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EP1135543A1 - Preparation of workpieces for cold forming - Google Patents

Preparation of workpieces for cold forming

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Publication number
EP1135543A1
EP1135543A1 EP99969750A EP99969750A EP1135543A1 EP 1135543 A1 EP1135543 A1 EP 1135543A1 EP 99969750 A EP99969750 A EP 99969750A EP 99969750 A EP99969750 A EP 99969750A EP 1135543 A1 EP1135543 A1 EP 1135543A1
Authority
EP
European Patent Office
Prior art keywords
workpieces
solution
acid
lactic acid
rinsing
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
Application number
EP99969750A
Other languages
German (de)
French (fr)
Other versions
EP1135543B1 (en
Inventor
Klaus-Dieter Nittel
Uwe Rau
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.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
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Filing date
Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP1135543A1 publication Critical patent/EP1135543A1/en
Application granted granted Critical
Publication of EP1135543B1 publication Critical patent/EP1135543B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C22/00—Chemical 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
    • C23C22/78—Pretreatment 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 treatment with acidic reaction lubricants containing phosphate ions.
  • Acidic reaction lubricants have an oily character and are characterized in that, in addition to an organic lubricant, they contain constituents which are capable of forming a conversion coating on the surface of the workpiece to be formed (US Pat. Nos. 3,525,651, 2,739,915) , DE-B-21 02 295, EP-A-24 062, EP-A-25 236).
  • the most important reaction lubricants in practice contain phosphoric acid or zinc phosphate as the component that forms the conversion coating. In the presence of phosphoric acid, the treatment of the workpieces to be reshaped essentially produces iron phosphate layers, and when using reaction phosphates containing zinc phosphate, conversion layers of zinc phosphate or zinc iron phosphate are used.
  • reaction lubricants which are usually applied in dipping, produce a firmly integrated conversion coating on the surface of the workpiece, which ensures that there is a high degree of separation of the workpiece and the forming tool during the forming process takes place, on the other hand there is a firm bond of the organic lubricant on the workpiece surface.
  • the subsequent processing of the workpieces which usually follows before contact with the reaction lubricant, is carried out by drying, if appropriate after rinsing again with an alkaline solution of an anti-rust agent such as borax, soda, nitrite, phosphate or sodium hydroxide solution or mixtures thereof. Drying is necessary because acidic reaction lubricants are sensitive to constant water entry.
  • Reactive lubricant disadvantageous.
  • the mere drying is associated with rust, which has an adverse effect on the phosphatability of the workpiece by the required density and adhesive strength of the phosphate layer is not guaranteed.
  • the pre-drying rinsing with a solution of alkaline rust inhibitor is associated with a considerable introduction of salt into the acidic reaction lubricant, which on the one hand leads to considerable sludge formation and on the other hand reduces the functionality due to the constant introduction of alkaline substances.
  • the layer formation is hindered because acidic reaction lubricants only stain the alkaline workpiece surface unevenly.
  • the object of the invention is to provide a method for preparing phosphatable workpieces for non-cutting cold forming using acidic reaction lubricants, which does not have the aforementioned disadvantages, in which the workpieces are introduced into the process step of treatment with the acidic reaction lubricant in a rust-free state, and in which the acidic reaction lubricant can be acted upon properly without adversely affecting it.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the workpieces are rinsed with a solution which contains lactic acid and has a pH below 3 before drying.
  • Workpieces that can be phosphated for cold forming consist in particular of steel in the form of wire, tube, profiles, round blanks, etc., which are formed by drawing, cold extrusion, rolling, etc.
  • the pH value can be set below 3 using lactic acid alone. For cost reasons, however, it is advisable to use phosphoric acid and / or sulfuric acid to adjust the pH. According to an advantageous embodiment of the invention, phosphoric acid is preferred since the finally applied reaction lubricant contains phosphate ions and consequently the phosphate ions derived from the phosphoric acid are unavoidably introduced with the flushing solution.
  • a preferred embodiment of the invention provides for rinsing the workpieces with a solution which contains 1 to 50 g / 1 lactic acid.
  • Lactic acid concentration outside the preferred range leads to usable lactate layers, lactic acid concentrations in the preferred range result in lactate layers which are particularly advantageous with regard to corrosion protection and activation of the lubricating layer formation.
  • Another expedient embodiment of the invention is to rinse the workpieces with a solution which contains lactic acid and phosphoric acid in a weight ratio of 1: 9 to 9: 1. This configuration is particularly advantageous taking into account both the layer quality and the cost situation.
  • the solution containing lactic acid can be rinsed at a solution temperature of 20 to 90 ° C. According to a further advantageous embodiment of the invention, it is advisable to rinse the workpieces with a solution at a temperature of 60 to 80 ° C.
  • the invention is illustrated by the following example.
  • 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
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (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

Vorbereitung von Werkstücken für die Kaltmrtfor ung Preparation of workpieces for cold milling
Beschreibungdescription
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 treatment with acidic 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 in that, in addition to an organic lubricant, they contain constituents which are capable of forming a conversion coating on the surface of the workpiece to be formed (US Pat. Nos. 3,525,651, 2,739,915) , DE-B-21 02 295, EP-A-24 062, EP-A-25 236). The most important reaction lubricants in practice contain phosphoric acid or zinc phosphate as the component that forms the conversion coating. In the presence of phosphoric acid, the treatment of the workpieces to be reshaped essentially produces iron phosphate layers, and when using reaction phosphates containing zinc phosphate, conversion layers of zinc phosphate or zinc iron phosphate are used. The reaction lubricants, which are usually applied in dipping, produce a firmly integrated conversion coating on the surface of the workpiece, which ensures that there is a high degree of separation of the workpiece and the forming tool during the forming process takes place, on the other hand there is a firm bond of the organic lubricant 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 InKontakt -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 treatment stages for the usual preparation of workpieces, especially pipes, consist of bright annealing under protective gas at approx. 920 ° C, the subsequent pickling in hydrochloric acid or sulfuric acid and a possibly multi-stage water rinse. The subsequent processing of the workpieces, which usually follows before contact with the reaction lubricant, is carried out by drying, if appropriate after rinsing again with an alkaline solution of an anti-rust agent such as borax, soda, nitrite, phosphate or sodium hydroxide solution or mixtures thereof. Drying is necessary because 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 saurenBoth the mere drying as well as the drying with previous rinsing with rust preventive solutions is with regard to the subsequent treatment with the acidic
Reaktionsschmiermittel nachteilig. Die bloße Trocknung ist mit einem Rostbefall verbunden, der sich auf die Phosphatierbarkeit des Werkstückes nachteilig auswirkt, indem die erforderliche Dichte und Haf festigkeit 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.Reactive lubricant disadvantageous. The mere drying is associated with rust, which has an adverse effect on the phosphatability of the workpiece by the required density and adhesive strength of the phosphate layer is not guaranteed. The pre-drying rinsing with a solution of alkaline rust inhibitor is associated with a considerable introduction of salt into the acidic reaction lubricant, which on the one hand leads to considerable sludge formation and on the other hand reduces the functionality due to the constant introduction of alkaline substances. In addition, the layer formation is hindered because acidic reaction lubricants only stain the alkaline 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 to provide a method for preparing phosphatable workpieces for non-cutting cold forming using acidic reaction lubricants, which does not have the aforementioned disadvantages, in which the workpieces are introduced into the process step of treatment with the acidic reaction lubricant in a rust-free state, and in which the acidic reaction lubricant can be acted upon properly without adversely affecting it.
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 object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the workpieces are rinsed with a solution which contains lactic acid and has a pH below 3 before drying.
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 that can be phosphated for cold forming consist in particular of steel in the form of wire, tube, profiles, round blanks, etc., which are formed by drawing, cold extrusion, rolling, etc.
Durch die Spülung mit der Milchsäure enthaltenden Lösung entsteht auf der Werkstückoberfläche eine aus Eisenlactat gebildete Schicht, die durch eine violette Farbe erkennbar ist. Diese Schicht ist nicht nur rostschützend, sondern wirkt auf die Schichtbildung bei der Behandlung mit dem sauren Reaktionsschmiermittel aktivierend .By rinsing with the solution containing lactic acid, a layer formed from iron lactate is formed on the workpiece surface, which is recognizable by a violet color. This layer is not only rust-proof, it also activates the layer formation during treatment with the acidic 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.Although it is known from DE-B-2103086, workpieces after an alkaline cleaning and before phosphating with subsequent electrocoating at a temperature below 60 ° C. with an aqueous solution, the pH of which is adjusted to 4 to 5.5 with lactic acid and which contains nonionic surfactant. However, it warns of treatment in such a way that lactate layers are formed, with reference to a possible impairment in the subsequent application of the phosphate layer. As a result of the warning given in this document against a method of working that would cause the formation of a lactate layer As a result, it was in no way to be expected that such an iron lactate layer would have a positive effect not only with regard to corrosion protection, but in particular with regard to the subsequent treatment with the acidic reaction lubricant.
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 pH value can be set below 3 using lactic acid alone. For cost reasons, however, it is advisable to use phosphoric acid and / or sulfuric acid to adjust the pH. According to an advantageous embodiment of the invention, phosphoric acid is preferred since the finally applied reaction lubricant contains phosphate ions and consequently the phosphate ions derived from the phosphoric acid are unavoidably introduced with the flushing solution.
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/1 Milchsäure enthält. Obgleich auch eineAccordingly, when phosphoric acid and / or sulfuric acid are also used, a preferred embodiment of the invention provides for rinsing the workpieces with a solution which contains 1 to 50 g / 1 lactic acid. Although one too
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.Lactic acid concentration outside the preferred range leads to usable lactate layers, lactic acid concentrations in the preferred range result in lactate layers which are particularly advantageous with regard to corrosion protection and activation of the lubricating layer formation.
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 is to rinse the workpieces with a solution which contains lactic acid and phosphoric acid in a weight ratio of 1: 9 to 9: 1. This configuration is particularly advantageous taking into account both the layer quality and the cost situation.
Die Spülung mit der Milchsäure enthaltenden Lösung kann mit einer Lösungstemperatur von 20 bis 90°C erfolgen. Gemäß einer weiteren vorteilhaften Ausführungsform der Erfindung empfiehlt es sich, die Werkstücke mit einer Lösung einer Temperatur von 60 bis 80°C zu spülen.The solution containing lactic acid can be rinsed at a solution temperature of 20 to 90 ° C. According to a further advantageous embodiment of the invention, it is advisable to rinse 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.
Bei spi elAt game
Unter Schutzgas bei ca. 920°C blankgeglühte Rohre der Stahlqualität St34/2 wurden zunächst in einer Beizlösung von 50°C, enthaltendTubes 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/1 Schwefelsäure 60 g/1 Eisen II150 g / 1 sulfuric acid 60 g / 1 iron II
für die Dauer von 15 min. gebeizt und anschließend in zwei Stufen mit kaskadenartig geführtem Spülwasser gespült.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, dieThen the still wet tubes were rinsed with a solution according to the invention, the
10 g/1 Milchsäure 20 g/1 Phosphorsäure10 g / 1 lactic acid 20 g / 1 phosphoric acid
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.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 . 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.The pipes dried after rinsing showed no rust and had an iron oxide-containing lactate layer with a blue-violet appearance. The subsequent treatment with the reaction lubricant led to perfect lubricant layers. The reaction lubricant was not impaired in any way. For comparison, tubes of the same quality were subjected to the process described above, but instead of rinsing with the solution containing lactic acid, a third rinse was carried out 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 on, there was a considerable amount of rust, which was responsible for an uneven formation of phosphate layers in terms of density and adhesive strength in the subsequent treatment with the same reaction lubricant.

Claims

Patentansprüche claims
1. Verfahren zur Vorbereitung von phosphatierbaren Werkstücken für die spanlose Kaltumformung durch saures Beizen, Spülen, Trocknen und Behandeln mit sauren, Phosphationen enthaltenden Reaktionsschmiermitteln, dadurch gekennzeichnet, daß man die Werkstücke vor dem Trocknen mit einer Lösung spült, die Milchsäure enthält und einen pH- Wert unterhalb 3 aufweist.1. A process for the preparation of phosphatable workpieces for non-cutting cold forming by acid pickling, rinsing, drying and treatment with acidic reaction lubricants containing phosphate ions, characterized in that the workpieces are rinsed with a solution containing lactic acid and a pH before drying. Has a value below 3.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Werkstücke mit einer Lösung spült, die zusätzlich Phosphorsäure enthält .2. The method according to claim 1, characterized in that the workpieces are rinsed with a solution which additionally contains phosphoric acid.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man die Werkstücke mit einer Lösung spült, die 1 bis 50 g/1 Milchsäure enthält .3. The method according to claim 1 or 2, characterized in that the workpieces are rinsed with a solution containing 1 to 50 g / 1 lactic acid.
4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man die Werkstücke mit einer Lösung spült, die Milchsäure und Phosphorsäure in einem Gewichtsverhältnis von 1 : 9 bis 9 : 1 enthält.4. The method according to claim 1, 2 or 3, characterized in that the workpieces are rinsed with a solution containing lactic acid and phosphoric acid in a weight ratio of 1: 9 to 9: 1.
5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Werkstücke mit einer Lösung einer Temperatur von 60 bis 80 °C spült. 5. The method according to one or more of claims 1 to 4, characterized in that the workpieces are rinsed with a solution of 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

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

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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
TWI457432B (en) * 2008-01-30 2014-10-21 Chemetall Gmbh Process for coating metallic surface with a wax-coataining lubricant composition
TWI457431B (en) * 2008-01-30 2014-10-21 Chemetall Gmbh Process for coating a metallic surface with a 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0018983A1 *

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WO2000018983A1 (en) 2000-04-06
US6482273B1 (en) 2002-11-19
ATE218629T1 (en) 2002-06-15
ES2178504T3 (en) 2002-12-16
DE19844391C2 (en) 2003-01-09
DE59901680D1 (en) 2002-07-11
DE19844391A1 (en) 2000-04-13
EP1135543B1 (en) 2002-06-05

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