Low-Phosphorus Engine Oils 667
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Fig. 11—Baseline (GF-3 as reference oil) cylinder bore micrograph at worn section. Each spot analyzed has similar but different elements deposited on
the surface of the cylinder bore.

low-phosphorus oil blended with the organomolybdenum ester
only. The worn piston ring segment shows a slight increase in
molybdenum concentration. The EDS images in Fig. 12 show ev-
idence of molybdenum deposition on the cylinder bore surface in
this case, presumably from the organomolybdenum additive.
XPS SURFACE ANALYSIS OF WORN SCAR ON
CYLINDER BORES
Representative XPS graphs of worn cylinder bore surfaces
are shown on Figs. 14 and 15. The scans of the worn cylinder
bore surfaces indicate that the following elemental and electron
 668 P. LIN ET AL.
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Fig. 12—SEM/EDS of a worn section of the cylinder bore obtained from Sample 3.

configurations are present: Ca2p, Fe2p3, Mo3p3, S2p, P2p, Zn2p3,
O1s, and C1s. This suggests the likely existence of four categories of
chemical compounds on the worn cylinder bore surfaces, includ-
ing iron oxides (Fe2 O3 , FeO), Mo compounds (MoO3 , MoS2 ),
sulfur and its compounds (S, FeSO4 ), and phosphates (FePO4 ).
The phosphorus level is significantly reduced on Sample 3 as com-
pared to the baseline sample. This may be due to competition of
the ZnDTP with the organomolybdenum ester additive and the
reduced amount of phosphorus in the tribofilm likely led to the
increased wear observed in Sample 3 (Komvopoulos (15)). The
depth profiles of XPS show that, in all cases, a thick oxide has
formed and a high concentration of Ca was found on all of the
worn cylinder bore surfaces. When calcium phosphate is present
in a tribofilm, the antiwear effectiveness can be reduced (Kasrai
(16)). On the other hand, the deposition of CaCO3 in the tribofilm
can lead to enhanced antiwear ability (Kasrai (17)). The tribolog-
ical effects of calcium in the tribofilm are beyond the scope of the
present study.
 Friction and Wear of Low-Phosphorus Engine Oils 669
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Fig. 13—SEM/EDS showing both worn and unworn sections of the piston ring obtained with Sample 3.

Figures 14 and 15 show XPS depth profiles for samples run
with a frequency of 40 Hz and a load of 120 N. Comparing the
depth profiles in Figs. 14 and 15, the depth profiles for the baseline
show no formation of molybdenum on the worn cylinder bore
surface. However, molybdenum was formed on the worn cylinder
bore surface for Sample 3 under a frequency of 40 Hz and a load
of 120 N. On the other hand, boron was not formed on the worn
cylinder bore surface under any of the test conditions. This shows
that boron is not a good surface protector. This may be due to
the differences in surface interaction between the boron and/or
organomolybdenum ester additives with the production cast iron
block.
DISCUSSION OF A POSSIBLE SURFACE REACTION
MODEL
From the above surface analysis results, it is clear that the major
additive elements, such as Mo, S, P, Zn, O, and Ca, are present on
the worn surfaces of cylinder bores under the operating conditions
tested. This is consistent with the possible mechanism proposed in
previous research (Tung and Emley (2); Cavdar and Ludema (18),
(19)) as shown in Fig. 16, in which ZnDTC/ZnDTP, organomolyb-
denum compounds, and metal oxides interact to form effective
continuous films.
In this surface reaction model, organomolybdenum and
ZnDTC/ZnDTP decomposition compounds form long-chain
 670 P. LIN ET AL.
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Fig. 14—XPS and depth profiles of worn cylinder bore surface from baseline at a frequency of 40 Hz and a load of 120 N. The elements deposited on the
cylinder bore surfaces are Ca2p, S2p, Zn2p3, and P2p. There is a high concentration of Ca deposited on the worn surface.

polyphosphates and mix with molybdenum additives to form an
organic induced reaction (OIC: organic iron compound) layer.
The metallo-organic interactive compounds can further combine
with metal oxides (OMM: oxides metal mixture) at elevated tem-
peratures and loading. Antiwear pads of iron phosphates and
a durable antiwear film containing higher concentrations of S,
Zn, Mo, and P are formed (called OIC-Zn film). The OMM
layers wear out and are diminished during the sliding process,
but the OIC-Zn films form a strong protective layer to resist
wear and scuffing. In addition, OIC-Zn films can induce film
formation of iron oxide, metallic iron, and iron carbide. These
ZnDTC/ZnDTP and organomolybdenum induced films have a
much higher loading capacity and serve as antiwear and anti-
scuffing films to protect iron substrates. The elements found on
the worn surfaces of the tested cylinders support the above model.
However, the relatively high cylinder wear produced using blend,
2 and blend 6, which both contain ZnDTC and ZnDTP, is not
consistent with the model. This suggests that additional tribolog-
ical reactions are taking place that are not accounted for in the
model.
There are several possibilities for the transfer of chemical
compounds onto the worn cylinder bore surfaces elements that
are coming from the decomposed products of ZnDTC/ZnDTP
and organomolybdenum ester and transfer films between the

Fig. 15—XPS and depth profiles of worn cylinder bore surface from Sample 3 at a frequency of 40 Hz and a load of 120 N. The elements deposited on
the cylinder bore surfaces are Ca2p, S2p, Zn2p3, Mo3p3, and P2p. There is molybdenum and a high concentration of Ca deposited on the worn
surface.
 Friction and Wear of Low-Phosphorus Engine Oils
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Fig. 16—Film formation mechanism due to surface interaction among the ZnDTC/ZnDTP and organomolybdenum compounds and metal oxides during
the lubricated sliding process (Tung and Emley (2); Cavdar and Ludema (18), (19)).
elements in the piston ring coatings and the reactive compounds
of the lubricant additives. The ZnDTC/ZnDTP and organo-
molybdenum ester additives affect the oxidation and carboniza-
tion on the cylinder bore surfaces. The existence of oxygen on
the worn surfaces of cylinder bores indicates the presence of ox-
idation reactions due to friction and heating. On the other hand,
in the case of piston ring surfaces, there is no oxygen content
found on the worn piston ring surfaces using the baseline GF-
3 oil, but there is a low oxygen content formed on worn pis-
ton ring surfaces using oil containing the organomolybdenum
ester.
SUMMARY AND CONCLUSIONS
r Friction coefficients for experimentally formulated lubricants
containing molybdenum or boron were found to be lower than
that of the reference lubricant GF-3 engine oil, with the same
viscosity grade, SAE 5W-30. Based on the results, molybdenum
shows better performance in friction reduction than boron.
r The wear resistance of cylinder bore segments lubricated with a
matrix of oils containing different levels of phosphorus, boron,
molybdenum ester, and other additives was studied, and the
friction characteristics were determined from bench tests. The
organomolybdenum-ester is effective in reducing friction in
low-phosphorus engine oils. However, increased wear is pos-
sible if formulations are not properly balanced with antiwear
additives.
r The prototype engine oil with 0.05 wt% P and no supplemen-
tal additives did not show any benefit in friction reduction,
although it showed the best wear resistance (the lowest wear
671
depth) of all the test lubricants for a frequency of 40 Hz with a
load of 120 N.
r None of the specially formulated test oils were better in both
friction and wear performance than the baseline GF-3 oil.
Therefore, these test oils need additional improvements be-
fore testing in fired engines.
r SEM/EDS surface analyses show evidence of surface films con-
taining molybdenum on cylinder bore surfaces. The XPS sur-
face analysis also confirms the formation of the tribofilms.
r Significant amounts of calcium and oxygen have been identified
on these cylinder bore surfaces. Additional studies are needed
to determine their effect on friction and wear.
ACKNOWLEDGMENTS
The authors wish to thank Drs. James A. Spearot and Michael
L. McMillan for their technical support. The authors also wish to
acknowledge the help of Drs. Zheng Ma and Ben Zhou (GM Pow-
ertrain), Mr. Charles Gossel, and Mark Rosetto (North America
Materials Testing Group) for wear testing and surface charac-
terization. The authors would also like to thank Maria Militello
and Stephen Swarin for the XPS surface analysis. In addition, the
authors thank Glenn Clever and Mark Gillman of GM Powertrain
for helping to prepare piston ring and cylinder bore materials.
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 672 P. LIN ET AL.
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