U.S. patent application number 16/151454 was filed with the patent office on 2019-05-02 for lubricating oil compositions with engine wear protection.
The applicant listed for this patent is ExxonMobil Research and Engineering Company. Invention is credited to Smruti A. DANCE, Candice I. PELLIGRA, Jordan C. SMITH.
Application Number | 20190127658 16/151454 |
Document ID | / |
Family ID | 63966117 |
Filed Date | 2019-05-02 |
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United States Patent
Application |
20190127658 |
Kind Code |
A1 |
PELLIGRA; Candice I. ; et
al. |
May 2, 2019 |
LUBRICATING OIL COMPOSITIONS WITH ENGINE WEAR PROTECTION
Abstract
A method for improving wear control of a steel surface
lubricated with a lubricating oil through the generation of
fast-forming tribofilms. The method includes: (i) using as the
lubricating oil a formulated oil, the formulated oil having a
composition comprising at least one lubricating oil base stock as a
major component, and at least one detergent, as a minor component;
and (ii) forming a tribofilm on the steel surface. The time for the
tribofilm to reach 95% of its saturation coverage (t.sub.95,sat) on
the steel surface is less than about 50 minutes, as determined by a
high frequency reciprocating rig (HFRR) in accordance with a
modified version of ASTM D6079. A lubricating oil including an
ester base stock, an alkylated naphthalene base stock, or mixtures
thereof, as a major component; and at least one detergent including
an alkaline earth metal salicylate, an alkaline earth metal
sulfonate, or mixtures thereof, as a minor component.
Inventors: |
PELLIGRA; Candice I.;
(Rutledge, PA) ; DANCE; Smruti A.; (Robbinsville,
NJ) ; SMITH; Jordan C.; (Marlton, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ExxonMobil Research and Engineering Company |
Annandale |
NJ |
US |
|
|
Family ID: |
63966117 |
Appl. No.: |
16/151454 |
Filed: |
October 4, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62578696 |
Oct 30, 2017 |
|
|
|
62578723 |
Oct 30, 2017 |
|
|
|
62578711 |
Oct 30, 2017 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 159/24 20130101;
C10M 159/20 20130101; C10N 2040/255 20200501; C10M 107/02 20130101;
C10N 2030/52 20200501; C10M 2203/1025 20130101; C10M 133/16
20130101; C10M 2203/1006 20130101; C10M 2207/144 20130101; C10N
2050/025 20200501; C10M 2207/262 20130101; C10M 2207/2805 20130101;
C10M 169/04 20130101; C10M 2207/142 20130101; C10M 2215/28
20130101; C10N 2030/10 20130101; C10N 2030/54 20200501; C10M 133/56
20130101; C10M 129/68 20130101; C10N 2030/06 20130101; C10M 129/54
20130101; C10M 141/08 20130101; C10M 2203/1065 20130101; C10N
2020/02 20130101; C10M 129/34 20130101; C10N 2010/02 20130101; C10M
2219/046 20130101; C10N 2010/04 20130101; C10M 155/04 20130101;
C10M 2203/065 20130101; C10M 135/10 20130101; C10N 2030/45
20200501; C10N 2040/25 20130101; C10N 2060/14 20130101; C10M 101/02
20130101; C10M 105/06 20130101; C10N 2030/04 20130101; C10N 2030/44
20200501; C10M 105/32 20130101; C10M 2219/044 20130101; C10N
2020/04 20130101; C10M 2203/1025 20130101; C10N 2020/02 20130101;
C10M 2207/262 20130101; C10N 2010/04 20130101; C10M 2219/046
20130101; C10N 2010/04 20130101; C10M 2215/28 20130101; C10N
2060/14 20130101; C10M 2207/144 20130101; C10N 2010/04 20130101;
C10M 2219/044 20130101; C10N 2010/04 20130101; C10M 2207/262
20130101; C10N 2010/04 20130101; C10M 2219/046 20130101; C10N
2010/04 20130101; C10M 2207/144 20130101; C10N 2010/04 20130101;
C10M 2219/044 20130101; C10N 2010/04 20130101; C10M 2203/1025
20130101; C10N 2020/02 20130101; C10M 2215/28 20130101; C10N
2060/14 20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04; C10M 105/32 20060101 C10M105/32; C10M 105/06 20060101
C10M105/06; C10M 129/54 20060101 C10M129/54; C10M 135/10 20060101
C10M135/10; C10M 141/08 20060101 C10M141/08 |
Claims
1. A method for improving wear control of a steel surface
lubricated with a lubricating oil, said method comprising: (i)
using as the lubricating oil a formulated oil, said formulated oil
having a composition comprising at least one lubricating oil base
stock as a major component; and at least one detergent, as a minor
component; and (ii) forming a tribofilm on the steel surface;
wherein the time for the tribofilm to reach 95% of its saturation
coverage (t.sub.95,sat) on the steel surface is less than about 50
minutes, as determined by a high frequency reciprocating rig (HFRR)
in accordance with a modified version of ASTM D6079; and wherein,
in tribofilm formation measurements of the lubricating oil by a
mini-traction machine (MTM) in Stribeck mode, the number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s is achieved, which correlates to onset of the tribofilm
formation on the steel surface, is about 2 or less.
2. The method of claim 1 wherein elongation of timing chain due to
wear of chain link pins is less than about 0.07%, as determined by
Ford Chain Wear (FCW) test conducted in accordance with ILSAC GF-6
specification.
3. The method of claim 1 wherein the lubrication regime at the
steel surface comprises boundary- and mixed-layer lubrication
contacts.
4. The method of claim 1 wherein the steel surface comprises the
surface of a timing chain.
5. The method of claim 1 for improving soot-induced wear control of
a steel surface.
6. The method of claim 1 wherein the at least one detergent
comprises an alkaline earth metal salicylate, an alkaline earth
metal sulfonate, or mixtures thereof.
7. The method of claim 1 wherein the at least one detergent
comprises an alkaline earth metal salicylate, a mixture of alkaline
earth metal salicylates, an alkaline earth metal sulfonate, a
mixture of alkaline earth metal sulfonates, or a mixture of
alkaline earth metal salicylates and alkaline earth metal
sulfonates, all having the same or different total base number
(TBN).
8. The method of claim 1 wherein, for a mixture of alkaline earth
metal salicylates and alkaline earth metal sulfonates, all having
the same or different total base number (TBN), the weight ratio of
alkaline earth metal salicylates to alkaline earth metal sulfonates
is from about 1:100 to about 100:1.
9. The method of claim 1 wherein, for a mixture of alkaline earth
metal salicylates having the same or different total base number
(TBN), the weight ratio of a first alkaline earth metal salicylate
to a second alkaline earth metal salicylate is from about 1:100 to
about 100:1; or wherein, for a mixture of alkaline earth metal
sulfonates having the same or different total base number (TBN),
the weight ratio of a first alkaline earth metal sulfonate to a
second alkaline earth metal sulfonate is from about 1:100 to about
100:1.
10. The method of claim 1 wherein the total amount of soap
delivered by the at least one detergent is about 0.4 weight percent
to about 0.7 weight percent of the lubricating oil, or about 0.8
weight percent to about 1.3 weight percent of the lubricating
oil.
11. The method of claim 1 wherein the at least one lubricating oil
base stock comprises an ester base stock, an alkylated naphthalene
base stock, or mixtures thereof.
12. The method of claim 1 wherein the lubricating oil base stock
further comprises a Group I, Group II, Group III, Group IV or Group
V base oil.
13. The method of claim 1 wherein the at least one detergent is
present in an amount of from about 0.001 weight percent to about 20
weight percent, based on the total weight of the formulated
oil.
14. The method of claim 1 wherein the lubricating oil base stock is
present in an amount of from about 6 weight percent to about 95
weight percent, based on the total weight of the formulated
oil.
15. The method of claim 1 wherein the formulated oil further
comprises one or more of an antiwear additive, viscosity modifiers,
antioxidant, other detergent, dispersant, pour point depressant,
corrosion inhibitor, metal deactivator, seal compatibility
additive, anti-foam agent, inhibitor, and anti-rust additive.
16. The method of claim 1 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO).
17. A lubricating oil composition comprising at least one
lubricating oil base stock as a major component; and at least one
detergent, as a minor component; wherein the at least one
lubricating oil base stock and the at least one detergent are
present in an amount sufficient for the lubricating oil to form a
tribofilm on a steel surface; wherein the time for the tribofilm to
reach 95% of its saturation coverage (t.sub.95,sat) on the steel
surface is less than about 50 minutes, as determined by a high
frequency reciprocating rig (HFRR) in accordance with a modified
version of ASTM D6079; and wherein, in tribofilm formation
measurements of the lubricating oil by a mini-traction machine
(MTM) in Stribeck mode, the number of Stribeck passes (S.sub.n)
until an increase in traction coefficient at 10 mm/s is achieved,
which correlates to onset of the tribofilm formation on the steel
surface, is about 2 or less.
18. A method for improving wear control of a steel surface
lubricated with a lubricating oil, said method comprising: (i)
using as the lubricating oil a formulated oil, said formulated oil
having a composition comprising at least one lubricating oil base
stock as a major component; and at least one detergent, as a minor
component; and (ii) forming a tribofilm on the steel surface;
wherein the at least one lubricating oil base stock comprises an
alkylated naphthalene base stock; wherein the at least one
detergent comprises an alkaline earth metal salicylate, an alkaline
earth metal sulfonate, or mixtures thereof, wherein the total
amount of soap delivered by the at least one detergent is about 0.4
weight percent to about 0.7 weight percent of the lubricating oil;
wherein the total boron concentration is about 100 to about 260
parts per million in the lubricating oil; wherein the time for the
tribofilm to reach 95% of its saturation coverage (t.sub.95,sat) on
the steel surface is less than about 50 minutes, as determined by a
high frequency reciprocating rig (HFRR) in accordance with a
modified version of ASTM D6079; and wherein, in tribofilm formation
measurements of the lubricating oil by a mini-traction machine
(MTM) in Stribeck mode, the number of Stribeck passes (S.sub.n)
until an increase in traction coefficient at 10 mm/s is achieved,
which correlates to onset of the tribofilm formation on the steel
surface, is about 2 or less.
19. The method of claim 18 wherein elongation of timing chain due
to wear of chain link pins is less than about 0.07%, as determined
by Ford Chain Wear (FCW) test conducted in accordance with ILSAC
GF-6 specification.
20. The method of claim 18 wherein the lubrication regime at the
steel surface comprises boundary- and mixed-layer lubrication
contacts.
21. The method of claim 18 wherein the steel surface comprises the
surface of a timing chain.
22. The method of claim 18 for improving soot-induced wear control
of a steel surface.
23. The method of claim 18 wherein the at least one detergent
comprises an alkaline earth metal salicylate, a mixture of alkaline
earth metal salicylates, an alkaline earth metal sulfonate, a
mixture of alkaline earth metal sulfonates, or a mixture of
alkaline earth metal salicylates and alkaline earth metal
sulfonates, all having the same or different total base number
(TBN).
24. The method of claim 18 wherein, for a mixture of alkaline earth
metal salicylates and alkaline earth metal sulfonates, all having
the same or different total base number (TBN), the weight ratio of
alkaline earth metal salicylates to alkaline earth metal sulfonates
is from about 1:100 to about 100:1.
25. The method of claim 18 wherein, for a mixture of alkaline earth
metal salicylates having the same or different total base number
(TBN), the weight ratio of a first alkaline earth metal salicylate
to a second alkaline earth metal salicylate is from about 1:100 to
about 100:1; or wherein, for a mixture of alkaline earth metal
sulfonates having the same or different total base number (TBN),
the weight ratio of a first alkaline earth metal sulfonate to a
second alkaline earth metal sulfonate is from about 1:100 to about
100:1.
26. The method of claim 18 wherein the total amount of soap
delivered by the at least one detergent is about 0.45 weight
percent to about 0.65 weight percent of the lubricating oil.
27. The method of claim 18 wherein the lubricating oil base stock
further comprises a Group I, Group II, Group III, Group IV or Group
V base oil.
28. The method of claim 18 wherein the at least one detergent is
present in an amount of from about 0.001 weight percent to about 20
weight percent, based on the total weight of the formulated
oil.
29. The method of claim 18 wherein the lubricating oil base stock
is present in an amount of from about 6 weight percent to about 95
weight percent, based on the total weight of the formulated
oil.
30. The method of claim 18 wherein the formulated oil further
comprises one or more of an antiwear additive, viscosity modifiers,
antioxidant, other detergent, dispersant, pour point depressant,
corrosion inhibitor, metal deactivator, seal compatibility
additive, anti-foam agent, inhibitor, and anti-rust additive.
31. The method of claim 18 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO).
32. A lubricating oil composition comprising at least one
lubricating oil base stock as a major component; and at least one
detergent, as a minor component; wherein the at least one
lubricating oil base stock comprises an alkylated naphthalene base
stock, an ester base stock, or mixtures thereof; wherein the at
least one detergent comprises an alkaline earth metal salicylate,
an alkaline earth metal sulfonate, or mixtures thereof; wherein the
total amount of soap delivered by the at least one detergent is
about 0.4 weight percent to about 0.7 weight percent of the
lubricating oil; wherein the total boron concentration is about 100
to about 260 parts per million in the lubricating oil; wherein the
at least one lubricating oil base stock and the at least one
detergent are present in an amount sufficient for the lubricating
oil to form a tribofilm on a steel surface; wherein the time for
the tribofilm to reach 95% of its saturation coverage
(t.sub.95,sat) on the steel surface is less than about 50 minutes,
as determined by a high frequency reciprocating rig (HFRR) in
accordance with a modified version of ASTM D6079; and wherein, in
tribofilm formation measurements of the lubricating oil by a
mini-traction machine (MTM) in Stribeck mode, the number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s is achieved, which correlates to onset of the tribofilm
formation on the steel surface, is about 2 or less.
33. A method for improving wear control of a steel surface
lubricated with a lubricating oil, said method comprising: (i)
using as the lubricating oil a formulated oil, said formulated oil
having a composition comprising at least one lubricating oil base
stock as a major component; and at least one detergent, as a minor
component; and (ii) forming a tribofilm on the steel surface;
wherein the at least one lubricating oil base stock comprises an
alkylated naphthalene base stock; wherein the at least one
detergent comprises an alkaline earth metal salicylate, an alkaline
earth metal sulfonate, or mixtures thereof; wherein the total
amount of soap delivered by the at least one detergent is about 0.8
weight percent to about 1.3 weight percent of the lubricating oil,
provided that the alkaline earth metal sulfonate is present in an
amount of about 50 weight percent to about 100 weight percent of
the total detergent; wherein the total boron concentration is about
50 to about 150 parts per million in the lubricating oil; wherein
the time for the tribofilm to reach 95% of its saturation coverage
(t.sub.95,sat) on the steel surface is less than about 50 minutes,
as determined by a high frequency reciprocating rig (HFRR) in
accordance with a modified version of ASTM D6079; and wherein, in
tribofilm formation measurements of the lubricating oil by a
mini-traction machine (MTM) in Stribeck mode, the number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s is achieved, which correlates to onset of the tribofilm
formation on the steel surface, is about 2 or less.
34. The method of claim 33 wherein elongation of timing chain due
to wear of chain link pins is less than about 0.07%, as determined
by Ford Chain Wear (FCW) test conducted in accordance with ILSAC
GF-6 specification.
35. The method of claim 33 wherein the lubrication regime at the
steel surface comprises boundary- and mixed-layer lubrication
contacts.
36. The method of claim 33 wherein the steel surface comprises the
surface of a timing chain.
37. The method of claim 33 for improving soot-induced wear control
of a steel surface.
38. The method of claim 33 wherein the at least one detergent
comprises an alkaline earth metal salicylate, a mixture of alkaline
earth metal salicylates, an alkaline earth metal sulfonate, a
mixture of alkaline earth metal sulfonates, or a mixture of
alkaline earth metal salicylates and alkaline earth metal
sulfonates, all having the same or different total base number
(TBN).
39. The method of claim 33 wherein, for a mixture of alkaline earth
metal salicylates and alkaline earth metal sulfonates, all having
the same or different total base number (TBN), the weight ratio of
alkaline earth metal salicylates to alkaline earth metal sulfonates
is from about 1:100 to about 100:1.
40. The method of claim 33 wherein, for a mixture of alkaline earth
metal salicylates having the same or different total base number
(TBN), the weight ratio of a first alkaline earth metal salicylate
to a second alkaline earth metal salicylate is from about 1:100 to
about 100:1; or wherein, for a mixture of alkaline earth metal
sulfonates having the same or different total base number (TBN),
the weight ratio of a first alkaline earth metal sulfonate to a
second alkaline earth metal sulfonate is from about 1:100 to about
100:1.
41. The method of claim 33 wherein the total amount of soap
delivered by the at least one detergent is about 0.85 weight
percent to about 1.25 weight percent of the lubricating oil.
42. The method of claim 33 wherein the lubricating oil base stock
further comprises a Group I, Group II, Group III, Group IV or Group
V base oil.
43. The method of claim 33 wherein the at least one detergent is
present in an amount of from about 0.001 weight percent to about 20
weight percent, based on the total weight of the formulated
oil.
44. The method of claim 33 wherein the lubricating oil base stock
is present in an amount of from about 6 weight percent to about 95
weight percent, based on the total weight of the formulated
oil.
45. The method of claim 33 wherein the formulated oil further
comprises one or more of an antiwear additive, viscosity modifiers,
antioxidant, other detergent, dispersant, pour point depressant,
corrosion inhibitor, metal deactivator, seal compatibility
additive, anti-foam agent, inhibitor, and anti-rust additive.
46. The method of claim 33 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO).
47. A lubricating oil composition comprising at least one
lubricating oil base stock as a major component; and at least one
detergent, as a minor component; wherein the at least one
lubricating oil base stock comprises an alkylated naphthalene base
stock; wherein the at least one detergent comprises an alkaline
earth metal salicylate, an alkaline earth metal sulfonate, or
mixtures thereof; wherein the total amount of soap delivered by the
at least one detergent is about 0.8 weight percent to about 1.3
weight percent of the lubricating oil, provided that the alkaline
earth metal sulfonate is present in an amount of about 50 weight
percent to about 100 weight percent of the total detergent; wherein
the total boron concentration is about 50 to about 150 parts per
million in the lubricating oil; wherein the at least one
lubricating oil base stock and the at least one detergent are
present in an amount sufficient for the lubricating oil to form a
tribofilm on a steel surface; wherein the time for the tribofilm to
reach 95% of its saturation coverage (t.sub.95,sat) on the steel
surface is less than about 50 minutes, as determined by a high
frequency reciprocating rig (HFRR) in accordance with a modified
version of ASTM D6079; and wherein, in tribofilm formation
measurements of the lubricating oil by a mini-traction machine
(MTM) in Stribeck mode, the number of Stribeck passes (S.sub.n)
until an increase in traction coefficient at 10 mm/s is achieved,
which correlates to onset of the tribofilm formation on the steel
surface, is about 2 or less.
48. A method for improving wear control of a steel surface
lubricated with a lubricating oil, said method comprising: (i)
using as the lubricating oil a formulated oil, said formulated oil
having a composition comprising at least one lubricating oil base
stock as a major component; and at least one detergent, as a minor
component; and (ii) forming a tribofilm on the steel surface;
wherein the at least one lubricating oil base stock comprises an
ester base stock, an alkylated naphthalene base stock, or mixtures
thereof, wherein the at least one detergent comprises an alkaline
earth metal sulfonate; wherein the total amount of soap delivered
by the at least one detergent is about 0.1 weight percent to about
1.0 weight percent of the lubricating oil; wherein the total boron
concentration is about 100 to about 260 parts per million in the
lubricating oil; wherein the time for the tribofilm to reach 95% of
its saturation coverage (t.sub.95,sat) on the steel surface is less
than about 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079; and wherein, in tribofilm formation measurements of the
lubricating oil by a mini-traction machine (MTM) in Stribeck mode,
the number of Stribeck passes (S.sub.n) until an increase in
traction coefficient at 10 mm/s is achieved, which correlates to
onset of the tribofilm formation on the steel surface, is about 2
or less.
49. The method of claim 48 wherein elongation of timing chain due
to wear of chain link pins is less than about 0.07%, as determined
by Ford Chain Wear (FCW) test conducted in accordance with ILSAC
GF-6 specification.
50. The method of claim 48 wherein the lubrication regime at the
steel surface comprises boundary- and mixed-layer lubrication
contacts.
51. The method of claim 48 wherein the steel surface comprises the
surface of a timing chain.
52. The method of claim 48 for improving soot-induced wear control
of a steel surface.
53. The method of claim 48 wherein the total amount of soap
delivered by the at least one detergent is about 0.15 weight
percent to about 0.95 weight percent of the lubricating oil.
54. The method of claim 48 wherein the lubricating oil base stock
further comprises a Group I, Group II, Group III, Group IV or Group
V base oil.
55. The method of claim 48 wherein the at least one detergent is
present in an amount of from about 0.001 weight percent to about 20
weight percent, based on the total weight of the formulated
oil.
56. The method of claim 48 wherein the lubricating oil base stock
is present in an amount of from about 6 weight percent to about 95
weight percent, based on the total weight of the formulated
oil.
57. The method of claim 48 wherein the formulated oil further
comprises one or more of an antiwear additive, viscosity modifiers,
antioxidant, other detergent, dispersant, pour point depressant,
corrosion inhibitor, metal deactivator, seal compatibility
additive, anti-foam agent, inhibitor, and anti-rust additive.
58. The method of claim 48 wherein the lubricating oil is a
passenger vehicle engine oil (PVEO).
59. A lubricating oil composition comprising at least one
lubricating oil base stock as a major component; and at least one
detergent, as a minor component; wherein the at least one
lubricating oil base stock comprises an ester base stock, an
alkylated naphthalene base stock, or mixtures thereof; wherein the
at least one detergent comprises an alkaline earth metal sulfonate;
wherein the total amount of soap delivered by the at least one
detergent is about 0.1 weight percent to about 1.0 weight percent
of the lubricating oil; wherein the total boron concentration is
about 100 to about 260 parts per million in the lubricating oil;
wherein the at least one lubricating oil base stock and the at
least one detergent are present in an amount sufficient for the
lubricating oil to form a tribofilm on a steel surface; wherein the
time for the tribofilm to reach 95% of its saturation coverage
(t.sub.95,sat) on the steel surface is less than about 50 minutes,
as determined by a high frequency reciprocating rig (HFRR) in
accordance with a modified version of ASTM D6079; and wherein, in
tribofilm formation measurements of the lubricating oil by a
mini-traction machine (MTM) in Stribeck mode, the number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s is achieved, which correlates to onset of the tribofilm
formation on the steel surface, is about 2 or less.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/578,696, and co-pending U.S. Provisional
Application Nos. 62/578,723 and 62/578,711, all filed on Oct. 30,
2017, the entire contents of which are incorporated herein by
reference.
FIELD
[0002] This disclosure relates to methods for improving wear
control of a steel surface lubricated with a lubricating oil,
through the generation of fast-forming tribofilms. The lubricating
oils are useful in internal combustion engines.
BACKGROUND
[0003] Current formulation strategies for low wear rely on
modifying the treat rate and identity of zinc
dialkyldithiophosphates (ZDDPs) or other antiwear additives to form
tribofilms. However, phosphorus volatility limits, restricting the
type and concentration of ZDDP components in a formulations,
significantly reduces the utility of ZDDP as a lever for modifying
tribofilm properties. Furthermore, the new GF-6 wear Ford Chain
Wear test is developed to protect against protection from
soot-induced wear. Common strategies for reducing wear in typical
valvetrain wear tests are thus not always effective.
[0004] During low-speed operation of light-duty passenger vehicle
engines, moving metal surfaces in the engine and valvetrain
assemblies are typically exposed to boundary- and mixed-layer
lubrication contacts. In these lubrication regimes, the lubricant
film thickness is insufficient to adequately separate metal
surfaces, and microscale asperities come into contact which causes
plastic deformation (wear) to occur. Thus, to protect against wear
under low-speed conditions, lubricants are formulated to contain
thermomechanically-activated species which deposit on or react with
steel surfaces. The formed layer, or tribofilm, acts as a barrier
to prevent metal-metal contact and potential wear. ZDDPs are
considered to be the main contributor to tribofilm formation.
Unfortunately, ZDDPs release volatile phosphorus as a decomposition
product which can poison catalytic converters, and thus strict
limits on phosphorus and phosphorus volatility have been
established for modern engine oil specifications.
[0005] Prior to ILSAC GF-6, North American industry wear tests were
solely concerned with low-temperature valvetrain wear, a
performance attribute again tested with the Sequence IVB valvetrain
wear test in the GF-6 category. Low-wear formulation strategies
thus rely on ZDDP and other antiwear additives such as ashless or
molybdenum-containing compounds which are most often associated
with boundary-/mixed-layer lubrication contacts found in the
valvetrain. However, the ILSAC GF-6 category introduces a new type
of wear test for the category, the Ford Chain Wear (FCW) test, in
which wear (elongation) of the timing chain is the rated
parameter.
[0006] The FCW test is performed in a gasoline direct-injection
(GDI) engine, a fuel delivery configuration which produces some
amount of soot content. The test was designed to qualify lubricants
in protection against soot-induced wear. This is a new performance
attribute in North America, and it has been shown that formulation
strategies which work in the more typical valvetrain wear test
Sequence IVB are not equally successful in the FCW test.
Identifying new strategies for how to ensure wear protection in the
FCW test is critical for successful GF-6 lubricant development.
[0007] A major challenge in engine oil formulation is achieving
wear protection in the FCW test for successful GF-6 lubricant
development.
SUMMARY
[0008] This disclosure relates to methods for improving wear
control of a steel surface lubricated with a lubricating oil,
through the generation of fast-forming tribofilms. The lubricating
oil formulation features of this disclosure permit the formation of
fast-forming tribofilms on steel surfaces under loading/temperature
conditions relevant to light-duty passenger vehicle operation.
These fast-forming tribofilms provide superior wear protection in
FCW testing. The lubricating oils are useful in internal combustion
engines.
[0009] This disclosure relates in part to methods for reducing
chain wear by formulating engine lubricants which exhibit
fast-forming tribofilms. The lubricant formulation strategies of
this disclosure enable fast formation of tribofilms on steel
surfaces in boundary/mixed layer lubrication contacts in order to
reduce wear. The methods of this disclosure are surprising, as the
formulation features corresponding to fast tribofilm generation and
consequent low wear in the FCW test do not adhere to expected
strategies for reducing soot-induced wear, which is a key feature
of the FCW test.
[0010] This disclosure relates in part to a method for improving
wear control of a steel surface lubricated with a lubricating oil.
The method comprises: (i) using as the lubricating oil a formulated
oil, the formulated oil having a composition comprising at least
one lubricating oil base stock as a major component; and at least
one detergent, as a minor component; and (ii) forming a tribofilm
on the steel surface. The time for the tribofilm to reach 95% of
its saturation coverage (t.sub.95,sat) on the steel surface is less
than about 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079. In tribofilm formation measurements of the lubricating
oil by a mini-traction machine (MTM) in Stribeck mode, the number
of Stribeck passes (S.sub.n) until an increase in traction
coefficient at 10 mm/s is achieved, which correlates to onset of
the tribofilm formation on the steel surface, is about 2 or
less.
[0011] This disclosure also relates in part to a lubricating oil
composition comprising at least one lubricating oil base stock as a
major component, and at least one detergent, as a minor component.
The at least one lubricating oil base stock and the at least one
detergent are present in an amount sufficient for the lubricating
oil to form a tribofilm on a steel surface. The time for the
tribofilm to reach 95% of its saturation coverage (t.sub.95,sat) on
the steel surface is less than about 50 minutes, as determined by a
high frequency reciprocating rig (HFRR) in accordance with a
modified version of ASTM D6079. In tribofilm formation measurements
of the lubricating oil by a mini-traction machine (MTM) in Stribeck
mode, the number of Stribeck passes (S.sub.n) until an increase in
traction coefficient at 10 mm/s is achieved, which correlates to
onset of the tribofilm formation on the steel surface, is about 2
or less.
[0012] This disclosure further relates in part to a method for
improving wear control of a steel surface lubricated with a
lubricating oil. The method comprises: (i) using as the lubricating
oil a formulated oil, the formulated oil having a composition
comprising at least one lubricating oil base stock as a major
component; and at least one detergent, as a minor component; and
(ii) forming a tribofilm on the steel surface. The at least one
lubricating oil base stock comprises an alkylated naphthalene base
stock. The at least one detergent comprises an alkaline earth metal
salicylate, an alkaline earth metal sulfonate, or mixtures thereof.
The total amount of soap delivered by the at least one detergent is
about 0.4 weight percent to about 0.7 weight percent of the
lubricating oil. The total boron concentration is about 100 to
about 260 parts per million in the lubricating oil. The time for
the tribofilm to reach 95% of its saturation coverage
(t.sub.95,sat) on the steel surface is less than about 50 minutes,
as determined by a high frequency reciprocating rig (HFRR) in
accordance with a modified version of ASTM D6079. In tribofilm
formation measurements of the lubricating oil by a mini-traction
machine (MTM) in Stribeck mode, the number of Stribeck passes
(S.sub.n) until an increase in traction coefficient at 10 mm/s is
achieved, which correlates to onset of the tribofilm formation on
the steel surface, is about 2 or less.
[0013] This disclosure yet further relates in part to a lubricating
oil composition comprising at least one lubricating oil base stock
as a major component, and at least one detergent, as a minor
component. The at least one lubricating oil base stock comprises an
alkylated naphthalene base stock, an ester base stock, or mixtures
thereof. The at least one detergent comprises an alkaline earth
metal salicylate, an alkaline earth metal sulfonate, or mixtures
thereof. The total amount of soap delivered by the at least one
detergent is about 0.4 weight percent to about 0.7 weight percent
of the lubricating oil. The total boron concentration is about 100
to about 260 parts per million in the lubricating oil. The at least
one lubricating oil base stock and the at least one detergent are
present in an amount sufficient for the lubricating oil to form a
tribofilm on a steel surface. The time for the tribofilm to reach
95% of its saturation coverage (t.sub.95,sat) on the steel surface
is less than about 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079. In tribofilm formation measurements of the lubricating
oil by a mini-traction machine (MTM) in Stribeck mode, the number
of Stribeck passes (S.sub.n) until an increase in traction
coefficient at 10 mm/s is achieved, which correlates to onset of
the tribofilm formation on the steel surface, is about 2 or
less.
[0014] This disclosure still further relates in part to a method
for improving wear control of a steel surface lubricated with a
lubricating oil. The method comprises: (i) using as the lubricating
oil a formulated oil, the formulated oil having a composition
comprising at least one lubricating oil base stock as a major
component; and at least one detergent, as a minor component; and
(ii) forming a tribofilm on the steel surface. The at least one
lubricating oil base stock comprises an alkylated naphthalene base
stock. The at least one detergent comprises an alkaline earth metal
salicylate, an alkaline earth metal sulfonate, or mixtures thereof.
the total amount of soap delivered by the at least one detergent is
about 0.8 weight percent to about 1.3 weight percent of the
lubricating oil, provided that the alkaline earth metal sulfonate
is present in an amount of about 50 weight percent to about 100
weight percent of the total detergent. The total boron
concentration is about 50 to about 150 parts per million in the
lubricating oil. The time for the tribofilm to reach 95% of its
saturation coverage (t.sub.95,sat) on the steel surface is less
than about 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079. In tribofilm formation measurements of the lubricating
oil by a mini-traction machine (MTM) in Stribeck mode, the number
of Stribeck passes (S.sub.n) until an increase in traction
coefficient at 10 mm/s is achieved, which correlates to onset of
the tribofilm formation on the steel surface, is about 2 or
less.
[0015] This disclosure also relates in part to a lubricating oil
composition comprising at least one lubricating oil base stock as a
major component, and at least one detergent, as a minor component.
The at least one lubricating oil base stock comprises an alkylated
naphthalene base stock. The at least one detergent comprises an
alkaline earth metal salicylate, an alkaline earth metal sulfonate,
or mixtures thereof. The total amount of soap delivered by the at
least one detergent is about 0.8 weight percent to about 1.3 weight
percent of the lubricating oil, provided that the alkaline earth
metal sulfonate is present in an amount of about 50 weight percent
to about 100 weight percent of the total detergent. The total boron
concentration is about 50 to about 150 parts per million in the
lubricating oil. The at least one lubricating oil base stock and
the at least one detergent are present in an amount sufficient for
the lubricating oil to form a tribofilm on a steel surface. The
time for the tribofilm to reach 95% of its saturation coverage
(t.sub.95,sat) on the steel surface is less than about 50 minutes,
as determined by a high frequency reciprocating rig (HFRR) in
accordance with a modified version of ASTM D6079. In tribofilm
formation measurements of the lubricating oil by a mini-traction
machine (MTM) in Stribeck mode, the number of Stribeck passes
(S.sub.n) until an increase in traction coefficient at 10 mm/s is
achieved, which correlates to onset of the tribofilm formation on
the steel surface, is about 2 or less.
[0016] This disclosure further relates in part to a method for
improving wear control of a steel surface lubricated with a
lubricating oil. The method comprises: (i) using as the lubricating
oil a formulated oil, the formulated oil having a composition
comprising at least one lubricating oil base stock as a major
component; and at least one detergent, as a minor component; and
(ii) forming a tribofilm on the steel surface. The at least one
lubricating oil base stock comprises an ester base stock, an
alkylated naphthalene base stock, or mixtures thereof. The at least
one detergent comprises an alkaline earth metal sulfonate. The
total amount of soap delivered by the at least one detergent is
about 0.1 weight percent to about 1.0 weight percent of the
lubricating oil. The total boron concentration is about 100 to
about 260 parts per million in the lubricating oil. The time for
the tribofilm to reach 95% of its saturation coverage
(t.sub.95,sat) on the steel surface is less than about 50 minutes,
as determined by a high frequency reciprocating rig (HFRR) in
accordance with a modified version of ASTM D6079. In tribofilm
formation measurements of the lubricating oil by a mini-traction
machine (MTM) in Stribeck mode, the number of Stribeck passes
(S.sub.n) until an increase in traction coefficient at 10 mm/s is
achieved, which correlates to onset of the tribofilm formation on
the steel surface, is about 2 or less.
[0017] This disclosure yet further relates in part to a lubricating
oil composition comprising at least one lubricating oil base stock
as a major component, and at least one detergent, as a minor
component. The at least one lubricating oil base stock comprises an
ester base stock, an alkylated naphthalene base stock, or mixtures
thereof. The at least one detergent comprises an alkaline earth
metal sulfonate. The total amount of soap delivered by the at least
one detergent is about 0.1 weight percent to about 1.0 weight
percent of the lubricating oil. The total boron concentration is
about 100 to about 260 parts per million in the lubricating oil.
The at least one lubricating oil base stock and the at least one
detergent are present in an amount sufficient for the lubricating
oil to form a tribofilm on a steel surface. The time for the
tribofilm to reach 95% of its saturation coverage (t.sub.95,sat) on
the steel surface is less than about 50 minutes, as determined by a
high frequency reciprocating rig (HFRR) in accordance with a
modified version of ASTM D6079. In tribofilm formation measurements
of the lubricating oil by a mini-traction machine (MTM) in Stribeck
mode, the number of Stribeck passes (S.sub.n) until an increase in
traction coefficient at 10 mm/s is achieved, which correlates to
onset of the tribofilm formation on the steel surface, is about 2
or less.
[0018] It has been surprisingly found that, in accordance with this
disclosure, improvements in wear control of a steel surface
lubricated with a lubricating oil are obtained, through the
generation of fast-forming tribofilms. The formulation features
corresponding to fast tribofilm generation and consequent low wear
in the FCW test do not adhere to expected strategies for reducing
soot-induced wear, which is a key feature of the FCW test.
[0019] In particular, it has been surprisingly found that, in
accordance with this disclosure, the time for the tribofilm to
reach 95% of its saturation coverage (t.sub.95,sat) on the steel
surface is less than about 50 minutes, as determined by a high
frequency reciprocating rig (HFRR) in accordance with a modified
version of ASTM D6079. Also, it has been surprisingly found that,
in tribofilm formation measurements of the lubricating oil by a
mini-traction machine (MTM) in Stribeck mode, the number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s is achieved, which correlates to onset of the tribofilm
formation on the steel surface, is about 2 or less. Further, it has
been surprisingly found that, in accordance with this disclosure,
elongation of timing chain due to wear of chain link pins is less
than about 0.07%, as determined by the FCW test conducted in
accordance with ILSAC GF-6 specification.
[0020] Other objects and advantages of the present disclosure will
become apparent from the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 shows formulations prepared in accordance with the
Examples, and the results of FCW testing, including MTM Stribeck
measurements, S.sub.N, and tribofilm friction saturation in HFRR
measurements, t.sub.95,sat., in accordance with the Examples.
[0022] FIG. 2 shows comparative formulations prepared in accordance
with the Examples, and the results of FCW testing, including MTM
Stribeck measurements, S.sub.N, and tribofilm friction saturation
in HFRR measurements, t.sub.95,sat, in accordance with the
Examples.
[0023] FIG. 3 shows a plot of timing chain elongation in the FCW
test as a function of S.sub.N and t.sub.95,sat., in accordance with
the Examples.
[0024] FIG. 4 shows a summary of low-wear, high-wear, and
borderline FCW formulations based on S.sub.N and t.sub.95,sat.,in
accordance with the Examples.
[0025] FIG. 5 shows formulations prepared in accordance with the
Examples, and the results of FCW testing, including MTM Stribeck
measurements, S.sub.N, and tribofilm friction saturation in HFRR
measurements, t.sub.95,sat., in accordance with the Examples. In
particular, FIG. 5 shows S.sub.N and t.sub.95,sat for low-soap
samples varying ratio of sulfonate to salicylate soap, at 0.6
weight percent soap and constant detergent metals composition.
[0026] FIG. 6 shows formulations prepared in accordance with the
Examples, and the results of MTM Stribeck measurements, S.sub.N,
and tribofilm friction saturation in HFRR measurements,
t.sub.95,sat., in accordance with the Examples. In particular, FIG.
6 shows S.sub.N and t.sub.95,sat for low-soap samples varying ratio
of sulfonate to salicylate soap, at 0.4 weight percent soap.
[0027] FIG. 7 shows formulations prepared in accordance with the
Examples, and the results of MTM Stribeck measurements, S.sub.N,
and tribofilm friction saturation in HFRR measurements,
t.sub.95,sat., in accordance with the Examples. In particular, FIG.
7 shows S.sub.N and t.sub.95,sat for low-soap samples varying ratio
of sulfonate to salicylate soap, at 0.7 weight percent soap and
constant detergent metals composition.
[0028] FIG. 8 shows formulations prepared in accordance with the
Examples, and the results of MTM Stribeck measurements, S.sub.N,
and tribofilm friction saturation in HFRR measurements,
t.sub.95,sat., in accordance with the Examples. In particular, FIG.
8 shows S.sub.N and t.sub.95,sat for low-soap samples varying ratio
of sulfonate to salicylate soap, at 0.8 weight percent soap and
constant detergent metals composition.
[0029] FIG. 9 shows formulations prepared in accordance with the
Examples, and the results of MTM Stribeck measurements, S.sub.N,
and tribofilm friction saturation in HFRR measurements,
t.sub.95,sat., in accordance with the Examples. In particular, FIG.
9 shows S.sub.N and t.sub.95,sat for low-soap samples varying ratio
of sulfonate to salicylate soap, at 1.3 weight percent soap and
constant detergent metals composition.
DETAILED DESCRIPTION
[0030] All numerical values within the detailed description and the
claims herein are modified by "about" or "approximately" the
indicated value, and take into account experimental error and
variations that would be expected by a person having ordinary skill
in the art. The phrase "major amount" as it relates to components
included within the lubricating oils of the specification and the
claims means greater than or equal to 50 wt. %, or greater than or
equal to 60 wt. %, or greater than or equal to 70 wt. %, or greater
than or equal to 80 wt. %, or greater than or equal to 90 wt. %
based on the total weight of the lubricating oil. The phrase "minor
amount" as it relates to components included within the lubricating
oils of the specification and the claims means less than 50 wt. %,
or less than or equal to 40 wt. %, or less than or equal to 30 wt.
%, or greater than or equal to 20 wt. %, or less than or equal to
10 wt. %, or less than or equal to 5 wt. %, or less than or equal
to 2 wt. %, or less than or equal to 1 wt. %, based on the total
weight of the lubricating oil. The phrase "essentially free" as it
relates to components included within the lubricating oils of the
specification and the claims means that the particular component is
at 0 weight % within the lubricating oil, or alternatively is at
impurity type levels within the lubricating oil (less than 100 ppm,
or less than 20 ppm, or less than 10 ppm, or less than 1 ppm). The
phrase "other lubricating oil additives" as used in the
specification and the claims means other lubricating oil additives
that are not specifically recited in the particular section of the
specification or the claims. For example, other lubricating oil
additives may include, but are not limited to, antioxidants,
detergents, dispersants, antiwear additives, corrosion inhibitors,
viscosity modifiers, metal passivators, pour point depressants,
seal compatibility agents, antifoam agents, extreme pressure
agents, friction modifiers and combinations thereof.
[0031] It has now been found that improved wear control can be
attained of a steel surface through the generation of fast-forming
tribofilms. The lubricating oil formulation features of this
disclosure permit the formation of fast-forming tribofilms on steel
surfaces under loading/temperature conditions relevant to
light-duty passenger vehicle operation. These fast-forming
tribofilms provide superior wear protection in FCW testing. In
particular, the lubricant formulation strategies of this disclosure
enable fast formation of tribofilms on steel surfaces in
boundary/mixed layer lubrication contacts in order to reduce
wear.
[0032] Also, for the lubricating oils of this disclosure, it has
been found that the time for the tribofilm to reach 95% of its
saturation coverage (t.sub.95,sat) on the steel surface is less
than about 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079.
[0033] Further, for the lubricating oils of this disclosure, it has
been found that in tribofilm formation measurements of the
lubricating oil by a mini-traction machine (MTM) in Stribeck mode,
the number of Stribeck passes (S.sub.n) until an increase in
traction coefficient at 10 mm/s is achieved, which correlates to
onset of the tribofilm formation on the steel surface, is about 2
or less.
[0034] Still further, for the lubricating oils of this disclosure,
it has been found that elongation of timing chain due to wear of
chain link pins is less than about 0.07%, as determined by FCW test
in accordance with ILSAC GF-6 specification.
[0035] In an embodiment, the lubrication regime at the steel
surface comprises boundary- and mixed-layer lubrication contacts
and, in particular, the steel surface comprises the surface of a
timing chain.
[0036] In an embodiment, the methods of this disclosure improve
soot-induced wear control of a steel surface through the generation
of fast-forming tribofilms.
[0037] The present disclosure provides lubricant compositions with
excellent antiwear properties attained through the generation of
fast-forming tribofilms. Antiwear additives are generally required
for reducing wear in operating equipment where two solid surfaces
engage in contact. In the absence of antiwear chemistry, the
surfaces can rub together causing material loss on one or both
surfaces which can eventually lead to equipment malfunction and
failure. Antiwear additives can produce a protective surface layer
which reduces wear and material loss. Most commonly the materials
of interest are metals such as steel and other iron-containing
alloys. However, other materials such as ceramics, polymer
coatings, diamond-like carbon, corresponding composites, and the
like can also be used to produce durable surfaces in modern
equipment. The lubricant compositions of this disclosure can
provide antiwear properties to such surfaces through the generation
of fast-forming tribofilms.
[0038] The lubricant compositions of this disclosure provide
advantaged wear, including advantaged wear and friction,
performance in the lubrication of internal combustion engines,
power trains, drivelines, transmissions, gears, gear trains, valve
trains, gear sets, and the like, through the generation of
fast-forming tribofilms. Preferably, the lubricating oil
formulations of this disclosure permit the formation of
fast-forming tribofilms on steel surfaces under loading/temperature
conditions relevant to light-duty passenger vehicle operation.
[0039] Also, the lubricant compositions of this disclosure provide
advantaged wear, including advantaged wear and friction,
performance in the lubrication of mechanical components, which can
include, for example, pistons, piston rings, cylinder liners,
cylinders, cams, tappets, lifters, bearings (journal, roller,
tapered, needle, ball, and the like), gears, valves, and the like,
through the generation of fast-forming tribofilms under
loading/temperature conditions relevant to light-duty passenger
vehicle operation.
[0040] Further, the lubricant compositions of this disclosure
provide advantaged wear, including advantaged wear and friction,
performance as a component in lubricant compositions, which can
include, for example, lubricating liquids, semi-solids, solids,
greases, dispersions, suspensions, material concentrates, additive
concentrates, and the like.
[0041] Also, the lubricant compositions of this disclosure provide
advantaged wear, including advantaged wear and friction,
performance in spark-ignition internal combustion engines,
compression-ignition internal combustion engines, mixed-ignition
(spark-assisted and compression) internal combustion engines, and
the like, through the generation of fast-forming tribofilms under
loading/temperature conditions relevant to light-duty passenger
vehicle operation.
[0042] Further, the lubricant compositions of this disclosure
provide advantaged wear, including advantaged wear and friction,
performance through the generation of fast-forming tribofilms on
lubricated surfaces that include, for example, the following:
metals, metal alloys, non-metals, non-metal alloys, mixed
carbon-metal composites and alloys, mixed carbon-nonmetal
composites and alloys, ferrous metals, ferrous composites and
alloys, non-ferrous metals, non-ferrous composites and alloys,
titanium, titanium composites and alloys, aluminum, aluminum
composites and alloys, magnesium, magnesium composites and alloys,
ion-implanted metals and alloys, plasma modified surfaces; surface
modified materials; coatings; mono-layer, multi-layer, and gradient
layered coatings; honed surfaces; polished surfaces; etched
surfaces; textured surfaces; mircro and nano structures on textured
surfaces; super-finished surfaces; diamond-like carbon (DLC), DLC
with high-hydrogen content, DLC with moderate hydrogen content, DLC
with low-hydrogen content, DLC with near-zero hydrogen content, DLC
composites, DLC-metal compositions and composites, DLC-nonmetal
compositions and composites; ceramics, ceramic oxides, ceramic
nitrides, FeN, CrN, ceramic carbides, mixed ceramic compositions,
and the like; polymers, thermoplastic polymers, engineered
polymers, polymer blends, polymer alloys, polymer composites;
materials compositions and composites containing dry lubricants,
that include, for example, graphite, carbon, molybdenum, molybdenum
disulfide, polytetrafluoroethylene, polyperfluoropropylene,
polyperfluoroalkylethers, and the like.
Lubricating Oil Base Stocks and Co-Base Stocks
[0043] A wide range of lubricating base oils is known in the art.
Lubricating base oils that are useful in the present disclosure are
natural oils, mineral oils and synthetic oils, and unconventional
oils (or mixtures thereof) can be used unrefined, refined, or
rerefined (the latter is also known as reclaimed or reprocessed
oil). Unrefined oils are those obtained directly from a natural or
synthetic source and used without added purification. These include
shale oil obtained directly from retorting operations, petroleum
oil obtained directly from primary distillation, and ester oil
obtained directly from an esterification process. Refined oils are
similar to the oils discussed for unrefined oils except refined
oils are subjected to one or more purification steps to improve at
least one lubricating oil property. One skilled in the art is
familiar with many purification processes. These processes include
solvent extraction, secondary distillation, acid extraction, base
extraction, filtration, and percolation. Rerefined oils are
obtained by processes analogous to refined oils but using an oil
that has been previously used as a feed stock.
[0044] Groups I, II, III, IV and V are broad base oil stock
categories developed and defined by the American Petroleum
Institute (API Publication 1509; www.API.org) to create guidelines
for lubricant base oils. Group I base stocks have a viscosity index
of between about 80 to 120 and contain greater than about 0.03%
sulfur and/or less than about 90% saturates. Group II base stocks
have a viscosity index of between about 80 to 120, and contain less
than or equal to about 0.03% sulfur and greater than or equal to
about 90% saturates. Group III stocks have a viscosity index
greater than about 120 and contain less than or equal to about
0.03% sulfur and greater than about 90% saturates. Group IV
includes polyalphaolefins (PAO). Group V base stock includes base
stocks not included in Groups I-IV. The table below summarizes
properties of each of these five groups.
TABLE-US-00001 Base Oil Properties Saturates Sulfur Viscosity Index
Group I <90 and/or >0.03% and .gtoreq.80 and <120 Group II
.gtoreq.90 and .ltoreq.0.03% and .gtoreq.80 and <120 Group III
.gtoreq.90 and .ltoreq.0.03% and .gtoreq.120 Group IV
polyalphaolefins (PAO) Group V All other base oil stocks not
included in Groups I, II, III or IV
[0045] Natural oils include animal oils, vegetable oils (castor oil
and lard oil, for example), and mineral oils. Animal and vegetable
oils possessing favorable thermal oxidative stability can be used.
Of the natural oils, mineral oils are preferred. Mineral oils vary
widely as to their crude source, for example, as to whether they
are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils
derived from coal or shale are also useful. Natural oils vary also
as to the method used for their production and purification, for
example, their distillation range and whether they are straight run
or cracked, hydrorefined, or solvent extracted.
[0046] Group II and/or Group III hydroprocessed or hydrocracked
base stocks are also well known base stock oils.
[0047] Synthetic oils include hydrocarbon oil. Hydrocarbon oils
include oils such as polymerized and interpolymerized olefins
(polybutylenes, polypropylenes, propylene isobutylene copolymers,
ethylene-olefin copolymers, and ethylene-alphaolefin copolymers,
for example). Polyalphaolefin (PAO) oil base stocks are commonly
used synthetic hydrocarbon oil. By way of example, PAOs derived
from C.sub.8, C.sub.10, C.sub.12, C.sub.14 olefins or mixtures
thereof may be utilized. See U.S. Pat. Nos. 4,956,122; 4,827,064;
and 4,827,073.
[0048] The number average molecular weights of the PAOs, which are
known materials and generally available on a major commercial scale
from suppliers such as ExxonMobil Chemical Company, Chevron
Phillips Chemical Company, BP, and others, typically vary from
about 250 to about 3,000, although PAO's may be made in viscosities
up to about 150 cSt (100.degree. C.). The PAOs are typically
comprised of relatively low molecular weight hydrogenated polymers
or oligomers of alphaolefins which include, but are not limited to,
C.sub.2 to about C.sub.32 alphaolefins with the C.sub.8 to about
C.sub.16 alphaolefins, such as 1-octene, 1-decene, 1-dodecene and
the like, being preferred. The preferred polyalphaolefins are
poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures
thereof and mixed olefin-derived polyolefins. However, the dimers
of higher olefins in the range of C.sub.12 to C.sub.18 may be used
to provide low viscosity base stocks of acceptably low volatility.
Depending on the viscosity grade and the starting oligomer, the
PAOs may be predominantly dimers, trimers and tetramers of the
starting olefins, with minor amounts of the lower and/or higher
oligomers, having a viscosity range of 1.5 cSt to 12 cSt. PAO
fluids of particular use may include 3 cSt, 3.4 cSt, and/or 3.6 cSt
and combinations thereof. Mixtures of PAO fluids having a viscosity
range of 1.5 cSt to approximately 150 cSt or more may be used if
desired. Unless indicated otherwise, all viscosities cited herein
are measured at 100.degree. C.
[0049] The PAO fluids may be conveniently made by the
polymerization of an alphaolefin in the presence of a
polymerization catalyst such as the Friedel-Crafts catalysts
including, for example, aluminum trichloride, boron trifluoride or
complexes of boron trifluoride with water, alcohols such as
ethanol, propanol or butanol, carboxylic acids or esters such as
ethyl acetate or ethyl propionate. For example the methods
disclosed by U.S. Pat. No. 4,149,178 or 3,382,291 may be
conveniently used herein. Other descriptions of PAO synthesis are
found in the following U.S. Pat. Nos. 3,742,082; 3,769,363;
3,876,720; 4,239,930; 4,367,352; 4,413,156; 4,434,408; 4,910,355;
4,956,122; and 5,068,487. The dimers of the C.sub.14 to C.sub.18
olefins are described in U.S. Pat. No. 4,218,330.
[0050] Other useful lubricant oil base stocks include wax isomerate
base stocks and base oils, comprising hydroisomerized waxy stocks
(e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker
bottoms, etc.), hydroisomerized Fischer-Tropsch waxes,
Gas-to-Liquids (GTL) base stocks and base oils, and other wax
isomerate hydroisomerized base stocks and base oils, or mixtures
thereof. Fischer-Tropsch waxes, the high boiling point residues of
Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with
very low sulfur content. The hydroprocessing used for the
production of such base stocks may use an amorphous
hydrocracking/hydroisomerization catalyst, such as one of the
specialized lube hydrocracking (LHDC) catalysts or a crystalline
hydrocracking/hydroisomerization catalyst, preferably a zeolitic
catalyst. For example, one useful catalyst is ZSM-48 as described
in U.S. Pat. No. 5,075,269, the disclosure of which is incorporated
herein by reference in its entirety. Processes for making
hydrocracked/hydroisomerized distillates and
hydrocracked/hydroisomerized waxes are described, for example, in
U.S. Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as
well as in British Patent Nos. 1,429,494; 1,350,257; 1,440,230 and
1,390,359. Each of the aforementioned patents is incorporated
herein in their entirety. Particularly favorable processes are
described in European Patent Application Nos. 464546 and 464547,
also incorporated herein by reference. Processes using
Fischer-Tropsch wax feeds are described in U.S. Pat. Nos. 4,594,172
and 4,943,672, the disclosures of which are incorporated herein by
reference in their entirety.
[0051] Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived
base oils, and other wax-derived hydroisomerized (wax isomerate)
base oils be advantageously used in the instant disclosure, and may
have useful kinematic viscosities at 100.degree. C. of about 2 cSt
to about 50 cSt, preferably about 2 cSt to about 30 cSt, more
preferably about 3 cSt to about 25 cSt, as exemplified by GTL 4
with kinematic viscosity of about 4.0 cSt at 100.degree. C. and a
viscosity index of about 141. These Gas-to-Liquids (GTL) base oils,
Fischer-Tropsch wax derived base oils, and other wax-derived
hydroisomerized base oils may have useful pour points of about
-20.degree. C. or lower, and under some conditions may have
advantageous pour points of about -25.degree. C. or lower, with
useful pour points of about -30.degree. C. to about -40.degree. C.
or lower. Useful compositions of Gas-to-Liquids (GTL) base oils,
Fischer-Tropsch wax derived base oils, and wax-derived
hydroisomerized base oils are recited in U.S. Pat. Nos. 6,080,301;
6,090,989, and 6,165,949 for example, and are incorporated herein
in their entirety by reference.
[0052] The hydrocarbyl aromatics can be used as a base oil or base
oil component and can be any hydrocarbyl molecule that contains at
least about 5% of its weight derived from an aromatic moiety such
as a benzenoid moiety or naphthenoid moiety, or their derivatives.
These hydrocarbyl aromatics include alkyl benzenes, alkyl
naphthalenes, alkyl biphenyls, alkyl diphenyl oxides, alkyl
naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A,
alkylated thiodiphenol, and the like. The aromatic can be
mono-alkylated, dialkylated, polyalkylated, and the like. The
aromatic can be mono- or poly-functionalized. The hydrocarbyl
groups can also be comprised of mixtures of alkyl groups, alkenyl
groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other
related hydrocarbyl groups. The hydrocarbyl groups can range from
about C.sub.6 up to about C.sub.60 with a range of about C.sub.8 to
about C.sub.20 often being preferred. A mixture of hydrocarbyl
groups is often preferred, and up to about three such substituents
may be present. The hydrocarbyl group can optionally contain
sulfur, oxygen, and/or nitrogen containing substituents. The
aromatic group can also be derived from natural (petroleum)
sources, provided at least about 5% of the molecule is comprised of
an above-type aromatic moiety. Viscosities at 100.degree. C. of
approximately 2 cSt to about 50 cSt are preferred, with viscosities
of approximately 3 cSt to about 20 cSt often being more preferred
for the hydrocarbyl aromatic component. In one embodiment, an alkyl
naphthalene where the alkyl group is primarily comprised of
1-hexadecene is used. Other alkylates of aromatics can be
advantageously used. Naphthalene or methyl naphthalene, for
example, can be alkylated with olefins such as octene, decene,
dodecene, tetradecene or higher, mixtures of similar olefins, and
the like. Alkylated naphthalene and analogues may also comprise
compositions with isomeric distribution of alkylating groups on the
alpha and beta carbon positions of the ring structure. Distribution
of groups on the alpha and beta positions of a naphthalene ring may
range from 100:1 to 1:100, more often 50:1 to 1:50 Useful
concentrations of hydrocarbyl aromatic in a lubricant oil
composition can be about 2% to about 25%, preferably about 4% to
about 20%, and more preferably about 4% to about 15%, depending on
the application.
[0053] Alkylated aromatics such as the hydrocarbyl aromatics of the
present disclosure may be produced by well-known Friedel-Crafts
alkylation of aromatic compounds. See Friedel-Crafts and Related
Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York,
1963. For example, an aromatic compound, such as benzene or
naphthalene, is alkylated by an olefin, alkyl halide or alcohol in
the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and
Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See
Olah, G. A. (ed.), Inter-science Publishers, New York, 1964. Many
homogeneous or heterogeneous, solid catalysts are known to one
skilled in the art. The choice of catalyst depends on the
reactivity of the starting materials and product quality
requirements. For example, strong acids such as AlCl.sub.3,
BF.sub.3, or HF may be used. In some cases, milder catalysts such
as FeCl.sub.3 or SnCl.sub.4 are preferred. Newer alkylation
technology uses zeolites or solid super acids.
[0054] Esters comprise a useful base stock. Additive solvency and
seal compatibility characteristics may be secured by the use of
esters such as the esters of dibasic acids with monoalkanols and
the polyol esters of monocarboxylic acids. Esters of the former
type include, for example, the esters of dicarboxylic acids such as
phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic
acid, maleic acid, azelaic acid, suberic acid, sebacic acid,
fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl
malonic acid, alkenyl malonic acid, etc., with a variety of
alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol,
2-ethylhexyl alcohol, etc. Specific examples of these types of
esters include dibutyl adipate, di(2-ethylhexyl) sebacate,
di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate,
diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl
sebacate, etc.
[0055] Particularly useful synthetic esters are those which are
obtained by reacting one or more polyhydric alcohols, preferably
the hindered polyols (such as the neopentyl polyols, e.g.,
neopentyl glycol, trimethylol ethane,
2-methyl-2-propyl-1,3-propanediol, trimethylol propane,
pentaerythritol and dipentaerythritol) with alkanoic acids
containing at least about 4 carbon atoms, preferably C.sub.5 to
C.sub.30 acids such as saturated straight chain fatty acids
including caprylic acid, capric acid, lauric acid, myristic acid,
palmitic acid, stearic acid, arachic acid, and behenic acid, or the
corresponding branched chain fatty acids or unsaturated fatty acids
such as oleic acid, or mixtures of any of these materials.
[0056] Suitable synthetic ester components include the esters of
trimethylol propane, trimethylol butane, trimethylol ethane,
pentaerythritol and/or dipentaerythritol with one or more
monocarboxylic acids containing from about 5 to about 10 carbon
atoms. These esters are widely available commercially, for example,
the Mobil P-41 and P-51 esters of ExxonMobil Chemical Company.
[0057] Also useful are esters derived from renewable material such
as coconut, palm, rapeseed, soy, sunflower and the like. These
esters may be monoesters, di-esters, polyol esters, complex esters,
or mixtures thereof. These esters are widely available
commercially, for example, the Mobil P-51 ester of ExxonMobil
Chemical Company.
[0058] Engine oil formulations containing renewable esters are
included in this disclosure. For such formulations, the renewable
content of the ester is typically greater than about 70 weight
percent, preferably more than about 80 weight percent and most
preferably more than about 90 weight percent.
[0059] Other useful fluids of lubricating viscosity include
non-conventional or unconventional base stocks that have been
processed, preferably catalytically, or synthesized to provide high
performance lubrication characteristics.
[0060] Non-conventional or unconventional base stocks/base oils
include one or more of a mixture of base stock(s) derived from one
or more Gas-to-Liquids (GTL) materials, as well as
isomerate/isodewaxate base stock(s) derived from natural wax or
waxy feeds, mineral and or non-mineral oil waxy feed stocks such as
slack waxes, natural waxes, and waxy stocks such as gas oils, waxy
fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal
crackates, or other mineral, mineral oil, or even non-petroleum oil
derived waxy materials such as waxy materials received from coal
liquefaction or shale oil, and mixtures of such base stocks.
[0061] GTL materials are materials that are derived via one or more
synthesis, combination, transformation, rearrangement, and/or
degradation/deconstructive processes from gaseous carbon-containing
compounds, hydrogen-containing compounds and/or elements as feed
stocks such as hydrogen, carbon dioxide, carbon monoxide, water,
methane, ethane, ethylene, acetylene, propane, propylene, propyne,
butane, butylenes, and butynes. GTL base stocks and/or base oils
are GTL materials of lubricating viscosity that are generally
derived from hydrocarbons; for example, waxy synthesized
hydrocarbons, that are themselves derived from simpler gaseous
carbon-containing compounds, hydrogen-containing compounds and/or
elements as feed stocks. GTL base stock(s) and/or base oil(s)
include oils boiling in the lube oil boiling range (1)
separated/fractionated from synthesized GTL materials such as, for
example, by distillation and subsequently subjected to a final wax
processing step which involves either or both of a catalytic
dewaxing process, or a solvent dewaxing process, to produce lube
oils of reduced/low pour point; (2) synthesized wax isomerates,
comprising, for example, hydrodewaxed or hydroisomerized cat and/or
solvent dewaxed synthesized wax or waxy hydrocarbons; (3)
hydrodewaxed or hydroisomerized cat and/or solvent dewaxed
Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy
hydrocarbons, waxes and possible analogous oxygenates); preferably
hydrodewaxed or hydroisomerized/followed by cat and/or solvent
dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed or
hydroisomerized/followed by cat (or solvent) dewaxing dewaxed, F-T
waxes, or mixtures thereof.
[0062] GTL base stock(s) and/or base oil(s) derived from GTL
materials, especially, hydrodewaxed or hydroisomerized/followed by
cat and/or solvent dewaxed wax or waxy feed, preferably F-T
material derived base stock(s) and/or base oil(s), are
characterized typically as having kinematic viscosities at
100.degree. C. of from about 2 mm.sup.2/s to about 50 mm.sup.2/s
(ASTM D445). They are further characterized typically as having
pour points of -5.degree. C. to about -40.degree. C. or lower (ASTM
D97). They are also characterized typically as having viscosity
indices of about 80 to about 140 or greater (ASTM D2270).
[0063] In addition, the GTL base stock(s) and/or base oil(s) are
typically highly paraffinic (>90% saturates), and may contain
mixtures of monocycloparaffins and multicycloparaffins in
combination with non-cyclic isoparaffins. The ratio of the
naphthenic (i.e., cycloparaffin) content in such combinations
varies with the catalyst and temperature used. Further, GTL base
stock(s) and/or base oil(s) typically have very low sulfur and
nitrogen content, generally containing less than about 10 ppm, and
more typically less than about 5 ppm of each of these elements. The
sulfur and nitrogen content of GTL base stock(s) and/or base oil(s)
obtained from F-T material, especially F-T wax, is essentially nil.
In addition, the absence of phosphorus and aromatics make this
materially especially suitable for the formulation of low SAP
products.
[0064] The term GTL base stock and/or base oil and/or wax isomerate
base stock and/or base oil is to be understood as embracing
individual fractions of such materials of wide viscosity range as
recovered in the production process, mixtures of two or more of
such fractions, as well as mixtures of one or two or more low
viscosity fractions with one, two or more higher viscosity
fractions to produce a blend wherein the blend exhibits a target
kinematic viscosity.
[0065] The GTL material, from which the GTL base stock(s) and/or
base oil(s) is/are derived is preferably an F-T material (i.e.,
hydrocarbons, waxy hydrocarbons, wax).
[0066] Base oils for use in the formulated lubricating oils useful
in the present disclosure are any of the variety of oils
corresponding to API Group I, Group II, Group III, Group IV, and
Group V oils and mixtures thereof, preferably API Group II, Group
III, Group IV, and Group V oils and mixtures thereof, more
preferably the Group III to Group V base oils due to their
exceptional volatility, stability, viscometric and cleanliness
features. Minor quantities of Group I stock, such as the amount
used to dilute additives for blending into formulated lube oil
products, can be tolerated but should be kept to a minimum, i.e.
amounts only associated with their use as diluent/carrier oil for
additives used on an "as-received" basis. Even in regard to the
Group II stocks, it is preferred that the Group II stock be in the
higher quality range associated with that stock, i.e. a Group II
stock having a viscosity index in the range 100<VI<120.
[0067] The base oil constitutes the major component of the engine
oil lubricant composition of the present disclosure and typically
is present in an amount ranging from about 6 to about 99 weight
percent or from about 6 to about 95 weight percent, preferably from
about 50 to about 99 weight percent or from about 70 to about 95
weight percent, and more preferably from about 85 to about 95
weight percent, based on the total weight of the composition. The
base oil may be selected from any of the synthetic or natural oils
typically used as crankcase lubricating oils for spark-ignited and
compression-ignited engines. The base oil conveniently has a
kinematic viscosity, according to ASTM standards, of about 2.5 cSt
to about 18 cSt (or mm.sup.2/s) at 100.degree. C. and preferably of
about 2.5 cSt to about 12.5 cSt (or mm.sup.2/s) at 100.degree. C.,
often more preferably from about 2.5 cSt to about 10 cSt. Mixtures
of synthetic and natural base oils may be used if desired.
Bi-modal, tri-modal, and additional combinations of mixtures of
Group I, II, III, IV, and/or V base stocks may be used if
desired.
[0068] The co-base stock component is present in an amount
sufficient for providing solubility, compatibility and dispersancy
of polar additives in the lubricating oil. The co-base stock
component is present in the lubricating oils of this disclosure in
an amount from about 1 to about 99 weight percent, preferably from
about 5 to about 95 weight percent, and more preferably from about
10 to about 90 weight percent.
Detergents
[0069] Illustrative detergents useful in this disclosure include,
for example, alkaline earth metal salicylates, alkaline earth metal
sulfonates, and mixtures thereof.
[0070] In an embodiment, the present disclosure provides a
detergent additive useful in lubricating oil compositions
comprising a salicylate detergent, a sulfonate detergent, a mixture
of salicylate detergents, a mixture of sulfonate detergents, or a
mixture of salicylate and sulfonate detergents, all of varying
total base number (TBN). In one preferred mode, mixtures of low,
medium, and high TBN detergents are used.
[0071] Within the scope of the present disclosure, a low TBN
detergent is defined as having a TBN of less than about 100. A
medium TBN detergent is defined as having a TBN of between about
100 and 200. A high TBN detergent is defined as having a TBN of
greater than about 200.
[0072] Low TBN refers to neutral to low-overbased detergents,
medium TBN refers to medium overbased-detergents, and high TBN
refers to high-overbased detergents. These terms are used
descriptively to describe the general differences between the TBN
of the detergents used and are meant to describe in general terms
the differences between the contained calcium levels and the
presence or absence and/or the degree of overbasing derived by the
carbonation of the calcium salicylate in the presence of excess
(over and beyond stoichiometric quantities) of calcium bases to
form overbased calcium carbonate complexed calcium salicylate
detergents.
[0073] In an embodiment, mixed TBN detergents of the present
disclosure are incorporated into lubricating oil compositions. In
one preferred mode, at least two of about 0.2% to about 4% of low
TBN detergent, about 0.2% to about 4% of medium TBN detergent, and
about 0.2% to about 4% of high TBN detergent (all percentages based
on total weight of the lubricating oil composition and based on an
active ingredient basis which excludes oil diluents and the like
used in commercial products) are added to the lubricating oil
composition. In one embodiment, all three detergents are added.
Preferably the detergent is (i) a salicylate detergent, more
preferably a calcium or magnesium salicylate detergent, (ii) a
sulfonate detergent, more preferably a calcium or magnesium
sulfonate detergent, (iii) a mixture of salicylate detergents, more
preferably a mixture of calcium and/or magnesium salicylate
detergents, (iv) a mixture of sulfonate detergents, more preferably
a mixture of calcium and/or magnesium sulfonate detergents, or (v)
a mixture of salicylate detergents and sulfonate detergents, more
preferably a mixture of calcium and/or magnesium salicylate
detergents and sulfonate detergents.
[0074] Salicylate detergents may be prepared by reacting a basic
metal compound with at least one salicylic acid compound and
removing free water from the reaction product. Useful salicylates
include long chain alkyl salicylates. One useful family of
compositions is of the formula
##STR00001##
where R is a hydrogen atom or an alkyl group having 1 to about 30
carbon atoms, n is an integer from 1 to 4, and M is an alkaline
earth metal. Preferred are alkyl chains of at least C11, preferably
C13 or greater. R may be optionally substituted with substituents
that do not interfere with the detergent's function. M is
preferably, calcium, magnesium, or barium. More preferably, M is
calcium or magnesium.
[0075] Hydrocarbyl-substituted salicylic acids may be prepared from
phenols by the Kolbe reaction. See U.S. Pat. No. 3,595,791, which
is incorporated herein by reference in its entirety, for additional
information on synthesis of these compounds. The metal salts of the
hydrocarbyl-substituted salicylic acids may be prepared by double
decomposition of a metal salt in a polar solvent such as water or
alcohol.
[0076] Sulfonate detergents may be prepared from sulfonic acids
that are typically obtained by sulfonation of alkyl substituted
aromatic hydrocarbons. Hydrocarbon examples include those obtained
by alkylating benzene, toluene, xylene, naphthalene, biphenyl and
their halogenated derivatives (chlorobenzene, chlorotoluene, and
chloronaphthalene, for example). The alkylating agents typically
have about 3 to 70 carbon atoms. The alkaryl sulfonates typically
contain about 9 to about 80 or more carbon atoms, more typically
from about 16 to 60 carbon atoms.
[0077] M. W. Ranney in "Lubricant Additives" published by Noyes
Data Corporation of Parkridge, N.J. (1973) discloses a number of
overbased metal salts of various sulfonic acids that are useful as
detergents and dispersants in lubricants. The book entitled
"Lubricant Additives", C. V. Smallheer and R. K. Smith, published
by the Lezius-Hiles Co. of Cleveland, Ohio (1967), similarly
discloses a number of overbased sulfonates which are useful as
detergents.
[0078] The detergents useful in this disclosure provide select
levels of soap content to the lubricating oil compositions, which
is discussed in more detail in the Examples herein. By one
approach, the detergent provides a lower soap content, e.g., about
0.2 to about 0.9 percent soap content, or about 0.3 to about 0.8
percent soap content, or about 0.4 to about 0.7 percent soap
content, to the final lubricating oil composition, for any ratio of
alkaline earth metal salicylate soap to alkaline earth metal
sulfonate soap.
[0079] In other approaches, the detergent provides a higher soap
content, e.g., about 0.6 to about 1.5 percent soap, or about 0.7 to
about 1.4 percent soap, or about 0.8 to about 1.3 percent soap, to
the final lubricating oil composition, when alkaline earth metal
sulfonate soap comprises from about 50 to about 100 percent of the
total detergent soap.
[0080] In still other approaches, when the alkaline earth metal
sulfonate soap comprises about 100 percent of the total detergent
soap, the total amount of soap delivered is about 0.1 weight
percent to about 1.0 weight percent, preferably about 0.4 weight
percent to about 0.6 weight percent, more preferably 0.5 weight
percent, of the lubricating oil.
[0081] Soap content generally refers to the amount of neutral
organic acid salt and reflects a detergent's cleansing ability, or
detergency, and dirt suspending ability. The soap content can be
determined by the following formula, using an exemplary calcium
sulfonate detergent represented by
(RSO.sub.3).sub.vCa.sub.w(CO.sub.3).sub.x(OH).sub.y with v, w, x,
and y denoting the number of sulfonate groups, the number of
calcium atoms, the number of carbonate groups, and the number of
hydroxyl groups respectively):
soap content = formula weight of [ ( RSO 3 ) 2 Ca ] effective
formula weight .times. 100 ##EQU00001##
[0082] Effective formula weight is the combined weight of all the
atoms that make up the formula
(RSO.sub.3).sub.vCa.sub.w(CO.sub.3).sub.x(OH).sub.y plus that of
any other lubricant components. Further discussion on determining
soap content can be found in Fuels and Lubricants Handbook,
Technology, Properties, Performance, and Testing, George Totten,
editor, ASTM International, 2003, the relevant portions thereof
incorporated herein by reference.
[0083] In the lubricating oil composition of this disclosure, when
mixtures of salicylate detergents are used, of the same or
different TBN, the weight ratio of a first salicylate detergent to
a second salicylate detergent is from about 1:200 to about 200:1,
or from about 1:100 to about 100:1, or from about 1:50 to about
50:1, or from about 1:25 to about 25:1, or from about 1:10 to about
10:1, or from about 1:5 to about 5:1.
[0084] In the lubricating oil composition of this disclosure, when
mixtures of sulfonate detergents are used, of the same or different
TBN, the weight ratio of a first sulfonate detergent to a second
sulfonate detergent is from about 1:200 to about 200:1, or from
about 1:100 to about 100:1, or from about 1:50 to about 50:1, or
from about 1:25 to about 25:1, or from about 1:10 to about 10:1, or
from about 1:5 to about 5:1.
[0085] In the lubricating oil composition of this disclosure, when
mixtures of salicylate detergents and sulfonate detergents are
used, of the same or different TBN, the weight ratio of the
salicylate detergent to the sulfonate detergent is from about 1:200
to about 200:1, or from about 1:100 to about 100:1, or from about
1:50 to about 50:1, or from about 1:25 to about 25:1, or from about
1:10 to about 10:1, or from about 1:5 to about 5:1.
[0086] The detergent concentration in the lubricating oils of this
disclosure can range from about 0.001 weight percent to about 20
weight percent, or about 0.01 weight percent to about 10 weight
percent, or about 0.5 to about 6.0 weight percent, or about 0.6 to
5.0 weight percent, or from about 0.8 weight percent to about 4.0
weight percent, based on the total weight of the lubricating
oil.
[0087] As used herein, the detergent concentrations are given on an
"as delivered" basis. Typically, the active detergent is delivered
with a process oil. The "as delivered" detergent typically contains
from about 20 weight percent to about 100 weight percent, or from
about 40 weight percent to about 60 weight percent, of active
detergent in the "as delivered" detergent product.
Other Additives
[0088] The formulated lubricating oil useful in the present
disclosure may additionally contain one or more of the other
commonly used lubricating oil performance additives including but
not limited to antiwear additives, dispersants, other detergents,
viscosity modifiers, corrosion inhibitors, rust inhibitors, metal
deactivators, extreme pressure additives, anti-seizure agents, wax
modifiers, viscosity modifiers, fluid-loss additives, seal
compatibility agents, lubricity agents, anti-staining agents,
chromophoric agents, defoamants, demulsifiers, densifiers, wetting
agents, gelling agents, tackiness agents, colorants, and others.
For a review of many commonly used additives, see Klamann in
Lubricants and Related Products, Verlag Chemie, Deerfield Beach,
Fla.; ISBN 0-89573-177-0. Reference is also made to "Lubricant
Additives" by M. W. Ranney, published by Noyes Data Corporation of
Parkridge, N J (1973); see also U.S. Pat. No. 7,704,930, the
disclosure of which is incorporated herein in its entirety. These
additives are commonly delivered with varying amounts of diluent
oil, that may range from 5 weight percent to 50 weight percent.
[0089] The additives useful in this disclosure do not have to be
soluble in the lubricating oils. Insoluble additives in oil can be
dispersed in the lubricating oils of this disclosure.
[0090] The types and quantities of performance additives used in
combination with the instant disclosure in lubricant compositions
are not limited by the examples shown herein as illustrations.
Antiwear Additives
[0091] A metal alkylthiophosphate and more particularly a metal
dialkyl dithio phosphate in which the metal constituent is zinc, or
zinc dialkyl dithio phosphate (ZDDP) can be a useful component of
the lubricating oils of this disclosure. ZDDP can be derived from
primary alcohols, secondary alcohols or mixtures thereof. ZDDP
compounds generally are of the formula
Zn[SP(S)(OR.sup.1)(OR.sup.2)].sub.2
where R.sup.1 and R.sup.2 are C.sub.1-C.sub.18 alkyl groups,
preferably C.sub.2-C.sub.12 alkyl groups. These alkyl groups may be
straight chain or branched. Alcohols used in the ZDDP can be
propanol, 2-propanol, butanol, secondary butanol, pentanols,
hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl
hexanol, alkylated phenols, and the like. Mixtures of secondary
alcohols or of primary and secondary alcohol can be preferred.
Alkyl aryl groups may also be used.
[0092] Preferable zinc dithiophosphates which are commercially
available include secondary zinc dithiophosphates such as those
available from for example, The Lubrizol Corporation under the
trade designations "LZ 677A", "LZ 1095" and "LZ 1371", from for
example Chevron Oronite under the trade designation "OLOA 262" and
from for example Afton Chemical under the trade designation "HITEC
7169".
[0093] The ZDDP is typically used in amounts of from about 0.3
weight percent to about 1.5 weight percent, preferably from about
0.4 weight percent to about 1.2 weight percent, more preferably
from about 0.5 weight percent to about 1.0 weight percent, and even
more preferably from about 0.6 weight percent to about 0.8 weight
percent, based on the total weight of the lubricating oil, although
more or less can often be used advantageously. Preferably, the ZDDP
is a secondary ZDDP and present in an amount of from about 0.6 to
1.0 weight percent of the total weight of the lubricating oil.
Dispersants
[0094] During engine operation, oil-insoluble oxidation byproducts
are produced. Dispersants help keep these byproducts in solution,
thus diminishing their deposition on metal surfaces. Dispersants
used in the formulation of the lubricating oil may be ashless or
ash-forming in nature. Preferably, the dispersant is ashless. So
called ashless dispersants are organic materials that form
substantially no ash upon combustion. For example,
non-metal-containing or borated metal-free dispersants are
considered ashless. In contrast, metal-containing detergents
discussed above form ash upon combustion.
[0095] Suitable dispersants typically contain a polar group
attached to a relatively high molecular weight hydrocarbon chain.
The polar group typically contains at least one element of
nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain
50 to 400 carbon atoms.
[0096] A particularly useful class of dispersants are the
(poly)alkenylsuccinic derivatives, typically produced by the
reaction of a long chain hydrocarbyl substituted succinic compound,
usually a hydrocarbyl substituted succinic anhydride, with a
polyhydroxy or polyamino compound. The long chain hydrocarbyl group
constituting the oleophilic portion of the molecule which confers
solubility in the oil, is normally a polyisobutylene group. Many
examples of this type of dispersant are well known commercially and
in the literature. Exemplary U.S. patents describing such
dispersants are U.S. Pat. Nos. 3,172,892; 3,2145,707; 3,219,666;
3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904;
3,632,511; 3,787,374 and 4,234,435. Other types of dispersant are
described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025;
3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574;
3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250;
3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. A
further description of dispersants may be found, for example, in
European Patent Application No. 471 071, to which reference is made
for this purpose.
[0097] Hydrocarbyl-substituted succinic acid and
hydrocarbyl-substituted succinic anhydride derivatives are useful
dispersants. In particular, succinimide, succinate esters, or
succinate ester amides prepared by the reaction of a
hydrocarbon-substituted succinic acid compound preferably having at
least 50 carbon atoms in the hydrocarbon substituent, with at least
one equivalent of an alkylene amine are particularly useful.
[0098] Succinimides are formed by the condensation reaction between
hydrocarbyl substituted succinic anhydrides and amines. Molar
ratios can vary depending on the polyamine. For example, the molar
ratio of hydrocarbyl substituted succinic anhydride to TEPA can
vary from about 1:1 to about 5:1. Representative examples are shown
in U.S. Pat. Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746;
3,322,670; and 3,652,616, 3,948,800; and Canada Patent No.
1,094,044.
[0099] Succinate esters are formed by the condensation reaction
between hydrocarbyl substituted succinic anhydrides and alcohols or
polyols. Molar ratios can vary depending on the alcohol or polyol
used. For example, the condensation product of a hydrocarbyl
substituted succinic anhydride and pentaerythritol is a useful
dispersant.
[0100] Succinate ester amides are formed by condensation reaction
between hydrocarbyl substituted succinic anhydrides and alkanol
amines. For example, suitable alkanol amines include ethoxylated
polyalkylpolyamines, propoxylated polyalkylpolyamines and
polyalkenylpolyamines such as polyethylene polyamines. One example
is propoxylated hexamethylenediamine. Representative examples are
shown in U.S. Pat. No. 4,426,305.
[0101] The molecular weight of the hydrocarbyl substituted succinic
anhydrides used in the preceding paragraphs will typically range
between 800 and 2,500 or more. The above products can be
post-reacted with various reagents such as sulfur, oxygen,
formaldehyde, carboxylic acids such as oleic acid. The above
products can also be post reacted with boron compounds such as
boric acid, borate esters or highly borated dispersants, to form
borated dispersants generally having from about 0.1 to about 5
moles of boron per mole of dispersant reaction product.
[0102] Mannich base dispersants are made from the reaction of
alkylphenols, formaldehyde, and amines. See U.S. Pat. No.
4,767,551, which is incorporated herein by reference. Process aids
and catalysts, such as oleic acid and sulfonic acids, can also be
part of the reaction mixture. Molecular weights of the alkylphenols
range from 800 to 2,500. Representative examples are shown in U.S.
Pat. Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953;
3,798,165; and 3,803,039.
[0103] Typical high molecular weight aliphatic acid modified
Mannich condensation products useful in this disclosure can be
prepared from high molecular weight alkyl-substituted
hydroxyaromatics or HNR.sub.2 group-containing reactants.
[0104] Hydrocarbyl substituted amine ashless dispersant additives
are well known to one skilled in the art; see, for example, U.S.
Pat. Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209,
and 5,084,197.
[0105] Preferred dispersants include borated and non-borated
succinimides, including those derivatives from mono-succinimides,
bis-succinimides, and/or mixtures of mono- and bis-succinimides,
wherein the hydrocarbyl succinimide is derived from a
hydrocarbylene group such as polyisobutylene having a Mn of from
about 500 to about 5000, or from about 1000 to about 3000, or about
1000 to about 2000, or a mixture of such hydrocarbylene groups,
often with high terminal vinylic groups. Other preferred
dispersants include succinic acid-esters and amides,
alkylphenol-polyamine-coupled Mannich adducts, their capped
derivatives, and other related components.
[0106] Polymethacrylate or polyacrylate derivatives are another
class of dispersants. These dispersants are typically prepared by
reacting a nitrogen containing monomer and a methacrylic or acrylic
acid esters containing 5-25 carbon atoms in the ester group.
Representative examples are shown in U.S. Pat. Nos. 2,100,993, and
6,323,164. Polymethacrylate and polyacrylate dispersants are
normally used as multifunctional viscosity modifiers. The lower
molecular weight versions can be used as lubricant dispersants or
fuel detergents.
[0107] Illustrative preferred dispersants useful in this disclosure
include those derived from polyalkenyl-substituted mono- or
dicarboxylic acid, anhydride or ester, which dispersant has a
polyalkenyl moiety with a number average molecular weight of at
least 900 and from greater than 1.3 to 1.7, preferably from greater
than 1.3 to 1.6, most preferably from greater than 1.3 to 1.5,
functional groups (mono- or dicarboxylic acid producing moieties)
per polyalkenyl moiety (a medium functionality dispersant).
Functionality (F) can be determined according to the following
formula:
F=(SAP.times.M.sub.n)/((112,200.times.AI)-(SAP.times.98))
wherein SAP is the saponification number (i.e., the number of
milligrams of KOH consumed in the complete neutralization of the
acid groups in one gram of the succinic-containing reaction
product, as determined according to ASTM D94); M.sub.n is the
number average molecular weight of the starting olefin polymer; and
A.I. is the percent active ingredient of the succinic-containing
reaction product (the remainder being unreacted olefin polymer,
succinic anhydride and diluent).
[0108] The polyalkenyl moiety of the dispersant may have a number
average molecular weight of at least 900, suitably at least 1500,
preferably between 1800 and 3000, such as between 2000 and 2800,
more preferably from about 2100 to 2500, and most preferably from
about 2200 to about 2400. The molecular weight of a dispersant is
generally expressed in terms of the molecular weight of the
polyalkenyl moiety. This is because the precise molecular weight
range of the dispersant depends on numerous parameters including
the type of polymer used to derive the dispersant, the number of
functional groups, and the type of nucleophilic group employed.
[0109] Polymer molecular weight, specifically M.sub.n, can be
determined by various known techniques. One convenient method is
gel permeation chromatography (GPC), which additionally provides
molecular weight distribution information (see W. W. Yau, J. J.
Kirkland and D. D. Bly, "Modern Size Exclusion Liquid
Chromatography", John Wiley and Sons, New York, 1979). Another
useful method for determining molecular weight, particularly for
lower molecular weight polymers, is vapor pressure osmometry (e.g.,
ASTM D3592).
[0110] The polyalkenyl moiety in a dispersant preferably has a
narrow molecular weight distribution (MWD), also referred to as
polydispersity, as determined by the ratio of weight average
molecular weight (Mw) to number average molecular weight (M.sub.n).
Polymers having a Mw/M.sub.n of less than 2.2, preferably less than
2.0, are most desirable. Suitable polymers have a polydispersity of
from about 1.5 to 2.1, preferably from about 1.6 to about 1.8.
[0111] Suitable polyalkenes employed in the formation of the
dispersants include homopolymers, interpolymers or lower molecular
weight hydrocarbons. One family of such polymers comprise polymers
of ethylene and/or at least one C.sub.3 to C.sub.2 alpha-olefin
having the formula H.sub.2C.dbd.CHR.sup.1 wherein R.sup.1 is a
straight or branched chain alkyl radical comprising 1 to 26 carbon
atoms and wherein the polymer contains carbon-to-carbon
unsaturation, and a high degree of terminal ethenylidene
unsaturation. Preferably, such polymers comprise interpolymers of
ethylene and at least one alpha-olefin of the above formula,
wherein R.sup.1 is alkyl of from 1 to 18 carbon atoms, and more
preferably is alkyl of from 1 to 8 carbon atoms, and more
preferably still of from 1 to 2 carbon atoms.
[0112] Another useful class of polymers is polymers prepared by
cationic polymerization of monomers such as isobutene and styrene.
Common polymers from this class include polyisobutenes obtained by
polymerization of a C.sub.4 refinery stream having a butene content
of 35 to 75% by weight, and an isobutene content of 30 to 60% by
weight. A preferred source of monomer for making poly-n-butenes is
petroleum feedstreams such as Raffinate II. These feedstocks are
disclosed in the art such as in U.S. Pat. No. 4,952,739. A
preferred embodiment utilizes polyisobutylene prepared from a pure
isobutylene stream or a Raffinate I stream to prepare reactive
isobutylene polymers with terminal vinylidene olefins.
Polyisobutene polymers that may be employed are generally based on
a polymer chain of from 1500 to 3000.
[0113] The dispersant(s) are preferably non-polymeric (e.g., mono-
or bis-succinimides). Such dispersants can be prepared by
conventional processes such as disclosed in U.S. Patent Application
Publication No. 2008/0020950, the disclosure of which is
incorporated herein by reference.
[0114] The dispersant(s) can be borated by conventional means, as
generally disclosed in U.S. Pat. Nos. 3,087,936, 3,254,025 and
5,430,105.
[0115] Such dispersants may be used in an amount of about 0.01 to
20 weight percent or 0.01 to 10 weight percent, preferably about
0.5 to 8 weight percent, or more preferably 0.5 to 4 weight
percent. Or such dispersants may be used in an amount of about 2 to
12 weight percent, preferably about 4 to 10 weight percent, or more
preferably 6 to 9 weight percent. On an active ingredient basis,
such additives may be used in an amount of about 0.06 to 14 weight
percent, preferably about 0.3 to 6 weight percent. The hydrocarbon
portion of the dispersant atoms can range from C.sub.60 to
C.sub.1000, or from C.sub.70 to C.sub.300, or from C.sub.70 to
C.sub.200. These dispersants may contain both neutral and basic
nitrogen, and mixtures of both. Dispersants can be end-capped by
borates and/or cyclic carbonates. Nitrogen content in the finished
oil can vary from about 200 ppm by weight to about 2000 ppm by
weight, preferably from about 200 ppm by weight to about 1200 ppm
by weight. Basic nitrogen can vary from about 100 ppm by weight to
about 1000 ppm by weight, preferably from about 100 ppm by weight
to about 600 ppm by weight.
[0116] As used herein, the dispersant concentrations are given on
an "as delivered" basis. Typically, the active dispersant is
delivered with a process oil. The "as delivered" dispersant
typically contains from about 20 weight percent to about 80 weight
percent, or from about 40 weight percent to about 60 weight
percent, of active dispersant in the "as delivered" dispersant
product.
Other Detergents
[0117] Illustrative other detergents useful in this disclosure
include, for example, alkali metal detergents, alkaline earth metal
detergents, or mixtures of one or more alkali metal detergents and
one or more alkaline earth metal detergents. A typical detergent is
an anionic material that contains a long chain hydrophobic portion
of the molecule and a smaller anionic or oleophobic hydrophilic
portion of the molecule. The anionic portion of the detergent is
typically derived from an organic acid such as a sulfur-containing
acid, carboxylic acid (e.g., salicylic acid), phosphorus-containing
acid, phenol, or mixtures thereof. The counterion is typically an
alkaline earth or alkali metal. The detergent can be overbased.
[0118] The detergent can be a metal salt of an organic or inorganic
acid, a metal salt of a phenol, or mixtures thereof. The metal can
be an alkali metal, an alkaline earth metal, and mixtures thereof.
The organic or inorganic acid is selected from an aliphatic organic
or inorganic acid, a cycloaliphatic organic or inorganic acid, an
aromatic organic or inorganic acid, and mixtures thereof.
[0119] The metal can be an alkali metal, an alkaline earth metal,
and mixtures thereof. Particularly, the metal can be calcium (Ca),
magnesium (Mg), and mixtures thereof.
[0120] The organic acid or inorganic acid can be a
sulfur-containing acid, a carboxylic acid, a phosphorus-containing
acid, and mixtures thereof.
[0121] In an embodiment, the metal salt of an organic or inorganic
acid or the metal salt of a phenol can be calcium phenate,
magnesium phenate, an overbased detergent, and mixtures
thereof.
[0122] Salts that contain a substantially stochiometric amount of
the metal are described as neutral salts and have a total base
number (TBN, as measured by ASTM D2896) of from 0 to 80. Many
compositions are overbased, containing large amounts of a metal
base that is achieved by reacting an excess of a metal compound (a
metal hydroxide or oxide, for example) with an acidic gas (such as
carbon dioxide). Useful detergents can be neutral, mildly
overbased, or highly overbased. These detergents can be used in
mixtures of neutral, overbased, highly overbased calcium phenates
and/or magnesium phenates. The TBN ranges can vary from low, medium
to high TBN products, including as low as 0 to as high as 600. The
TBN delivered by the detergent is between 1 and 20. The TBN
delivered by the detergent can be between 1 and 12. Mixtures of
low, medium, high TBN can be used, along with mixtures of calcium
and magnesium metal based detergents, and including phenates and
carboxylates. A detergent mixture with a metal ratio of 1, in
conjunction of a detergent with a metal ratio of 2, and as high as
a detergent with a metal ratio of 5, can be used. Borated
detergents can also be used.
[0123] Alkaline earth phenates are another useful class of
detergent. These detergents can be made by reacting alkaline earth
metal hydroxide or oxide (CaO, Ca(OH).sub.2, BaO, Ba(OH).sub.2,
MgO, Mg(OH).sub.2, for example) with an alkyl phenol or sulfurized
alkylphenol. Useful alkyl groups include straight chain or branched
C.sub.1-C.sub.30 alkyl groups, particularly, C.sub.4-C.sub.20 or
mixtures thereof. Examples of suitable phenols include
isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol,
and the like. It should be noted that starting alkylphenols may
contain more than one alkyl substituent that are each independently
straight chain or branched and can be used from 0.5 to 6 weight
percent. When a non-sulfurized alkylphenol is used, the sulfurized
product may be obtained by methods well known in the art. These
methods include heating a mixture of alkylphenol and sulfurizing
agent (including elemental sulfur, sulfur halides such as sulfur
dichloride, and the like) and then reacting the sulfurized phenol
with an alkaline earth metal base.
[0124] Alkaline earth metal phosphates are also used as detergents
and are known in the art.
[0125] Detergents may be simple detergents or what is known as
hybrid or complex detergents. The latter detergents can provide the
properties of two detergents without the need to blend separate
materials. See U.S. Pat. No. 6,034,039.
[0126] Illustrative detergents include calcium phenates, magnesium
phenates, and other related components (including borated
detergents), and mixtures thereof. Illustrative mixtures of
detergents include calcium phenate and magnesium phenate. Overbased
detergents are also used.
[0127] The detergent concentration in the lubricating oils of this
disclosure can range from about 0.5 to about 6.0 weight percent,
preferably about 0.6 to 5.0 weight percent, and more preferably
from about 0.8 weight percent to about 4.0 weight percent, based on
the total weight of the lubricating oil.
[0128] As used herein, the detergent concentrations are given on an
"as delivered" basis. Typically, the active detergent is delivered
with a process oil. The "as delivered" detergent typically contains
from about 20 weight percent to about 100 weight percent, or from
about 40 weight percent to about 60 weight percent, of active
detergent in the "as delivered" detergent product.
Viscosity Modifiers
[0129] Viscosity modifiers (also known as viscosity index improvers
(VI improvers), and viscosity improvers) can be included in the
lubricant compositions of this disclosure.
[0130] Viscosity modifiers provide lubricants with high and low
temperature operability. These additives impart shear stability at
elevated temperatures and acceptable viscosity at low
temperatures.
[0131] Suitable viscosity modifiers include high molecular weight
hydrocarbons, polyesters and viscosity modifier dispersants that
function as both a viscosity modifier and a dispersant. Typical
molecular weights of these polymers are between about 10,000 to
1,500,000, more typically about 20,000 to 1,200,000, and even more
typically between about 50,000 and 1,000,000.
[0132] Examples of suitable viscosity modifiers are linear or
star-shaped polymers and copolymers of methacrylate, butadiene,
olefins, or alkylated styrenes. Polyisobutylene is a commonly used
viscosity modifier. Another suitable viscosity modifier is
polymethacrylate (copolymers of various chain length alkyl
methacrylates, for example), some formulations of which also serve
as pour point depressants. Other suitable viscosity modifiers
include copolymers of ethylene and propylene, hydrogenated block
copolymers of styrene and isoprene, and polyacrylates (copolymers
of various chain length acrylates, for example). Specific examples
include styrene-isoprene or styrene-butadiene based polymers of
50,000 to 200,000 molecular weight.
[0133] Olefin copolymers are commercially available from Chevron
Oronite Company LLC under the trade designation "PARATONE.RTM."
(such as "PARATONE.RTM. 8921" and "PARATONE.RTM. 8941"); from Afton
Chemical Corporation under the trade designation "HiTEC.RTM." (such
as "HiTEC.RTM. 5850B"; and from The Lubrizol Corporation under the
trade designation "Lubrizol.RTM. 7067C". Hydrogenated polyisoprene
star polymers are commercially available from Infineum
International Limited, e.g., under the trade designation "SV200"
and "SV600". Hydrogenated diene-styrene block copolymers are
commercially available from Infineum International Limited, e.g.,
under the trade designation "SV 50".
[0134] The polymethacrylate or polyacrylate polymers can be linear
polymers which are available from Evnoik Industries under the trade
designation "Viscoplex.RTM." (e.g., Viscoplex 6-954) or star
polymers which are available from Lubrizol Corporation under the
trade designation Asteric.TM. (e.g., Lubrizol 87708 and Lubrizol
87725).
[0135] Illustrative vinyl aromatic-containing polymers useful in
this disclosure may be derived predominantly from vinyl aromatic
hydrocarbon monomer. Illustrative vinyl aromatic-containing
copolymers useful in this disclosure may be represented by the
following general formula:
A-B
wherein A is a polymeric block derived predominantly from vinyl
aromatic hydrocarbon monomer, and B is a polymeric block derived
predominantly from conjugated diene monomer.
[0136] In an embodiment of this disclosure, the viscosity modifiers
may be used in an amount of less than about 10 weight percent,
preferably less than about 7 weight percent, more preferably less
than about 4 weight percent, and in certain instances, may be used
at less than 2 weight percent, preferably less than about 1 weight
percent, and more preferably less than about 0.5 weight percent,
based on the total weight of the formulated oil or lubricating
engine oil. Viscosity modifiers are typically added as
concentrates, in large amounts of diluent oil.
[0137] As used herein, the viscosity modifier concentrations are
given on an "as delivered" basis. Typically, the active polymer is
delivered with a diluent oil. The "as delivered" viscosity modifier
typically contains from 20 weight percent to 75 weight percent of
an active polymer for polymethacrylate or polyacrylate polymers, or
from 8 weight percent to 20 weight percent of an active polymer for
olefin copolymers, hydrogenated polyisoprene star polymers, or
hydrogenated diene-styrene block copolymers, in the "as delivered"
polymer concentrate.
Antioxidants
[0138] Antioxidants retard the oxidative degradation of base oils
during service. Such degradation may result in deposits on metal
surfaces, the presence of sludge, or a viscosity increase in the
lubricant. One skilled in the art knows a wide variety of oxidation
inhibitors that are useful in lubricating oil compositions. See,
Klamann in Lubricants and Related Products, op cite, and U.S. Pat.
Nos. 4,798,684 and 5,084,197, for example.
[0139] Useful antioxidants include hindered phenols. These phenolic
antioxidants may be ashless (metal-free) phenolic compounds or
neutral or basic metal salts of certain phenolic compounds. Typical
phenolic antioxidant compounds are the hindered phenolics which are
the ones which contain a sterically hindered hydroxyl group, and
these include those derivatives of dihydroxy aryl compounds in
which the hydroxyl groups are in the o- or p-position to each
other. Typical phenolic antioxidants include the hindered phenols
substituted with C.sub.6+ alkyl groups and the alkylene coupled
derivatives of these hindered phenols. Examples of phenolic
materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl
phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol;
2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl
phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful
hindered mono-phenolic antioxidants may include for example
hindered 2,6-di-alkyl-phenolic proprionic ester derivatives.
Bis-phenolic antioxidants may also be advantageously used in
combination with the instant disclosure. Examples of ortho-coupled
phenols include: 2,2'-bis(4-heptyl-6-t-butyl-phenol);
2,2'-bis(4-octyl-6-t-butyl-phenol); and
2,2'-bis(4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols
include for example 4,4'-bis(2,6-di-t-butyl phenol) and
4,4'-methylene-bis(2,6-di-t-butyl phenol).
[0140] Effective amounts of one or more catalytic antioxidants may
also be used. The catalytic antioxidants comprise an effective
amount of a) one or more oil soluble polymetal organic compounds;
and, effective amounts of b) one or more substituted
N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered
phenol compounds; or a combination of both b) and c). Catalytic
antioxidants are more fully described in U.S. Pat. No. 8,048,833,
herein incorporated by reference in its entirety.
[0141] Non-phenolic oxidation inhibitors which may be used include
aromatic amine antioxidants and these may be used either as such or
in combination with phenolics. Typical examples of non-phenolic
antioxidants include: alkylated and non-alkylated aromatic amines
such as aromatic monoamines of the formula R.sup.8R.sup.9R.sup.10N
where R.sup.8 is an aliphatic, aromatic or substituted aromatic
group, R.sup.9 is an aromatic or a substituted aromatic group, and
R.sup.10 is H, alkyl, aryl or R.sup.11S(O).sub.xR.sup.12 where
R.sup.11 is an alkylene, alkenylene, or aralkylene group, R.sup.12
is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and
x is 0, 1 or 2. The aliphatic group R.sup.8 may contain from 1 to
about 20 carbon atoms, and preferably contains from about 6 to 12
carbon atoms. The aliphatic group is a saturated aliphatic group.
Preferably, both R.sup.8 and R.sup.9 are aromatic or substituted
aromatic groups, and the aromatic group may be a fused ring
aromatic group such as naphthyl. Aromatic groups R.sup.8 and
R.sup.9 may be joined together with other groups such as S.
[0142] Typical aromatic amines antioxidants have alkyl substituent
groups of at least about 6 carbon atoms. Examples of aliphatic
groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally,
the aliphatic groups will not contain more than about 14 carbon
atoms. The general types of amine antioxidants useful in the
present compositions include diphenylamines, phenyl naphthylamines,
phenothiazines, imidodibenzyls and diphenyl phenylene diamines.
Mixtures of two or more aromatic amines are also useful. Polymeric
amine antioxidants can also be used. Particular examples of
aromatic amine antioxidants useful in the present disclosure
include: p,p'-dioctyldiphenylamine;
t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and
p-octylphenyl-alpha-naphthylamine.
[0143] Sulfurized alkyl phenols and alkali or alkaline earth metal
salts thereof also are useful antioxidants.
[0144] Preferred antioxidants include hindered phenols, arylamines.
These antioxidants may be used individually by type or in
combination with one another. Such additives may be used in an
amount of about 0.01 to 5 weight percent, preferably about 0.01 to
1.5 weight percent, more preferably zero to less than 1.5 weight
percent, more preferably zero to less than 1 weight percent.
Pour Point Depressants (PPDs)
[0145] Conventional pour point depressants (also known as lube oil
flow improvers) may be added to the compositions of the present
disclosure if desired. These pour point depressant may be added to
lubricating compositions of the present disclosure to lower the
minimum temperature at which the fluid will flow or can be poured.
Examples of suitable pour point depressants include
polymethacrylates, polyacrylates, polyarylamides, condensation
products of haloparaffin waxes and aromatic compounds, vinyl
carboxylate polymers, and terpolymers of dialkylfumarates, vinyl
esters of fatty acids and allyl vinyl ethers. U.S. Pat. Nos.
1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479; 2,666,746;
2,721,877; 2,721,878; and 3,250,715 describe useful pour point
depressants and/or the preparation thereof. Such additives may be
used in an amount of about 0.01 to 5 weight percent, preferably
about 0.01 to 1.5 weight percent.
Seal Compatibility Agents
[0146] Seal compatibility agents help to swell elastomeric seals by
causing a chemical reaction in the fluid or physical change in the
elastomer. Suitable seal compatibility agents for lubricating oils
include organic phosphates, aromatic esters, aromatic hydrocarbons,
esters (butylbenzyl phthalate, for example), and polybutenyl
succinic anhydride. Such additives may be used in an amount of
about 0.01 to 3 weight percent, preferably about 0.01 to 2 weight
percent.
Antifoam Agents
[0147] Anti-foam agents may advantageously be added to lubricant
compositions. These agents retard the formation of stable foams.
Silicones and organic polymers are typical anti-foam agents. For
example, polysiloxanes, such as silicon oil or polydimethyl
siloxane, provide antifoam properties. Anti-foam agents are
commercially available and may be used in conventional minor
amounts along with other additives such as demulsifiers; usually
the amount of these additives combined is less than 1 weight
percent and often less than 0.1 weight percent.
Inhibitors and Antirust Additives
[0148] Antirust additives (or corrosion inhibitors) are additives
that protect lubricated metal surfaces against chemical attack by
water or other contaminants. A wide variety of these are
commercially available.
[0149] One type of antirust additive is a polar compound that wets
the metal surface preferentially, protecting it with a film of oil.
Another type of antirust additive absorbs water by incorporating it
in a water-in-oil emulsion so that only the oil touches the metal
surface. Yet another type of antirust additive chemically adheres
to the metal to produce a non-reactive surface. Examples of
suitable additives include zinc dithiophosphates, metal phenolates,
basic metal sulfonates, fatty acids and amines. Such additives may
be used in an amount of about 0.01 to 5 weight percent, preferably
about 0.01 to 1.5 weight percent.
Friction Modifiers
[0150] A friction modifier is any material or materials that can
alter the coefficient of friction of a surface lubricated by any
lubricant or fluid containing such material(s). Friction modifiers,
also known as friction reducers, or lubricity agents or oiliness
agents, and other such agents that change the ability of base oils,
formulated lubricant compositions, or functional fluids, to modify
the coefficient of friction of a lubricated surface may be
effectively used in combination with the base oils or lubricant
compositions of the present disclosure if desired. Friction
modifiers that lower the coefficient of friction are particularly
advantageous in combination with the base oils and lube
compositions of this disclosure.
[0151] Illustrative friction modifiers may include, for example,
organometallic compounds or materials, or mixtures thereof.
Illustrative organometallic friction modifiers useful in the
lubricating engine oil formulations of this disclosure include, for
example, molybdenum amine, molybdenum diamine, an
organotungstenate, a molybdenum dithiocarbamate, molybdenum
dithiophosphates, molybdenum amine complexes, molybdenum
carboxylates, and the like, and mixtures thereof. Similar tungsten
based compounds may be preferable.
[0152] Other illustrative friction modifiers useful in the
lubricating engine oil formulations of this disclosure include, for
example, alkoxylated fatty acid esters, alkanolamides, polyol fatty
acid esters, borated glycerol fatty acid esters, fatty alcohol
ethers, and mixtures thereof.
[0153] Illustrative alkoxylated fatty acid esters include, for
example, polyoxyethylene stearate, fatty acid polyglycol ester, and
the like. These can include polyoxypropylene stearate,
polyoxybutylene stearate, polyoxyethylene isosterate,
polyoxypropylene isostearate, polyoxyethylene palmitate, and the
like.
[0154] Illustrative alkanolamides include, for example, lauric acid
diethylalkanolamide, palmic acid diethylalkanolamide, and the like.
These can include oleic acid diethyalkanolamide, stearic acid
diethylalkanolamide, oleic acid diethylalkanolamide,
polyethoxylated hydrocarbylamides, polypropoxylated
hydrocarbylamides, and the like.
[0155] Illustrative polyol fatty acid esters include, for example,
glycerol mono-oleate, saturated mono-, di-, and tri-glyceride
esters, glycerol mono-stearate, and the like. These can include
polyol esters, hydroxyl-containing polyol esters, and the like.
[0156] Illustrative borated glycerol fatty acid esters include, for
example, borated glycerol mono-oleate, borated saturated mono-,
di-, and tri-glyceride esters, borated glycerol mono-sterate, and
the like. In addition to glycerol polyols, these can include
trimethylolpropane, pentaerythritol, sorbitan, and the like. These
esters can be polyol monocarboxylate esters, polyol dicarboxylate
esters, and on occasion polyoltricarboxylate esters. Preferred can
be the glycerol mono-oleates, glycerol dioleates, glycerol
trioleates, glycerol monostearates, glycerol distearates, and
glycerol tristearates and the corresponding glycerol
monopalmitates, glycerol dipalmitates, and glycerol tripalmitates,
and the respective isostearates, linoleates, and the like. On
occasion the glycerol esters can be preferred as well as mixtures
containing any of these. Ethoxylated, propoxylated, butoxylated
fatty acid esters of polyols, especially using glycerol as
underlying polyol can be preferred.
[0157] Illustrative fatty alcohol ethers include, for example,
stearyl ether, myristyl ether, and the like. Alcohols, including
those that have carbon numbers from C.sub.3 to C.sub.50, can be
ethoxylated, propoxylated, or butoxylated to form the corresponding
fatty alkyl ethers. The underlying alcohol portion can preferably
be stearyl, myristyl, C.sub.11-C.sub.13 hydrocarbon, oleyl,
isosteryl, and the like.
[0158] The lubricating oils of this disclosure exhibit desired
properties, e.g., wear control, in the presence or absence of a
friction modifier.
[0159] Useful concentrations of friction modifiers may range from
0.01 weight percent to 5 weight percent, or about 0.1 weight
percent to about 2.5 weight percent, or about 0.1 weight percent to
about 1.5 weight percent, or about 0.1 weight percent to about 1
weight percent. Concentrations of molybdenum-containing materials
are often described in terms of Mo metal concentration.
Advantageous concentrations of Mo may range from 25 ppm to 700 ppm
or more, and often with a preferred range of 50-200 ppm. Friction
modifiers of all types may be used alone or in mixtures with the
materials of this disclosure. Often mixtures of two or more
friction modifiers, or mixtures of friction modifier(s) with
alternate surface active material(s), are also desirable.
[0160] When lubricating oil compositions contain one or more of the
additives discussed above, the additive(s) are blended into the
composition in an amount sufficient for it to perform its intended
function. Typical amounts of such additives useful in the present
disclosure are shown in Table 1 below.
[0161] It is noted that many of the additives are shipped from the
additive manufacturer as a concentrate, containing one or more
additives together, with a certain amount of base oil diluents.
Accordingly, the weight amounts in the table below, as well as
other amounts mentioned herein, are directed to the amount of
active ingredient (that is the non-diluent portion of the
ingredient). The weight percent (wt. %) indicated below is based on
the total weight of the lubricating oil composition.
TABLE-US-00002 TABLE 1 Typical Amounts of Other Lubricating Oil
Components Approximate Approximate Wt. % Wt. % Compound (Useful)
(Preferred) Dispersant 0.1-20 0.1-8 Detergent 0.1-20 0.1-8 Friction
Modifier 0.01-5 0.01-1.5 Antioxidant 0.1-5 0.1-1.5 Pour Point
Depressant 0.0-5 0.01-1.5 (PPD) Anti-foam Agent 0.001-3 0.001-0.15
Viscosity Modifier (solid 0.1-2 0.1-1 polymer basis) Antiwear 0.2-3
0.5-1 Inhibitor and Antirust 0.01-5 0.01-1.5
[0162] The foregoing additives are all commercially available
materials. These additives may be added independently but are
usually precombined in packages which can be obtained from
suppliers of lubricant oil additives. Additive packages with a
variety of ingredients, proportions and characteristics are
available and selection of the appropriate package will take the
requisite use of the ultimate composition into account.
[0163] The following non-limiting examples are provided to
illustrate the disclosure.
EXAMPLES
[0164] Formulations were prepared as described herein. All of the
ingredients used herein are commercially available. PCMO (passenger
car motor oil) formulations were prepared as described herein.
[0165] The lubricating oil base stocks used in the formulations
were Group III-V base oils, including ester base stocks and
alkylated naphthalene base stocks.
[0166] The detergents used in the formulations were alkaline earth
metal salicylates, alkaline earth metal sulfonates, and mixtures
thereof.
[0167] The additive package used in the formulations included
conventional additives in conventional amounts. Conventional
additives used in the formulations were one or more of an
antioxidant, dispersant, pour point depressant, corrosion
inhibitor, metal deactivator, seal compatibility additive,
anti-foam agent, inhibitor, anti-rust additive, optional friction
modifier, optional antiwear additive, and other optional lubricant
performances additives.
[0168] Formulation strategies were identified which protect against
wear in the FCW test, as identified by demonstrating fast rates of
tribofilm formation. The FCW test is a new test in the ILSAC GF-6
specification. It tests soot-induced wear, which is a new
performance attribute for the North American specification. In the
FCW test, elongation of the timing chain due to wear of chain link
pins is the rated parameter. While no limits have been formally set
for the FCW test at the current stage of development, for purposes
of this disclosure, low wear samples exhibit less than 0.07% chain
elongation, which is a conservative estimate of the expected test
limits. In previous generations of ILSAC GF-X categories, only
valvetrain wear performance was tested. The valvetrain wear test
introduced with ILSAC GF-6 is the Sequence IVB wear test.
[0169] Various engine oil formulations were tested in both the FCW
and IVB tests, to determine if effective formulation strategies for
wear reduction were common between both tests. In fact, there were
significant differences between the performance levels of the
formulations in each test, and in several cases, highly effective
valvetrain-wear protecting formulations did not provide adequate
protection in the FCW test (see Table 2 below). This demonstrates
the difference in wear mechanisms between the two tests, and
emphasizes the necessity within the industry for determining how to
prevent soot-induced wear, since well-understood methods of
providing protection in valvetrain wear tests is not
sufficient.
[0170] A FCW test conducted in accordance with ILSAC GF-6
specification was used for measuring wear. Additionally, a Sequence
IVB test in accordance with ILSAC GF-6 specification was used for
measuring wear. Table 2 shows wear performance comparison of
example Use a superscript 3 formulations in both the FCW and
Sequence IVB tests.
TABLE-US-00003 TABLE 2 FCW timing chain Seq. IVB Intake Lifters
elongation Avg Volume Loss (.mu.m3) Formulation 1 0.041 1.56 Low
Wear High Wear Formulation 2 0.065 1.24 Low Wear Borderline Wear
Formulation 3 0.062 1.42 Low Wear High Wear Formulation 4 0.043
1.15 Low Wear Borderline Wear
[0171] For purposes of this disclosure, the FCW test is a fired
engine dynamometer test which uses a 2.0 L Ford Ecotech spark
ignition, four stroke, in-line 4-cylinder gasoline turbocharged
direct injection (GTDI) engine as the test apparatus. The engine
uses a dual overhead cam, four valves per cylinder (2 intake; 2
exhaust), and direct acting mechanical bucket lifter valve train
design. The engine uses a timing chain, and timing chain elongation
is reported as the pass/fail parameter. A new timing chain is first
measured after a short break-in cycle in the test lubricant. The
test sequence is performed, and a final timing chain measurement is
taken and compared against the initial measurement to calculate
timing chain elongation. The test sequence is comprised of repeated
test cycles. A test cycle is comprised of two stages and two
ramping periods as shown, totaling four hours of test time. The
test cycle is repeated 54 times for a total test length of 216
hours. Engine operating conditions for the two stages that make up
a test cycle are described below.
TABLE-US-00004 Stage Time (min) Stage 1 120 Ramp 1-2 30 Stage 2 60
Ramp 2-1 30
TABLE-US-00005 Parameter Units Stage 1 Stage 2 Duration min 120 60
Engine Speed rpm 1550 .+-. 5 2500 .+-. 5 Torque NtM 50 .+-. 2 128
.+-. 2 Oil Gallery Temperature .degree. C. 50 .+-. 0.5 100 .+-. 0.5
Coolant Out Temperature .degree. C. 45 .+-. 0.5 85 .+-. 0.5 Coolant
Flow L/min 40 .+-. 2 70 .+-. 2 Inlet Air Pressure kPa 0.05 .+-.
0.02 Coolant Pressure kPa 70 .+-. 2 Inlet Air Temperature .degree.
C. 32 .+-. 0.5 Exhaust Back Pressure kPa 104 .+-. 2 107 .+-. 2 Air
Charge Temperature .degree. C. 30 .+-. 0.5 AFR Lambda 0.78 .+-.
0.05 1 .+-. 0.05 Blowby Outlet Temperature .degree. C. 23 .+-. 2 78
.+-. 2 Humidity g/kg 11.4 .+-. 1.0 Blowby L/min n/a 65-75
[0172] In the FCW test, elongation of the timing chain due to wear
of chain link pins is the rated parameter. While no limits have
been formally set for the FCW test at the current stage of
development, for purposes of this disclosure, low wear samples
exhibit less than 0.07% chain elongation, which is a conservative
estimate of the expected test limits.
[0173] For purposes of this disclosure, the Sequence IVB engine
valve train wear test is a fired engine dynamometer lubricant test
which evaluates the ability of a test lubricant to reduce valve
train wear. The test method is a low temperature cyclic test, with
a total running duration of 200 hours.
[0174] The Sequence IVB uses a Toyota 2NR-FE water cooled, 4 cycle,
in-line cylinder, 1.5 liter engine as the test apparatus. The
engine incorporates a dual overhead cam, four valves per cylinder
(2 intake; 2 exhaust), and direct acting mechanical bucket lifter
valve train design. The critical test parts (camshafts, direct
acting mechanical bucket lifters) are replaced each test. A 95
minute run-in schedule, followed by a 100 hour aging schedule, for
silicon (Si) pacification, is conducted whenever the long block or
cylinder head are replaced with new components.
[0175] The Sequence IVB valve train wear test is a flush and run
type of lubricant test with one 6 minute engine oil system flush
and three 38 minute engine oil system flushes conducted prior to
the actual test start. The test sequence is repeated for 24,000
test cycles. Each cycle consists of four stages as outlined
below.
TABLE-US-00006 Ramp to Ramp to Parameter Units Stage 1 Stage 1
Stage 2 Stage 2 Duration sec 8 7 8 7 Engine Speed r/min 4300 to 800
800 to 4300 800 4300 Engine Torque N m 25 25 25 25 Oil Gallery
Temperature .degree. C. 55 to 53 53 53 to 55 55 Coolant In
Temperature .degree. C. 49 49 49 49 Intake Air Temperature .degree.
C. 32 32 32 32 Intake Air Pressure kPa 0.07 0.07 0.07 0.07 Intake
Air Humidity g/kg 11.5 11.5 11.5 11.5 Exhaust Back Pressure kPa-abs
104.5 to 103.5 103.5 to 104.5 103.5 104.5 Differential Coolant
.degree. C. 5 to 2 2 2 to 5 5 Temperature Rocker Cover Coolant
.degree. C. 20 20 20 20 Outlet Temperature
[0176] Both the FCW test and the Sequence IVB test are part of the
draft ILSAC GF-6 specification, in particular, the draft ILSAC
GF-6A Recommendations for Passenger Car Engine Oils dated May 11,
2017, and the draft ILSAC GF-6B Recommendations for Passenger Car
Engine Oils dated May 11, 2016, all of which are incorporated
herein by reference in their entirety.
[0177] A strong correlation was found between wear performance in
the FCW test and fast tribofilm growth rate. In accordance with
this disclosure, growth rate of the tribofilm is defined in two
ways: (1) # of Stribeck passes to tribofilm saturation in an MTM
Stribeck measurement, S.sub.N, and (2) time to 95% of tribofilm
friction saturation in HFRR measurements, t.sub.95,sat. Conditions
for the MTM Stribeck test are set forth in Table 3 below.
Conditions for the HFRR test are set forth in Table 4 below.
[0178] An integrated MTM friction in Stribeck mode at 140.degree.
C., was used to determine growth rate of tribofilms. The number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s was achieved, which correlates to onset of the tribofilm
formation on the steel surface, was measured to determine growth
rate of the tribofilms. The MTM testing conditions are set forth in
Table 3 below.
TABLE-US-00007 TABLE 3 Test type Ball-on-disk, mini-traction
machine Test description MTM Stribeck Ball/disk motion Co-motion
Ball material/radius AISI 52100/<0.02 .mu.m/19.05 mm Disk
material/diameter AISI 52100/<0.01 .mu.m/46 mm Bath temperature
100.degree. C. Ball speed 5-5000 mm/s Slide to roll (SRR) ratio 50%
Ball Load 1 GPa # of Passes 10 passes
[0179] MTM experiments were run under Stribeck conditions (Table
3), in which a single slide-to-roll ratio is maintained while
sweeping through various ball speeds and consequently different
lubrication regimes. The Stribeck sweeps are repeated 10 times in
order to track the evolution of film formation. Film formation is
evidenced by increasing traction coefficient at the same rolling
speed, as measured in the MTM Stribeck experiment as a function of
the number of Stribeck passes. It is believed that the lubrication
conditions that contribute to wear of the timing chain are in the
boundary layer/mixed regime, at low speeds. Thus, the traction
coefficient measured at rolling speeds of 10 mm/s is most relevant
to the conditions contributing to wear in the FCW test. To evaluate
speed of tribofilm formation, we evaluate the number of Stribeck
passes, S.sub.N, until there is an observable increase in traction
coefficient at 10 mm/s which correlates to the onset of tribofilm
formation.
[0180] A tribometer, a HFRR, was used for measuring wear. Test
configuration was an oscillating ball-on-disk, with an applied load
and heating, and with ball and disk hardware immersed in oil.
Friction was measured with a load cell, and film thickness between
the rubbing surfaces of the ball and disk were measured
electrically.
[0181] Wear performance was evaluated as described above using a
HFRR test. The HFRR is commercially available from PCS Industries.
The test equipment and procedure are similar to the ASTM D6079
method. The HFRR test conditions were as follows: temperature
100.degree. C.; test duration 2 hours; stroke length 1 mm;
frequency 10 Hz; and load 400 grams. Wear was measured on the disk.
The ball is 6 mm diameter ANSI E-52100 steel, Rockwell C hardness
of 58-66. The disc is AISI E-52100 steel, Vickers HV30 hardness of
.about.200.
[0182] Friction and percent film thickness were measured in
real-time during the test. At the end of each test, the disk was
removed and wear depth was measured. A mechanical stylus profile
was used to measure the depth of the wear scar along three lines
perpendicular to the long axis of the wear scar at three positions
along the length of the scar. Wear performance was represented as
the depth of the scars at the deepest point along these three
lines. The time for the tribofilm to reach 95% of its saturation
coverage (t.sub.95,sat) on the steel surface was determined by the
HFRR test in accordance with a modified version of ASTM D6079. The
HFRR testing conditions are set forth in Table 4 below.
TABLE-US-00008 TABLE 4 Test type High-frequency reciprocating rig
Ball/disk motion Reciprocating Ball material/roughness/diameter
AISI 52100/<0.05 .mu.m/6.0 mm Disk material/roughness/diameter
AISI 52100/<0.02 .mu.m/10.0 mm Bath temperature 100.degree. C.
Reciprocating Frequency 10 Hz Path Length 1 mm Ball Load 400 g
Length 2.25 h Data output interval 1 s
[0183] In HFRR tests (Table 4), tribofilm coverage can be directly
observed via electrical by observing the tribofilm coverage as a
function of time. Running the HFRR test for 2.25 hour provides
enough time for the tribofilm to saturate in all cases (constant %
coverage as rate of formation balances rate of loss). For some
chemistries, the evolution of the tribofilm is a two-step process,
with an initial film growth followed by a reduction in the film
coverage signal, and then growth of a secondary film chemistry. It
is believed that it is the formation of this early (initial) film
growth that is responsible for instantaneous coverage/fast
replenishment of tribofilms, thus the saturation of this first film
signal is considered for t.sub.95,sat when it is present. To
account for slight oscillations in tribofilm thickness in the
saturation region, for evaluation of tribofilm-formation speed, the
time it takes for the tribofilm to reach 95% of its saturation
coverage, t.sub.95,sat, is used as the measured parameter.
[0184] Formulations were prepared by blending at least detergent,
into a base stock and/or a co-base stock. The additives were made
with several compositions using similar synthetic conditions: The
formulations are set forth in FIGS. 1, 2, 5, 6, 7, 8 and 9.
[0185] The lubricant compositions in FIGS. 1 and 2 were tested in
the FCW test. The number of Stribeck passes to tribofilm saturation
in an MTM Stribeck measurement, S.sub.N, was measured. The time to
95% of tribofilm friction saturation in HFRR measurements,
t.sub.95,sat. was also measured. Inventive Examples (FIG. 1) are
those in which timing chain stretch is less than 0.07%, and
Comparative Examples (FIG. 2) are those formulations for which the
timing chain stretch is greater than 0.07%.
[0186] The data from FIGS. 1 and 2 is plotted in FIG. 3 to
emphasize the correlation between lower S.sub.N and t.sub.95,sat,
and lower timing chain elongation in the FCW test. These results
show that adequate wear protection in the FCW test (<0.07%
timing chain elongation) can be achieved by guaranteeing
fast-forming tribofilms which exhibit t.sub.95,sat less than or
equal to 50 minutes, and that this is also often correlated with an
S.sub.N of 2. FIG. 3 shows a plot of timing chain elongation in the
FCW test as a function of S.sub.N and t.sub.95,sat. Low-wear timing
chain elongation limit is marked on the horizontal axis, and
threshold value for t.sub.95,sat corresponding to low-wear oils is
marked on the vertical axis.
[0187] The correlation observed between low-wear FCW test
formulations and those exhibiting fast tribofilm formation in
tribological testing validates the use of the bench test to screen
for low-wear, fast tribofilm-forming lubricant formulations by
determining S.sub.N and t.sub.95,sat. A summary of the formulation
space which meets the requirement for low-wear FCW candidates is
provided in FIG. 4. Low-wear formulations are those which exhibit
t.sub.95,sat less than 50 minutes, high-wear formulations are those
which exhibit t.sub.95,sat greater than 50 minutes, and borderline
formulations are those which exhibit t.sub.95,sat equal to 50
minutes. FIG. 4 shows a summary of low-wear, high-wear, and
borderline FCW formulations based on S.sub.N and t.sub.95,sat.
[0188] The formulation ranges which serve as Inventive Examples for
the fast tribofilm-forming strategy include those with low
detergent soap content. This is a very surprising result in light
of the role of detergent soap in preventing aggregation of solids
and cleaning surfaces, such as to prevent soot-induced abrasion and
deposition of polar species like soot on surfaces. In the case of
the FCW test, it is the unique ability of an oil to form tribofilms
at a fast rate, as measured in HFRR, which is important for
preventing wear.
[0189] The detergent composition is a key lever for controlling the
speed of tribofilm formation. Formulations were developed in which
the ratio of salicylate to sulfonate detergent soap content was
varied from 0%-100% sulfonate soap, keeping metals constant at 0.2
weight percent (0.12 weight percent Ca and 0.08 weight percent Mg)
where possible. 5% alkylate naphthalene (AN) was used as the Group
V base stock. Comparisons were made at five different soap levels:
0.4 weight percent, 0.6 weight percent, 0.7 weight percent, 0.84
weight percent, and 1.3 weight percent total of formulation. FCW
timing chain elongation data was generated.
[0190] A comparison of S.sub.N and t.sub.95,sat of 0.6 weight
percent soap samples is presented in FIG. 5. In all cases, ranging
from all-salicylate formulations to all-sulfonate formulations,
t.sub.95,sat is less than 50 (Inventive Examples 2-6). S.sub.N
equals 2 for all samples in FIG. 2 except for the 75% salicylate
case, again corresponding to the definition of a low-wear FCW oil.
It is unclear why the 75% salicylate sample showed slower film
growth in MTM, but the reciprocating wear contact associated with
the true FCW test wear mechanism means that the values for
t.sub.95,sat are likely more representative over an extended data
set than S.sub.N.
[0191] With a t.sub.95,sat equal to 50 minutes, the 75% salicylate
soap formulation is a fast-forming, low-wear formulation. The
consistency of fast tribofilm-formation speed for all samples shown
in FIG. 2 demonstrates that ensuring low total soap content of
0.6%, utilizing any combination of high or low-TBN, Ca- or Mg-,
salicylate or sulfonate detergents, will result in a low-wear,
fast-forming tribofilm. It is expected that the relationship
between soap and antiwear film generation is the competitive
adsorption of soap molecules to the polar steel surface with other
antiwear agents. With this understanding, therefore, formulations
containing fewer soap molecules (lower total soap content) would
form as quickly or quicker than formulations at 0.6 weight percent
soap. Therefore, any formulations with total soap content less than
or equal to 0.6 weight percent will be fast tribofilm-formers. FIG.
5 shows S.sub.N and t.sub.95,sat for low-soap samples varying ratio
of sulfonate to salicylate soap, at 0.6 weight percent soap and
constant detergent metals composition.
[0192] This conclusion is verified by comparing of S.sub.N and
t.sub.95,sat for samples with even lower soap (0.4 weight percent),
and varying ratio of sulfonate to salicylate soap in FIG. 6. Total
detergent ash content was dropped and the ratio of calcium to
magnesium was increased in order to achieve low soap content with
available componentry (i.e., only high TBN Mg sulfonate detergents
available). At this extremely low soap content, 100% sulfonate, 0%
sulfonate, and 50% sulfonate samples exhibited t.sub.95,sat less
than or equal to 50 and S.sub.N of 2 or 3 (see Inventive Examples
7-9).
[0193] To further demonstrate that detergent ash content and type
are not primary drivers in determining fast film-forming ability,
the metals composition of the 50% sulfonate sample was formulated
with all-Ca detergents and higher total metals content. Fast
tribofilm formation was still confirmed for this all-Ca 50%
sulfonate sample, as ensured by the low soap content of the sample.
FIG. 6 shows S.sub.N and t.sub.95,sat for low-soap samples varying
ratio of sulfonate to salicylate soap, at 0.4 weight percent
soap.
[0194] FIGS. 7 and 8 compare formulations at equal soap content and
detergent metals with ratios of sulfonate to salicylate detergent
soap ranging from 0%-100%, but with intermediate total detergent
soap contents of 0.7 weight percent and 0.8 weight percent,
respectively. 5% AN was again used as Group V base stock. Tribofilm
formation behavior at even intermediate soap levels is observed to
be significantly different from that of low soap samples. Though
the MTM response, S.sub.N, shows an increase from 2 to 4 passes
required for tribofilm formation at 0.7 weight percent soap, this
slowing effect is not observed in HFRR measurements which are more
characteristic of the actual FCW wear mechanism. Samples at 0%,
50%, and 100% sulfonate soap (Inventive Examples 10-12) all show
t.sub.95,sat less than 50 at this intermediate soap level. However,
increasing the soap content just 0.1 weight percent to 0.8 weight
percent total soap changes tribofilm formation behavior at
increased levels of salicylate soap. The 100% sulfonate detergent
sample, Inventive Example 15, is clearly a low-wear formulation
with S.sub.N equal to 2 and t.sub.95,sat less than 50 min. The 75%
and 50% sulfonate soap formulations began forming tribofilms at the
3.sup.rd MTM pass and have t.sub.95,sat about 50 min.
[0195] Again, as the reciprocating wear contact in the FCW test is
best represented by HFRR as opposed to MTM, these borderline values
would be expected sufficient to give a low-wear FCW oil, despite
taking an extra pass in MTM Stribeck to form. On the other hand,
Comparative Examples F and G at 100% and 75% salicylate detergent,
respectively, result in higher S.sub.N and t.sub.95,sat than what
is required for adequate wear protection in the FCW test. These
results suggest that for formulations with less than or equal to
0.7 weight percent total soap, fast-forming tribofilms sufficient
to protect against wear in the FCW test will be obtained with any
ratio of sulfonate to salicylate soap. Above 0.7 weight percent
total soap, fast tribofilm-forming behavior is dependent on the
ratio of sulfonate to salicylate soap.
[0196] FIG. 7 shows S.sub.N and t.sub.95,sat for low-soap samples
varying ratio of sulfonate to salicylate soap, at 0.7 weight
percent soap and constant detergent metals composition. FIG. 8
shows S.sub.N and t.sub.95,sat for low-soap samples varying ratio
of sulfonate to salicylate soap, at 0.8 weight percent soap and
constant detergent metals composition.
[0197] To explore the behavior of tribofilm formation speed at
greater than 0.8 weight percent, tribological testing was performed
on samples with varying ratios of soap type and constant detergent
metals at very high soap content of 1.3 weight percent. S.sub.N and
t.sub.95,sat for samples prepared at 0%, 50%, and 100% sulfonate
soap at high total soap content are presented in FIG. 9.
Surprisingly, even with a 60% increase in the overall soap content,
the tribofilm formation speed behavior is similar to that observed
for 0.8 weight percent soap samples. At 0% and 50% sulfonate soap
(Inventive Examples 16 and 17) t.sub.95,sat is less than 50 and
S.sub.N equals 2 or 3, corresponding to low wear samples. At 100%
salicylate soap, Comparative Example G, both t.sub.95,sat and
S.sub.N drastically increase. These results show that requirements
for fast-forming tribofilms observed at 0.8 weight percent soap are
maintained through very high levels of soap content. Therefore, it
is concluded that above 0.7 weight percent soap content, only
detergent compositions consisting of 50% sulfonate soap or greater
will provide adequate wear protection in the FCW test via fast
tribofilm formation. FIG. 9 shows S.sub.N and t.sub.95,sat for
low-soap samples varying ratio of sulfonate to salicylate soap, at
1.3 weight percent soap and constant detergent metals
composition.
PCT and EP Clauses:
[0198] 1. A method for improving wear control of a steel surface
lubricated with a lubricating oil, said method comprising: (i)
using as the lubricating oil a formulated oil, said formulated oil
having a composition comprising at least one lubricating oil base
stock as a major component; and at least one detergent, as a minor
component; and (ii) forming a tribofilm on the steel surface;
wherein the time for the tribofilm to reach 95% of its saturation
coverage (t.sub.95,sat) on the steel surface is less than 50
minutes, as determined by a high frequency reciprocating rig (HFRR)
in accordance with a modified version of ASTM D6079; and wherein,
in tribofilm formation measurements of the lubricating oil by a
mini-traction machine (MTM) in Stribeck mode, the number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s is achieved, which correlates to onset of the tribofilm
formation on the steel surface, is 2 or less.
[0199] 2. A method for improving wear control of a steel surface
lubricated with a lubricating oil, said method comprising: (i)
using as the lubricating oil a formulated oil, said formulated oil
having a composition comprising at least one lubricating oil base
stock as a major component; and at least one detergent, as a minor
component; and (ii) forming a tribofilm on the steel surface;
wherein the at least one lubricating oil base stock comprises an
alkylated naphthalene base stock; wherein the at least one
detergent comprises an alkaline earth metal salicylate, an alkaline
earth metal sulfonate, or mixtures thereof; wherein the total
amount of soap delivered by the at least one detergent is 0.4
weight percent to 0.7 weight percent of the lubricating oil;
wherein the total boron concentration is 100 to 260 parts per
million in the lubricating oil; wherein the time for the tribofilm
to reach 95% of its saturation coverage (t.sub.95,sat) on the steel
surface is less than 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079; and wherein, in tribofilm formation measurements of the
lubricating oil by a mini-traction machine (MTM) in Stribeck mode,
the number of Stribeck passes (S.sub.n) until an increase in
traction coefficient at 10 mm/s is achieved, which correlates to
onset of the tribofilm formation on the steel surface, is 2 or
less.
[0200] 3. A method for improving wear control of a steel surface
lubricated with a lubricating oil, said method comprising: (i)
using as the lubricating oil a formulated oil, said formulated oil
having a composition comprising at least one lubricating oil base
stock as a major component; and at least one detergent, as a minor
component; and (ii) forming a tribofilm on the steel surface;
wherein the at least one lubricating oil base stock comprises an
alkylated naphthalene base stock; wherein the at least one
detergent comprises an alkaline earth metal salicylate, an alkaline
earth metal sulfonate, or mixtures thereof; wherein the total
amount of soap delivered by the at least one detergent is 0.8
weight percent to 1.3 weight percent of the lubricating oil,
provided that the alkaline earth metal sulfonate is present in an
amount of 50 weight percent to 100 weight percent of the total
detergent; wherein the total boron concentration is 50 to 150 parts
per million in the lubricating oil; wherein the time for the
tribofilm to reach 95% of its saturation coverage (t.sub.95,sat) on
the steel surface is less than 50 minutes, as determined by a high
frequency reciprocating rig (HFRR) in accordance with a modified
version of ASTM D6079; and wherein, in tribofilm formation
measurements of the lubricating oil by a mini-traction machine
(MTM) in Stribeck mode, the number of Stribeck passes (S.sub.n)
until an increase in traction coefficient at 10 mm/s is achieved,
which correlates to onset of the tribofilm formation on the steel
surface, is 2 or less.
[0201] 4. A method for improving wear control of a steel surface
lubricated with a lubricating oil, said method comprising: (i)
using as the lubricating oil a formulated oil, said formulated oil
having a composition comprising at least one lubricating oil base
stock as a major component; and at least one detergent, as a minor
component; and (ii) forming a tribofilm on the steel surface;
wherein the at least one lubricating oil base stock comprises an
ester base stock, an alkylated naphthalene base stock, or mixtures
thereof; wherein the at least one detergent comprises an alkaline
earth metal sulfonate; wherein the total amount of soap delivered
by the at least one detergent is 0.1 weight percent to 1.0 weight
percent of the lubricating oil; wherein the total boron
concentration is 100 to 260 parts per million in the lubricating
oil; wherein the time for the tribofilm to reach 95% of its
saturation coverage (t.sub.95,sat) on the steel surface is less
than 50 minutes, as determined by a high frequency reciprocating
rig (HFRR) in accordance with a modified version of ASTM D6079; and
wherein, in tribofilm formation measurements of the lubricating oil
by a mini-traction machine (MTM) in Stribeck mode, the number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s is achieved, which correlates to onset of the tribofilm
formation on the steel surface, is 2 or less.
[0202] 5. The method of clauses 1-4 wherein elongation of timing
chain due to wear of chain link pins is less than 0.07%, as
determined by Ford Chain Wear (FCW) test conducted in accordance
with ILSAC GF-6 specification.
[0203] 6. The method of clauses 1-4 wherein the lubrication regime
at the steel surface comprises boundary- and mixed-layer
lubrication contacts.
[0204] 7. The method of clauses 1-4 wherein the steel surface
comprises the surface of a timing chain.
[0205] 8. The method of clauses 1-4 for improving soot-induced wear
control of a steel surface.
[0206] 9. The method of clauses 1-3 wherein the at least one
detergent comprises an alkaline earth metal salicylate, a mixture
of alkaline earth metal salicylates, an alkaline earth metal
sulfonate, a mixture of alkaline earth metal sulfonates, or a
mixture of alkaline earth metal salicylates and alkaline earth
metal sulfonates, all having the same or different total base
number (TBN).
[0207] 10. The method of clauses 1-3 wherein, for a mixture of
alkaline earth metal salicylates and alkaline earth metal
sulfonates, all having the same or different total base number
(TBN), the weight ratio of alkaline earth metal salicylates to
alkaline earth metal sulfonates is from 1:100 to 100:1.
[0208] 11. The method of clauses 1-3 wherein, for a mixture of
alkaline earth metal salicylates having the same or different total
base number (TBN), the weight ratio of a first alkaline earth metal
salicylate to a second alkaline earth metal salicylate is from
1:100 to 100:1; or wherein, for a mixture of alkaline earth metal
sulfonates having the same or different total base number (TBN),
the weight ratio of a first alkaline earth metal sulfonate to a
second alkaline earth metal sulfonate is from 1:100 to 100:1.
[0209] 12. A lubricating oil composition comprising at least one
lubricating oil base stock as a major component; and at least one
detergent, as a minor component; wherein the at least one
lubricating oil base stock and the at least one detergent are
present in an amount sufficient for the lubricating oil to form a
tribofilm on a steel surface; wherein the time for the tribofilm to
reach 95% of its saturation coverage (t.sub.95,sat) on the steel
surface is less than 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079; and wherein, in tribofilm formation measurements of the
lubricating oil by a mini-traction machine (MTM) in Stribeck mode,
the number of Stribeck passes (S.sub.n) until an increase in
traction coefficient at 10 mm/s is achieved, which correlates to
onset of the tribofilm formation on the steel surface, is 2 or
less.
[0210] 13. A lubricating oil composition comprising at least one
lubricating oil base stock as a major component; and at least one
detergent, as a minor component; wherein the at least one
lubricating oil base stock comprises an alkylated naphthalene base
stock, an ester base stock, or mixtures thereof; wherein the at
least one detergent comprises an alkaline earth metal salicylate,
an alkaline earth metal sulfonate, or mixtures thereof; wherein the
total amount of soap delivered by the at least one detergent is 0.4
weight percent to 0.7 weight percent of the lubricating oil;
wherein the total boron concentration is 100 to 260 parts per
million in the lubricating oil; wherein the at least one
lubricating oil base stock and the at least one detergent are
present in an amount sufficient for the lubricating oil to form a
tribofilm on a steel surface; wherein the time for the tribofilm to
reach 95% of its saturation coverage (t.sub.95,sat) on the steel
surface is less than 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079; and wherein, in tribofilm formation measurements of the
lubricating oil by a mini-traction machine (MTM) in Stribeck mode,
the number of Stribeck passes (S.sub.n) until an increase in
traction coefficient at 10 mm/s is achieved, which correlates to
onset of the tribofilm formation on the steel surface, is 2 or
less.
[0211] 14. A lubricating oil composition comprising at least one
lubricating oil base stock as a major component; and at least one
detergent, as a minor component; wherein the at least one
lubricating oil base stock comprises an alkylated naphthalene base
stock; wherein the at least one detergent comprises an alkaline
earth metal salicylate, an alkaline earth metal sulfonate, or
mixtures thereof; wherein the total amount of soap delivered by the
at least one detergent is 0.8 weight percent to 1.3 weight percent
of the lubricating oil, provided that the alkaline earth metal
sulfonate is present in an amount of 50 weight percent to 100
weight percent of the total detergent; wherein the total boron
concentration is 50 to 150 parts per million in the lubricating
oil; wherein the at least one lubricating oil base stock and the at
least one detergent are present in an amount sufficient for the
lubricating oil to form a tribofilm on a steel surface; wherein the
time for the tribofilm to reach 95% of its saturation coverage
(t.sub.95,sat) on the steel surface is less than 50 minutes, as
determined by a high frequency reciprocating rig (HFRR) in
accordance with a modified version of ASTM D6079; and wherein, in
tribofilm formation measurements of the lubricating oil by a
mini-traction machine (MTM) in Stribeck mode, the number of
Stribeck passes (S.sub.n) until an increase in traction coefficient
at 10 mm/s is achieved, which correlates to onset of the tribofilm
formation on the steel surface, is 2 or less.
[0212] 15. A lubricating oil composition comprising at least one
lubricating oil base stock as a major component; and at least one
detergent, as a minor component; wherein the at least one
lubricating oil base stock comprises an ester base stock, an
alkylated naphthalene base stock, or mixtures thereof; wherein the
at least one detergent comprises an alkaline earth metal sulfonate;
wherein the total amount of soap delivered by the at least one
detergent is 0.1 weight percent to 1.0 weight percent of the
lubricating oil; wherein the total boron concentration is 100 to
260 parts per million in the lubricating oil; wherein the at least
one lubricating oil base stock and the at least one detergent are
present in an amount sufficient for the lubricating oil to form a
tribofilm on a steel surface; wherein the time for the tribofilm to
reach 95% of its saturation coverage (t.sub.95,sat) on the steel
surface is less than 50 minutes, as determined by a high frequency
reciprocating rig (HFRR) in accordance with a modified version of
ASTM D6079; and wherein, in tribofilm formation measurements of the
lubricating oil by a mini-traction machine (MTM) in Stribeck mode,
the number of Stribeck passes (S.sub.n) until an increase in
traction coefficient at 10 mm/s is achieved, which correlates to
onset of the tribofilm formation on the steel surface, is 2 or
less.
[0213] All patents and patent applications, test procedures (such
as ASTM methods, UL methods, and the like), and other documents
cited herein are fully incorporated by reference to the extent such
disclosure is not inconsistent with this disclosure and for all
jurisdictions in which such incorporation is permitted.
[0214] When numerical lower limits and numerical upper limits are
listed herein, ranges from any lower limit to any upper limit are
contemplated. While the illustrative embodiments of the disclosure
have been described with particularity, it will be understood that
various other modifications will be apparent to and can be readily
made by those skilled in the art without departing from the spirit
and scope of the disclosure. Accordingly, it is not intended that
the scope of the claims appended hereto be limited to the examples
and descriptions set forth herein but rather that the claims be
construed as encompassing all the features of patentable novelty
which reside in the present disclosure, including all features
which would be treated as equivalents thereof by those skilled in
the art to which the disclosure pertains.
[0215] The present disclosure has been described above with
reference to numerous embodiments and specific examples. Many
variations will suggest themselves to those skilled in this art in
light of the above detailed description. All such obvious
variations are within the full intended scope of the appended
claims.
* * * * *
References