EP0315532B1 - Process for lubricating the surface of metallic pieces made of copper and iron or copper alloys in cold or hot deforming operations, and means for using this lubrication - Google Patents
Process for lubricating the surface of metallic pieces made of copper and iron or copper alloys in cold or hot deforming operations, and means for using this lubrication Download PDFInfo
- Publication number
- EP0315532B1 EP0315532B1 EP88402758A EP88402758A EP0315532B1 EP 0315532 B1 EP0315532 B1 EP 0315532B1 EP 88402758 A EP88402758 A EP 88402758A EP 88402758 A EP88402758 A EP 88402758A EP 0315532 B1 EP0315532 B1 EP 0315532B1
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- EP
- European Patent Office
- Prior art keywords
- fluoride
- copper
- cold
- lanthanide
- lanthane
- 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.)
- Expired - Lifetime
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- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/18—Compounds containing halogen
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- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/06—Metal compounds
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/22—Carboxylic acids or their salts
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- 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
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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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- 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
- C10N2040/242—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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- 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
- C10N2040/246—Iron or steel
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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
- C10N2040/247—Stainless steel
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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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
Definitions
- the subject of the invention is a method of lubricating the surface of metal parts, of copper or of alloys based on iron or copper, which have to be deformed cold or hot.
- lubrication means used in the above process, these means essentially comprising a lubricating agent as well as compositions containing this agent.
- the alloys concerned are those in which copper or iron constitute the main element and which include in particular brasses, bronzes, cupronickels, nickel silver, steels, cast irons and stainless steels.
- the means used to date to lower the friction coefficient consist in carrying out a surface preparation on the part to be deformed followed by lubrication.
- Surface preparation can consist of degreasing, pickling, shot blasting, refining, phosphating, oxalation, galvanization or copper plating, or a combination of several of these treatments.
- Molybdenum disulphide and graphite are satisfactory from the point of view of lowering the friction coefficient but have a certain number of major drawbacks, since they are used in the form of very sticky powders or dispersions which are very sticky and difficult to remove, they cause soiling of the work station, soiling of the workshop and soiling on the treated parts and the tools.
- the method, according to the invention, of lubricating the surface of metallic pieces of copper or of alloys based on iron or copper, intended to be deformed cold or hot is characterized by the fact that after the preparation of the traditional surface, at least one of the lanthanide halides from the group consisting of lanthanum fluoride and cerium fluoride is applied to the surface of said parts, preferably in the form of a dispersion aqueous or oily or a mixture with a wax or dry soap powder.
- a subject of the invention is also the use for the lubrication of the surface of metallic parts made of copper or of alloys based on iron or copper, to be deformed cold or hot, of a lubricating agent essentially consisting of minus one of the lanthanide halides from the group consisting of lanthanum fluoride and cerium fluoride.
- the above lubricating agent is preferably used in the form of an aqueous dispersion or in the form of a mixture with dry powder soap.
- the lanthanide halides can be used in the form of aqueous or oily dispersions or coated in a wax or else as a mixture with dry powder soap.
- aqueous dispersions can also contain one or more sequestering agents, one or more anti-corrosion agents, one or more agents or several of these different products at the same time.
- the sequestering agents can be chosen from the group comprising EDTA, NTA, phosphonates of alkali metal or alkanolamine salts and polyphosphates.
- the anti-corrosion agents can be chosen from the alkali metal or alkanolamine salts of sulfonic acids, carboxylic, oleylsarcosinic acids and alkylarylsulfonamidocarboxylic acids.
- the preservatives can be chosen from formalin, triazine derivatives, orthophenylformol or its sodium salt.
- the oily dispersions can contain mineral oils of petroleum origin which can be paraffinic oils, naphthenic oils, aromatic oils.
- the oil can also be a synthetic oil such as a polyalfaolefin or an alkylate, a vegetable oil such as rapeseed oil, castor oil, soybean or animal oil such as bacon oil , beef foot oil.
- These oily dispersions may also contain synthetic fatty esters such as polyethylene glycol esters and viscosity adjuvants such as aluminosilicates and modified carboxylic derivatives.
- They can also contain one or more dispersing agents, one or more preservatives or even several of these products.
- the dispersing agents can be calcium or aluminum alkylarylsulfonates.
- the preservatives can be chosen from triazine derivatives.
- the waxes used to coat the lanthanide halides can be waxes of mineral origin such as microcrystalline waxes or paraffins as well as animal or vegetable waxes.
- fatty acid esters in particular polyglycol carboxylates such as polyethylene glycol oleate.
- Dry powdered soaps can be formed by the reaction products between alkaline and / or alkaline-earth hydroxides with at least one fatty acid of natural or synthetic origin having a carbon chain from C10 to C22.
- inert fillers which can be carbonates, sulfates or water.
- the lubricating agent When the lubricating agent is applied in the form of an aqueous or oily dispersion or in the form of a mixture with a wax, its concentration in the application medium is from 0.05 to 60% by weight; it is preferably from 0.05 to 5% by weight in the case of an aqueous dispersion, from 0.1 to 15% by weight in the case of an oily dispersion and from 5 to 60% by weight in the case of '' a mixture with a wax and 0.05 to 5% by weight in the case of a mixture with a powdered soap.
- aqueous dispersions or the oily dispersions it is possible to use powders or liquids comprising, in addition to at least one of the lanthanide halides from the group consisting of lanthanum fluoride and cerium fluoride, the other constituents of the dispersions in concentrated form.
- These concentrated products may have a content of at least one of the above lanthanide halides which is respectively from 5 to 30% by weight in the case of those intended to provide the aqueous dispersions and from 1 to 50% in the case of those intended to provide oily dispersions.
- Dilution at the time of application is carried out using water for aqueous dispersions and using an oil or a petroleum solvent in the case of oily dispersions.
- the cerium fluoride used is in the form of a white powder with 98% purity with a particle size such that 74% of the grains have a size less than 100 ⁇ m.
- This test makes it possible to determine the coefficient of friction existing between a tool and a material subjected to plastic deformation under special conditions of surface and lubrication.
- the rings used for the test are made of XC 10 quality steel and have the following dimensions: - outside diameter 42 mm - internal diameter 21 mm - height 7 mm.
- the tools used for the test are composed of two flat piles of quality Z 20 OC 12 steel.
- the reduction in height of the ring during the tests varies from 20 to 40%.
- the rings were lubricated by soaking at room temperature in dispersions at 5% by weight of graphite, molybdenum disulphide or cerium fluoride in a naphthenic oil with a viscosity of 75 centistokes at 40 ° vs.
- a comparative test is carried out carried out under industrial conditions and consisting of a "front spinning" operation carried out on parts of the hollow steel slab type.
- the plots intended to be subjected to prior spinning are prepared, by successively carrying out a phosphating which can be carried out with a phosphating bath of the type marketed under the brand THERMOGRANODINE 701® by the Applicant Company and implemented in a manner usual, this phosphating being followed by coating by dipping in an aqueous dispersion of Mos2 comprising 5% by weight of this product.
- outside diameters ⁇ 1, ⁇ 2, ⁇ 3 and the inside diameter ⁇ int. are specific to the shape of the part and appear in the single figure, which shows said part in axial section, respectively in a, b, c and d.
- the parts deformed after treatment by implementing the process according to the invention are easy to handle and of cleaner appearance than with the usual process.
- composition of the lubricating bath PROLUB TS 438 Lubricant Soap: 5% by weight in water 5% by weight of PROLUB TS 438 lubricating soap and 0.5% by weight of CeF3 in water Duration of treatment 5 minutes 5 minutes Bath temperature 80 ° C 80 ° C
- a comparative test is carried out under industrial conditions by cold deformation of pieces of stainless steel of grade Z6 C13, the deformation being carried out using a mechanical press with a power of 600 T.
- Two series of plots are prepared for deformation respectively by applying techniques of the prior art for the first series and the process according to the invention for the second.
- the two lubricant treatments are preceded by a surface preparation treatment, identical in both cases and consisting of an oxalation based on oxalic acid salts which can be provided by means of the product marketed by the Applicant Company under the brand THERMOGRANODINE SS1 and SS5.
- the lubricant treatment according to the prior art successively comprises a treatment using an anionic lubricant PROLUB TS 438 at 5% by weight in water, the duration being 5 minutes and the temperature of 80 ° C. then a coating by dipping in a dispersion at 5% by weight of MoS2 in water, the duration being 1 minute and the bath temperature of 60 ° C.
- the lubricant treatment according to the invention comprises a single stage of treatment using an aqueous dispersion containing 0.5% by weight of CeF3 which also contains 5% by weight of PROLUB TS 438, the duration being 5 minutes and the temperature of the dispersion of 80 ° C.
- a comparative test of hot spinning of brass is carried out under industrial conditions, consisting of heating brass billets to 750 ° C. and then carrying out hot spinning to obtain a wire with a diameter varying from 5 to 11 mm, the dies being previously lubricated.
- This lubrication is ensured in accordance with the prior art by a solid lubricant, namely graphite, coated at a rate of 50% by weight in a paraffin wax of drop point of 80 ° C. while the lubrication according to the invention has been carried out. using a mixture of 50% by weight of CeF3 in the same paraffinic wax.
- the spinning carried out after lubrication according to the invention leads to a cleaner looking thread, unlike what happens when the lubricant according to the prior art is used. There is no abnormal wear on the die.
- the test is carried out on a wire drawing bench comprising eight dies allowing a total reduction from a diameter of 2.4 mm at the inlet to a diameter of 0.69 mm at the outlet.
- the drawing wire is made of 0.45% carbon steel and is galvanized. Its resistance is 180 kg / cm2.
- a lubricating power evaluation test is carried out according to the automotive standard CNOMO D 55 1136 on a 4-ball machine Shell Royal Dutch.
- the average diameter of the wear imprint is measured with a load of 100 kg. A small diameter qualifies good lubrication. The test is carried out at room temperature. TABLE VII Lubricants treated Footprint diameter Paraffinic oil 1.6mm Paraffinic oil + 5% MoS2 0.45mm Paraffinic oil + 5% CeF3 0.35mm Paraffinic oil + 5% LaF3 0.45mm
- the lanthanum fluoride used is in the form of a white powder of purity greater than 99% and with a particle size such that at least 74% of the grains have a size less than 100 microns.
- cerium fluoride and the lanthanum fluoride can be considered as additives making it possible to obtain satisfactory lubrication and comparable to molybdenum disulphide, while imparting an appearance more flattering to the treated parts.
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- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Mounting, Exchange, And Manufacturing Of Dies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
L'invention a pour objet un procédé de lubrification de la surface de pièces métalliques, en cuivre ou en alliages à base de fer ou de cuivre, devant être déformées à froid ou à chaud.The subject of the invention is a method of lubricating the surface of metal parts, of copper or of alloys based on iron or copper, which have to be deformed cold or hot.
Elle vise également, et ce à titre des produits industriels nouveaux, des moyens de lubrification mis en oeuvre dans le susdit procédé, ces moyens comprenant essentiellement un agent lubrifiant ainsi que des compositions contenant cet agent.It also relates, and as new industrial products, lubrication means used in the above process, these means essentially comprising a lubricating agent as well as compositions containing this agent.
Les alliages concernés sont ceux dans lesquels le cuivre ou le fer constituent l'élément principal et qui comprennent notamment les laitons, les bronzes, les cupronickels, le maillechort, les aciers, les fontes et les aciers inoxydables.The alloys concerned are those in which copper or iron constitute the main element and which include in particular brasses, bronzes, cupronickels, nickel silver, steels, cast irons and stainless steels.
Lorsqu'un métal ou alliage doit être déformé à froid, notamment lorsqu'il est à la température ambiante avant l'opération de déformation qui peut être une extrusion, une frappe à froid, un étirage ou un tréfilage, ou lorsqu'on modifie la limite d'élasticité du métal en élevant sa température avant l'opération de déformation, qui peut alors être un matriçage, forgeage ou estampage, il convient de réduire auparavant les forces de frottement, pour ramener les pressions de formage à un niveau compatible avec la résistance des matériaux constitutifs de l'outillage utilisé.When a metal or alloy must be deformed cold, in particular when it is at room temperature before the deformation operation which can be an extrusion, cold stamping, drawing or drawing, or when the yield strength of the metal by raising its temperature before the deformation operation, which can then be a stamping, forging or stamping, it is advisable to reduce the friction forces beforehand, to reduce the forming pressures to a level compatible with the resistance of the constituent materials of the tools used.
Il est connu d'avoir recours dans ce but à une lubrification permettant d'obtenir un très bas coefficient de frottement qui doit être maintenu pendant toute la durée de l'opération de déformation, pour que la pièce formée présente un bon état de surface et pour que soit évitée une usure trop rapide de l'outillage.It is known to use for this purpose lubrication to obtain a very low coefficient of friction which must be maintained throughout the duration of the deformation operation, so that the formed part has a good surface condition and so that is avoided too rapid wear of the tool.
Les moyens utilisés jusqu'à ce jour pour abaisser le coefficient de frottement consistent à réaliser sur la pièce à déformer une préparation de surface suivie d'une lubrification.The means used to date to lower the friction coefficient consist in carrying out a surface preparation on the part to be deformed followed by lubrication.
La préparation de surface peut être constituée par un dégraissage, un décapage, un grenaillage, un affinage, une phosphatation, une oxalatation, une galvanisation ou un cuivrage, ou par une combinaison de plusieurs de ces traitements.Surface preparation can consist of degreasing, pickling, shot blasting, refining, phosphating, oxalation, galvanization or copper plating, or a combination of several of these treatments.
Le métal ainsi préparé est ensuite revêtu d'une couche lubrifiante qui peut être constituée
- * par une huile lubrifante à base d'huiles minérales, animales, végétales ou de synthèse comprenant des additifs dits d'extrême-pression, des esters gras naturels ou de synthèse et des agents anti-oxydants,
- * par un savon résultant de la réaction entre un acide gras d'origine naturelle ou de synthèse, ayant une chaîne carbonée comprise entre C₁₀ et C₂₂ et un hydroxyde alcalin, une amine ou une alcanolamine, ce savon comprenant en outre des agents dispersants, des séquestrants évitant la formation de savons insolubles, des bactéricides et des fongicides ou
- * par un lubrifiant solide utilisé seul ou en dispersion dans l'un des deux produits décrits ci-dessus, les lubrifiants solides les plus couramment utilisés étant le bisulfure de molybdène pour les déformations à froid et le graphite pour les déformations à chaud.
- * by a lubricating oil based on mineral, animal, vegetable or synthetic oils comprising so-called extreme pressure additives, natural or synthetic fatty esters and antioxidants,
- * by a soap resulting from the reaction between a fatty acid of natural or synthetic origin, having a carbon chain between C₁₀ and C₂₂ and an alkali hydroxide, an amine or an alkanolamine, this soap further comprising dispersing agents, sequestrants avoiding the formation of insoluble soaps, bactericides and fungicides or
- * by a solid lubricant used alone or in dispersion in one of the two products described above, the most commonly used solid lubricants being molybdenum disulphide for cold deformation and graphite for hot deformation.
Le bisulfure de molybdène et le graphite donnent satisfaction du point de vue de l'abaissement du coefficient de frottement mais présentent un certain nombre d'inconvénients majeurs, car mis en oeuvre sous forme de poudres ou de dispersions noires très collantes et difficiles à éliminer, ils occasionnent des salissures du poste de travail, des salissures de l'atelier et des salissures sur les pièces traitées et les outillages.Molybdenum disulphide and graphite are satisfactory from the point of view of lowering the friction coefficient but have a certain number of major drawbacks, since they are used in the form of very sticky powders or dispersions which are very sticky and difficult to remove, they cause soiling of the work station, soiling of the workshop and soiling on the treated parts and the tools.
De plus, les difficultés qu'il y a à éliminer le bisulfure de molybdène et le graphite des surfaces traitées posent des problèmes au moment des opérations subséquentes à la déformation, c'est-à-dire par exemple avant la mise en peinture, l'usinage, un nouveau cycle de déformation et autres traitements thermiques qui peuvent être entravées par la présence de soufre dans le cas du bisulfure de molybdène.In addition, the difficulties involved in removing molybdenum disulphide and graphite from the treated surfaces pose problems during post-deformation operations, that is to say for example before painting, machining, a new deformation cycle and other heat treatments which can be hampered by the presence of sulfur in the case of molybdenum disulfide.
Enfin le colmatage des circuits de distribution est fréquent en raison toujours des mêmes difficultés d'élimination des produits en question.Finally, clogging of the distribution circuits is frequent due to the same difficulties in eliminating the products in question.
L'ensemble des inconvénients liés à l'utilisation du bisulfure de molybdène et du graphite a conduit l'homme de l'art dans les vingt dernières années à étudier des compositions lubrifiantes à base de sels minéraux ou de produits de synthèse auxquels leur manque d'efficacité a interdit de trouver des applications industrielles d'envergure.All the drawbacks linked to the use of molybdenum disulphide and graphite have led those skilled in the art in the last twenty years to study lubricating compositions based on mineral salts or on synthetic products which lack them. efficiency has prevented the finding of large-scale industrial applications.
Et c'est à la Société Demanderesse que revient le mérite d'avoir apporté à l'issue de recherches approfondies, une solution à ce difficile problème en trouvant qu'il était possible de conférer aux surfaces de pièces métalliques devant être déformées à froid ou à chaud un coefficient de frottement au moins aussi faible qu'avec le bisulfure de molybdène ou avec le graphite, sans entraîner les inconvénients inhérents à l'utilisation de ces produits, en traitant lesdites pièces métalliques, après la préparation de surface traditionnelle, (qui peut comprendre un dégraissage, un grenaillage, un affinage, une phosphatation, une oxalatation ou plusieurs de ces traitements) avec au moins l'un des halogénures de lanthanide du groupe constitué par le fluorure de lanthane et par le fluorure de cérium, qui est de préférence mis en oeuvre sous la forme d'une dispersion aqueuse ou huileuse ou enrobé dans une cire ou encore en mélange avec un savon sec en poudre, les produits en question, qui sont aisément éliminables, n'étant ni noirs, ni collants.And it is to the Applicant Company that the credit is due for having brought, after thorough research, a solution to this difficult problem by finding that it was possible to give the surfaces of metal parts to be deformed cold or when hot a coefficient of friction at least as low as with molybdenum disulphide or with graphite, without causing the drawbacks inherent in the use of these products, by treating said metal parts, after traditional surface preparation, (which may include degreasing, shot blasting, refining, phosphating, oxalation or more of these treatments) with at least one of the lanthanide halides from the group consisting of lanthanum fluoride and cerium fluoride, which is preferably used in the form of an aqueous or oily dispersion or coated in a wax or in a mixture with a dry powder soap, the products in question, which are easily removable, being neither black nor sticky.
Il s'ensuit que le procédé, conforme à l'invention, de lubrification de la surface de pièces métalliques en cuivre ou en alliages à base de fer ou de cuivre, destinées à être déformées à froid ou à chaud, est caractérisé par le fait qu'après la préparation de la surface traditionnelle, on applique à la surface desdites pièces au moins l'un des halogénures de lanthanide du groupe constitué par le fluorure de lanthane et par le fluorure de cérium, de préférence sous la forme d'une dispersion aqueuse ou huileuse ou d'un mélange avec une cire ou un savon sec en poudre.It follows that the method, according to the invention, of lubricating the surface of metallic pieces of copper or of alloys based on iron or copper, intended to be deformed cold or hot, is characterized by the fact that after the preparation of the traditional surface, at least one of the lanthanide halides from the group consisting of lanthanum fluoride and cerium fluoride is applied to the surface of said parts, preferably in the form of a dispersion aqueous or oily or a mixture with a wax or dry soap powder.
L'invention a également pour objet l'utilisation pour la lubrification de la surface de pièces métalliques en cuivre ou en alliages à base de fer ou de cuivre, devant être déformées à froid ou à chaud, d'un agent lubrifiant essentiellement constitué par au moins l'un des halogénures de lanthanide du groupe constitué par le fluorure de lanthane et par le fluorure de cérium.A subject of the invention is also the use for the lubrication of the surface of metallic parts made of copper or of alloys based on iron or copper, to be deformed cold or hot, of a lubricating agent essentially consisting of minus one of the lanthanide halides from the group consisting of lanthanum fluoride and cerium fluoride.
Le susdit agent lubrifiant est, de préférence, mis en oeuvre sous la forme d'une dispersion aqueuse ou sous la forme d'un mélange avec un savon sec en poudre.The above lubricating agent is preferably used in the form of an aqueous dispersion or in the form of a mixture with dry powder soap.
Les susdits dispersions et mélanges ainsi que les concentrés à partir desquels on prépare les dispersions, constituent des produits ou mélanges industriels nouveaux.The above-mentioned dispersions and mixtures, as well as the concentrates from which the dispersions are prepared, constitute new industrial products or mixtures.
On signale que le fluorure de cérium a déjà été ajouté à des graisses destinées à être utilisées dans des conditions extrêmes de température ou de pression (brevet US No. 4.507.214) et que les fluorures de cérium et de lanthane ont été mis en oeuvre dans la coulée sous pression de métaux fondus (brevet US No. 3.380.280).It is reported that cerium fluoride has already been added to greases intended to be used under extreme conditions of temperature or pressure (US Patent No. 4,507,214) and that the cerium and lanthanum fluorides have been used in the die casting of molten metals (patent US No. 3.380.280).
Mais, ces documents antérieurs non seulement ne concernent pas la déformation à froid et à chaud de métaux à base de cuivre ou de fer, mais de plus ne contiennent aucune suggestion de nature à inciter l'homme de l'art à appliquer les composés en question à ce domaine technique.However, these prior documents not only do not relate to the cold and hot deformation of metals based on copper or iron, but moreover do not contain any suggestion capable of inducing a person skilled in the art to apply the compounds in question. question to this technical area.
Comme indiqué plus haut, les halogénures de lanthanide peuvent être mis en oeuvre sous la forme de dispersions aqueuses ou huileuses ou enrobés dans une cire ou encore en mélange avec un savon sec en poudre.As indicated above, the lanthanide halides can be used in the form of aqueous or oily dispersions or coated in a wax or else as a mixture with dry powder soap.
En ce qui concerne tout d'abord les dispersions aqueuses d'halogénures de lanthanide, elles comprennent des agents tensio-actifs à action mouillante ou dispersante, qui peuvent être choisis parmi
- les dérivés anioniques et notamment d'une part des sels formés entre un hydroxyde alcalin, une amine ou une alcanolamine et un acide gras d'origine naturelle ou de synthèse ayant une chaîne carbonée de C₁₀ à C₂₂ et d'autre part par les sels d'un hydroxyde alcalin, d'une amine ou d'une alcanolamine d'un corps gras sulfoné ou sulfaté, d'alcools gras sulfatés, d'amides gras sulfatés, de non-ioniques sulfatés, d'hydrocarbures sulfonés, d'alkylaryles sulfonatés,
- des dérivés non-ioniques et notamment des esters de polyéthylèneglycol, des dérivés oxyéthylénés et oxypropylénés d'alcools à poids moléculaire élevé, d'amides, d'amides substitués, d'acides gras, d'esters ou d'amines.
- anionic derivatives and in particular on the one hand the salts formed between an alkali hydroxide, an amine or an alkanolamine and a fatty acid of natural or synthetic origin having a carbon chain from C₁₀ to C₂₂ and on the other hand by the salts d '' an alkali hydroxide, an amine or an alkanolamine of a sulfonated or sulfated fatty substance, sulfated fatty alcohols, sulfated fatty amides, sulfated nonionics, sulfonated hydrocarbons, sulfonated alkylaryls ,
- nonionic derivatives and in particular polyethylene glycol esters, oxyethylenated and oxypropylenated derivatives of high molecular weight alcohols, amides, substituted amides, fatty acids, esters or amines.
Ces dispersions aqueuses peuvent également contenir un ou plusieurs agents séquestrants, un ou plusieurs agents anti-corrosion, un ou plusieurs agents de conservation ou encore à la fois plusieurs de ces différents produits.These aqueous dispersions can also contain one or more sequestering agents, one or more anti-corrosion agents, one or more agents or several of these different products at the same time.
Les agents séquestrants peuvent être choisis dans le groupe comprenant l'EDTA, le NTA, les phosphonates de sels de métaux alcalins ou d'alcanolamine et les polyphosphates.The sequestering agents can be chosen from the group comprising EDTA, NTA, phosphonates of alkali metal or alkanolamine salts and polyphosphates.
Les agens anti-corrosion peuvent être choisis parmi les sels de métaux alcalins ou d'alcanolamines d'acides sulfoniques, d'acides carboxyliques, oléylsarcosiniques et d'acides alkylarylsulfonamidocarboxyliques.The anti-corrosion agents can be chosen from the alkali metal or alkanolamine salts of sulfonic acids, carboxylic, oleylsarcosinic acids and alkylarylsulfonamidocarboxylic acids.
Les agents de conservation peuvent être choisis parmi le formol, les dérivés triaziniques, l'orthophénylformol ou son sel de sodium.The preservatives can be chosen from formalin, triazine derivatives, orthophenylformol or its sodium salt.
Les dispersions huileuses peuvent contenir des huiles minérales d'origine pétrolière qui peuvent être des huiles paraffiniques, des huiles naphténiques, des huiles aromatiques. L'huile peut également être une huile de synthèse telle qu'une polyalfaoléfine ou un alkylat, une huile végétale telle que l'huile de colza, l'huile de ricin, l'huile de soja ou animale telle que l'huile de lard, l'huile de pied de boeuf. Ces dispersions huileuses peuvent contenir, en outre, des esters gras de synthèse tels que des esters de polyéthylèneglycol et des adjuvants de viscosité tels que des aluminosilicates et les dérivés carboxyliques modifiés.The oily dispersions can contain mineral oils of petroleum origin which can be paraffinic oils, naphthenic oils, aromatic oils. The oil can also be a synthetic oil such as a polyalfaolefin or an alkylate, a vegetable oil such as rapeseed oil, castor oil, soybean or animal oil such as bacon oil , beef foot oil. These oily dispersions may also contain synthetic fatty esters such as polyethylene glycol esters and viscosity adjuvants such as aluminosilicates and modified carboxylic derivatives.
Elles peuvent également contenir un ou plusieurs agents de dispersion, un ou plusieurs agents de conservation ou encore à la fois plusieurs de ces produits.They can also contain one or more dispersing agents, one or more preservatives or even several of these products.
Les agents de dispersion peuvent être des alkylarylsulfonates de calcium ou d'aluminium.The dispersing agents can be calcium or aluminum alkylarylsulfonates.
Les agents de conservation peuvent être choisis parmi les dérivés triaziniques.The preservatives can be chosen from triazine derivatives.
Les cires utilisées pour enrober les halogénures de lanthanide peuvent être des cires d'origine minérale telles que les cires microcristallines ou les paraffines ainsi que des cires d'origine animale ou végétale.The waxes used to coat the lanthanide halides can be waxes of mineral origin such as microcrystalline waxes or paraffins as well as animal or vegetable waxes.
Elles peuvent contenir, en outre, des agents de texture permettant de modifier l'aspect du produit final tels que des esters d'acides gras, notamment des carboxylates de polyglycol tels que l'oléate de poléthylèneglycol.They may also contain texturing agents which make it possible to modify the appearance of the final product, such as fatty acid esters, in particular polyglycol carboxylates such as polyethylene glycol oleate.
Les savons secs en poudre peuvent être formés par les produis de réaction entre les hydroxydes alcalins et/ou alcalino-terreux avec au moins un acide gras d'origine naturelle ou de synthèse ayant une chaîne carbonée de C₁₀ à C₂₂.Dry powdered soaps can be formed by the reaction products between alkaline and / or alkaline-earth hydroxides with at least one fatty acid of natural or synthetic origin having a carbon chain from C₁₀ to C₂₂.
Il est enfin possible de prévoir dans les susdits produits lubrifiants des charges inertes qui peuvent être des carbonates, des sulfates ou de l'eau.It is finally possible to provide in the above lubricating products inert fillers which can be carbonates, sulfates or water.
L'application de l'agent lubrifiant et des dispersions et mélanges pour sa mise en oeuvre conforme à l'invention sur la surface des pièces à déformer peut être effectuée
- par aspersion à l'aide d'un pistolet pneumatique,
- au trempé à froid ou à chaud,
- manuellement par enduction au pinceau, à la brosse, au rouleau ou encore
- par frottement d'un bâton de cire,
- par enrobage par passage dans une boîte à savon en poudre de tréfilage.
- by spraying using a pneumatic gun,
- cold or hot soaking,
- manually by coating with a brush, brush, roller or
- by rubbing a stick of wax,
- by coating by passage through a soap box in wire drawing powder.
Lorsque l'agent lubrifiant est appliqué sous la forme d'une dispersion aqueuse ou huileuse ou sous la forme d'un mélange avec une cire, sa concentration dans le milieu d'application est de 0,05 à 60% en poids; il est préférentiellement de 0,05 à 5% en poids dans le cas d'une dispersion aqueuse, de 0,1 à 15% en poids dans le cas d'une dispersion huileuse et de 5 à 60% en poids dans le cas d'un mélange avec une cire et de 0,05 à 5% en poids dans le cas d'un mélange avec un savon en poudre.When the lubricating agent is applied in the form of an aqueous or oily dispersion or in the form of a mixture with a wax, its concentration in the application medium is from 0.05 to 60% by weight; it is preferably from 0.05 to 5% by weight in the case of an aqueous dispersion, from 0.1 to 15% by weight in the case of an oily dispersion and from 5 to 60% by weight in the case of '' a mixture with a wax and 0.05 to 5% by weight in the case of a mixture with a powdered soap.
Pour constituer les dispersions aqueuses ou les dispersions huileuses, on peut avoir recours à des poudres ou à des liquides comportant, outre au moins l'un des halogénures de lanthanide du groupe constitué par le fluorure de lanthane et par le fluorure de cérium, les autres constituants des dispersions sous forme concentrée.To constitute the aqueous dispersions or the oily dispersions, it is possible to use powders or liquids comprising, in addition to at least one of the lanthanide halides from the group consisting of lanthanum fluoride and cerium fluoride, the other constituents of the dispersions in concentrated form.
Ces produits concentrés peuvent avoir une teneur en au moins l'un des susdits halogénures de lanthanide qui est respectivement de 5 à 30% en poids dans le cas de ceux destinés à fournir les dispersions aqueuses et de 1 à 50% dans le cas de ceux destinés à fournir des dispersions huileuses.These concentrated products may have a content of at least one of the above lanthanide halides which is respectively from 5 to 30% by weight in the case of those intended to provide the aqueous dispersions and from 1 to 50% in the case of those intended to provide oily dispersions.
La dilution au moment de l'application, si elle est nécessaire, est réalisée à l'aide d'eau pour les dispersions aqueuses et à l'aide d'une huile ou d'un solvant pétrolier dans le cas de dispersions huileuses.Dilution at the time of application, if necessary, is carried out using water for aqueous dispersions and using an oil or a petroleum solvent in the case of oily dispersions.
Par ailleurs, les agents lubrifiants peuvent être introduits dans le milieu d'application simultanément à un lubrifiant classique, et avantageusement, on peut mettre à la disposition de l'utilisateur, séparément les uns des autres, un ensemble de produits permettant de réaliser le procédé conforme à l'invention, à savoir:
- un premier produit essentiellement constitué d'halogénure de lanthanide, notamment de fluorure de cérium et/ou de lanthane à une concentration de 1 à 99,9%, et
- dans le cas de la réalisation du procédé par mise en oeuvre d'une dispersion aqueuse, un second produit conduisant au dépôt d'un savon, ou
- dans le cas de la réalisation du procédé par mise en oeuvre d'une dispersion huileuse, un troisième produit constitué par une huile pouvant comporter les additifs prévus dans ce cas,
- dans le cas de la réalisation du procédé par mélange avec un savon sec en poudre, un quatrième produit constitué par ce savon sec en poudre,
- a first product essentially consisting of lanthanide halide, in particular of cerium fluoride and / or lanthanum at a concentration of 1 to 99.9%, and
- in the case of carrying out the process by using an aqueous dispersion, a second product leading to the deposition of a soap, or
- in the case of carrying out the process by using an oily dispersion, a third product consisting of an oil which may contain the additives provided for in this case,
- in the case of carrying out the method by mixing with dry powder soap, a fourth product consisting of this dry powder soap,
Avant d'illustrer l'invention à l'aide des exemples comparatifs qui suivent et dans lesquels sont indiqués quelques modes de réalisation avantageux mais nullement limitatifs de l'invention, on souligne un avantage particulier résidant dans la possibilité de réaliser sur un même lieu de production, et avec une gamme unique de préparation de surfaces et de lubrification, la déformation de pièces diverses qui, dans la mesure où on appliquait les techniques de l'art antérieur, nécessitaient des préparations de surfaces différentes.Before illustrating the invention with the aid of the comparative examples which follow and in which are indicated some advantageous but in no way limitative embodiments of the invention, a particular advantage lies in the possibility of carrying out on the same place of production, and with a unique range of surface preparation and lubrication, the deformation of various parts which, insofar as the techniques of the prior art were applied, required different surface preparations.
On procède à un essai comparatif en utilisant successivement, dans le test dit de l'anneau, des dispersions dans l'huile de fluorure de cérium, de graphite et de bisulfure de molybdène. Les graphites et bisulfures de molybdène utilisés sont de qualité couramment utilisée pour ce type d'application, à savoir
- un graphite en poudre ayant une granulométrie telle que 50% des grains ont une taille inférieure à 8 µm et 100% une taille inférieure à 32 µm, la surface spécifique BET étant de 16 m²/g, ce graphite pouvant être celui de qualité T10 de LONZA,
- un bisulfure de molybdène en poudre de 99% de pureté et d'une granulométrie telle que 50% des grains ont une taille inférieure à 8 µm, par exemple celui de qualité n° 4 de la Société KS PAUL.
- a powdered graphite having a particle size such that 50% of the grains have a size less than 8 μm and 100% a size less than 32 μm, the BET specific surface being 16 m² / g, this graphite can be that of quality T10 of LONZA,
- a molybdenum disulphide in powder of 99% purity and with a particle size such that 50% of the grains have a size less than 8 μm, for example that of quality No. 4 from the company KS PAUL.
Le fluorure de cérium utilisé se présente sous la forme de poudre blanche à 98% de pureté d'une granulométrie telle que 74% des grains ont une taille inférieure à 100 µm.The cerium fluoride used is in the form of a white powder with 98% purity with a particle size such that 74% of the grains have a size less than 100 μm.
Le test de l'anneau utilisé pour mesurer le coefficient de frottement obtenu à l'aide des différentes dispersions huileuses est décrit dans l'ouvrage "Metal deformation process : friction and lubrication" par J.A. SCHEY, pages 270-271, édité par Marcel Dekker en 1970.The ring test used to measure the coefficient of friction obtained using the different oily dispersions is described in the book "Metal deformation process: friction and lubrication" by JA SCHEY, pages 270-271, edited by Marcel Dekker in 1970.
Ce test permet de déterminer le coefficient de frottement existant entre un outil et un matériau soumis à une déformation plastique dans des conditions particulières de surface et de lubrification.This test makes it possible to determine the coefficient of friction existing between a tool and a material subjected to plastic deformation under special conditions of surface and lubrication.
Ainsi, lorsqu'un anneau en métal est écrasé entre deux tas plats, on constate que le diamètre d'alésage, pour un écrasement donné, dépend des conditions de frottement; plus les frottements sont faibles, plus l'alésage est grand.Thus, when a metal ring is crushed between two flat piles, it can be seen that the bore diameter, for a given crushing, depends on the friction conditions; the lower the friction, the larger the bore.
Les anneaux utilisés pour l'essai sont en acier de qualité XC 10 et présentent les dimension suivantes:
L'outillage utilisé pour le test est composé de deux tas plats en acier de qualité Z 20 OC 12. La réduction de hauteur de l'anneau lors des essais varie de 20 à 40%.The tools used for the test are composed of two flat piles of quality Z 20 OC 12 steel. The reduction in height of the ring during the tests varies from 20 to 40%.
Les résultats des mesures de la variation de hauteur et de la variation du diamètre intérieur permettent, par l'intermédiaire d'abaques préétablies, de déduire la valeur du coefficient de frottement du contact.The results of the measurements of the variation in height and the variation in the internal diameter make it possible, by means of pre-established charts, to deduce the value of the coefficient of friction of the contact.
Dans le cadre du présent exemple, les anneaux ont été lubrifiés par trempage à température ambiante dans des dispersions à 5% en poids de graphite, de bisulfure de molybdène ou de fluorure de cérium dans une huile naphténique de viscosité égale à 75 centistokes à 40°C.In the context of the present example, the rings were lubricated by soaking at room temperature in dispersions at 5% by weight of graphite, molybdenum disulphide or cerium fluoride in a naphthenic oil with a viscosity of 75 centistokes at 40 ° vs.
Les résultats obtenus sont réunis dans le tableau I.
Cet exemple met en évidence le fait que l'agent lubrifiant selon l'invention permet d'obtenir des coefficients de frottement satisfaisants pour un résultat visuellement plus flatteur et sans que la pièce traitée comporte des salissures.This example highlights the fact that the lubricating agent according to the invention makes it possible to obtain satisfactory coefficients of friction for a visually more flattering result and without the treated part having dirt.
On procède à un essai comparatif réalisé dans les conditions industrielles et consistant en une opération de "filage avant" effectuée sur des pièces du type lopins creux en acier.A comparative test is carried out carried out under industrial conditions and consisting of a "front spinning" operation carried out on parts of the hollow steel slab type.
Classiquement, on prépare les lopins destinés à être soumis au filage avant, en procédant sucessivement à une phosphatation qui peut être réalisée avec un bain de phosphatation du type de celui commercialisé sous la marque THERMOGRANODINE 701® par la Société Demanderesse et mis en oeuvre de manière habituelle, cette phosphatation étant suivie d'une enduction au trempé dans une dispersion aqueuse de Mos₂ comportant 5% en poids de ce produit.Conventionally, the plots intended to be subjected to prior spinning are prepared, by successively carrying out a phosphating which can be carried out with a phosphating bath of the type marketed under the brand THERMOGRANODINE 701® by the Applicant Company and implemented in a manner usual, this phosphating being followed by coating by dipping in an aqueous dispersion of Mos₂ comprising 5% by weight of this product.
Il est impossible de réaliser le susdit filage avant en procédant à la phosphatation suivie d'une simple lubrification par dépôt de savon : en effet, il se produit alors une détérioration rapide de l'outillage et les pièces obtenues sont hors cotes.It is impossible to carry out the above-mentioned prior spinning by carrying out phosphating followed by simple lubrication by depositing soap: in fact, there is a rapid deterioration of the tooling and the parts obtained are out of dimension.
Dans le présent essai comparatif, on soumet deux séries de 600 lopins du type identifié ci-dessus successivement à une phosphatation à l'aide de THERMOGRANODINE 701 et à une lubrification au trempé en utilisant dans le premier cas une dispersion aqueuse classique à 5% en poids de MoS₂, et dans le deuxième cas un mélange d'une dispersion aqueuse à 0,5% en poids de CeF₃ et d'une solution à 5% en poids d'un agent tensio-actif anionique, constitué par un savon, en l'occurrence du stéarate de sodium, par exemple celui commercialisé par la Société Demanderesse sous la marque PROLUB TS 438 et qui conduit au dépôt d'un savon lubrifiant.In the present comparative test, two series of 600 pieces of the type identified above are subjected successively to a phosphating using THERMOGRANODINE 701 and to a dip lubrication using in the first case a conventional aqueous dispersion at 5% by weight of MoS₂, and in the second case a mixture of an aqueous dispersion at 0.5% by weight of CeF₃ and a 5% by weight solution of an anionic surfactant, consisting of a soap, in this case sodium stearate, for example that sold by the Applicant Company under the brand PROLUB TS 438 and which leads to the deposition of a lubricating soap.
Les conditions de la mise en oeuvre de la lubrification sont réunies dans le tableau II.
Le contrôle dimensionnel effectué sur les 600 pièces, déformées après traitement selon le procédé conforme à l'invention, fournit des résultats identiques à ceux enregistrés après traitement selon le procédé conforme à l'art antérieur; ces résultats montrent que les pièces déformées sont conformes aux tolérances rappelées dans le tableau III:
Les diamètres extérieurs ⌀ 1, ⌀ 2, ⌀ 3 et le diamètre intérieur ⌀ int. sont spécifiques à la forme de la pièce et apparaissent sur la figure unique, qui montre ladite pièce en coupe axiale, respectivement en a, b, c et d.The outside diameters ⌀ 1, ⌀ 2, ⌀ 3 and the inside diameter ⌀ int. are specific to the shape of the part and appear in the single figure, which shows said part in axial section, respectively in a, b, c and d.
Le contrôle des angles de déformation par projection de profil indique des résultats similaires pour les deux procédés.The control of the deformation angles by profile projection indicates similar results for the two methods.
Les pièces déformées après traitement par mise en oeuvre du procédé conforme à l'invention sont aisément manipulables et d'aspect plus propre qu'avec le procédé habituel.The parts deformed after treatment by implementing the process according to the invention are easy to handle and of cleaner appearance than with the usual process.
Cet exemple démontre par conséquent que grâce à l'invention, il est possible de réaliser industriellement des déformations à froid de pièces qui nécessitaient dans l'art antérieur la mise en oeuvre de bisulfure de molybdène; l'avantage apporté par l'invention réside dans l'aspect propre des pièces obtenues, ce qui n'est pas le cas pour les pièces traitées selon l'art antérieur qui doivent être nettoyées avant les opérations subséquentes.This example therefore demonstrates that, thanks to the invention, it is possible to carry out industrial cold deformations of parts which in the prior art required the use of molybdenum disulphide; the advantage provided by the invention lies in the clean appearance of the parts obtained, which is not the case for the parts treated according to the prior art which must be cleaned before the subsequent operations.
On procède à un essai comparatif réalisé dans les conditions industrielles et consistant en une opération de filage avant puis de filage arrière sur des lopins en acier à l'aide d'une presse hydraulique d'une puissance de 600 T (vitesse d'avancement du poinçon = 40 mm/s).A comparative test is carried out carried out under industrial conditions and consisting of a front spinning operation then a rear spinning operation on steel plots using a hydraulic press with a power of 600 T (forward speed of the punch = 40 mm / s).
Deux séries de 2100 lopins du type susdit sont soumises aux opérations successives de filage avant et arrière après traitement de lubrification selon le procédé de l'art antérieur pour la première série et selon le procédé conforme à l'invention pour la deuxième série, chacun de ces traitements étant effectué après phosphatation avec le produit THERMOGRANODINE 701 qui est un bain de phosphatation commercialisé par la Société Demanderesse et qui est mis en oeuvre de manière habituelle. Dans le tableau IV, on a réuni les caractéristiques des deux traitement de lubrification.
Les opérations de filage avant puis de filage arrière étant effectuées, on prélève 50 pièces sur chaque série et on les soumet aux contrôles dimensionnels classiques et à la mesure comparative de l'écart type. Les résultats enregistrés sont réunis dans le tableau V.
A l'examen de ces résultats, on constate que le procédé de lubrification selon l'invention permet de réaliser industriellement les opérations de déformation à froid avec plus de fiabilité que le procédé selon l'art antérieur.On examination of these results, it can be seen that the lubrication method according to the invention makes it possible to carry out the cold deformation operations industrially with more reliability than the method according to the prior art.
On procède à un essai comparatif réalisé dans les conditions industrielles et consistant en une opération de filage arrière de pièces en acier; il s'agit de deux séries de 500 lopins en acier; l'opération est réalisée à l'aide d'une presse hydraulique d'une puissance de 1600 T (vitesse du poinçon = 50 mm/s).We carry out a comparative test carried out in industrial conditions and consisting of a rear spinning operation of steel parts; these are two series of 500 pieces of steel; the operation is carried out using a hydraulic press with a power of 1600 T (speed of the punch = 50 mm / s).
Les lopins sont préalablement phosphatés au moyen d'un bain de THERMOGRANODINE 701®, puis ils sont lubrifiés:
- en ce qui concerne la première série successivement à l'aide d'un savon anionique, par exemple le PROLUB TS 438 à 5% en poids dans l'eau (pendant 5 minutes à 80°C) puis à l'aide de MoS₂ en poudre appliqué au pinceau,
- en ce qui concerne la deuxième série, par trempage dans une dispersion aqueuse contenant 5% en poids d'un savon anionique pouvant être constitué par celui commercialisé sous la marque PROLUB TS 438 et 0,5% en poids de CeF₃, la durée du trempage étant de 5 minutes et la température de la dispersion de 80°C.
- as regards the first series successively using an anionic soap, for example PROLUB TS 438 at 5% by weight in water (for 5 minutes at 80 ° C.) then using MoS₂ in powder applied with a brush,
- as regards the second series, by soaking in an aqueous dispersion containing 5% by weight of an anionic soap which may consist of that sold under the brand PROLUB TS 438 and 0.5% by weight of CeF₃, the duration of the soaking being 5 minutes and the temperature of the dispersion 80 ° C.
Après l'opération de filage arrière, le contrôle dimensionnel effectué sur les deux séries de 500 pièces s'est avéré conforme aux normes et identique dans les deux cas. On souligne l'avantage constitué par l'aspect plus propre et le caractère non salissant des pièces lubrifiées par mise en oeuvre du procédé selon l'invention qui, de surcroît, permet de réaliser la lubrification en une seule étape alors qu'il en faut deux dans le procédé selon l'art antérieur.After the rear spinning operation, the dimensional check carried out on the two series of 500 pieces was found to comply with the standards and identical in both cases. The advantage constituted by the cleaner appearance and the non-dirtying nature of the parts lubricated by the implementation of the method according to the invention which underlines, moreover, makes it possible to carry out the lubrication in a single step when it is necessary. two in the process according to the prior art.
D'un point de vue plus général et en rapport avec les exemples 2, 3 et 4 qui sont réalisés sur le même lieu de production industrielle, on souligne que, dans le cas de la lubrification selon l'art antérieur, il est courant d'avoir recours à des procédés différents en fonction des difficultés de déformation, alors que le procédé selon l'invention permet d'utiliser une gamme unique de préparation de surfaces dans les trois cas.From a more general point of view and in relation to Examples 2, 3 and 4 which are carried out on the same place of industrial production, it is emphasized that, in the case of lubrication according to the prior art, it is common to '' use different methods depending on the deformation difficulties, while the method according to the invention allows the use of a range unique surface preparation in all three cases.
On procède à un essai comparatif dans des conditions industrielles en procédant à la déformation à froid de lopins en acier inoxydable de nuance Z6 C13, la déformation étant réalisée à l'aide d'une presse mécanique d'une puissance de 600 T.A comparative test is carried out under industrial conditions by cold deformation of pieces of stainless steel of grade Z6 C13, the deformation being carried out using a mechanical press with a power of 600 T.
Deux séries de lopins sont préparées en vue de la déformation respectivement par mise en oeuvre des techniques de l'art antérieur pour la première série et du procédé conforme à l'invention pour la seconde.Two series of plots are prepared for deformation respectively by applying techniques of the prior art for the first series and the process according to the invention for the second.
Les deux traitements lubrifiants sont précédés par un traitement de préparation de surface, identique dans les deux cas et constitué par une oxalatation à base de sels de l'acide oxalique qui peuvent être apportés au moyen du produit commercialisé par la Société Demanderesse sous la marque THERMOGRANODINE SS1 et SS5.The two lubricant treatments are preceded by a surface preparation treatment, identical in both cases and consisting of an oxalation based on oxalic acid salts which can be provided by means of the product marketed by the Applicant Company under the brand THERMOGRANODINE SS1 and SS5.
Le traitement lubrifiant selon l'art antérieur comprend successivement un traitement à l'aide d'un savon lubrifiant anionique PROLUB TS 438 à 5% en poids dans l'eau, la durée étant de 5 minutes et la température de 80°C puis une enduction au trempé dans une dispersion à 5% en poids de MoS₂ dans l'eau, la durée étant de 1 minutes et la température du bain de 60°C.The lubricant treatment according to the prior art successively comprises a treatment using an anionic lubricant PROLUB TS 438 at 5% by weight in water, the duration being 5 minutes and the temperature of 80 ° C. then a coating by dipping in a dispersion at 5% by weight of MoS₂ in water, the duration being 1 minute and the bath temperature of 60 ° C.
Le traitement lubrifiant selon l'invention comprend une étape unique de traitement à l'aide d'une dispersion aqueuse à 0,5% en poids de CeF₃ qui contient également 5% en poids de PROLUB TS 438, la durée étant de 5 minutes et la température de la dispersion de 80°C.The lubricant treatment according to the invention comprises a single stage of treatment using an aqueous dispersion containing 0.5% by weight of CeF₃ which also contains 5% by weight of PROLUB TS 438, the duration being 5 minutes and the temperature of the dispersion of 80 ° C.
Les résultats obtenus après l'opération de déformation sont réunis dans le tableau VI :
On souligne de plus que, dans cet exemple, le traitement de lubrification selon l'invention a été réalisé en une seule étape alors qu'il a fallu procéder en deux étapes dans le traitement selon l'art antérieur.It is further underlined that, in this example, the lubrication treatment according to the invention was carried out in a single step whereas it was necessary to proceed in two stages in the treatment according to the prior art.
On procède à un essai comparatif de filage à chaud de laiton dans des conditions industrielles consistant à chauffer à 750°C des billettes de laiton puis à réaliser le filage à chaud pour obtenir un fil de diamètre variant de 5 à 11 mm, les filières étant lubrifiées auparavant.A comparative test of hot spinning of brass is carried out under industrial conditions, consisting of heating brass billets to 750 ° C. and then carrying out hot spinning to obtain a wire with a diameter varying from 5 to 11 mm, the dies being previously lubricated.
Cette lubrification est assurée conformément à l'art antérieur par un lubrifiant solide à savoir du graphite, enrobé à raison de 50 % en poids dans une cire paraffinique de point de goutte de 80°C alors que la lubrification selon l'invention a été réalisée à l'aide d'un mélange à 50% en poids de CeF₃ dans la même cire paraffinique.This lubrication is ensured in accordance with the prior art by a solid lubricant, namely graphite, coated at a rate of 50% by weight in a paraffin wax of drop point of 80 ° C. while the lubrication according to the invention has been carried out. using a mixture of 50% by weight of CeF₃ in the same paraffinic wax.
Le filage réalisé après lubrification selon l'invention conduit à un fil d'aspect plus propre contrairement à ce qui se passe lors de l'utilisation du lubrifiant selon l'art antérieur. On ne constate aucune usure anormale de la filière.The spinning carried out after lubrication according to the invention leads to a cleaner looking thread, unlike what happens when the lubricant according to the prior art is used. There is no abnormal wear on the die.
On procède à un essai industriel de tréfilage à sec de fils d'acier galvanisé. La lubrification est faite à l'aide de "boîtes à savon" dans lesquelles le savon lubrifiant est introduit sec. Le passage du fil dans la "boîte à savon" permet d'obtenir un enrobage de lubrifiant par liquéfaction sur le fil chaud du savon sec, permettant le passage dans la filière.An industrial test of dry drawing of galvanized steel wire is carried out. Lubrication is made using "soap boxes" in which the lubricating soap is introduced dry. Passing the wire through the "soap box" makes it possible to obtain a coating of lubricant by liquefaction on the hot wire of the dry soap, allowing passage through the die.
L'essai est réalisé sur un banc de tréfilage comportant huit filières permettant une réduction totale à partir d'un diamètre de 2,4 mm à l'entrée jusqu'à un diamètre de 0,69 mm en sortie.The test is carried out on a wire drawing bench comprising eight dies allowing a total reduction from a diameter of 2.4 mm at the inlet to a diameter of 0.69 mm at the outlet.
Le fil à tréfiler est composé d'acier à 0,45% de carbone et il est galvanisé. Sa résistance est de 180 kg/cm².The drawing wire is made of 0.45% carbon steel and is galvanized. Its resistance is 180 kg / cm².
L'adjonction de 1% de CeF₃ dans un produit PROLUB TN 110 commercialisé par la Compagnie Française de Produits Industriels et constitué de stéarate de sodium, permet de réaliser le tréfilage à une vitesse de 540 m/min alors que le PROLUB TN 110 seul ne le permet pas. Dans ce dernier cas, on assiste à une usure rapide des filières et à la casse du fil.The addition of 1% of CeF₃ in a PROLUB TN 110 product marketed by the Compagnie Française de Produits Industriels and consisting of sodium stearate, enables wire drawing to be carried out at a speed of 540 m / min whereas PROLUB TN 110 alone does not not allow it. In the latter case, there is rapid wear of the dies and breakage of the wire.
Un essai d'évaluation de pouvoir lubrifiant est réalisé suivant la norme automobile CNOMO D 55 1136 sur machine 4 billes Shell Royal Dutch.A lubricating power evaluation test is carried out according to the automotive standard CNOMO D 55 1136 on a 4-ball machine Shell Royal Dutch.
Il s'agit d'un essai comparatif réalisé en additionnant à une huile paraffinique de viscosité 620 centistokes à 40°C telle que l'ENERPAR 27 commercialisée par la Société Française BP, différents agents de lubrification identifiés dans le tableau VII.This is a comparative test carried out by adding to a paraffinic oil of viscosity 620 centistokes at 40 ° C. such as ENERPAR 27 marketed by the Société Française BP, various lubrication agents identified in Table VII.
On mesure, par une charge de 100 kg le diamètre moyen d'empreinte d'usure. Un petit diamètre qualifie une bonne lubrification. L'essai est réalisé à température ambiante.
Le fluorure de lanthane mis en oeuvre se présente sous la forme d'une poudre blanche de pureté supérieure à 99% et d'une granulométrie telle qu'au moins 74% des grains ont une taille inférieure à 100 microns.The lanthanum fluoride used is in the form of a white powder of purity greater than 99% and with a particle size such that at least 74% of the grains have a size less than 100 microns.
A l'examen des résultats réunis dans le tableau VII, on peut conclure que le fluorure de cérium et le fluorure de lanthane peuvent être considérés comme des additifs permettant d'obtenir une lubrification satisfaisante et comparable au bisulfure de molybdène, tout en conférant un aspect plus flatteur aux pièces traitées.On examining the results collated in Table VII, it can be concluded that the cerium fluoride and the lanthanum fluoride can be considered as additives making it possible to obtain satisfactory lubrication and comparable to molybdenum disulphide, while imparting an appearance more flattering to the treated parts.
Claims (10)
- Process for lubricating the surface of metal parts, made of copper or of iron- or copper-based alloys, intended for cold or warm deforming operations, characterized by the fact that, after the conventional surface preparation, there is applied to the surface of said parts at least one lanthanide halide of the group consisting of lanthane fluoride and cerium fluoride.
- Process according to claim 1, characterized by the fact that the lanthanide halide is applied in the form of an aqueous or oily dispersion, or of a mixture with a wax or of a mixture with a pulverulent dry soap.
- Process according to one of claims 1 and 2, characterized by the fact that the application onto the surface of the parts to be worked of the lanthanide halide in the form of an aqueous dispersion, of an oily dispersion, of a mixture with a wax or of a mixture with a pulverulent dry soap is performed- by spraying by means of an air gun,- by cold or warm dipping,- manually by painter's brush coating, painting roller coating,- by rubbing a wax stick, or still- by rubbing with dry soap in the form of powder.
- Process according to one of claims 1 to 3, characterized by the fact that the aqueous dispersion by way of which lanthanide halide is implemented, comprises at least one surfactant having a wetting or dispersing action.
- Use for the lubrication of the surface of metal parts made of copper or of iron- or copper-based alloys, intended to be cold or warm deformed, of a lubricating agent essentially consisting of at least one of the lanthanide halides selected from the group consisting of lanthane fluoride and cerium fluoride.
- Aqueous dispersion comprising a surfactant having a wetting or dispersing action and from 0.05 to 5% by weight of at least one of the lanthanide halides of the group consisting of lanthane fluoride and cerium fluoride.
- Wax-based mixture comprising from 5 to 60% by weight of at least one of the lanthanide halides of the group consisting of lanthane fluoride and cerium fluoride.
- Concentrated product for the preparation of the aqueous dispersion according to claim 6, comprising a surfactant having a wetting or dispersing action, from 5 to 30% by weight of at least one of the lanthanide halides of the group consisting of lanthane fluoride and cerium fluoride, and possibly a pulverulent dry soap.
- Mixture on the basis of pulverulent dry soap comprising from 0.05 to 5% by weight of at least one of the lanthanide halides of the group consisting of lanthane fluoride and cerium fluoride.
- Use for the lubrication of the surface of metal parts made of copper or of iron- or copper-based alloys, intended to be cold or warm deformed, of an oily dispersion comprising from 0.1 to 15% by weight of at least one of the lanthanide halides of the group consisting of lanthane fluoride and cerium fluoride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88402758T ATE87968T1 (en) | 1987-11-06 | 1988-11-03 | METHOD OF LUBRICATION OF THE SURFACE OF METALLIC MATERIALS MADE OF COPPER OR IRON AND COPPER ALLOYS DURING COLD OR HOT FORMING AND MEANS TO PERFORM SUCH LUBRICATION. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8715437 | 1987-11-06 | ||
FR8715437A FR2622818B1 (en) | 1987-11-06 | 1987-11-06 | METHOD OF LUBRICATING THE SURFACE OF METAL PARTS, OF COPPER OR OF IRON OR COPPER-BASED ALLOYS, TO BE COLD-FORMED OR HOT-FORMED AND MEANS OF LUBRICATION IMPLEMENTED |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0315532A1 EP0315532A1 (en) | 1989-05-10 |
EP0315532B1 true EP0315532B1 (en) | 1993-04-07 |
Family
ID=9356581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88402758A Expired - Lifetime EP0315532B1 (en) | 1987-11-06 | 1988-11-03 | Process for lubricating the surface of metallic pieces made of copper and iron or copper alloys in cold or hot deforming operations, and means for using this lubrication |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0315532B1 (en) |
AT (1) | ATE87968T1 (en) |
CA (1) | CA1311462C (en) |
DE (1) | DE3880084T2 (en) |
ES (1) | ES2039673T3 (en) |
FR (1) | FR2622818B1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2035069A1 (en) * | 1990-02-07 | 1991-08-08 | Lawrence R. Cohen | Method of warm forming and extrusion of metal and metal working compositions useful therein |
FR2660930A1 (en) * | 1990-04-13 | 1991-10-18 | Ceramiques Composites | LUBRICANT FOR CERAMIC SURFACE AND LUBRICATION METHOD. |
GB9117622D0 (en) * | 1991-08-15 | 1991-10-02 | Exxon Chemical Patents Inc | Improved calcium carboxylate antiwear additives |
DE10330520A1 (en) * | 2003-03-01 | 2004-09-16 | Ks Aluminium Technologie Ag | Production of a cylinder crankcase with at least one cooling channels in an intermediate wall between adjacent cylinder recesses useful in the automobile industry for shortening vehicles |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4507214A (en) * | 1983-11-02 | 1985-03-26 | Union Oil Company Of California | Rare earth halide grease compositions |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB799192A (en) * | 1956-05-16 | 1958-08-06 | Shell Res Ltd | Improvements in or relating to metal working and cutting processes |
US3215630A (en) * | 1964-11-12 | 1965-11-02 | Cincinnati Milling Machine Co | Cutting composition |
US3830280A (en) * | 1971-01-25 | 1974-08-20 | Mallory & Co Inc P R | Rare earth flouride lubricant for die casting components |
-
1987
- 1987-11-06 FR FR8715437A patent/FR2622818B1/en not_active Expired - Fee Related
-
1988
- 1988-11-03 DE DE8888402758T patent/DE3880084T2/en not_active Expired - Fee Related
- 1988-11-03 CA CA000582166A patent/CA1311462C/en not_active Expired - Fee Related
- 1988-11-03 EP EP88402758A patent/EP0315532B1/en not_active Expired - Lifetime
- 1988-11-03 ES ES198888402758T patent/ES2039673T3/en not_active Expired - Lifetime
- 1988-11-03 AT AT88402758T patent/ATE87968T1/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4507214A (en) * | 1983-11-02 | 1985-03-26 | Union Oil Company Of California | Rare earth halide grease compositions |
Also Published As
Publication number | Publication date |
---|---|
EP0315532A1 (en) | 1989-05-10 |
FR2622818B1 (en) | 1990-03-16 |
CA1311462C (en) | 1992-12-15 |
ATE87968T1 (en) | 1993-04-15 |
DE3880084D1 (en) | 1993-05-13 |
ES2039673T3 (en) | 1993-10-01 |
FR2622818A1 (en) | 1989-05-12 |
DE3880084T2 (en) | 1993-07-22 |
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