[0002] The Kyoto Protocol provides for a reduction in the annual greenhouse gas emissions
of the industrialized countries within the so-called first commitment period (2008-2012)
by an average of 5.2 percent compared to the level of 1990.
[0003] The greenhouse gases regulated by the Kyoto Protocol include the greenhouse gas carbon
dioxide (CO
2). The CO
2 emissions are mainly produced by burning fossil fuels, such as gasoline and diesel
fuel. For this reason, the global transportation sector, which is expected to be dependent
on fossil fuels for the foreseeable future, plays an important and significant role.
[0004] For this reason, the Association of European Automobile Manufacturers ACEA (Association
de Constructeurs Européens d'Automobiles) has pledged to the European Union to reduce
the average CO
2 emissions from the European vehicle fleet by 25% by the year 2008 compared to 1995.
[0005] Assuming that an average car emitted 186 grams of CO
2/km in 1995, this means for the year 2008 a reduction of emissions to 140 grams of
CO
2/km (2008), which is equivalent to a reduction the average fuel consumption to 6.0
liters per 100 kilometers for gasoline vehicles and 5.3 liters for diesel vehicles
per 100 kilometers according to the New European Vehicle Cycle (NEFC/NEDC). Binding
limits for CO
2 emissions of new cars were agreed to at the EU level at the end of 2008. The corresponding
EU Regulation 443/2009 provides that starting in 2012 an average of at least 65 percent
of the European new car fleet must not emit more than 130 grams of CO
2/km. By 2015, this limit is applied in several stages to the total fleet with the
target of reducing emissions to 95 grams of CO
2/km by 2020.
[0006] An emission standard for motor vehicles sets limits for carbon monoxide (CO), nitrogen
oxides (NO
X), hydrocarbons (HC) and particulate matter (PM) and subdivides the vehicles into
pollutant classes, to which certain emission code numbers are assigned, which are
used,
inter alia, to calculate the road tax and the assignment to pollutant groups for environmental
zones. The limits differ for both the type of the engine (gasoline or diesel) as well
as for the type of vehicle (cars, trucks and buses, cycles and mopeds) and are subject
to increasing scrutiny in the European Community.
[0007] Since September 1, 2009, the Euro-5 standard is applied throughout Europe to the
type test for new passenger cars, which is binding since January 1, 2011 for all newly
registered vehicles.
[0008] For trucks, the Euro 6 standard is applied from January 1, 2013 throughout Europe
to the type test, which is binding since January 1, 2014 for all newly registered
vehicles.
[0009] The types of vehicles found today in all areas of the transportation sector, such
as passenger cars, commercial vehicles and buses, motorcycles and mopeds, stationary
facilities and marine propulsion and auxiliary machinery, use as an energy source
fossil fuels, such as gasoline and diesel fuel, light and heavy fuel oils or gases.
The combustion of these fossil fuels produces greenhouse gases, in particular carbon
dioxide (CO
2) as a reference value. The road traffic in Germany contributes to about 20% of the
CO
2 emissions, making it one of the largest producers of CO
2 emissions.
[0010] The engines used in the transportation sector are subject to extreme demands and
operating conditions. Many factors affect the service life, the performance, the driving
characteristics, the emissions and much more. A key component for the optimal operation
of the engines is the appropriate selection of the engine oil (lubricant).
[0011] High-quality engine oils, especially partially and/or fully synthetic formulations
have a positive impact on all relevant factors. In addition to the now well-known
beneficial effects, such as reducing the internal friction, reliable lubrication of
the moving parts, long-term aging stability (Long-Life), build-up of wear-resistant
coatings, good cold start behavior, prevention of deposits and good transport of contaminants,
the viscosity gains increasing importance.
[0012] Nearly all European vehicle manufacturers today use engine oils with the viscosity
grade 5W-30 (range for passenger cars) and 10W-40 (range for trucks).
[0013] To meet the increasingly stringent demands on the reduction of CO
2 emissions, increasingly developments of ever thinner engine oils are also promoted
in addition to structural design measures. Lower viscosity grades, such as e.g. 0W-20
or even 0W-16 are under discussion. However, this may result in a failure/breakage
of the lubricating film under severe thermal engine loads, which could cause engine
damage.
[0014] Oil-soluble liquid organic molybdenum compounds are known for use as additives for
lubricant compositions. Organic molybdenum amide complexes are known, for example,
from
EP 0 546 357 B1, which can be prepared by the reacting fatty oils with an amino compound and a molybdenum
source.
[0015] These organic molybdenum complexes are used due to their friction-reducing (antifriction)
and wear-reducing properties and as antioxidants in lubricant additives, for example
for engine oils.
[0016] A commercially available lubricant additive is MOLYVAN
® 855 distributed by Vanderbilt Chemicals, LLC, which comprises molybdenum complexes
of N, N-bis(hydroxyethyl) cocoalkyl amides. The oil soluble molybdenum additive MOLYVAN
® 855 is also mentioned in patent
US 5,641,731 A, which teaches as preferred a total content of 0.1 wt.-% to 2 wt.-% of molybdenum
in the lubricant. Patent
US 4,889,647 discloses organic molybdenum complexes of the aforementioned type as well as structural
chemical formulas and manufacturing methods for these compounds; for example, the
compounds can be produced from seed oils such as coconut oil, diethanolamine, and
molybdenum trioxide. Organic molybdenum complexes that are chemically very similar
to these compounds are described in
EP 0 546 357 B1. These are also fatty oil amides, wherein the fatty oil is reacted with a 2-(2-aminoethyl)
amino ethanol.
[0017] Lubricating oil compositions containing alkyl ammonium tungstate compounds having
anti-friction and abrasion-reducing properties are described in
EP 1 618 172 B1. These are organo-ammonium metal compounds consisting of polytungstate ions and dialkyl-ammonium
ions of the type R
2NH
2+, wherein the radicals -R are long-chain alkyl groups. One example for such group
is di-tridecyl ammonium tungstate, which can be prepared by reacting tungstic acid
hydrate with di-tridecylamine. In the teaching of
EP 1 618 172 B1, it is recommended to add this additive based on organo-ammonium tungsten in a sufficient
amount so as to produce a final concentration of 0.05 wt.-% to 2.0 wt.-% in the lubricant.
[0018] A dialkyl ammonium tungstate compound of the aforementioned type as a lubricant additive
is offered by the company Vanderbilt Chemicals, LLC. under the product name VANLUBE
® W 324.
[0019] US 7,879,777 B2 describes an additive for a lubricating composition which contains a combination
of three components, namely a secondary diarylamine antioxidant, an organic molybdenum
compound and an organo-ammonium tungsten compound. The organic molybdenum compound
may be, for example, a dialkyl-dithio-carbamate or the aforementioned MOLYVAN
® 855 (Vanderbilt Chemicals, LLC). Various organo-ammonium tungsten compounds may be
used. However, for this known additive for lubricants, weight ratios of these compounds
are recommended, wherein the amount of tungsten in the additive is greater than the
amount of molybdenum. The recommended weight ratio of molybdenum to tungsten in the
additive is 1:2 to 1:8.5, assuming the indicated lower limit and upper limits, respectively.
Even if one selects the maximum amount of the specified range for molybdenum (350
ppm) and the minimum amount of the specified range for tungsten (100 ppm), the ratio
of molybdenum: tungsten is about 3.5:1. Furthermore, for this conventional lubricant
composition, a maximum content of 350 ppm (0.035 wt.-%) is recommended; larger amounts
of molybdenum are viewed as critical to avoid, because they cause formation of deposits
in the lubricant so that the lubricant no longer meets the required standards (GF-5
specification).
[0020] It is therefore the object of the invention to further improve a lubricant composition
of the aforementioned type with respect to reduction of friction, reduction of abrasion,
increase in the engine power and reduction of fuel consumption.
[0021] This problem is solved with a lubricant composition according to the invention of
the aforementioned type having the features of claim 1.
[0022] According to the invention, the lubricant composition is a composition which in addition
to other components, is comprised of at least one organic molybdenum compound, also
at least one alkyl- or aryl-substituted ammonium tungstate, with the proviso that
the ratio by weight of molybdenum to tungsten in the lubricant is at least 2.5:1.
Preferably, the lubricant composition has a minimum amount of Mo at greater than 350
ppm, and more preferably, at a maximum of 700 ppm.
[0023] Extensive tests in conjunction with the present invention have shown that the combination
of organic molybdenum compounds, in particular of the above-mentioned type with organically
substituted ammonium tungsten compounds in lubricating compositions have surprisingly
lead to unexpected effects, significantly improving various properties of the lubricant
composition. Here, surprisingly synergistic effects have been observed, i.e. the combination
of the above compounds results in a significantly greater improvement in the desired
lubricating properties than would be the case if only one of the two components in
the form of additives were added to a lubricant, as long as the two components are
admixed to the lubricant with specific relative weight ratios.
[0024] It was also found that adding solely the tungsten compound to the lubricant composition
does not result in any significant improvement in the desired properties, especially
in a reduction of the coefficient of friction and abrasion. The addition of the tungsten
compound is only effective when additionally an organic molybdenum compound is also
added to the lubricant composition. However, the simultaneous addition of the tungsten
compound and the organic molybdenum compound result in a significant improvement in
the performance of the lubricant composition in comparison to the exclusive addition
of an equivalent amount of the molybdenum compound, which means that the tungsten
compound produces an effect when being added simultaneously with the molybdenum compound.
This provides clear evidence that the simultaneous addition of the tungsten compound
and the molybdenum compound results in a synergistic effect.
[0025] In addition, varying degrees of improvements are also attained with the simultaneous
addition of both compounds to the lubricating composition, which leads to the conclusion
that the ratio of the amounts of molybdenum to tungsten in the lubricant composition
affects their preferred properties. It has been observed that there is a range of
an optimal ratio for both compounds. The improved properties occur to a lesser extent
outside this range, meaning that further addition of one or the other compound to
increase or decrease the weight ratio of the two compounds in the lubricant composition
produces a less apparent synergistic effect.
[0026] The lubricant composition according to the invention can be used, for example, for
engine oils, but applications as transmission oil or hydraulic oil may also be considered.
[0027] According to a preferred embodiment of the present invention, the weight ratio of
molybdenum to tungsten in the lubricant may be between about 3:1 and about 10:1. Preferably,
a weight ratio of molybdenum to tungsten in the lubricant is between about 4:1 and
about 8:1. Particularly preferred, the weight ratio of molybdenum to tungsten in the
lubricant is in the order of at least about 5:1.
[0028] As already mentioned above, the experiments in the context of the present invention
have led to the realization that not only the relative ratio of the two compounds
is important, but that also the respective absolute amount of these compounds in the
lubricant composition is a factor affecting the properties of the lubricant. For example,
the beneficial properties do surprisingly not improve further when the amount of the
one or the other compound is increased beyond a certain percentage. Without being
restricted to theory, the reason for this may be that the respective organic compounds
of molybdenum and tungsten decompose or oxidize when present in larger weight proportions,
causing deposits of decomposition and/or oxidation products of these compounds in
the lubricant, which may significantly diminish their properties by, for example,
causing increased abrasion and increased coefficients of friction or adherence of
such products to engine parts. Furthermore, the maximum solubility of the organic
molybdenum and tungsten compounds in the lubricant may also play a role. The compounds
of the invention have good initial oil solubility; however, chemical changes can be
introduced in these compounds by aging and/or temperature effects during operation,
also in conjunction with other components of the lubricant, which could then lower
the solubility in the lubricant.
[0029] Preferably, in another embodiment of the present invention, the organic molybdenum
compound may be added to the lubricant in an amount such that the amount of molybdenum
in the lubricant is less than 0.1 wt.-% Mo based on the total weight of the lubricant
composition. More preferably, the amount of molybdenum in the lubricant is less than
about 0.07 wt.-% (700 ppm) and greater than about 0.038 wt.-% (380 ppm) Mo based on
the total weight of the lubricant composition. It has been shown within the context
of the present invention that contrary to the information in the prior art, an amount
of more than 400 ppm of molybdenum in the lubricant produces particularly advantageous
properties of the lubricant, when a comparatively small amount of ammonium tungstate
is added within the range of the aforementioned weight ratios of Mo and W. This was
by no means expected based on the disclosure of the above-mentioned
US 7,879,777 B2.
[0030] The ammonium tungstate is preferably added to the lubricant composition in an amount
such that the amount of tungsten in the lubricant is less than 0.05 wt.-% based on
the total weight of the lubricant composition. More preferably, the amount of tungsten
in the lubricant is less than or equal to 0.02 wt.-% (200 ppm) based on the total
weight of the lubricant composition. The amount of tungsten in the lubricant may,
for example, only be about 0.01 wt.-% (100 ppm) or below 100 ppm, for example in the
range from about 50 ppm to about 95 ppm.
[0031] Preferably, within the context of the present invention, an organic molybdenum compound
in the form of an organic molybdenum complex is used, which is prepared starting from
at least one long chain fatty oil, diethanolamine or 2-(2-aminoethyl) amino ethanol,
and molybdenum trioxide. Particularly preferred are compounds wherein the long chain
fatty acid oil is an oil of a saturated fatty acid having 8 to 18 carbon atoms, in
particular selected from the group comprising caprylic acid, capric acid, lauric acid,
myristic acid, palmitic acid or stearic acid, or an unsaturated fatty acid with up
to 18 C-atoms, in particular oleic acid or linoleic acid, or a mixture of two or more
fatty acid oils of the aforementioned type. Within the context of the invention, for
example organic molybdenum compounds of the aforedescribed type can be used, as are
present in the additive having the trade name MOLYVAN
® 855 manufactured by the company Vanderbilt Chemicals, LLC, which has been mentioned
above, as well as in the corresponding cited patents.
[0032] Preferably, within the context of the present invention, an ammonium tungstate in
the form of an organo-ammonium metal compound is used, including polytungstate ions
and dialkyl-ammonium ions of the type R
2NH
2+, wherein the radicals -R are long chain alkyl groups, for example, tridecyl groups.
[0033] Another object of the present invention is a method for preparing a lubricant composition
of the aforementioned type, wherein the lubricant composition is prepared by adding
one or more additives to a base lubricant composition.
[0034] The lubricant composition according to the invention may be prepared, for example,
by adding to a lubricant base composition a first additive containing the organic
molybdenum compound in a higher concentration and a second additive containing the
ammonium tungstate in a higher concentration, wherein the first additive and the second
additive are each added to the lubricant composition in a suitable amount resulting
in the respective percentages of molybdenum and tungsten and the weight ratio of molybdenum
to tungsten in the final lubricating composition commensurate with the above results.
[0035] Alternatively, however, the lubricant composition can also be prepared by using only
a single additive, wherein in this variant the additive includes both the organic
molybdenum compound in a higher concentration as well as the ammonium tungstate in
a higher concentration, wherein the additive contains the molybdenum compound and
the ammonium tungstate in a defined relative weight ratio and wherein the additive
with the aforementioned combined ingredients is added to the lubricant composition
in such an amount so that the respective percentage of molybdenum and tungsten, as
well as the weight ratio of molybdenum to tungsten, results in the final lubricant
composition commensurate with the above discussion.
[0036] The features recited in the dependent claims relate to preferred further developments
of the solution of the object according to the invention. Further advantages of the
invention will become apparent from the following detailed description.
[0037] Exemplary embodiments of the present invention will now be described with reference
to the appended drawings, which show in:
- Figure 1
- a diagram illustrating the engine power in hp of a test vehicle which was tested with
an engine oil according to the present invention, as a function of engine speed;
- Figure 2
- a diagram illustrating in a comparison the coefficients of friction for various engine
oil compositions measured in a test apparatus.
Example 1:
[0038] Engine oils prepared by adding additives based on a combination of the organic ammonium
tungsten compound (VANLUBE
® W 324) and the organic molybdenum compound (MOLYVAN
® 855, both available from Vanderbilt Chemicals, LLC, Norwalk Connecticut, USA) to
a freely selected standard engine oil formulation for internal combustion engines,
were tested with regard to a reduction of fuel consumption (fuel economy) and CO
2 emission levels and compared in each case with a reference oil.
[0039] The following reference oil was used: Castrol Edge FST 5W-30.
[0040] Two oil formulations according to the invention with the designation "Pantere Speed
5W-30" by the Applicant were compared therewith, wherein one oil with the test number
T0438-13/0003 contained the aforementioned molybdenum compound and the tungsten compound
in a ratio of 5:1 and the other oil with the test number T0438-13/0004 contained the
aforementioned molybdenum compound and the tungsten compound in a ratio of 6:1. The
aforementioned molybdenum compounds and tungsten compounds were added to the reference
oil in the form of additives. It should be noted that the reference oil is a recommended
oil meeting the highest standards, which is regarded in the industry as an already-optimized
oil in terms of friction properties. The fuel consumption was compared in each case
with the fuel consumption when using the reference oil.
[0041] The experiments were performed at the internationally recognized and accredited company
ISP Salzbergen GmbH & Co. KG, wherein the strict driving conditions according to the
NEDC cycle (New European Driving Cycle) were applied. A BMW 520d (F10) was used as
a test vehicle. The results are listed in Table 1 below. A chassis dynamometer of
the type ECDM 48L-4x4 from the company MAHA-AIP GmbH & Co. KG and a gas sampling and
analysis system from the company Horiba MEXA-7400HLE and Horiba CVS-7400S were used
for the experiments, with the gases CO/CO
2, NO
X and HC being analyzed.
Table 1
Summary of test results |
Test No. |
Oil Designation |
Fuel Consumption [L/100km] |
Average Fuel Consumption [L/100 km] |
Minimum Consumption Compared to T0438-13/0002 [%] |
Scattering [%] |
T0438-13/0002 |
Castrol Edge FST 5W-30 |
4.85 |
4.85 |
--- |
0.00 |
4.85 |
T0438-13/0003 |
Pantere Speed 5W-30 |
4.79 |
4.78 |
1.44 |
0.42 |
4.77 |
T0438-13/0004 |
Pantere Speed 5W-30 |
4.80 |
4.77 |
1.65 |
1.25 |
4.74 |
4.76 |
4.78 |
[0042] The results listed in the table above indicate that the oil formulations according
to the invention reduce the fuel consumption of a warm engine by 1.44% and 1.65%,
respectively, compared to the reference oil. These values were obtained under strict
experimental test conditions, simulating ideal driving conditions of the engine, which
is usually not attainable under actual traffic conditions. The experience gained by
the applicant has demonstrated that significantly greater fuel economy can be attained
with common driving in traffic.
Example 2:
[0043] It could be demonstrated with a sports car Model GT 3 from the company Porsche having
a standard rated power of 420 hp that the use of a lubricant composition according
to the invention as engine oil results in a significant increase in the engine power.
This is illustrated in the graph of Figure 1. The engine power of the test vehicle
was measured on a dynamometer. The nominal power of this individual test vehicle measured
by the manufacturer during a factory acceptance test was 435 hp. Figure 1 shows that
a nominal power of about 458 hp was measured when a lubricant composition according
to the invention with the designation Pantere Racing 10W60 was used in the vehicle,
which represents an increase of power of more than 5%, which is due solely to the
use of the lubricant.
Example 3:
[0044] Friction and wear characteristics were measured in tests with a vibration-friction-wear
tester (SRV), whereby different oils for truck engines having compositions according
to the invention were tested with the two molybdenum and tungsten compounds mentioned
in Example 1 and having varying composition ratios and compared with a reference oil
LSAP 10W-40, which did not contain these compounds. In this SRV test, a steel ball
was moved back and forth under pressure on a steel plate with an oscillating motion.
[0045] The test results are shown in the following Table 2 and illustrated in the graph
of Figure 2. Two experiments were performed for each oil composition, with minimum,
maximum and final friction values shown in Figure 2. Figure 2 clearly shows that the
coefficients of friction for all oil compositions according to the invention 2 to
8 are improved over those of the reference oil 1. Particularly advantageous are the
values for the oil 2, which has a ratio of Mo:W in the oil of about 6:1, and the absolute
amounts of the Mo-compound were 505 ppm and of the tungsten compound 84 ppm.
Table 2
Determination of friction and wear characteristics in Oscillation friction wear tester
(SRV) |
Sample |
Run |
Wear Scar Diameter [Ø, µm] |
Friction Coefficient [µ] |
Mo:W ppm |
Mo:W |
Ø1 |
Ø2 |
ØAverage |
µmin |
µmax |
µend |
oil 1 |
1 |
495 |
484 |
490 |
0.11 |
0.12 |
0.12 |
--- |
--- |
2 |
484 |
482 |
483 |
0.11 |
0.13 |
0.17 |
oil 2 |
1 |
523 |
478 |
501 |
0.06 |
0.09 |
0.07 |
505:84 |
6:1 |
2 |
512 |
488 |
500 |
0.06 |
0.10 |
0.07 |
oil 3 |
1 |
511 |
509 |
510 |
0.07 |
0.10 |
0.07 |
492:98 |
5:1 |
2 |
518 |
495 |
507 |
0.07 |
0.09 |
0.07 |
oil 4 |
1 |
535 |
505 |
520 |
0.07 |
0.10 |
0.07 |
482:118 |
4:1 |
2 |
516 |
514 |
515 |
0.07 |
0.11 |
0.07 |
oil 5 |
1 |
500 |
484 |
492 |
0.07 |
0.10 |
0.07 |
442:148 |
3:1 |
2 |
500 |
493 |
497 |
0.07 |
0.10 |
0.07 |
oil 6 |
1 |
515 |
495 |
505 |
0.07 |
0.10 |
0.08 |
393:197 |
2:1 |
2 |
530 |
523 |
527 |
0.08 |
0.11 |
0.08 |
oil 7 |
1 |
516 |
495 |
506 |
0.08 |
0.13 |
0.09 |
295:295 |
1:1 |
2 |
505 |
497 |
501 |
0.08 |
0.10 |
0.08 |
oil 8 |
1 |
514 |
493 |
504 |
0.09 |
0.11 |
0.09 |
197:393 |
1:2 |
2 |
499 |
466 |
483 |
0.1 |
0.11 |
0.10 |
Date of test |
: October 2013 |
Normal force |
: 300 N |
Tester |
: Rigo |
Frequency |
: 20 Hz |
Test Specimen |
: Disc 100Cr6; Ø 24 x 7.9 mm [Rz 0.5 µm] lapped |
Temperature |
: 40-140°C |
|
: Ball 100Cr6, Ø 10 mm, DIN 51401-2, polished |
Time |
: 100 min |
[0046] The improvement over the reference oil becomes gradually smaller with decreasing
molybdenum content and increasing tungsten content. Very good results are obtained
with the oils 2 to 5. For the oil 5, the ratio of molybdenum to tungsten is 3:1 and
the absolute amount of molybdenum was 442 ppm.
Example 4:
[0047] The ability of the inventive combination to retain or improve the frictional performance
of an aged lubricating oil was tested. The aforementioned molybdenum compound and
the tungsten compound were combined with the reference oil of Example 1. To simulate
aging, oils were subjected to a modified High Temperature Corrosion Bench Test (HTCBT).
In this test, oil is exposed to oxidative conditions in the presence of four catalytic
metals: lead copper, tin and phosphor bronze. The HTCBT test herein was based on the
ASTM test method D6594, but modified such that the temperature was increased to 165°C,
and test length reduced to 48 hours. The friction response of the oxidatively aged
oil was measured using a PCS Instruments MTM2 Mini-Traction Machine. The friction
versus velocity (Stribeck curve) was determined for each fresh and aged oil at temperatures
of 60°C- 140°C in 20 °C intervals.
[0048] A comparison of oil performance across boundary, and elastohydrodynamic lubricating
regimes was made by integrating the area under each Stribeck curve. This integral
is commonly referred to as the Stribeck Friction Coefficient (SFC). Lower values of
SFC indicate that less energy is absorbed by the lubricant across all lubrication
regimes. Lower values relative to the baseline formulation would therefore be expected
to correlate with better performance in fuel economy engine tests. SFC results are
shown in Table 3.
Table 3
Determination of friction at various temperatures in aged oils under slip/roll conditions
using Mini Traction Machine (MTM) |
Sample |
Relative Change in Srtibeck Friction Coefficient (SFC-SFC0)/SFC0 |
Mo:W |
Mo:W |
60°C |
80 °C |
100 °C |
120 °C |
140 °C |
ppm |
ratio |
Castrol Edge FST 5W-30 |
0% |
0% |
0% |
0% |
0% |
0:0 |
0 |
Oil 9 comparative |
3.60% |
7.50% |
6.70% |
0.07% |
2.66% |
250:100 |
2.5 |
Oil 10 |
0.13% |
-5.64% |
-13.67% |
-14.75% |
-16.41 % |
500:50 |
10 |
Oil 11 |
1.21% |
-5.24% |
-12.96% |
-23.75% |
-17.64% |
500:200 |
2.5 |
Oil 12 |
2.27% |
-2.10% |
-4.72% |
-12.83% |
-15.02% |
700:100 |
7 |
Slide:Roll Ratio |
: 50% |
Load |
:35N |
|
|
|
Sliding Velocity Profile |
: 1000 mm/s - 100 mm/s, step 100 mm/s, hold 2 min/step |
|
|
: 100 mm/s - 10 mm/s, step 10 mm/s, hold 2min/step |
[0049] In Table 3, the reference oil is a recommended oil meeting the highest standards,
which is regarded in the industry as an already-optimized oil in terms of friction
properties. Oil 9 is a comparative composition using molybdenum and tungsten values
described in
US 7,879,777 B2. As can be seen from the table, Comparative Oil 9, which has less than the required
inventive amount of molybdenum (i.e. at least 350 ppm) does not impart improved frictional
performance by reducing the SFC relative to the reference oil. In contrast to this,
oils 10-12 show that the inventive combinations of molybdenum and tungsten impart
improved frictional performance to the oils, even after the oils have been severely
oxidatively stressed. It is noteworthy that in comparing Oils 11 and 9, each with
the same Mo:W ratio, it is the critical minimum amount of Mo that is responsible for
the large improvement, despite the prior art recommendation to avoid such a high amount.
This benefit is particularly substantial at elevated working temperatures.
1. Lubricant composition containing at least one oil-soluble organic molybdenum compound,
characterized in that this compound further contains at least one alkyl- or aryl-substituted ammonium tungstate,
wherein the weight ratio of molybdenum to tungsten in the lubricant is at least 2.5:1,
and the amount of molybdenum in the lubricant composition is at least 350 ppm based
on the total weight of the lubricant composition.
2. Lubricant composition according to claim 1, characterized in that the weight ratio of molybdenum to tungsten in the lubricant is between about 3:1
and about 10:1.
3. Lubricant composition according to claim 1, characterized in that the weight ratio of molybdenum to tungsten in the lubricant is between about 4:1
and about 8:1.
4. Lubricant composition according to one of the claims 1 to 3, characterized in that the amount of molybdenum in the lubricant is less than 0.1 wt.-% Mo based on the
total weight of the lubricant composition.
5. Lubricant composition according to one of the claims 1 to 4, characterized in that the amount of molybdenum in the lubricant is less than or equal to 700 ppm and greater
than 350 ppm Mo based on the total weight of the lubricant composition.
6. Lubricant composition according to one of the claims 1 to 5, characterized in that the amount of tungsten in the lubricant is less than or equal to 500 ppm based on
the total weight of the lubricant composition.
7. Lubricant composition according to one of the claims 1 to 6, characterized in that the amount of tungsten in the lubricant is less than or equal to 200 ppm based on
the total weight of the lubricant composition.
8. Lubricant composition according to one of the claims 1 to 7, characterized in that the weight ratio of molybdenum to tungsten in the lubricant is at least about 5:1.
9. Lubricant composition according to one of the claims 1 to 8, characterized in that the organic molybdenum compound is an organic molybdenum complex, prepared from at
least one long chain fatty acid oil, diethanolamine or 2-(2-aminoethyl) amino ethanol,
and molybdenum trioxide.
10. Lubricant composition according to claim 9, characterized in that the long chain fatty acid oil is an oil of a saturated fatty acid having 8 to 18
carbon atoms, in particular selected from the group consisting of caprylic acid, capric
acid, lauric acid, myristic acid, palmitic acid and stearic acid, or an unsaturated
fatty acid with up to 18 carbon atoms, in particular oleic acid or linoleic acid,
or a mixture of two or more fatty acid oils of the aforementioned type.
11. Lubricant composition according to one of the claims 1 to 10, characterized in that the ammonium tungstate is an organo-ammonium metal compound comprising polytungstate
ions and dialkyl-ammonium ions of the type R2NH2+, wherein the radicals -R are long-chain alkyl groups.
12. Method for preparing a lubricant composition according to one of the claims 1 to 11,
characterized in that the lubricant composition is prepared by adding to a lubricant base composition a
first additive containing the organic molybdenum compound in a higher concentration
and a second additive containing the ammonium tungstate in a higher concentration,
wherein the first additive and the second additive are each added to the lubricant
composition in such an amount that the respective percentages of molybdenum and tungsten
and the weight ratio of molybdenum to tungsten in the final lubricating composition
are obtained in accordance with one of the claims 1 to 11.
13. Method for preparing a lubricant composition according to one of the claims 1 to 11,
characterized in that the lubricant composition is prepared by adding to a lubricant base composition an
additive which contains the organic molybdenum compound in a higher concentration
as well as the ammonium tungstate in a higher concentration and which contains the
molybdenum compound and the ammonium tungstate in a defined relative weight ratio
to one another, wherein the additive with the aforementioned combined ingredients
is added in each case to the lubricant composition in an amount such that the respective
percentages of molybdenum and tungsten and the weight ratio of molybdenum to tungsten
in the final lubricating composition are obtained according to one of the claims 1
to 11.