EP0141758B1 - Compositions lubrifiantes contenant des additifs solides - Google Patents
Compositions lubrifiantes contenant des additifs solides Download PDFInfo
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- EP0141758B1 EP0141758B1 EP84420144A EP84420144A EP0141758B1 EP 0141758 B1 EP0141758 B1 EP 0141758B1 EP 84420144 A EP84420144 A EP 84420144A EP 84420144 A EP84420144 A EP 84420144A EP 0141758 B1 EP0141758 B1 EP 0141758B1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/18—Compounds containing halogen
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/081—Inorganic acids or salts thereof containing halogen
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/082—Inorganic acids or salts thereof containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/241—Manufacturing joint-less pipes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/242—Hot working
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/243—Cold working
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/245—Soft metals, e.g. aluminum
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/246—Iron or steel
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- C—CHEMISTRY; METALLURGY
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/247—Stainless steel
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- C—CHEMISTRY; METALLURGY
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol fueled engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- the present invention relates to lubricant compositions containing dispersed particles of lithium fluoride, calcium and / or barium.
- a particularly recommended means consists in preparing a concentrated dispersion by mixing, for example in a ball mill, fluorides with lubricating oils.
- dispersant In order to stabilize the dispersion, it is recommended to add a dispersant to the medium, the definition and quantity of which are chosen, in a known manner, as a function of the oil.
- These dispersants are usually chosen from calcium or barium alkylaryl sulphonates, calcium or barium alkylphenates and polysuccinimides.
- an ashless additive of the polysuccinimide type As dispersant.
- compositions based on synthetic oils such as lubricating esters, esters of dicarboxylic acids and monoalcohols, esters of neopentyl polyols and mono carboxylic acids, polyethers obtained by fixing alkylene oxides on compounds with atom atoms mobile hydrogen and fluorides according to the invention are particularly interesting.
- the dispersions in oils of mixtures of calcium and barium fluorides in the respective proportions by weight from 60 to 35 for 40 to 65 and particularly in the proportions of 1 eutectic, that is to say 38% by weight of calcium fluoride and 62% by weight of barium fluoride lead to more advantageous results than by using calcium and barium fluorides alone and characterized by their presence of the lubricant compositions of the present invention.
- Z is constituted by a hydrogen atom and R 1 is a hydrogen atom or an alkyl radical containing from 1 to 6 carbon atoms, an aryl radical or a cyclanic radical from 3 to 10 carbon atoms, or R and Z are identical or different alkyl radicals containing from 1 to 6 carbon atoms, or Z is the group while R, is hydrogen, or an alkyl radical containing from 1 to 6 carbon atoms or the group R and R 'being either a hydrogen atom or the methyl group CH 3 , or R 1 and Z together form a linear alkylene radical of 3 to 10 carbon atoms.
- compositions containing the two types of fluorides have friction and wear reduction properties over a wide range of loads and temperatures and lead to results superior to those obtained with traditional additives such as zinc alkyldithiophosphates.
- compositions of the invention find application in 7 engines, transmissions hy hydraulics, deformation without metal chips, etc.
- compositions containing as base oil the mineral oil “200 Neutral Solvent” and as additives LiF, CaF 2 , BaF 2 , the eutectic CaF 2 - BaF z containing 38% by weight of CaF 2 and 62% by weight of BaF 2 are determined using the EP Shell 4-ball machine, the description of which is given in "Annual Book of ASTM Standards", Part 24 (1979), pages 680 to 688.
- the anti-wear test consists in applying a constant load of 70 daN for 1 hour then in measuring the diameters of the wear marks on the three fixed balls.
- the load capacity test consists of measuring the diameters of the wear marks as a function of the load applied. The results are expressed in Wear Charge Index (I.C.U.). The operating conditions and the calculation method of the I.C.U. are described in ASTM method 2783-71 T.
- the metal fluoride dispersions are stabilized by the ashless dispersant polysuccinimide (OLOA 1200).
- Table 1 Also shown in Table 1 are the values of the binding load and the welding load which show that the metallic fluorides have a more marked effect at high loads than at low loads.
- a dispersion of barium fluoride and calcium barium eutectic is prepared in a polyether (Emkarox FC 31-140), obtained by fixing a mixture of 75 parts by weight of ethylene oxide and 25 parts by weight of propylene oxide on trimethylolpropane and having an average molecular weight of 1500.
- a polyether (Emkarox FC 31-140) obtained by fixing a mixture of 75 parts by weight of ethylene oxide and 25 parts by weight of propylene oxide on trimethylolpropane and having an average molecular weight of 1500.
- the tests are carried out on a sphere-plane tribometer with the metallic couple Steel 100 C6 (Sphere), Cast iron G (Plan).
- the principle diagram of the sphere-plane contact geometry tribometer appears in the review WEAR, 53 (1979), p. 10.
- the load is 1 daN, the sliding speed of 1 mm s ⁇ 1 , the sliding length of 1 cm: 0.1 ml of lubricant deposited in the contact is used and the temperature is raised by 20 ° C min ⁇ 1 .
- Table 3 gives the results obtained with the compositions tested, that is to say the film breaking temperature and the value of the coefficient of friction before breaking.
- Example 12 shows that no friction reducing film is formed, the value of the coefficient of friction indicated is that obtained before the disappearance of the lubricant, in dry friction. , it reaches the value of 0.37 corresponding to the non-lubricated friction between steel and cast iron GL.
- compositions and the results obtained are given in Table 4.
- Table 5 shows the results obtained by dispersing in three oils containing all the conventional additives, except the anti-wear zinc dialkyldithiophosphates, 1% by weight of BaF z or of CaF 2 / BaF 2 mixture in the proportions of 1 eutectic containing 38% by weight of CaF 2 and 62% by weight of BaF 2 .
- the main additives of these oils are polymethacrylates as freezing inhibitors and improving the viscosity index, polysuccinimides as dispersants, calcium alkylarylsulfonates as detergents.
- Diesel oil has the particularity of containing both as dispersant-detergents, a calcium phenate, a calcium sulfonate and a polysuccinimide.
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- Inorganic Chemistry (AREA)
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Description
- La présente invention concerne des compositions lubrifiantes contenant à l'état dispersé des particules de fluorure de lithium, de calcium et/ou de baryum.
- Il est connu de disperser dans les huiles des lubrifiants solides tels que le bisulfure de molybdène, le graphite ou ses dérivés ou encore le polytétra- fluoréthylène. Ces additifs présentent l'inconvénient de ne pas posséder une stabilité thermique et chimique très performante.
- La dispersion sous forme de particules submi- croniquesdefluorure de lithium, florure de calcium et/ou fluorure de baryum dans les huiles lubrifiantes de base minérales ou synthétiques, augmente considérablement la capacité de charge de ces huiles de base.
- Ces particules sont introduites par tous moyens connus dans les huiles de base. Un moyen particulièrement recommandé consiste à préparer une dispersion concentrée par mélange, par exemple dans un broyeur à bille, des fluorures aux huiles lubrifiantes.
- On peut ainsi obtenir des dispersions concentrées stables contenant jusqu'à 50% en poids de fluorure dans les huiles, comme par exemple les huiles raffinées aux solvants « 1 00 Neutral» à «500 Neutral». Bien que pouvant être utilisés tels quels, ces concentrés peuvent être dilués dans des huiles appartenant de préférence à la même famille chimique que celle de l'huile du concentré. Ces dilutions sont fonction de l'utilisation ultérieure de la composition lubrifiante. Les dispersions concentrées ou diluées peuvent facilement ne contenir que des particules de fluorure de taille inférieure à 0,5 micron.
- Afin de stabiliser la dispersion, il est recommandé d'ajouter au milieu un dispersant dont la définition et la quantité sont choisies, de façon connue, en fonction de l'huile. Ces dispersants sont habituellement choisis parmi les alkylaryl sul- fonates de calcium ou de baryum, alkylphénates de calcium ou de baryum et polysuccinimides. A titre d'exemple, pour les huiles raffinées aux solvants on préfère utiliser comme dispersant un additif sans cendre du type polysuccinimide.
- L'effet des compositions lubrifiantes est mis en évidence, en particulier lorsque les charges appliquées aux pièces en contact ou aux surfaces frot- tantes sont moyennes ou fortes: dans ces cas, on peut constater une limitation de l'usure par rapport aux compositions lubrifiantes classiques. Les propriétés des compositions à base d'huiles synthétiques comme les esters lubrifiants, les esters de diacides carboxyliques et de monoalcools, les esters de néopentylpolyols et de monoacides carboxyliques, les polyéthers obtenus par fixation d'oxydes d'alkylènes sur les composés à atomes d'hydrogène mobiles et de fluorures selon l'invention sont particulièrement intéressants.
- Bien que les propriétés des fluorures de lithium, calcium et baryum soient voisines, les dispersions dans les huiles de mélanges de fluorures de calcium et de baryum dans les proportions respectives en poids de 60 à 35 pour 40 à 65 et particulièrement dans les proportions de l'eutectique, c'est-à-dire 38% en poids de fluorure de calcium et 62% en poids de fluorure de baryum, conduisent à des résultats plus intéressants qu'en utilisant les fluorures de calcium et de baryum seuls et caractérisent par leur présence les compositions lubrifiantes de la présente invention.
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- Rz est l'hydrogène ou un radical alkyle inférieur comportant de 1 à 3 atomes de carbone,
- a possède la valeur de 2 ou 4.
- R1 et Z répondent aux définitions suivantes:
- Z est constitué par un atome d'hydrogène et R1 est un atome d'hydrogène ou un radical alkyle contenant de 1 à 6 atomes de carbone, un radical aryle ou un radical cyclanique de 3 à 10 atomes de carbone, ou R et Z sont des radicaux alkyles identiques ou différents contenant de 1 à 6 atomes de carbone, ou Z est le groupement
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- Les compositions contenant les deux types de fluorures présentent des propriétés de réduction de frottement et de l'usure dans un large domaine ' de charges et de températures et conduisent à des résultats supérieurs à ceux obtenus avec les additifs traditionnels tels que les alkyldithiophosphates de zinc.
- Les compositions de l'invention trouvent leur 7 application dans les moteurs, les transmissions hydrauliques, les déformations sans copeaux des métaux, etc.
- Les exemples non limitatifs suivants servent à illustrer l'invention. Ceux n'incorporant pas la caractéristique de l'invention sont évidemment cités à titre comparatif.
- Le pouvoir anti-usure et la capacité de charge de compositions contenant comme huile de base l'huile minérale «200 Neutral Solvent» et comme additifs LiF, CaF2, BaF2, l'eutectique CaF2 - BaFz contenant 38% en poids de CaF2 et 62% en poids de BaF2 sont déterminés à l'aide de la machine 4 billes E.P. Shell dont la description figure dans «Annual Book of ASTM Standards», Part 24 (1979), pages 680 à 688.
- L'essai anti-usure consiste à appliquer une charge constante de 70 daN pendant 1 heure puis à mesurer les diamètres des empreintes d'usure sur les trois billes fixes.
- L'essai de capacité de charge consiste à mesurer les diamètres des empreintes d'usure en fonction de la charge appliquée. Les résultats sont exprimés en Indice Charge Usure (I.C.U.). Les conditions opératoires et le mode de calcul de l'I.C.U. sont décrits dans la méthode ASTM 2783-71 T.
- Les résultats figurent dans le tableau 1.
- Les dispersions de fluorures métalliques sont stabilisées par le dispersant sans cendre polysuccinimide (OLOA 1200).
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- On prépare une dispersion de fluorure de baryum et d'eutectique calcium-baryum dans un po- lyéther (Emkarox FC 31 -140), obtenu par fixation d'un mélange de 75 parties en poids d'oxyde d'éthylène et 25 parties en poids d'oxyde de propylène sur le triméthylolpropane et possédant une masse moléculaire moyenne de 1500. Les compositions et les résultats selon la norme ASTM 2783-71 T, sont donnés dans le tableau 2.
- Cette série d'exemples met en évidence la formation de films réactionnels avec les dispersions de fluorures ainsi que leur bonne résistance thermique dans les conditions tribologiques suivantes:
- Les essais sont effectués sur tribomètre sphère-plan avec le couple métallique Acier 100 C6 (Sphère), Fonte G (Plan). Le schéma de principe du tribomètre à géométrie de contact sphère-plan figure dans la revue WEAR, 53 (1979), p. 10. La charge est de 1 daN, la vitesse de glissement de 1 mm s―1, la longueur de glissement de 1 cm: on utilise 0,1 ml de lubrifiant déposé dans le contact et on élève la température de 20° C min―1.
- Pour les compositions utilisées, à 275° C, l'huile a disparu par évaporation et décomposition ther- mo-oxydante, mais on poursuit le frottement à sec tout en continuant à élever la température.
- Le tableau 3 donne les résultats obtenus avec les compositions essayées, c'est-à-dire la température de rupture du film et la valeur du coefficient de frottement avant rupture.
- En comparaison de l'exemple 16 selon l'invention, l'exemple 12 montre qu'il ne se forme pas de film réducteur de frottement, la valeur du coefficient de frottement indiquée est celle obtenue avant la disparition du lubrifiant, en frottement à sec, il atteint la valeur de 0,37 correspondant au frottement non lubrifié acier-fonte GL.
- Les exemples suivants montrent les avantages que l'on tire de l'association des fluorures de calcium ou de calcium-baryum aux additifs anti-usure organiques fluorés solubles dans les bases lubrifiantes. Les amines et amino-alcools à chaînes fluorées, qui sont de remarquables additifs anti-usure dans le domaine des faibles charges et des charges moyennes, apportent un effet anti-usure complémentaire, ce qui permet d'obtenir des compositions efficaces dans un large domaine de températures et de charges.
- Les essais ont été effectués dans les conditions décrites précédemment pour les exemples 1 à 8.
-
- Les résultats de ces exemples montrent que les dispersions de fluorures restent efficaces lorsqu'elles sont associées aux additifs traditionnels entrant dans la composition des huiles pour moteurs à combustion interne, tels que les inhibiteurs de figeage, les additifs améliorant l'indice de viscosité, les additifs anti-oxydants, et anti-corrosifs. Les essais, usure et capacité de charge ont été effectués avec la machine à 4 billes EP Shell dans les conditions identiques à celles des essais des exemples 1 à 8.
- Dans le tableau 5 figurent les résultats obtenus en dispersant dans trois huiles contenant tous les additifs classiques, hormis les dialkyldithiophos- phates de zinc anti-usure, 1 % en poids de BaFz ou de mélange CaF2/BaF2 dans les proportions de l'eutectique contenant 38% en poids de CaF2 et 62% en poids de BaF2.
- Ces trois compositions, sans dialkyldithiophos- phates de zinc, correspondent respectivement à:
- - une huile SAE 15 W 40 classique pour moteurs à essence;
- - une huile SAE 10 W 30 à base semi-synthétique (mélange d'ester de triméthylolpropane et de polyoléfines) pour moteurs à essence;
- - une huile SAE 15 W 30 pour moteurs Diesel.
- Les principaux additifs de ces huiles sont des polyméthacrylates comme inhibiteurs de figeage et améliorant l'indice de viscosité, des polysuccinimides comme dispersants, des alkylarylsulfonates de calcium comme détergents.
-
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8313953A FR2551454B1 (fr) | 1983-08-31 | 1983-08-31 | Compositions lubrifiantes contenant des fluorures de lithium, de calcium et/ou de baryum |
FR8313953 | 1984-08-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0141758A1 EP0141758A1 (fr) | 1985-05-15 |
EP0141758B1 true EP0141758B1 (fr) | 1986-09-17 |
Family
ID=9291909
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84420144A Expired EP0141758B1 (fr) | 1983-08-31 | 1984-08-29 | Compositions lubrifiantes contenant des additifs solides |
Country Status (5)
Country | Link |
---|---|
US (1) | US4584116A (fr) |
EP (1) | EP0141758B1 (fr) |
JP (1) | JPS60149695A (fr) |
DE (2) | DE141758T1 (fr) |
FR (1) | FR2551454B1 (fr) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2599378B1 (fr) * | 1986-05-30 | 1988-07-29 | Atochem | Lubrifiants et nouveaux composes polyfluores utilisables comme additifs |
US4888122A (en) * | 1986-11-24 | 1989-12-19 | Mccready David F | Engine oil additive dry lubricant powder |
US5061389A (en) * | 1990-04-19 | 1991-10-29 | Man-Gill Chemical Co. | Water surface enhancer and lubricant for formed metal surfaces |
US5137097A (en) * | 1990-10-30 | 1992-08-11 | Modular Engineering | Modular drill bit |
US5895603A (en) * | 1992-09-21 | 1999-04-20 | Mccready; David F. | Engine oil additive |
US5877128A (en) * | 1996-04-26 | 1999-03-02 | Platinum Research Organization Ltd. | Catalyzed lubricant additives and catalyzed lubricant systems designed to accelerate the lubricant bonding reaction |
US6258758B1 (en) | 1996-04-26 | 2001-07-10 | Platinum Research Organization Llc | Catalyzed surface composition altering and surface coating formulations and methods |
US5869436A (en) * | 1996-10-15 | 1999-02-09 | American Eagle Technologies, Inc. | Non-toxic antimicrobial lubricant |
US6004909A (en) * | 1997-07-18 | 1999-12-21 | American Eagle Technologies, Inc. | Non-toxic antimicrobial lubricant |
EP1169420B1 (fr) | 1999-03-10 | 2008-09-10 | Rolls-Royce Corporation | Composition de revêtement aqueuse contenant une émulsion de résine silicone comme liant |
WO2007084347A2 (fr) * | 2006-01-13 | 2007-07-26 | Platinum Intellectual Property Lp | Système et procédé d'incorporation in situ, en continu, de composition chimique anti-usure à une huile de moteur à l'aide d'un système de filtre |
WO2011163592A2 (fr) | 2010-06-24 | 2011-12-29 | Board Of Regents, The University Of Texas System | Composés d'alkylphosphorofluoridothioates présentant un faible volume d'usure et procédés de synthèse et d'utilisation de ceux-ci |
WO2013169779A1 (fr) | 2012-05-07 | 2013-11-14 | Board Of Regents, The University Of Texas System | Mélanges synergiques de liquides ioniques avec d'autres liquides ioniques et/ou avec des thiophosphates sans cendres pour des applications anti-usure et/ou de réduction du frottement |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3227761A (en) * | 1962-12-26 | 1966-01-04 | Monsanto Res Corp | Fluorine-containing amines |
DE1594511A1 (de) * | 1966-01-21 | 1970-12-17 | Dow Corning Gmbh | Gesenkschmierstoffe |
US3775318A (en) * | 1970-02-25 | 1973-11-27 | Midwest Research Inst | Mixtures of alkaline earth metal fluorides bonded to bearing surface with aluminum phosphate |
US4094799A (en) * | 1976-12-20 | 1978-06-13 | Atlantic Richfield Company | Solid particles-containing lubricating oil composition and method for using same |
GB2018285A (en) * | 1978-04-03 | 1979-10-17 | Atlantic Richfield Co | Improved solid particles-containing lubricating oil composition and method for using same |
FR2445078A1 (fr) * | 1978-12-20 | 1980-07-18 | Ibm France | Procede et dispositif pour detecter une sequence pseudo-aleatoire de deux symboles dans un recepteur de donnees utilisant une modulation a double bande laterale-porteuses en quadrature |
FR2520377B1 (fr) * | 1982-01-22 | 1985-09-13 | Ugine Kuhlmann | Application des amines a chaine polyfluoree comme additifs pour lubrifiants |
-
1983
- 1983-08-31 FR FR8313953A patent/FR2551454B1/fr not_active Expired
-
1984
- 1984-08-02 US US06/637,039 patent/US4584116A/en not_active Expired - Fee Related
- 1984-08-29 EP EP84420144A patent/EP0141758B1/fr not_active Expired
- 1984-08-29 DE DE198484420144T patent/DE141758T1/de active Pending
- 1984-08-29 DE DE8484420144T patent/DE3460770D1/de not_active Expired
- 1984-08-31 JP JP59180826A patent/JPS60149695A/ja active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60149695A (ja) | 1985-08-07 |
JPS6224479B2 (fr) | 1987-05-28 |
DE141758T1 (de) | 1985-12-05 |
DE3460770D1 (en) | 1986-10-23 |
EP0141758A1 (fr) | 1985-05-15 |
FR2551454A1 (fr) | 1985-03-08 |
FR2551454B1 (fr) | 1986-06-27 |
US4584116A (en) | 1986-04-22 |
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