EP0232929A1 - Process for facilitating the cold-forming of stainless steel - Google Patents
Process for facilitating the cold-forming of stainless steel Download PDFInfo
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- EP0232929A1 EP0232929A1 EP87200060A EP87200060A EP0232929A1 EP 0232929 A1 EP0232929 A1 EP 0232929A1 EP 87200060 A EP87200060 A EP 87200060A EP 87200060 A EP87200060 A EP 87200060A EP 0232929 A1 EP0232929 A1 EP 0232929A1
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- Prior art keywords
- oxalate
- stainless steel
- coating
- cold
- facilitating
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- 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
- C23C22/05—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 using aqueous solutions
- C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/46—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
Definitions
- the invention relates to a method for facilitating the cold forming of stainless steel by applying an oxalate coating and then a lubricant.
- the oxalation solutions used to produce the oxalate coating contain, as the main constituent, oxalic acid, additives, such as fluoride or chloride, which cause the pickling attack, and sodium thiosulfate or the like, which act as accelerators in the nucleation in the layer.
- oxalation solution By immersing the workpiece in such an oxalation solution, an oxalate coating of a suitable layer weight can be produced, to which a lubricating layer is applied in a next operation using a metal soap solution or dispersion.
- a layer system is currently the best form of preparation of stainless steels for cold forming, provided that conventional degrees of forming are intended.
- the high-quality and highly corrosion-resistant stainless steels are particularly disadvantageous with regard to the formation of oxalate coatings, since the layer formation reaction is severely hampered when using conventional oxalation solutions.
- the content of the bath components causing the pickling attack such as fluoride or chloride, has been increased, but this has the consequence that the treatment time takes longer and the coating formation is unsatisfactory.
- the object of the invention to provide a process for facilitating the cold forming of stainless steels, can be remedied with the particular the above-mentioned problems and also results in highly corrosion-resistant stainless steels to strongly adherent coatings, so that a galling or K is altversch Droughened even in severe cold forming.
- 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 oxalate coating is applied by contact with an oxalating solution which contains.
- water-soluble polymers are polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyacrylic acid, casein, glue and the like. Polyvinyl alcohol and polyvinyl pyrrolidone are preferred.
- the concentrations of the active constituents of the oxalation solution are significant insofar as there is no sufficient reaction with the stainless steel with respect to oxalic acid below 20 g / l and no further increase in reactivity can be achieved above 100 g / l.
- the oxide film does not dissolve sufficiently from the stainless steel surface at a concentration below 5 g / l, so that the formation of the coating proceeds only with difficulty. At concentrations above 50 g / 1 there is practically no additional effect.
- water-soluble polymer do not lead to an improvement in the coating adhesion at concentrations below the lower limit, and the maximum adhesion is reached at concentrations at the upper limit.
- Metal soaps are particularly suitable as lubricants for application to the oxalate coating.
- iron soaps are formed by reaction with the oxalate coating and the soap solution.
- Calcium, barium, zinc soaps and the like dispersed in water form layers of lubricant of the corresponding soaps on the workpiece surface.
- metal soap powder of the aforementioned type the entry of the workpiece into the die.
- the oxalate coating is applied by contact with an oxalating solution which has a temperature of 70 to 100 ° C., preferably 85 to 95 ° C.
- hydroxylammonium sulfate in combination with oxalic acid is able to quickly and easily bring about a complete removal of the oxide film and also to accelerate the formation of the oxalate coating.
- oxalation solutions which additionally contain fluoride and / or chloride can also be used in the process according to the invention.
- the water-soluble polymer contained in the oxalation solution is firmly incorporated into the oxalate coating during the formation of the coating, so that it does not do so even when rinsed with water Will get removed. As a result of the installation, a high binding and adhesive effect is also achieved.
- Sodium thiosulfate is used primarily for nucleation and is therefore particularly responsible for the fine grain of the oxalate coating produced.
- lubricant was applied by treatment with a sodium stearate solution (70 g / l; 75 ° C; 3 min) before hot air drying.
- the wire rods treated and weighed with the individual oxalation solutions - as indicated above - were placed in a 5% strength by weight aqueous solution of chromic acid at 80 ° C. for a period of 15 min. submerged. The wire rods were then weighed back and the layer weights were converted into g / m 2 .
- the adhesion or abrasion resistance of the respective oxalate coatings was tested - also with wire rod.
- the individual wire rods were tested in a reproducible manner and for a certain time that was identical for all samples using an Amsler testing machine (brake pad against wheel principle).
- the friction body KIMWIPE ® from Jujo Kimberly K.K.
- the weight of the remaining oxalate coating was then determined using the aforementioned method.
- the degree of relief of the cold forming was determined with the help of the tube blankets provided with the various oxalate coatings.
- the forming was done in two stages after the stopper was pulled and further on 16 mm diameter and 1.5 mm wall thickness (cross-sectional reduction 35.2%).
- the pulling speed was 17.8 m / min.
- Pipe blanks made of Incolloy 800 (20 Cr, 32 Ni) were used as test objects. used.
- Example 1 The treatment was carried out according to the procedure of Example 1 (without soaping). The layer weights were then determined, as indicated in Example 1.
- test results show that proper oxalate coatings were formed using the oxalating process used in the invention. Although there were certain differences in the layer weight, they possessed the properties necessary for cold forming to a sufficient extent.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Erleichterung der Kaltumformung von Edelstahl durch Aufbringen eines Oxalatüberzuges und daran anschließend eines Schmiermittels.The invention relates to a method for facilitating the cold forming of stainless steel by applying an oxalate coating and then a lubricant.
Es ist bekannt, Edelstähle zur Erleichterung der Kaltumformung, z.B. durch Rohrzug oder Kaltstauchen, mit einem Oxalatüberzug und einem anschließend aufgebrachten Schmiermittel zu versehen. Die zur Erzeugung des Oxalatüberzuges eingesetzten Oxalatierungslösungen enthalten als Hauptbestandteil Oxalsäure, Zusatzstoffe, wie Fluorid oder Chlorid, die den Beizangriff bewirken, und Natriumthiosulfat oder dergl., die als Beschleuniger bei der Kristallkeimbildung in der Schicht wirken. Durch Eintauchen des Werkstückes in eine derartige Oxalatierungslösung läßt sich ein Oxalatüberzug von geeignetem Schichtgewicht erzeugen, auf den in einem nächsten Arbeitsgang mit Hilfe einer Metallseifenlösung oder -dispersion eine Schmierschicht aufgebracht wird. Ein solches Schichtsystem stellt die derzeit beste Form der Vorbereitung von Edelstählen für die Kaltumformung dar, sofern herkömmliche Umformungsgrade beabsichtigt sind.It is known to use stainless steels to facilitate cold forming, e.g. by pipe drawing or cold upsetting, with an oxalate coating and a subsequently applied lubricant. The oxalation solutions used to produce the oxalate coating contain, as the main constituent, oxalic acid, additives, such as fluoride or chloride, which cause the pickling attack, and sodium thiosulfate or the like, which act as accelerators in the nucleation in the layer. By immersing the workpiece in such an oxalation solution, an oxalate coating of a suitable layer weight can be produced, to which a lubricating layer is applied in a next operation using a metal soap solution or dispersion. Such a layer system is currently the best form of preparation of stainless steels for cold forming, provided that conventional degrees of forming are intended.
In jüngerer Zeit geht jedoch der Trend dahin, Edelstähle zunehmend schwereren Kaltumformungsgraden zu unterwerfen. Insbesondere beim Kaltstauchen sind mitunter Reduktionsgrade von 80 % und mehr erwünscht. Bei derartig hohen Umformungsgraden weisen jedoch die nach bekannten Verfahren erzeugten Oxalatüberzüge nicht mehr die erforderliche Haftung auf, so daß der Oxalatüberzug entfernt wird und es zum Anfressen oder Kaltverschweißen kommt. Die Folge ist, daß ein Austausch der Kaltumformungswerkzeuge unvermeidbar ist und ein erheblicher Teil der produzierten Artikel Ausschuß darstellt. Das bedeutet, daß sich Effizienz und Ausstoß bei der Kaltumformung verringern, was mit beträchtlichen Verlusten verbunden ist.More recently, however, there has been a trend towards subjecting stainless steels to increasingly severe degrees of cold forming. In the case of cold upsetting in particular, degrees of reduction of 80% and more are sometimes desirable. With such high degrees of deformation, however, the oxalate coatings produced by known processes no longer have that necessary liability, so that the oxalate coating is removed and there is erosion or cold welding. The result is that an exchange of the cold forming tools is inevitable and represents a significant part of the articles produced committee. This means that the efficiency and output during cold forming are reduced, which is associated with considerable losses.
Parallel zum vorgenannten Trend zu zunehmend schwereren Umformungen geht die Forderung nach Edelstählen mit immer höherer Korrosionsfestigkeit, insbesondere beim Einsatz in der chemischen Industrie. Auch bei der Gewinnung von Erdöl mit ständig tiefer reichenden Bohrlöchern, die mit der Einwirkung hochkorrosiver Gase verbunden ist, können die bislang gebräuchlichen Edelstä'hle nicht mehr eingesetzt werden. Es sind statt dessen solche mit erheblich höherem Korrosionswiderstand erforderlich. Derartige Edelstähle enthalten häufig 20 Gew.-% Nickel und mehr sowie 20 Gew.-% Chrom und mehr.In parallel with the aforementioned trend towards increasingly severe transformations, the demand for e goes delstählen with ever higher corrosion resistance, particularly when used in the chemical industry. Even in the extraction of oil with constantly deeper boreholes, which is associated with the action of highly corrosive gases, the previously used stainless steel can no longer be used. Instead, those with significantly higher corrosion resistance are required. Such stainless steels often contain 20% by weight of nickel and more and 20% by weight of chromium and more.
Gerade die hochwertigen und hochkorrosionsfesten Edelstähle verhalten sich hinsichtlich der Ausbildung von Oxalatüberzügen nachteilig, indem die Schichtbildungsreaktion bei Verwendung herkömmlicher Oxalatierungslösungen stark behindert ist. Um mit dem Problem fertig zu werden, hat man den Gehalt der den Beizangriff bewirkenden Badbestandteile, wie Fluorid oder Chlorid, erhöht, was jedoch zur Folge hat, daß die Behandlungsdauer mehr Zeit in Anspruch nimmt und die Überzugsausbildung nicht zufriedenstellend ist.The high-quality and highly corrosion-resistant stainless steels are particularly disadvantageous with regard to the formation of oxalate coatings, since the layer formation reaction is severely hampered when using conventional oxalation solutions. In order to deal with the problem, the content of the bath components causing the pickling attack, such as fluoride or chloride, has been increased, but this has the consequence that the treatment time takes longer and the coating formation is unsatisfactory.
Die vorgenannten Probleme haben dazu geführt, daß man bei der Erleichterung der Kaltumformung von Edelstählen die Technologie der Erzeugung von Konversionsüberzügen verlassen und sich statt dessen dem Studium der Bildung von nicht mit dem Grundmetall reagierenden Harzüberzügen zugewandt hat. Jedoch sind derartige Harzüberzüge bislang den Oxalatüberzügen noch immer unterlegen.The foregoing problems have resulted in abandoning conversion coating technology in facilitating cold forming of stainless steels, and instead have turned to studying the formation of resin coatings which do not react with the base metal. However, such resin coatings have so far been inferior to oxalate coatings.
Aufgabe der Erfindung ist, ein Verfahren zur Erleichterung der Kaltumformung von Edelstählen bereitzustellen, mit dem insbesondere die vorstehend angesprochenen Probleme behoben werden können und das auch bei hochkorrosionsfesten Edelstählen zu haftfesten Überzügen führt, so daß selbst bei schweren Kaltumformungen ein Anfressen oder Kaltverschweißen vermieden wird.The object of the invention to provide a process for facilitating the cold forming of stainless steels, can be remedied with the particular the above-mentioned problems and also results in highly corrosion-resistant stainless steels to strongly adherent coatings, so that a galling or K is altverschweißen avoided even in severe cold forming.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man den Oxalatüberzug durch Kontakt mit einer Oxalatierungslösung aufbringt, die
Besonders geeignete wasserlösliche Polymere sind Polyvinylalkohol, Polyvinylpyrrolidon, Polyethylenglykol, Polyacrylsäure, Kasein, Leim und dergl. Polyvinylalkohol und Polyvinylpyrrolidon sind bevorzugt.Particularly suitable water-soluble polymers are polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyacrylic acid, casein, glue and the like. Polyvinyl alcohol and polyvinyl pyrrolidone are preferred.
Die Konzentrationen der wirksamen Bestandteile der Oxalatierungslösung sind insofern bedeutend, als bezüglich Oxalsäure unterhalb 20 g/l keine ausreichende Reaktion mit dem Edelstahl erfolgt und oberhalb 100 g/1 keine weitere Steigerung der Reaktivität erzielbar ist. Hinsichtlich Hydroxylammoniumsulfat erfolgt bei einer Konzentration unterhalb 5 g/1 keine ausreichende Auflösung des Oxidfilms von der Edelstahloberfläche, so daß die Überzugsausbildung nur schwer fortschreitet. Bei Konzentrationen über 50 g/1 tritt praktisch kein zusätzlicher Effekt auf.The concentrations of the active constituents of the oxalation solution are significant insofar as there is no sufficient reaction with the stainless steel with respect to oxalic acid below 20 g / l and no further increase in reactivity can be achieved above 100 g / l. With regard to hydroxylammonium sulfate, the oxide film does not dissolve sufficiently from the stainless steel surface at a concentration below 5 g / l, so that the formation of the coating proceeds only with difficulty. At concentrations above 50 g / 1 there is practically no additional effect.
Die Gehalte an wasserlöslichem Polymer führen bei Konzentrationen unterhalb der unteren Grenze zu keiner Verbesserung der Überzugshaftung, bei Konzentrationen an der oberen Grenze ist das Maximum an Haftung erreicht.The contents of water-soluble polymer do not lead to an improvement in the coating adhesion at concentrations below the lower limit, and the maximum adhesion is reached at concentrations at the upper limit.
Bezüglich der Gehalte an Natriumthiosulfat hat sich gezeigt, daß unterhalb 0,1 g/1 praktisch keine Kristallkeimbildung auf Edelstahl erfolgt und daß oberhalb 10 g/1 starker Geruch von Schwefelverbindungen infolge Zersetzung auftritt, die mit zunehmender Badbenutzung fortschreitet.Regarding the contents of sodium thiosulfate, it has been shown that below 0.1 g / 1 there is practically no nucleation on stainless steel and that above 10 g / 1 there is a strong odor of sulfur compounds due to decomposition, which progresses with increasing use of the bath.
Als Schmiermittel zur Aufbringung auf den Oxalatüberzug sind insbesondere Metallseifen geeignet. Bei Einsatz von wäßrigen Lösungen von Natriumseifen werden durch Reaktion mit dem Oxalatüberzug und der Seifenlösung Eisenseifen gebildet. In Wasser dispergierte Kalzium-, Barium-, Zinkseifen und dergl. lassen auf der Werkstückoberfläche Schmiermittelschichten der entsprechenden Seifen entstehen. Im Falle des Kaltziehens ist es zweckmäßig, Metallseifenpulver der vorgenannten Art unmittelbar vor dem Eintritt des Werkstücks in die Matrize aufzubringen.Metal soaps are particularly suitable as lubricants for application to the oxalate coating. When using aqueous solutions of sodium soaps, iron soaps are formed by reaction with the oxalate coating and the soap solution. Calcium, barium, zinc soaps and the like dispersed in water form layers of lubricant of the corresponding soaps on the workpiece surface. In the case of cold drawing, it is advisable to immediately add metal soap powder of the aforementioned type the entry of the workpiece into the die.
Gemäß einer bevorzugten Ausgestaltung der Erfindung bringt man den Oxalatüberzug durch Kontakt mit einer Oxalatierungslösung, die eine Temperatur von 70 bis 100°C, vorzugsweise von 85 bis 95°C, aufweist, auf.According to a preferred embodiment of the invention, the oxalate coating is applied by contact with an oxalating solution which has a temperature of 70 to 100 ° C., preferably 85 to 95 ° C.
Die mit der Konzeption der Erfindung gewonnenen Erkenntnisse deuten darauf hin, daß die in Oxalatierungslösungen üblichen, den Beizangriff bewirkenden Zusätze, wie Fluorid und Chlorid, nicht in der Lage sind, die auf der Edelstahloberfläche stets befindlichen, kompliziert zusammengesetzten Oxidfilme von Chrom, Nickel und Eisen vollständig aufzulösen.. Dies ist jedoch die Voraussetzung für die Ausbildung eines einwandfrei haftenden Oxalatüberzuges.The knowledge gained with the conception of the invention indicates that the additives which cause pickling, such as fluoride and chloride, which are customary in oxalation solutions, are not able to remove the complex oxide films of chromium, nickel and iron which are always present on the stainless steel surface dissolve completely .. However, this is the prerequisite for the formation of a perfectly adhering oxalate coating.
Demgegenüber ist jedoch Hydroxylammoniumsulfat in Verbindung mit Oxalsäure imstande, schnell und einfach eine völlige Entfernung des Oxidfilmes zu bewirken und zudem die Ausbildung des Oxalatüberzuges zu beschleunigen. Dies gilt insbesondere auch bei hochkorrosionsfesten Edelstählen, deren Oxidfilm besonders resistent ist und mit Fluorid- oder Chloridzusätzen kaum entfernbar ist. Dessen ungeachtet können auch beim erfindungsgemäßen Verfahren Oxalatierungslösungen zum Einsatz kommen, die zusätzlich Fluorid und/oder Chlorid enthalten.In contrast, however, hydroxylammonium sulfate in combination with oxalic acid is able to quickly and easily bring about a complete removal of the oxide film and also to accelerate the formation of the oxalate coating. This applies in particular to highly corrosion-resistant stainless steels, whose oxide film is particularly resistant and can hardly be removed with fluoride or chloride additives. Nevertheless, oxalation solutions which additionally contain fluoride and / or chloride can also be used in the process according to the invention.
Das in der Oxalatierungslösung enthaltene wasserlösliche Polymer wird bei der Überzugsbildung in den Oxalatüberzug fest eingebaut, so daß es auch durch Wasserspülung nicht entfernt wird. Infolge des Einbaues wird zudem ein hoher Binde- und Hafteffekt erzielt.The water-soluble polymer contained in the oxalation solution is firmly incorporated into the oxalate coating during the formation of the coating, so that it does not do so even when rinsed with water Will get removed. As a result of the installation, a high binding and adhesive effect is also achieved.
Natriumthiosulfat dient primär der Keimbildung und ist damit insbesondere für die Feinkörnigkeit des erzeugten Oxalatüberzuges verantwortlich.Sodium thiosulfate is used primarily for nucleation and is therefore particularly responsible for the fine grain of the oxalate coating produced.
Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.
Es wurden folgende Oxalatierungslösungen eingesetzt:
- 1. Walzdraht der Edelstahlqualität SUS 316 mit den Abmessungen
- 2. Rohrluppen der Edelstahlqualität SUS 304 mit den Abmessungen
- Die vorgenannten Testobjekte wurden nach dem Verfahrensgang
- Reinigen (alkalischer Reiniger; 20 g/l; 80°C; 10 min) Wasserspülen
- Beizen (5 Gew.-% HN03; 5 Gew.-% HF; 60°C; 5 min) Wasserspülen
- Oxalatierung (mit den vorgenannten Lösungen; 90°C; 10 min)
- Wasserspülen
- Heißlufttrocknen
behandelt.
- 1. SUS 316 stainless steel wire rod with the dimensions
- 2. Tube blanks of stainless steel quality SUS 304 with the dimensions
- The aforementioned test objects were made after the procedure
- Clean (alkaline cleaner; 20 g / l; 80 ° C; 10 min). Rinse water
- Pickling (5% by weight HN0 3 ; 5% by weight HF; 60 ° C; 5 min) water rinsing
- Oxalation (with the aforementioned solutions; 90 ° C; 10 min)
- Rinse water
- Hot air drying
treated.
Im Falle der Rohrluppen erfolgte noch ein Schmiermittelauftrag durch Behandlung mit einer Natriumstearatlösung (70 g/l; 75°C; 3 min) vor der Heißlufttrocknung.In the case of tube blanks, lubricant was applied by treatment with a sodium stearate solution (70 g / l; 75 ° C; 3 min) before hot air drying.
Zur Ermittlung des Gewichtes des erzeugten Oxalatüberzuges wurden die mit den einzelnen-Oxalatierungslösungen - wie vorstehend angegeben - behandelten und gewogenen Walzdrähte in eine 5 Gew.-%ige wäßrige Lösung von Chromsäure von 80°C während einer Dauer von 15 min. getaucht. Dann wurden die Walzdrähte zurückgewogen und die Schichtgewichte in g/m2 umgerechnet.To determine the weight of the oxalate coating produced, the wire rods treated and weighed with the individual oxalation solutions - as indicated above - were placed in a 5% strength by weight aqueous solution of chromic acid at 80 ° C. for a period of 15 min. submerged. The wire rods were then weighed back and the layer weights were converted into g / m 2 .
Die Haftung bzw. Abriebfestigkeit der jeweiligen Oxalatüberzüge wurde - ebenfalls bei Walzdraht - geprüft. Hierzu wurden die einzelnen Walzdrähte in reproduzierbarer Weise und für eine bestimmte, für alle Proben identische Zeit mit einer Amsler-Prüfmaschine (Prinzip Bremsklotz gegen Rad) getestet. Der Reibkörper (KIMWIPE ® der Fa. Jujo Kimberly K.K.) war mit Aceton getränkt. Anschließend erfolgte die Ermittlung des Gewichtes des verbliebenen Oxalatüberzuges nach der vorgenannten Methode.The adhesion or abrasion resistance of the respective oxalate coatings was tested - also with wire rod. For this purpose, the individual wire rods were tested in a reproducible manner and for a certain time that was identical for all samples using an Amsler testing machine (brake pad against wheel principle). The friction body (KIMWIPE ® from Jujo Kimberly K.K.) was soaked in acetone. The weight of the remaining oxalate coating was then determined using the aforementioned method.
Der Grad der Erleichterung der Kaltumformung wurde mit Hilfe der mit den verschiedenen Oxalatüberzügen versehenen Rohrluppen ermittelt. Die Umformung erfolgte nach dem Stopfenzug in zwei Stufen
auf 16 mm Durchmesser und 1,5 mm Wandstärke (Querschnittsreduktion 35,2 %).The degree of relief of the cold forming was determined with the help of the tube blankets provided with the various oxalate coatings. The forming was done in two stages after the stopper was pulled
on 16 mm diameter and 1.5 mm wall thickness (cross-sectional reduction 35.2%).
Die Ziehgeschwindigkeit lag bei 17,8 m/min.The pulling speed was 17.8 m / min.
Die jeweiligen Testergebnisse sind nachfolgend zusammengestellt.
Die innerhalb des erfindungsgemäßen Verfahrens eingesetzten Oxalatierungslösungen führten beim Haftungstest in allen Fällen zu Restüberzugsgewichten von mehr als 2 g/m2, wodurch die überlegene Haftung gegenüber herkömmlichen, gemäß Vergleich geprüften Oxalatierungslösungen nachgewiesen ist.The oxalation solutions used in the process according to the invention in all cases led to residual coating weights of more than 2 g / m 2 in the adhesion test, which demonstrates the superior adhesion compared to conventional oxalation solutions tested according to comparison.
Im Ziehtest an Rohrluppen zeigten sich bei Anwendung des erfindungsgemäßen Verfahrens keinerlei Anfressen oder Kaltverschweißen, wohingegen im Vergleichsversuch in der zweiten Ziehstufe an der inneren Rohroberfläche Anfreßerscheinungen festzustellen waren.In the drawing test on tube blanks, no seizure or cold welding was found when using the method according to the invention, whereas in the comparative experiment in the second drawing step, signs of seizure were found on the inner tube surface.
Zur Erzeugung der Oxalatüberzüge dienten wiederum die Oxalatierungslösungen gemäß Beispiel 1.The oxalation solutions according to Example 1 were again used to produce the oxalate coatings.
Als Testobjekte wurden Rohrluppen aus Incolloy 800 (20 Cr, 32 Ni)
Die Behandlung erfolgte nach dem Verfahrensgang des Beispiels 1 (ohne Beseifung). Anschließend wurden - wie im Beispiel 1 angegeben - die Schichtgewichte bestimmt.
Die Testergebnisse zeigen, daß mit Hilfe des innerhalb der Erfindung eingesetzten Oxalatierverfahrens einwandfreie Oxalatüberzüge gebildet wurden. Obgleich sie hinsichtlich des Schichtgewichtes gewisse Unterschiede aufwiesen, besaßen sie die für die Kaltumformung notwendigen Eigenschaften in ausreichendem Maße.The test results show that proper oxalate coatings were formed using the oxalating process used in the invention. Although there were certain differences in the layer weight, they possessed the properties necessary for cold forming to a sufficient extent.
Demgegenüber wurden mit den beim Vergleich eingesetzten Oxalatierungslösungen keine Oxalatüberzüge ausgebildet.In contrast, no oxalate coatings were formed with the oxalation solutions used in the comparison.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87200060T ATE51423T1 (en) | 1986-01-21 | 1987-01-16 | PROCESSES TO FACILITATE THE COLD FORMING OF STAINLESS STEEL. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61010752A JPS62170484A (en) | 1986-01-21 | 1986-01-21 | Method for lubricating stainless steel before cold working |
| JP10752/86 | 1986-01-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0232929A1 true EP0232929A1 (en) | 1987-08-19 |
| EP0232929B1 EP0232929B1 (en) | 1990-03-28 |
Family
ID=11759045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87200060A Expired - Lifetime EP0232929B1 (en) | 1986-01-21 | 1987-01-16 | Process for facilitating the cold-forming of stainless steel |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0232929B1 (en) |
| JP (1) | JPS62170484A (en) |
| AT (1) | ATE51423T1 (en) |
| DE (2) | DE3700933A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020165035A1 (en) * | 2019-02-14 | 2020-08-20 | Chemetall Gmbh | Simplified method for pretreating metal substrates for cold forming and reactive lubricant therefor |
| WO2021170707A1 (en) | 2020-02-25 | 2021-09-02 | Chemetall Gmbh | One-step pretreatment method of metallic substrates for metal cold forming |
| WO2021170706A1 (en) | 2020-02-25 | 2021-09-02 | Chemetall Gmbh | One-step pretreatment method of metallic substrates for metal cold forming |
| WO2022207901A1 (en) | 2021-04-01 | 2022-10-06 | Chemetall Gmbh | One-step pretreatment method of metallic substrates at non-neutral ph values for metal cold forming |
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| JP2002088387A (en) * | 2000-09-14 | 2002-03-27 | Sakai Chem Ind Co Ltd | Metal processing using lubricant composition not containing chlorine |
| ITMN20060021A1 (en) * | 2006-03-23 | 2007-09-24 | Gilcotubi S R L | PRODUCTION SYSTEM FOR STAINLESS AND WELDABLE TUBULAR STRUCTURES WITH HIGH MECHANICAL RESISTANCE AND ITS PRODUCT OBTAINED |
| US11607929B2 (en) | 2018-08-09 | 2023-03-21 | Hanon Systems | Thermal cycle resistant fastening system for refrigerant fitting |
| CN111500955B (en) * | 2020-04-17 | 2021-08-24 | 抚顺特殊钢股份有限公司 | Manufacturing process of N06625 alloy profiled bar for nuclear power evaporator |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2759862A (en) * | 1952-03-11 | 1956-08-21 | Devex Corp | Coating compositions and method of treating ferrous surfaces therewith |
| CA930651A (en) * | 1971-01-12 | 1973-07-24 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Energy, Mines, And Resources | Forming oxalate conversion coatings on iron or steel |
| US3860434A (en) * | 1972-08-26 | 1975-01-14 | Oxy Metal Finishing Corp | Alloyed steel treatment with protein containing composition |
| FR2272192A1 (en) * | 1974-05-20 | 1975-12-19 | Parker Ste Continentale | Lubricating support layer formation - improving cold forming methods, prodn. and tool life |
-
1986
- 1986-01-21 JP JP61010752A patent/JPS62170484A/en active Granted
-
1987
- 1987-01-15 DE DE19873700933 patent/DE3700933A1/en not_active Withdrawn
- 1987-01-16 AT AT87200060T patent/ATE51423T1/en not_active IP Right Cessation
- 1987-01-16 EP EP87200060A patent/EP0232929B1/en not_active Expired - Lifetime
- 1987-01-16 DE DE8787200060T patent/DE3762053D1/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2759862A (en) * | 1952-03-11 | 1956-08-21 | Devex Corp | Coating compositions and method of treating ferrous surfaces therewith |
| CA930651A (en) * | 1971-01-12 | 1973-07-24 | Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Energy, Mines, And Resources | Forming oxalate conversion coatings on iron or steel |
| US3860434A (en) * | 1972-08-26 | 1975-01-14 | Oxy Metal Finishing Corp | Alloyed steel treatment with protein containing composition |
| FR2272192A1 (en) * | 1974-05-20 | 1975-12-19 | Parker Ste Continentale | Lubricating support layer formation - improving cold forming methods, prodn. and tool life |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN, Band 5, Nr. 136 (C-69)[808], 28. August 1981; & JP-A-56 72090 (NIPPON PARKERIZING K.K.) 16.06.1981 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020165035A1 (en) * | 2019-02-14 | 2020-08-20 | Chemetall Gmbh | Simplified method for pretreating metal substrates for cold forming and reactive lubricant therefor |
| CN113454196A (en) * | 2019-02-14 | 2021-09-28 | 凯密特尔有限责任公司 | Simplified method for pretreating metal substrates for cold forming and reactive lubricant for this purpose |
| US20220119730A1 (en) * | 2019-02-14 | 2022-04-21 | Chemetall Gmbh | Simplified method for pretreating metal substrates for cold forming and reactive lubricant therefor |
| WO2021170707A1 (en) | 2020-02-25 | 2021-09-02 | Chemetall Gmbh | One-step pretreatment method of metallic substrates for metal cold forming |
| WO2021170706A1 (en) | 2020-02-25 | 2021-09-02 | Chemetall Gmbh | One-step pretreatment method of metallic substrates for metal cold forming |
| WO2022207901A1 (en) | 2021-04-01 | 2022-10-06 | Chemetall Gmbh | One-step pretreatment method of metallic substrates at non-neutral ph values for metal cold forming |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0129872B2 (en) | 1989-06-14 |
| DE3700933A1 (en) | 1987-07-30 |
| EP0232929B1 (en) | 1990-03-28 |
| JPS62170484A (en) | 1987-07-27 |
| DE3762053D1 (en) | 1990-05-03 |
| ATE51423T1 (en) | 1990-04-15 |
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