Lubricating composition containing olefin and process of lubrication of solid surfaces in particular out of aluminium
FRENCH REPUBLIC DEPARTMENT INDUSTRY SERVICE iNTELLECTUAL INDUSTRIELLE of the On PROBLEMS PATENT P.V. n International Classification 1.324.456 C 10 m Olefin-based lubricating composition and method of lubricating of solid surfaces in particular aluminium. Society said: GENERAL. ELECTRIC COMPANY residing in the United States of America. Demanded 10 April 1962, to 12m Issued by stopped 11 March 1963. The present invention relates to- [...] ongoing regulatory improved, more particularly it is relates to surfaces lubricated with lubricants and thereof for which one of the surfaces is a metallic composition or aluminum, is of a composition containing at least 50 weight of aluminium, for example alloys of alu- minimum, the lubricants comprising a mixture body components (1) an olefin long chain of at least 10 carbon atoms and (21 an organic body group-containing polar, a linear long chain, a radical saturated aliphatic having at least 11 atoms of an alkyl carbon and less than straight chain of 1 to 3 carbon atoms bone separated from the long chain radical by the polar group. For short, the term " aluminium or com- aluminum position " includes not only- aluminum member itself, but also corn- positions in which aluminum is present in an amount of at least 50% of the weight total composition, such as, aluminum alloys, andc. Lubrication Prior assays aluminum surfaces have been carried out. Thus is wished lubricating surfaces movable with respect to each other, one of which is a composition metal containing at least 50% by weight aluminum, for example, pure aluminum, aluminum alloys, andc. Lubrication for such aluminum surfaces is especially dif- [...] the case where there is close-conditions sion end requiring lubrication in boundary lubrication conditions i.e. a solid-solid contact real, for example, for- attitude exist on a support prior to deposition of a hydrodynamic film or when the form of 3-41266 novel solid surfaces, for example, by forming a metal wire by passing through a die, during the aluminum cutting, for example, on a lathe, or a punch press, forming an aluminum wire, for example, by stamping, extrusion, centrifugation, cold rolling. For convenience, this type of lubrication will be referred to herein as "boundary lubrication". Under such conditions, it has been found that the aluminum compositions are lubricated with great difficulty due to the fact that under conditions of extreme pressure boundary lubrication, the aluminum surface tends to scrape, is scraping or scratching, even when it is are taken great care. There is no known lubricant which meets the requirement of the "boundary lubrication" compositions containing aluminum at _AOE280A2AO> least 50 Unexpectedly it has been found that a mixture of long-chain olefin of at least 10 carbon atoms and body-containing organic polar group described above can be used as lubricant between two solid surfaces which move relative to the other, re, even in high pressure conditions, or in many instances, these mixtures can be used as additives to the other lubricants known for ones improved boundary lubrication or at least one surface to be lubricated and an aluminum surface. When using the body mixture in the aluminum surfaces lubricating, is found that the coefficient of friction is greatly reduced and the tendency to scuffing, or galling, especially under conditions of boundary lubrication, is materially The booklet Price: 2 francs 63 2191,0 73,266 1 reduced and in many instances, completely eliminated. Furthermore, it is found out that the improved lubricating performance lubricating compositions is added in that a surface moving on another surface in the presence of the lubricants gives a beautiful polished to the aluminium surface, increased 'ant further the ease with which these lubricant compositions can contribute to I' [...] lubrication. In addition to the lubricant compositions according to the invention, particularly suitable ' to lubricate the surfaces in relative motion with respect to each other, of which one is aluminum, it is also possible to use lubricant compositions of the invention to obtain the improved lubrication other solid surfaces in relative motion to each other, particularly when one of these surfaces is a metal used in the manufacture of forms of structure, for example iron, molybdenum, silver, copper, beryllium, tungsten, magnesium, titanium, zirconium, chromium, nickel, cobalt, aluminum, tin, etc, and various compositions of metals, e. g. alloys of the aforesaid metals examples of which are constituted by the type steels, the brass, the various magnesium alloys, cobalt, zinc, zirconium, beryllium, iron (e.g. stainless steel), etc other surface can be made of the same metal or of the different metal or it may be another solid substance, such as wood, moulded synthetic resins, laminates, etc, or a special composition of substances, such as porous metal, graphite, graphite impregnated metal, soft bearing alloy, for instance a metal anti-friction, etc, or compositions for example very hard metal carbides, metal nitrides, andc. The in that the mixture of bodies according to the invention can be used as lubricant for two solid surfaces moving relative to one another or at least one of the surfaces is aluminum, and is entirely unexpected in any way could not be predicted because the old impressions show that the usual lubricants, the lubricating materials and techniques conventional lubricants are not effective in many conditions for portions movable relative to each other having one surface which is aluminum. This is due to the fact that aluminium or aluminium alloys are relatively soft and using the customary lubricants for aluminum, same lubricants containing extreme pressure additives for enhancing the load characteristics of the lubricant on the support, occasioning wear undesirable abrasions and final seizure aluminum comprising the parts movable relative to each other. This spring particularly a recent article of R.D. [...] and J. Willis, listing "development lubricants for cold rolling aluminum alloys" in the "Journal of the Institute of Metal" pages 88 481-492 (1960) wherein the authors indicate the disadvantage of having unsaturated as lubricant additives for cold rolling aluminium alloys. The long-chain olefins used in the invention have the general formula: R '- R CR = C- R-" or R and R 'are monovalent radicals selected from the group consisting of hydrogen and fluorine and in addition R' is selected from the group consisting of methyl, fluoromethyl, difluoromethyl trifluoromethyl and, and R " is an aliphatic radical monovalent saturated straight-chain selected from the group consisting of linear alkyl radicals having at least 8 carbon atoms and linear fluoroalkyl radicals having at least 8 carbon atoms. Preferably, R " does not exceed 30 carbon atoms although can be used longer chain radicals, it will be understood naturally that can be used for these olefin mixtures the use of the invention. The ester compound in this particular class of lubricants, to be free of olefinic unsaturation, comprises a body having the formula: (II) Q-X-Z Z is a radical saturated straight-chain aliphatic, linear, monovalent, selected from the class of linear alkyl groups and fluoroalkyl linear 11 to 30 or more carbon atoms, X is; a bivalent radical selected from the group O oxy (-0-1. thio (-S -), carbonyl (-C -), Caret 0 [...] (- 0-C - 0 -), carbonyl oxy (- 0-C -) which tends 0,0 to include the radical (-C - 0 -), sulfoxy (-S -) and O [...] I-S-)-X and Z together represent the 0 group [...] -XZ which comprises the radicals: 0 0,0 0,0 1 It II II I! -0Z, -S-Z, CZ-O-C-OZ, O-C-Z, -C-OZ, and-S-Z-S-Z it 0 or Z is defined as before. Q is a straight-chain monovalent lower alkyl of 1 to 3 carbon atoms selected from the group alkyl radical yielding and fluoroalkyl radicals as, methyl, ethyl, propyl, fluoromethyl, difluoromethyl, trifluoromethyl; 1.2-difluoroethyl, perfluoropropyl, andc. Among the components normal (as opposed to the components branched chain), represented by the formula I, comprise, for example, the decene -1, dodecene -1, tetradecene -1, dodecene -2,2-tetradecene, pentadecene -2,1-hexadecene (ketene), octadecene -1, octadecene -2,1 - 1- [...] ; 1.2- [...] -1 ; 1-1 - 1- [...][...] ;- [...] 1.1.2.2-2 etc, as well as mixtures of such olefins. Among the radicals Z component, comprise, for example, the radicals undecyl, [...], tetradecyl, hexadecyl, pentadecyl, eicosyl, docosyl, [...], [...], [...] ;- [...] 1.1.1,-2.2, [...], [...], andc. Examples of body in the scale of the formula II are, for example, methyl myristate, methyl palmitate, methyl stearate, [...] ethyl, n-propyl myristate, ethyl palmitate, methyl behenate, acetate-decyl, dodecyl acetate, propionate [...], monofluoromethyl stearate; 1.1 palmitate-fluoroethyl, [...] trifluoromethyl, [...] methyl, difluoromethyl palmitate, methyl [...], [...] fluoro acetate, [...] fluoromethyl, methyl dodecyl ether, ethyl tetradecyl ether, ethyl ether [...], ethyl sulfide [...], propyl sulfide [...], dodecyl methyl ketone, ethyl carbonate [...], [...] sulfoxide, sulfone ethyl hexadecyl, tetradecyl ethyl ether, ethyl sulfide eicosyl, methyl carbonate Mono [...], fluoromethyl dodecyl ether, methyl sulfone [...], methyl sulfoxide, [...], [...] ethyl, 2-fluoroethyl sulfide; 1,2-difluoro-propyl [...] ketone, sulfone fluoroethyl [...], [...] methyl ether, andc. The proportions of the two components may vary greatly and generally preferred proportions such that the combination of the two provides the desired characteristics of lubrication and fluid is a mixture which has a solidification temperature, well below room temperature, for example, below 15 °C, thereby making the lubricant useful in a wide range of temperatures. In general, it has been found that the constituent olefin is advantageously present in an amount equal to about 5 to 95 The blend can be used above components, single, or with other lubricants well known, for example, mineral oils of lubricating viscosity, fats obtained from such lubricating oils, silicone lubricating oils, lubricating oils diester, polyester lubricating oils, lubricating oils silicate ester, andc. May be advantageously utilized aqueous emulsions of the lubricant compositions according to the invention, either alone, or in combinations with other cutting oils well known in applications for cutting and crushing. The lubricants are particularly useful on lubricating solid surfaces which move relative to each other when one of the surfaces is aluminum. When a solid surface moves relative to another with a lubricant between the two surfaces, there may be a complete film of lubricant between the two surfaces, or there may be varying degrees of contact between the surfaces, the first condition exists in the case of ideal hydrodynamic lubrication while the last is characteristic of the boundary lubrication. Pent The obtain the complete hydrodynamic lubrication under certain conditions ideal on supports but is influenced by factors such as design of the two solid surfaces, load on the surfaces and the relative speed. However, even in these conditions, is boundary lubrication during stop and start and from a practical point of view, is approached rather than perfect hydrodynamic lubrication or reaches. Therefore, a possible chance of lubricants improve the boundary lubrication solid surfaces moving relative to the other when one of the surfaces is aluminum, is a line has been greatly desired in the past. Besides enhancing the lubrication features by the lubricants according to the invention, of two solid surfaces when the two are made of aluminium, should be also include that the lubricants are also useful in these cases when one of the surfaces is of aluminium and the other into another solid material, such as various metals as the [...], molybdenum, copper, tungsten, magnesium, zirconium, chromium, nickel, etc, alloys of these metals such as steels, the brass, magnesium alloys, aluminum, iron, zinc, andc. Additionally the other surface can be another solid material dn as wood, synthetic resins molded, laminated products, etc, or of special compositions such as porous metal, graphite, metal impregnated graphite, alloys soft bearing, as bearing alloy or very hard compositions such as carbides, metal nitrides, andc. Lubrication of the above metals alone, other than aluminum using the compositions of the present invention is not excluded. Therefore, the lubrication of surfaces where one of the surfaces is titanium, beryllium, tungsten, etc, useful for making forms of structures is included in the scope of the invention. Nominally, in the construction of the apparatus in which the one of the solid surfaces moves relative to another, the two solid surfaces are at the same material if the a [...] be equal on the two parts or one of the surfaces is made of a material less hard than the other when the wear is to be substantially over the entire portion that is less hard. This is traditionally performed when one of the parts is easier to replace than the other or when cutting or is formed one of the parts by the other. A concentration even in a small amount is for example, at least 15 [...] by weight, of compositions according to the invention in another lubricant boundary lubrication will improve the properties thereof. In general, it has been found that for a solid surface of aluminum when the other surface moves in relation to the first is also aluminum, the coefficient of friction is generally greatly improved when at least 50 Also, the lubricating compositions are formed by this aluminum materials, for example, stretch, folding, and other extrusion and finished with a very mild. [...] said materials are used as lubricants without dilution, the composition can be formed of aluminum with mirror finish polishing, which is difficult to achieve using lubricants previously known. Typical examples of various compositions from aluminum (including aluminum alloys) that are lubricated by lubricants according to the invention are those disclosed and pages 851-853 865-968 of the metals Handbook, flight. 1, "and Selection Properties of Metals American Society for Metals, novelty, Ohio, Eighth Edition (1961)", for example, aluminum alloys which contain high purity more than 99% aluminum, e. g. alloys Ec, alloy 1060,1100 alloy, etc, aluminum alloys with other metals, for example, copper, silica, tin, zinc, etc, as the further described pages 955-958 of the reference above. Mineral oils or hydrocarbon The typical of lubricating viscosity are the hydrocarbon lubricating oils obtained from the oil. The products normally have viscosities of from 25 and 10,000 [...] (S.U.S.) Universal second and may be formed of a single hydrocarbon mixture. It is contemplated that other lubricants [...] silicone oils, silicate ester, diester or polyester as well as mixtures thereof suitable lubricant for the invention without leaving the field of the invention. The compositions according to the invention, corresponding to the above general formula of liquid products vary solid. The solids dissolved in lubricating oils or fluids are capable of giving rise to fluids and fats dependent improving the lubricating properties of the composition and concentration. To obtain the consistency of the grease desired for the lubricating greases, may be added non-abrasive fillers such as silica gel, carbon black, diatomaceous earth, molybdenum sulfide, tin sulfide, graphite, etc, or incorporate soaps to provide a gel structure. In particular soaps useful are metal soaps as soaps alkali or alkaline earth fatty acids, but may also be used other soaps, as zinc soaps, tin, lead, copper, etc, fatty acid. Can be a grease composition particularly desirable dn from lithium stearate or lithium hydroxystearate. Can be these grease compositions by any well-known methods. Naturally It will appear to those skilled that can be added in addition to agents for lowering the pour point, stabilizers, inhibitors, in particular inhibitors of other oxidation and to these lubricant compositions to give the sheath the additional properties called additive properties. In order that those skilled in the art can better understand the practice of the invention, the following examples are given of illustration but not of limitation. In all these examples, the percentages are by weight. The apparatus used for testing these lubricants, indicated in the following examples under the conditions of boundary lubrication, is described in the following scheme on which the single Figure indicates partially, sectional, the portion of an analyzer for standard four-ball wear modified to assess the lubricating compositions using metals in various shapes other than balls. The apparatus includes an analyzer modified four-ball wear described in an article by R. G. Larson listing "Etude of lubrication using a machine of the type to 4 balls, Lubrication Engineering 1, page 35, August 1945". The machine is modified by replacing the four balls and their cavity by a cutting and a washer as shown in Figure. The rider 1 aluminum, is cup-shaped and is rotated at speeds selected in advance with respect to the stationary washer 2 also aluminum, by a shaft 3 of engine to which the jumper 1 is fastened with bolts 4 and 4'. The washer 2 are secured to the base 5 of the chamber 6 by means of a bolt 7 through the medium of a [...] membrane which is adapted to ensure the alignment between the washer 2 and the jumper 1. A lubricant reservoir 8 to be examined is positioned around the apparatus. The chamber 6 has a series of ball holder one of which is indicated at 9 which moves on the membrane 10, which forms the uppermost part of the plunger 11, connected to a hydraulic system (not shown) for establishing various loads between the samples 1 and 2 of the test. When the jumper 1 rotates relative to the washer by rotation in a clockwise direction of the shaft 3, the chamber 6 will rotate on the membrane 10 by the force of friction existing between the membranes 1 and 2. The force required to avoid this rotation is measured by a strain transducer attached to the arm 12. The modification makes it possible to calculate the coefficient of friction and inspection of jumpers 1 and 2 enables the evaluation of the amount and type of wear. By means of the apparatus, or in the following measures on subsequent runs when the jumper having a flat annular surface of 0,393 square inch (0,270 cm square) rotates at 0.88 [...] to give a speed of inches per second 0.0461 surface, (1.17 mm) with respect to the tested sound washer a load of 10 kg. These conditions are those of the friction region and represent the boundary condition the more difficult for the operation of a bearing of the point of view of lubrication. In these assays, the jumper and the washer are made of aluminum. All percentages are by weight, and the tests performed at room temperature (about 22 °C) for one hour except mention opposite. In some of the examples below, the jumper and the washer are of a material other than aluminum, more precisely they are stainless steel and titanium to show the flexibility of the lubricants. the washer shows no discernable wear with the exception of a high polished. Compared, when it is attempted to the ketene alone in the same conditions, using the same and the jumper same both stainless steel washer, the coefficient of friction is very erratic and has a broad dispersion between 0.27 c- 0,4. Furthermore, the surface of the washer has deep trenches indicating excess wear- sive. introduced, as lubricant blends in the ap- such described above in which the staple and the washer are both aluminum, of ketene mixtures (prepared and placed in the commerce by Matheson, and Coleman Bell of East Rutherford, New-Jersey) (as also in the name alpha- [...] or hexadecene- and methyl stearate, and a mixture of n _AOE280A2AO> decene -1 and methyl stearate in the pro- portions indicated. Furthermore, equal is subjected- member testing the ketene single, stearate methyl dissolved in another liquid medium (because methyl stearate is a solid at room temperature), cetane single, to comparing the results obtained by using the various products and indicating properties [...] ! tensioned using the combination of an olefinic hydrocarbon and a composition according to the formula II. Furthermore, for evaluating the effect using the above compositions as lubricants in the apparatus described above, is also assessed i mixtures or ketene n- [...] stearate or isopropyl stearate. Finally, is subjected to the test also j a vegetable oil to show the effect of the j poly-unsaturated ester in a molecule. The vegetable oil (specifically i corn oil) is formed essentially glycerides; fatty acid containing the acid residues! following, expressed by weight:1 to 62% 34 linoleic acid, oleic acid 19 to 49c/ <, hexa acid! decenoic 0.2 to 1.6 A lubricant comprises, in weight per cent, 5-95 of one or more olefines <FORM:0988063/C4-C5/1> and 95-5 of one or more compounds Q-X-Z, wherein R is hydrogen or fluorine; R1 is hydrogen, fluorine, methyl, mono-, di-, or tr-fluoromethyl; R11 is a linear C7+ alkyl or fluoroalkyl radical; X is -O-; -S-, <FORM:0988063/C4-C5/2> Z is a linear C10+ alkyl or fluoroalkyl radical, and Q is a C1- 3 alkyl radical. A long list of suitable compounds is given. They can be used in emulsion form and can be mixed with mineral oils and their greases, di-ester, polyester, silicone and silicate ester oils. To form greases thickeners can be added, e.g. silica gel, carbon black, diatomaceous earth, graphite, molybdenum and tin sulphides, zinc, tin, lead, copper, alkali metal, alkaline earth metal soaps of fatty acids and particularly lithium stearate or hydroxystearate. Specifications 988,061 and 988,062 are referred to. 1° The lubricant composition comprises 5 to 95% by weight of stearate [...] and 95 to 5% ketene; 2° The lubricant composition comprises 5 to 95% by weight of methyl stearate and 95 to 5% of decene -1; 3° The lubricant composition comprises 5 to 95% by weight of ethyl ether tetradecyl, and 95 to 5% of tetradecene -2. II. A lubricating composition comprising a mixture of ingredients containing a minor proportion of lubricating fluid consisting of lubricating fluids to said silicone esters, to hydrocarbons, esters and polyesters to the silicates and a major proportion of a mixture of ingredients comprising fai by weight of 5 to 95% of an olefin having the formula I above and (b) of 95 to 5% of a compound having the formula II above, said composition being characterized in that the compound (a) is methyl stearate and the compound (b) is the ketene. III. An apparatus comprising in combination at least two solid parts between which there is relative motion, one of said parts at least being a metal and a film of lubricant between the said parts comprising by weight of (a) 5 to 95% of an olefin having the formula I above and (b) of 95 to 5% of a compound having the formula II above, characterized by the following features, alone or in combination: 1° The said parts comprise a metal consisting of aluminum and the aluminum alloys containing at least 50% by weight of aluminum and the lubricant film between the said parts comprises a mixture of ingredients by weight compound (a) 5 to 95% of methyl stearate and (b) 95 to 5% of ketene or (has] of 5 to 95% and methyl stearate (b L of 95 to 5% of decene -1; 2° One of the parts is a stainless steel and the film of lubricant between the said parts comprises a mixture of ingredients by weight of compound (a) 5 to 95 (b) 95 to 5% of decene -1. IV. A grease comprising a thickening and a lubricating composition comprising a mixture of ingredients comprising by weight (a) 5 to 95 of fc of an olefin having the formula T above and (b) of 95 to 5 1° The compound (a) is methyl stearate and the compound (b) is the ketene; 2° The compound (a) is methyl stearate and the compound (b) is the [...] -1. V. A ' method of lubricating two solid surfaces between which there is relative motion, at least one surface being made of metal, of maintaining between the two surfaces a composition comprising by weight (a) 5 to 95% of an olefin having the formula I above and (b) of 95 to 5 VI. A method of forming a metal composition that includes maintaining a lubricant film between the metal composition and a part to be formed by subjecting the metal composition to a force sufficient to create a relative movement between said metal composition and said part to be formed and to produce a movement of the portion of said metal composition relative to the remainder thereof, said lubricating composition comprising by weight of (a) 5 to 95% of an olefin having the formula I above and (b) of 95 to 5 fe of a compound having the formula II above said method being characterized in that the composition of metal which is subject to the forming is a aluminum composition consisting of aluminium and alloys of aluminium in which 50% by weight are formed by the [...] and the lubricant is a mixture comprising by weight of 5 to 95% of ketene and 95 to 5 Said Society: COMPAGNIE GENERAL ELECTRIC For proxy: Beau of [...], André [...] & g. [...] [...] For the booklets, be directed to [...] Nationale, 27, the street Convention, Paris (15'). Lubricants [...] Mean of the friction j Notes on ia wear surface . [...] 100 0.11 0.27-0.38 0,1 1 1! Gearbox very high as when the surface is machined, j Many abrasions. ! H very [...] Gearbox after 1. Methyl stearate 30%... 0,1 ; Polished surface, no visible wear. Methyl stearate 40% 0,1 ; Polished surface, no visible wear. 50% methyl stearate 0,09 1 polished surface, no visible wear. 30% methyl stearate 0,11 : Polished surface, no visible wear. Stearate [...] of 30% 0.1-0.24 Burrows and scrapes in 40 mins. 0.14-0.4 : Many abrasions and grooves. 0.12-0.34 0.2 -0.7 Many abrasions. [...] 50% 20% methyl stearate oil 80% 150 SUS 0.2-0.25 [...]. 0,4-> 0.68 0.14 Many abrasions, frozen in position. [...]. Methyl stearate 30°0 * A all times during the i ' test, the coefficient of friction is erratic and varies in the boundaries exposed.