Tribology Transactions

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Lubricant Additive Effects on Engine Oil

Pumpability at Low Temperatures—Detergents
and High Ethylene Olefin Copolymer Viscosity
Modifiers

Michael J. Covitch STLE member

To cite this article: Michael J. Covitch STLE member (2007) Lubricant Additive Effects on Engine
Oil Pumpability at Low Temperatures—Detergents and High Ethylene Olefin Copolymer
Viscosity Modifiers, Tribology Transactions, 50:1, 68-73, DOI: 10.1080/10402000601105540

To link to this article: http://dx.doi.org/10.1080/10402000601105540

Published online: 06 Oct 2010.

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 Tribology Transactions, 50: 68-73, 2007
Copyright C Society of Tribologists and Lubrication Engineers
ISSN: 1040-2004 print / 1547-357X online
DOI: 10.1080/10402000601105540
Lubricant Additive Effects on Engine Oil Pumpability at
Low Temperatures—Detergents and High Ethylene Olefin
Copolymer Viscosity Modifiers
MICHAEL J. COVITCH, STLE Member
The Lubrizol Corporation
29400 Lakeland Boulevard
Wickliffe, OH 44092
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Passenger car and heavy-duty diesel engine manufacturers
recognize the need to ensure that engine oils maintain ade-
quate low-temperature pumpability performance throughout
their working life. For over two decades, the Mini Rotary Vis-
cometer (MRV TP-1) bench test has been used to develop oils
that have protected engines from oil starvation failure during
cold weather startup. The test was created to measure the low
temperature flow properties of fresh oils. During engine op-
eration, a number of changes take place in the lubricant—both
chemical and physical—that can influence oil pumpability. This
paper presents a systematic evaluation of the role that various
common lubricant additives play in affecting MRV viscosity and
pour point and reinforces the notion that new oil MRV is not
necessarily a good predictor of used oil pumpability.
KEY WORDS
Detergent; Dispersant; Pour Point Depressant; Viscosity Index
Improver; Degradation; Interaction; Low Temperatures; Internal
Combustion Engine Oils; Mineral Basestocks; Pour Point; Viscos-
ity; Viscosity-Temperature Behavior
INTRODUCTION
Engine oils are formulated with pour point depressants (PPDs)
to counteract the formation of wax crystal networks at low tem-
peratures. These relatively fragile structures are strong enough
to impede oil flow and can be easily characterized by standard
ASTM low shear rate, low-temperature rheological methods such
as the Mini Rotary Viscometer (MRV ASTM D 4684), Brookfield
(ASTM D 2983), Scanning Brookfield (ASTM D 5133), and Pour
Point (ASTM D 97, D 5950, D 5985). For many years, the en-
gine oil formulator selected a particular PPD that satisfied the
MRV requirements of SAE J300 for the fresh oil. No considera-
tion was given to retaining adequate low-temperature oil pumpa-
Presented at the STLE Annual Meeting
in Calgary, Alberta, Canada
May 7-11, 2006
Manuscript approved August 9, 2006
Review led by Lois Gschwender
68
bility during engine operation. Today, however, both passenger
car and commercial heavy-duty diesel engine OEMs are recog-
nizing the importance of pumpability retention during the life of
the lubricant and have appended used oil MRV requirements to a
number of laboratory dynamometer tests (see Table 1). This poses
new challenges to the lubricant formulator. What used to be a
relatively inexpensive exercise, confirming adequate PPD perfor-
mance, now entails running expensive engine tests. Therefore, the
justification for understanding the complex relationships between
lubricant additive chemistries and base oil wax (and the changes
that take place during engine operation) has never been greater.
Li, et al. (1) conducted a detailed study of how the molec-
ular structure of alkylbenzene sulfonate detergents can affect
the pour point of formulated motor oils. In some base oil sys-
tems, over-based sulfonate detergents with linear (i.e., polyethy-
lene) alkyl substituents can act as pour point depressants and
can lower pour point and MRV viscosity as effectively as con-
ventional poly(alkylmethacrylate) PPDs (PAMA). The authors
demonstrate that this effect is only observed for linear sulfonate
detergents, not for branched (i.e., polypropylene) alkyl sulfonates.
Neither metal type nor degree of over-basing was found to be criti-
cal. The over-based detergent micelle concentrates the polar head
groups of the detergent molecules into the micelle core, allow-
ing the alkyl groups to extend outwardly. This molecular arrange-
ment of alkyl groups is proposed to be similar to the adjacency of
alkyl side-chains in PAMA PPDs. The over-based detergent mi-
celle core serves the same function as the polymer backbone of a
conventional PPD.
Kinker, et al. (10) also acknowledged that detergents with lin-
ear alkyl chains and some organic friction modifiers have the po-
tential to control wax crystallization at low temperatures. The au-
thors observed that an SAE 5W-30 oil formulated with an ILSAC
GF-3 additive package and a commercial OCP viscosity modifier
(ethylene content was not specified) in API Group II base oils
met SAE J300 MRV limits without PPD. However, conditioning
this oil in a New York City taxi test resulted in severe MRV fail-
ure. Adding a PPD to the used oil or running the taxi test with
an oil formulated with an appropriate PPD were effective in pro-
viding adequate low-temperature pumpability control during use.
The authors explain this loss of MRV protection in the absence
of PPD as follows: “After exposure to engine conditioning the
 Lubricant Additive Effects on Engine Pumpability 69

TABLE 1—ORIGINAL EQUIPMENT MANUFACTURERS’ USED OIL MRV SPECIFICATIONS

Oil Life in Applicable MRV Limit MRV

Engine Viscosity (mPa-s, Temp.
Specification Engine Test (hours) Grade(s) max) (◦ C) Comments

API CJ-4 Mack T-11 180 SAE 0W, 5W, 10W, and 25,000 −20 yield stress < 35 Pa
15W
Caterpillar ECF-3 Mack T-11 180 SAE 15W-40 25,000 −20 yield stress < 35 Pa
and Cummins
CES 200081
Mack/Volvo Mack T-11 180 SAE 15W-40 18,000 −20 35 Pa max yield stress
97468-15 and
Renault 97468-13
DDC PGOS Mack T-11 180 SAE 15W-40 18,000 −20 35 Pa max yield stress
93K217
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ILSAC GF-4 Seq. IIIGA 100 SAE 0W-20, 0W-30, 60,000 SAE J300 T Meet MRV max limit
5W-20, 5W-30, 10W-30 or T + 5◦ C of original grade or
next higher W grade
DaimlerChrysler Seq. IIIGA 100 SAE 5W-20, 5W-30, 40,000 (5W-XX) SAE J300 T Service fill. Meet MRV
MS-6395 10W-30 50,000 or T + 5◦ C max limit of original
(10W-XX) grade or next higher
60,000 W grade
(15W-XX)
DaimlerChrysler Seq. IIIGA 100 SAE 5W-20 40,000 (5W-XX) −35 or −30 Factory fill. Meet
MS-10797 50,000 MRV max limit of
(10W-XX) original grade or
next higher W grade
General Motors Seq. IIIGA 100 SAE 0W-30, 5W-20, 60,000 SAE J300 T Service Fill. Meet
GM6094M 5W-30, 10W-30 or T + 5◦ C MRV max limit of
original grade or
next higher W grade
General Motors Seq. IIIGA 100 SAE 0W-30, 5W-30, 20,000 SAE J300 T Meet MRV max limit
Corvette ILSAC 10W-30 or T + 5◦ C of original grade or
GF-4 GM4718M next higher W grade

detergent becomes involved, as it should, with highly polar molec-
ular species created through oxidation processes or neutralizing
acidic compounds. Then a lack of interaction with hydrophobic
wax compounds is to be expected as well as the consequent loss of
pour point depressing activity.” Another SAE 5W-30 oil was also
run in the Sequence IIIGA test, with and without PPD. Again, se-
vere degradation of MRV viscosity and yield stress was observed
when PPD was absent, whereas the PPD-treated oil maintained
good low temperature oil pumpability after the IIIGA test.
Bansal, et al. (2) contrasted the new and used oil MRV perfor-
mance of engine oils formulated with several commercial viscos-
ity modifiers (VM) and pour point depressants (PPD). One VM,
a semi-crystalline high-ethylene olefin copolymer (HEOCP), was
reported to “experience dramatic loss of . . . low temperature per-
formance under a broad range of aging conditions,” and no PPD
in the study was effective in eliminating used oil MRV yield stress
with this VM. A non-crystalline amorphous olefin copolymer, a
hydrogenated styrene diene polymer, and a PAMA VM were rel-
atively well-behaved, however. Since the PPDs used in this paper
were not described in detail, it is not possible to exclude the possi-
bility that some other PPD(s) might be able to successfully control
the MRV viscosity of oils containing the HEOCP VM in aged oils.
The authors conclude that the VM plays a more critical role than
the PPD in controlling used oil pumpability.
Papke, et al. (3) also observed the detrimental effects of a
HEOCP viscosity modifier on oils aged in taxi field tests and a
road simulator. The MRV properties of used oils formulated with
non-crystalline VM chemistries suffered from contamination with
low amounts of a factory fill oil formulated with an HEOCP VM.
These authors found that used oil MRV viscosity and yield stress
for these used oils could be brought into compliance by increasing
PPD concentration. Similar conclusions were drawn by Li, et al.
(4). Batko, et al. (5) attribute the MRV sensitivity of this polymer
to its tendency to form polymer networks at low temperatures.
They also point out that lubricants blended with waxy API Group
I base oils tend to show a higher degree of MRV degradation
during aging than those containing Group II basestocks.
The purposes of this paper are (a) to examine to a greater
level of detail the relationship between detergent and other com-
mon engine oil lubricant additive chemistries on low temperature
oil rheology and (b) to apply a PPD fingerprinting technique to
deepen our understanding of the peculiar MRV behavior of a 50
SSI commercial HEOCP viscosity modifier and its interaction with
base oils and pour point depressants.
EXPERIMENTAL
An homologous series of poly(alkylmethacrylate) pour point
depressants were synthesized by free radical polymerization in an
 70 M. J. COVITCH
API Group I mineral oil. The average alkyl side-chain length of
the monomer feedstock was systematically varied across the range
that is most effective for base oils used in automotive crankcase
lubricants. In this paper the PPDs are numbered sequentially, with
the higher numbers indicating longer side-chain lengths. Molec-
ular weight was controlled to yield weight average molecular
weights of 33,000 to 42,000 as measured by gel permeation chro-
matography, calibrated with monodisperse polystyrene standards.
The PPD fingerprinting technique is a useful method to char-
acterize the waxy portions of base oils and formulated lubricants.
Two hundred-gram aliquots of test oil are treated with equal con-
centrations (typically 0.1% by weight on an active polymer basis)
of each PPD in the homologous series. The blended oils are then
subjected to one or more low temperature ASTM rheological tests
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as mentioned above. The shape of the viscosity vs. PPD chain-
length curve characterizes its low temperature flow behavior and
can be used to identify the optimum PPD for that oil.
All base oils, additives, and viscosity modifiers were commer-
cial products, except as noted.
Additive Effects on Low-Temperature Oil Rheology
Mineral oil-based formulated engine oils are occasionally
found to meet the low temperature requirements of SAE J300,
the SAE Engine Oil Viscosity Classification Standard, in the ab-
sence of a conventional pour point depressant (Li, et al. (1)). As an
example, an SAE 10W-40 heavy-duty diesel lubricant was blended
in a North American API Group I 150N base oil (the same oil will
be used in a number of experiments cited throughout this paper)
with no pour point depressant, an amorphous 22 SSI OCP viscos-
ity modifier, and an API CH-4 performance additive. As shown
in Table 2, it readily met the MRV requirement of 60,000 mPa·s
maximum at −30◦ C for a 10 W oil. Adding PPD did not affect the
MRV viscosity or the Scanning Brookfield performance, although
it lowered the pour point by 6◦ C. The low-temperature properties
of this formulated oil were unaffected by PPD side-chain length at
the PPD concentrations evaluated herein. To confirm that the ad-
ditive package was responsible for this excellent low-temperature
performance, the 150 N base oil was treated with the same set of
PPDs. The results are shown graphically in Fig. 1. Without PPD,
the base oil had a pour point of −18◦ C, and PPDs 1-3 were more
TABLE 2—LOW TEMPERATURE RHEOLOGICAL PROPERTIES OF AN API
CH-4, SAE 10W-40 HEAVY-DUTY DIESEL LUBRICANT FORMULATED
WITH A VARIETY OF PAMA PPDS
Scanning
MRV ASTM D Brookfield
Viscosity 5985 Pour Temperature
PPD mPa·s, −30◦ C Point, ◦ C @ 300Pa· s, ◦ C
None 31,300 −33 −29.3
1 30,600 −39 −29.5
2 30,200 −39 −29.4
3 30,800 −39 −29.8
4 30,000 −39 −29.9
5 30,600 −39 −29.6
6 31,400 −39 −29.6
7 31,900 −39 −29.5
Fig. 1—Pour point measurements of a fully formulated API CH-4, SAE
10W-40 heavy-duty diesel lubricant compared with its 150N min-
eral oil. PPD numerical code is proportional to average polymer
side-chain length.
effective than the others in lowering the pour point to as low as
−39◦ C. Addition of the additive package and viscosity modifier
reduced the pour point in the absence of PPD by 15◦ C, whereas
these additives were less influential in the presence of PPD.
The API CH-4 additive used in this example consisted
of two calcium over-based sulfonate detergents, two calcium
over-based phenate detergents, two polyisobutylene-based ash-
less dispersants, a secondary zinc dithiophosphate anti-wear
agent/anti-oxidant, and an ashless anti-oxidant. To determine
which components are the most responsible for the pour point
depressing properties of this additive package, a statistically de-
signed matrix of experiments was carried out. The design consisted
of a 1/2 26 fractional factorial with four replicated center points. The
additives included in this study are described in Table 3. The anti-
oxidant concentrations were held constant. To eliminate possible
VM effects, the oils were blended without VM.
Thirty-six additive packages were prepared, using the 150 N
API Group I oil of this study in the packages to compensate for
lower additive levels required by the experimental design. Each
additive package was blended at equal concentration in the 150 N
oil, and ASTM D 5985 pour points were measured. The rotational
pour point method also provides a “no-flow temperature,” re-
ported to the nearest 0.1◦ C, which is also called the “freeze point.”
Statistical regression analysis of the data identified those factors
that had a significant (95% confidence level) effect on pour point
and/or freeze point. The results are summarized in Table 4. Both
linear over-based sulfonate detergents S1 and S2 significantly re-
duce pour point and freeze point, with the lower TBN detergent
TABLE 3—API CH-4 ADDITIVE PACKAGE COMPONENT VARIABLES IN-
CLUDED IN POUR POINT STATISTICAL EXPERIMENTAL DESIGN MATRIX
Additive Code Description
S1 Mid TBN linear calcium sulfonate detergent
S2 High TBN linear calcium sulfonate detergent
P1 Mid TBN branched calcium phenate detergent
P2 High TBN branched calcium phenate detergent
D1 High TBN ashless polyisobutylene dispersant
D2 Low TBN ashless polyisobutylene dispersant
 Lubricant Additive Effects on Engine Pumpability
TABLE 4—PREDICTIVE EQUATIONS DESCRIBING THE EFFECTS OF ADDITIVE COMPONENT CONCENTRATION ON POUR POINT AND FREEZE POINT. NSS = NOT
STATISTICALLY SIGNIfiCANT. TABLE ENTRIES REPRESENT NUMERICAL CONSTANTS TO BE MULTIPLIED BY THEIR RESPECTIVE ADDITIVE CONCENTRATIONS (AT
FINAL BLEND LEVEL). THE SUMMATION OF THESE TERMS PLUS THE CONSTANT IS THE PREDICTOR OF THE MEASUREMENT. FOR EXAMPLE, FREEZE POINT =
−21.06 − [1.93 ∗ S1] − [1.29 ∗ S2] + [0.079 ∗ S1 ∗ S2] + [0.032 ∗ D1]
Measurement Constant S1 S2
Pour point −18.6 −2.14 −1.30
Freeze point −21.06 −1.93 −1.29
S1 having a larger effect than S2. This effect is slightly mitigated
by a positive interaction term S1∗S2. Neither over-based phenate
detergent was influential. The ashless dispersant D1 slightly raises
the pour point, whereas D2 has no significant effect.
These results reinforce the conclusions of Li, et al. (1), namely:
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(a) linear sulfonate detergents can lower pour point in some base
oils, (b) the effect is observed for different degrees of over-basing,
and (c) linear alkyl substituents are necessary for pour point de-
pression. The current study shows that these conclusions apply
to branched over-based phenate detergents as well, although no
experiments on linear phenates were performed. Polyisobutylene-
based dispersants also have a highly branched microstructure and
do not significantly reduce pour point.
It is well documented (Rudnick (6); Xiong (7)) that the effec-
tiveness of polymeric pour point depressants falls off drastically
below a critical molecular weight. In other words, it is important to
establish an ordered string of linear alkyl side chains of minimum
string length (degree of polymerization). Extending this under-
standing to the case of over-based linear sulfonate detergents, one
might expect that non-over-based or so-called neutral linear sul-
fonate detergents have very little pour point depressing activity.
To test this hypothesis, both branched and linear neutral alkyl
sulfonate detergents were synthesized. In addition, branched ver-
sions of S1 and S2 over-based detergents were made. The neutral
sulfonates were blended into the API CH-4 additive package to
deliver the same level of alkyl benzene sulfonate as provided by
both S1 and S2. The packages were again blended in the 150N
mineral oil, and the pour point results are summarized in Fig. 2.
The linear neutral sulfonate detergent lowers the baseline pour
Fig. 2—Sulfonate detergent chemistry effects on pour point of a fully
formulated API CH-4, SAE 10W-40 heavy-duty diesel lubricant.
Sulfonate detergent mix X-Y identifies the detergent types where
X = S1 type and Y = S2 type. L = Linear alkyl. B = Branched
alkyl. Neutral = Not over-based.
71
S1∗S2 S1∗P1 P1 P2 D1 D2
0.076 0.10 −0.20 nss 0.030 nss
0.079 nss nss nss 0.032 nss
point by only 3◦ C, which is within the experimental error of the
test method. The branched neutral and over-based sulfonate de-
tergents have no pour point reducing properties.
The mixtures of branched and linear over-based detergents in
Fig. 2 reinforce the conclusion from the statistical experimental
design that S1 provides more pour point depression than S2. The
pour point for a mixture of linear S1 and branched S2 is 9◦ C lower
than a mixture of branched S1 and linear S2.
Implications to Used Engine Oils
Under circumstances illustrated above, it is possible to for-
mulate an engine oil with low-temperature rheology largely con-
trolled by the over-based linear alkyl sulfonate detergents in the
additive package. There are two scenarios that have the poten-
tial to compromise low-temperature oil pumpability in use. The
reader is again referred to Fig. 1. In the first scenario, a pour point
depressant is not used in the formulation. Alternately, a pour point
depressant is present, but it is not matched properly for the base
oil and viscosity modifier. In either case, the new oil MRV vis-
cosity is well within specification. For example, PPD6 in Fig. 1 is
very effective in the formulated oil but is clearly not well suited
to the base oil. During engine operation, the over-based sulfonate
detergents are slowly neutralized by acids of combustion. If either
there is no PPD or the wrong PPD present, the low-temperature
pumpability protection of the oil could be in serious jeopardy.
A simple experiment was conducted to simulate this effect. An
SAE 40 CH-4 engine oil was formulated with an additive package
containing S1 as the sole detergent, and neither a pour point de-
pressant nor a viscosity modifier were present. The pour point was
−39◦ C. A second oil was formulated with a neutral linear sulfonate
detergent to deliver the same level of alkyl benzene sulfonate; its
pour point was −20◦ C. The first oil was neutralized in the labo-
ratory with a stoichiometric quantity of 1N aqueous hydrochloric
acid based upon ASTM D 2986 Total Base Number of the first oil,
purged with nitrogen to remove water and filtered through paper.
Its pour point rose from −39◦ C to −20◦ C. The first oil also was
neutralized with an organic acid, a polypropylene alkylated ben-
zene sulfonic acid, and passed through filter paper. The pour point
was −19◦ C. These simple experiments show that the low temper-
ature benefits of linear sulfonate detergents are only temporary,
and formulating with a proper PPD can provide the level of low
temperature pumpability protection needed for the long haul.
Pour Point Depressant Interactions with Base Oils
and Viscosity Modifiers
A number of studies were cited in the Introduction that
highlighted MRV problems (yield stress) in aged oils containing
 72 M. J. COVITCH

LEOCP is totally amorphous, it should not show any specific in-

teractions with the base oil and PPD at low temperatures. When
PPD2 through PPD5 are added, the MRV viscosity dramatically
falls into the SAE J300 passing regime. This is fairly typical behav-
ior for a non-interacting VM and an additive package that shows
no pour point depressant activity in these particular base oils. The
behavior of the HEOCP oil, however, is far from typical. With no
added PPD, this oil exhibits low MRV viscosity with no yield stress,
suggesting that the VM is acting as a pour point depressant. In the
presence of PPDs, as PPD code increases, the MRV viscosity dras-
tically rises, developing yield stress. As the PPD side-chain length
increases further, the MRV viscosity comes back under control.
This is a clear demonstration that the HEOCP can show antago-
Fig. 3—Comparison of HEOCP and LEOCP viscosity modifiers in an SAE
nistic behavior in the presence of certain pour point depressants
10W-30 ILSAC GF-4 engine oil. Increasing PPD code number indi-
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cates longer alkyl side-chains. Measured MRV viscosities greater that would otherwise function well with the base oils and the per-
than 100,000 mPa·s were assigned a value of 100,000 in this formance additive. Since the MRV viscosity curves converge at
figure.
PPD5 in Fig. 3, this antagonism seems to have been eliminated
with longer side-chain PPDs.
The following possible explanation for this behavior is offered,
HEOCP viscosity modifiers. Other non-crystalline polymers did
albeit a hypothesis at this time. The polyethylene sequence length
not develop even close to the same level of yield stress during
distribution along the HEOCP backbone is proposed to be quite
aging. It is logical to assume that the longer ethylene sequences
broad. When PPD is not present, the HEOCP molecule tends to
in the HEOCP polymer tend to crystallize with wax in the base
self crystallize, intra-molecularly, and shrink in size, as the temper-
oil. It is also reasonable to suggest that these internal oligomers of
ature drops to about 10◦ C (Kapuscinski, et al. (8)). As the tem-
ethylene can co-crystallize with the linear alkyl side-chains of con-
perature continues to decrease, progressively shorter polyethylene
ventional pour point depressants and over-based detergents. Thus,
sequences become eligible for crystallization, with like segments
there could be complex multi-body crystalline interactions taking
or with other species with which they can crystallize (such as waxy
place at low temperatures in commercial engine oils containing
paraffins, detergents or PPDs). This is described pictorially in Fig.
HEOCP. Any changes in the base oil (oxidation, volatility), the
4. Pour point depressants crystallize over a range of temperatures,
VM (shear degradation to lower molecular weight species), and
depending upon their alkyl side-chain length distribution. The av-
the detergent (neutralization by acids) that occur during engine
erage crystallization temperature is proportional to the average
aging can upset the delicate balance and thereby impact used oil
side-chain length. If the PPD co-crystallizes with the HEOCP be-
MRV performance.
fore wax begins to form (shown as PPD8 in Figure 4), the HEOCP
Applying the homologous series of PAMA PPDs to this prob-
molecule will be interpenetrated with PAMA and at least partially
lem is useful to illustrate the complexity of the interplay among
shielded from crystallization with other species at lower tempera-
base oil, VM, and PPD at low temperatures. A commercial SAE
tures. If, however, the PPD (PPD1 for example) crystallizes in the
10W-30 passenger car engine oil formulation containing a semi-
same temperature regime as the HEOCP and the wax, multiple in-
crystalline 50 SSI (9) HEOCP VM was selected to compare its PPD
teraction sites between polymer chains and wax crystals can form
fingerprint against that of a similar lubricant formulated with an
simultaneously. This can lead to the formation of fragile networks
amorphous 50 SSI low ethylene olefin copolymer (LEOCP) VM.
The base oil was a mixture of API Group I and II stocks, and
an ILSAC GF-4 additive package was added at its recommended
concentration. The MRV viscosity is plotted against PPD code in
Fig. 3. In the absence of PPD, the LEOCP oil has high yield stress,
which indicates that the additive package does not function as a
pour point depressant in this particular base oil system. Since the

Fig. 5—Incorporation of a longer alkyl side-chain PAMA PPD (PPD8) in

an SAE 10W-30 ILSAC GF-4 engine oil containing HEOCP. Mea-
Fig. 4—Descriptive representation of component crystallization at sub- sured MRV viscosities greater than 100,000 mPa·s were assigned
ambient temperatures. a value of 100,000 in this figure.
 Lubricant Additive Effects on Engine Pumpability
that can trigger the onset of yield stress in the fluid. According
to this model, a critical PPD side-chain length should exist above
which networks cannot form. In the case described in Fig. 3, the
critical PPD is PPD5.
Perhaps, then, an effective approach for formulating with
HEOCP viscosity modifiers would be to require the presence of a
small amount of a longer side-chain PAMA PPD. In Fig. 5, PPD8
was added to the SAE 10W-30 oil containing HEOCP, and the
seven PPDs were added in addition to PPD8. The concentration
of PPD8 was fixed at 40% of the normal PPD treatment level.
This formulation approach eliminated the polymer/PPD antago-
nism observed in the absence of PPD8. This experiment surely
does not prove that the model is correct, but the results are at
least consistent with its principles.
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CONCLUSIONS
1. Lubricant additives that contain short polyethylene-like chains
can co-crystallize with wax molecules found in some base oils.
This is the same mechanism whereby conventional pour point
depressants lower MRV viscosity and pour point.
2. Over-based linear alkyl sulfonate detergents can function as
very effective pour point depressants in some engine oil for-
mulations, but neutral linear alkyl sulfonate detergents are far
less effective. Therefore, neutralization of detergent TBN dur-
ing engine operation can destroy the pour point depressing
capability of the fresh oil over-based detergents.
3. In certain mineral oils, a 50 SSI high-ethylene OCP viscosity
modifier also can depress pour point and MRV viscosity in
the absence of PPDs. Antagonistic MRV behavior with certain
pour point depressants is seen for a HEOCP VM but not for
an amorphous OCP viscosity modifier of equal shear stability
index. This adds another layer of complexity to the problem of
predicting how to control used oil MRV performance.
4. A model to explain HEOCP/PPD/base oil wax interactions
provides some direction in learning how to choose effective
73
PPDs for use with semi-crystalline polymeric viscosity modi-
fiers such as HEOCP.
RECOMMENDATION
Engine oil developers are encouraged to routinely test new oil
formulations without PPD in the Mini Rotary Viscometer. If the
MRV viscosity is low, extra care should be taken to select the right
pour point depressant for the job.
ACKNOWLEDGEMENT
The author wishes to recognize the capable assistance of Susan
V. Cowling in the statistical design and data analysis of lubricant
additive effects on pour point.
REFERENCES
(1) S. Li, Blackmon, J., Demange, A. and Jao, T. C. (2004), “Linear Sulfonate
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(2) Bansal, J. G., Chu, C. and Outten, E. F. (2004), “In-Service Low Temperature
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