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Control of Low-Temperature Sludge
In Passenger-Car Engines
R. L. Willis and E. C. Ballard,
E. I. du Pont de Nemours & Co., Inc.
This paper was presented at the SAE Golden Anniversary Annual Meeting, Detroit, Jan. 11, 1955.
EofARLY in 1954, Biswell, Catlin, Froning, and
Robbins' reported the discovery of a new class
detergents for hydrocarbon systems. These new
detergents, which are nitrogen-containing poly-
mers, appeared to be particularly effective in con-
trolling sludge formation in engines operated at
low or moderate temperatures. These are the oper-
ating conditions encountered by most passenger
cars.
In order to discover the reason for this unusual
detergent activity, a study was made of several
factors affecting the dispersancy and solubilization
of solid particles in hydrocarbons. This study
showed differences in behavior between the new
and older types of detergents which provided im-
portant leads to a better appreciation of the way
in which detergents function. It is the purpose of
this paper to describe the results of this investiga-
tion and to relate them to engine performance.
Action of Detergents
Over the past several years, considerable atten-
tion has been given to determining the mechanism
by which detergents function in lubricating oils.
While this mechanism is not yet completely under-
stood, sufficient information has now been devel-
oped to permit a rational explanation of most of
the phenomena observed.
Materials which function as detergents in lubri-
cating oil must possess at least one polar and one
nonpolar group. The nonpolar group provides oil
solubility for the molecule, while the polar group
is of such a nature that it is attracted to the par-
ticles of sludge. These detergent molecules tend
to cluster together to form micelles containing
many molecules. Fig. 1 shows electron photomicro-
1 "New Class of Polymeric Dispersants for Hydrocarbon Systems," by
C. B. Biswell, W. E. Catlin, J. F. Froning, and G. B. Robbins. Presented
at National ACS Meeting, Kansas City, Mo., 1954.
2 "An Electron Microscope Study of Performance of Detergent Gil," by
J. B. Peri. Presented at SAE National Fuels & Lubricants Meeting, Chicago,
November 5, 1953.
Volume 63, 1955 777
graphs of two samples of new oil. One sample is a
carefully filtered neutral, and the other sample is
the same filtered base oil to which a barium petro-
leum sulfonate has been added. The micelles of
the detergent are clearly visible in the additive-
containing sample. They are 2 to 4 millimicrons in
diameter and 5 to 20 millimicrons in length.
One way in which a detergent functions is by
keeping sludge particles in suspension. The avail-
able evidence indicates that the detergent mole-
cules or micelles orient themselves around the
sludge particles which develop in the oil, and that
this coating of detergent prevents the particles
from agglomerating. During the service life of the
oil, the number of sludge particles gradually in-
creases, while the number of unattached detergent
molecules or free-floating micelles decreases. 2 The
sludge particles may or may not possess an elec-
trical charge attributable to the detergent. There
T HIS paper evaluates a new class of detergents,
I specially effective in controlling sludge for-
mation at the low or moderate temperatures most
often encountered in passenger-car operation.
This new Detergent C (a copolymer of lauryl
methacrylate plus diethylaminoethyl methacry-
late) has undergone extensive bench and labora-
tory tests in comparison with three other major
classes of detergent. It exhibits, among other
attributes:
1. Complete solubilization of sludge.
2. Complete carbon suspension under both wet
and dry conditions.
3. Residual detergency, as indicated by dis-
persancy in blotter tests under wet and dry
conditions.
4. Ability to prevent agglomeration and precipi-
tation of sludge formed during oxidation of lubri-
cating oils, with and without presence of water.
5. Effective sludge suspension after 40-hr lab-
oratory tests, and after several months of storage.
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Fig. 1 – Electron photomicrographs of oils without additive ( left) and
with barium sulfonate (right). Micelle formation is visible in oil con-
taining detergent. Pictures were taken at 17,000x and enlarged to
90,000x (shown here somewhat reduced in size)
is some disagreement in the literature as to
whether these charges are responsible for the
stability, or lack of stability, exhibited by the
sludge dispersions. 3, 4'
Fig. 2 shows photomicrographs of oil samples
withdrawn from a passenger-car engine operated
in the laboratory on an oil containing 0.5% active
ingredient of a barium petroleum sulfonate. The
first picture shows the oil before it was placed in
the engine, while the others show samples of the
oil after 5, 15, and 40 hr of operation. It can be
seen that as small particles of sludge are formed,
the micelles of detergent cluster around each par-
ticle and tend to keep them dispersed. As the oil
continues in use, the micelles are gradually de-
pleted, and agglomeration of particles proceeds.
Some detergents are capable of keeping the size
of sludge particles so small that, for all practical
purposes, it can be said that the particles are in
778
solution. This solubilization of sludge is the most
effective way in which a detergent can function.
As shown by Spindt and Wolfe, 6 engine sludge in
suspension in the lubricating oil does not tend to
deposit on engine parts until the concentration
becomes excessive. The deposition tendency of this
sludge is reduced if the sludge is solubilized by the
detergent.
Many laboratory engine tests and also road tests
have indicated that not all detergents perform
adequately under low or moderate temperature
operating conditions. The foregoing concepts of
detergency are inadequate to explain these differ-
ences in performance. For this reason, bench and
engine tests were conducted with representative
examples from four different classes of detergents
having known differences in low-temperature per-
formance. The detergents studied were a basic
barium phenate, a basic barium petroleum sulfo-
nate, a metal-containing experimental detergent,
and a nitrogen-containing polymeric detergent.
This last detergent, an example of the new class
of materials,' is a copolymer of lauryl methacrylate
and diethylaminoethyl methacrylate having the
structure shown in Fig. 3. It will be referred to as
Detergent C. The sulfonate and phenate selected
for this work had the best low-temperature labora-
tory engine performance of the five or six of each
class investigated.
3 See Journal of Institute of Petroleum, Vol. 39, 1953, pp. 677-687: "De-
tergency of Carbon Black, VI," by F. H. Garner, C. W. Nutt, and M. F.
Mohtadi.
See Journal of Physical Chemistry, Vol. 48, 1944, p. 125: "Study of
Colloidal System Carbon Dispersed in Xylene," by V. R. Damarell and
A. Urbanic.
5 See Journal of Physical and Colloid Chemistry, Vol. 55, 1951, p. 1527:
"Electrophoresis in Non-Aqueous Media," by M. Hayek.
6 "Why and Wherefore of Engine Deposits," by R. S. Soindt and C. L.
Wolfe. Presented at SAE National West Coast Meeting, Seattle, Aug. 15,
1951.
Fig. 2 – Electron photomicro-
graphs at 38,000x showing
barium petroleum sulfonate
micelle depletion in oil samples
taken from multicylinder en-
gine test (shown here some-
what reduced in size)
SAE Transactions
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Bench Test Performance of Detergents

Sludge Suspension – The ability of the four de- The Authors
tergents to suspend sludge was examined using a R. L. WILLIS (M '52) is a research chemist in the
Petroleum Laboratory of E. I. du Pont de Nemours Co., Inc.
test described by Biswell et al.' This interesting He received a B.S in Chemical Engineering from the Uni-
technique measures the ability of detergents to versity of Pennsylvania in 1941 and a chemical engineering
suspend oil-insoluble sludge when the sludge is degree from Princeton University in 1942. Mr. Willis
joined du Pont in 1942 as a production supervisor on the
precipitated in the presence of the detergent. It is Manhattan Project, assuming his present position in 1946.
carried out by adding a benzene solution of the His work is primarily concerned with lubricating oils and
oil-insoluble resins from oxidized oil to a kerosene additives.
solution of the detergent. The benzene is then evap- E. C. BALLARD ( M '55) is a supervisor of research
orated under controlled conditions, leaving behind on lubricating oils and lubricating oil additives in the
Petroleum Laboratory of E. I. du Pont de Nemours Co.,
the original kerosene. The physical state in which Inc. He received a Ph D. in Organic Chemistry from the
the sludge appears in the benzene-free kerosene University of Minnesota in 1940. Prior to becoming as-
is determined by the effectiveness of the detergent sociated with the Petroleum Laboratory in 1950, Dr. Bal-
lard did research and development work on pigments, syn-
present in the system. Fig. 4 illustrates the dif- thetic rubber, petrochemicals and tetraethyl lead in other
ferences in performance of the four detergents laboratories of du Pont.
when evaluated at a concentration of 0.5 weight-
percent active ingredients in this test. The photo-
graphs show the sample vials as they appeared
in less than one day. The suspending ability of
5 hr after the evaporation of the benzene. When
Detergent B is lost when one volume per cent water
no detergent was present, all the sludge settled
is present in the kerosene. Under these conditions,
to the bottom of the vial. Detergent A showed
Detergent C retains its effectiveness. These results
some suspending ability, while Detergents B and
are shown in Fig. 6. Photographs of these mix-
D failed to keep the sludge in suspension. Deter-
tures, taken after settling for one day, are shown
gent C gave complete solubilization of the sludge.
in Fig. 7. The effect of water on the performance
Discrete sludge particles could be detected in all
of the detergents is evident.
vials except that containing Detergent C, which
Several samples of detergents of the types repre-
remained bright and clear for several months. Even
sented by Detergents A and B were found to ex-
at electron microscope magnifications of 10,000x,
hibit suspending ability for carbon in both wet and
no sludge could be seen in the Detergent C system.
dry kerosene. However, detergents of these types
Carbon Suspension – In addition to the organic
sludge which must be kept dissolved or in suspen-
sion, carbon from partially burned fuel must be C H5 Cr3
prevented from depositing in the lubrication sys-
tem. For this reason, a test was carried out to CH2 C CH2 C
determine the ability of the four detergents, at a
concentration of 0.5 weight per cent active ingre- C=0 0=0
dient, to suspend a finely divided carbon in kero-
sene under both wet and dry conditions. The
0 0
performance of detergents in the presence of water C12 H25 CH2CH2N(C2H5)2
is considered to be important, because water is —x Y
present in crankcase oils during low-temperature Fig. 3 – Chemical structure of Detergent C (lauryl methacrylate
engine operation. This water enters the crankcase diethylaminoethyl methacrylate)
either as condensate from blowby gas during
engine operation, 7 or as condensate which forms
as a result of engine breathing during periods in AtARS

which the engine is not in operation.

For these experiments, a fine carbon black was
milled into a heavy white oil on an ink mill. A
sufficient amount of the carbon-oil paste was dis-
persed in each kerosene-detergent solution with a
Waring Blendor to form a suspension containing
0.5 weight per cent of carbon. As shown in Fig. 5,
Detergents B and C maintain complete suspension
of the carbon for more than six days, whereas
Detergents A and D lose their suspending power
M. DE - ERGE?;:" DE ERGE1, r DE T tERGi

7 "Oil Filtration Problems with High Detergency Lubricants," by H. M.

Gadebusch, R. T. Karr, and W. B. Bassett. Presented at SAE National Fig. 4 – Sample vials containing kerosene-sludge systems, showing wide
Fuels & Lubricants Meeting, Chicago, Oct. 31, 1951. range in sludge-suspending ability of detergents

Volume 63, 1955 779
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were generally not very effective in the presence
of water.
Because crankcase oils eventually become acid
during the normal use period, the carbon-suspend-
ing ability of several detergents of various types
was determined in the presence of two volume per
cent of a 10 weight per cent hydrochloric acid solu-
tion. The quantity of acid was sufficient to more
than neutralize the basicity of the kerosene-
detergent system. Under these conditions, Deter-
DETERGENT: 0.5 WT. % ACTIVE INGREDIENT
100
1\_ \—DETERGENT B
gent C was the only effective dispersant.
"Blotter" Tests – Gates and co-workers 8 have
recognized the importance of water, and have re-
ported that the effectiveness of a detergent oil can
be neutralized by engine-coolant leakage into the
crankcase, and also by the presence of aqueous
blowby condensate in the oil. Gates and also Edgar9
have used "blotter" or filter-paper spot tests to
evaluate the residual detergency of used engine
oils. In such tests, when a drop of the oil contain-
ing an effective detergent is placed on a piece of
filter paper, the dispersed sludge flows out with
the oil into the paper, giving a large, dark oil spot.
If the detergent properties of the oil have been
exhausted, the sludge remains in its original posi-
tion on the paper, and only clear oil spreads out

DETERGENT C
into the paper. The blotter test performance of
used oils formulated with the four different deter-
47--DETERGENT,A gents has been determined. The essentially water-
free used oils for this experiment were taken from
50 Buda diesel engines operated for 50 hr at 175 F
of—DETERGENT oil temperature and 195 F coolant temperature.
The oil spots illustrated in Fig. 8 show the residual
detergency of the used oils as well as the effect of
the addition of 0.5% water. In the dry systems,
0 2 3 4

5

6
Detergents A, B, and C all show good detergency
as indicated by the large black spots, while Deter-
DAYS gent D is marginal in performance. One-half per
Fig. 5— Effect of detergent on suspension of carbon in dry kerosene cent water neutralizes the Detergents A and D and
decreases the efficiency of Detergent B. Water has
DETERGENT: 0.5 WT. % ACTIVE INGREDIENT no effect on the dispersancy of Detergent C.
Oxidation Tests – The ability of the detergents
100 to prevent the agglomeration and precipitation of
DETERGENT C sludge formed during the oxidation of lubricating
oils was determined using the MacCoull test equip-
DETERGENT B
"On-the-Spot Testing of Used Lubricating Oils," by V. A. Gates, R. F.
Bergstrom, T. S. Hodgson, and L. A. Wendt. Presented at SAE National
50 West Coast Meeting, Los Angeles, Aug. 17, 1954.
9 "High Additive Oils in the City, on the Long Lines, and Off the Road,"
DETERGENT A by J. A. Edgar. Presented at SAE National West Coast Meeting, Seattle,
jr DETERGENT D Aug. 14, 1951.

USED
I I I I I I
0
I 2 3 4 5 6
DAYS
Fig. 6— Effect of detergent on suspension of carbon in wet kerosene
ERGE%T A
DETERGENT DETERGENT ,

E KEROSINE
USED OILS WITH C .TE,

uc i EAGENT DETERGENT Ot 7 ERGE

4

Fig. 7— Sample vials containing kerosene suspensions of carbon, showing Fig. 8 — Used-oil spot tests, indicating that water neutralizes effective-
dispersant performance of representative detergents in presence and ness of Detergent A, harms that of Detergent B, and has no effect on
in absence of water. 1: no detergent, 2: Detergent A; 3: Detergent B; that of Detergent C. Detergent D exhibits little, if any, residual deter-
4: Detergent C; 5: Detergent D gency even in dry oil

780 SAE Transactions

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ment. 1° The base oil used was an SAE 10W Mid- small oil samples removed periodically from ti
continent solvent-refined neutral, carefully filtered engine. In addition, the gradual development anew
to remove tramp solids. The detergents were added growth of the sludge particles was followed by
at a concentration of 0.5 weight per cent active an examination of these used-oil samples with an
ingredient. Duplicate samples of these treated oils electron microscope. The base oil used in these
were oxidized at 200 F, and 2 ml of water was tests was a solvent-refined Midcontinent neutral
added every 30 min to one set of samples. Oxida- of 140 SUS at 100 F. It was carefully filtered to
tion was not extensive even after 60 hr in the test remove tramp particles which might otherwise
equipment. However, examination of the oxidized have been mistaken for sludge. One weight per cent
oils under the electron microscope did show that of a zinc dialkyldithiophosphate antioxidant and
the type of detergent present exerts considerable 0.5 weight per cent, on an active ingredient basis,
influence on the nature and the extent of sludge of the required detergent were added to this filtered
formation. This study also demonstrated that oil. The concentration of the detergent was set at
water increases the rate at which sludge develops. a value lower than used in service, in order that
These results are illustrated in Fig. 9. The electron depletion of the detergent would be appreciable
photomicrographs show plainly the effect of water during the course of the 40-hr engine test. The
on the quantity and particle size of the sludge. tests were all started without the separate break-
The peculiar feathery sludge particles formed in in, using 6 qt of oil rather than the customary 4 qt.
the presence of Detergent B were obtained repeat- This procedure prevented contamination of the
edly; they were not present in the unoxidized oil. test oil with sludge from the break-in period, and
The ability of Detergent C to minimize sludge also provided sufficient oil for completion of all
formation, and the insensitivity of the polymer the tests without further oil additions. The engine
system to water, are illustrated quite clearly by was operated on a non-leaded fuel. A representa-
these photomicrographs, which were selected to tive 15 ml sample of oil was withdrawn from the
represent the typical, or average, of approximately crankcase each hour. These small samples were
10 pictures taken on each oil. In turn, the 10 pic- used in sludge settling tests and electron micro-
tures were typical of some 25 to 40 visual observa- scope studies, after gradual detergent depletion.
tions made on each oil. The engine scores obtained from these tests are
summarized in Table 1. It is evident that at equal
Effect of Detergents on Sludge Development in Lab Engines concentrations the different types of detergents
Certain of the techniques used in the bench test vary widely in their effect on piston varnish and
work have been applied to an engine study of overall engine score. Detergent C, as might be pre-
these detergents. The gradual loss of oil deter- dicted from the previously discussed bench test re-
gency during a series of FL-2 11 engine tests was sults, was very effective in minimizing sludge and
followed by observing the sludge settling rates of varnish formation. Although the oil containing De-
tergent A actually gave a lower piston score than
the base oil, it did show some improvement in over-
all engine cleanliness. Detergents B and D had little
10 See SAE Transactions, Vol. 50 (August), 1942, pp. 338-345: "An Oil effect on the oil performance under these conditions.
Corrosion Tester," by N. MacCoull, E. A. Ryder, and A. C. Scholp.
". "Laboratory Engine Tests of Sulfur in Motor Gasoline Field Test
Fuels." Report of Coordinating Research Council, Inc., January, 1950.
The tendency of the sludge to settle out of the
used oils was studied visually following vigorous
shaking of the samples. These settling tests were
repeated several months later on the same samples
with the same results, indicating that once the oils
were removed from the engine their detergent qual-
ities were quite stable. The settling rates obtained
indicate that Detergent A loses its effectiveness
after 6-8 hr of engine operation, Detergent B at ap-
proximately 15 hr, and Detergent D at 4 hr. Deter-
gent C effectively suspends sludge for the complete
40-hr test. The results obtained are illustrated in
Fig. 10, which shows photographs taken after four
days of settling of the oil samples taken after 0, 3,
6, 10, 15, and 40 hr of engine operation. The base oil
showed no tendency to suspend sludge, and, there-
fore, samples of it were not photographed. The
physical appearance of the sludge at the 10- and
40-hr points of the tests is illustrated by the elec-
Fig. 9 — Electron photomicrographs at 3800x of sludge from oils oxi- tron photomicrographs in Fig. 11. Small sludge
dized at 200 F in MacCoull apparatus. Water accelerates oxidation particles can be observed in the 10-hr samples of all
and formation of sludge particles four detergent oils. The 40-hr photographs indi-

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Table 1 – FL-2 Engine Test Scores Obtained in the Table 2 – FL-2 Engine Performance of the
Sludge Development Study Four Different Detergents
Oil: Solvent-refined SAE lOW antioxidant Oil: Solvent-refined SAE 30 + antioxidant
Fuel: 10% alkylate. 90% catalytic cracked, unleaded Fuel: 100% thermal reformate -I- 3 ml tel/gal
Piston Score Piston Score
(10 = Clean) Engine Score (10 = Clean) Engine Score
Active --------- (50 = Clean) Active (50 = Clean)
Ingredient, No. 1 Average Ingredient, No. 1 Average
Detergent weight % Piston Piston Varnish Sludge Detergent weight % Piston Piston Varnish Sludge
None 3.5 5.0 30 38 None 4.5 5.9 29 39
A 0.5 1.0 3.7 33 44 A 1.2 2.5 4.1 30 40
B 0.5 4.5 6.0 32 37 B 1.0 5.5 7.5 38 41
C 0.5 7.0 8.3 39 47 C 1.0 8.0 9.3 42 43
D 0.5 4.6 5.8 36 35 D 1.0 7.0 8.3 41 43

cate that in the case of Detergents A, B, and D the gent oils is small enough to pass through efficient
small particles have agglomerated very extensively, lubricating oil filters. At 40 hr, however, such filters
whereas in the oil containing Detergent C there has would trap most of the sludge in all of the oils ex-
been little change in particle size, although the cept that containing Detergent C. In this oil, only a
number of particles has increased somewhat. Much few of the particles are of filterable size – that is,
of the sludge from the 10-hr samples of the deter- larger than 1 to 2 microns in diameter.?
Representative samples of sludge were photo-
graphed again through the electron microscope af-
ter the samples had been stored for several months.
No observable change in particle-size distribution
or particle shape occurred during this storage pe-
riod. This result suggests that growth or agglomer-
ation of sludge particles normally occurs only dur-
ing periods of engine operation as the detergent is
gradually depleted. Agglomeration can also occur
in the presence of some detergents during periods
of nonoperation, if the water content of the oil is
increased by condensation or coolant leakage into
the crankcase.

Performance of Detergents in Lab Engine Tests

The four detergents were evaluated in a Mid-
continent solvent-refined SAE 30 base oil at a con-
centration of approximately 1% active ingredient,
using both the FL-2 and EX-3 procedures. The first
of these is a steady-duty 40-hr test with low coolant
Fig. 10 – Used-oil samples, showing detergent depletion and gradual
failure of the oils to suspend sludge temperature, which offers an accelerated means for
evaluating fuel or lubricant performance at low en-
gine temperatures. The second is a cyclic 96-hr pro-
DETERGENT - cedure, currently under development by the Coordi-
73Tecnoris
nating Research Council, which has incorporated
into it periods of operation under both high- and
low-temperature conditions. The results of these
.,F7E?GE'4,
engine tests, summarized in Tables 2 and 3, indicate
that engine cleanliness is a function of the type of
DETERGENT A detergent used. Detergent A has little effect on over-
all engine cleanliness in either test, but increases
varnish formation on the pistons. Detergents B and
: 7;G: •17.
D decrease piston and engine varnish in the FL-2
test, but allow somewhat more varnish to form than
DE ?Ef?T T with the base oil in the EX-3 procedure. In both
procedures, engine cleanliness is improved by De-
9ET. -RB NT C tergent C. In addition to the variation that these
detergents exhibit in their ability to control var-
nish and sludge formation, they also show differ-
Fig. 11 – Electron photomicrographs at 3800x of sludge from used ences in their ability to control the plugging of the
oils, showing that all four detergents have some ability to minimize narrow slotted oil rings used in the EX-3 procedure.
particle size during first 10 hr of engine operation. Differences in
performance become apparent after 40 hr (shown here somewhat Detergent C, and to a lesser extent Detergents B
reduced in size) and D, reduced oil-ring plugging in this procedure.

782 SAE Transactions
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Table 3 - EX-3 Engine Performance of the Table 4 - Effect of Type of Detergent on the
Four Different Detergents Sludge Content of Used Oils
Oil: Solvent-refined SAE 30 + antioxidant Test: FL-2
Fuel: 100% thermal reformate -I- 3 ml tel/gal Of I: Solvent-refined SAE 30 + antioxidant
Narrow Fuel: 100% thermal reformats + 3 ml tel/gal
Engine Score
(50 = Clean) Slot Oil Average Sludge Content of Oils.
Active Average
Ingredient, Piston Score Ring,
Vo plugging Active n-Pentane Benzene Insoluble
Detergent weight % (10 = Clean) Varnish Sludge Resins,
Ingredient, Number Insolubles, lnsolubles,
None 5.2 30 35 38 weight % weight % weight %
29 Detergent weight % of Tests
A 1.0 3.5 28 40
38 14 Noneb 27 1.94 1.16 0.78
a 1.0 4.2 24 0.65
43 7 None 5 1.87 1.22
C 1.0 8.6 40
1.23 0.68
4.5 23 36 12 A Type 1.2 4 1.91
1.0 2.43 1.63 0.80
B Type 1.5 5
C 0.5 56 1.17 0.83 0.34
C 1.0 11 0.86 0.67 0.19
C 1.5 3 0.61 0.55 0.06
Type 1.0 4 2.33 1.02 1.31

ASTM Method - D893-52T.

b Ne antioxidant.
Sludge analyses on the used oils from the above
engine tests show that oils containing Detergent C
contain less oil-insoluble material than any of the
other oils. This information is substantiated by the
analytical results from a large number of FL-2
tests which are presented in Table 4. These data
strongly suggest that the type of detergent influ-
ences the benzene insolubles and the insoluble resin
content of the oil. Detergents of Type D structure
appear to increase the insoluble resins in the used

oil to a level higher than that found in the base oils, BASE OIL DETERGENT E
whereas detergents similar to A and B have but 1.4 WT. % ACTIVE INGREDIENT
little effect on these resins. Detergent C markedly
decreases the insoluble resin content of the used oil.
In the case of this last detergent, sufficient data are
available to illustrate the effect of detergent con-
centration on the sludge content of the oil; as the
detergent dosage increases, the sludge content de-
creases. The low sludge content of used oils con-
taining Detergent C may be related to the ability of

this detergent to solubilize sludge, as was demon- DETERGENT C DETERGENT C
strated in the sludge suspension tests already de- 1.0 WT. % ACTIVE INGREDIENT 2.0 WT. % ACTIVE INGREDIENT'
scribed. It is possible that Detergent C also de-
Fig. 12 - Oil screens from extended service test
creases the rate of the condensation and polymeri-
zation reactions which transform low molecular
weight fuel and oil oxidation products into varnish
and sludge. The low level of benzene-insoluble ma-
terial encountered in the engine oils with low in-
soluble resins suggests a relationship between the
two materials. Indeed, it seems quite likely that the
same reactions that lead to insoluble resins can con-
tinue and convert these resins into higher-mole-
cular-weight, benzene-insoluble materials. Confir-
mation of the data shown in Table 4 has been ob-
tained from analysis of used oils from EX-3 tests BASE OIL DETERGENT E
1. 4 WT. % ACTIVE INGREDIENT
and L-4" high-temperature engine tests.

Field Performance of Detergents

The data from bench tests and laboratory engine
tests indicate that considerable differences in low-
temperature performance exist among different
types of detergents. These results have been sub-
stantiated by several road tests. One of these road
tests involved both city and country driving in
DETERGENT C.
DETERGENT C
convoy for 40,000 miles, and was run using Mid- 1.0 WT. % ACTIVE INGREDIENT

2.0 WI % ACTIVE INGREDIENT
continent solvent-refined SAE 30 oils containing
Detergent C in two cars and Detergent F (a deter- Fig. 13 - Timing gear covers from extended service test

Volume 63, 1955 783

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gent similar to Detergent A) in two others. Aver-
age analyses of used oils taken from this test are
given in Table 5. The oil drain period was 2500
miles, and the results presented in the table are the
averages obtained after analyzing the individual
used-oil samples from every drain period of each
car. The performances of the two cars on each oil
were in good agreement, and the differences be-
tween the two oils were clearcut ; Detergent C min-
imized insoluble-resin formation to a much greater
extent than did Detergent F. The reduction of the
benzene-insoluble contents from 0.97 and 1.16
weight per cent with the oil containing Detergent
F to 0.45 and 0.42 weight per cent with Detergent C
also was significant.
Another field test involved extended urban and
Table 5 - Effect of Detergents on the
Sludge Content of Road Test Oils
Oil: Solvent-refined SAE 30 + antioxidant
Test: 40,000 miles per vehicle
2,500-mile drain periods
1 2
Detergent C, weight %
Active Ingredient
Detergent F, weight %
- -
Active Ingredient
New Oil Ash, weight %
1.3
0.28
Used Oil Analysis,'
n-Pentane Insolubles, weight % 1.73
Benzene Insolubles, weight %
Insoluble Resins, weight %
0.97
0.76
ASTM Method D893-52T. Each value is the average of the analyses of the 16 oil drain
samples obtained during the 40.000 miles of operation.
784
DETERGENT E
1.4 WT. % ACTIVE INGREDIENT
Fig. 14- Blocks and side plates of
engines from extended service
test
ETERG
AcrwE INsREDIENT
suburban operation. The results of this test agree
with the laboratory engine tests and show that De-
tergent E ( a detergent similar to Detergent A) , at
an active ingredient level of 1.4 weight per cent, did
not markedly improve engine cleanliness during low
and moderate temperature operation over that ob-
tained with the base oil. In contrast to the appear-
ance of the engines lubricated with the base oil or
oil containing the Detergent E, all of the engines
lubricated with oils containing Detergent C were
clean. Photographs of parts from representative
engines at the end of the test on the base oil, an oil
containing Detergent E, and two oils containing
Detergent C are shown in Figs. 12, 13, and 14.
Summary and Conclusions
1. Various types of detergents, including a new
ashless, polymeric type, have been evaluated for
their performance at low engine temperatures.
2. Detergent types vary widely in their ability to
maintain engine cleanliness under low-temperature
conditions.
Vehicle
3. Detergents which are effective at high engine
3 4
temperatures are not necessarily effective at low
1.5 1.5 engine temperatures.
1.3
0.28
-
0.09
-
0.09
4. Bench tests show that many detergents lose
2.05 0.59
their effectiveness when evaluated in systems con-
0.57
1.16 0.45 0.42 taining small amounts of water. The performance
0.89 0.14 0.15
of detergents in low-temperature engine service is
believed to be related to their sensitivity to water.
5. Bench tests and analytical data from used en-
SAE Transactions
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gine oils indicate that the benzene insolubles and the

insoluble resin content of used oils is influenced by Table A - 72-Hr Modified EX-3 Engine Test
the type and the amount of detergent in the oil. Series I Detergent
Nondetergent Detergency
6. Extensive low-temperature service tests have Piston Rating 2.3 3.5 7.0
Total Varnish 24.3 27.6 40.5
confirmed the conclusions reached in the laboratory. Oil Screen 2.0 3.0 9.0
Total Sludge' 15.8 20.6 27.5
Total Engine 40.1 48.1 68.0
DISCUSSION 5
Corrected to - of total numerical sludge rating.
9
Commends Attention to
Stop-and-Go Driving Needs
- J. G. Moxey tory, bench, and field test operation. If what they have
Sun Oil Co. discovered can be substantiated by further field testing with
THE
TH resultant clean engines, then this discovery portends to be
new additive described by these authors has been
specifically at the low and intermediate tempera- one of the most important in the field of automotive motor
ture ranges that are so typical of passenger-car service, oils since oxidation inhibitors were used to produce clean
and I think it has been almost inevitable that eventually and corrosion free L-4 tests.
the path of motor-oil additive development would turn in The paper is timely because the problem of low-tempera-
this direction. ture sludge formation in V-8 engines is becoming more
Most of the oils we now have were developed primarily acute as engine horsepowers go up and the distance between
to provide protection at the high-temperature, severe-duty stoplights becomes less.
end of the scale. We've been very fortunate, however, in In the winter of 1953, we did some work which confirms
that these same oils have done a pretty good job of pro- the authors' contention that wide differences exist in the
tection at the low-temperature end. Such features as low- ability of various detergent additives to minimize sludge
temperature corrosion and wear resistance are a very im- formation in engines. Our objectives were:
portant part of our current oils. Whether it was planned 1. To determine the effect of oil drain periods on varnish
that way or not, I don't think any of us need to be too
apologetic about the performance of the oils that are now
being used commercially in passenger-car service.
But that doesn't mean that we shouldn't continue to
make progress. And it makes sense to me that we should
include in our additive development programs the search
for materials aimed specifically at typical stop-and-go
passenger-car operation.
I don't believe the du Pont people intend that their new
additive should be a replacement for all of the materials
that are now used. There are many performance features
that these polymers make no attempt to provide. But they
apparently have made a real advance in providing engine
cleanliness under the temperature conditions that we have
to contend with in passenger-car operation.
My other thought is in connection with the performance
of the additive. We've been doing work with it, as I imagine -,
most oil companies have. Our results have been pretty
much the same as those of the authors. Fig. A — Dispersion of drain samples after 24-hr settling—left pair: MIL
Table A shows results from a modification of the EX-3 detergency, middle pair: Series 1 detergency, right pair: Detergent C
procedure that we've been using in our laboratory. The
three oils all used the same type of base stock. The first CAR ,4 CAR 4
column is for a nondetergent oil containing only an anti- as000 MILE DRAIN
oxidant. The second is a typical Series I product. And the
760 mite DRAIN
last column is an oil incorporating the du Pont additive,
Detergent C. The differences are of the same order of
magnitude as those described in the paper.
Fig. A illustrates the solubilizing properties of the addi-
tive. These are drain samples from duplicate FL-2 tests on
three different oils as indicated. They've been allowed to
settle for 24 hr, and the ability of the polymer to maintain CAR
the contaminants in suspension is quite apparent. MO MILE DRAIN
Corroborates Findings
With Ashless Detergent C
—R. I. Potter
Standard Oil Co. (Ohio)
THE authors have presented a most important and timely
TH
first, because it has developed a new approach in
studying and defining sludge particle size growth by means
of the electron microscope, and second, because their re-
search has revealed another of nature's secrets in the crea-
tion of an ashless detergent dispersant, seemingly unaffected
by moisture under low-duty engine operating conditions.
This ashless detergent appears to have a long period of Fig. B — Oil screens from test cars after 750-, 1500-, and 3000-mile
effectiveness even under most adverse conditions of labora- drain periods

Volume 63, 1955 785

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

and sludge formations under stop-and-go driving conditions,

using a common test fuel and an oil containing a sizable
Table B - Used Oil Analyses
amount of metallic detergent.
Car No. Drain Interval, Mlles Detergent Rating
82.6
2. To compare the effectiveness of a metallic detergent
1 750 Metallic
3 1500 Metallic 80.3 with an experimental ashless detergent of the same type
4 3000 Metallic 72.0 as Detergent C referred to by the authors.
2 3000 Ashless 77.0

Note: All of these engines were in reasonably clean condition Engine Buildup
because of the low mileage operated - 3000.
Four 1952 overhead-valve V-8 engines of a well known
make were carefully rebuilt after about 25,000 miles of
operation. New hydraulic valve lifters, new oil filters, and
clean filter cases went into each test engine. Then the en-
gines were reassembled in a completely clean condition.
Ethylene glycol-type permanent antifreeze was used as
coolant in conjunction with 156 F thermostats.

6 AIN
Fig. C - Filters from test cars after 750-, 1500-, and 3000-mile drain
periods
arf ?Lj
W.:t4 mlLeadi Jfiai.lp 4w. id-a
Fig. D - Oil screen from test car operated on oil treated with experi-
mental additive C after 3000 miles
Fig. E - Oil filter from test car operated on oil treated with additive
C after 3000 miles
Fig. F - Sludge-settling behavior of used motor oils in 15-month test.
Left to right: premium, MIL-L-2104A, 5-2, and Ashless Detergent C
Operations
Cars were parked outside at all times. Long trips were
avoided. Driver assignments were changed each week. Car
travel averaged about 25 miles per day, and oil was drained
while hot. Total mileage was 3000 miles.
Three oil drain periods for respective cars were used:
750-, 1500-, and 3000-mile intervals.
Test Results
Figs. B and C show how the drain periods affected the
oil screens and filters from cars 1, 3, and 4. They offer
visible proof that the filter elements from the 1500- and
3000-mile drain period cars weighed almost % lb more than
did the filter from the 750-mile drain period car.
It can be seen from this test that a vehicle operated under
these severe home-to-work conditions, using a common
winter grade fuel and oil containing a sizable amount of
metallic detergent, should be drained either once a month
or after 1000 miles of operation. This conclusion relates
favorably with the API Committee recommendation that
"crankcases should be drained after not over 60 days, or
500 miles of travel in this type of service."
Ashless Detergent Results
Concurrently with the three cars already described, a
fourth car, No. 2, was operated on an oil treated with an
experimental ashless type Additive C without drain for a
3000-mile period. Figs. D and E show the oil screen and
filter from this engine, which compare favorably in condi-
tion with the screen and filter of the 750-mile drain opera-
tion using the metallic detergent (Car 1).
Combined Sludge and Varnish Ratings
The used oil analyses (Table B) indicated that the ash-
less detergent oil was capable of suspending some three
to seven times as many oil contaminants as the metallic
detergent - probably due to the fine dispersion of these
solids, as pointed out by the authors.
This property of sludge and insoluble contaminant sus-
pension is further observed in another of our tests, as
shown in Fig. F, where four used oil samples of the quali-
ties premium, MIL-L-2104A, S-2, and Ashless Detergent C
were settled for a 15-month period. Each of these oils was
operated under stop-and-go city driving conditions for over
4000 miles without draining. The amount of settling
appears to vary proportionately with the detergent dis-
persant quality of the oil - the premium oil on the left
containing the least detergent shows the most settling, and
the ashless type, Detergent C treated oil on the right, shows
very little separation.
We can conclude then with the authors that the use of
an electron microscope to determine the effectiveness of
detergents to prevent sludge particle size growth in oil is
a much more effective and novel method than waiting for
used oil samples to settle. Although the work described
here is limited and a great deal more road testing is neces-
sary, the results substantiate that large differences exist
between the metallic and ashless type C detergents in their
ability to keep filters, oil screens, and engine parts free
from sludge under low-temperature operating conditions.

786 SAE Transactions