EP0029762A1 - Lubrifying lacquers based on fluorinated graphite, and processes for their preparation and their use - Google Patents

Lubrifying lacquers based on fluorinated graphite, and processes for their preparation and their use Download PDF

Info

Publication number
EP0029762A1
EP0029762A1 EP80401554A EP80401554A EP0029762A1 EP 0029762 A1 EP0029762 A1 EP 0029762A1 EP 80401554 A EP80401554 A EP 80401554A EP 80401554 A EP80401554 A EP 80401554A EP 0029762 A1 EP0029762 A1 EP 0029762A1
Authority
EP
European Patent Office
Prior art keywords
graphite fluoride
varnishes
glycerin
preparation
aqueous dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP80401554A
Other languages
German (de)
French (fr)
Other versions
EP0029762B1 (en
Inventor
Elisabeth Schoch
Michel Jean André Rebiffe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Produits Chimiques Ugine Kuhlmann
Ugine Kuhlmann SA
Original Assignee
Produits Chimiques Ugine Kuhlmann
Ugine Kuhlmann SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Produits Chimiques Ugine Kuhlmann, Ugine Kuhlmann SA filed Critical Produits Chimiques Ugine Kuhlmann
Priority to AT80401554T priority Critical patent/ATE2151T1/en
Publication of EP0029762A1 publication Critical patent/EP0029762A1/en
Application granted granted Critical
Publication of EP0029762B1 publication Critical patent/EP0029762B1/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
    • 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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • 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
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/042—Carbon; Graphite; Carbon black halogenated, i.e. graphite fluoride
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/042—Sulfate esters
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/061—Coated particles
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to lubricant varnish compositions based on water, glycerin and graphite fluoride, their preparation and their use.
  • Solid lubricants such as molybdenum disulphide, graphite and graphite fluoride, only rarely apply as a dry powder to the surfaces to be lubricated. It is most often preferred to use them in the form of dispersions in oil, in organic solvents or in water, or also in the form of greases or pastes. On many metal parts it is even more advantageous to deposit a lubricating varnish adhering to the metal.
  • varnishes based on molybdenum disulphide and heat-hardening binders, such as sugar syrups, silicones, asphalts, glycerin.
  • Such varnishes are described in particular in publications of the NACA (National Advisory Committee for Aeronautics): Technical Note 2628 of February 1952 and Technical Note 2802 of October 1952.
  • the particle size of the solid lubricant must be closely related to the roughness of the metal surface. The lower the roughness, the finer the particle size of the solid lubricant must be to obtain good adhesion of the varnish to the metal.
  • Graphite fluorides are solid lubricants, which have many advantages over molybdenum disulfide. They correspond to the general formula (CF), in which x can vary from approximately 0.8 to 1.2 and n is undetermined.
  • CF general formula
  • Aqueous dispersions of graphite fluoride can be prepared by grinding for example 20 parts by weight of graphite fluoride with a particle size of 5 ⁇ m in the presence of 70 parts by weight of water and 10 parts by weight of DISPERGINE CB (registered trademark of the Applicant for the sodium salt of a condensate of naphthalenesulfonic acid and formalin).
  • the final particle size of the graphite fluoride in the dispersion is approximately 1 ⁇ m.
  • glycerin is incorporated into the aqueous dispersion of graphite fluoride, so as to have a graphite fluoride / glycerin ratio equal to 0.4, and this composition is sprayed on aluminum or l steel, a very irregular and poorly adherent film is obtained after cooking.
  • compositions are obtained which, after drying for one hour at 250 ° C, form brilliant varnishes, adhering very strongly to all types of metals and resistant perfectly in the water. These compositions are very easy to apply by spraying and make it possible to obtain very thin films, 4 to 5 ⁇ m thick, with high lubricating power.
  • the choice of heat-hardening binder is critical. If instead of glycerin, a sugar syrup is used, like the "molasse spread", we obtain a kind of non-stable and non-sprayable fat.
  • the choice of dispersant, used as stabilizer of the aqueous dispersion of graphite fluoride is also critical. If DISPERGINE CB is replaced by OLOA 246 B (trademark registered by the Company OROGIL for a calcium sulfonate) or by PLURONIC P 103 or F 88 (registered trademarks of the applicant for sequenced oxide condensates of propylene and ethylene oxide), varnishes are obtained which have no adhesion to aluminum.
  • the graphite fluoride / glycerine ratio can vary between 0.3 and 1, but preferably between 0.5 and 0.8.
  • compositions (I) and (II) of Example 1 are sprayed onto ordinary steel, stainless steel and aluminum plates at various degrees of polishing, so as to obtain, after cooking for one hour at 250 ° C, varnishes having a thickness of 4 to 5 ⁇ m in thickness.
  • the adhesion of the varnish to the metal is considered to be good to very good, and the film formed on the surface of the metal withstands the drop of water test.
  • the lubricating power of the compositions (I) and (II) of Example 1 is measured on a ball-plane machine, which makes it possible to record the coefficient of friction as a function of the temperature.
  • An XC 38 steel disc is polished to the chosen roughness and covered with the product to be tested. This disc, rotating at constant speed, is subjected to the pres sion exerted by a fixed ball made of 100 C 6 steel.
  • the lubricating power of a simple 2/1 mixture of glycerin and graphite fluoride (A of Example 1) was measured under the same conditions and the lubricating power of an aqueous dispersion of graphite fluoride (B of Example 1). The results obtained are listed in Table 1.
  • the friction stability is good if during the measurement the variations at CF of the coefficient of friction are less than or equal to 0.01. Stability is average if A CF ⁇ 0.02 and poor if ⁇ CF> 0.02.
  • composition (I) of Example 1 is used to improve the lubrication of bearings constituted by a steel strip covered with sintered brass balls and impregnated with polytetrafluoroethylene. A single coat is enough to obtain, after drying at 250 ° C for 1 hour, a very correct varnish. In comparison, if the simple mixture A of Example 1 is used, several layers must be applied, and the resulting varnish completely lacks adhesion.
  • the composition (I) of Example 1 is used to lubricate a device made of cast aluminum intended for the manufacture of parts of agglomerated polyurethane.
  • This device consists of a cylindrical ring in which slides a tightly adjusted cylinder. While the mixture A of Example 1 gave, after cooking, a non-adherent varnish, the composition (I) sprayed inside the ring and on the cylinder gave an adherent and lubricating varnish.
  • composition (I) of Example 1 was sprayed on pieces of refractory steel used in a brazing installation and called to withstand temperatures of 500 to 600 ° C. and splashes of brazing. After drying, composition (I) gave an adherent, resistant varnish well under severe conditions of use.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

Lubricating varnishes for metals obtained by mixing a dispersion of graphite fluoride in glycerine with a separately prepared aqueous dispersion of graphite fluoride, stabilized by a salt of a condensate of naphthalene sulfonic acid with formol.

Description

La présente invention concerne des compositions de vernis lubrifiants à base d'eau, de glycérine et de fluorure de graphite, leur préparation et leur mise en oeuvre.The present invention relates to lubricant varnish compositions based on water, glycerin and graphite fluoride, their preparation and their use.

Les lubrifiants solides, tels que le bisulfure de molybdène, le graphite et le fluorure de graphite, ne s'appliquent que rarement à l'état de poudre sèche sur les surfaces à lubrifier. On préfère le plus souvent les utiliser sous forme de dispersions dans l'huile, dans des solvants organiques ou dans l'eau, ou encore sous forme de graisses ou de pâtes. Sur de nombreuses pièces métalliques il est encore plus avantageux de déposer un vernis lubrifiant adhérant au métal.Solid lubricants, such as molybdenum disulphide, graphite and graphite fluoride, only rarely apply as a dry powder to the surfaces to be lubricated. It is most often preferred to use them in the form of dispersions in oil, in organic solvents or in water, or also in the form of greases or pastes. On many metal parts it is even more advantageous to deposit a lubricating varnish adhering to the metal.

Il est connu de former des vernis à base de bisulfure de molybdène et de liants durcissant à la chaleur, tels les sirops de sucre, les silicones, les asphaltes, la glycérine. De tels vernis sont décrits en particulier dans des publications du NACA (National Advisory Committee for Aeronautics) : Technical Note 2628 de février 1952 et Technical Note 2802 d'octobre 1952.It is known to form varnishes based on molybdenum disulphide and heat-hardening binders, such as sugar syrups, silicones, asphalts, glycerin. Such varnishes are described in particular in publications of the NACA (National Advisory Committee for Aeronautics): Technical Note 2628 of February 1952 and Technical Note 2802 of October 1952.

L'adhérence de ces vernis aux surfaces métalliques dépend de plusieurs facteurs :

  • - la rugosité de la surface métallique à traiter, fonction elle-même du mode de polissage. Ainsi la rectification donne des rugosités allant de 0,1 à 0,4 micromètre (µm), tandis que par sablage il est difficile d'obtenir une rugosité inférieure à 1 µm.
  • - La granulométrie du lubrifiant solide, qui peut varier de 10 µm à moins d'un µm, suivant le mode de préparation et de broyage utilisé.
  • - La nature de la surface métallique à lubrifier : nuance d'acier, acier inoxydable, acier réfractaire, laiton, fonted'aluminium, carbure de tungstène, zamak, etc...
The adhesion of these varnishes to metal surfaces depends on several factors:
  • - the roughness of the metal surface to be treated, itself a function of the polishing mode. Thus the rectification gives roughness ranging from 0.1 to 0.4 micrometer (µm), while by sandblasting it is difficult to obtain a roughness less than 1 µm.
  • - The particle size of the solid lubricant, which can vary from 10 µm to less than 1 µm, depending on the method of preparation and grinding used.
  • - The nature of the metal surface to be lubricated: steel grade, stainless steel, refractory steel, brass, aluminum font, tungsten carbide, zamak, etc.

La granulométrie du lubrifiant solide doit être étroitement liée à la rugosité de la surface métallique. Plus la rugosité est faible, plus fine doit être la granulométrie du lubrifiant solide pour obtenir une bonne adhérence du vernis sur le métal.The particle size of the solid lubricant must be closely related to the roughness of the metal surface. The lower the roughness, the finer the particle size of the solid lubricant must be to obtain good adhesion of the varnish to the metal.

Les fluorures de graphite sont des lubrifiants solides, qui présentent de nombreux avantages sur le bisulfure de molybdène. Ils répondent à la formule générale (CF) , dans laquelle x peut varier d'environ 0,8 à 1,2 et n est indéterminé. Lorsqu'on veut préparer des vernis lubrifiants à base de fluorure de graphite en se fondant sur les enseignements de l'art antérieur, on se heurte à de nombreuses difficultés.Graphite fluorides are solid lubricants, which have many advantages over molybdenum disulfide. They correspond to the general formula (CF), in which x can vary from approximately 0.8 to 1.2 and n is undetermined. When one wants to prepare lubricating varnishes based on graphite fluoride based on the teachings of the prior art, one encounters many difficulties.

Les vernis, contenant 2 parties en poids de glycérine et une partie en poids de fluorure de graphite (avec un rapport F/C = x = 0,9) de granulométrie moyenne 1 pm, adhèrent fortement après chauffage à 250°C, sur les pièces en acier, telles que les poussoirs de moteurs d'automobiles, et sur les aciers alliés au chrome et au chrome-manganèse. Mais sur l'acier inoxydable l'adhérence est moins bonne. Il en est de même sur les métaux autres que l'acier. Cette mauvaise adhérence provient d'une part de la nature du métal, et d'autre part du fait que le mélange de glycérine et de fluorure de graphite est relativement pâteux et donne des films trop épais. Si l'on cherche à diluer ce mélange par de l'eau pour le rendre moins visqueux, on obtient un vernis qui décante rapidement, et qui est par conséquent difficile à stocker. De plus l'adhérence sur les métaux est très insuffisante.The varnishes, containing 2 parts by weight of glycerin and one part by weight of graphite fluoride (with an F / C ratio = x = 0.9) with an average particle size of 1 μm, strongly adhere after heating to 250 ° C. steel parts, such as tappets for automobile engines, and on steels alloyed with chromium and chromium-manganese. But on stainless steel the adhesion is less good. The same is true for metals other than steel. This poor adhesion comes on the one hand from the nature of the metal, and on the other hand from the fact that the mixture of glycerin and graphite fluoride is relatively pasty and gives films which are too thick. If one seeks to dilute this mixture with water to make it less viscous, one obtains a varnish which settles quickly, and which is consequently difficult to store. In addition, the adhesion to metals is very insufficient.

On peut préparer des dispersions aqueuses de fluorure de graphite en broyant par exemple 20 parties en poids de fluorure de graphite de granulométrie 5 pm en présence de 70 parties en poids d'eau et de 10 parties en poids de DISPERGINE CB (marque déposée de la demanderesse pour le sel de sodium d'un condensat d'acide naphtalènesulfonique et de formol). La granulométrie finale du fluorure de graphite dans la dispersion est d'environ 1 µm.Aqueous dispersions of graphite fluoride can be prepared by grinding for example 20 parts by weight of graphite fluoride with a particle size of 5 μm in the presence of 70 parts by weight of water and 10 parts by weight of DISPERGINE CB (registered trademark of the Applicant for the sodium salt of a condensate of naphthalenesulfonic acid and formalin). The final particle size of the graphite fluoride in the dispersion is approximately 1 μm.

Lorsqu'une telle dispersion est pulvérisée seule sur les métaux ferreux et sur l'aluminium, elle donne, après cuisson à 250°C, un film uniforme, assez peu lubrifiant, et qui ne résiste pas à l'action de l'eau : un goutte à goutte d'eau sur une plaque d'acier recouverte d'un tel film provoque rapidement l'écaillage et le décollage du film.When such a dispersion is sprayed alone on ferrous metals and on aluminum, it gives, after baking at 250 ° C, a uniform film, not very lubricating, and which does not resist the action of water: a drop by drop of water on a steel plate covered with such a film quickly causes the film to peel and take off.

Si l'on incorpore de la glycérine à la dispersion aqueuse de fluorure de graphite, de façon à avoir un rapport fluorure de graphite/glycérine égal à 0,4, et que l'on pulvérise cette composition sur de l'aluminium ou de l'acier, on obtient après cuisson un film très irrégulier et peu adhérent.If glycerin is incorporated into the aqueous dispersion of graphite fluoride, so as to have a graphite fluoride / glycerin ratio equal to 0.4, and this composition is sprayed on aluminum or l steel, a very irregular and poorly adherent film is obtained after cooking.

Si d'autre part on mélange directement de la poudre de fluorure de graphite, de la glycérine et une solution aqueuse de DISPERGINE CB, on obtient des compositions qui, appliquées sur aluminium et séchées à 250°C, donnent des vernis adhérents, mais qui ne résistent pas au test de la goutte d'eau.If, on the other hand, graphite fluoride powder, glycerin and an aqueous solution of DISPERGINE CB are mixed directly, compositions are obtained which, applied on aluminum and dried at 250 ° C., give adherent varnishes, but which do not withstand the drop test.

De façon tout-à-fait inattendue, la demanderesse a découvert qu'en préparant d'abord un mélange de glycérine et de poudre de fluorure de graphite, et en ajoutant à ce mélange une dispersion aqueuse de fluorure de graphite sta- - bilisée à la DISPERGINE CE, on obtient des compositions qui, après séchage d'une heure à 250°C, forment des vernis brillants, adhérant très fortement à tous les types de métaux et résistant parfaitement à l'eau. Ces compositions sont très faciles à appliquer par pulvérisation et permettent d'obtenir des films très minces, de 4 à 5 µm d'épaisseur, à haut pouvoir lubrifiant.Quite unexpectedly, the Applicant has discovered that by first preparing a mixture of glycerin and graphite fluoride powder, and by adding to this mixture mixes an aqueous dispersion of graphite fluoride stabilized with CE DISPERGIN, compositions are obtained which, after drying for one hour at 250 ° C, form brilliant varnishes, adhering very strongly to all types of metals and resistant perfectly in the water. These compositions are very easy to apply by spraying and make it possible to obtain very thin films, 4 to 5 μm thick, with high lubricating power.

Dans les compositions suivant l'invention, le choix du liant durcissant à la chaleur est critique. Si au lieu de la glycérine, on utilise un sirop de sucre, comme le "spread molasse", on obtient une sorte de graisse non éta- lable et non pulvérisable. Le choix du dispersant, utilisé comme stabilisant de la dispersion aqueuse de fluorure de graphite est également critique. Si l'on remplace la DISPERGINE CB par l'OLOA 246 B (marque déposée par la Société OROGIL pour un sulfonate de calcium) ou par des PLURONIC P 103 ou F 88 (marques déposées de la demanderesse pour des condensats séquencés d'oxyde de propylène et d'oxyde d'éthylène), on obtient des vernis ne présentant aucune adhérence sur l'aluminium.In the compositions according to the invention, the choice of heat-hardening binder is critical. If instead of glycerin, a sugar syrup is used, like the "molasse spread", we obtain a kind of non-stable and non-sprayable fat. The choice of dispersant, used as stabilizer of the aqueous dispersion of graphite fluoride is also critical. If DISPERGINE CB is replaced by OLOA 246 B (trademark registered by the Company OROGIL for a calcium sulfonate) or by PLURONIC P 103 or F 88 (registered trademarks of the applicant for sequenced oxide condensates of propylene and ethylene oxide), varnishes are obtained which have no adhesion to aluminum.

Par contre, le rapport fluorure de graphite/glycérine peut varier entre 0,3 et 1, mais de préférence entre 0,5 et 0,8.On the other hand, the graphite fluoride / glycerine ratio can vary between 0.3 and 1, but preferably between 0.5 and 0.8.

Les exemples suivants, non limitatifs, illustrent l'invention.The following nonlimiting examples illustrate the invention.

EXEMPLE 1EXAMPLE 1

  • A) On mélange intimement 100 parties en poids de fluorure de graphite (CFx)n, avec x = 0,9, de granulométrie 1 pm, avec 200 parties en poids de glycérine.A) 100 parts by weight of graphite fluoride (CF x ) n , with x = 0.9, of particle size 1 μm, are intimately mixed with 200 parts by weight of glycerin.
  • B) On prépare d'autre part 100 parties en poids d'une dispersion aqueuse stabilisée de fluorure de graphite, en broyant 20 parties en poids de fluorure de graphite en présence de 70 parties en poids d'eau et de 10 parties en poids de DISPERGINE CB en poudre.B) On the other hand, 100 parts by weight of a stabilized aqueous dispersion of graphite fluoride are prepared, by grinding 20 parts by weight of graphite fluoride in the presence of 70 parts by weight of water and 10 parts by weight of DISPERGINE CB powder.
  • C) A 50 parties du mélange A, on ajoute 50 parties de la dispersion B, et on homogénéise. On obtient ainsi une composition lubrifiante présentant un rapport fluorure de graphite/glycérine égal à 0,80 (Composition I).C) To 50 parts of mixture A, 50 parts of dispersion B are added, and homogenization is carried out. A lubricating composition is thus obtained having a graphite fluoride / glycerin ratio equal to 0.80 (Composition I).
  • D) A 62 parties du mélange A, on ajoute 38 parties de la dispersion B et on homogénéise. On obtient ainsi une composition lubrifiante présentant un rapport fluorure de graphite/glycérine égal à 0,68 (Composition II).D) To 62 parts of mixture A, 38 parts of dispersion B are added and homogenization is carried out. A lubricating composition is thus obtained having a graphite fluoride / glycerin ratio equal to 0.68 (Composition II).
EXEMPLE 2EXAMPLE 2

Les compositions (I) et (II) de l'exemple 1 sont pulvérisées sur des plaques d'acier ordinaire, d'acier inoxydable et d'aluminium à divers degrés de polissage, de manière à obtenir, après cuisson d'une heure à 250°C, des vernis ayant une épaisseur de 4 à 5 pm d'épaisseur. Dans tous les cas l'adhérence du vernis au métal est considérée comme bonne à très bonne, et le film formé à la surface du métal résiste au test de la goutte d'eau.The compositions (I) and (II) of Example 1 are sprayed onto ordinary steel, stainless steel and aluminum plates at various degrees of polishing, so as to obtain, after cooking for one hour at 250 ° C, varnishes having a thickness of 4 to 5 μm in thickness. In all cases, the adhesion of the varnish to the metal is considered to be good to very good, and the film formed on the surface of the metal withstands the drop of water test.

EXEMPLE 3EXAMPLE 3

Le pouvoir lubrifiant des compositions (I) et (II) de l'exemple 1 est mesuré sur une machine bille-plan, qui permet d'enregistrer le coefficient de frottement en fonction de la température. Un disque en acier XC 38 est poli à la rugosité choisie et recouvert du produit à tester. Ce disque, tournant à vitesse constante, est soumis à la pression exercée par une bille fixe en acier 100 C 6. A titre comparatif on a mesuré dans les mêmes conditions le pouvoir lubrifiant d'un simple mélange 2/1 de glycérine et de fluorure de graphite (A de l'exemple 1) et le pouvoir lubrifiant d'une dispersion aqueuse de fluorure de graphite (B de l'exemple 1). Les résultats obtenus sont consignés dans le Tableau 1.

Figure imgb0001
The lubricating power of the compositions (I) and (II) of Example 1 is measured on a ball-plane machine, which makes it possible to record the coefficient of friction as a function of the temperature. An XC 38 steel disc is polished to the chosen roughness and covered with the product to be tested. This disc, rotating at constant speed, is subjected to the pres sion exerted by a fixed ball made of 100 C 6 steel. For comparison, the lubricating power of a simple 2/1 mixture of glycerin and graphite fluoride (A of Example 1) was measured under the same conditions and the lubricating power of an aqueous dispersion of graphite fluoride (B of Example 1). The results obtained are listed in Table 1.
Figure imgb0001

La stabilité du frottement est bonne si au cours de la mesure les variations à CF du coefficient de frottement sont inférieures ou égales à 0,01. La stabilité est moyenne si A CF ≦0,02 et mauvaise si Δ CF> 0,02.The friction stability is good if during the measurement the variations at CF of the coefficient of friction are less than or equal to 0.01. Stability is average if A CF ≦ 0.02 and poor if Δ CF> 0.02.

EXEMPLE 4EXAMPLE 4

La composition (I) de l'exemple 1 est utilisée pour améliorer la lubrification de coussinets constitués par une bande d'acier recouverte de billes de laiton frittées et imprégnées de polytétrafluoréthylène. Une seule couche suffit pour obtenir, après séchage à 250°C pendant 1 heure, un vernis très correct. En comparaison, si l'on utilise le simple mélange A de l'exemple 1, il faut appliquer plusieurs couches, et le vernis résultant manque totalement d'adhérence.The composition (I) of Example 1 is used to improve the lubrication of bearings constituted by a steel strip covered with sintered brass balls and impregnated with polytetrafluoroethylene. A single coat is enough to obtain, after drying at 250 ° C for 1 hour, a very correct varnish. In comparison, if the simple mixture A of Example 1 is used, several layers must be applied, and the resulting varnish completely lacks adhesion.

EXEMPLE 5EXAMPLE 5

La composition (I) de l'exemple 1 est utilisée pour lubrifier un dispositif en fonte d'aluminium destiné à la fabrication de pièces en polyuréthanne aggloméré. Ce dispositif est constitué d'un anneau cylindrique dans lequel coulisse un cylindre étroitement ajusté. Alors que le mélange A de l'exemple 1 donnait après cuisson un vernis non adhérent, la composition (I) pulvérisée à l'intérieur de l'anneau et sur le cylindre a donné un vernis adhérent et lubrifiant.The composition (I) of Example 1 is used to lubricate a device made of cast aluminum intended for the manufacture of parts of agglomerated polyurethane. This device consists of a cylindrical ring in which slides a tightly adjusted cylinder. While the mixture A of Example 1 gave, after cooking, a non-adherent varnish, the composition (I) sprayed inside the ring and on the cylinder gave an adherent and lubricating varnish.

EXEMPLE 6EXAMPLE 6

Cet exemple montre que les vernis selon l'invention peuvent être utilisés pour lubrifier des pièces soumises à des températures très élevées.This example shows that the varnishes according to the invention can be used to lubricate parts subjected to very high temperatures.

La composition (I) de l'exemple 1 a été pulvérisée sur des pièces en acier réfractaire utilisées dans une installation de brasage et appelées à supporter des températures de 500 à 600°C et des projections de brasure. Après séchage, la composition (I) a donné un vernis adhérent, résistant bien aux conditions sévères d'utilisation.The composition (I) of Example 1 was sprayed on pieces of refractory steel used in a brazing installation and called to withstand temperatures of 500 to 600 ° C. and splashes of brazing. After drying, composition (I) gave an adherent, resistant varnish well under severe conditions of use.

EXEMPLE 7EXAMPLE 7

Sur une pièce en carbure de tungstène, qui présentait un poli miroir, rendant très difficile l'accrochage des vernis, on a appliqué le mélange A de l'exemple 1, et constaté que le vernis n'avait aucune adhérence. Au contraire la composition (I) de l'exemple 1 a donné un vernis adhérant bien.On a piece of tungsten carbide, which had a mirror polish, making it very difficult to attach the varnishes, mixture A of Example 1 was applied, and found that the varnish had no adhesion. On the contrary the composition (I) of Example 1 gave a varnish which adheres well.

Claims (8)

1. Procédé de préparation de vernis lubrifiants pour métaux, caractérisé en ce qu'il comprend les étapes suivantes : - Préparation d'un constituant A par mélange d'une poudre de fluorure de graphite avec de la glycérine. - Préparation d'une dispersion aqueuse B de fluorure de graphite, stabilisée par le sel de sodium d'un condensat d'acide naphtalènesulfonique avec le formol. - Mélange du constituant A avec la dispersion B, de manière à ce que le rapport pondéral fluorure de graphite total/glycérine soit compris entre 0,3 et 1. 1. Process for the preparation of lubricating varnishes for metals, characterized in that it comprises the following stages: - Preparation of component A by mixing a powder of graphite fluoride with glycerin. - Preparation of an aqueous dispersion B of graphite fluoride, stabilized by the sodium salt of a condensate of naphthalenesulfonic acid with formalin. - Mixture of component A with dispersion B, so that the weight ratio of total graphite fluoride / glycerin is between 0.3 and 1. 2. Procédé selon la revendication 1, caractérisé en ce que le mélange de poudre de fluorure de graphite et de glycérine se fait dans le rapport de 2 à 1.2. Method according to claim 1, characterized in that the mixture of graphite fluoride powder and glycerin is done in the ratio of 2 to 1. 3. Procédé selon les revendications 1 et 2, caractérisé en ce que la poudre de fluorure de graphite a une granulométrie de 1 à 5 micromètres.3. Method according to claims 1 and 2, characterized in that the graphite fluoride powder has a particle size of 1 to 5 micrometers. 4. Procédé selon les revendications 1 à 3, caractérisé en ce que la dispersion aqueuse de fluorure de graphite contient de 5 à 50 % en poids de fluorure de graphite.4. Method according to claims 1 to 3, characterized in that the aqueous dispersion of graphite fluoride contains from 5 to 50% by weight of graphite fluoride. 5. Procédé selon les revendications 1 à 4, caractérisé en ce que les particules de fluorure de graphite dans la dispersion aqueuse ont une granulométrie d'environ 1 micromètre.5. Method according to claims 1 to 4, characterized in that the particles of graphite fluoride in the aqueous dispersion have a particle size of about 1 micrometer. 6. Procédé selon les revendications 1 à 5, caractérisé en ce que la dispersion aqueuse de fluorure de graphite contient de 5 à 15 % en poids de sel de sodium d'un condensat d'acide naphtalène sulfonique avec le formol.6. Method according to claims 1 to 5, characterized in that the aqueous dispersion of graphite fluoride contains from 5 to 15% by weight of sodium salt of a condensate of naphthalene sulfonic acid with formalin. 7. Vernis lubrifiants obtenus selon les revendications 1 à 6.7. Lubricant varnishes obtained according to claims 1 to 6. 8. Procédé d'application des vernis lubrifiants selon la revendication 7, caractérisé en ce que les vernis sont étalés ou pulvérisés sur le métal à revêtir et cuits pendant une durée d'environ une heure à une température d'environ 250°C.8. A method of applying lubricant varnishes according to claim 7, characterized in that the varnishes are spread or sprayed on the metal to be coated and baked for a period of about one hour at a temperature of about 250 ° C.
EP80401554A 1979-11-13 1980-10-31 Lubrifying lacquers based on fluorinated graphite, and processes for their preparation and their use Expired EP0029762B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80401554T ATE2151T1 (en) 1979-11-13 1980-10-31 FLUORINATED GRAPHITE-BASED ENAMEL LUBRICANTS AND PROCESSES FOR THEIR PRODUCTION AND USE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7927887 1979-11-13
FR7927887A FR2469438A1 (en) 1979-11-13 1979-11-13 LUBRICANT VARNISH BASED ON GRAPHITE FLUORIDE AND PROCESSES FOR THEIR PREPARATION AND APPLICATION

Publications (2)

Publication Number Publication Date
EP0029762A1 true EP0029762A1 (en) 1981-06-03
EP0029762B1 EP0029762B1 (en) 1982-12-29

Family

ID=9231584

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80401554A Expired EP0029762B1 (en) 1979-11-13 1980-10-31 Lubrifying lacquers based on fluorinated graphite, and processes for their preparation and their use

Country Status (11)

Country Link
US (1) US4354948A (en)
EP (1) EP0029762B1 (en)
JP (1) JPS5676472A (en)
AT (1) ATE2151T1 (en)
BR (1) BR8007365A (en)
CA (1) CA1144143A (en)
DE (1) DE3061519D1 (en)
FR (1) FR2469438A1 (en)
IL (1) IL61111A (en)
SU (1) SU1075983A3 (en)
ZA (1) ZA806272B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4770797A (en) * 1986-03-31 1988-09-13 Allied-Signal Inc. Carbon fluoride chloride lubricant
US4746248A (en) * 1987-02-19 1988-05-24 E. I. Du Pont De Nemours And Company Anchor bolt assembly
JPH01127920U (en) * 1988-02-25 1989-08-31
JPH01299891A (en) * 1988-05-26 1989-12-04 Asahi Glass Co Ltd Lubricating oil composition for chain
US4984938A (en) * 1988-08-25 1991-01-15 H&S Machine & Supply Company, Inc. Coated washer for an anchor bolt system

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE278510C (en) * 1914-04-01
FR2416258A1 (en) * 1978-02-07 1979-08-31 Mitsubishi Heavy Ind Ltd LUBRICANT FOR PLASTIC METAL WORK

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE274510C (en) * 1900-01-01
CA499584A (en) * 1954-01-26 J. Morway Arnold Lubricant
US905649A (en) * 1906-08-20 1908-12-01 William Humphrey Knowles Lubricant.
US2083176A (en) * 1935-06-29 1937-06-08 Acheson Colloids Corp Lubrication of rubber
US2176879A (en) * 1937-11-20 1939-10-24 Acheson Colloids Corp Method of disintegrating, dispersing and stabilizing graphite and product
US3071543A (en) * 1960-07-12 1963-01-01 Mcgee Chemical Company Inc Solid lubricant containing compositions
US3341454A (en) * 1963-02-25 1967-09-12 Hodson Corp Lubricant composition
JPS49964B1 (en) * 1968-05-27 1974-01-10 Nippon Carbon Co Ltd
JPS4919750B1 (en) * 1970-12-21 1974-05-20
JPS5223983B2 (en) * 1972-07-07 1977-06-28
JPS54125366A (en) * 1978-03-24 1979-09-28 Hitachi Funmatsu Yakin Kk Lubricant for plastic working

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE278510C (en) * 1914-04-01
FR2416258A1 (en) * 1978-02-07 1979-08-31 Mitsubishi Heavy Ind Ltd LUBRICANT FOR PLASTIC METAL WORK

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 81, No. 14, 7 Octobre 1974, ref. No. 81234b, page 225 Columbus, Ohio, US & JP-A-49 027 443 (MONOLON CO. LTD.: NIPPON CARBON CO. LTD.) (11.3.1974). *

Also Published As

Publication number Publication date
DE3061519D1 (en) 1983-02-03
EP0029762B1 (en) 1982-12-29
BR8007365A (en) 1981-05-26
ATE2151T1 (en) 1983-01-15
IL61111A0 (en) 1980-11-30
IL61111A (en) 1983-11-30
FR2469438A1 (en) 1981-05-22
JPS637225B2 (en) 1988-02-16
FR2469438B1 (en) 1981-10-30
SU1075983A3 (en) 1984-02-23
US4354948A (en) 1982-10-19
JPS5676472A (en) 1981-06-24
ZA806272B (en) 1981-09-30
CA1144143A (en) 1983-04-05

Similar Documents

Publication Publication Date Title
KR101000428B1 (en) Sliding bearing
JP5060223B2 (en) Piston for internal combustion engine
JP5199670B2 (en) Piston ring having a coated sliding surface and coating agent
CN102459544A (en) Film composition for sliding member
JP4767234B2 (en) Sliding coating structure
CN108339930B (en) Water-based release agent applied to aluminum alloy die castings and preparation method thereof
JP2582543B2 (en) Corrosion resistant composition for metal coating, its use and bolts coated with it
EP0029762B1 (en) Lubrifying lacquers based on fluorinated graphite, and processes for their preparation and their use
JPH07238936A (en) Slide bearing material
CN109054951A (en) A kind of stamping processing solid lubricant film and preparation method thereof of aluminum alloy plate materials
US20030213698A1 (en) Process for lubrication-treating aluminum or aluminum alloy material
JP2018150528A (en) Dry lubricant film composition and slide member comprising slide layer constituted by the dry lubricant film composition
CN104087154A (en) Copper-based molybdenum disulfide nano composite coating as well as preparation method and coating process thereof
FI84084B (en) KORROSIONSINHIBERANDE BELAEGGNINGSKOMPOSITION FOER METALLUNDERLAG
Daodon et al. Vanadium nitride and titanium nitride coatings for anti-galling behavior in ironing of aluminum alloy cups
EP3144144B1 (en) Slide member with coating film and method for forming coating film
JP4490119B2 (en) Dry lubricating film forming composition
US4770797A (en) Carbon fluoride chloride lubricant
CN1258725A (en) High-temperature anti-sticking lubricant
JP3962285B2 (en) Composite plating film
JPS5833902B2 (en) Metal pretreatment paint composition
JPH06264255A (en) Stainless steel sheet excellent in workability and corrosion resistance
JP2003138217A (en) Coating composition for rust-preventive lubrication
JP2778972B2 (en) Graphite dispersed Co-Ni based self-lubricating alloy
JPS6035987B2 (en) Aluminum↓-Lead-based bearing manufacturing method

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19801106

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LU NL SE

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 2151

Country of ref document: AT

Date of ref document: 19830115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3061519

Country of ref document: DE

Date of ref document: 19830203

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19921005

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19921014

Year of fee payment: 13

Ref country code: AT

Payment date: 19921014

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19921021

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19921026

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19921031

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19921103

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19921110

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19921116

Year of fee payment: 13

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19931031

Ref country code: LI

Effective date: 19931031

Ref country code: GB

Effective date: 19931031

Ref country code: CH

Effective date: 19931031

Ref country code: BE

Effective date: 19931031

Ref country code: AT

Effective date: 19931031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19931101

BERE Be: lapsed

Owner name: PCUK PRODUITS CHIMIQUES UGINE KUHLMANN

Effective date: 19931031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19940501

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19931031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19940630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 80401554.3

Effective date: 19940610

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT