EP0315532A1 - Verfahren zur Schmierung der Oberfläche metallischer Werkstoffe aus Kupfer oder Eisen- und Kupferlegierungen währendder Kalt- oder Warmumformung und Mittel, um diese Schmierung auszuführen - Google Patents

Verfahren zur Schmierung der Oberfläche metallischer Werkstoffe aus Kupfer oder Eisen- und Kupferlegierungen währendder Kalt- oder Warmumformung und Mittel, um diese Schmierung auszuführen Download PDF

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Publication number
EP0315532A1
EP0315532A1 EP88402758A EP88402758A EP0315532A1 EP 0315532 A1 EP0315532 A1 EP 0315532A1 EP 88402758 A EP88402758 A EP 88402758A EP 88402758 A EP88402758 A EP 88402758A EP 0315532 A1 EP0315532 A1 EP 0315532A1
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EP
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Prior art keywords
soap
copper
mixture
lanthanide halide
weight
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EP88402758A
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English (en)
French (fr)
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EP0315532B1 (de
Inventor
Joseph Schapira
Patrick Droniou
Patrick Hilaire
Jean-Louis Seratinsky
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Compagnie Francaise de Produits Industriels SA
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Compagnie Francaise de Produits Industriels SA
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Priority to AT88402758T priority Critical patent/ATE87968T1/de
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    • C10N2010/00—Metal present as such or in compounds
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • 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
    • C10N2040/241—Manufacturing joint-less pipes
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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.
  • a lubricating layer which can be constituted * 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.
  • Molybdenum disulphide and graphite are satisfactory from the point of view of lowering the coefficient of friction but have a 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 lanthanide halide is applied to the surface of said parts, preferably in the form of an aqueous or oily dispersion or of a mixture with a wax or a dry powdered soap .
  • the lubricating agent according to the invention intended for the lubrication of the surface of metallic pieces of copper or of iron-based or copper-based alloys, which must be deformed cold or hot, is characterized in that it consists essentially of at least one lanthanide halide.
  • the above lubricating agent is preferably used in the form of an aqueous or oily dispersion or in the form of a mixture with a wax or a dry powdered soap.
  • the lanthanide halides coming into consideration in the context of the invention are preferably fluorides, chlorides and iodides, fluorides being very particularly preferred; the preferred lanthanides are yttrium, lanthanum, cerium and neodymium, and more particularly lanthanum and cerium; the lanthanides of the group comprising samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and thorium can also be used.
  • 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.
  • the aqueous dispersions of lanthanide halides generally comprise surfactants with wetting or dispersing action, which can be chosen from - the anionic derivatives and in particular on the one hand of the salts formed between an alkaline 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 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, alkylaryl sulfonates, - non-ionic derivatives and in particular polyethylene glycol esters, oxyethylenated and oxypropylenated derivatives of high molecular weight alcohols, amides, substituted amides,
  • 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 application of the lubricating agent and of the dispersions and mixtures for its implementation in accordance with the invention on the surface of the parts to be deformed can be carried out - 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.
  • the lubricating agent according to the invention When the lubricating agent according to the invention 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% in 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 the lanthanide halide or halides, the other constituents of the dispersions in concentrated form.
  • These concentrated products may have a content of at least one lanthanide halide 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 lubricants according to the invention can be introduced into the application medium simultaneously with a conventional lubricant, and advantageously, a set of products can be made available to the user, separately from each other.
  • 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 in this case, - in the case of carrying out the process by mixing with a dry powder soap, a fourth product consisting of this dry powder soap, the first and the second, the third or the fourth product, as the case may be, which can be marketed in the form of "kits".
  • a comparative test is carried out using successively, in the so-called ring test, oil dispersions of cerium fluoride, graphite and molybdenum disulphide.
  • the graphites and molybdenum disulphides used are of the quality commonly used for this type of application, namely - a powdered graphite having a particle size such that 50% of the grains have a size less than 8 ⁇ m and 100% a size less than 32 ⁇ m, the BET specific surface being 16 m2 / g, this graphite can be that of quality T10 from 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 ⁇ m, for example that of quality No. 4 from the company KS PAUL.
  • 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 pieces 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 of that marketed under the trademark 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.
  • a phosphating bath of the type of that marketed under the trademark 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
  • the pieces are phosphated beforehand using a THERMOGRANODINE 701® bath, then they are lubricated: - 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 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.
  • an anionic soap for example PROLUB TS 438 at 5% by weight in water (for 5 minutes at 80 ° C) then using MoS2 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.
  • 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 a satisfactory lubrication and comparable to molybdenum disulphide, while imparting an appearance more flattering to the treated parts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Chemically Coating (AREA)
  • Mounting, Exchange, And Manufacturing Of Dies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP88402758A 1987-11-06 1988-11-03 Verfahren zur Schmierung der Oberfläche metallischer Werkstoffe aus Kupfer oder Eisen- und Kupferlegierungen währendder Kalt- oder Warmumformung und Mittel, um diese Schmierung auszuführen Expired - Lifetime EP0315532B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88402758T ATE87968T1 (de) 1987-11-06 1988-11-03 Verfahren zur schmierung der oberflaeche metallischer werkstoffe aus kupfer oder eisenund kupferlegierungen waehrendder kalt- oder warmumformung und mittel, um diese schmierung auszufuehren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8715437 1987-11-06
FR8715437A FR2622818B1 (fr) 1987-11-06 1987-11-06 Procede de lubrification de la surface de pieces metalliques,en cuivre ou en alliages a base de fer ou de cuivre,devant etre deformees a froid ou a chaud et moyens de lubrification mis en oeuvre

Publications (2)

Publication Number Publication Date
EP0315532A1 true EP0315532A1 (de) 1989-05-10
EP0315532B1 EP0315532B1 (de) 1993-04-07

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Country Status (6)

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EP (1) EP0315532B1 (de)
AT (1) ATE87968T1 (de)
CA (1) CA1311462C (de)
DE (1) DE3880084T2 (de)
ES (1) ES2039673T3 (de)
FR (1) FR2622818B1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442661A1 (de) * 1990-02-07 1991-08-21 Witco Corporation Verfahren zur warmen Umformung von Metallen und Metallbearbeitungszusammensetzungen dafür
EP0452189A1 (de) * 1990-04-13 1991-10-16 Rhone-Poulenc Chimie Schmiermittel für keramische Oberfläche und Verfahren zur Schmierung
WO1993004150A1 (en) * 1991-08-15 1993-03-04 Exxon Chemical Patents Inc. Improved calcium carboxylate antiwear additives

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10330520A1 (de) * 2003-03-01 2004-09-16 Ks Aluminium Technologie Ag Zylinderkurbelgehäuse mit vergossenem Kühlkanal

Citations (3)

* Cited by examiner, † Cited by third party
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442661A1 (de) * 1990-02-07 1991-08-21 Witco Corporation Verfahren zur warmen Umformung von Metallen und Metallbearbeitungszusammensetzungen dafür
EP0452189A1 (de) * 1990-04-13 1991-10-16 Rhone-Poulenc Chimie Schmiermittel für keramische Oberfläche und Verfahren zur Schmierung
FR2660930A1 (fr) * 1990-04-13 1991-10-18 Ceramiques Composites Lubrifiant pour surface en ceramique et procede de lubrification.
JPH04227688A (ja) * 1990-04-13 1992-08-17 Rhone Poulenc Chim セラミック表面用の乾性潤滑剤及び潤滑方法
WO1993004150A1 (en) * 1991-08-15 1993-03-04 Exxon Chemical Patents Inc. Improved calcium carboxylate antiwear additives

Also Published As

Publication number Publication date
CA1311462C (en) 1992-12-15
FR2622818A1 (fr) 1989-05-12
ATE87968T1 (de) 1993-04-15
ES2039673T3 (es) 1993-10-01
FR2622818B1 (fr) 1990-03-16
DE3880084D1 (de) 1993-05-13
DE3880084T2 (de) 1993-07-22
EP0315532B1 (de) 1993-04-07

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