EP1135543B1 - Preparation of workpieces for cold forming - Google Patents

Preparation of workpieces for cold forming Download PDF

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Publication number
EP1135543B1
EP1135543B1 EP99969750A EP99969750A EP1135543B1 EP 1135543 B1 EP1135543 B1 EP 1135543B1 EP 99969750 A EP99969750 A EP 99969750A EP 99969750 A EP99969750 A EP 99969750A EP 1135543 B1 EP1135543 B1 EP 1135543B1
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EP
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Prior art keywords
workpieces
acid
solution
lactic acid
rinsing
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Expired - Lifetime
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EP99969750A
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German (de)
French (fr)
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EP1135543A1 (en
Inventor
Klaus-Dieter Nittel
Uwe Rau
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Chemetall GmbH
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Chemetall GmbH
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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
    • C23C22/78Pretreatment of the material to be coated

Definitions

  • the invention relates to a method for preparing phosphatable workpieces for non-cutting cold forming by acid pickling, rinsing, drying and treating with acid, Reaction lubricants containing phosphate ions.
  • Acidic reaction lubricants have an oily character and are characterized by the fact that they are next to an organic Lubricants contain ingredients that are required to form a Conversion coating on the surface of the to be formed Workpiece are capable (US-A-3 525 651, US-A-2 739 915, DE-B-21 02 295, EP-A-24 062, EP-A-25 236).
  • the in practice by far the most important reaction lubricant contained as the conversion coating forming component phosphoric acid or Zinc phosphate.
  • phosphoric acid Treatment of the workpieces to be formed essentially Iron phosphate layers, when using zinc phosphate containing reaction lubricants from conversion layers Zinc phosphate or zinc iron phosphate.
  • the usually in Reaction lubricants applied by immersion generate on the
  • the surface of the workpiece is an integral part Conversion coating, which ensures that when forming a high degree of separation of workpiece and forming tool takes place, on the other hand, a firm bond of the organic Lubricant is given on the workpiece surface.
  • the first stages of treatment for the usual preparation of Workpieces, especially pipes, consist of the Bright annealing under protective gas at approx. 920 ° C, the subsequent one Pickling in hydrochloric acid or sulfuric acid and one if necessary multi-stage water flushing.
  • a rust preventive such as borax, soda, Nitrite, phosphate or sodium hydroxide solution or mixtures thereof.
  • the Drying is required because of acidic reaction lubricants are sensitive to constant water entry.
  • the object of the invention is a method for preparation of phosphatable workpieces for non-cutting cold forming to provide using acidic reaction lubricants, which does not have the aforementioned disadvantages, in which the Workpieces in the process stage of treatment with the acid Reaction lubricants are introduced in a rust-free condition and with a perfect exposure to the acid Reaction lubricant without its disadvantageous Impairment is achievable.
  • the task is solved by the procedure of the beginning mentioned type according to the invention in the manner is designed that the workpieces with before drying a solution that contains lactic acid and a pH below 3.
  • Workpieces suitable for phosphating intended for cold forming consist in particular of steel in the form of wire, tube, Profiles, circular blanks etc., which can be pulled, cold extruded, Rolls etc. are formed.
  • This layer is not only rust-proof, but also acts on the layer formation in the treatment with the acid Activating reaction lubricant.
  • the adjustment of the pH value below 3 can be done with Lactic acid. However, for cost reasons it is expedient, in addition to adjusting the pH To use phosphoric acid and / or sulfuric acid.
  • Phosphoric acid is preferred because the final applied Reaction lubricant contains phosphate ions and therefore with Rinsing solution entered inevitably, from the phosphoric acid originating phosphate ions are not alien.
  • Another expedient embodiment of the invention exists in rinsing the workpieces with a solution that Lactic acid and phosphoric acid in a weight ratio of 1: 9 to 9: 1 contains. This configuration is under Consideration of both the layer quality and the Cost situation particularly advantageous.
  • the rinse with the solution containing lactic acid can be carried out with a solution temperature of 20 to 90 ° C.
  • the workpieces with a solution at a temperature of 60 to 80 ° C.
  • Tubes of steel quality St34 / 2 bright annealed under protective gas at approx. 920 ° C were initially contained in a pickling solution of 50 ° C 150 g / l sulfuric acid 60 g / l Iron II for a period of 15 min. pickled and then rinsed in two stages with cascade-like rinsing water.
  • the still wet tubes were rinsed with a solution according to the invention, the 10 g / l lactic acid 20 g / l phosphoric acid contained and had a pH of ⁇ 3.
  • the temperature of the rinsing solution was 70 ° C. and the rinsing time was 3 minutes.
  • the tubes were then allowed to air dry and treated with the residual moisture adhering in a conventional manner with an acidic reaction lubricant containing phosphate ions and formed by tube drawing.
  • the pipes dried after rinsing showed nothing Rust attack and had a lactate layer containing iron oxide of a blue-violet appearance.
  • the subsequent treatment with the reaction lubricant led to flawless Lubricant layers. Somehow The reaction lubricant was not adversely affected.
  • tubes of the same quality were the same as above subject to the procedure described, but was carried out instead of rinsing with the solution containing lactic acid a third rinse with warm water.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Lubricants (AREA)
  • Metal Extraction Processes (AREA)
  • Polarising Elements (AREA)

Abstract

The invention relates to a method for preparing workpieces suitable for phosphatizing for chipless cold forming by acid pickling, rinsing, drying and treatment with acid reaction lubricants containing phosphate ions. According to said method the workpieces are rinsed before drying with a solution which contains lactic acid, has a pH below 3 and preferably a temperature of between 60 and 80° C. Preferred embodiments of the invention consist of rinsing the workpieces with a solution which in addition contains phosphoric acid, has a lactic acid concentration of between 1 and 50 g/l and a weight ratio of lactic acid to phosphoric acid of between 1:9 and 9:1.

Description

Die Erfindung betrifft ein Verfahren zur Vorbereitung von phosphatierbaren Werkstücken für die spanlose Kaltumformung durch saures Beizen, Spülen, Trocknen und Behandeln mit sauren, Phosphationen enthaltenden Reaktionsschmiermitteln.The invention relates to a method for preparing phosphatable workpieces for non-cutting cold forming by acid pickling, rinsing, drying and treating with acid, Reaction lubricants containing phosphate ions.

Saure Reaktionsschmiermittel besitzen einen öligen Charakter und zeichnen sich dadurch aus, daß sie neben einem organischen Gleitmittel Bestandteile enthalten, die zur Ausbildung eines Konversionsüberzuges auf der Oberfläche des umzuformenden Werkstückes befähigt sind (US-A-3 525 651, US-A-2 739 915, DE-B-21 02 295, EP-A-24 062, EP-A-25 236). Die in der Praxis mit Abstand wichtigsten Reaktionsschmiermittel enthalten als den Konversionsüberzug bildende Komponente Phosphorsäure oder Zinkphosphat. In Gegenwart von Phosphorsäure entstehen bei der Behandlung der umzuformenden Werkstücke im wesentlichen Eisenphosphatschichten, bei Verwendung von Zinkphosphat enthaltenden Reaktionsschmiermitteln Konversionsschichten aus Zinkphosphat bzw. Zinkeisenphosphat. Die in der Regel im Tauchen applizierten Reaktionsschmiermittel erzeugen auf der Oberfläche des Werkstückes einen festverwachsenen Konversionsüberzug, der gewährleistet, daß bei der Umformung ein hohes Maß an Trennung von Werkstück und Umformwerkzeug erfolgt, andererseits eine feste Bindung des organischen Gleitmittels auf der Werkstückoberfläche gegeben ist.Acidic reaction lubricants have an oily character and are characterized by the fact that they are next to an organic Lubricants contain ingredients that are required to form a Conversion coating on the surface of the to be formed Workpiece are capable (US-A-3 525 651, US-A-2 739 915, DE-B-21 02 295, EP-A-24 062, EP-A-25 236). The in practice by far the most important reaction lubricant contained as the conversion coating forming component phosphoric acid or Zinc phosphate. In the presence of phosphoric acid Treatment of the workpieces to be formed essentially Iron phosphate layers, when using zinc phosphate containing reaction lubricants from conversion layers Zinc phosphate or zinc iron phosphate. The usually in Reaction lubricants applied by immersion generate on the The surface of the workpiece is an integral part Conversion coating, which ensures that when forming a high degree of separation of workpiece and forming tool takes place, on the other hand, a firm bond of the organic Lubricant is given on the workpiece surface.

Die ersten Behandlungsstufen für die übliche Vorbereitung von Werkstücken, insbesondere von Rohren, besteht aus dem Blankglühen unter Schutzgas bei ca. 920°C, dem anschließenden Beizen in Salzsäure oder Schwefelsäure und einer gegebenenfalls mehrstufigen Wasserspülung. Die sich üblicherweise anschließende Weiterbehandlung der Werkstücke vor dem In-Kontakt-Bringen mit dem Reaktionsschmiermittel erfolgt durch Trocknung, gegebenenfalls nach erneuter Spülung mit einer alkalischen Lösung eines Rostschutzmittels, wie Borax, Soda, Nitrit, Phosphat oder Natronlauge bzw. Mischungen hiervon. Die Trocknung ist erforderlich, da saure Reaktionsschmiermittel empfindlich auf einen ständigen Wassereintrag reagieren.The first stages of treatment for the usual preparation of Workpieces, especially pipes, consist of the Bright annealing under protective gas at approx. 920 ° C, the subsequent one Pickling in hydrochloric acid or sulfuric acid and one if necessary multi-stage water flushing. Which is usually Subsequent further processing of the workpieces before bringing them into contact with the reaction lubricant Drying, if necessary after rinsing again with a alkaline solution of a rust preventive, such as borax, soda, Nitrite, phosphate or sodium hydroxide solution or mixtures thereof. The Drying is required because of acidic reaction lubricants are sensitive to constant water entry.

Sowohl die bloße Trocknung, wie auch die Trocknung mit vorheriger Spülung mit Rostschutzmittellösungen ist im Hinblick auf die folgende Behandlung mit dem sauren Reaktionsschmiermittel nachteilig. Die bloße Trocknung ist mit einem Rostbefall verbunden, der sich auf die Phosphatierbarkeit des Werkstückes nachteilig auswirkt, indem die erforderliche Dichte und Haftfestigkeit der gebildeten Phosphatschicht nicht gewährleistet ist. Die vor der Trocknung praktizierte Spülung mit einer Lösung alkalischer Rostschutzmittel ist mit einer beträchtlichen Salzeinschleppung in das saure Reaktionsschmiermittel verbunden, was einerseits zu einer erheblichen Schlammbildung und andererseits zur Verminderung der Funktionsfähigkeit wegen ständigen Eintrags alkalischer Substanzen führt. Darüber hinaus ist die Schichtausbilung behindert, da saure Reaktionsschmiermittel die alkalische Werkstückoberfläche nur ungleichmäßig anbeizen.Both the mere drying as well as the drying with previous rinsing with rust inhibitor solutions is in consideration on the following treatment with the acid Reactive lubricant disadvantageous. The mere drying is with a rust attack, which affects the phosphatability of the workpiece adversely affects by the required Density and adhesive strength of the phosphate layer not formed is guaranteed. The rinse practiced before drying with a solution of alkaline rust inhibitor is with a considerable introduction of salt into the acidic Reaction lubricant connected, which leads to a considerable sludge formation and on the other hand for reduction the functionality due to constant entry of alkaline Leads substances. In addition, the stratification hinders, because acidic reaction lubricants the alkaline Pickle the workpiece surface unevenly.

Aufgabe der Erfindung ist es, ein Verfahren zur Vorbereitung von phosphatierbaren Werkstücken für die spanlose Kaltumformung unter Einsatz saurer Reaktionsschmiermittel bereitzustellen, das die vorgenannten Nachteile nicht aufweist, bei dem die Werkstücke in die Verfahrensstufe der Behandlung mit dem sauren Reaktionsschmiermittel in rostfreiem Zustand eingeführt werden und bei dem eine einwandfreie Einwirkung des sauren Reaktionsschmiermittels ohne dessen nachteilige Beeinträchtigung erreichbar ist.The object of the invention is a method for preparation of phosphatable workpieces for non-cutting cold forming to provide using acidic reaction lubricants, which does not have the aforementioned disadvantages, in which the Workpieces in the process stage of treatment with the acid Reaction lubricants are introduced in a rust-free condition and with a perfect exposure to the acid Reaction lubricant without its disadvantageous Impairment is achievable.

Die Aufgabe wird gelöst, in dem das Verfahren der eingangs genannten Art entsprechend der Erfindung in der Weise ausgestaltet wird, daß man die Werkstücke vor dem Trocknen mit einer Lösung spült, die Milchsäure enthält und einen pH-Wert unterhalb 3 aufweist.The task is solved by the procedure of the beginning mentioned type according to the invention in the manner is designed that the workpieces with before drying a solution that contains lactic acid and a pH below 3.

Für die Kaltumformung bestimmte phosphatierbare Werkstücke bestehen insbesondere aus Stahl in Form von Draht, Rohr, Profilen, Ronden etc., die durch Ziehen, Kaltfließpressen, Walzen etc. umgeformt werden.Workpieces suitable for phosphating intended for cold forming consist in particular of steel in the form of wire, tube, Profiles, circular blanks etc., which can be pulled, cold extruded, Rolls etc. are formed.

Durch die Spülung mit der Milchsäure enthaltenden Lösung entsteht auf der Werkstückoberfläche eine aus Eisenlactat gebildete Schicht, die durch eine violette Farbe erkennbar ist.By rinsing with the solution containing lactic acid an iron lactate is formed on the workpiece surface formed layer, which is recognizable by a violet color.

Diese Schicht ist nicht nur rostschützend, sondern wirkt auf die Schichtbildung bei der Behandlung mit dem sauren Reaktionsschmiermittel aktivierend.This layer is not only rust-proof, but also acts on the layer formation in the treatment with the acid Activating reaction lubricant.

Zwar ist es aus DE-B-2103086 bekannt, Werkstücke nach einer alkalischen Reinigung und vor der Phosphatierung mit anschließender Elektrotauchlackierung bei einer Temperatur unterhalb 60°C mit einer wässrigen Lösung, deren pH-Wert mit Milchsäure auf 4 bis 5,5 eingestellt ist und die nichtionisches Tensid enthält, in Berührung zu bringen. Jedoch wird darin von einer Behandlung in der Weise, daß Lactatschichten gebildet werden, unter Hinweis auf eine mögliche Beeinträchtigung bei der anschließenden Aufbringung der Phosphatschicht gewarnt. Infolge der in diesem Dokument ausgesprochenen Warnung vor einer Arbeitsweise, die die Ausbildung einer Lactatschicht zur Folge hat, war in keiner Weise zu erwarten, daß sich eine derartige Eisenlactatschicht nicht nur bezüglich des Korrosionsschutzes, insbesondere aber im Hinblick auf die anschließende Behandlung mit dem sauren Reaktionsschmiermittel positiv auswirkt.It is known from DE-B-2103086, workpieces according to a alkaline cleaning and before phosphating with subsequent electrodeposition at a temperature below 60 ° C with an aqueous solution, the pH value with Lactic acid is set to 4 to 5.5 and the nonionic Contains surfactant to get in touch. However, it is from treatment in such a way that lactate layers are formed be aware of a possible impairment warned of the subsequent application of the phosphate layer. As a result of the warning given in this document a method of working which involves the formation of a lactate layer As a result, it was in no way expected that a such iron lactate layer not only in terms of Corrosion protection, but especially with regard to the subsequent treatment with the acidic reaction lubricant has a positive effect.

Die Einstellung des pH-Wertes unterhalb 3 kann allein mit Milchsäure erfolgen. Aus Kostengründen ist es jedoch zweckmäßig, zur Einstellung des pH-Wertes zusätzlich Phosphorsäure und/oder Schwefelsäure zu verwenden. Hierbei ist entsprechend einer vorteilhaften Ausgestaltung der Erfindung Phosphorsäure bevorzugt, da das abschließend aufgebrachte Reaktionsschmiermittel Phosphationen enthält und mithin die mit Spüllösung unvermeidbar eingetragenen, von der Phosphorsäure stammenden Phosphationen nicht artfremd sind.The adjustment of the pH value below 3 can be done with Lactic acid. However, for cost reasons it is expedient, in addition to adjusting the pH To use phosphoric acid and / or sulfuric acid. Here is according to an advantageous embodiment of the invention Phosphoric acid is preferred because the final applied Reaction lubricant contains phosphate ions and therefore with Rinsing solution entered inevitably, from the phosphoric acid originating phosphate ions are not alien.

Demzufolge sieht bei Mitverwendung von Phosphorsäure und/oder Schwefelsäure eine bevorzugte Ausführungsform der Erfindung vor, die Werkstücke mit einer Lösung zu spülen, die 1 bis 50 g/l Milchsäure enthält. Obgleich auch eine Milschsäurekonzentration außerhalb des bevorzugten Bereiches zu brauchbaren Lactatschichten führt, ergeben Milchsäurekonzentrationen im bevorzugten Bereich Lactatschichten, die hinsichtlich Korrosionsschutz und Aktivierung der Schmierschichtausbildung besonders vorteilhaft sind.Accordingly, when using phosphoric acid and / or Sulfuric acid is a preferred embodiment of the invention before rinsing the workpieces with a solution that is 1 to 50 Contains g / l lactic acid. Although one too Lactic acid concentration outside the preferred range leads usable lactate layers Lactic acid concentrations in the preferred range Lactate layers, which with regard to corrosion protection and Activation of the lubricant layer formation is particularly advantageous are.

Eine weitere zweckmäßige Ausgestaltung der Erfindung besteht darin, die Werkstücke mit einer Lösung zu spülen, die Milchsäure und Phosphorsäure in einem Gewichtsverhältnis von 1 : 9 bis 9 : 1 enthält. Diese Ausgestaltung ist unter Berücksichtigung sowohl der Schichtqualität als auch der Kostensituation besonders vorteilhaft.Another expedient embodiment of the invention exists in rinsing the workpieces with a solution that Lactic acid and phosphoric acid in a weight ratio of 1: 9 to 9: 1 contains. This configuration is under Consideration of both the layer quality and the Cost situation particularly advantageous.

Die Spülung mit der Milchsäure enthaltenden Lösung kann mit einer Lösungstemperatur von 20 bis 90°C erfolgen. The rinse with the solution containing lactic acid can be carried out with a solution temperature of 20 to 90 ° C.

Gemäß einer weiteren vorteilhaften Ausführungsform der Erfindung empfiehlt es sich, die Werkstücke mit einer Lösung einer Temperatur von 60 bis 80°C zu spülen.According to a further advantageous embodiment of the Invention, it is recommended that the workpieces with a solution at a temperature of 60 to 80 ° C.

Die Erfindung wird anhand des nachfolgenden Beispiels näher erläutert.The invention is illustrated by the following example explained.

Beispielexample

Unter Schutzgas bei ca. 920°C blankgeglühte Rohre der Stahlqualität St34/2 wurden zunächst in einer Beizlösung von 50°C, enthaltend 150 g/l Schwefelsäure 60 g/l Eisen II für die Dauer von 15 min. gebeizt und anschließend in zwei Stufen mit kaskadenartig geführtem Spülwasser gespült.Tubes of steel quality St34 / 2 bright annealed under protective gas at approx. 920 ° C were initially contained in a pickling solution of 50 ° C 150 g / l sulfuric acid 60 g / l Iron II for a period of 15 min. pickled and then rinsed in two stages with cascade-like rinsing water.

Anschließend wurden die noch nassen Rohre entsprechend der Erfindung mit einer Lösung gespült, die 10 g/l Milchsäure 20 g/l Phosphorsäure enthielt und einen pH-Wert von < 3 aufwies. Es betrugen die Temperatur der Spüllösung 70°C und die Spüldauer 3 min. Anschließend wurden die Rohre an der Luft antrocknen gelassen und mit der anhaftenden Restfeuchte in konventioneller Weise mit einem sauren, Phosphationen enthaltenden Reaktionsschmiermittel behandelt und durch Rohrzug umgeformt.Then the still wet tubes were rinsed with a solution according to the invention, the 10 g / l lactic acid 20 g / l phosphoric acid contained and had a pH of <3. The temperature of the rinsing solution was 70 ° C. and the rinsing time was 3 minutes. The tubes were then allowed to air dry and treated with the residual moisture adhering in a conventional manner with an acidic reaction lubricant containing phosphate ions and formed by tube drawing.

Die nach der Spülung angetrockneten Rohre zeigten keinerlei Rostbefall und besaßen eine Eisenoxid enthaltende Lactatschicht von blauviolettem Aussehen. Die sich anschließende Behandlung mit dem Reaktionsschmiermittel führte zu einwandfreien Schmiermittelschichten. Eine irgendwie geartete Beeinträchtigung des Reaktionsschmiermittels erfolgte nicht. The pipes dried after rinsing showed nothing Rust attack and had a lactate layer containing iron oxide of a blue-violet appearance. The subsequent treatment with the reaction lubricant led to flawless Lubricant layers. Somehow The reaction lubricant was not adversely affected.

Zum Vergleich wurden Rohre gleicher Qualität dem vorstehend beschriebenen Verfahrensgang unterworfen, jedoch erfolgte anstelle der Spülung mit der Milchsäure enthaltenden Lösung eine dritte Spülung mit warmem Wasser.For comparison, tubes of the same quality were the same as above subject to the procedure described, but was carried out instead of rinsing with the solution containing lactic acid a third rinse with warm water.

Nach Antrocknung der Rohre zeigte sich ein beträchtlicher Rostbefall, der bei der anschließenden Behandlung mit dem gleichen Reaktionsschmiermittel für eine ungleichmäßige Phosphatschichtausbildung hinsichtlich Dichte und Haftfestigkeit verantwortlich war.After the pipes had dried, a considerable amount was evident Rust attack, which is the result of subsequent treatment with the same reaction lubricant for an uneven Phosphate layer formation in terms of density and Adhesion was responsible.

Claims (5)

  1. Method for preparing phosphatizable workpieces for non-cutting cold-forming by acid pickling, rinsing, drying and treatment with acid reaction lubricants containing phosphate ions, characterised in that the before drying, the workpieces are rinsed with a solution which contains lactic acid and has a pH value of below 3.
  2. Method according to claim 1, characterised in that the workpieces are rinsed with a solution which additionally contains phosphoric acid.
  3. Method according to claim 1 or 2, characterised in that the workpieces are rinsed with a solution which contains 1 to 50 g/l of lactic acid.
  4. Method according to claim 1, 2 or 3, characterised in that the workpieces are rinsed with a solution which contains lactic acid and phosphoric acid in a weight ratio of 1 : 9 to 9 : 1.
  5. Method according to one or more of claims 1 to 4, characterised in that the workpieces are rinsed with a solution having a temperature of 60 to 80°C.
EP99969750A 1998-09-28 1999-09-21 Preparation of workpieces for cold forming Expired - Lifetime EP1135543B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19844391 1998-09-28
DE19844391A DE19844391C2 (en) 1998-09-28 1998-09-28 Process for preparing workpieces for cold forming
PCT/EP1999/006978 WO2000018983A1 (en) 1998-09-28 1999-09-21 Preparation of workpieces for cold forming

Publications (2)

Publication Number Publication Date
EP1135543A1 EP1135543A1 (en) 2001-09-26
EP1135543B1 true EP1135543B1 (en) 2002-06-05

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EP99969750A Expired - Lifetime EP1135543B1 (en) 1998-09-28 1999-09-21 Preparation of workpieces for cold forming

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US (1) US6482273B1 (en)
EP (1) EP1135543B1 (en)
AT (1) ATE218629T1 (en)
DE (2) DE19844391C2 (en)
ES (1) ES2178504T3 (en)
WO (1) WO2000018983A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI457433B (en) * 2008-01-30 2014-10-21 Chemetall Gmbh Process for coating metallic surfaces with a phosphate layer and then with a polymer lubricant layer
TWI457431B (en) * 2008-01-30 2014-10-21 Chemetall Gmbh Process for coating a metallic surface with a lubricant composition
TWI457432B (en) * 2008-01-30 2014-10-21 Chemetall Gmbh Process for coating metallic surface with a wax-coataining lubricant composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB665993A (en) 1947-07-23 1952-02-06 Plasco Ltd Process and composition for producing a dyeable corrosion-resistant coating on zinc and zinc alloys
DE975008C (en) 1952-08-06 1961-08-03 American Chem Paint Co Process for the production of phosphate coatings on zinc and its alloys
DE2103086C3 (en) * 1971-01-23 1979-11-15 Metallgesellschaft Ag, 6000 Frankfurt Process for the surface treatment of workpieces made of iron and steel
US3795548A (en) * 1972-01-10 1974-03-05 Oxy Metal Finishing Corp Procedure for surface treatment of iron and steel
JPH0696773B2 (en) * 1989-06-15 1994-11-30 日本ペイント株式会社 Method for forming zinc phosphate film on metal surface
US5624480A (en) 1993-04-07 1997-04-29 Henkel Corporation Composition and process for substitutionally plating zinciferous surfaces
DE4433946A1 (en) 1994-09-23 1996-03-28 Henkel Kgaa Phosphating process without rinsing

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DE59901680D1 (en) 2002-07-11
DE19844391C2 (en) 2003-01-09
ATE218629T1 (en) 2002-06-15
US6482273B1 (en) 2002-11-19
WO2000018983A1 (en) 2000-04-06
ES2178504T3 (en) 2002-12-16
EP1135543A1 (en) 2001-09-26
DE19844391A1 (en) 2000-04-13

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