EP0025236A1 - Lubrifiant réactif et procédé pour la préparation de métaux pour la déformation à froid - Google Patents

Lubrifiant réactif et procédé pour la préparation de métaux pour la déformation à froid Download PDF

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Publication number
EP0025236A1
EP0025236A1 EP80200736A EP80200736A EP0025236A1 EP 0025236 A1 EP0025236 A1 EP 0025236A1 EP 80200736 A EP80200736 A EP 80200736A EP 80200736 A EP80200736 A EP 80200736A EP 0025236 A1 EP0025236 A1 EP 0025236A1
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Prior art keywords
weight
component
amount
lubricant
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
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EP80200736A
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German (de)
English (en)
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EP0025236B1 (fr
Inventor
Peter F. King
George J. Beyer
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GEA Group AG
Continentale Parker Ste
Continentale Parker SA
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Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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Priority to AT80200736T priority Critical patent/ATE2683T1/de
Publication of EP0025236A1 publication Critical patent/EP0025236A1/fr
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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
    • C23C22/05Chemical 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 aqueous solutions
    • C23C22/06Chemical 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 aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07Chemical 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 aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08Orthophosphates
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
    • C10M2207/28Esters
    • 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
    • C10M2207/28Esters
    • 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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    • C10M2215/00Organic 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
    • 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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    • C10M2215/08Amides
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
    • C10M2215/082Amides containing hydroxyl groups; Alkoxylated derivatives
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26Amines
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
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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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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/241Manufacturing joint-less pipes
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • 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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    • C10N2040/244Metal 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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    • C10N2040/244Metal 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
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    • C10N2070/02Concentrating of additives

Definitions

  • the invention relates to an aqueous acidic reaction lubricant for the treatment of metal surfaces prior to cold forming, containing phosphate ions and emulsifiable organic lubricant components, and to a method for preparing metals for cold forming using this reactive 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 in it.
  • 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 too uneven lead coatings.
  • the agents also require careful monitoring and supplementation of the layer-forming components of the phosphating solution.
  • Austrian Patent 189 151 in which an aqueous solution and / or dispersion of an aliphatic phosphate having 8 to 18 carbon atoms, optionally together with metal ions and the solubility-increasing amines, in a pH range between 3.0 and 5.5 is used and the solution film applied to the surfaces is dried, preferably at elevated temperature.
  • 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.
  • Reactive lubricants based on phosphoric acid with contents of long-chain amines or amides are also known which contain only a small proportion of water and considerable amounts of organic lubricants (British patent specification 891 150 and German specification 12 10 296).
  • 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 arises from the accumulation of metal ions which get into the emulsion as a result of the pickling attack on the metal surface. Even at comparatively low concentrations, about 0.2% by weight, they cause demulsification or demixing, so that the reaction lubricant can no longer function properly.
  • the object of the present invention is to provide the known in particular to avoid the aforementioned disadvantages and to provide an aqueous acidic reaction lubricant which is versatile, produces effective lubricant coatings on metal surfaces, is stable over a wide range of applications and is practically not prone to demulsification.
  • 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 chelating agent can be used as a free acid or as a mono-.
  • Di, tri and / or tetraalkali or ammonium salt can be used. Equivalent amounts should be added when using the salts.
  • 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 0.25 to 3.0% by weight, in particular components a) in an amount of 1.5 to 6% by weight, b) in an amount of 2 up to 6% by weight of component c) in an amount of 0.5 to 4% by weight and d) in an amount of 0.5 to 2.0% by weight or components a) in an amount from 1.5 to 3% by weight, b) in 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 2.0% 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.
  • 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.
  • the oxazoline wax used as component c) is not only distinguished as a good emulsifier, but is also for a considerable improvement in the thermal stability lity of the reaction lubricant, especially at temperatures above 71 ° C, at which demulsification can easily occur - recognizable by a floating oil layer.
  • the formula has a particularly suitable oxazoline wax
  • R 1 , 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, for example, under the trade name Wax TS 254, Wax TS 254 A, Wax TS 254 AA, Wax TS 970, Alkaterge E and Alkaterge T from the company IMC Chemical Group, Inc., Hillsdale, Illinois (NP Division). available.
  • 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, especially 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 drawing resistance during the deformation process, the wear of the drawing tool and can lead to scoring.
  • Reaction lubricants are therefore preferably used which contain 0.1 to 5% by weight of an ammonium salt formed from carboxylic acid with 7 to 18 C atoms and aliphatic amine with up to 12 C atoms as inhibitor; in particular, salts of alkanolamine, preferably triethanolamine, are used , preferably salts of triethanolamine with octanoic acid or with stearic acid.
  • An inhibitor of the aforementioned type is available in the form of a solution containing 40% by weight of a salt of triethanolamine with octanoic acid 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 chelating agent not only improves the stability of the emulsion when the iron contents reach or exceed 0.2% by weight, but surprisingly also shows a corrosion-inhibiting effect.
  • a synergistic effect can be determined, so that optimal corrosion protection is achieved with comparatively low concentrations of chelating agent and corrosion inhibitor.
  • the chelating agent is able to re-emulsify a treatment bath that has already been demulsified by high iron contents. For this purpose, it is advisable to stir vigorously while adding the chelating agent. Finally, the chelating agent increases the drying rate during the drying of the reaction lubricant, so that time and energy are saved.
  • 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 concentrate can be used as such or after suitable dilution with water to treat the metal surfaces.
  • 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 reaction lubricant can be applied as usual, for example by dipping, 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 thereby 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 forming.
  • the above-mentioned concentrate was diluted 1: 1 by volume with water and the treatment bath obtained was brought to a temperature of 77 ° C.
  • reaction lubricant thus obtained was used for a long time to treat workpieces. Iron dissolved, which reached a concentration of 0.2% by weight. An examination of the treatment bath showed that demulsification was already beginning to emerge.
  • a fresh treatment bath according to Example 1 was modified such that tetrasodium ethylenediaminetetraacetic acid was added in an amount of 1% by weight as a chelating agent.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Lubricants (AREA)
  • Forging (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Chemical Treatment Of Metals (AREA)
EP80200736A 1979-08-07 1980-08-02 Lubrifiant réactif et procédé pour la préparation de métaux pour la déformation à froid Expired EP0025236B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80200736T ATE2683T1 (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
US6468279A 1979-08-07 1979-08-07
US64682 1979-08-07

Publications (2)

Publication Number Publication Date
EP0025236A1 true EP0025236A1 (fr) 1981-03-18
EP0025236B1 EP0025236B1 (fr) 1983-03-02

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ID=22057604

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EP80200736A Expired EP0025236B1 (fr) 1979-08-07 1980-08-02 Lubrifiant réactif et procédé pour la préparation de métaux pour la déformation à froid

Country Status (14)

Country Link
EP (1) EP0025236B1 (fr)
JP (1) JPS5632595A (fr)
KR (1) KR840000654B1 (fr)
AR (1) AR225452A1 (fr)
AT (1) ATE2683T1 (fr)
AU (1) AU535470B2 (fr)
BR (1) BR8004943A (fr)
CA (1) CA1149371A (fr)
DE (1) DE3062209D1 (fr)
ES (1) ES494476A0 (fr)
IT (1) IT1132535B (fr)
PH (1) PH15744A (fr)
PT (1) PT71659A (fr)
ZA (1) ZA804457B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0120822A1 (fr) * 1983-02-10 1984-10-03 Berol Kemi Ab Procédé de travail mécanique de fonte et solution aqueuse concentrée destinée à l'usinage du procédé
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers
CN117340173A (zh) * 2023-12-06 2024-01-05 成都先进金属材料产业技术研究院股份有限公司 抑制镍铜合金锻造过程中开裂的方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6131213A (ja) * 1984-07-23 1986-02-13 Yuuhoo Chem Kk 離型剤組成物
JPS6171131A (ja) * 1984-09-14 1986-04-12 Takeo Hayashi 潤滑性金属板
DE3447346A1 (de) * 1984-12-24 1986-06-26 Dow Corning GmbH, 8000 München Schmierstoff fuer wasserarmaturen, wie wasserhaehne und dergleichen
JPS61263748A (ja) * 1985-05-17 1986-11-21 日本製箔株式会社 成形用金属薄板
JP4727932B2 (ja) * 2004-01-16 2011-07-20 株式会社日中製作所 後入れランナ
JP4627415B2 (ja) * 2004-05-06 2011-02-09 スギムラ化学工業株式会社 金属加工用潤滑剤、金属加工用固形潤滑膜の形成方法

Citations (5)

* Cited by examiner, † Cited by third party
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
GB2002812A (en) * 1977-08-16 1979-02-28 Pyrene Chemical Services Ltd Lubricant composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
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
GB2002812A (en) * 1977-08-16 1979-02-28 Pyrene Chemical Services Ltd Lubricant composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0120822A1 (fr) * 1983-02-10 1984-10-03 Berol Kemi Ab Procédé de travail mécanique de fonte et solution aqueuse concentrée destinée à l'usinage du procédé
US11104823B2 (en) 2015-04-15 2021-08-31 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers
CN117340173A (zh) * 2023-12-06 2024-01-05 成都先进金属材料产业技术研究院股份有限公司 抑制镍铜合金锻造过程中开裂的方法
CN117340173B (zh) * 2023-12-06 2024-03-08 成都先进金属材料产业技术研究院股份有限公司 抑制镍铜合金锻造过程中开裂的方法

Also Published As

Publication number Publication date
ES8106021A1 (es) 1981-07-16
AU535470B2 (en) 1984-03-22
IT8024022A0 (it) 1980-08-06
ES494476A0 (es) 1981-07-16
PT71659A (en) 1980-09-01
DE3062209D1 (en) 1983-04-07
ZA804457B (en) 1982-03-31
BR8004943A (pt) 1981-02-17
ATE2683T1 (de) 1986-03-15
PH15744A (en) 1983-03-18
CA1149371A (fr) 1983-07-05
AR225452A1 (es) 1982-03-31
IT1132535B (it) 1986-07-02
JPS616116B2 (fr) 1986-02-24
KR830003597A (ko) 1983-06-21
JPS5632595A (en) 1981-04-02
EP0025236B1 (fr) 1983-03-02
KR840000654B1 (ko) 1984-05-09
AU6068180A (en) 1982-02-11

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