U.S. patent application number 16/844593 was filed with the patent office on 2020-07-30 for nano-additives enabled advanced lubricants.
The applicant listed for this patent is PIXELLIGENT TECHNOLOGIES LLC UCHICAGO ARGONNE, LLC THE TRUSTEES OF THE UNIVERSITY OF PENNSYLVANIA. Invention is credited to Robert CARPICK, Zhiyun CHEN, Gregory COOPER, Nicholaos G. DEMAS, Robert A. ERCK, George R. FENSKE, Nitya GOSVAMI, Aaron C. GRECO, Andrew JACKSON, Harman KHARE, Imene LAHOUIJ, Wei XU.
Application Number | 20200239802 16/844593 |
Document ID | 20200239802 / US20200239802 |
Family ID | 1000004753989 |
Filed Date | 2020-07-30 |
Patent Application | download [pdf] |
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United States Patent
Application |
20200239802 |
Kind Code |
A1 |
LAHOUIJ; Imene ; et
al. |
July 30, 2020 |
NANO-ADDITIVES ENABLED ADVANCED LUBRICANTS
Abstract
The presently disclosed technology relates to a nano-additives
to improve the performance of lubricants, oils, and greases. More
specifically, the presently disclosed technology relates to
applying capped metal oxide nanoparticles, such as capped zirconia
nanoparticles, in the lubricants to produce a tribofilms on the
lubricating surfaces to provide wear protection to the said
surfaces. Also, the interaction of the capped zirconia
nanoparticles with other commonly used additives in lubricants may
further optimize the performance of the resulting tribofilms.
Inventors: |
LAHOUIJ; Imene;
(Philadelphia, PA) ; CARPICK; Robert;
(Philadelphia, PA) ; JACKSON; Andrew; (Baltimore,
MD) ; KHARE; Harman; (Philadelphia, PA) ;
GOSVAMI; Nitya; (Philadelphia, PA) ; DEMAS; Nicholaos
G.; (Chicago, IL) ; ERCK; Robert A.; (Chicago,
IL) ; GRECO; Aaron C.; (Chicago, IL) ; FENSKE;
George R.; (Chicago, IL) ; XU; Wei;
(Baltimore, MD) ; COOPER; Gregory; (Baltimore,
MD) ; CHEN; Zhiyun; (Baltimore, MD) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
PIXELLIGENT TECHNOLOGIES LLC
UCHICAGO ARGONNE, LLC
THE TRUSTEES OF THE UNIVERSITY OF PENNSYLVANIA |
Baltimore
Chicago
Philadelphia |
MD
IL
PA |
US
US
US |
|
|
Family ID: |
1000004753989 |
Appl. No.: |
16/844593 |
Filed: |
April 9, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15569271 |
Oct 25, 2017 |
10647938 |
|
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PCT/US2016/030678 |
May 4, 2016 |
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16844593 |
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62156400 |
May 4, 2015 |
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62163116 |
May 18, 2015 |
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62163126 |
May 18, 2015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B82Y 30/00 20130101;
C10M 2209/1033 20130101; C10N 2040/04 20130101; C10N 2020/06
20130101; C10N 2020/061 20200501; C10N 2030/58 20200501; C10M
2229/025 20130101; C10M 171/06 20130101; C10M 2201/14 20130101;
C10M 141/10 20130101; C10M 2203/1006 20130101; C10N 2010/08
20130101; C10N 2050/10 20130101; C10M 2205/00 20130101; C10M
2207/2805 20130101; C10M 125/10 20130101; C10M 2223/045 20130101;
C10N 2050/02 20130101; C10M 2205/0285 20130101; C10N 2040/25
20130101; B82Y 40/00 20130101; C10N 2040/02 20130101 |
International
Class: |
C10M 125/10 20060101
C10M125/10; B82Y 40/00 20060101 B82Y040/00; C10M 171/06 20060101
C10M171/06; C10M 141/10 20060101 C10M141/10 |
Claims
1. A lubricant comprising zirconia nanoparticles, wherein the
zirconia nanoparticles are capped with at least one capping agent,
and wherein the lubricant has a minimum transmittance of larger
than 50% when measured in a cuvette with a 10 mm path length when
the dispersion contains 10% by weight nanoparticles in the
lubricant.
2. The lubricant of claim 1, wherein the lubricant comprises an
oil, a grease or a synthetic, mineral or natural lubricant and/or
contains at least one of synthetic hydrocarbon, an ester, a
silicone or a polyglycol.
3. The lubricant of claim 1, wherein the lubricant is a stable
dispersion and exhibits less than 10% change in optical
transmittance, when measured in a cuvette with 10 mm optical path,
after 1 month of storage to greater than 3 years storage.
4. The lubricant of claim 1, wherein the lubricant further
comprises at least one lubricant additive selected from the group
consisting of anti-wear (AW) additives, friction modifiers (FM),
anti-oxidants, extreme pressure (EP) additives, anti-foaming
agents, detergents, dispersants, and pour point depressants.
5. The lubricant of claim 1, wherein the lubricant further
comprises zinc dialkyldithiophosphates (ZDDP).
6. The lubricant of claim 1, wherein the lubricant has a viscosity
in the range of 2 to 1000 mPas (cP) at a temperature of 100.degree.
C.
7. The lubricant of claim 1, wherein the lubricant is a crankcase
lubricant for internal combustion engines, a lubricating oil for
geared transmissions in vehicles and wind turbine drivetrains, or a
lubricant for rolling bearing elements.
8. The lubricant of claim 1, wherein the zirconia nanoparticles
have a size which is 4-20 nm.
9. The lubricant of claim 1, wherein the zirconia nanoparticles are
present in an amount of 0.01 to 10 wt. %, based on total weight of
the lubricant.
10. The lubricant of claim 1, wherein the nanoparticles comprise
nanocrystals.
11. The lubricant of claim 5, wherein the zinc
dialkyldithiophosphates (ZDDP) is present in an amount of 0.01 to 2
wt. %, based on total weight of the lubricant.
12. The lubricant of claim 1, wherein the nanoparticles in use
undergo selective removal of the at least one capping agent due to
tribological stresses.
13. A tribofilm which comprises the lubricant of claim 1, wherein
the at least one capping agent is removed due to tribological
stresses.
Description
[0001] This application is a continuation of U.S. application Ser.
No. 15/569,271 filed on May 4, 2016 (now U.S. Pat. No. ______),
which in turn is the U.S. national phase of International
Application No. PCT/US2016/030678 filed May 4, 2016, which
designated the U.S. and claims benefit of U.S. Provisional
Application Nos. 62/156,400, 62/163,116, 62/163,126, filed May 4,
2015, May 18, 2015 and May 18, 2015, respectively, the entire
contents of each of which are hereby incorporated herein by
reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] This application is partially supported by a US Dept. of
Energy Corporate Research and Development Agreement (CRADA) No.
1200801 and US Dept. of Energy Small Business Innovation Research
(SBIR) Phase I and II Grants No. DE-SC0009222.
[0003] This presently disclosed technology pertains, among other
things, to a lubricant containing nano-additives for oils and
greases. The present disclosure provides a zirconia nanoparticles
dispersion in oils with or without other additives. The function of
these nano-additives are to form a protective tribofilm on
contacting surfaces. The tribofilm may supplement the boundary and
fluid film formed by the lubricant to provide wear and/or friction
reduction and thus enable the use of lubricants with lower
viscosity.
[0004] Lubricating oils and greases are commonly used in a variety
of applications, for example: crankcase lubricants for internal
combustion engines, lubricating oils for geared transmissions in
vehicles and wind turbine drivetrains, and grease or oil lubricants
for rolling element bearings. The lubricant provides protection
against, among other damage including corrosion, wear of the
contacting surfaces through a pressurized fluid film and/or the
formation of a solid tribofilm generated during operation. While a
fluid film is governed by the viscosity of the oil, the tribofilm
formation is typically provided by chemical additives that react to
form a solid film on the surface. In efforts to improve efficiency
of mechanical drives there is a trend to reduce the viscosity of
the lubricating oils to lower the churning or viscous loses. To
maintain the durability of components, the performance requirements
of the lubricant additives are more demanding, specifically for
friction and wear.
[0005] The chemical additives traditionally used in lubricants to
provide protective tribofilms are referred to as Anti-Wear (AW) and
Extreme Pressure (EP) additives. Furthermore Friction Modifiers
(FM) are used to maintain a low shear surface at the contact. These
additives come in a variety of forms but most are organometallic
compounds containing phosphorus, sulfur, and zinc. These compounds
chemically react with the contacting surfaces to form an amorphous
and/or crystalline solid tribofilm. While the mechanisms
responsible for tribofilm formation from organometallics is still a
topic of ongoing research, in practice it is generally observed
that a certain level of shear, pressure, and/or temperature is
required to nucleate and grow a tribofilm with organometallic
compounds. Furthermore, in automotive applications, the phosphorus
and sulfur content of these additives have been shown to have a
detrimental impact on the exhaust after treatment catalysts; this
has led to tighter restrictions on allowable content of these
compounds in the lubricant.
[0006] The use of nanoparticles as an additive to lubricants to
provide AW, EP, and FM performance qualities presents an innovative
approach to supplement or replace the use of organometallic
compounds or other additive chemistries. The mechanisms governing
the formation of a tribofilm from nanoparticles are fundamentally
different than those of the chemical additives, which presents
potential advantages in certain contact configurations. Therefore,
inorganic nanoparticles, particles less than 100 nm in diameter,
have recently been a subject of interest as friction modifier or
anti-wear agent for lubricants. There have been many studies on the
subject (H. Spikes, Lubr. Sci. 20 (2008), pp. 103-136; J. Tannous
et al., Tribol. Lett. 41 (2011), pp 55-64; A. Hernandez Batterz et
al., Wear 265 (2008), pp. 422-428; H. Kato and K. Komai, Wear 262
(2007), pp 36-41). These studies, however, all suffer from (1) the
lack of control on the quality of nanoparticles, i.e. the size and
size distribution, and (2) lack of dispersion stability in the
oils. The results, therefore, were not conclusive regarding the
benefit the nanoparticle additives provided. It is now understood
that to enable the advantages provided by nanoparticle additives
and to avoid any detrimental consequences, the nanoparticles have
to meet certain considerations include: dispersion and suspension,
stability at elevated temperature, compatibility and synergy with
other lubricant additives, and interaction compatibility with
contacting surfaces.
[0007] In the past few years, Pixelligent has developed a family of
inorganic nanoparticles and nanocrystals which have small size
(typically smaller than 10 nm diameter), with a narrow size
distribution, and most importantly, an engineered surface chemistry
so that they can be dispersed into common base stocks without
observable impact on the appearance, viscosity, and shelf-life of
the oils. Nanoparticles will be understood to include nanocrystals.
Because Pixelligent's nanoparticles are much smaller than typical
asperities of almost all practical manufactured surfaces in
tribological applications, and also because of the quality and
stability of the dispersion, true nano-scale control of the
tribological behavior has been observed, and the benefits of the
nanoparticle additives can be leveraged for reducing friction and
wear.
[0008] This presently disclosed technology provides, among other
things, that a zirconia nanoparticle dispersion in oils with or
without other additives forms a protective tribofilm that is
self-limiting and self-regenerating in rolling, sliding, or
rolling-sliding contact. This is achieved through well-dispersed,
capped nanoparticles to maintain a stable, homogeneous distribution
and avoiding agglomeration of particles. The nano-scale size of the
particle, 4-20 nm, is critical in enabling the additive to enter
the contact while avoiding any unintended detrimental effects. If
the nanoparticles are not capped or dispersed attractive forces
bring the particles together causing agglomeration and leading to
fall-out of suspension. The agglomerations lead to a non-uniform
mixture in the oil and if the agglomeration is large and hard
enough can lead to abrasion of the contacting surface resulting in
increased wear.
[0009] In addition to having a well dispersed nanoparticle that
enters the contact, this presently disclosed technology provides a
nanoparticle that, once in contact, adheres strongly to the
component surface and grows a thick tribofilm (30 nm to 500 nm).
The nucleation of this tribofilm occurs in sliding, rolling, or
rolling-sliding contacts, and at temperature ranges of -50.degree.
C. to 160.degree. C. and beyond, thus extending the conditions that
traditional AW and EP additives form tribofilms.
[0010] The present disclosure provides nano-additives for
lubricants, oils, and greases. During operation, the said
nano-additive may build protective, self-limiting,
self-regenerating tribofilms in rolling, sliding, or
rolling-sliding contacts. Such a tribofilm may reduce wear and/or
friction at the lubricating contacts. Such a tribofilm may
supplement the boundary, mixed, elasto-hydrodynamic (EHL) and/or
hydrodynamic film formed by the lubricant thus allowing lubricant
viscosity reduction.
[0011] The presently disclosed lubricants, oils, and greases may
include any mineral and synthetic oils including synthetic
hydrocarbons, esters, polyglycols, silicones, and ionic
liquids.
[0012] The present disclosure provides a zirconia nanoparticle
dispersion, in pure oils or oils with other lubricant additives
comprising anti-wear (AW) additives such as zinc
dialkyldithiophosphates (ZDDP), or friction modifiers (FM),
anti-oxidants, extreme pressure (EP) additives, anti-foams,
detergents, dispersants, pour point depressants, or any other
commonly used lubricant additives.
[0013] The presently disclosed zirconia nanoparticles may be capped
with surface capping agents as previously described in any of U.S.
Pat. Nos. 8,883,903; 9,328,432; 9,202,688 and 8,920,675, the entire
contents of each of which are incorporated herein by reference.
[0014] The presently disclosed zirconia nanoparticles may have size
smaller than 20 nm, or smaller than 15 nm, or smaller than 10 nm,
or smaller than 5 nm.
[0015] The presently disclosed zirconia nanoparticle dispersion may
demonstrate higher clarity. Said dispersion with 10 wt % capped
zirconia nanoparticles, when measured in a cuvette with 10 mm
optical path, demonstrates optical transmittance higher that 50%,
or higher than 60%, or higher than 70%, or higher than 80%, or
higher than 90%, or higher than 95%, or higher than 99%.
[0016] The presently disclosed zirconia nanoparticle dispersion may
demonstrate high stability. Said dispersion with 10 wt % capped
zirconia nanoparticles, when measured in a cuvette with 10 mm
optical path, demonstrates change in optical transmittance less
than 10%, or less than 5%, or less than 1%, after 1 month storage,
or after 3 month storage, or after 6 month storage, or after 1 year
storage, or after 2 year storage, or after 3 year storage.
[0017] The presently disclosed zirconia nanoparticles may form a
tribofilm on tribologically contacting surfaces in relative motion
and under tribological stress. Said tribofilm may be highly dense
and polycrystalline. Said tribofilm may have thickness in the range
of 30 nm to 500 nm. Said tribofilm may have a hardness less than or
equal to 7.3 GPa, and modulus less than or equal to about 160 GPa
when measured with nano-indentation.
[0018] The small size and superb dispersibility of the
nanoparticles enable them to enter the space separating asperities
on the surfaces in a tribological contact. The mechanism of the
tribofilm formation may be that under tribological stress, the
capping agents on the nanoparticle surface are removed, the
nanoparticles are bonded to the rubbing surfaces to form nucleation
sites, the nanoparticles coalesce onto the nucleation sites, and
then undergo grain coarsening to form an integral tribofilm. The
tribofilm growth is stress driven and higher stress leads to faster
nucleation and tribofilm growth process.
[0019] The presently disclosed tribofilm may demonstrate
self-limiting thickness during its formation under a given
tribological condition. The maximum film thickness may be 30 nm-50
nm, or 50 nm-100 nm, or 100 nm-200 nm, or 200 nm-300 nm, or 300
nm-400 nm, or 400 nm-500 nm, or 500 nm or larger.
[0020] The presently disclosed tribofilm may have surface RMS
roughness equal to or less than 2 nm, or 2 nm-5 nm, or 5 nm-10 nm,
or 10 nm-50 nm, or 50 nm-100 nm, or 100 nm-500 nm.
[0021] The presently disclosed tribofilm has carbon content of
10%-15%, or 5%-10%, or less than 5%, as measured by EDX, EELS, or
FTIR.
[0022] The presently disclosed tribofilm may have high adhesion to
the substrates as measured the by tape test.
[0023] The presently disclosed tribofilm may not be removed by acid
such as 10% hydrochloric acid solution, or base, such as 10%
tetramethylammonium hydroxide (TMAH) solution.
[0024] The presently disclosed tribofilm may form under pure
sliding, pure rolling, or mixed rolling-sliding conditions.
[0025] The presently disclosed tribofilm may form in the
temperature range of -50 C to 160 C, or 0 C to 160 C, or 20 C to
130 C.
[0026] The presently disclosed tribofilm may form on a steel
surface, or a silicon surface, an amorphous carbon surface or a
ceramic such as yttria-stabilized zirconia surface.
[0027] The presently disclosed tribofilm may form on surfaces with
RMS surface roughness larger than 5 nm.
[0028] The presently disclosed tribofilm may form with an oil with
10 wt % capped ZrO2 nanoparticles, or 1 wt % capped ZrO2
nanoparticles, or 0.1 wt % capped ZrO2 nanoparticles, or 0.01 wt %
capped ZrO2 nanoparticles.
[0029] The presently disclosed tribofilm may form under
tribological contact 10 nm or wider, or 1 um or wider, or 150 um or
wider, or 1 mm or wider.
[0030] The presently disclosed tribofilm may be formed in the
presence of ZrO2 nanoparticles together with anti-wear (AW)
additives such as zinc dialkyldithiophosphates (ZDDP), or friction
modifiers (FM), anti-oxidants, extreme pressure (EP) additives,
anti-foams, detergent, dispersants, pour point depressants, or any
other commonly used lubricant additives.
[0031] The presently disclosed technology provides a method of
forming a solid film on a lubricated surface that includes placing
a lubricant in a contact region defined by two surfaces in
proximity, sliding and/or rolling said surfaces so as to produce a
pressure and/or shear stress on the lubricated surface in the
contact region, and thereby forming the solid film in the contact
region, wherein the solid film is adhered to at least one of the
surfaces in the contact region, the lubricant containing at least
partially capped, metal oxide nanocrystals.
[0032] Metal oxide nanocrystals of the presently disclosed
technology include zinc oxide, hafnium oxide, zirconium oxide,
hafnium-zirconium oxide, titanium-zirconium oxide and/or yttrium
oxide.
[0033] Methods of the presently disclosed technology provide solid
films that persists after formation and in the absence of said
sliding and/or rolling forces.
[0034] Pressures useful in methods of the presently disclosed
technology may range from 100 MPa to 5 GPa, 100 MPa to 200 MPa, 200
MPa to 400 MPa, 400 MPa to 800 MPa, 800 MPa to 1.5 GPa, 1.5 GPa to
3 GPa, 3 GPa to 5 GPa or 5 GPa to 10 GPa.
[0035] Shear stresses useful in methods of the presently disclosed
technology may range from 10 MPa to 0.5 GPa, 10 MPa to 100 MPa, 100
MPa to 200 MPa, 200 MPa to 500 MPa, or 500 MPa to 1 GPa.
[0036] Methods of the presently disclosed technology provide or
include lubricants having at least partially capped nanocrystals in
an amount of 0.01 to 2 percent by weight of the lubricant, 0.01 to
0.05 percent by weight of the lubricant, 0.05 to 0.1 percent by
weight of the lubricant, 0.1 to 0.2 percent by weight of the
lubricant, 0.2 to 0.3 percent by weight of the lubricant, 0.3 to
0.4 percent by weight of the lubricant, 0.4 to 0.5 percent by
weight of the lubricant, 0.5 to 0.75 percent by weight of the
lubricant, 0.75 to 1 percent by weight of the lubricant, 1 to 1.5
percent by weight of the lubricant, 1.5 to 2 percent by weight of
the lubricant, or 2 to 10 percent by weight of the lubricant.
[0037] Methods of the presently disclosed technology involve or
include formation of the solid film at a temperature in a contact
region during the sliding and/or rolling in the range of
-100.degree. C. to 200.degree. C., -100.degree. C. to -50.degree.
C., -50.degree. C. to -25.degree. C., -25.degree. C. to 0.degree.
C., 0.degree. C. to 10.degree. C., 10.degree. C. to 20.degree. C.,
20.degree. C. to 30.degree. C., 30.degree. C. to 40.degree. C.,
40.degree. C. to 50.degree. C., 50.degree. C. to 60.degree. C.,
60.degree. C. to 70.degree. C., 70.degree. C. to 80.degree. C.,
80.degree. C. to 90.degree. C., 90.degree. C. to 100.degree. C.,
100.degree. C. to 125.degree. C., 125.degree. C. to 150.degree. C.,
150.degree. C. to 175.degree. C., 175.degree. C. to 200.degree.
C.
[0038] Lubricants of the presently disclosed technology may include
a ZDDP additive, optionally present in an amount of 0.01 to 2
percent by weight of the lubricant, 0.01 to 0.05 percent by weight
of the lubricant, 0.05 to 0.1 percent by weight of the lubricant,
0.1 to 0.2 percent by weight of the lubricant, 0.2 to 0.3 percent
by weight of the lubricant, 0.3 to 0.4 percent by weight of the
lubricant, 0.4 to 0.5 percent by weight of the lubricant, 0.5 to
0.75 percent by weight of the lubricant, 0.75 to 1 percent by
weight of the lubricant, 1 to 1.5 percent by weight of the
lubricant, 1.5 to 2 percent by weight of the lubricant, or 2 to 10
percent by weight of the lubricant.
[0039] Methods of the presently disclosed technology include
forming the solid film on at least one surface or two surfaces that
contains a steel composition.
[0040] Methods of the presently disclosed technology are able to
form films and films formed according to the presently disclosed
technology have a film hardness of 1 to 20 GPa, 100 MPa to 200 MPa,
200 MPa to 500 MPa, 500 MPa to 750 MPa, 750 MPa to 1 GPa, 1 GPa to
2 GPa, 2 GPa to 3 GPa, 3 GPa to 5 GPa, 5 GPa to 7 GPa, 7 GPa to 10
GPa, 10 GPa to 15 GPa, 15 GPa to 20 GPa.
[0041] Methods of the presently disclosed technology are able to
form films and films formed according to the presently disclosed
technology have Young's modulus of 50 GPa to 300 GPa, 50 GPa to 75
GPa, 75 GPa to 100 GPa, 100 GPa to 125 GPa, 125 GPa to 150 GPa, 150
GPa to 200 GPa, or 200 GPa to 250 GPa.
[0042] Methods according to the presently disclosed technology may
involve or include a sliding or rolling of the surfaces in the
contact region to induce a shear rate on the lubricant in the range
of 0 to 10.sup.7 sec.sup.-1, 0 to 10.sup.2 sec.sup.-1, 10.sup.2 to
10.sup.3 sec.sup.-1, 10.sup.3 to 10.sup.4 sec.sup.-1, 10.sup.4 to
10.sup.5 sec.sup.-1, 10.sup.5 to 10.sup.6 sec.sup.-1, or 10.sup.6
to 10.sup.7 sec.sup.-1, or a shear rate that induces a tribological
shear stress.
[0043] Methods of the presently disclosed technology further
optionally include or involve formation of an elasto-hydrodynamic
lubricant (EHL) film and/or a boundary lubricant film and/or
hydrodynamic lubricant film in the contact region.
[0044] Lubricants included in the methods of the presently
disclosed technology and films formed by the methods may be an oil
or a grease, or a synthetic, mineral or a natural lubricant, or
contain at least one of a synthetic hydrocarbon, an ester, a
silicone, a polyglycol or an ionic liquid, or is an oil having a
viscosity in the range of 2 to 1000 mPas (cP), 2 cP to 10 cP, 10 cP
to 50 cP, 50 cP to 100 cP, 100 cP to 500 cP, or 500 cP to 1000 cP,
at a temperature of 100.degree. C.
[0045] Methods of the presently disclosed technology and films
provided by the presently disclosed technology may include
lubricants containing at least one of an anti-wear (AW) additive, a
friction modifier such as zinc dialkyldithiophosphates (ZDDP), or
friction modifiers (FM), anti-oxidants, extreme pressure (EP)
additives, anti-oxidants, anti-foams, detergents, dispersants, pour
point depressants, or any other commonly used lubricant
additives.
[0046] The presently disclosed technology provides a solid film on
a lubricated surface containing a metal oxide crystallite, the
crystallite having a mean size of 5-20 nm, 5 to 100 nm, 5 nm to 10
nm, 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm,
50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, or
90 nm to 100 nm, the film having an atomic ratio of carbon to metal
in the range of 0 to 0.05, or 0.05 to 0.1, or 0.1 to 0.15, or 0.15
to 0.2, or 0.2 to 0.25, or 0.25 to 0.3, or 0.3 to 0.35, or 0.35 to
0.4, or 0.1 to 0.4.
[0047] Solid films of the presently disclosed technology optionally
have a thickness of 20 to 500 nm, 20 nm to 50 nm, 50 nm to 100 nm,
100 nm to 200 nm, 200 nm to 300 nm, 300 nm to 400 nm, or 400 nm to
500 nm.
[0048] Solid films of the presently disclosed technology may have a
film density 1.5-6 g/cm.sup.3, 1.5 to 2 g/cm.sup.3, 2 to 3
g/cm.sup.3, 3 to 4 g/cm.sup.3, 4 to 5 g/cm.sup.3, or 5 to 6
g/cm.sup.3.
[0049] The presently disclosed technology provides a method of
delivering at least partially capped nanocrystals into the
lubricated contact between two surfaces formed by sliding and/or
rolling said surfaces so as to produce a pressure and/or shear
stress on the lubricated surface and thereby forming a solid film,
wherein the solid film is adhered to at least one of the surfaces,
the lubricant comprising at least partially capped, metal oxide
nanocrystals having a mean size of 3 nm to 20 nm, 3 nm to 5 nm, 5
nm to 10 nm, 10 nm to 15 nm, or 15 nm to 20 nm.
[0050] Methods of the presently disclosed technology provide solid
films on at least two surfaces that may be portions of a piston
ring-cylinder liner contact, a cam and lifter contact, a contact
between a rolling element and races, gear teeth, or a hydrodynamic
bearing shell and a rotor, or a hydrostatic bearing and stator or
any other tribological contact surface with locally high pressures
as described herein. The presently disclosed technology further
provides a piston ring-cylinder liner contact, a cam and lifter
contact, a contact between a rolling element and races, gear teeth,
or a hydrodynamic bearing shell and a rotor, or a hydrostatic
bearing and stator, or any other tribological contact surface with
locally high pressures as described herein, containing a solid film
of the presently disclosed technology.
BRIEF DESCRIPTION OF TABLES
[0051] TABLE 1: Surface parameters of the samples used in Example
1.
[0052] TABLE 2: Exemplary modulus and hardness measurement results
of the tribofilm
BRIEF DESCRIPTION OF DRAWINGS
[0053] FIG. 1A: is an exemplary illustration of the reciprocating
ball-on-flat tester used in Example 1--schematic of contact
configuration--reciprocating ball-on-flat.
[0054] FIG. 1B: is an exemplary illustration of the reciprocating
ball-on-flat tester used in Example 1--schematic of contact
configuration-reciprocating ring-on-liner.
[0055] FIG. 2A: Profilometric images of optical profilometric image
a slide-honed cylinder liner surface.
[0056] FIG. 2B: Profilometric images of optical profilometric image
a top compression ring surface.
[0057] FIG. 3A: A photo of the Micro-Pitting Rig (MPR) used in the
examples.
[0058] FIG. 3B: A close-up photo of the MPR used in Example 1 shows
the lubricant at rest covering the lower portion of the test
rings.
[0059] FIG. 4: Provides a schematic of the MPR contact
configuration.
[0060] FIG. 5A. Optical Images of Tribofilms formed by ball-on-flat
test after 1 minute.
[0061] FIG. 5B. Optical Images of Tribofilms formed by ball-on-flat
test after 5 minutes.
[0062] FIG. 5C. Optical Images of Tribofilms formed by ball-on-flat
test after 20 minutes.
[0063] FIG. 6A. Optical image of ball test scar after room
temperature ball-on-flat test using PAO4+1 wt % capped ZrO2
nanoparticles (PAO is poly-alpha-olefins).
[0064] FIG. 6B. Optical image of flat test track after room
temperature ball-on-flat test using PAO4+1 wt % capped ZrO2
nanoparticles.
[0065] FIG. 7A: SEM-EDX (Scanning Electron Microscopy--Electron
Dispersion Spectroscopy) spectrum taken outside the flat wear track
on the flat formed by 2 wt % capped ZrO2 nanoparticles in PAO oil
showing Fe as the dominant element.
[0066] FIG. 7B: SEM-EDX spectrum taken inside the flat wear track
showing Zr as the dominant element.
[0067] FIG. 8A: Optical profilometer image and line scan (solid
lines) of a tribofilm formed by 1 wt % capped ZrO2 nanoparticles in
PAO at 70.degree. C. on a 52100 flat.
[0068] FIG. 8B: Optical profilometer line scan showing
approximately 350 nm buildup of tribofilm on the surface of the
flat.
[0069] FIG. 8C: Region evaluated for the buildup rate of the
tribofilm (box).
[0070] FIG. 9: An exemplary micrograph showing tribofilm formation
on a liner after a test at 100.degree. C. using PAO10+1 wt % capped
ZrO2 nanocrystals.
[0071] FIG. 10. EDX spectrum performed inside wear track of a flat
tested with Mobil 1 10W30 and 1 wt % capped ZrO2 nanoparticles.
[0072] FIG. 11: Evolution of tribofilm formation on the ring under
for pure sliding during an MPR test.
[0073] FIG. 12: Evolution of tribofilm formation on the ring up to
2 hours during an MPR test.
[0074] FIG. 13A: SEM image of an area inside the test track on the
ring after an MPR test.
[0075] FIG. 13B: EDX spectrum of an area inside the test track on
the ring after an MPR test.
[0076] FIG. 14A: SEM image of an area inside the test track on the
ring focused on a groove.
[0077] FIG. 14B: EDX spectrum of an area inside the test track on
the ring focused on a groove.
[0078] FIG. 15: A schematic of the AFM configuration used for
generating tribofilms.
[0079] FIG. 16A: The tribofilm growth volume as function of mean
contact stress, in an AFM set up.
[0080] FIG. 16B: The tribofilm growth volume as function normal
load, in an AFM set up, demonstrating stress-driven behavior.
[0081] FIG. 17A: An exemplary aerial view of the tribofilm
generated by an AFM.
[0082] FIG. 17B: An exemplary top view of the tribofilm generated
by an AFM.
[0083] FIG. 17C: An exemplary line scan of the tribofilm generated
by an AFM.
[0084] FIG. 18: Cross-sectional imaging of the zirconia tribofilms
at different magnification showing polycrystalline structure.
[0085] FIG. 19A: A cross-sectional TEM image of a tribofilm formed
by AFM.
[0086] FIG. 19B: Cross-sectional EDX mapping of the same tribofilm
showing that zirconia tribofilms are deficient in carbon-containing
capping agents and the composition of Fe and Zr formed
compositional gradients inside the tribofilm at different
depths.
[0087] FIG. 20A: Growth rates and cycles to tribofilms nucleation
plotted for various sub-ambient test temperatures. Under tested
contact conditions, tribofilm growth is observed for all
temperatures between -25.degree. C. and 25.degree. C. although some
variation in growth rate is observed.
[0088] FIG. 20B: Growth rates and cycles to tribofilms nucleation
plotted for various sub-ambient test temperatures--reducing
interfacial temperature reduces the cycles-to-nucleation resulting
in a more rapid growth initiation.
[0089] FIG. 21: Cross-sectional TEM image of a tribofilm formed by
AFM using a PAO4 base oil consisting of 9 wt. % zirconia with 0.8%
wt. % ZDDP. Cross-sectional images show that ZDDP restricts grain
coalescence and growth normally seen in pure zirconia
tribofilms.
[0090] FIG. 22: Cross-sectional TEM image of a tribofilm formed by
AFM using a PAO4 base oil consisting of 9 wt. % zirconia with 0.8%
wt. % ZDDP (left) and EDX analysis performed across the
cross-section of this tribofilms (right). EDX confirms the presence
of zirconia in the tribofilms, as well as phosphorous, sulfur and
zinc, which confirms that these tribofilms consist of a ZDDP phase
mixed with zirconia.
[0091] The present disclosure provides the following additional
embodiments.
EXAMPLES
[0092] Test Equipment
[0093] Reciprocating Rig
[0094] Experiments were performed with two contact configurations
(ball-on-flat and ring-on-liner) on the same reciprocating
tribometer. The ball-on-flat configuration used 52100 steel
counterfaces and 12.7-mm (1/2-in.) diameter balls (Grade 25)
sliding against mirror-polished flats (Sq=10 nm). The load of 15.6
N produced an initial peak Hertzian contact pressure of 1 GPa. The
ring-on-liner configuration used specimens extracted from
components in a commercial heavy-duty diesel engine. During all
machining operations to extract test specimens, the original
surfaces of the piston rings and cylinder liners were protected in
order to retain the original surface roughness and honing pattern.
The liners were gray cast iron with a typical honing pattern, and
the ring was steel that had been coated with CrN by physical vapor
deposition (PVD). The cylinder liner was mounted onto a
reciprocating table on the bottom of the test rig, while the piston
ring was stationary. The curvature of the ring was adjusted so that
a Hertzian contact width of 10 mm was achieved. A load of 200 N
produced a contact pressure of approximately 110 MPa, which is
similar to the contact pressure experienced by the top compression
ring at the top dead center (TDC) position in severe service.
Schematics for the two contact configurations are shown in FIG. 1A
and FIG. 1B. FIG. 2A and FIG. 2B shows profilometric images of the
cylinder liner and top-compression ring surfaces, respectively.
Their surface parameters are given in Table 1.
[0095] The cylinder liner was mounted onto a reciprocating table on
the bottom of the test rig, while the piston ring was stationary.
The curvature of the ring was adjusted so that a Hertzian contact
width of 10 mm was achieved. A load of 200 N produced a contact
pressure of approximately 110 MPa, which is similar to the contact
pressure experienced by the top compression ring at TDC in severe
service.
[0096] A small amount of oil (0.3 ml) was applied at the interface
of the test components to create a thin layer at the start of each
test. The tests were conducted at 1 Hz reciprocating frequency for
1 hour using a stroke length of 20 mm. Heating elements were
embedded into the reciprocating table, and the temperature was
controlled by a temperature control unit. Tests were performed at
70.degree. C., 100.degree. C., 130.degree. C., and 160.degree. C.
respectively.
[0097] Micro-Pitting Rig (MPR)
[0098] FIG. 3A is a photo of the Micro-Pitting Rig (MPR) available
at ANL. It consists of a center roller in contact with three larger
rings. FIG. 3B shows the lubricant at rest covering the lower
portion of the test rings. The lubricant is supplied to the contact
via splash lubrication. Both the rings and the barrel are
uni-directionally satin ground. The contacting area is flat and
approximately 1 mm wide. The roughness of a ring is approximately
150 nm. The rotation speed of the rings and roller are
independently controlled allowing for a range of slide-to-roll
(SRR) speed ratios. The load, speed, temperature, and SRR can all
be controlled and set to a condition that is relevant for
replicating gear tooth contact. Additionally, the materials and
surface roughness of the samples can be tailored to match that of
the gear components. During a test, the MPR is capable of measuring
the friction force between the roller and the rings, as well as the
vibration developed at the contact, indicating the severity of the
accumulated surface damage. After a test, the roller and ring
samples are analyzed to quantify the amount of surface wear.
Further examination of the samples can be used to characterize the
protective tribofilm that formed on the surface from the lubricant
additives. MPR tests were performed to evaluate the friction and
wear (and/or pitting) performance of lubricants formulated with
ZrO2 nanocrystal additives.
[0099] Characterization Techniques
[0100] Surface Profilometry
[0101] An interferometric non-contact optical profilometer
(Bruker.RTM., ContourGT, San Jose, Calif.) was used for measuring
roughness, finish, and texture of a surface. Due to optical
interference, micrographs of thin transparent films show colors
that are a function of film thickness. In order to show the true
surface of a tribofilm, the test components were coated with a thin
layer of gold.
[0102] Microscopy
[0103] The wear tracks on the flats and cylinder liners after the
tests were examined with an Olympus STM6 optical microscope, an FEI
Quanta 400F scanning electron microscope (SEM), a Hitachi S-4700-II
SEM, both equipped with energy dispersive x-ray spectroscopy (EDX)
capability.
[0104] Nano-Indentation
[0105] A nanoindenter (Hysitron TI-950 Tribo-Indenter) was used to
determine the hardness and modulus of these tribofilms formed on
surfaces, under displacement control using a standard Berkovich
tip. The same tip was used under scanning probe microscopy (SPM)
mode to image the surface topography. The nanoindenter monitors and
records the load and displacement of the indenter during
indentation with a force resolution of about 1 nN and a
displacement resolution of about 0.2 nm. The samples were placed on
a magnetic horizontal holder and positioned with the aid of an
optical microscope located above the sample. The area function
parameters of the tip were calibrated using a fused quartz sample,
and tip-shape calibration is based on determining the area function
of the indenter tip.
Example 1
[0106] Capped nanocrystals can be dispersed into base oil with
multiple capping agents at least as high as 10 wt % without
significantly affecting the viscosity and appearance of the oil.
Concentrations of 0.5 wt. %, 1 wt. %, 2 wt. % and 10%, three
different, capping agents, temperature (25.degree. C., 70.degree.
C., 130.degree. C., 160.degree. C.), time (5 mins, 20 mins, 60
mins, 4 hrs, 24 hrs), and type of oil were parameters that were
investigated.
[0107] An important observation is the formation of a unique
tribofilm by ZrO2 nanocrystal additives regardless of temperature.
A tribofilm started to form on the flat during the ball-on-flat
test only 1 minute after the test started, and a thick and dense
(as judged by optical profilometry) tribofilm was fully formed on
the flat 20 minutes into the test, as shown in FIG. 5. Due to the
relatively long stroke length, the flat experienced much less
rubbing than the ball, on which a thick and dense tribofilm was
fully formed after 20 minutes.
[0108] The formation of a tribofilm was also observed at room
temperature using PAO4 as base oil with 1 wt % capped
ZrO.sub.2.nanocrystals The ball test scar and flat test track are
shown in FIG. 6A and FIG. 6B, respectively.
[0109] A prominent zirconium peak in the SEM-EDX spectrum was found
in the wear track (FIG. 7B) but it was absent outside the wear
track (FIG. 7A), indicating that the tribofilm was zirconium-rich
and the tribofilm had indeed originated from the ZrO.sub.2
nanocrystal additives.
[0110] The tribofilms were semi-transparent so a thin gold layer
was coated on the ball and flat by thermal evaporation to assure
the accuracy when examined with optical profilometer. An optical
image of a tribofilm obtained by the optical profilometer is shown
in FIG. 8A. Instead of a net loss of material characteristic of
wear, there was actually a net increase of material on the wear
track. Line scans (vertical solid line) across the film revealed
that the tribofilm has a height of about 350 nm above the flat
surface (FIG. 8C).
[0111] Quantitative evaluation of the area marked in the FIG. 8B by
a solid rectangle showed a net nanocrystal-based tribofilm build-up
rate of 62,700 .mu.m3 per mm of sliding distance per hour,
approximately 1/300 of the total nanocrystal loading included in
the amount of oil used in the tests. This indicated that there are
significant amounts of nanocrystals left to continue re-generating
the tribofilm. The tribofilm was also relatively smooth, the root
mean square (RMS) roughness of the tribofilm was measured to be 170
nm while for the mirror polished flat the value was 40 nm.
[0112] A tribofilm was also formed on liner segments in
ring-on-liner tests at a range of conditions as shown in an
exemplary image in FIG. 9.
[0113] The modulus and hardness of the tribofilm were also measured
using nano-indentation, and exemplary results are shown in Table 2,
together with the results of the steel flat. The tribofilm possess
very impressive modulus and hardness, only .about.30% less than
52100 in both cases. A tribofilm that is hard, but slightly softer
than the surface material can provide sufficient load bearing
capability as a rubbing surface while serving as a protective,
regenerative layer if the stress is too high.
[0114] A tribofilm also formed by adding capped ZrO.sub.2
nanoparticles in a fully formulated oil (Mobil 1 10W30). The
presence of Zr was confirmed with EDX after a test. The result is
shown in FIG. 10.
[0115] A tribofilm formed under pure rolling conditions in an MPR
test, at a load of 200 N, speed of 2 m/s, and a temperature of
70.degree. C., as early as 15 minutes (143,000 cycles), continued
to grow over time, and became more uniform throughout the test. The
film was maintained up to 24 hours of testing (13.8 million
cycles). The evolution of the tribofilm is shown in FIG. 11.
[0116] A tribofilm also formed under a combination of rolling and
sliding conditions in an MPR using capped ZrO2 nanocrystals loaded
mineral oil. The evolution of the tribofilm is shown in FIG.
12.
[0117] FIG. 13A showed an SEM image of part of the tribofilm inside
the test track on the ring after the MPR test. And EDX analysis was
performed and indicated the presence of Zr on the test track on the
ring, as shown in FIG. 13B. Also, grooves were observed on the
tribofilm and an SEM image of the groove is shown in FIG. 14A, and
EDX inside the grooves showed no Zr (FIG. 14B) which means that the
grooves are not filled with ZrO2 nanocrystals.
Example 2
[0118] Tribofilms with the capped ZrO2 nanocrystals were also
generated in an atomic force microscope (AFM) at the interface
formed by a steel microsphere (ranging between 10 and 100 .mu.m in
diameter) against either a 52100 steel substrate, or a silicon
substrate or a yttria-stabilized zirconia substrate (illustrated in
FIG. 15). The contact stress at the sliding contact was varied
between 0.1 GPa and 1 GPa. Zirconia tribofilms exhibit a
stress-driven growth process where increasing the contact stress
increases the thickness of the tribofilms (FIG. 16). Increasing
surface roughness increases the rate of tribofilm growth. These
tribofilms are strongly bound to the substrate and resist removal
during continued sliding with the AFM probe in either base oil or
in dry sliding.
[0119] Using the AFM, tribofilms with lateral dimensions as small
as 2 .mu.m and as large as 50 .mu.m were generated, with local
thickness varying from 10 nm to 200 nm (example shown in FIG.
17).
[0120] Tribofilms in the AFM were generated in concentrations of
capped zirconia nanoparticles ranging from 0.01 wt. % in PAO4 to 10
wt. % in PAO4. Additionally, tribofilms were generated in other
base stocks, including mPAO SYN65.
[0121] Using the AFM, tribofilms were generated at temperatures
ranging from -25.degree. C. to 130.degree. C. (FIG. 20 shows a
range of temperature from -25.degree. C. to 25.degree. C.).
[0122] Tribofilm microstructure and chemical composition were
analyzed by performing focused-ion beam (FIB) milling to produce a
cross-sectional sample of the tribofilm, followed by observation in
scanning electron and transmission electron microscopes
(SEM/TEM).
[0123] Cross-sectional imaging of the tribofilms show a nearly
fully dense microstructure with no observable voids. Diffraction
analysis confirms that the tribofilms consist of a mostly
polycrystalline structure, identified to be zirconia. Through cross
sectional imaging, evidence of grain growth and coalescence of
individual 5 nm zirconia nanoparticles is also seen, as shown in
FIG. 18.
[0124] Through these cross-sectional images and accompanying
chemical spectroscopy (such as EDX, EELS and FTIR), it is confirmed
that zirconia tribofilms are deficient in carbon, indicating that
tribological stresses during sliding result in the removal of
capping agents prior to tribofilms formation (FIG. 19).
[0125] The mechanism of tribofilms growth as deduced from these
images is as follows: nanoparticles undergo selective removal of
surface ligands, i.e. capping agents, at the sliding contact due to
tribological stresses. In the absence of dispersing ligands, the
nanoparticles interact strongly with the substrate and each other
and tribological stresses cause the nanoparticles to bind strongly
to the substrate and to each other, resulting in the nucleation and
growth of a compact tribofilm. As the film grows, stress-driven
grain coarsening occurs. Tribofilms generated in the sliding
contact of the AFM show superior mechanical properties. The modulus
and hardness of these films was measured to be about 160 GPa and
7.3 GPa, respectively. These values approach known literature
values of bulk zirconia.
[0126] Tribofilms in the AFM were also generated with a mixture of
capped zirconia nanoparticles mixed with zinc
dialkyldithiophosphates (ZDDP) anti-wear additives. In these
measurements, zirconia was added to a PAO4 base oil in either 9 wt.
%, 1 wt. %, 0.1 wt. % or 0.01 wt. %, and mixed with 0.8 wt. % ZDDP.
With this oil containing both ZDDP and capped zirconia
nanoparticles, measurements were made at a variety of temperatures
including 25.degree. C., 15.degree. C., 5.degree. C. and -5.degree.
C. Other parameters for these AFM tests (load, speed, etc.) were
similar to those indicated in example 2. For all tested
temperatures, and for all concentrations of capped zirconia mixed
with ZDDP additive, a tribofilm growth and formation was observed
in the AFM. Similar results are expected for lower temperatures,
such as -15.degree. C. and -25.degree. C. These zirconia-ZDDP
tribofilms were morphologically similar to pure zirconia
tribofilms. However, for identical test conditions and durations,
the zirconia-ZDDP tribofilms generated had a significantly higher
thickness (i.e. volume) compared to pure zirconia tribofilms. In
addition, tribofilms formed within the AFM with zirconia-ZDDP mixed
in PAO4 were found to nucleate on the surface much more rapidly in
comparison to pure zirconia tribofilms, which resulted in a
significantly rapid tribofilms growth initiation.
[0127] Cross-sectional imaging of tribofilms formed in oils
containing both zirconia and ZDDP exhibit zirconia nanocrystal
sizes of 5 nm, which indicate that ZDDP is effective in inhibiting
grain growth and coalescence as is seen in pure zirconia tribofilms
(FIG. 21). Chemical spectroscopy of FIB/SEM cross-sections of these
ZDDP-zirconia tribofilms indicate the presence of both zirconia, as
well as zinc, phosphorous and sulfur, and a relative high
concentration of carbon, which confirm that these tribofilms
consist of a distinct zirconia phase as well as a distinct ZDDP
phase (FIG. 22).
TABLE-US-00001 TABLE 1 Surface parameters of the samples used in
Example 1. Liner Liner (slide-honed) (slide-honed) PVD CrN Ring PVD
CrN Ring 10 .times. 0.55 50 .times. 1.0 10 .times. 0.55 50 .times.
1.0 Sa (.mu.m) 0.662 0.175 0.822 0.208 Sq (.mu.m) 0.936 0.224 1.451
0.268 Ssk (--) -2.132 -0.655 -0.991 0.77 Sku (--) 10.238 4.867
41.51 20.88 Sp (.mu.m) 2.951 1.363 36.524 10.297 Sv (.mu.m) -10.932
-1.869 -33.041 -3.407 Sz (.mu.m) 13.883 3.231 69.565 13.703
TABLE-US-00002 TABLE 2 Exemplary Modulus and Hardness Measurement
Results of the Tribofilm Surface Modulus (GPa) Hardness(GPa)
Tribofilm 148.40 7.04 52100 steel 216.83 11.48
The contents of all references referred to herein are incorporated
in their entirety in this disclosure.
* * * * *