EP0442661A1 - Verfahren zur warmen Umformung von Metallen und Metallbearbeitungszusammensetzungen dafür - Google Patents

Verfahren zur warmen Umformung von Metallen und Metallbearbeitungszusammensetzungen dafür Download PDF

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Publication number
EP0442661A1
EP0442661A1 EP91300991A EP91300991A EP0442661A1 EP 0442661 A1 EP0442661 A1 EP 0442661A1 EP 91300991 A EP91300991 A EP 91300991A EP 91300991 A EP91300991 A EP 91300991A EP 0442661 A1 EP0442661 A1 EP 0442661A1
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Prior art keywords
composition
lubricant
metal
rare earth
weight percent
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EP91300991A
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English (en)
French (fr)
Inventor
Lawrence B. Cohen
Edward J. Gudowicz
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Witco Corp
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Witco Corp
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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/404Fatty vegetable or animal oils obtained from genetically modified species
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/404Fatty vegetable or animal oils obtained from genetically modified species
    • C10M2207/4045Fatty vegetable or animal oils obtained from genetically modified species used as base material
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/12Polysaccharides, e.g. cellulose, biopolymers
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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    • C10N2040/20Metal working
    • C10N2040/241Manufacturing joint-less pipes
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    • C10N2040/20Metal working
    • C10N2040/242Hot working
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/243Cold working
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    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/245Soft metals, e.g. aluminum
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/246Iron or steel
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/247Stainless steel
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    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01Emulsions, colloids, or micelles

Definitions

  • the present invention generally relates to the warm forming and extrusion of metals and to improvements in compositions that can advantageously be used in these metal working operations. More particularly, this invention is directed to the warm forming and extrusion of metals at temperatures above about 600°C (1,100°F). In this regard, an important aspect of the present invention is directed to the use of rare earth metal halides, such as cerium or lanthanum trifluoride, in compositions used in the warm forming and extrusion of steel.
  • rare earth metal halides such as cerium or lanthanum trifluoride
  • Warm forming and extrusion of metal are processes generally involving applying a metal working, lubricant composition to the surface of the metal prior to the deformation thereof.
  • these compositions need to meet a variety of requirements. For example, in addition to lubrication performance, they must provide protection of the metal surface from abrasion and like damage. Furthermore, they should be relatively easy to apply and remove as well as compatible with subsequently applied coating materials.
  • metal working lubricant compositions are homogeneous blends formulated for a specific application where certain properties are favored over others but which necessarily are a compromise between conflicting requirements.
  • Heterogeneous metal working lubricants such as for example dispersions of lubricant substances in water or other volatile medium are also known. Such heterogeneous lubricants are intended, upon application to a metal workpiece and evaporation of the volatile medium, to leave a continuous homogeneous lubricant film on the metal workpiece.
  • compositions useful in the warm forming of metal generally employ a range of oils, waxes, soaps and occasionally polymeric materials, each of which has advantages for specific applications.
  • U.S. Patent No. 4,687,587 to Daglish et al. discloses a lubricant for metal forming comprising discrete particles of a waxy material having a softening point above the metal-forming temperatures in a solid or viscous monomeric organic carrier.
  • U.S. Patent No. 3,873,458 to Parkinson discloses a process for cold forming or shaping metal having a resin-oil coating prepared from a dispersion of a copolymer of ethylene and acrylic acid in a lubricant oil.
  • U.S. Patent No. 3,167,511 to Crawford et al. discloses the use of chlorinated polypropylene in a lubricating oil as a lubricant for broaching, cutting and rolling metal.
  • These and other lubricants known in the art fail to provide the needed lubrication and surface protection to a metal workplace during the forming or extrusion thereof at temperatures above about 1,100°F (about 600°C).
  • a precoating is often applied to the metal before the application of the lubricant.
  • This precoating can contain, for example, lime, zinc phosphate and/or soaps.
  • the use of such a precoating procedure also fails to permit the warm forming and extrusion of metal at the high temperatures desired for the forming and extrusion of numerous metal parts, particularly those made from hard metals.
  • rare earth trifluorides such as lanthanum trifluoride and cerium trifluoride are useful as solid lubricants. See Rare Earth Fluorides and Oxides--An Exploratory Study of Their Use as Solid Lubricants at Temperatures to 1,800°F (about 1,000°C) NASA TND-5301, 1969).
  • U.S. Patent No. 4,507,214 to Aldorf discloses the use of rare earth metal halides in a lubricating grease to form a lubricating composition to lubricate wheel bearings.
  • U.S. Patent No. 4,715,972 to Pacholke likewise describes the use of cerium fluoride as one of several solid lubricant particle additives for gear oil.
  • U.S. Patent No. 3,830,280 to Larsen discloses the use of rare earth halide such as cerium trifluoride or lanthanum trifluoride as lubricants for die casting components. None of these prior art disclosures, however, contains any suggestion of a liquid metal working lubricant composition which is suitable for the warm forming and extrusion of metals at high temperatures, e.g. temperatures above about 600°C (1,1000°F).
  • An object of this invention is to provide an improved composition and method useful for lubrication in the warm forming and extrusion of metals especially at high temperatures.
  • An embodiment of the present invention provides a metal working lubricant composition which is stable and does not decompose at elevated temperatures above about 600°C (1,100°F).
  • the invention may be embodied in a metal working composition which exhibits improved lubricating characteristics during metal forming and extrusion at high temperatures but also protects the surface of the metal workpiece from corrosion and abrasion, continues to provide lubrication after the cooling of the metal, but is readily removable from the metal workpiece after the latter has been removed from the form.
  • the present invention is directed to improvements in methods for warm forming and extrusion of metals, and to compositions useful therein. These improvements permit the performance of those metal working operations at temperatures of up to about 1000°C (1,800°F) and higher.
  • compositions thereof which are especially useful in warm forming and extruding metal involve the use of a rare earth metal halide in such compositions.
  • These compositions are liquids having a viscosity less than about 1,500 S.U.S. at about 38°C (100°F) and include a liquid base, viscosity enhancer increasing the viscosity of the composition to between about 150 and about 1,500 S.U.S. at 100°F (about 38°C); a lubricant effective at elevated temperatures of at least about 400°F (about 200°C), and a rare earth metal halide.
  • Optional components include graphite and/or molybdenum disulfide.
  • liquid lubricant is generally applied to the metal by flooding, dipping, brushing or spraying on the part, preferably on a continuous process with the overflow being collected and returned to a central reservoir for recirculation. Consequently it is required that the lubricant composition be a liquid. In order that it be able to provide the necessary lubrication it should have a viscosity at 100°F (about 38°C) of between about 150 and about 1,500 S.U.S. Liquid compositions of this viscosity can be pumped and at the same time furnish the needed lubricity. Following application of the liquid lubricant deformation of takes place followed by removal of the lubricant from the formed product. Often the metal workpiece has a precoating which can contain lime, zinc phosphate and/or soaps.
  • the incorporation of rare earth metal halides into the lubricant composition increases the temperature at which metal forming can be effected to about 1,800°F (about 1000°C) and higher. This is a significant increase from prior methods which have an upper limit of effective performance of about 1,100°F (about 600°C).
  • the present process can be performed at temperatures between about 300°F (about 150°C) and 1,800°F (about 1000°C).
  • the process is performed at temperatures between about 900°F (about 480°C) and 1,500°F (about 820°C).
  • liquid lubricant is applied so that a lubricant film is present between the extruded billet and the die.
  • the viscosity of this liquid composition should be between about 150 and about 1,500 S.U.S. at 100° F (about 38°C).
  • a rare earth metal halide in the lubricant composition raises the temperature at which extrusions can be effected in an efficient manner to about 1,800°F (about 1000°C) and higher. Prior compositions do not afford the necessary lubrication and metal protection properties at these high temperatures.
  • temperatures of up to about 1,800°F (about 1000°C) and higher they are particularly valuable in applications using the ferrous metals e.g. steel as well as other metals such as, for example, copper, bronze, brass and aluminum. These methods can be performed at temperatures between about 300°F (about 150°C) and 1,800°F (about 1000°C). For the forming and extrusion of many objects, however, temperatures between about 900°F (about 480°C) and 1,500°F (about 820°C) are generally employed.
  • compositions can be used to perform the present methods.
  • a particularly useful oil-based composition comprises the following components:
  • lubricant composition of this invention Among optional components of the lubricant composition of this invention are graphite and molybdenum disulfide.
  • the amount of the liquid base component in the composition will vary with the specific method being performed and the metal being warm formed or extruded. In general this component constitutes from about 40 to about 90 weight percent of the composition.
  • the base be a fat, e.g. a triglyceride. Since triglycerides are made by esterifying the three hydroxy groups of glycerin with fatty acids, often the triglycerides will contain unreacted fatty acids. Fatty acids are in general straight-chain compounds, containing from about 8 to about 18 carbon atoms. A particularly useful triglyceride, prime burning lard oil, is about 99.5 weight percent triglycerides or related compounds and less than 0.5 weight percent fatty acids. Another useful base is soybean oil having lubricating viscosities from 50 S.U.S. to about 1,000 S.U.S. at 100°F (about 38°C). Also useful are oleic acid, sulfurized lard oil, marine oil triglyceride, rape seed oil, tall oil and paraffin oil.
  • the viscosity enhancer Since the purpose of the viscosity enhancer is to have a liquid composition with a viscosity of from about 150 to about 1,000 S.U.S. at 100°F (about 38°C), a variety of materials that will increase viscosity of a liquid can be used.
  • a particularly useful viscosity enhancer is asphaltic material.
  • the viscosity enhancer In addition to increasing the viscosity of the liquid base, it also improves the adhesion of the composition and imparts lubricity. In general the viscosity enhancer should be present in an amount of from about 2 to about 25 weight percent of the composition.
  • Other viscosity enhancers that can be used in the present composition are polybutene, aluminum stearate and degras.
  • lubricants can be used as the low temperature lubricant composition of the present composition so long as they provide efficient lubrication at a temperature of at least about 400°F (about 200°C) and preferably from about 400°F (about 200°C) to about 1,100°F (about 600°C).
  • a particular class of lubricants of value in the present compositions are sulfur-containing compounds. These lubricants are well known in the art and provide good lubrication properties at temperatures up to about 1,100°F (about 600°C). Sulfurized mineral oil and sulfurized fatty oil are useful for this component. Examples of other such materials are sulfurized fat, mineralized sulfur, sulfurized hydrocarbons, sulfurized caster oil, sulfurized and chlorinated oil, and the like.
  • the sulfurized compound can be present in an amount of from about 5 to about 50 weight percent of the lubricant composition; however, for most purposes this amount will be between about 10 and about 20 weight percent.
  • the metal working lubricant composition includes a rare earth metal halide, preferably fluoride. While other halides such as the chloride are known, available and useful, the fluorides are more preferred. In particular the race earth trifluorides such as lanthanum trifluoride and cerium trifluoride are preferred. Normally these rare earth metal halides are present in amounts of up to from about 2 to about 30 weight percent or higher of the composition with an amount of from about 5 to 10 percent being generally desired. The particle size of the rare earth metal fluoride should be relatively fine.
  • solid lubricants can also be included in the present composition as optional components.
  • These solid lubricants which include molybdenum disulfide and graphite can each be present in amounts up to about 10 weight percent of the composition. Their presence can improve the overall lubricity of the composition.
  • lubricants that can be included in the present compositions include mica, calcium carbonate and zinc stearate.
  • the molybdenum disulfide, other optional solid lubricants and the rare earth metal halide can be incorporated as finely divided powders having a particle size for example, from about 0.01 microns ( ⁇ m) to about 100 microns ( ⁇ m), preferably from about 0.1 to about 45 microns ( ⁇ m). This invention, however, is not limited to any specific particle size component.
  • composition of this invention can be prepared by standard procedures known to the art. In general they can be prepared by mixing the ingredients at a slightly elevated temperature. In order to make a uniform mixture, the rare earth metal trifluoride should be added slowly with mixing. Sufficient mixing, about an hour, should be performed so as to obtain a uniform composition. As an alternative procedure, the composition of the present invention can be prepared by milling its components.
  • compositions which can be lower in cost and toxicity.
  • Such compositions are composed of the same components as the oil-based compositions; i.e. liquid base, viscosity enhancer, lower temperature lubricant effective at temperatures of at least about 400° F (about 200°C) and rare earth metal halide.
  • the aqueous compositions utilize a viscosity enhancer.
  • this can be any material that increases the viscosity of the composition to between about 150 and 1,500 S.U.S. at 100°F (about 38°C) and is water compatible.
  • Useful materials include cellulose compounds such as sodium carboxymethyl cellulose, glycols, such as diethylene glycol, propylene glycol and butylene glycol, and certain specialized waxes, such as Carbowax 3350.
  • wetting agents and dispersants Since it is more difficult to obtain a uniform mixture in water than in oil, usually there should also be present in the composition wetting agents and dispersants. As is general with water-based compositions containing solid components, the wetting agents and dispersants assist in retaining particles in dispersion so that the composition will be uniform. Numerous dispersants and wetting agents are known in the art.
  • Optional components in an aqueous composition of the present invention include defoamers,anti-microbial agents and corrosion inhibitors. These components can perform useful functions in the present compositions.
  • a glycol such as diethylene glycol, propylene glycol or butylene glycol may be used in the composition as the viscosity enhancer.
  • the heretofore described lubricant compositions provide excellent lubrication in the warm forming and extrusion of metals at temperatures in excess of 1,100°F (about 600°C).
  • the composition is stable at temperatures higher than 1,100°F (about 600°C) and is stable at 1,800°F (about 1000°C) or higher.
  • the composition protects the metal from corrosion and abrasion and can be easily applied and removed by conventional means.
  • the present composition is applied to the metal by conventional methods such as dipping, flooding, brushing or spraying.
  • the viscosity of the composition be between about 500 and 1,000 S.U.S. at 100°F (about 38°C).
  • the metals for which the present composition may be used are steel, copper, bronze, brass, aluminum and the like.
  • Other metals may also be used in the present method for warm forming which comprises applying deformation pressure to metal which has been coated with the present composition. This method is especially applicable to metals being formed at temperatures up to and in excess of 1,100°F (about 600°C) and up to about 1,800°F (about 1000°C) and higher.
  • composition of the present invention can be used in the extrusion of metals.
  • metal including those previously described as being applicable for metal forming are coated with the present composition and extruded at temperatures up to about 1,800°F (about 1000°C) and higher.
  • the composition of the present invention provides excellent lubrication and protection of the metal from corrosion and abrasion.
  • EXTRUDOIL 519HT a commercially available metal working lubricant
  • EXTRUDOIL 519HT-MOS molybdenum disulfide
  • EXTRUDOIL 519HT-MOS molybdenum disulfide
  • cerium trifluoride a metal working composition chemically identical to the EXTRUDOIL 519HT-MOS which also included cerium trifluoride.
  • EXTRUDOIL 519HT a commercially available metal working lubricant
  • EXTRUDOIL 519HT-MOS a chemically identical commercial metal working lubricant which also includes molybdenum disulfide
  • EXTRUDOIL 519HT-MOS a metal working composition chemically identical to the EXTRUDOIL 519HT-MOS which also included cerium trifluoride.
  • EXTRUDOIL 519HT and EXTRUDOIL 519HT-MOS are available from Witco Corporation, Allied-Kelite Division.
  • the EXTRUDOIL 519HT product is composed of #1 Lard Oil (a prime burning lard containing 99.5 weight percent glyceride derivatives and less than 0.5 weight percent free fatty acids), an asphaltic viscosity enhancer, and a lubricant constituent made up of a sulfurized fatty oil and a sulfur-containing mineral oil.
  • the EXTRUDOIL 519HT-MOS contains the same ingredients as EXTRUDOIL 519HT in the same relative amounts and, in addition includes 10 percent, by weight, of a molybdenum disulfide dispersion.
  • the metal working lubricant product embodying the present invention contained the same ingredients as the EXTRUDOIL 519HT in the same relative amounts and, in addition, included 5 percent, by weight, each of a molybdenum disulfide dispersion and cerium trifluoride.
  • the EXTRUDOIL 519HT metal working lubricant which did not contain molybdenum disulfide or a rare earth metal halide worked well within the temperature range of 800-900°F (about 430-480°C). Increasing the temperature beyond 900°F (about 480°C) decomposed the composition and at these higher temperatures there was insufficient lubrication to form the lobe.
  • the EXTRUDOIL 519HT-MOS metal working lubricant containing molybdenum disulfide but not containing a rare earth halide permitted formation of the lobe at temperatures between about 1,000°F (about 540°C) and 1,100°F (about 600°C). Increasing the temperature beyond 1,100°F (about 600°C) decomposed the composition and mused insufficient lubrication to form the lobe.
  • the metal working lubricant which contained cerium trifluoride permitted formation of the lobes at temperatures of 1,500°F (about 820°C) and above without any observable breakdown of the metal working lubricant.
  • compositions can be used effectively at temperatures not readily lubricated by prior petroleum-based compositions. This permits the ready formation of warm molded and extruded parts efficiently at temperatures of about 1,500°F (about 820°C) and higher.
  • Examples 2-9 describe oil based compositions
  • Examples 10-13 describe aqueous compositions of the present invention
  • Examples 14 and 15 describe concentrates which are readily dispersible in water.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
  • Forging (AREA)
EP91300991A 1990-02-07 1991-02-06 Verfahren zur warmen Umformung von Metallen und Metallbearbeitungszusammensetzungen dafür Ceased EP0442661A1 (de)

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EP (1) EP0442661A1 (de)
JP (1) JPH04213392A (de)
CA (1) CA2035069A1 (de)

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Publication number Priority date Publication date Assignee Title
CN1034670C (zh) * 1994-01-06 1997-04-23 王学绍 一种制备节能润滑油的方法
DE102008016348A1 (de) * 2008-03-29 2009-10-15 Stefan Graichen Hochtemperaturschmiermittel, insbesondere Gesenkschmiermittel, enthaltend mindestens einen Oxidationskatalysator
CN106118820A (zh) * 2016-06-23 2016-11-16 巢湖鹏远金属焊管有限公司 一种钢热挤压用润滑剂

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DE2647375A1 (de) * 1976-10-20 1978-04-27 Dow Corning Gmbh Schmierstoffkonzentrat auf wasserbasis
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DE2647375A1 (de) * 1976-10-20 1978-04-27 Dow Corning Gmbh Schmierstoffkonzentrat auf wasserbasis
US4507214A (en) * 1983-11-02 1985-03-26 Union Oil Company Of California Rare earth halide grease compositions
EP0315532A1 (de) * 1987-11-06 1989-05-10 Compagnie Francaise De Produits Industriels Verfahren zur Schmierung der Oberfläche metallischer Werkstoffe aus Kupfer oder Eisen- und Kupferlegierungen währendder Kalt- oder Warmumformung und Mittel, um diese Schmierung auszuführen

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1034670C (zh) * 1994-01-06 1997-04-23 王学绍 一种制备节能润滑油的方法
DE102008016348A1 (de) * 2008-03-29 2009-10-15 Stefan Graichen Hochtemperaturschmiermittel, insbesondere Gesenkschmiermittel, enthaltend mindestens einen Oxidationskatalysator
DE102008016348B4 (de) * 2008-03-29 2010-07-29 Stefan Graichen Hochtemperaturschmiermittel und dessen Verwendung in einem Verfahren zum Warmumformen von Metallen
CN106118820A (zh) * 2016-06-23 2016-11-16 巢湖鹏远金属焊管有限公司 一种钢热挤压用润滑剂

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CA2035069A1 (en) 1991-08-08

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