Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
Motor Oil Blend for Modifying the Plastic Response of Steel
10 Background of the Invention
The field of this invention relates to the latest technology for substantially
reducing steel-to-steel wear along
with eliminating the need for Zinc Dialkyldithiophosphates (ZDDP) in motor
oils as an anti-wear component. The
composition of this invention has been shown to modify the plastic response of
steel while having a positive influence
on the chemical reactivity of the surfaces subjected to being worn down due to
friction. Specifically, based on the
tribological testing detailed in US 14/699,924, spectroscopic analysis of the
wear tracks of an engine disk revealed that
chemical elements like P, S, Mn, Zn, which can be from the ZDDP in the oil,
were not detected. This suggests that this
composition inhibits the reaction of ZDDP and renders it unnecessary for
reducing wear.
This is important, because today there is a movement within a number of states
and countries to remove or
substantially reduce the need for ZDDP in motor oils. Environmentalists in the
US have lobbied both State and Federal
departments to legislate such a ban. Unfortunately, governments have been
reluctant to issue or enforce such a ban
until a cost-effective alternative becomes available which can have the same
or better anti-wear performance results as
ZDDP, while eliminating the need for ZDDP itself.
There are in fact two types of zinc-thiophosphates universally added to motor
oils used today: zinc di-alkyl-di-
thiophosphates (which is ZDDP proper), and / or zinc di-thiophosphate (which
is often abbreviated to ZDTP). Unless
otherwise specified, when the acronym ZDDP is used in this disclosure, it is
being used to refer to either of these, with
or without the di-alkyl group. And specifically, the composition of this
invention eliminates the need for either of
ZDDP-proper, or ZDTP to be used in motor oils any longer.
The automotive industry was much simpler in the early days. Engines bearings
were made from a soft
tin/copper/antimony alloy, commonly referred to as babbitt. This alloy is
relatively inert chemically and has the ability
to absorb small amounts of foreign particulate material. But, as engine
horsepower increased, babbitt alloy surfaces
proved to be inadequate to bear the increased loading on these surfaces.
Thus, the need for harder bearings arose, and new types of bearings with
cadmium / silver, cadmium / nickel,
and copper / lead construction were developed. Such bearings were much
stronger, but were not as chemically inert as
babbitt and could be attacked by the acids generated from oil oxidation. These
new bearings were unable to absorb
foreign material such as carbon, grit and wear debris into the bearing
material, and consequently, improvements in oil
filtration were developed and used in vehicles to decrease premature wear.
Further, bearing corrosion inhibitors, anti-wear agents and acid inhibitor
compounds were developed to protect
these new bearings. There was a need to protect the bearings against both
corrosive and mechanical wear, and many of
these compounds served both functions. Compounds such as sulfurized sperm
oil, organic phosphates,
dithiocarbonates and dithiophosphates were experimented with to reduce
premature wear. In 1941, Lubrizol developed
1
CA 2972633 2018-08-24
CA 02972633 2017-06-28
POLSP019PCT
Zinc Dialkyldithiophosphates, which remain the most commonly-used form of
ZDDP, and introduced these to the
market.
Initially, ZDDP was added to motor oils in low concentrations of less than
0.3% by volume as a bearing
passivator, defined as treating or coating a metal in order to reduce the
chemical reactivity of its surface. In addition,
ZDDP was found to be a remarkably effective anti-wear agent; a true extreme-
pressure (EP) additive for heavily loaded
steel-on-steel sliding mechanisms such as camshafts and valve lifters or
tappets. During these years, there was little if
any concern about the impact of ZDDP upon the environment.
For years, these ZDDP additives have been providing sufficient anti-wear
service, starting with the early days
of gasoline and diesel non-detergent motor oils, through the present day.
Diesel engines of more than half a century
ago, which generally operated at lower speeds and were more massively built,
did not exhibit the same wear problems.
But in a gasoline engine, the valve train is more heavily stressed due to the
higher engine speeds, and these additives
have played and continue to play an important role in reducing wear.
Current and previous motor oils have depended upon the use of ZDDP as a means
to protect against premature
wear between bearing surfaces and from steel-to-steel contact. In view
especially of the detrimental impact of ZDDP
on the environment, it would be desirable to have available a replacement
additive which can eliminate the need for
ZDDP, which additive at the same time provides the same level of protection ¨
and even better protection ¨ for engine
components.
In US Patent 7,745,382, which was the first of several US and foreign patents
issued to Ronald J. Sloan and
assigned to BestI inc International Research Inc. (BestLine) who are the
inventor and assignee for the present
application as well, it was disclosed that a synthetic lubricant additive
comprising polymerized alpha-olefins (PA0s),
hydroisomerized hydro-treated severe hydrocracked base oil, and synthetic
sulfonates could provide better engine
lubrication and reduce engine wear, and that in fact the PAOs and the base
oils could be the primary composition for a
broad range of lubricants useful in many different circumstances including and
beyond automotive applications, and as
applied to many different materials including and beyond steel. This includes
diesel fuel additives (US 8,062,388 et.
seq.), gasoline additives (US 7,931,704 et. seq.), general purpose lubricants
(US 8,022,020 et. seq.), marine lubricants
(US 8,334,244 et. seq.) and even golf club cleaners (US 8,071,522 et. seq.).
But until the tribological testing detailed in US 14/699,924, the tribological
mechanism underlying the
effectiveness of BestLine's synthetic lubricant additive was not fully
understood. This testing established that not only
did this PAO, base oil and (optionally) synthetic sulfonate composition
enhance lubrication, but this composition was
also found to modin) the plastic response of the investigated steel and to
influence the chemical reactivity of the worn
surfaces. Particularly, as noted above, because elements like P. S. Mn, Zn
were not detected when this composition
was added to engine oils with ZDDP, this means that this composition inhibits
the reaction of ZDDP and renders ZDDP
unnecessary for reducing wear if the PAO and base oil is employed as a
substitute.
Thus, it was only with the new understandings first disclosed in US
14/699,924, that consideration could be
given to adding this PAO, base oil and optionally synthetic sulfonate
composition to motor oils, while at the same time
removing all of the ZDDP and / or ZDTP from these very same motor oils. Thus,
the addition of this PAO, base oil,
sulfonate composition to motor oils simultaneously with the removal of all
forms of ZDDP not only reduces engine
wear by superior lubrication, but also favorably modifies the plastic response
of all steel elements which it lubricates,
and at the same time solves an important environmental problem.
The use of this composition to improve motor oils while removing the
environmental hann caused by ZDDP
and ZDTP is applicable to all of the five groups of motor oil as defined by
the American Petroleum Institute (API).
2
Specifically, the September 2011 standards of the API specify as follows:
"All base stocks are divided into five general categories
a. Group
I base stocks contain less than 90 percent saturates and/or greater than 0.03
percent sulfur and have a viscosity index greater than or equal to 80 and less
than 120 using the test
methods specified in Table E-1.
b. Group
II base stocks contain greater than or equal to 90 percent saturates and less
than or equal to 0.03 percent sulfur and have a viscosity index greater than
or equal to 80 and less
than 120 using the test methods specified in Table E-1.
c. Group
III base stocks contain greater than or equal to 90 percent saturates and less
than or equal to 0.03 percent sulfur and have a viscosity index greater than
or equal to 120 using the
test methods specified in Table E-1.
d. Group
IV base stocks are polyalphaolefins (PAO). PAOs can be interchanged
without additional qualification testing as long as the interchange PAO meets
the original PAO
manufacturer's specifications in physical and chemical properties. The
following key properties need
to be met in the substituted stock:
1) Kinematic viscosity at 100 C, 40 C, and -40 C
2) Viscosity index
3) NOACK volatility
4) Pour point
5) Unsaturates
e. Group
V base stocks include all other base stocks not included in Group I, II, III,
or
IV.
Table E-1 Analytical Methods for Base Stock
Property Test Method
Saturates ASTM D2007
Viscosity index ASTM D2270
Sulfur ASTM D1552
(use one listed method) ASTM D2622
ASTM D3I20
ASTM D4294
ASTM D4927"
Summary of the Invention
An additive and related method for modifying the plastic response of steel,
the additive comprising:
polymerized alpha olefins; hydroisomerized hydro-treated severe hydrocracked
base oil; and optionally, synthetic
sulfonates. A tribological study detailed in US 14/699,924 and herein
concludes that: (1) This additive significantly
reduces wear of the carbon steel disk to 6% of the wear observed in pure oil
without additive; (2) There is no obvious
effect of the additive on friction except a slightly better stability with
time of the coefficient of friction; (3) The additive
appears to inhibit the reaction of ZDDP and renders ZDDP unnecessary for
reducing wear. This suggests that the
3
CA 2972633 2018-08-24
additive may be a replacement for ZDDP in motor oils; and (4) The additive was
found to modify the plastic response
of the investigated steel and to influence the chemical reactivity of the worn
surfaces. Although testing was not
conducted to establish the coefficient of friction, as this will be concluded
at a later time, previous testing supports that
the friction is reduced.
This invention is for a synthetic lubricant additive that can be added at
various ratios to provide the need
protect against steel-to-steel wear or between bearing and steel surfaces, as
well as related method of manufacturing
this additive and related methods of its use. Further, this additive can be
added to synthetic, synthetic blends and non-
synthetic motor oils (motor oils in all of Groups I through V) to provide them
with the anti-wear protection necessary in
today's high speed and low speed gasoline and diesel motor oils. Further the
invention allows steel under extreme
pressure to yield or to respond to plastic deformation without the fracturing
of the metal surface.
The additive incorporates the use of polymerized alpha olefins (PAO);
hydroisomerized hydro-treated severe
hydrocracked base oil; and optionally, synthetic sulfonates. Further, one can
optionally employ vacuum distilled non
aromatic solvents and liquefied polytetrafluoroethylene (PTFE) and when
combined into the additive a specific
sequence, this forms a finished product that exceeds the metal-protecting
capability and benefits of ZDDP while
providing an environmentally-friendly replacement. Further this product
provides protection against steel-to-steel
contact while positively influencing the chemical reactivity of worn metal
surfaces. Further this product in independent
testing reported in published application US 2015/0247103 Al has demonstrated
the ability to modify the plastic
response of steel placed under extreme pressure.
As previous indicated the ingredients of this additive when blended in a very
specific sequence under specific
conditions will provide a lubricant that has shown its ability to replace the
need for ZDDP as an anti-wear agent in
motors oils. The blending is a combination of accurately-controlled sheering
and homogenization of the compounds
resulting in a long-term stable blend. Once blended in a specific sequence,
simple purification or physical separation,
such as distillation or freezing, does not constitute synthesis, in the
manner, for example, of making synthetic Group III
and Group IV from crude oil via a chemical reaction.
The finished product is a combination of:
= Polymerized Alpha-Olefins
= Hydroisomerized hydro-treated severe hydrocracked base oil
= Optionally, Synthetic sulfonates
= Optionally, vacuum distilled non aromatic solvents (less than 0.5%
aromatics)
= Optionally, liquefied polytetrafluoroethylene (PTFE) comprising a stable
aqueous disbursement
Synthetic lubricants have been successfully used for some time. They have the
ability to offer very-high-
viscosity index, low volatility, superior oxidation resistance, high thermal
stability, excellent temperature fluidity and
low toxicity to the environment. These characteristics in a finished lubricant
are very important in modern high-speed
and high-horsepower engines. Further these characteristics benefit the long
term goals of being less toxic to the
environment while providing maximum protection for automotive components.
This synthetic lubricant when tested has demonstrated the ability to provide
and exceed the anti-wear
protection currently provided by the inclusion of ZDDP in motor oils. The
synthetic lubricant can provide the
necessary anti-wear in automotive, diesel and marine motor oil, but without
the environmental impact of ZDDP. It has
the ability to blend with, and be effective with, all of Group I, II, III, IV
and Group base oils.
In its preferred embodiment, disclosed here is an environmentally-improved
motor oil blend and related
methods for properly lubricating components of an engine and favorably
modifying a plastic response of components
4
CA 2972633 2019-11-04
CA 02972633 2017-06-28
WO 2016/123279 PCT/US2016/015256
of the engine, the blend being free of zinc di-alkyl-di-thiophosphates (ZDDP)
and free of zinc di-thiophosphate
(ZDTP), comprising: a motor oil selected from the motor oil group consisting
of Group I, Group II, Group III, Group
IV, and Group V motor oils; a motor oil additive comprising alpha-olefins and
hydroisomerized hydro-treated severe
hydrocracked base oil; ZDDP omitted from the chemical constituents of the
motor oil; and ZDTP omitted from the
chemical constituents of the motor oil.
Detailed Description
The preferred blending ratios for each of the components of this additive are
shown below. It is important to
maintain a blend of components falling within the following percentages:
Polymerized alpha-olefins (PAO): It is preferred that these comprise from 20%
to 60% by volume. It is most
preferred that these comprise approximately 55% by volume. One may also use
alpha-olefins (AO) which have not
been polymerized. though PAOs are preferred. One may also use the modern
metallocene poly-alpha-olefins (mPAO)
which have higher viscosity indexes than conventional PAOs.
Hydroisomerized high viscosity index (VI) hydro-treated (HT) severe hydro-
cracked base oils: It is preferred
that these comprise from 5% to 55% by volume. It is more preferred that these
comprise from 7% to 25% by volume.
It is most preferred that these comprise approximately 21% by volume. It is
preferred, but not required, that these base
oils have a viscosity grade 32. One may also use can also saturated
hydrocarbons, process oil and hydraulic oil for this
base oil.
Synthetic sulfonates: These are preferred, albeit optional ingredients. It is
preferred that when used these
comprise from 0.05% to 10% by volume. It is most preferred that these comprise
approximately 3% by volume. It is
preferred that these synthetic sulfonates comprise a total base number (TBN)
from 200 to 600. It is most preferred that
these comprise a 300 TBN. One may also use thixotropic calcium sulfonates.
Vacuum Distilled Low-Viscosity and Low-Aromatic Solvents: Often referred to as
aliphatic or mineral
spirits, these are optional ingredients. It is preferred that when used, these
comprise from 10% to 40% by volume. It is
most preferred that these comprise approximately 21.5% by volume. The low-
aromatic range is preferred to be less
than 0.5% aromatic. It is preferred that these solvents have a VOC Exemption,
defined by the California Air Resources
Board as including those compounds "not expected to meaningfully contribute to
ozone formation due to their low
reactivity in the atmosphere." The envisioned low viscosity is in the
approximate range of 40C mm2/s (ASTM D 445)
and viscosity at 25C cSt 2.60 and at 40C cSt 1.98 (ASTM D 445).
Liquefied Polytetrafluoroethylene (RIFE): This is an optional ingredient. When
used, it is preferred that
these comprise from 0.001% to 10% by volume. It is most preferred that these
comprise approximately 0.45% by
volume. The PTFE should be liquefied to avoid agglomeration, and preferably
comprise a stable aqueous dispersion of
PIFE particles in water or oil. If oil is used, it is preferred to use 150
solvent neutral petroleum oil or an approximate
equivalent.
The following describes the preferred method for blending these components to
produce this motor oil
additive.
Initially, the alpha olefins, and the base oils are blended until the liquid
is a consistent amalgamation without
any appearance of separation, to yield a first blend. Blending is based on
speed of the agitator, and temperature will
dictate the amount of time for the blend to complete. The blending time range
may vary from 4 to 6 hours. The ideal
temperature for each component is between 22 to 30 degrees centigrade for
optimum blending.
5
CA 02972633 2017-06-28
WO 2016/123279 PCT/US2016/015256
Further, the vacuum distilled non-aromatic solvent and synthetic sulfonates
are blended together to yield a
second blend. This second blend may be prepared in a much smaller, high-speed,
enclosed blender. This second blend
is then added to the first blend.
If PTFE is used, then the first and second blends are finally blended together
with the P1FE.
If low-aromatic aliphatic solvent is used, then the first and second blends
are blended with additional low-
aromatic aliphatic solvents to produce a third blend. Then, if PTFE is used,
all of the foregoing is blended together
with the PTFE.
It is preferred that there is an approximate 25% / 75% ratio of calcium
sulfonates to aliphatic or mineral
spirit, when these are used.
This third blend, or the mineral spirits alone absent the synthetic
sulfonates, together with the balance of the
ingredients, added to the first blend and the agitator is run until the
components appear to have thoroughly blended into
a consistent liquid. Following the blending, the product is sheered by a high
speed sheering pump until the product is
consistent. The sheering provides a stable flow viscosity exhibiting Newtonian
behavior and greatly enhances the shelf
life when there are substantial differences in specific gravity of each
component.
The preferred blending equipment used in this process is as follows: This
process involves several blending
and holding tanks in which the product can be weighed and then pumped through
control valves to maintain consistent
flow and pressure. The blending should be performed in an enclosed tank to
reduce product evaporation loss and
prevent exposure to open spark. Blending equipment can be by a combination of
high- or low-speed blending
apparatus. The size or volume of the tank is not critical to the blend.
Sheering equipment should have a range of 60 to
5200 cycles per second with a typical speed of 3600 cycle per second and be
capable of making stable emulsions of
products with oil ingredients providing liquid suspensions and dispersions
without aeration.
This motor additive is then combined with a motor oil selected from the motor
oil group consisting of Group I,
Group IL Group III, Group IV, and Group V motor oils, without the use of ZDDP
of ZDTP, to provide an
environmentally-improved motor oil blend for properly lubricating components
of an engine and favorably modifying a
plastic response of components of the engine. The preferred blend ratio is
from 85% to 95% by volume of motor oil,
and from 5% to 15% by volume of the motor oil additive.
To create the motor-oil blend, the motor oil and the additive are combined
together, and this combination is
then simply mixed with a high-speed blender before being packaged. Given the
chemical characteristics of motor oil
and of the additive, there should be minimal or no separation thereafter while
the packaged blend is maintained on a
shelf, i.e., the blend should remain homogeneous for whatever shelf-life the
motor oil blend may have before it is
poured by a user into an engine.
While not the preferred mode of usage, one could take a motor oil with no ZDDP
and no ZDTP and introduce
that into an engine separately from introducing the lubricant. However, in
this circumstance the user would need to
take care to maintain an optimum mix of 85% to 95% by volume of motor oil and
5% to 15% by volume of the motor
oil additive. Using a blend that is already combined in the desired ratios is
preferred because the user need not then be
concerned with maintaining the ratio of motor oil to additive within the
desired ranges, and the possibility of user
mistake is eliminated.
Referring to the API properties laid out earlier in the background of the
invention, the overall combination of
the motor oil with the lubricant, depending upon the viscosity of the host
motor oil without ZDDP or ZDTP, will have
the following characteristics: 1) For some selected temperatures: 100 C,
kinematic viscosity 1.7 to 102.0; 40 C,
kinematic viscosity 5.4 to 1350; -40 C; kinematic viscosity 2,704 to 35,509.
2) Viscosity index: 90 to 200. 3)
6
CA 02972633 2017-06-28
POLSP019PCT
NOACK Volatility 0.6 to 99.5. 4) Pour point up to -20 to -61C. Again, these
ranges are dependent on the viscosity of
the host oil. Finally, 5) the POA (or AO or mPAO) base should have a PAO
Unsaturates viscosity grade from PA0-2
to PAO-100.
Generally, for motor oil blends, the range from PA0-2 to PAO-10 is sufficient.
However, for other lubricating
applications in which it is desirable to remove environmentally-undesirable
chemicals such as ZDDP and ZDTP replace
them with the alpha-olefin and base oil additive of this disclosure, given the
understanding disclosed in US 62/109,172
regarding how this additive favorably modifies plastic response and influences
chemical reactivity, one may find it
desirable to use alpha-olefins in the higher range up to and including PAO-100
for other lubricating applications, as
outlined further below.
Specifically, it is also understood and disclosed here that the base
combination of alpha-olefins and
hydroisomerized hydro-treated severe hydrocracked base oil can serve as a
replacement for environmentally-
undesirable chemicals not only in motor oils, but in other lubricating / anti-
wear agents and applications including, but
not limited to:
= Gear Oils
= Automatic Transmission Fluids
= Hydraulic Fluids
= Greases
= Turbine Oils and Fluids
= Metal Working Oils
= Chain Lubes
= Compressor Lubricants
= Conveyor Lubricants
= Paper Machine Oil
= Form Oils
= Way Oils
= Drill Oils
= Drawing and Stamping Oil
= Bar Oils
= 2 Cycle Oil
= Steam Oil
The ability to omit environmentally-undesirable chemicals in this broad range
of circumstances, which
chemicals are widely thought to be essential to providing proper lubrication
and protecting against wear, emanates from
the disclosure in US 14/699,924 that this base combination of alpha-olefins
and hydroisomerized hydro-treated severe
hydrocracked base oil modifies the plastic response of steel and changes the
chemical reactivity of the surfaces
subjected to being worn down due to friction whereby these environmentally-
undesirable chemicals were not detected
under spectroscopic analysis of the wear tracks. So while a very important
application of this disclosure is to motor oils
because of the widespread usage of these oils and the consequent substantial
environmental impact of these oils, it is
also understood that the same favorable plastic response modifications and
chemical reactivity changes will also
transpire in many other applications, which enables this disclosure to be
fruitfully applied to those other applications as
well, and particularly, to the removal from fluids, lubricants and oils
generally of environmentally-undesirable
chemicals widely regarded to be essential for proper lubrication and anti-wear
protection.
7
=
The knowledge possessed by someone of ordinary skill in the art at the time of
this disclosure, including but
not limited to the prior art disclosed with this application, is understood to
be part and parcel of this disclosure, even if
in the interest of economy express statements about the specific knowledge
understood to be possessed by someone of
ordinary skill are omitted from this disclosure. While reference may be made
in this disclosure to the invention
comprising a combination of a plurality of elements, it is also understood
that this invention is regarded to comprise
combinations which omit or exclude one or more of such elements, even if this
omission or exclusion of an element or
elements is not expressly stated herein, unless it is expressly stated herein
that an element is essential to applicant's
combination and cannot be omitted. It is further understood that the related
prior art may include elements from which
this invention may be distinguished by negative claim limitations, even
without any express statement of such negative
limitations herein. It is to be understood, between the positive statements of
applicant's invention expressly stated
herein, and the prior art and knowledge of the prior art by those of ordinary
skill even if not expressly reproduced here
for reasons of economy, that any and all such negative claim limitations
supported by the prior art are also considered
to be within the scope of this disclosure and its associated claims, even
absent any express statement herein about any
particular negative claim limitations.
Finally, while only certain preferred features of the invention have been
illustrated and described, many
modifications, changes and substitutions will occur to those skilled in the
art. It is, therefore, to be understood that the
appended claims are intended to cover all such modifications and changes as
fall within the true spirit of the invention.
8
CA 2972633 2019-11-04
