EP3134497A1 - Metal sheet and method for improving the deformability of a metal sheet - Google Patents

Metal sheet and method for improving the deformability of a metal sheet

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Publication number
EP3134497A1
EP3134497A1 EP15719678.3A EP15719678A EP3134497A1 EP 3134497 A1 EP3134497 A1 EP 3134497A1 EP 15719678 A EP15719678 A EP 15719678A EP 3134497 A1 EP3134497 A1 EP 3134497A1
Authority
EP
European Patent Office
Prior art keywords
sheet
polyvinyl alcohol
coating
aqueous solution
metal sheet
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
EP15719678.3A
Other languages
German (de)
French (fr)
Other versions
EP3134497B1 (en
Inventor
Ronald Fluch
Bernhard Strauss
Andreas Muhr
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.)
Voestalpine Stahl GmbH
Original Assignee
Voestalpine Stahl GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Voestalpine Stahl GmbH filed Critical Voestalpine Stahl GmbH
Publication of EP3134497A1 publication Critical patent/EP3134497A1/en
Application granted granted Critical
Publication of EP3134497B1 publication Critical patent/EP3134497B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • B21D22/201—Work-pieces; preparation of the work-pieces, e.g. lubricating, coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel

Definitions

  • the invention relates to a sheet and a method for improving the formability of a sheet, in which prior to forming the sheet, an aqueous solution with polyvinyl alcohol is applied to the sheet and then dried and in a subsequent step, the coated sheet surface is oiled.
  • DE69906555T2 discloses treating the sheet with an aqueous solution containing zinc and sulfate ions before applying the oil film. Subsequently, the applied solution is dried, which produces a layer with a basis zinchydroxysulfate on the sheet, which layer unfolds a lubricating effect during forming together with an overlying oil film and thus improves the tribological properties of the sheet.
  • This forming aid is relatively difficult to remove from the sheet and thus adverse effects in subsequent processing steps of the sheet are unavoidable.
  • such forming aids show adverse effects during welding as well as during the bonding of a formed sheet.
  • the invention has therefore, starting from the above-described prior art, the task of providing a method for improving the formability of a sheet, which can easily, easily and reproducibly produce a uniform coating.
  • this coating should be easily removable for subsequent process steps.
  • the invention achieves this object by applying and drying an aqueous solution comprising polyvinyl alcohol, optionally a defoamer, optionally a tracer and the remainder of water, as well as unavoidable production-related impurities, to the sheet.
  • PVA polyvinyl alcohol
  • the handling of the process can be further simplified if the solution optionally has a defoamer, preferably n-octanol.
  • a hydrophobization of the surface of the sheet can be made possible by adding n-octanol in order to increase the corrosion resistance.
  • this composition may also have a tracer in order to be able to easily recognize the coating according to the invention on the metal sheet, for example by metrological means.
  • a tensile pressure forming preferably a deep drawing or drawing and deep drawing
  • a thixotropic oil can be distinguished for oiling.
  • substances or chemical elements used to detect the presence of certain components and / or their amounts commonly referred to as "tracers”. These substances can, for example, emit fluorescence radiation when irradiated with visible light or with ultraviolet radiation and are known for various technical fields of use.
  • the composition can have impurities with in each case not more than 0.05% by weight and not more than 1% by weight in total.
  • polyvinyl alcohol and steel materials can form a particularly strong cohesive connection with a uniform layer thickness.
  • the method according to the invention can be distinguished in the case of a protective-coated sheet, if the aqueous solution is applied to the protective coating with polyvinyl alcohol and dried.
  • this compound forms a particularly stable compound with uniform surface distribution with polyvinyl alcohol, which can ensure complete wetting of the sheet surface with oil.
  • the method can thus reproducibly produce sheets with relatively high tribological properties.
  • High layer thicknesses can be reliably produced if the solution has polyvinyl alcohol up to the solubility limit in water. Among other things, this can avoid that the uniformity of the coating is impaired by disruptive flocculation of polyvinyl alcohol.
  • Comparable simple parameters to be observed for the formation of the solution may result if this solution has 0.5 to 15 wt .-% polyvinyl alcohol.
  • this can result in a sufficiently high tribological property in order to reliably fulfill tight process parameters during forming.
  • this may already be sufficient for a solution with 0.9 to 8 wt .-%, polyvinyl alcohol.
  • aqueous solution with a wet film thickness of 0.1 to 10 ⁇ applied to the plate this may be the uniformity of the layer thickness conducive. Especially a wet film thickness with 1 to 5 ⁇ can lead to improved tribological properties.
  • aqueous solution has partially hydrolyzed polyvinyl alcohol having a degree of hydrolysis of from 72 to 97 mol%, this can further simplify the process and thus further increase its reproducibility.
  • fully hydrolyzed polyvinyl alcohol having a degree of hydrolysis greater than 97 mol% may additionally show improved tribological properties, as a result of which, for example, the amount of polyvinyl alcohol required can be reduced.
  • the formability of the sheet can be further improved if the sheet is surface-coated with 0.5 to 3 g / m A 2 oil.
  • mineral oil preferably a thixotropic oil, may be distinguished for this purpose.
  • n-octanol can be used as defoamer.
  • the invention has also set itself the task of creating a sheet with a forming aid, with which a comparatively narrow process window can be adhered to during forming.
  • the invention achieves the stated object with regard to the sheet in that the coating consists of polyvinyl alcohol, optionally a tracer and production-related unavoidable impurities.
  • the sheet can be coated with a have the same high tribological property to ensure adequate lubrication even at high forming forces.
  • the layer of polyvinyl alcohol ensures that the sheet is heavily wetted with oil, which can prevent film breakage during forming.
  • the sheet metal can thus steadfastly follow even the tight radii of the forming tools and even adhere to narrow process windows during forming, which can occur especially with thin sheets.
  • the layer with polyvinyl alcohol is relatively easy to remove, for example by means of an alkaline cleaning process, and also leads in known cohesive compounds to no adverse effects, especially since polyvinyl alcohol is known from the prior art in adhesive bonds as a primer.
  • polyvinyl alcohol oxidizes without residue during welding or soldering processes and can therefore not adversely affect such compounds, which the invention can distinguish from multicomponent systems in comparison to the prior art.
  • even thin coatings can be measured using the optional tracer.
  • the sheet consists of a steel material, the connection of the coating with polyvinyl alcohol can be facilitated - and thus the deformation behavior of the steel sheet can be further improved.
  • the sheet has a protective coating, in particular based on Zn, to which protective coating the coating with polyvinyl alcohol adjoins, synergy effects between protective coating and polyvinyl alcohol can be used to improve their cohesive connection and thus the forming behavior of the sheet can be further improved.
  • a sufficient improvement in the forming behavior of the sheet can be shown when the coating with polyvinyl alcohol has a coating weight of at least 0.5 mg / m A 2, in particular at least 10 mg / m A 2
  • the properties of the sheet with regard to its formability can be further improved if the film with polyvinyl alcohol is followed by an oil film with a layer weight of 0.5 to 3 g / m A 2.
  • mineral oil preferably a thixotropic oil, may be distinguished for this purpose.
  • the invention may be distinguished when an aqueous solution which comprises polyvinyl alcohol, optionally a defoamer, optionally a tracer and the remainder of water and inevitable impurities due to its production, is used to coat an oil-free sheet to improve the formability of the sheet which has been oiled after coating.
  • an aqueous solution which comprises polyvinyl alcohol, optionally a defoamer, optionally a tracer and the remainder of water and inevitable impurities due to its production, is used to coat an oil-free sheet to improve the formability of the sheet which has been oiled after coating.
  • the aqueous solution is extremely stable due to the small number of components and thus can allow a reproducible coating.
  • this can be of particular importance for steel sheets - especially for sheets with a protective coating preferably Zn-based.
  • Fig. 1 is an enlarged fragmentary sectional view of a coated sheet and Fig. 2 is a comparative diagram of different coated thin sheets.
  • inventive sheet 1 sheet B and C
  • thin sheet A on the protective coating 2 which has a Zn base
  • a full-surface covering coating 3 of polyvinyl alcohol A full surface covering RP4107S oil film 4 made of mineral oil is then applied to this coating 3 in order to increase, for example, the corrosion resistance of the metal sheet 1 as well.
  • the sliding friction coefficients ⁇ were then measured according to the standard ISO 15359, namely over several tests n on the same sheet A, B and C, which can be seen in FIG. Table 2 shows the sliding friction coefficients ⁇ which are averaged over several tests n on the same sheet A, B and C respectively.
  • Table 1 shows the sliding friction coefficients ⁇ which are averaged over several tests n on the same sheet A, B and C respectively.
  • the coating 3 according to the invention of polyvinyl alcohol in the thin sheets B and C leads to no deterioration of the sliding friction coefficient ⁇ over the number of tests n. According to the invention, however, the thin sheets B and C can still guarantee low sliding friction coefficients ⁇ even in the last attempt. The coating 3 can therefore steadfast ensure a particularly low coefficient of sliding friction ⁇ .
  • FIG. 2 it can be seen from FIG. 2 that with fully hydrolyzed polyvinyl alcohol having a degree of hydrolysis greater than 97 mol% in the aqueous solution, a small proportion is sufficient in comparison with the solution of thin sheet B to ensure improved tribological properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Lubricants (AREA)

Abstract

A metal sheet (1) and a method for improving the deformability of a metal sheet (1) are shown, in which method, prior to the deformation of the metal sheet (1), an aqueous solution comprising polyvinyl alcohol is applied to the metal sheet (1) and is then dried and, in a subsequent step, the thus coated metal sheet surface is oiled. In order to be able to reproducibly create an especially advantageous deformable metal sheet (1), it is proposed that an aqueous solution comprising polyvinyl alcohol, optionally a defoaming agent, optionally a tracer, and the rest water and unavoidable contaminants of the manufacturing process, by applied and dried on the metal sheet (1).

Description

Blech und Verfahren zur Verbesserung der Umformbarkeit eines Blechs  Sheet metal and method for improving the formability of a sheet
Technisches Gebiet Technical area
Die Erfindung betrifft ein Blech und ein Verfahren zur Verbesserung der Umformbarkeit eines Blechs, bei dem vor dem Umformen des Blechs eine wässrige Lösung mit Polyvinylalkohol auf das Blech aufgebracht und danach getrocknet wird und in einem nachfolgenden Schritt die damit beschichtete Blechoberfläche geölt wird. The invention relates to a sheet and a method for improving the formability of a sheet, in which prior to forming the sheet, an aqueous solution with polyvinyl alcohol is applied to the sheet and then dried and in a subsequent step, the coated sheet surface is oiled.
Stand der Technik State of the art
Diverse Umformhilfen für schutzbeschichtete Bleche sind aus dem Stand der Technik bekannt - beispielsweise ein Ölfilm am Blech. Various forming aids for protective coated sheets are known from the prior art - for example, an oil film on the sheet.
Zur Weiterbildung dieser Umformhilfe offenbart die DE69906555T2, das Blech vor dem Auftragen des Ölfilms mit einer wässrigen Lösung zu behandeln, die Zink- und Sulfationen enthält. Anschließend wird die aufgetragene Lösung getrocknet, was auf dem Blech eine Schicht mit einer Zinkhydroxysulfat Basis erzeugt, welche Schicht beim Umformen gemeinsam mit einem darüber liegenden Ölfilm eine schmierende Wirkung entfaltet und so die tribologischen Eigenschaften des Blechs verbessert. Nachteilig ist jedoch, dass diese Umformhilfe vergleichsweise schwer vom Blech zu entfernbar ist und damit nachteilige Effekte bei nachfolgenden Verarbeitungsschritten des Blechs nicht zu vermeiden sind. Zudem zeigen derartige Umformhilfen nachteilige Effekte beim Schweißen als auch beim Verkleben eines umgeformten Blechs. Zudem ist aus dem Stand der Technik bekannt (US6455476B1 ), vor einem Umformen eines Blechs eine wässrige Lösung mit Polyvinylalkohol, organische Salze und einem Schmiermittel aufzubringen, was nach einer Trocknung eine feste Schmier- stoffbeschichtung ausbildet. Nachteilig bedarf diese wässrige Lösung mit Ihrer Vielzahl an Komponenten einer besonderen Handhabung, insbesondere um eine ausreichende Anbindung des Polyvinylalkohols an der Metalloberfläche sicherzustellen. For further development of this forming aid, DE69906555T2 discloses treating the sheet with an aqueous solution containing zinc and sulfate ions before applying the oil film. Subsequently, the applied solution is dried, which produces a layer with a basis zinchydroxysulfate on the sheet, which layer unfolds a lubricating effect during forming together with an overlying oil film and thus improves the tribological properties of the sheet. The disadvantage, however, is that this forming aid is relatively difficult to remove from the sheet and thus adverse effects in subsequent processing steps of the sheet are unavoidable. In addition, such forming aids show adverse effects during welding as well as during the bonding of a formed sheet. In addition, it is known from the prior art (US Pat. No. 6,454,476 B1) to apply an aqueous solution with polyvinyl alcohol, organic salts and a lubricant before forming a sheet, which after drying forms a solid lubricant coating. Disadvantageously, this aqueous solution with its multitude of components requires special handling, in particular in order to ensure a sufficient binding of the polyvinyl alcohol to the metal surface.
Darstellung der Erfindung Presentation of the invention
Die Erfindung hat sich daher ausgehend vom eingangs geschilderten Stand der Technik die Aufgabe gestellt, ein Verfahren zur Verbesserung der Umformbarkeit eines Blechs zu schaffen, das einfach, unkompliziert anwendbar und reproduzierbar eine gleichmäßige Beschichtung erzeugen kann. Zudem soll diese Beschichtung für nachfolgende Verfahrensschritte leicht entfernbar sein. The invention has therefore, starting from the above-described prior art, the task of providing a method for improving the formability of a sheet, which can easily, easily and reproducibly produce a uniform coating. In addition, this coating should be easily removable for subsequent process steps.
Die Erfindung löst die gestellte Aufgabe dadurch, dass auf das Blech eine wässrige Lösung, die Polyvinylalkohol, optional einen Entschäumer, optional einen Tracer und als Rest Wasser sowie herstellungsbedingt unvermeidbare Verunreinigungen aufweist, aufgebracht und getrocknet wird. The invention achieves this object by applying and drying an aqueous solution comprising polyvinyl alcohol, optionally a defoamer, optionally a tracer and the remainder of water, as well as unavoidable production-related impurities, to the sheet.
Wird auf das Blech eine wässrige Lösung mit Polyvinylalkohol und als Rest Wasser sowie herstellungsbedingt unvermeidbare Verunreinigungen aufgebracht und danach getrocknet, kann zunächst auf verfahrenstechnische Weise reproduzierbar eine besonders gleichmäßige Schicht auf dem Blech erzeugt werden. Überraschend stellte sich zudem heraus, dass sich in Kombination mit einem nach dem Trocknen der Schicht aufgebrachten Ölfilm die tribologischen Eigenschaften des Blechs erheblich verbessern - und das obwohl keine weiteren Komponenten zum Erreichen dieser tribologischen Eigenschaften in der wässrigen Lösung vorgeschlagen werden, wie dies im Stand der Technik der Fall ist. Da außerdem durch ein Missen die- ser weiteren Komponenten die erfindungsgemäße Lösung äußerst stabil ist, kann das Verfahren auch besonders reproduzierbar durchgeführt werden. If an aqueous solution with polyvinyl alcohol and the remainder of water and, as a result of the preparation, unavoidable impurities are applied to the sheet and then dried, a particularly uniform layer can be reproducibly produced on the sheet in a procedural manner. Surprisingly, it has also been found that, in combination with an oil film applied after the drying of the layer, the tribological properties of the sheet improve considerably - even though no further components for achieving these tribological properties in the aqueous solution are proposed, as was the case in the prior art Technique is the case. In addition, because of a lack of the further components of the invention, the solution is extremely stable, the method can also be carried out particularly reproducible.
Daher konnte selbst unter Umformbedingungen hoher Kontaktbeanspruchung ausreichend den auftretenden Schädigungsmechanismen entgegengewirkt und zugleich für auch ausreichende Reibbedingungen zum Erreichen einer hohen Prozessqualität gesorgt werden. Dies führte dazu, dass selbst enge Prozessfenster vom erfindungsgemäß beschichteten Blech eingehalten werden konnten. Außerdem konnte festgestellt werden, dass nachträglich aufgebrachte Öl besonders gut an der Beschichtung mit Polyvinylalkohol haftet, sodass reproduzierbar ein für ein Umformen vorbereitetes Blech geschaffen werden kann, was selbst lange Lagerzeiten standhält. Zudem ist die Beschichtung mit einer wässrigen Lösung, enthaltend Polyvinylalkohol (PVA), vergleichsweise unkompliziert und einfach handhabbar, was das erfindungsgemäße Verfahren vereinfacht und damit die Herstellungskosten des derart für das Umformen vorbehandelten Blechs reduziert - zumal für dieses erfindungsgemäße Verfahren keine besonderen Maßnahmen zur Gefahrenreduktion notwendig, was dieses ohne besondere Umweltauflagen unkompliziert anwendbar und damit kostengünstig macht. Therefore, even under forming conditions of high contact stress, it was possible to sufficiently counteract the damage mechanisms that occur and at the same time ensure sufficient friction conditions to achieve a high process quality. As a result, even narrow process windows of the sheet coated according to the invention could be maintained. In addition, it was found that subsequently applied oil adheres particularly well to the coating with polyvinyl alcohol, so that reproducibly prepared for forming a metal sheet can be created, which withstands even long storage times. In addition, the coating with an aqueous solution containing polyvinyl alcohol (PVA), comparatively straightforward and easy to handle, which simplifies the inventive method and thus reduces the cost of the thus pretreated for forming sheet metal - especially since no special measures for risk reduction necessary for this inventive method , which makes this uncomplicated and thus inexpensive without special environmental requirements.
Die Handhabung des Verfahrens kann weiter vereinfacht werden, wenn die Lösung optional einen Entschäumer, vorzugsweise n-Octanol, aufweist. Neben der entschäumenden Wirkung kann durch Zugabe von n-Octanol eine Hydrophobierung der Oberfläche des Blechs ermöglicht werden, um damit die Korrosionsbeständigkeit zu erhöhen.  The handling of the process can be further simplified if the solution optionally has a defoamer, preferably n-octanol. In addition to the defoaming effect, a hydrophobization of the surface of the sheet can be made possible by adding n-octanol in order to increase the corrosion resistance.
Optional kann diese Zusammensetzung auch noch einen Tracer aufweisen, um die erfindungsgemäße Beschichtung am Blech einfach erkennen zu können, beispielsweise mit messtechnischen Mitteln.  Optionally, this composition may also have a tracer in order to be able to easily recognize the coating according to the invention on the metal sheet, for example by metrological means.
Im Allgemeinen wird erwähnt, dass unter Umformen insbesondere ein Zugdruckumformen, vorzugsweise ein Tiefziehen bzw. Streck und Tiefziehen, verstanden werden kann, was beispielsweise zur Herstellung von Karosserieteilen Anwendung finden kann. Weiter wird im Allgemeinen erwähnt, dass sich zum Beölen ein thixotro- pes Öl auszeichnen kann. Zudem wird im Allgemeinen erwähnt, dass Substanzen bzw. chemische Elemente, die eingesetzt werden, um die Anwesenheit bestimmter Komponenten und/oder deren Mengen zu erkennen, üblicherweise als "Tracer" bezeichnet werden. Diese Substanzen können beispielsweise beim Bestrahlen mit sichtbarem Licht oder mit ultravioletter Strahlung eine Fluoreszenzstrahlung aussenden und sind für unterschiedliche technische Einsatzgebiete bekannt. Im Allgemeinen wird weiter erwähnt, dass die Zusammensetzung Verunreinigungen mit jeweils maximal 0,05 Gew.-% und gesamt höchstens 1 Gew.-% aufweisen kann. In general, it is mentioned that under reshaping in particular a tensile pressure forming, preferably a deep drawing or drawing and deep drawing, can be understood, which can be used, for example, for the production of body parts. Furthermore, it is generally mentioned that a thixotropic oil can be distinguished for oiling. In addition, it is generally mentioned that substances or chemical elements used to detect the presence of certain components and / or their amounts, commonly referred to as "tracers". These substances can, for example, emit fluorescence radiation when irradiated with visible light or with ultraviolet radiation and are known for various technical fields of use. In general, it is further mentioned that the composition can have impurities with in each case not more than 0.05% by weight and not more than 1% by weight in total.
Wird auf ein aus einem Stahlwerkstoff bestehendes Blech die wässrige Lösung mit Polyvinylalkohol aufgebracht und getrocknet, kann dies das Verfahren in der Handhabung erleichtern. Polyvinylalkohol und Stahlwerkstoffe können nämlich eine besonders feste stoffschlüssige Verbindung mit gleichmäßiger Schichtdicke ausbilden. If the aqueous solution with polyvinyl alcohol is applied and dried on a sheet consisting of a steel material, this can make the process easier to handle. Namely, polyvinyl alcohol and steel materials can form a particularly strong cohesive connection with a uniform layer thickness.
Besonders kann sich das erfindungsgemäße Verfahren bei einem schutzbeschichteten Blech auszeichnen, wenn auf dessen Schutzbeschichtung die wässrige Lösung mit Polyvinylalkohol aufgebracht und getrocknet wird. Vorzugsweise bei Schutzbeschichtung auf Zn-Basis geht diese mit Polyvinylalkohol eine besonders standfeste Verbindung mit gleichmäßiger Oberflächenverteilung ein, was eine vollständige Benetzung der Blechoberfläche mit Öl sicherstellen kann. Das Verfahren kann damit Bleche mit vergleichsweise hohen tribologischen Eigenschaften reproduzierbar erzeugen. In particular, the method according to the invention can be distinguished in the case of a protective-coated sheet, if the aqueous solution is applied to the protective coating with polyvinyl alcohol and dried. Preferably, with Zn-based protective coating, this compound forms a particularly stable compound with uniform surface distribution with polyvinyl alcohol, which can ensure complete wetting of the sheet surface with oil. The method can thus reproducibly produce sheets with relatively high tribological properties.
Hohe Schichtdicken können verlässlich erzeugt werden, wenn die Lösung Polyvinylalkohol bis zur Löslichkeitsgrenze in Wasser aufweist. Dies kann unter anderem vermeiden, dass die Gleichmäßigkeit der Beschichtung durch störende Ausflockungen von Polyvinylalkohol beeinträchtigt wird. High layer thicknesses can be reliably produced if the solution has polyvinyl alcohol up to the solubility limit in water. Among other things, this can avoid that the uniformity of the coating is impaired by disruptive flocculation of polyvinyl alcohol.
Vergleichsweise einfache einzuhaltende Parameter zur Ausbildung der Lösung können sich ergeben, wenn diese Lösung 0,5 bis 15 Gew.-% Polyvinylalkohol aufweist. Zudem kann sich damit eine ausreichend hohe tribologische Eigenschaft ergeben, um enge Prozessparameter beim Umformen verlässlich erfüllen zu können. Optional kann hierfür bereits eine Lösung mit 0,9 bis 8 Gew.-%, Polyvinylalkohol ausreichen. Comparable simple parameters to be observed for the formation of the solution may result if this solution has 0.5 to 15 wt .-% polyvinyl alcohol. In addition, this can result in a sufficiently high tribological property in order to reliably fulfill tight process parameters during forming. Optionally, this may already be sufficient for a solution with 0.9 to 8 wt .-%, polyvinyl alcohol.
Wird die wässrige Lösung mit einer Nassfilmdicke von 0,1 bis 10 μηπ auf das Blech aufgebracht, kann dies der Gleichmäßigkeit der Schichtdicke förderlich sein. Besonders eine Nassfilmdicke mit 1 bis 5 μηπ kann zu verbesserten tribologischen Eigenschaften führen. If the aqueous solution with a wet film thickness of 0.1 to 10 μηπ applied to the plate, this may be the uniformity of the layer thickness conducive. Especially a wet film thickness with 1 to 5 μηπ can lead to improved tribological properties.
Weist die wässrige Lösung teilhydrolysierten Polyvinylalkohol mit einem Hydrolysegrad von 72 bis 97 Mol.-% auf, kann dies das Verfahren weiter vereinfachen und damit dessen Reproduzierbarkeit weiter erhöhen. Insbesondere vollhydrolysierter Polyvinylalkohol mit einem Hydrolysegrad größer 97 Mol.-% kann zusätzlich verbesserte tribologische Eigenschaften zeigen, wodurch beispielsweise die Menge an benötigtem Polyvinylalkohol reduziert werden kann. If the aqueous solution has partially hydrolyzed polyvinyl alcohol having a degree of hydrolysis of from 72 to 97 mol%, this can further simplify the process and thus further increase its reproducibility. In particular, fully hydrolyzed polyvinyl alcohol having a degree of hydrolysis greater than 97 mol% may additionally show improved tribological properties, as a result of which, for example, the amount of polyvinyl alcohol required can be reduced.
Die Umformbarkeit des Blechs kann sich weiter verbessern, wenn das Blech mit 0,5 bis 3 g/mA2 Öl oberflächenbeschichtet wird. Insbesondere Mineralöl, vorzugsweise ein thixotropes Öl, kann sich hierfür auszeichnen. The formability of the sheet can be further improved if the sheet is surface-coated with 0.5 to 3 g / m A 2 oil. In particular, mineral oil, preferably a thixotropic oil, may be distinguished for this purpose.
Vorzugsweise kann n-Octanol als Entschäumer verwendet werden. Preferably, n-octanol can be used as defoamer.
Die Erfindung hat sich zudem die Aufgabe gestellt, ein Blech mit einer Umformhilfe zu schaffen, mit dem ein vergleichsweise enges Prozessfenster beim Umformen eingehalten werden kann. The invention has also set itself the task of creating a sheet with a forming aid, with which a comparatively narrow process window can be adhered to during forming.
Die Erfindung löst die gestellte Aufgabe hinsichtlich des Blechs dadurch, dass die Beschichtung aus Polyvinylalkohol, optional einen Tracer sowie herstellungsbedingt unvermeidbare Verunreinigungen besteht. The invention achieves the stated object with regard to the sheet in that the coating consists of polyvinyl alcohol, optionally a tracer and production-related unavoidable impurities.
Besteht die Beschichtung aus Polyvinylalkohol, optional einen Tracer sowie herstellungsbedingt unvermeidbare Verunreinigungen, kann das Blech mit einer ver- gleichsweise hohen tribologischen Eigenschaft versehen werden, um selbst bei hohen Umformkräften eine ausreichende Schmierung sicherzustellen. Die Schicht mit Polyvinylalkohol sorgt nämlich für eine starke Benetzung des Blechs mit Öl, was einen Filmabriss beim Umformen vermeiden kann. Das Blech kann so standfest selbst engen Radien der Umformwerkzeuge folgen und selbst enge Prozessfenster beim Umformen einhalten, was gerade bei Feinblechen eintreten kann. Außerdem ist die Schicht mit Polyvinylalkohol verhältnismäßig einfach entfernbar, beispielsweise mithilfe eines alkalischen Reinigungsprozesses, und führt zudem bei bekannten stoffschlüssigen Verbindungen zu keinen nachteiligen Effekten, zumal Polyvinylalkohol aus dem Stand der Technik bei Klebeverbindungen als Haftvermittler bekannt ist. Außerdem oxidiert Polyvinylalkohol bei Schweiß- oder Lötverfahren rückstandslos und kann damit auch solche Verbindungen nicht nachteilig beeinflussen, was die Erfindung gegenüber aus dem Stand der Technik mit Mehrkomponentensysteme auszeichnen kann. Zudem können mit dem optionalen Tracer selbst dünne Be- schichtungen messtechnisch erfasst werden. If the coating consists of polyvinyl alcohol, optionally a tracer, as well as unavoidable impurities due to the production, the sheet can be coated with a have the same high tribological property to ensure adequate lubrication even at high forming forces. The layer of polyvinyl alcohol ensures that the sheet is heavily wetted with oil, which can prevent film breakage during forming. The sheet metal can thus steadfastly follow even the tight radii of the forming tools and even adhere to narrow process windows during forming, which can occur especially with thin sheets. In addition, the layer with polyvinyl alcohol is relatively easy to remove, for example by means of an alkaline cleaning process, and also leads in known cohesive compounds to no adverse effects, especially since polyvinyl alcohol is known from the prior art in adhesive bonds as a primer. In addition, polyvinyl alcohol oxidizes without residue during welding or soldering processes and can therefore not adversely affect such compounds, which the invention can distinguish from multicomponent systems in comparison to the prior art. In addition, even thin coatings can be measured using the optional tracer.
Besteht das Blech aus einem Stahlwerkstoff, kann die Anbindung der Beschichtung mit Polyvinylalkohol erleichtert - und damit das Umformverhalten des Stahlblechs weiter verbessert werden. If the sheet consists of a steel material, the connection of the coating with polyvinyl alcohol can be facilitated - and thus the deformation behavior of the steel sheet can be further improved.
Weist das Blech eine Schutzbeschichtung, insbesondere auf Zn-Basis, auf, an welche Schutzbeschichtung die Beschichtung mit Polyvinylalkohol anschließt, können Synergieeffekte zwischen Schutzbeschichtung und Polyvinylalkohol zur Verbesserung deren stoffschlüssigen Verbindung genutzt und damit das Umformverhalten des Blechs weiter verbessert werden. If the sheet has a protective coating, in particular based on Zn, to which protective coating the coating with polyvinyl alcohol adjoins, synergy effects between protective coating and polyvinyl alcohol can be used to improve their cohesive connection and thus the forming behavior of the sheet can be further improved.
Eine ausreichende Verbesserung im Umformverhalten des Blechs kann sich zeigen, wenn die die Beschichtung mit Polyvinylalkohol ein Schichtgewicht von mindestens 0,5 mg/mA2, insbesondere mindestens 10 mg/mA2, aufweist Die Eigenschaften des Blechs hinsichtlich seiner Umformbarkeit können weiter verbessert werden, wenn an die Beschichtung mit Polyvinylalkohol ein Ölfilm mit einem Schichtgewicht von 0,5 bis 3 g/mA2 anschließt. Insbesondere Mineralöl, vorzugsweise ein thixotropes Öl, kann sich hierfür auszeichnen. A sufficient improvement in the forming behavior of the sheet can be shown when the coating with polyvinyl alcohol has a coating weight of at least 0.5 mg / m A 2, in particular at least 10 mg / m A 2 The properties of the sheet with regard to its formability can be further improved if the film with polyvinyl alcohol is followed by an oil film with a layer weight of 0.5 to 3 g / m A 2. In particular, mineral oil, preferably a thixotropic oil, may be distinguished for this purpose.
Besonders kann sich die Erfindung auszeichnen, wenn eine wässrige Lösung, die Polyvinylalkohol, optional einen Entschäumer, optional einen Tracer und als Rest Wasser sowie herstellungsbedingt unvermeidbare Verunreinigungen aufweist, zum Beschichten eines ölfreien Blechs zur Verbesserung der Umformbarkeit des nach dem Beschichten geölten Blechs verwendet wird. Dies insbesondere weil die wässrige Lösung durch die geringe Anzahl an Komponenten äußerst stabil ist und damit eine reproduzierbare Beschichtung erlauben kann. Vorzugsweise kann dies für Stahlbleche von besonderer Bedeutung sein - insbesondere für Bleche mit einer Schutzbeschichtung vorzugsweise auf Zn-Basis. In particular, the invention may be distinguished when an aqueous solution which comprises polyvinyl alcohol, optionally a defoamer, optionally a tracer and the remainder of water and inevitable impurities due to its production, is used to coat an oil-free sheet to improve the formability of the sheet which has been oiled after coating. This is particularly because the aqueous solution is extremely stable due to the small number of components and thus can allow a reproducible coating. Preferably, this can be of particular importance for steel sheets - especially for sheets with a protective coating preferably Zn-based.
Kurze Beschreibung der Zeichnung Short description of the drawing
Im Folgenden und in den Figuren wird die Erfindung beispielhaft anhand von Ausführungsbeispielen näher erläutert. Es zeigen In the following and in the figures, the invention will be explained in more detail by way of example with reference to exemplary embodiments. Show it
Fig. 1 eine vergrößerte abgerissene Schnittansicht auf ein beschichtetes Blech und Fig. 2 ein vergleichendes Diagramm verschieden beschichteter Feinbleche.  Fig. 1 is an enlarged fragmentary sectional view of a coated sheet and Fig. 2 is a comparative diagram of different coated thin sheets.
Weg zur Ausführung der Erfindung Way to carry out the invention
Zum Nachweis der erzielten Effekte wurden ident verzinkte Bleche bzw. Feinbleche A, B und C aus einem Stahlwerkstoff mit verschiedensten wässrigen Lösungen behandelt, getrocknet und nachfolgend geölt, und zwar mit einem Schichtgewicht von 2 g/mA2. Hierzu wird ein bekanntes Mineralöl bzw. die Stahlwerksbeölung RP4107S verwendet. Im Allgemeinen ist jedoch jedes andere thixotrope Öl denkbar. Die verschiedenen Zusammensetzungen der Lösungen samt der jeweiligen Filmdicke sind in der Tabelle 1 zu finden. To demonstrate the effects obtained ident galvanized sheets or thin sheets A, B and C treated from a steel material with a variety of aqueous solutions were dried and subsequently oiled, with a coating weight of 2 g / m A 2. For this purpose, a known mineral oil or used the steelwork oiling RP4107S. In general, however, any other thixotropic oil is conceivable. The different compositions of the solutions together with the respective film thickness can be found in Table 1.
Tabelle 1 : Versuchsübersicht  Table 1: Experiment overview
Auf dem Feinblech A wurde ausschließlich RP4107S als Umformhilfe appliziert. Die Feinbleche B und C wurden vorher mit der erfindungsgemäßen Lösung gemäß Tabelle 1 behandelt, welche Lösung anschließend getrocknet wurde. On the thin sheet A, only RP4107S was applied as a forming aid. The thin sheets B and C were previously treated with the inventive solution according to Table 1, which solution was then dried.
Damit ergibt sich am erfindungsgemäßen Blech 1 (Feinblech B und C) zum Unterschied zum Feinblech A auf der Schutzbeschichtung 2, die eine Zn-Basis aufweist, eine vollflächig abdeckende Beschichtung 3 aus Polyvinylalkohol. An diese Be- schichtung 3 wird anschließend ein vollflächig abdeckender RP4107S Ölfilm 4 aus Mineralöl aufgetragen, um damit beispielsweise auch die Korrosionsbeständigkeit des Blechs 1 zu erhöhen. This results in the inventive sheet 1 (sheet B and C), in contrast to the thin sheet A on the protective coating 2, which has a Zn base, a full-surface covering coating 3 of polyvinyl alcohol. A full surface covering RP4107S oil film 4 made of mineral oil is then applied to this coating 3 in order to increase, for example, the corrosion resistance of the metal sheet 1 as well.
Von den Blechen A, B und C wurden anschließend die Gleitreibungskoeffizienten μ entsprechend der Norm ISO 15359 gemessen, und zwar über mehrere Versuche n auf demselben Feinblech A, B und C, was der Fig. 2 entnommen werden kann. In Tabelle 2 sind hierzu jene Gleitreibungskoeffizienten μ zu finden, der über mehrere Versuche n auf demselben Feinblech A, B bzw. C gemittelt sind. Wie nun im Vergleich der Feinbleche A, B und C nach Tabelle 1 zu erkennen, zeigen die erfindungsgemäßen Umformhilfen auf den Feinblechen B und C überragende tribologische Eigenschaften, was zumindest durch deutlich reduzierte Gleitreibungskoeffizienten in Relation zu Feinblech A zum Ausdruck kommt. Zudem ist zu erkennen, dass die erfindungsgemäße Beschichtung 3 aus Polyvinylalkohol bei den Feinblechen B und C zu keiner Verschlechterung des Gleitreibungskoeffizienten μ über die Anzahl der Versuche n führt. Erfindungsgemäß können jedoch die Feinblechen B und C selbst beim letzten Versuch noch immer niedrige Gleitreibungskoeffizienten μ gewährleistet. Die Beschichtung 3 kann daher standfest einen besonders niedrigen Gleitreibungskoeffizient μ sicherstellen. Außerdem ist gemäß Fig. 2 zu erkennen, dass mit vollhydrolysiertem Polyvinylalkohol mit einem Hydrolysegrad größer 97 Mol.-% in der wässrigen Lösung ein geringer Anteil im Vergleich mit der Lösung von Feinblech B ausreicht, verbesserte tribologische Eigenschaften zu gewährleisten. From the sheets A, B and C, the sliding friction coefficients μ were then measured according to the standard ISO 15359, namely over several tests n on the same sheet A, B and C, which can be seen in FIG. Table 2 shows the sliding friction coefficients μ which are averaged over several tests n on the same sheet A, B and C respectively. As can now be seen in the comparison of the thin sheets A, B and C according to Table 1, the forming aids according to the invention on the thin sheets B and C outstanding tribological properties, which comes at least by significantly reduced sliding friction in relation to thin sheet A expression. In addition, it can be seen that the coating 3 according to the invention of polyvinyl alcohol in the thin sheets B and C leads to no deterioration of the sliding friction coefficient μ over the number of tests n. According to the invention, however, the thin sheets B and C can still guarantee low sliding friction coefficients μ even in the last attempt. The coating 3 can therefore steadfast ensure a particularly low coefficient of sliding friction μ. In addition, it can be seen from FIG. 2 that with fully hydrolyzed polyvinyl alcohol having a degree of hydrolysis greater than 97 mol% in the aqueous solution, a small proportion is sufficient in comparison with the solution of thin sheet B to ensure improved tribological properties.
Es ist somit gezeigt, dass die erfindungsgemäß vorgeschlagenen Verfahren bzw. auch das damit beschichtete Blech besonders für ein Umformen vorbereitet bzw. damit ein Umformen reproduzierbar durchgeführt werden kann. It is thus shown that the method proposed according to the invention or also the sheet coated therewith can be specially prepared for forming, or that a forming can be carried out reproducibly.

Claims

P a t e n t a n s p r ü c h e Patent claims
1 . Verfahren zur Verbesserung der Umformbarkeit eines Blechs (1 ), bei dem vor dem Umformen des Blechs (1 ) eine wässrige Lösung mit Polyvinylalkohol auf das Blech (1 ) aufgebracht und danach getrocknet wird und in einem nachfolgenden Schritt die damit beschichtete Blechoberfläche geölt wird, dadurch gekennzeichnet, dass auf das Blech (1 ) eine wässrige Lösung, die Polyvinylalkohol, optional einen Entschäumer, optional einen Tracer und als Rest Wasser sowie herstellungsbedingt unvermeidbare Verunreinigungen aufweist, aufgebracht und getrocknet wird. 1 . A method for improving the formability of a sheet (1), wherein before the forming of the sheet (1) an aqueous solution with polyvinyl alcohol is applied to the sheet (1) and then dried and in a subsequent step, the coated sheet surface is oiled, characterized in that an aqueous solution comprising polyvinyl alcohol, optionally an antifoam, optionally a tracer and the remainder water and, as a result of the preparation, unavoidable impurities, is applied to the sheet (1) and dried.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass auf ein aus einem Stahlwerkstoff bestehendes Blech (1 ) die wässrige Lösung mit Polyvinylalkohol aufgebracht und getrocknet wird. 2. The method according to claim 1, characterized in that applied to a steel material consisting of a steel sheet (1), the aqueous solution with polyvinyl alcohol and dried.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass auf eine Schutzbeschichtung (2), insbesondere auf Zn-Basis, des Blechs (1 ) die wässrige Lösung mit Polyvinylalkohol aufgebracht und getrocknet wird. 3. The method according to claim 1 or 2, characterized in that applied to a protective coating (2), in particular Zn-based, of the sheet (1), the aqueous solution with polyvinyl alcohol and dried.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Lösung Polyvinylalkohol bis zur Löslichkeitsgrenze in Wasser aufweist. 4. The method according to any one of claims 1 to 3, characterized in that the solution has polyvinyl alcohol to the Löslichkeitsgrenze in water.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Lösung 0,5 bis 15 Gew.-%, insbesondere von 0,9 bis 8 Gew.-%, Polyvinylalkohol aufweist. 5. The method according to any one of claims 1 to 4, characterized in that the solution has 0.5 to 15 wt .-%, in particular from 0.9 to 8 wt .-%, polyvinyl alcohol.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die wässrige Lösung mit einer Nassfilmdicke von 0,1 bis 10 μηπ, insbesondere von 1 bis 5 μηπ, auf das Blech (1 ) aufgebracht wird. 6. The method according to any one of claims 1 to 5, characterized in that the aqueous solution having a wet film thickness of 0.1 to 10 μηπ, in particular from 1 to 5 μηπ, is applied to the sheet (1).
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die wässrige Lösung teilhydrolysierten Polyvinylalkohol mit einem Hydrolysegrad von 72 bis 97 Mol.-% oder vollhydrolysierten Polyvinylalkohol aufweist. 7. The method according to any one of claims 1 to 6, characterized in that the aqueous solution partially hydrolyzed polyvinyl alcohol having a degree of hydrolysis of 72 to 97 mol .-% or fully hydrolyzed polyvinyl alcohol.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Blech (1 ) mit 0,5 bis 3 g/mA2 Öl oberflächenbeschichtet wird. 8. The method according to any one of claims 1 to 7, characterized in that the sheet (1) with 0.5 to 3 g / m A 2 oil is surface-coated.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass n-Octanol als Entschäumer verwendet wird. 9. The method according to any one of claims 1 to 8, characterized in that n-octanol is used as defoamer.
10. Blech mit einer wenigstens bereichsweise vorgesehenen Beschichtung (3), die Polyvinylalkohol aufweist, und mit einem Ölfilm (4) an der Beschichtung (3), dadurch gekennzeichnet, dass die Beschichtung (3) aus Polyvinylalkohol, optional einen Tracer sowie herstellungsbedingt unvermeidbare Verunreinigungen besteht. 10. sheet having an at least partially provided coating (3) comprising polyvinyl alcohol, and having an oil film (4) on the coating (3), characterized in that the coating (3) of polyvinyl alcohol, optionally a tracer and production-related unavoidable impurities consists.
1 1 . Blech nach Anspruch 10, dadurch gekennzeichnet, dass das Blech (1 ) aus einem Stahlwerkstoff besteht. 1 1. Sheet metal according to claim 10, characterized in that the sheet (1) consists of a steel material.
12. Blech nach Anspruch 10 oder 1 1 , dadurch gekennzeichnet, dass das Blech (1 ) eine Schutzbeschichtung (2), insbesondere auf Zn-Basis, aufweist, an welche Schutzbeschichtung (2) die Beschichtung (3) mit Polyvinylalkohol anschließt. 12. Sheet according to claim 10 or 1 1, characterized in that the sheet (1) has a protective coating (2), in particular Zn-based, to which protective coating (2) the coating (3) with polyvinyl alcohol connects.
13. Blech nach Anspruch 10, 1 1 oder 12, dadurch gekennzeichnet, dass die Beschichtung (3) mit Polyvinylalkohol ein Schichtgewicht von mindestens 0,5 mg/mA2, insbesondere mindestens 10 mg/mA2, aufweist. 13. Sheet according to claim 10, 1 1 or 12, characterized in that the coating (3) with polyvinyl alcohol has a coating weight of at least 0.5 mg / m A 2, in particular at least 10 mg / m A 2.
14. Blech nach einem der Ansprüche 10 bis 13, dadurch gekennzeichnet, dass an die Beschichtung (3) mit Polyvinylalkohol ein Ölfilm (4) mit einem Schichtgewicht von 0,5 bis 3 g/mA2 anschließt. 14. Sheet according to one of claims 10 to 13, characterized in that the coating (3) with polyvinyl alcohol, an oil film (4) with a coating weight of 0.5 to 3 g / m A 2 followed.
15. Verwendung einer wässrigen Lösung, die Polyvinylalkohol, optional einen Entschäumer, optional einen Tracer und als Rest Wasser sowie herstellungsbedingt unvermeidbare Verunreinigungen aufweist, zum Beschichten eines ölfreien Blechs (1 ) zur Verbesserung der Umformbarkeit des nach dem Beschichten geölten Blechs (1 )- 15. Use of an aqueous solution, the polyvinyl alcohol, optionally a defoamer, optionally a tracer and the remainder water and production reasons having unavoidable impurities for coating an oil-free sheet (1) for improving the formability of the sheet (1) oiled after coating
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