Patent Grant
9725669
This invention is in the field of tribology, more specifically formulations which provide good antiwear and beneficial friction properties.
Ionic liquids (ILs) are a new generation of antiwear additives that are superior to traditional antiwear additives such as ZDDP. Ionic liquids are most commonly defined as organic salts with melting points or glass transition temperature below 100° C. Although this description gives a clear idea of their ionic nature and their liquid state at a relatively low temperature, it is worthwhile to stress the importance of ILs in comparison to molten salts. Usually, fusion temperature of a salt is considerably high, for example 801° C. in the case of sodium chloride, which excludes its use in many applications. However, by the use of ILs, it is possible to benefit from properties emerging from ionic bonds between the moieties, but at a relatively low temperature, often significantly below room temperature. The provision and maintenance of these properties are in particular important for their use as lubricants to enable application over a wider range of temperature.
In order to decrease the melting temperature, ILs are generally constituted from an organic cation with low symmetry and a weakly coordinated anion. This way, lattice energy is lower and the anion-cation interaction is minimized due to the asymmetric and delocalized charge.
The reason for the growing interest in ILs can be explained by their excellent physical-chemical properties such as their large electrochemical window, controlled miscibility, high thermal stability, negligible vapor pressure, and in some cases, environmental harmlessness. In addition to these qualities, it is possible to obtain compounds with tailor-designed properties by tuning the structure through substitution and structural modification of the anion or of the cation. For example, changes in the anion can influence the chemical behavior and the stability of the IL while the use of different cations can affect physical properties, such as viscosity, melting point, and density.
In 2001, Ye et al. performed the first tribological investigation with ILs. C. Ye, W. Liu, Y. Chen, L. Yu: “Room-temperature ionic liquids: a novel versatile lubricant”. Chem. Commun., (2001), 2244-2245. This research group used imidazolium tetrafluoroborate as a lubricant for various tribo-pairs and, in all the experiments, the use of ILs showed significant friction reduction. After this initial research, many other researchers have studied the tribological behavior of ILs and the number of chemical structures investigated and papers published on this topic grows rapidly every year. In addition, dicationic ILs (DILs) have been investigated for their tribological behavior and showed good performances. The thermal stabilities of DILs are generally greater than those of most traditional monocationic ILs.
Zinc dialkyl dithiophosphates (ZDDPs) are the most common additives used in hydraulic, gear, and engine oils. The use of ZDDPs, however, presents disadvantages. For example, ash generation by ZDDPs is dangerous for engine oils, since it reduces significantly the durability of the after treatment system installed in the exhaust system to reduce undesired emissions, mainly carbon monoxide, unburned hydrocarbons, and oxides of nitrogen, generated in the engine.
Ashless thiophosphates also have been shown to exhibit superior wear performance, and have been shown to be superior to ZDDP in some aspects. U.S. Pat. Nos. 7,074,745 and 8,216,982 and Publication No. 2011/0319303 disclose ashless fluorothiophosphates. In addition, alkylthioperoxydithiophosphates are described in U.S. patent application Ser. No. 13/887,968, filed on May 6, 2013.
The present disclosure is directed to anti-wear and/or friction reducing formulations that include a mixture of at least one first ionic liquid and at least one ashless antiwear compound. The ashless antiwear compound can be a second ionic liquid or an ashless thiophosphate compound. The formulation desirably provides synergistic anti-wear and/or friction reducing properties.
The first IL can be a monocationic ionic liquid or a dicationic ionic liquid. The second IL is a dicationic ionic liquid. The ashless thiophosphate is desirably a thiophosphate, such as a fluorothiophosphate (FTP), an alkylphosphorofluoridothiolate, or an alkylthioperoxydithiophosphate.
The mixtures contain the ashless compound in an amount from 1 to 25% by weight.
The present disclosure further is directed to antiwear and/or friction reduction formulations comprising the above mixtures diluted up to 25% by weight in a base oil.
The present disclosure is moreover directed to using the above described mixtures and formulations as antiwear and/or friction reducing agents either in neat form or as combined with base oils.
Mixtures of ionic liquids provide higher friction and wear reduction than single ILs, both as neat lubricants and as additives in base oil. Often this improvement in antiwear and friction reducing properties is greater when increasing the temperature. In general, longer chain lengths yielded better tribological behavior and higher ionic liquid corrosion resistance. Improvement of the IL mixture was also effective when the mixture was diluted at an overall amount of 1% in a base oil. The anion has a bigger influence than the cation in thermal properties, and the IL mixture does not significantly reduce the best thermal resistance.
In addition, blends of IL with ashless thiophosphates also exhibit superior wear and friction performance when compared with each of the constituent compounds alone. The mixtures are compatible with traditional additives used in engine oil such as antioxidants and detergents. These mixtures have the potential to replace ZDDP as they are ashless in nature, stable, and compatible with existing additive packages and are reasonably priced. These additives have application in a range of consumer and industrial products including engine oils/transmission oils/gear oils for automobiles and commercial vehicles. Since the ionic liquids have a very low evaporation rate, they can reduce the evaporation of lubricant in the engine caused by the high temperatures. Additionally, this property makes them promising as lubricants and greases for vacuum applications.
While the mixtures contain phosphorus and sulfur they do not contain metal cations. In addition, they are very polar (both the ionic fluids as well as the fluorothiophosphates) and have a much greater affinity to metal surfaces and provide improved wear performance compared to ZDDP. The IL mixtures may be used at lower levels of phosphorus and sulfur compared to ZDDP and have the potential to reduce the extent of deposits on catalytic convertors and hence resulting in reduced undesired emissions from internal combustion engines. The ionic liquids can exhibit very high thermal stability up to more than 400° C. as determined by thermal analysis, making them good candidates for formulations that need high thermal resistance and low evaporation rates.
The present disclosure may take form in various components and arrangements of components, and in various process operations and arrangements of process operations. The present disclosure is illustrated in the accompanying drawings, throughout which like reference numerals may indicate corresponding or similar parts in the various figures. The drawings are only for purposes of illustrating preferred embodiments and are not to be construed as limiting the disclosure. Given the following enabling description, the novel aspects of the present disclosure should become evident to a person of ordinary skill in the art.
In the description below, ionic liquids generally are referred to as ionic liquids or ILs. Monocationic ionic liquids specifically are called MILs and dicationic ionic liquids (ionic pair at both ends) specifically are termed DILs. The invention comprises synergistic mixtures of a) ionic liquids and b) ionic liquids with ashless thiophosphate compounds. The mixtures are useful as antiwear and friction reduction compounds, both as undiluted neat formulations and when diluted with base oils.
Ionic Liquids
The general structures of monocationic ionic (MILs) and dicationic ionic liquids (DILs) are schematically presented as follows:
R denotes in all cases a substituent. Some examples of DILs are shown in
C represents the same or different cations including, but not limited to, pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, 1H-pyrazolium, 3H-pyrazolium, 4H-pyrazolium, 1-pyrazolinium, 2-pyrazolinium, 3-pyrazolinium, 2,3-dihydroimidazolium, 4,5-dihydroimidazolinium, 2,5-dihydroimidazolinium, thiazolium, oxazolium, 1,2,4-triazolium, 1,2,3-triazolium, pyrrolium, pyrrolidinium, imidazolidinium, pyrrolidinonium, ammonium (R1R2R3R4N+, R1R2R3HN+, R1R2H2N+, R1H3N+, H4N+), phosphonium, sulfonium, indolinium, quinolinium, isoquinolinium, quinoxalinium, benzimidazolium, acridinium, benzothiophenium, benzotriazolium, benzoxazinium, isoxazolium, morpholinium, benzoxadiazolium, benzoxazolium, 2-oxazolidinium, piperazinium, piperidinium, purinium, benzotriazolium, tetrazolium, thiadiazolium, thiomorpholinium, thiophenium, thiopyranium, thiouronium, uranium, guanidinium, 1,3-selenazolium, 1,3-azaphospholium, 1,2,4-diazaphospholium, diphosphorazolium, 1,3-thiaphospholium, 1,3-oxaphospholium, 1,3-selenphospholium, 1,3-phospholium, 1,3,4-azaphospholium, 1,3,4-diazaphospholium, 1,3,4-azadiphospholium, 1,3,4-triphospholium.
The most commonly used cations are ammonium, phosphonium, pyrrolidinium, piperidinium, imidazolium, and pyridinium.
A comprises at least one anion which can be chosen from the group halogenids, like Cl−, F−, Br− and I−, halogenphosphates, such as [PF6]−, halogenarsenates, such as [AsF6]−, [AsF3]− and halogenantimonates, such as [SbF6]−; anions can be used such as: [SO4]2−, [R1SO4]−, [S2O8]2−, [R1S2O8]−, [SO3]2−, [R1SO3]−, [SO2]2−, [R1SO2]−, [SO5]2−, [R1SO5]−, [S]2−, [R1S]−, [SCN]−, [R1OSO3]−, [CF3SO3]−, [CF3CF2SO3]−, [CF3CF2CF2SO3]−, [CF3CF2CF2CF2SO3]−, [CF3(CF2)nSO3]−, with n from 4 to 30, [HCF2CF2SO3]−, [CF3CHFCF2SO3]−, [HCClFCF2SO3]−, [HCF2CF2SO3]−, [CF3OCHFCF2SO3]−, [CF3CF2OCHFCF2SO3]−, [CF3CHFOCF2CF2SO3]−, [HCF2CF2OCF2CF2SO3]−, [CF2ICF2OCF2CF2SO3]−, [CF3CF2OCF2CF2SO3]−, carbonates such as [CO3]2−, [R1CO3]−, phosphorus containing anions such as [PO4]3−, [(R1O)2P(O)O]−, [(R1O)(R2O)(O)O]−, [(R1S)(R2O)P(O)O]−, [(R1O)(R2O)P(S)O]−, [(R1O)(R2O)P(O)S]−, [(R1)(R2O)P(S)S]−, [(R1S)(R2O)P(S)O]−, [(R1S)(R2O)P(O)S]−, [(R1S)(R2S)P(O)O]−, [(R1O)(R2S)P(S)S]−, [(R1S)(R2S)P(O)S]−, [(R1S)(R2S)P(S)O]−, [(R1S)(R2S)P(S)S]−, [P(C2F5)3F3]−, [P(CF3)3F3]−, [P(C2HF4)(CF3)2F3]−, [P(C2H2F3)3F3]−, [P(C2F5)(CF3)2F3]−, [P(C6F5)3F3]−, [P(C3F7)3F3]−, [P(C4F9)3F3]−, [P(C2F5)2F4]−, [R1R2P(O)O]−, [R1R2P(S)O]−, [R1R2P(O)S]−, [R1R2P(S)S]−, [(C2F5)2P(O)O]−, [(CF3)2P(O)O]−, [(C4F9)2P(O)O]−, [(C2F5)2P(O)O2]2−, [P(C2H5)2F4]−, [(R1O)P(O)O2]2−, [(R1S)P(O)O2]2−, [(R1O)P(S)O2]2−, [(R1O)P(O)OS]2−, [(R1S)P(S)O2]2−, [(R1O)P(O)S2]2−, [(R1S)P(O)OS]2−, [(R1O)P(S)OS]2−, [(R1S)P(S)OS]2−, [(R1O)P(S)S2]2−, [(R1S)P(S)S2]2−, [R1P(O)O2]2−, [R1P(S)O2]2−, [R1P(O)OS]2−, [R1P(S)OS]2−, [R1P)(O)S2]2−, [R1P(S)S2]2−, [CF3P(O)O2]2−, [CH3P(O)O2]2, [R1O)(R2)P(O)O]−, [(R1S)(R2)P(O)O]−, [(R1O)(R2)P(S)O]−, [(R1O)(R2)P(O)S]−, [(R1O)(R2)P(S)S]−, [(R1S)(R2)P(O)S]−, [(R1S)(R2)P(S)O]−, [R1R2P(O)O]−, [R1R2P(S)O]−, [R1R2P(O)S]−, [R1R2P(S)S]−, [(CH3O)2P(O)O]−, amino acid anions such as [R1CH(NH2)C(O)O]−, carboxylates such as [R1C(O)O]−, [CCl3C(O)O]−, [CF3C(O)O]−, [CF3CF2C(O)O]−, nitrogen containing anions such as [NO3]−, [R1SO2)2N]−, [(CF3SO2)2N]−, [(CF3CF2SO2)2N]−, [(CF2ISO2)2N]−, [(HCF2CF2SO2)2N]−, [(CF3CHFCF2SO2)2N]−, [R1SO2NC(O)R2]−, [R1C(O)NC(O)R2]−, [(FSO2)2N]−, [NR2]−, [N(CF3)2]−, [N(CN)2]−, [N(CN)3]−, boron containing anions such as [BO3]3−, [(R1O)BO2]2−, [(R1O)(R2O)BO]−, [BR1R2R3R4]−, [BF3(CF3)]−, [BF2(CF3)2]−, [BF(CF3)3]−, [B(CF3)4]−, [BF2(C2F5)2]−, [BF3(C2F5)]−, [BF(C2F5)3]−, [B(C2F5)4]−, [BF3(CN)]−, [BF2(CN)2]−, [BF(CN)3]−, [B(CN)4]−, [BX4]−, [B(C6H5)4]−, [B(OR1)4]−, [B(OCH3)2(OC2H5)2]−, [B(O2C2H4)2]−, [R1R2BO2]2−, [R1R2BO2]2−, [R1R2BO]−, bis[oxalato(2-)-O,O′]borate, saccharinate and silicon containing anions such as [SiO4]4−, [(R1O)SiO3]3−, [(R1O)(R2O)SiO2]2−, [(R1O)(R2O)(R3O)SiO]−, [R1SiO3]3−, [R1R2SiO2]2−, [R1R2R3SiO]−, further anions from the group of [(R1SO2)3C]−, [(CF3SO2)3C]−, [(CF3CF2SO2)3C]−, [(CN)3C]−, [R3C]−, [CF3CO2]−, [CN]−, [(R1O(O)C)2CR1]− can be chosen, where the substituents R1 to R4 are same or different, and can be hydrogen, substituted or unsubstituted linear or branched saturated or unsaturated carbon chains (preferably from 1-30 C atoms), substituted or unsubstituted aromatic or cycloaliphatic groups, which can be interrupted with heteroatoms like oxygen, sulfur, nitrogen, phosphorus and functional atom groups chosen from the following groups:—CH2O—, —C(O)—, —C(O)O—, —OC(O)—, —OC(O)O—, —OC(S)O—, —OC(O)S—, —SC(O)S—, —SC(S)O—, —SC(S)S—, —C(S)—, —CH(SH)—, —C(NH)—, —CH(NH2)—, —CH(OH)—, —NH—(O)C—, —NH—(O)CO—, —S(O)—, —SO2—, —SO3—, —N═N—, —NH—C(O)—NH—, —NH—C(S)—NH— or —S(O2)—NH—; in the case of linear or branched saturated and unsaturated carbon chains as well as substituted aromatic and cycloaliphatic groups, the substituents can be chosen from the group —OH, —NH2, —Cl, —F, —Br, —I, —CN, —CHN, —CSH, —COOH, —CHO, —C(O)CH3, —C(S)CH3, —C—S—CH3, —NH—C(S)—NH2, —NH—C(O)—NH2, —S(O2)Cl, —S(O2)Br, —S(O2)F, —S(O2)I, —S(O2)OH and C(O)X, where X for example F, Cl, Br, I, SO2 or NH2 is; the substituents R1 to R4 can also be end standing atoms or atom groups, chosen from the group —OH, —NH2, —Cl, —F, —Br, I, —CN, —CHN, —CSH, —COOH, —CHO, —C(O)CH3, —C(S)CH3, —NH—C(S)—NH2, —NH—C(O)—NH2, —S(O2)Cl, —S(O2)Br, —S(O2)F, —S(O2)I and C(O)X, where X for example is F, Cl, Br, I, SO2 or NH2.
The most widely used anions are tetrafluoroborate, hexafluorophosphate, bis(trifluoromethylsulfonyl)imide, triflate, dialkylphosphates and dialkyldithiophosphates.
P represents a connecting chain which can be substituted or unsubstituted linear or branched saturated or unsaturated carbon chain (preferably from 1-30 C atoms), or can contain one or more of the following groups as repeating units:
Substituted or unsubstituted ether groups, preferably ethylene glycol with the number of repeating units ranging from 1 to 300, preferably 2 to 100;
Isobutylene with the number of repeating units ranging from 1 to 300;
Dimethylsiloxane with the number of repeating units ranging from 1 to 450; or
n-Butylacrylate with the number of repeating units ranging from 1 to 120.
Furthermore, due to the synthetic procedure, all included ionic groups, without exception, can be attached to the connecting chain P via a triazine ring, resulting in ionic liquids which can contain one or more triazine rings incorporated between the connecting chain and ionic group.
Ashless Thiophosphate Compounds
Ashless thiophosphate compounds can be of several types. Generally, ashless thiophosphates that have been shown to be effective antiwear additives can be used. For example, fluorothiophosphate (FTP) compounds can be used, such as those of the general formula (RO)(R′O)P(S)F where R and R′ comprise the same or different substituents with linear or branched saturated or unsaturated carbon chains (preferably from 1-30 C atoms), substituted or unsubstituted aromatic or cycloaliphatic groups. Fluorothiophosphates are disclosed in U.S. Pat. Nos. 7,074,745 and 8,216,982 for example. Alkylphosphorofluoridothioates are disclosed in US Publication 2011/0319303. Another preferred class of ashless thiophosphates is alkylthioperoxydithiophosphates described in U.S. patent application Ser. No. 13/887,968 filed on May 6, 2013. Examples of one type of fluorothiophosphates are shown in
Mixtures with Ionic Liquids
The invention includes synergistic mixtures of at least one ionic liquid with another component. More specifically, the invention includes synergistic mixtures of MILs with DILs, synergistic mixtures of DILs and DILs, synergistic mixtures of MILs with ashless thiophosphates, synergistic mixtures of DILs with ashless thiophosphates, and synergistic three part mixtures of MILs, DILs, and ashless thiophosphates. The mixtures provide better antiwear activity than the individual components alone The amount of the individual neat components range from 1 to 99%, preferably from 5 to 25% for the minor components.
Mixtures with Ionic Liquids Diluted in Base Oils
The mixtures described above can also be used in combination with one or more base oils. The mixtures are combined with one or more base oils of group I, II, III, IV, or V as defined by the American Petroleum Institute (www.API.org, publication API 1509). The mixtures with ionic liquids are used in an amount of up to 99%, preferably 75%, more preferably 25%, and more preferably between about 1 and about 5% by weight in the base oil.
Additional components can be included in the formulations, such as detergents, dispersants, extreme pressure additives, antiwear additives, antifoam additives, demulsifying agents, corrosion inhibitor, biocides, viscosity index improvers, antioxidants, tackifiers, friction modifiers, emulsifying agents, dyes, thickeners, other surface active substances, and other performance additives.
The examples below serve to further illustrate the invention, to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and/or methods claimed herein are made and evaluated, and are not intended to limit the scope of the invention. In the examples, unless expressly stated otherwise, amounts and percentages are by weight, temperature is in degrees Celsius or is at ambient temperature, and environmental pressure is at or near atmospheric.
Methods and Materials—Ball-On-Flat Configuration
Ionic liquids were tested by Schwing-Reib-Verschleiss (SRV®) tribometer (Optimol Instruments Prüftechnik, Germany) with reciprocating ball-on-flat configuration. The experiments were performed following the guidelines of the standard method ASTM D 6425-05. According to this procedure, the load applied was 300 N and the experiments lasted 2 hours. Other parameters were: stroke of 1 mm and frequency of 50 Hz. Both balls and discs were purchased from Optimol Instruments Prüftechnik and the quality of the material was certified to be in conformity with international standards. The balls were made of steel AISI 52100 with a diameter of 10 mm, roughness of 0.012 μm, and hardness HRC 63±2. Discs were made of steel AISI 52100 with a diameter of 24 mm, thickness of 7.9 mm, and roughness of 0.56 μm. The initial maximum contact pressure, calculated as suggested by Stachowiak (G W Stachowiak and A W Batchelor. Engineering tribology. 3rd edn. Boston; Butterworth-Heinemann, 2005) for contact between a sphere and a flat surface, was 3.14 GPa. Experiments were performed twice at 50, 100, and 150° C. with neat DILs.
The ball wear scars were examined by optical microscope DM 2500 MH (Leica, Germany), and by SEM-EDS (Scanning Electron Microscopy Energy Dispersive Spectroscopy) analysis with ULTRA FE-SEM (Zeiss, Germany) as described by Pagano et al. Dicationic ionic liquids as lubricants. Proceedings of the Institution of Mechanical Engineers, Part J: Journal of Engineering Tribology November 2012 vol. 226 no. 11 952-964.
Average friction coefficient (COF) was calculated from measuring values after a running-in period of 500 s.
In order to study the thermal degradation of the ILs, Thermogravimetric Analysis (TGA) and Differential Scanning calorimetry (DSC) were applied. The equipment used for thermal analysis was the SDT Q600 (TA Instruments, USA), capable of performing both DSC and TGA simultaneously. The analyses were performed in a dynamic mode, with temperature linearly increasing at a rate of 10° C./min under a constant flow of nitrogen. The TGA and DSC experiments started at ambient temperature and finished at 500° C. The pans used for holding the samples were of platinum. For the characterization by TGA, the start temperature (Tstart) is defined as the temperature where a change in the rate of weight loss can be noticed. The onset temperature (Tonset) is determined as the intersection of two tangent lines to the curve; the first is taken in its initial steady phase and the second is taken from the area with fast decreasing of weight.
The following DILs were tested (DIL1, DIL2) as well as a 9:1 stoichiometric mixture of the two (DIL1+2). The ball-on-flat configuration was used.
This combination makes use of two cationic groups N-methylimidazolium which are connected by tetraethylene glycol. The cations are paired with bis(trifiuoromethanesulfonyl)imide (Tf2N) (DIL1) and methane sulfonate (DIL2) anions.
Results—Thermal Stability
Table I shows the results of thermal analysis. DIL1, DIL2, and DIL1+2 were all stable up to temperatures of at least 150° C., the highest temperature chosen for the tribological measurements. The DILs were in the liquid state at room temperature and no significant phase transitions were detected within the tribological measuring range. The base oil Synalox™ was also measured. Synalox™ is a polypropylene glycol monobutyl ether (CAS 9003-13-8) obtained from The Dow Chemical Company.
Results—Ball-On-Flat Configuration
SEM-EDS analysis was performed on the balls used for the experiments with DIL1+2. At 100° C., only small amounts of oxygen and sulfur were detected in the wear scar area. But at 150° C., both oxygen and sulfur were found in considerable quantities. It can be concluded that there is a change in the tribo-mechanism; at elevated temperature it appears that a more pronounced tribolayer has been originated due to the reactivity of the steel with the sulfur containing anions.
Methods and Materials—Configuration
For DILs in base oil, tribometrical experiments and analysis of the wear scars were carried out according to the methods and materials as described in Example 1. The tribometrical experiments were carried out at 100° C.
Synalox™ polypropylene glycol monobutyl ether (CAS 9003-13-8) was used as the base oil for binary mixtures with an overall amount of 1% (w/w) of the DILs.
X-ray Photoelectron Spectroscopy (XPS) was performed using a Thermo Fisher Scientific Theta Probe (East Grinstead, United Kingdom) with a monochromatic Al Kα X-ray source (hν=1486.6 eV). The base pressure during the measurements was consistently at 3×10−9 mbar. The samples for the XPS analysis were cleaned directly after the tribological experiment by immersion in toluene in an ultrasonic bath for 15 minutes at room temperature, followed by 2-propanol and petroleum ether for the same duration. Spots in and outside of the worn area of the tribometer discs were defined and analyzed with a spot size of 100 μm at pass energy of 50 eV for the detail spectra and the survey spectra were recorded at 200 eV pass energy. For the imaging XPS experiment, an area of 2.55 mm2 was scanned with a spot and step size of 100 μm, resulting in 285 measurement points. The elements were recorded as snap shots with a 15 eV wide binding energy window and a pass energy of 150.5 eV. The resulting analysis data was processed with the Avantage Data System software, using GaussianlLorentzian peak fitting.
Results—Ball-on-Flat Configuration
The mixture of 2 DILs shows better antiwear properties even when it is added to base oil. This phenomenon is illustrated in
X-ray Photoelectron Spectroscopy (XPS) showed that fluorine content was significantly higher in the worn area than outside. Further investigation of fluorine by a detail scan clearly showed that no organic fluorine was present in this tribologically stressed region. Instead, inorganic fluorine with a binding energy of 684.6 (±0.2) eV was detected, which suggests that the bis(trifluoromethylsulfonypimide anion is completely decomposed under these tribological conditions by the formation of an inorganic fluorine layer. Further sulfidic sulphur was detected at a binding energy of 161.7 (±0.1) eV in the wear track which gives additional evidence for breakup of the anionic structure. The distribution of the binding energies 684.6 (+0.2) eV, inorganic fluorine, and 161.7 (±0.1) eV were investigated by an imaging XPS experiment, which clearly showed that this binding energies are mainly located in the wear track.
The corrosion resistance of the DILs was also investigated by depositing the DILs over the surfaces of steel discs and analyzing the surface after exposure to DIL at 100° C. for one week. DIL1 and the mixture DIL1+2 presented no corrosion and no indication of etched surface. DIL2 presented slight homogeneous corrosion on the area of interest. Here, the corrosion resistance of the mixture is similar to the most stable ionic liquid.
Methods and Materials—Ball-on-Flat Configuration
A mixture of the MIL choline bis(2-ethylhexyl)phosphate (P-IL) and an FTP was examined using ball on disc configuration. The FTP was an alkylphosphorofluoridothioate, octadecylphosphoro fluoridothioate. The ball-on-flat configuration was used. The structure of the P-IL is shown below.
P-IL alone and the mixture of the P-IL and the FTP were diluted in a hydrocarbon base oil. The base oil was composed of 60 weight % SN 150W (group I base oil, mineral oil type) and 40 weight % BS 90W (brighstock) to give following viscosities: kinematic viscosity at 100° C.-10.4 mm2/s; kinematic viscosity at 40° C.-87.3 mm2/s, viscosity index −100. The concentration of P-IL and the mixture of the P-IL and the FTP were adjusted to give an overall phosphorus concentration of 1000 mg/kg in the base oil. The ratio was 80% P by P-IL and 20% P by FTP. The tribological test conditions performed on a Schwing-Reib-Verschleiss (SRV®) tribometer (Optimol Instruments Prüftechnik, Germany) with reciprocating ball-on-flat configuration are shown below. Both balls and discs were purchased from Optimol Instruments Prüftechnik and the quality of the material was certified to be in conformity with international standards. All tests with base oil alone and dilutions with MIL and MIL+FTP involved were repeated twice.
Wear scar analysis on both disc and ball was performed according to the procedure described by Hunger et al. Tribological characterisation and surface analysis of diesel lubricated sliding contacts. Tribol Schmierungstech 2010; 57:6-13) to provide wear volumina.
Results—Ball-on-Flat Configuration
Table 3 shows the COF and WV results for this example. ZDDP was also tested for comparison.
It is evident from the wear behavior that the friction coefficient in the test decreases from base oil to an oil with P-IL and it is further reduced as FTP is added to the mixture. The wear volume on the flat surface is a good indication of the efficacy of the lubricant in the tribological contact. The wear volume decreases from base oil alone to base oil (BO) with P-IL to base oil with P-IL-FTP (BO=1.4×106±1×105, BO+P-IL=1.6×105±4×104, BO+P-IL+FTP=3.1×104±4×103). Similar trends are seen for the wear behavior of the ball as shown in the table. The synergistic interaction between the P-IL and FTP is responsible for the improved wear behavior. The results are also shown in
Methods and Materials—Ball-on-Flat Configuration
A mixture of the MIL choline dibutyl dithiophosphate (TP-IL) and an FTP was examined using ball on disc configuration. The FTP was an alkylphosphorofluoridothiolate-octadecylphosphoro fluoridothioate. The ball-on-flat configuration was used. The structure of the TP-IL is shown below.
TP-IL and the mixture of the TP-IL and the FTP were diluted in a hydrocarbon base oil. The composition of the base oil was identical with that given in Example 3. The concentration of TP-IL and the mixture of the TP-IL and the FTP were adjusted to give an overall phosphorus concentration of 1000 mg/kg in the base oil. The ratio was 80% P by TP-IL and 20% P by FTP. The tribological test conditions were performed as described in Example 3.
Results—Ball-on-Flat Configuration
Table 4 shows the results for COF and wear scar evaluation for the base oil+TP-IL, base oil+FTP, base oil+TP-IL+FTP, and base oil+ZDDP.
The COF decreased from base oil alone to base oil with TP-IL and it was further reduced when FTP was added to the mixture. The wear volume on the flat surface is a good indication of the efficacy of the lubricant in the tribological contact. The wear volume also decreased from base oil alone to base Oil with TP-IL to base oil with TP-IL+FTP (BO=1.4×106±1×105, BO+TP-IL=2.6×105±1.4×105, BO+TP-IL+FTP=1.2×105). Similar trends were seen with the wear behavior of the ball as shown in the table. The synergistic interaction between the TP-IL and FTP is responsible for the improved wear behavior. The results are also shown in
Modifications and variations of the present invention will be apparent to those skilled in the art from the forgoing detailed description. All modifications and variations are intended to be encompassed by the following claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety.
This application claims priority to provisional application 61/643,681 filed on May 7, 2012.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2167784 | Svendsen | Aug 1939 | A |
| 2230654 | Plunkett | Jan 1941 | A |
| 2510112 | Holbrook | Jun 1950 | A |
| 2624713 | Hurley | Jan 1953 | A |
| 2884431 | Smith et al. | Apr 1959 | A |
| 2904398 | Smith | Sep 1959 | A |
| 2924508 | Gililand et al. | Feb 1960 | A |
| 2952514 | Smith | Sep 1960 | A |
| 2959544 | Smith et al. | Nov 1960 | A |
| 2993567 | Schachner | Jul 1961 | A |
| 3097063 | Gililand et al. | Jul 1963 | A |
| 3114889 | Christian | Dec 1963 | A |
| 3194762 | Browning et al. | Jul 1965 | A |
| 3247116 | Relling | Apr 1966 | A |
| 3432431 | Mitacek | Mar 1969 | A |
| 3493513 | Petriello | Feb 1970 | A |
| 3505229 | Skehan | Apr 1970 | A |
| 3536624 | Christian et al. | Oct 1970 | A |
| 3567521 | Toy et al. | Mar 1971 | A |
| 3592700 | Toy | Jul 1971 | A |
| 3607747 | Ishikawa | Sep 1971 | A |
| 3636172 | Gardner | Jan 1972 | A |
| 3640859 | Messina et al. | Feb 1972 | A |
| 3656700 | Gauvin | Apr 1972 | A |
| 3720722 | Wada et al. | Mar 1973 | A |
| 3723317 | Ulery | Mar 1973 | A |
| 3750911 | Ebner et al. | Aug 1973 | A |
| 3806455 | Siegart et al. | Apr 1974 | A |
| 3909431 | Figiel | Sep 1975 | A |
| 3933656 | Reick | Jan 1976 | A |
| 3969233 | Lucas | Jul 1976 | A |
| 4012493 | Layne et al. | Mar 1977 | A |
| 4021530 | Layne et al. | May 1977 | A |
| 4029870 | Brown et al. | Jun 1977 | A |
| 4034070 | Wojtowicz et al. | Jul 1977 | A |
| 4036718 | Brown et al. | Jul 1977 | A |
| 4052323 | Feneberger et al. | Oct 1977 | A |
| 4127491 | Reick | Nov 1978 | A |
| 4130492 | Longo et al. | Dec 1978 | A |
| 4224173 | Reick | Sep 1980 | A |
| 4252678 | Smith | Feb 1981 | A |
| 4313761 | Joyce et al. | Feb 1982 | A |
| 4349444 | Reick | Sep 1982 | A |
| 4363737 | Rodriguez | Dec 1982 | A |
| 4405469 | Hafner | Sep 1983 | A |
| 4465607 | Cottell | Aug 1984 | A |
| 4484954 | Tarancon | Nov 1984 | A |
| 4500678 | Kita et al. | Feb 1985 | A |
| 4545964 | Bergez et al. | Oct 1985 | A |
| 4584116 | Hermant et al. | Apr 1986 | A |
| 4615917 | Runge | Oct 1986 | A |
| 4638444 | Laragione et al. | Jan 1987 | A |
| 4657687 | Caporiccio et al. | Apr 1987 | A |
| 4741893 | Watanabe et al. | May 1988 | A |
| 4764056 | Zentgraf et al. | Aug 1988 | A |
| 4770797 | Syracuse et al. | Sep 1988 | A |
| 4803005 | Juhlke et al. | Feb 1989 | A |
| 4824690 | Heinecke et al. | Apr 1989 | A |
| 4832859 | Basset et al. | May 1989 | A |
| 4834894 | Scheld | May 1989 | A |
| 4857294 | Bridenne Alaux et al. | Aug 1989 | A |
| 4857492 | Bradley et al. | Aug 1989 | A |
| 4859357 | Germanaud et al. | Aug 1989 | A |
| 4888122 | McCready | Dec 1989 | A |
| 4892669 | Marcora et al. | Jan 1990 | A |
| 4917872 | Nakahara et al. | Apr 1990 | A |
| 4938945 | Mahmood et al. | Jul 1990 | A |
| 4983373 | Withers, Jr. et al. | Jan 1991 | A |
| 5004554 | Tohzuka et al. | Apr 1991 | A |
| 5009963 | Ohmi et al. | Apr 1991 | A |
| 5096145 | Phillips et al. | Mar 1992 | A |
| 5110657 | Ainslie | May 1992 | A |
| 5116900 | Flautt et al. | May 1992 | A |
| 5118434 | Meyer et al. | Jun 1992 | A |
| 5133886 | Hata | Jul 1992 | A |
| 5160646 | Scheid | Nov 1992 | A |
| 5188747 | Kai et al. | Feb 1993 | A |
| 5227081 | Sawa et al. | Jul 1993 | A |
| 5242506 | Barber et al. | Sep 1993 | A |
| 5286882 | Zuzich et al. | Feb 1994 | A |
| 5350727 | Tsurumi et al. | Sep 1994 | A |
| 5373986 | Rafferty et al. | Dec 1994 | A |
| 5380557 | Spiro | Jan 1995 | A |
| 5385683 | Ransom | Jan 1995 | A |
| 5447896 | Rao | Sep 1995 | A |
| 5460661 | Maynard, Jr. | Oct 1995 | A |
| 5595791 | Baumgart et al. | Jan 1997 | A |
| 5595962 | Caporiccio et al. | Jan 1997 | A |
| 5698483 | Ong et al. | Dec 1997 | A |
| 5767045 | Ryan | Jun 1998 | A |
| 5877128 | Greer | Mar 1999 | A |
| 6045692 | Bilski et al. | Apr 2000 | A |
| 6080899 | Bradley et al. | Jun 2000 | A |
| 6152978 | Lundquist | Nov 2000 | A |
| 6258758 | Greer | Jul 2001 | B1 |
| 6316377 | Fulton et al. | Nov 2001 | B1 |
| 6361678 | Childs et al. | Mar 2002 | B1 |
| 6362135 | Greer | Mar 2002 | B1 |
| 6413918 | Beatty et al. | Jul 2002 | B1 |
| 6436362 | Cuzzato | Aug 2002 | B1 |
| 6541430 | Beatty | Apr 2003 | B1 |
| 6630610 | Swain et al. | Oct 2003 | B2 |
| 6642186 | Beatty et al. | Nov 2003 | B2 |
| 6734320 | Beatty et al. | May 2004 | B2 |
| 6764984 | Beatty | Jul 2004 | B2 |
| 6835218 | Drozd et al. | Dec 2004 | B1 |
| 6955793 | Arencibia et al. | Oct 2005 | B1 |
| 6960555 | Anthony et al. | Nov 2005 | B2 |
| 7074745 | Shaub et al. | Jul 2006 | B2 |
| 7592287 | Kemnitz et al. | Sep 2009 | B2 |
| 7754662 | Aswath et al. | Jul 2010 | B2 |
| 7879776 | Patel et al. | Feb 2011 | B2 |
| 20010038048 | Blanton | Nov 2001 | A1 |
| 20030139300 | Beatty | Jul 2003 | A1 |
| 20050119135 | Shaub et al. | Jun 2005 | A1 |
| 20060014652 | Parekh et al. | Jan 2006 | A1 |
| 20060040832 | Zhang | Feb 2006 | A1 |
| 20060063683 | Parekh et al. | Mar 2006 | A1 |
| 20060281644 | Aswath et al. | Dec 2006 | A1 |
| 20070093397 | Patel et al. | Apr 2007 | A1 |
| 20080027231 | Armstrong et al. | Jan 2008 | A1 |
| 20100093577 | Ritchie | Apr 2010 | A1 |
| 20100137175 | Kunz et al. | Jun 2010 | A1 |
| 20110092399 | Schmidt-Amelunxen et al. | Apr 2011 | A1 |
| 20110319303 | Chen et al. | Dec 2011 | A1 |
| 20130296598 | Aswath et al. | Nov 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 101768121 | Jul 2010 | CN |
| 0856570 | Aug 1998 | EP |
| 804777 | Nov 1958 | GB |
| 10287402 | Oct 1998 | JP |
| WO 2011026990 | Mar 2011 | WO |
| Entry |
|---|
| Parekh et al. “Synthesis of Fluorinated ZDDP Compounds”, Tribol Lett, 34:141-153 (2009). |
| Number | Date | Country | |
|---|---|---|---|
| 20130331305 A1 | Dec 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61643681 | May 2012 | US |
