EP0024062B1 - Reaktionsschmiermittel und Verfahren zur Vorbereitung von Metallen für die Kaltverformung - Google Patents

Reaktionsschmiermittel und Verfahren zur Vorbereitung von Metallen für die Kaltverformung Download PDF

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Publication number
EP0024062B1
EP0024062B1 EP80200737A EP80200737A EP0024062B1 EP 0024062 B1 EP0024062 B1 EP 0024062B1 EP 80200737 A EP80200737 A EP 80200737A EP 80200737 A EP80200737 A EP 80200737A EP 0024062 B1 EP0024062 B1 EP 0024062B1
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EP
European Patent Office
Prior art keywords
carbon atoms
weight
lubricant
reactive lubricant
reactive
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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
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EP80200737A
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German (de)
English (en)
French (fr)
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EP0024062A1 (de
Inventor
Kenneth J. Hacias
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GEA Group AG
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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Application filed by Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Priority to AT80200737T priority Critical patent/ATE5325T1/de
Publication of EP0024062A1 publication Critical patent/EP0024062A1/de
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Publication of EP0024062B1 publication Critical patent/EP0024062B1/de
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C23C22/03Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02Water
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085Phosphorus oxides, acids or salts
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/281Esters of (cyclo)aliphatic monocarboxylic acids
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/282Esters of (cyclo)aliphatic oolycarboxylic acids
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/283Esters of polyhydroxy compounds
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/286Esters of polymerised unsaturated acids
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/22Heterocyclic nitrogen compounds
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/221Six-membered rings containing nitrogen and carbon only
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/225Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226Morpholines
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    • C10M2215/26Amines
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    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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    • C10M2217/06Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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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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    • C10N2040/241Manufacturing joint-less pipes
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    • C10N2040/20Metal working
    • C10N2040/242Hot working
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    • C10N2040/243Cold working
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    • C10N2050/01Emulsions, colloids, or micelles
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Definitions

  • the invention relates to an aqueous acidic reaction lubricant for the treatment of metal surfaces prior to cold working with a content of phosphate ion emulsifier and emulsifiable organic lubricant component as well as a method for preparing metals for cold working using this reaction lubricant.
  • agents are usually used which contain the acidic phosphating agent in a aqueous phase and, in it, or emulsify or disperse the organic phosphating agent.
  • U.S. Patent 3,525,651 a phosphating solution based on zinc phosphate, in which a solid mixture of fatty acid and water-soluble surfactant is dispersed, is used for a one-step process.
  • such agents have the disadvantage that their stability is very limited, so that there is a risk that they will separate and thus become unusable or lead to non-uniform coatings.
  • the agents also require careful monitoring and supplementation of the layer-forming components of the phosphating solution.
  • the coating formed is amorphous, thin and partly greasy, so that when pressure is applied, only a light, oily film is formed which is available as a lubricant.
  • the agents described in GB-A 1 421 386 for forming lubricating coatings contain, in addition to phosphate and layer-forming cations, such as in particular zinc ions, and long-chain fatty acids, a cationic emulsifier and fatty acid ester.
  • phosphate and layer-forming cations such as in particular zinc ions, and long-chain fatty acids, a cationic emulsifier and fatty acid ester.
  • the metal surfaces treated with this show signs of rust after a comparatively short period of time, which are associated with an increase in the drawing resistance during the deformation and excessive wear of the drawing tools.
  • Reactive phosphoric acid-based lubricants with long-chain amine or amide contents are also known which contain only a small proportion of water and considerable amounts of organic lubricants (British Patent 891,150 and German Auslegeschrift 1210296).
  • the agents because of their free phosphoric acid content, the agents often form only an insufficient phosphate layer and are unsatisfactory in terms of the requirements for some deformation treatments.
  • reaction lubricants of the aforementioned type Another problem with the use of reaction lubricants of the aforementioned type is the formation of rust on the metal surface during the drying process.
  • the presence of water vapor and the comparatively high content of free acid in the emulsion cause such rusting, particularly in areas which are difficult to access for the dry air.
  • Such a situation occurs in particular in the case of packed metal objects, for example wire coils, at the points where there is mutual contact and consequently the dry air has no access.
  • the presence of rust not only affects the appearance of the surface of the finished product, but also significantly increases the drag during the deformation process, the wear of the drawing tool and can lead to scoring.
  • the object of the present invention is to avoid the known disadvantages, in particular those mentioned above, and to provide an aqueous acidic reaction lubricant which is versatile in use, produces effective lubricant coatings on metal surfaces, is stable over a wide range of applications and is practically not susceptible to rust formation during drying leads.
  • Another object of the invention is to provide a method for preparing metals for cold working using this reaction lubricant which is simple to carry out.
  • the oxazoline wax is responsible for a considerable improvement in the thermal stability of the reaction lubricant, in particular at temperatures above 71 ° C., at which demulsification - which can be recognized by a floating oil layer - can easily occur.
  • the formula has a particularly suitable oxazoline wax
  • R i , R 2 and R 3 are the same or different and represent hydrocarbon radicals with 1 to 36 carbon atoms, which can also have alcohol, carboxyl and / or ester groups; However, R 2 can also be hydrogen.
  • Oxazoline waxes constructed in this way are e.g. B. available under the trade name Wax TS 254, Wax TS 254 A, Wax TS 254 AA, Wax TS 970, Alkaterge E and Alkaterge T from IMC Chemical Group, Inc., Hillsdale, IlIinois (NP Division).
  • the reaction lubricant to be used for the metal treatment can be prepared as a concentrate-like composition which lies in the upper concentration range claimed, so that a simple dilution with water can be carried out to prepare and supplement the working treatment emulsion.
  • the pH of the reaction lubricants is to be adjusted in such a way that on the one hand there is no excessive pickling attack on the metal surface, but on the other hand an adequate reaction necessary to form the phosphate layer takes place with it.
  • Preferred reaction lubricants are those which contain the components a) in an amount of 0.2 to 6% by weight, b) in an amount of 0.3 to 16% by weight, c) in an amount of 0.1 to 10% by weight and d) in an amount of 0.1 to 5% by weight, in particular components a) in an amount of 1.5 to 6% by weight, b) in an amount of 2 to 6 % By weight, component c) in an amount of 0.5 to 4% by weight and d) in an amount of 0.5 to 1.5% by weight or component a) in an amount of 1.5 to 3% by weight, b) in an amount of 2 to 6% by weight, c) in an amount of 0.5 to 4% by weight and d) in an amount of 0.5 to Contain 1.5% by weight.
  • a particularly advantageous lubricant layer is obtained if the lubricant component b) consists of up to 50% by weight of N-alkyl-1,3-diaminopropanedioleate.
  • the number of carbon atoms in the alkyl radical corresponds to the number of carbon atoms in tallow fatty acid.
  • Tallow fatty acid is a mixture of different defined fatty acids, so that the length of the alkyl chains - depending on the proportion of the individual fatty acids in the tallow - also varies in the lubricant component b).
  • this additive also has the ability to act as a boundary layer lubricant.
  • This lubricant also has a good emulsifying effect and, because of its cation activity, leads to a stable emulsion.
  • a further advantageous embodiment of the invention is provided by a reaction lubricant which additionally contains heavy metal ions, preferably iron or zinc ions.
  • heavy metal ions preferably iron or zinc ions.
  • Such additives activate the reaction lubricant by accelerating the formation of the phosphate layer.
  • the amount must be below the limit at which the emulsion begins to become unstable.
  • the content of iron or zinc ions is preferably 0.1 to 0.2% by weight.
  • iron is made available as an activating cation by the pickling attack, so that, in spite of being discharged with the treated metal surfaces, an addition can be omitted or reduced if necessary.
  • a further preferred composition of the reaction lubricant is given when the carboxylic acid and / or the alcohol of the organic lubricant component b) has 8 to 24 carbon atoms.
  • Salts of alkanolamine, preferably of triethanolamine, are used as inhibitors. Salts of triethanolamine with octanoic acid or with stearic acid are preferably used.
  • An inhibitor of the aforementioned type is in the form of a solution containing 40% by weight of a salt of Triethanolamine with octanoic acid available under the trade name Synkad 303, in particular Synkad 303 HT from Keil Chemical Division of Ferro Corporation, Indiana, USA.
  • the solution has a density of 1.07 g / cm 3 (at 25 ° C) and contains about 30% volatile components.
  • the corrosion-inhibiting effect of the amine / carboxylic acid salts according to feature d) is surprising insofar as other oil-soluble corrosion inhibitors in the reaction lubricant of the type claimed are not effective until the time at which the water content of the emulsion has not yet evaporated. That is, rusting occurs as long as the applied film still contains water. Corrosion inhibitors, such as amides or imidazoline, are likewise ineffective or unsuitable, probably because of the low pH of the reaction lubricant, in that they make the emulsion unstable and inhibit the formation of the phosphate layer. In contrast to this, the corrosion inhibitors to be used in the reaction lubricant according to the invention even have a stabilizing effect.
  • the pH of the reaction lubricant is preferably adjusted to a value in the range from 2.4 to 3.4, in particular 2.8 to 3.1. This can be done in particular with phosphoric acid.
  • the reaction lubricant according to the invention can be applied at temperatures which are in the range of ambient temperature and 93 ° C. However, the temperature range from 49 to 71 ° C. is preferred. Elevated temperatures are advantageous in that the activity of the reaction lubricant is increased and the formation of the phosphate coating is accelerated.
  • the application of the reaction lubricant can, as usual, e.g. B. by diving, spraying or flooding.
  • the immersion method is preferred because of the particularly intimate contact between the metal surface and the reaction lubricant. In order to maintain the homogeneity of the bath, simultaneous stirring is recommended.
  • the duration of the treatment depends on the composition and the concentration of the reaction lubricant, but also on its temperature and in particular the desired layer thickness.
  • the desired layer thickness depends on the degree of deformation.
  • the exposure time is preferably set to 1 to 20 minutes.
  • the coating formed in this way has a phosphate layer with embedded and / or deposited lubricant particles.
  • the coated metal parts are then dried. Temperatures in the range from ambient temperature to 177 ° C are suitable for this. However, the preferred drying temperatures are between 121 and 177 ° C.
  • the lubricant particles When drying at an elevated temperature, the lubricant particles flow together to form a film (coalesce). However, such film formation is not necessary to obtain satisfactory layers. Lubricant particles distributed in or on the phosphate layer also ensure satisfactory lubrication during the subsequent cold working.
  • the above-mentioned concentrate was diluted 1: 3 by volume with water and the treatment bath obtained was brought to a temperature of 77 ° C.
  • the treatment bath according to Example 1 was changed so that 0.5 g of triethanolamine octanate was added as a corrosion inhibitor per liter.
  • the triethanolamine octanate was prepared by neutralizing 0.25 g of triethanolamine and 0.25 g of octanoic acid.
  • Example 2 A second group of sheets was treated as in Example 1 with the reaction lubricant so produced. After drying, no rust or rusting of a maximum of 2% was observed.
  • reaction lubricant was prepared from the concentrate of Example 1 by mixing 227.1 l of concentrate with 1 287 l of water and heating to 71.degree.
  • a tube bundle with 250 steel tubes with a diameter of 12.7 mm, a wall thickness of 0.48 mm and a length of 3,658 mm was pickled in 10% by weight sulfuric acid by immersion treatment for 10 minutes and then twice each 1 Minute rinsed with cold water.
  • the tubes cleaned in this way were immersed twice as a bundle in the reaction lubricant for 2 minutes each and placed in a tube dryer, where they were dried at a temperature of 163 ° C. for 2 hours.
  • Example 3 The treatment bath according to Example 3 was modified such that 37.8 l of 70% triethanolamine octanate (trade name Synkad 303) were added as a corrosion inhibitor. The tube bundles were then treated as set out in Example 3.
  • reaction lubricant was heated to 71 ° C. and left at this temperature for 8 days without stirring. It was found that the emulsion remained stable and that there had been only a slight hydrolysis of the organic components.
  • reaction lubricants were heated to a temperature of 71 ° C. and kept at this temperature without stirring. After 4 days, no signs of instability were observed with any of the reaction lubricants.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Forging (AREA)
  • Physical Vapour Deposition (AREA)
EP80200737A 1979-08-07 1980-08-02 Reaktionsschmiermittel und Verfahren zur Vorbereitung von Metallen für die Kaltverformung Expired EP0024062B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80200737T ATE5325T1 (de) 1979-08-07 1980-08-02 Reaktionsschmiermittel und verfahren zur vorbereitung von metallen fuer die kaltverformung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6465279A 1979-08-07 1979-08-07
US64652 1979-08-07

Publications (2)

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EP0024062A1 EP0024062A1 (de) 1981-02-18
EP0024062B1 true EP0024062B1 (de) 1983-11-16

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EP (1) EP0024062B1 (es)
JP (1) JPS5635776A (es)
KR (1) KR840000653B1 (es)
AT (1) ATE5325T1 (es)
AU (1) AU525412B2 (es)
BR (1) BR8004950A (es)
CA (1) CA1149370A (es)
DE (1) DE3065613D1 (es)
ES (1) ES494475A0 (es)
IT (1) IT1132534B (es)
PH (1) PH15753A (es)
PT (1) PT71658B (es)
ZA (1) ZA804454B (es)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014212654A1 (de) * 2014-06-30 2015-12-31 Vacuumschmelze Gmbh & Co. Kg Reinigungs- und Passivierungslösung für Seltenerddauermagnete
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA826268B (en) * 1981-09-21 1983-07-27 Amchem Prod Process for the treatment of welding wire
US5178786A (en) * 1989-08-04 1993-01-12 The Lubrizol Corporation Corrosion-inhibiting compositions and functional fluids containing same
JPH07112827B2 (ja) * 1990-03-30 1995-12-06 株式会社小松製作所 閉回路油圧トランスミッションの油圧回路
DE4315271A1 (de) * 1993-05-07 1994-11-10 Laporte Gmbh Schmiermittelzusammensetzungen
JP4054539B2 (ja) * 2001-03-07 2008-02-27 日本パーカライジング株式会社 傾斜型2層潤滑皮膜を有する塑性加工用金属材料の製造方法
KR100973888B1 (ko) * 2007-12-27 2010-08-03 주식회사 포스코 결속흠 방지를 위한 윤활 방청제 조성물

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Publication number Priority date Publication date Assignee Title
DE1210296B (de) * 1958-04-24 1966-02-03 Heintz Mfg Company Mittel und Verfahren zur Behandlung von Metallen fuer die Kaltverformung
GB1204869A (en) * 1967-12-08 1970-09-09 Foseco Trading Ag Lubricants for cold-working metals
US3932287A (en) * 1971-01-19 1976-01-13 Oxy Metal Industries Corporation Reactive cold forming lubricant
GB1421386A (en) * 1973-09-19 1976-01-14 Pyrene Chemical Services Ltd Coating compostions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014212654A1 (de) * 2014-06-30 2015-12-31 Vacuumschmelze Gmbh & Co. Kg Reinigungs- und Passivierungslösung für Seltenerddauermagnete
DE102014212654B4 (de) 2014-06-30 2019-12-12 Vacuumschmelze Gmbh & Co. Kg Reinigungs- und Passivierungslösung für Seltenerddauermagnete, Verfahren und Verwendung
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers

Also Published As

Publication number Publication date
BR8004950A (pt) 1981-02-17
DE3065613D1 (en) 1983-12-22
ES8106562A1 (es) 1981-07-16
ATE5325T1 (de) 1983-12-15
PT71658B (en) 1981-06-11
ES494475A0 (es) 1981-07-16
AU525412B2 (en) 1982-11-04
IT8024021A0 (it) 1980-08-06
IT1132534B (it) 1986-07-02
KR840000653B1 (ko) 1984-05-09
CA1149370A (en) 1983-07-05
JPS5635776A (en) 1981-04-08
PT71658A (en) 1980-09-01
AU6048380A (en) 1981-02-12
KR830003596A (ko) 1983-06-21
EP0024062A1 (de) 1981-02-18
ZA804454B (en) 1982-01-27
PH15753A (en) 1983-03-18

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