EP1646459B1 - Method for the production of a press-hardened component - Google Patents
Method for the production of a press-hardened component Download PDFInfo
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- EP1646459B1 EP1646459B1 EP20040741163 EP04741163A EP1646459B1 EP 1646459 B1 EP1646459 B1 EP 1646459B1 EP 20040741163 EP20040741163 EP 20040741163 EP 04741163 A EP04741163 A EP 04741163A EP 1646459 B1 EP1646459 B1 EP 1646459B1
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- component
- press
- coating
- hardened
- blank
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- 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
- B21D35/00—Combined processes according to or processes combined with methods covered by groups B21D1/00 - B21D31/00
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/62—Quenching devices
- C21D1/673—Quenching devices for die quenching
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49616—Structural member making
- Y10T29/49622—Vehicular structural member making
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49826—Assembling or joining
- Y10T29/49885—Assembling or joining with coating before or during assembling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49826—Assembling or joining
- Y10T29/49888—Subsequently coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/8305—Miscellaneous [e.g., treated surfaces, etc.]
Definitions
- the invention relates to a method for producing a press-hardened component according to the preambles of independent claims 1 and 2.
- Such a material is, for example, the precoated boron steel marketed by Usinor under the trader Usibor 1500.
- the steel is provided with an AISi coating which, among other things, exhibits advantageous corrosion-inhibiting properties in the course of the subsequent heat treatment.
- the component is subjected to a preforming cut or a trimming step before the actual hot forming.
- a preforming cut or a trimming step before the actual hot forming.
- This is for example in the DE 101 49 221 C1 described.
- a method may cause corrosion problems because a commonly applied tape coating will be damaged during preforming.
- the object of the invention is to specify a press-hardened component as well as a production method for press-hardened components, which enables reliable corrosion protection for precoated, hot-workable steels.
- a first embodiment of the method according to the invention for the production of press-hardened components comprises the following method steps: a component blank is formed from the precoated semi-finished product by a cold-forming method, in particular a drawing method; the component blank is trimmed on the edge on a part of the production approximately corresponding boundary contour; the trimmed component blank is heated and press-hardened in a hot-forming tool; the press-hardened component blank is coated in a coating step with a corrosion-protective layer.
- this embodiment of the invention makes it possible to design the component manufacturing process in such a way that it is possible to dispense with the procedurally complex and costly final trimming of the hardened component.
- the edge regions are therefore already cut in the uncured state of the component and not only - as usual in hot forming usual - after the heating and hardening process.
- By pruning the workpiece already in the soft state significantly lower cutting forces are required than for cold-cutting hardened materials, resulting in reduced tool wear and a reduction in the maintenance cost of the cutting tools.
- the risk of rapid cracking due to the high notch sensitivity of these materials is significantly reduced when trimming the high strength material in the uncured state.
- the pre-coating provided on the semifinished product avoids scaling of the trimmed component blank in the hardening process, and the requirements for an inert atmosphere during curing can be reduced. In addition, the pre-coating prevents decarburization of the material during curing.
- a further layer which protects against corrosion is applied, so that the component is completely coated, ie also at the edges.
- the following method steps are carried out: the semifinished product precoated with a first layer is heated and press-hardened in a hot-forming tool; the component blank produced in this way is trimmed at the edge to a boundary contour corresponding to the component to be produced; the press-hardened, cut component blank is coated in a coating step with a second corrosion-protective layer.
- the trimming of the cured component is preferably carried out by means of a laser or water jet cutting method, by which a high-quality trimming of the component edges can be achieved.
- the subsequent application of the second corrosion protection layer ensures that the component is also protected against corrosion in the area of the trimmed edges.
- a corrosion-protective layer of zinc can be applied in a coating process that can be suitably integrated into a production process.
- the layer is applied to the press-hardened component blank by a thermal diffusion method, a readily controllable method can be used, with which preferably a layer of zinc or a zinc alloy can be applied, which is also suitable for complex component geometries and edge layering is.
- the layer thickness can be adjusted selectively between a few microns and over 100 microns.
- a thermal load of the component is low.
- Components can be used regardless of their size, dimensions, Configuration, complexity and weight are coated.
- a cleaning prior to the coating step with a dry cleaning, in particular blasting of the press-hardened component blank with glass particles or zinc particles, can be omitted, since the precoating substantially prevents scaling of the component blank during hot forming. This saves a process step; In addition, it is avoided that a small, but possibly disturbing component distortion occurs by blasting the components with particles.
- a good adhesion between the two coatings results.
- the second layer applied to the first layer of the precoat provides edge coating and coating of those areas where the first layer of the precoat e.g. was chipped in the pre-forming or cracked due to excessive friction.
- the component blank is cleaned of residues after the coating step, for example with ultrasound, and passivated, a surface is formed which gives a good primer for coatings, in particular primers of paints or coatings themselves.
- the component blank is tempered after the coating step. It is particularly advantageous if the component blank is coated with a zinc-containing layer, since an oxide is formed on the surface, which is suitable as a primer.
- a press-hardened component in particular a body component, from a semifinished product of unhardened, hot-workable steel sheet, which has been produced according to at least one embodiment of the method according to the invention, is particularly suitable for mass production with corresponding series production and combines a favorable weight reduction of the component with excellent corrosion protection.
- FIGS. 1a to 1e schematically show an inventive method for producing a spatially shaped, press-hardened component 1 from a semifinished product 2.
- a board 3 is used as a semifinished product 2, which is cut out of a developed coil 5.
- a composite sheet are used, as for example in the DE 100 49 660 A1 is described and which consists of a base plate and at least one reinforcing plate.
- a Taylored Blank can be used, which consists of several welded together sheets of different material thickness and / or different material properties.
- the semifinished product 2 may be a three-dimensionally shaped sheet-metal part produced by any forming process which is to undergo further deformation and a strength and / or rigidity increase with the aid of the method according to the invention.
- the semifinished product 2 consists of an unhardened, hot-forming steel sheet.
- a particularly preferred material is a boron-containing tempering steel, e.g. Usibor 1500, Usibor 1500 P or Usibor 1500 PC, which are distributed by the company Usinor under these trade names.
- the board 3 ( Fig. 1a ) are cut out of a unwound and straightened portion of a coil 5 from a precoated, thermoformable sheet.
- the coating is a coating of aluminum or an aluminum alloy, in particular a silicon-containing aluminum alloy AlSi.
- the thermoformable material is at this time in an uncured state, so that board 3 easily using conventional mechanical cutting means 4, for example, a scissors, can be cut out.
- the cutting of the board 3 is advantageously carried out with the help of a platinum press 6, which ensures an automated feed of the coil 5 and an automatic punching and removal of the cut-out board 3.
- board 3 is in 2a shown in a schematic perspective view.
- the cut-out blanks 3 are deposited on a stack 7 and fed in stacked form to a cold-forming station 8 (FIG. Fig. 1b ).
- a component blank 10 is formed in a second process step II from the circuit board 3 by means of the cold forming tool 8, for example a two-stage deep drawing tool 9.
- the board 3 has edge regions 11 which protrude beyond an outer contour 12 of the component 1 to be molded.
- the component blank 10 is formed close to the final contour.
- close-to-net shape should be understood to mean that those parts of the geometry of the finished component 1 which are accompanied by a macroscopic flow of material are completely formed in the component blank 10 after the cold-forming process has been completed. After completion of the cold forming process, only slight conformations of shape are required to produce the three-dimensional shape of the component 1, which require a minimum (local) material flow; the component blank 10 is in Fig. 2b shown.
- the near-net shape shaping can take place in a single deep-drawing step, or it can take place in several stages ( Fig. 1b ).
- the component blank 10 is in a Cutting device 15 is inserted and cut there (process step III, Fig. 1c ).
- the material is still in the uncured state at this time, so trimming can be accomplished by conventional mechanical cutting means 14 such as cutting knives, folding and / or punching tools.
- a separate cutting device 15 may be provided.
- the cutting means 14 may be integrated into the last stage 9 'of the deep-drawing tool 9, so that in the last deep-drawing stage 9' in addition to the final shaping of the sheet metal blank 10, the edge trimming takes place.
- the process steps II and III are integrated in a single processing station, in which the forming and cutting is carried out fully automatically.
- the removal of the component blank 17 from the processing station can be automated or there may be a manual removal and stacking of the component blanks 17.
- the trimmed component blank 17 is subjected to hot working in a hot forming area 26, in the course of which it is formed and hardened to a final shape of the component 1.
- the trimmed component blank 17 is inserted by a manipulator 20 in a continuous furnace 21, where it is heated to a temperature which is above the structural transformation temperature in the austenitic state; Depending on the grade of steel, this corresponds to heating to a temperature between 700 ° C and 1100 ° C.
- a favorable range is between 900 ° C and 1000 ° C.
- the atmosphere of the continuous furnace can be rendered inert by the addition of a protective gas, but the precoating of the blanks 3 already prevents at least a full-surface scaling of the blank surface.
- the uncoated interfaces of the edge contour 12 'of the trimmed component blanks 17 represent only a very small area ratio of the component blank 17, so that adhesion of a layer applied later is virtually unaffected.
- a suitable inert gas for inertization is e.g. Carbon dioxide or nitrogen.
- the heated trimmed component blank 17 is then inserted by means of a manipulator 22 in a hot-forming tool 23, in which the three-dimensional shape and the edge contour 12 'of the trimmed component blank 17 are brought to their desired level. Since the trimmed component blank 17 already has near net shape dimensions, only a slight adaptation of the shape is necessary during hot forming.
- the hot-forming tool 23 the trimmed component blank 17 is finished and rapidly cooled, resulting in a fine-grained martensitic or bainitic material structure is set. This step corresponds to a hardening of the component blank 18 and allows a targeted adjustment of the material strength. Details of such a curing process are eg in the DE 100 49 660 A1 described.
- the hardened component blank 18 is taken out of the hot forming tool 23 with a manipulator and optionally stacked until further processing. Because of the hot-forming process upstream near-net shape trimming of the component blank 10 and the shape adjustment of the edge contour 12 'in the hot forming tool 23, the component 18 after completion of the hot forming process already the desired outer contour 24 of the finished component 1, so that after the hot forming no time-consuming trimming the edge of the component is necessary.
- the component blank 18 can be quenched in a cooled hot forming tool 23. Since the surface is not scaled by the layer 33 of the precoating, a subsequent cleaning can be omitted.
- the cycle times in the production method are advantageously short.
- the cooling of the component blank 18 is a possible bottleneck.
- air-hardening or water-hardening materials for the components 1 can be used.
- the component blank 18 then only needs to cool down until sufficient heat resistance, rigidity and the associated Dimensional accuracy of the component blank 18 is reached. Then, the component blank 18 can be removed from the tool 23, so that the further heat treatment process takes place in the air or in water outside of the tool 23, which then very quickly after a few seconds again for receiving further component blanks 17 is available.
- the press-hardened component blank 18 is coated in a coating process with a corrosion of the component 1 preventing layer 34.
- drums 31 are charged with the press-hardened component blanks 18 and a zinc-containing powder, preferably a zinc alloy or a zinc-containing mixture, closed and introduced into a coating installation 30.
- the component blanks 18 are heated slowly at about 5-10 K / min with slow rotation of the drums 31 to about 300 ° C.
- the zinc or zinc alloy is distributed substantially homogeneously over the entire surface of the component blanks 18 and bonds to the surface.
- a uniform layer thickness arises on the component blanks 18, which can be set arbitrarily between a few ⁇ m and more than 100 ⁇ m, preferably between 5 ⁇ m and 120 ⁇ m.
- the layer 34 is weldable and gives a tensile strength that can be more than 1300 MPa for a component 1 made of BTR 165. In the thermal diffusion method There are practically no residues or emissions into the environment.
- the coating process is concluded with a passivation process in an adjacent passivation station 35, in which the drums 31 are discharged from the coating installation 30, cooled in a cooling station 36, ultrasonically freed of residues of the coating powder in a cleaning station 37 and in a tempering station 38 at a temperature of about 200 ° C for about 1 h, wherein the layer 34 is passivated.
- suitable passivating additives may also be added. Then the finished corrosion-protected components 1 can be removed from the drum 31.
- the zinc-containing layer 34 is applied to the press-hardened component blank 18 by a hot-dip galvanizing process in a coating area 40.
- Component blanks 18 are suspended in a submersible housing 41, which transports the component blanks 18 through a plurality of stations of the coating area 40.
- a flux station 42 the component blanks 18 are hung in a suitably tempered flux bath, preferably with zinc chloride at about 360 ° C, then dried in a drying station 43, preferably at 80 ° C and then in a galvanizing bath 44 at about 400 ° C. 450 ° C immersed and galvanized. Then the finished components 1 can be removed from the submersible housing 31.
- FIGS. 3a to 3d schematically show an alternative process flow for producing a spatially shaped, press-hardened component 1 from a semifinished product 2, in particular from a pre-coated circuit board 3.
- Fig. 3a Cut the board 3 in the platinum press 6 from a pre-coated, hot-forming sheet.
- the coated board 3 is subjected to a hot-forming step ( Fig. 3b ).
- the board 3 is inserted by a manipulator 20 'in a continuous furnace 21', in which the board 3 is heated to a temperature which is above the transition temperature in the austenitic microstructure state.
- the heated board 3 is inserted into a hot forming tool 23 ', in which from the circuit board 3, a component blank 10' of the desired three-dimensional shape is formed;
- the component blank 10 ' is cooled down so rapidly that it experiences a (component-wide or local) hardening.
- the continuous furnace 21 'and the hot forming tool 23' may be in a protective gas atmosphere 26 ', however, by pre-coating the boards 3 is a full-scale scaling of the boards 3 avoided.
- the hardened component blank 10 ' is transferred to a cutting device 15' ( Fig. 3c ), in which the component blank 10 'is trimmed at the edge to produce a blank 18' with edge contour 12.
- the trimming is preferably carried out with a laser 14 '.
- the cut edge portions 11 ' are disposed of.
- the 3d figure is the press-hardened and trimmed blank 18 '- analogous to the process stage V or V' of FIGS. 1e or 1f - coated in a coating system 30.
- the press-hardened, coated component 1 is particularly suitable as a body component in vehicle construction, which are produced in large quantities.
- the method according to the invention enables advantageous process control with short cycle times, all process steps have industrialization potential.
- a precoated material is a use of a conventional pre-forming possible.
- a conventional forming and trimming is possible even with high-strength materials, so that - when using the manufacturing process according to FIG. 1 -
- the costly laser cutting can be replaced at high volumes costly.
- Sheet metal components can be protected by this manufacturing method already in the development by conventional forming simulation on their production.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines pressgehärteten Bauteils gemäß den Oberbegriffen der unabhängigen Ansprüche 1 und 2.The invention relates to a method for producing a press-hardened component according to the preambles of
An Steifigkeit und Festigkeit von Karosseriebauteilen werden im Fahrzeugbau zunehmend hohe Anforderungen gestellt. Gleichzeitig wird jedoch im Interesse einer Gewichtsminimierung eine Verringerung der Materialdicke angestrebt. Eine Lösung zur Erfüllung der widersprüchlichen Anforderungen bieten hochfeste und höchstfeste Stahlwerkstoffe, welche die Herstellung von Bauteilen mit sehr hohen Festigkeiten bei gleichzeitiger geringer Materialdicke ermöglichen. Durch eine geeignete Wahl von Prozessparametem während eines bei diesen Werkstoffen üblichen Warmumformers können Festigkeits- und Zähigkeitswerte eines Bauteils gezielt eingestellt werden.The rigidity and strength of body components are becoming increasingly demanding in vehicle construction. At the same time, however, a reduction of the material thickness is desired in the interests of weight minimization. A solution to meet the contradictory requirements of high-strength and ultra-high-strength steel materials, which allow the production of components with very high strength while maintaining low material thickness. By a suitable choice of process parameters during a conventional hot converter for these materials, the strength and toughness values of a component can be adjusted in a targeted manner.
Ein solcher Werkstoff ist z.B. der von der Firma Usinor unter dem Handelsmann Usibor 1500 vertriebene vorbeschichtete Borstahl. Der Stahl ist mit einer AISi-Beschichtung versehen, die unter anderem im Rahmen der späteren Wärmebeharidlung vorteilhafte korrosionshemmende Eigenschaften zeigt.Such a material is, for example, the precoated boron steel marketed by Usinor under the trader Usibor 1500. The steel is provided with an AISi coating which, among other things, exhibits advantageous corrosion-inhibiting properties in the course of the subsequent heat treatment.
Zur Herstellung eines solchen Bauteils mit Hilfe der Warmumformung wird zunächst aus einem Coil eine Platine ausgeschnitten, die anschließend Oberhalb der Gefügeumwandlungstemperatur des Stahlwerkstoffs, Oberhalb derer das Werkstoffgefüge im austenitischen Zustand vorliegt, erwärmt, im erwärmten Zustand in ein Umformwerkzeug eingelegt und in die gewünschte Bauteilform umgeformt und unter mechanischer Fixierung des gewünschten Umformzustands abgekühlt, wobei eine Vergütung bzw. Härtung des Bauteils erfolgt.For the production of such a component by means of hot forming a circuit board is first cut out of a coil, which then above the structural transformation temperature of the steel material, above which the material structure is in the austenitic state, heated, placed in the heated state in a forming tool and formed into the desired component shape and cooled with mechanical fixation of the desired Umformzustands, wherein a compensation or curing of the component takes place.
Die Herstellung eines Struktur-Bauteils durch Warmumformung ist beispielsweise aus
Oftmals wird das Bauteil vor der eigentlichen Warmumformung einem Vorformschnitt oder einem Beschneidungsschritt unterzogen. Dies ist beispielsweise in der
Aufgabe der Erfindung ist, ein pressgehärtetes Bauteil sowie ein Herstellverfahren für pressgehärtete Bauteile anzugeben, welches einen sicheren Korrosionsschutz für vorbeschichtete, warm umformbare Stähle ermöglicht.The object of the invention is to specify a press-hardened component as well as a production method for press-hardened components, which enables reliable corrosion protection for precoated, hot-workable steels.
Die Aufgabe wird erfindungsgemäß mit den Merkmalen der unabhängigen Ansprüche 1 und 2 gelöst.The object is achieved with the features of the
Eine erste Ausführungsform des erfindungsgemäßen Verfahrens zur Herstellung von pressgehärteten Bauteilen umfasst die folgenden Verfahrensschritte: aus dem vorbeschichteten Halbzeug wird durch ein Kaltumformverfahren, insbesondere ein Ziehverfahren, ein Bauteil-Rohling geformt; der Bauteil-Rohling wird randseitig auf eine dem herzustellenden Bauteil näherungsweise entsprechende Berandungskontur beschnitten; der beschnittene Bauteil-Rohling wird erwärmt und in einem Warmumform-Werkzeug pressgehärtet; der pressgehärtete Bauteil-Rohling wird in einem Beschichtungsschritt mit einer vor Korrosion schützenden Schicht überzogen.A first embodiment of the method according to the invention for the production of press-hardened components comprises the following method steps: a component blank is formed from the precoated semi-finished product by a cold-forming method, in particular a drawing method; the component blank is trimmed on the edge on a part of the production approximately corresponding boundary contour; the trimmed component blank is heated and press-hardened in a hot-forming tool; the press-hardened component blank is coated in a coating step with a corrosion-protective layer.
Diese Ausgestaltung der Erfindung ermöglicht einerseits, den Bauteil-Herstellungsprozess so zu gestalten, dass auf die verfahrenstechnisch aufwändige und kostenintensive abschließende Beschneiden des gehärteten Bauteils verzichtet werden kann. Die Randbereiche werden daher bereits im ungehärteten Zustand des Bauteils abgeschnitten und nicht erst - wie herkömmlicherweise beim Warmumformen üblich - nach dem Erwärmungs- und Härteprozess. Indem das Werkstück bereits im weichen Zustand beschnitten wird, sind wesentlich geringere Schneidkräfte als zum kalten Schneiden gehärteter Werkstoffe erforderlich, was zu einem verminderten Werkzeugverschleiß und zu einer Reduktion der Instandhaltungskosten der Schneidwerkzeuge führt. Weiterhin wird beim Beschneiden des hochfesten Werkstoffs im ungehärteten Zustand die Gefahr einer schnellen Rissbildung aufgrund der hohen Kerbempfindlichkeit dieser Werkstoffe erheblich reduziert.On the one hand, this embodiment of the invention makes it possible to design the component manufacturing process in such a way that it is possible to dispense with the procedurally complex and costly final trimming of the hardened component. The edge regions are therefore already cut in the uncured state of the component and not only - as usual in hot forming usual - after the heating and hardening process. By pruning the workpiece already in the soft state, significantly lower cutting forces are required than for cold-cutting hardened materials, resulting in reduced tool wear and a reduction in the maintenance cost of the cutting tools. Furthermore, the risk of rapid cracking due to the high notch sensitivity of these materials is significantly reduced when trimming the high strength material in the uncured state.
Die auf dem Halbzeug vorgesehene Vorbeschichtung vermeidet ein Verzundern des beschnittenen Bauteil-Rohlings bei dem Härteprozess, und die Anforderungen an eine inerte Atmosphäre beim Härten können verringert werden. Außerdem verhindert die Vorbeschichtung eine Entkohlung des Werkstoffs beim Härten. Nach dem Härteprozess wird erfindungsgemäß eine weitere vor Korrosion schützende Schicht aufgebracht, so dass das Bauteil vollständig, also auch an den Kanten, beschichtet ist.The pre-coating provided on the semifinished product avoids scaling of the trimmed component blank in the hardening process, and the requirements for an inert atmosphere during curing can be reduced. In addition, the pre-coating prevents decarburization of the material during curing. After the hardening process, according to the invention, a further layer which protects against corrosion is applied, so that the component is completely coated, ie also at the edges.
In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens zur Herstellung von pressgehärteten Bauteilen werden die folgenden Verfahrensschritte durchgeführt: das mit einer ersten Schicht vorbeschichtete Halbzeug wird erwärmt und in einem Warmumform-Werkzeug pressgehärtet; der auf diese Weise erzeugte Bauteil-Rohling wird randseitig auf eine dem herzustellenden Bauteil entsprechende Berandungskontur beschnitten; der pressgehärtete, beschnittene Bauteil-Rohling wird in einem Beschichtungsschritt mit einer zweiten vor Korrosion schützenden Schicht überzogen.In a further embodiment of the method according to the invention for producing press-hardened components, the following method steps are carried out: the semifinished product precoated with a first layer is heated and press-hardened in a hot-forming tool; the component blank produced in this way is trimmed at the edge to a boundary contour corresponding to the component to be produced; the press-hardened, cut component blank is coated in a coating step with a second corrosion-protective layer.
In dieser Ausführungsform erfolgt das Beschneiden des gehärteten Bauteils vorzugsweise mit Hilfe eines Laser- oder des Wasserstrahl-Schneideverfahrens, durch die ein hochwertiger Beschnitt der Bauteilkanten erreicht werden kann. Das nachfolgende Aufbringen der zweiten Korrosionsschutzschicht stellt sicher, dass das Bauteil auch im Bereich der beschnittenen Ränder gegen Korrosion geschützt ist.In this embodiment, the trimming of the cured component is preferably carried out by means of a laser or water jet cutting method, by which a high-quality trimming of the component edges can be achieved. The subsequent application of the second corrosion protection layer ensures that the component is also protected against corrosion in the area of the trimmed edges.
Wird die Schicht mit einem Feuerverzinkungs-Verfahren auf den pressgehärteten Bauteil-Rohling aufgebracht, kann eine vor Korrosion schützende Schicht aus Zink in einem geeignet in einen Fertigungsprozess integrierbaren Beschichtungsverfahren aufgebracht werden.If the layer is applied to the press-hardened component blank by a hot-dip galvanizing process, a corrosion-protective layer of zinc can be applied in a coating process that can be suitably integrated into a production process.
Wird die Schicht mit einem thermischen Diffusions-Verfahren auf den pressgehärteten Bauteil-Rohling aufgebracht, kann ein gut steuerbares Verfahren eingesetzt werden, mit dem vorzugsweise eine Schicht aus Zink oder einer Zinklegierung aufgebracht werden kann, das auch für komplexe Bauteil-Geometrien und zur Kantenschichtung geeignet ist. Die Schichtdicke kann gezielt zwischen einigen µm und über 100 µm eingestellt werden. Eine thermische Belastung des Bauteils ist gering. Bauteile können unabhängig von ihrer Größe, den Abmessungen, Konfiguration, Komplexität und Gewicht beschichtet werden. Eine Reinigung vor dem Beschichtungsschritt mit einer Trockenreinigung, insbesondere ein Strahlen des pressgehärteten Bauteil-Rohlings mit Glaspartikeln oder Zinkpartikeln, kann entfallen, da durch die Vorbeschichtung ein Verzundern des Bauteil-Rohlings bei der Warmumformung im wesentlichen unterbleibt. Dadurch wird ein Prozessschritt eingespart; zusätzlich wird vermieden, dass ein zwar geringer, aber möglicherweise störender Bauteilverzug durch ein Strahlen der Bauteile mit Partikeln entsteht.If the layer is applied to the press-hardened component blank by a thermal diffusion method, a readily controllable method can be used, with which preferably a layer of zinc or a zinc alloy can be applied, which is also suitable for complex component geometries and edge layering is. The layer thickness can be adjusted selectively between a few microns and over 100 microns. A thermal load of the component is low. Components can be used regardless of their size, dimensions, Configuration, complexity and weight are coated. A cleaning prior to the coating step with a dry cleaning, in particular blasting of the press-hardened component blank with glass particles or zinc particles, can be omitted, since the precoating substantially prevents scaling of the component blank during hot forming. This saves a process step; In addition, it is avoided that a small, but possibly disturbing component distortion occurs by blasting the components with particles.
Bei einer Vorbeschichtung mit einer aluminiumhaltigen Schicht, vorzugsweise aus AlSi, und einer zinkhaltigen Beschichtung ergibt sich eine gute Haftung zwischen den beiden Beschichtungen. Zusätzlich ergibt sich ein guter Schutz des Werkstoffs gegen Wasserstoffversprödung, gegen die insbesondere Zink den Werkstoff schützen kann. Die zweite Schicht, die auf die erste Schicht der Vorbeschichtung aufgebracht ist, sorgt für eine Kantenbeschichtung und für eine Beschichtung solcher Bereiche, bei denen die erste Schicht der Vorbeschichtung z.B. bei der Vor-Umformung abgeplatzt ist oder durch zu hohe Reibung rissig wurde.In a pre-coating with an aluminum-containing layer, preferably of AlSi, and a zinc-containing coating, a good adhesion between the two coatings results. In addition, there is good protection of the material against hydrogen embrittlement, against which zinc in particular can protect the material. The second layer applied to the first layer of the precoat provides edge coating and coating of those areas where the first layer of the precoat e.g. was chipped in the pre-forming or cracked due to excessive friction.
Wird der Bauteil-Rohling nach dem Beschichtungsschritt von Rückständen gereinigt, beispielsweise mit Ultraschall, und passiviert, wird eine Oberfläche gebildet, die einen guten Haftgrund für Beschichtungen, insbesondere Grundierungen von Lacken oder Lacke selbst, ergibt.If the component blank is cleaned of residues after the coating step, for example with ultrasound, and passivated, a surface is formed which gives a good primer for coatings, in particular primers of paints or coatings themselves.
Vorteilhaft wird der Bauteil-Rohling nach dem Beschichtungsschritt getempert. Besonders vorteilhaft ist, wenn der Bauteil-Rohling mit einer zinkhaltigen Schicht beschichtet ist, da an der Oberfläche ein Oxid gebildet wird, welches als Haftgrund geeignet ist.Advantageously, the component blank is tempered after the coating step. It is particularly advantageous if the component blank is coated with a zinc-containing layer, since an oxide is formed on the surface, which is suitable as a primer.
Ein pressgehärtetes Bauteil, insbesondere ein Karosseriebauteil, aus einem Halbzeug aus ungehärtetem warm umformbaren Stahlblech, das nach zumindest einer der Weiterbildungen des erfindungsgemäßen Verfahrens hergestellt wurde, ist besonders geeignet, mit einer entsprechenden Serienfertigung in großen Stückzahlen hergestellt zu werden und verbindet eine vorteilhafte Gewichtsminderung des Bauteils mit einem ausgezeichneten Korrosionsschutz.A press-hardened component, in particular a body component, from a semifinished product of unhardened, hot-workable steel sheet, which has been produced according to at least one embodiment of the method according to the invention, is particularly suitable for mass production with corresponding series production and combines a favorable weight reduction of the component with excellent corrosion protection.
Weitere Vorteile und Ausgestaltungen der Erfindung sind den weiteren Ansprüchen und der Beschreibung zu entnehmen.Further advantages and embodiments of the invention can be taken from the further claims and the description.
Im folgenden ist die Erfindung anhand eines in einer Zeichnung dargestellten Ausführungsbeispiels näher erläutert.In the following the invention with reference to an embodiment shown in a drawing is explained in more detail.
Dabei zeigen:
- Fig. 1
- ein Verfahrensschema des erfindungsgemäßen Verfahrens eines pressgehärteten Bauteils mit 1a: Zuschneiden der Platine (Schritt I); 1b; Kaltumformung (Schritt II); 1c: Beschneiden der Ränder (Schritt III); 1d: Warmumformung (Schritt IV); 1e: Beschichtung (Schritt V); 1f: alternatives Verfahren zu Beschichtung (Schritt V');
- Fig. 2
- perspektivische Ansichten ausgewählter Zwischenstufen bei der Herstellung eines Bauteils mit 2a: ein vorbeschichtetes Halbzeug; 2b: ein daraus geformter Bauteil-Rohling; 2c: ein beschnittener Bauteil-Rohling; 2d: ein beschichteter Bauteil- Rohling;
- Fig.3
- einen alternativen Verfahrensablauf zur Herstellung eines pressgehärteten Bauteils mit 1a: Zuschneiden der Platine (Schritt I), 1 b: Warmumformung (Schritt II'); 1 c: Beschneiden der Ränder (Schritt III'); 1d: Beschichtung (Schritt IV').
- Fig. 1
- a process diagram of the method according to the invention of a press-hardened component with 1a: cutting the board (step I); 1b; Cold forming (step II); 1c: trimming the edges (step III); 1d: hot working (step IV); 1e: coating (step V); 1f: alternative method of coating (step V ');
- Fig. 2
- perspective views of selected intermediate stages in the production of a component with 2a: a precoated semi-finished product; 2b: a component blank formed therefrom; 2c: a trimmed component blank; 2d: a coated component blank;
- Figure 3
- an alternative process sequence for the production of a press-hardened component with 1a: Cutting the board (step I), 1 b: hot forming (step II '); 1 c: trimming the edges (step III '); 1d: coating (step IV ').
Die
Das Halbzeug 2 besteht aus einem ungehärtetem, warm umformbaren Stahlblech. Ein besonders bevorzugter Werkstoff ist ein borhaltiger Vergütungsstahl, z.B. Usibor 1500, Usibor 1500 P oder Usibor 1500 PC, welche von der Firma Usinor unter diesen Handelsnamen vertrieben werden.The
In einem ersten Prozessschritt I wird die Platine 3 (
Die ausgeschnittenen Platinen 3 werden auf einem Stapel 7 abgelegt und in gestapelter Form einer Kaltumformstation 8 zugeführt (
Je nach Komplexität des Bauteils 1 kann die endkonturnahe Formgebung in einem einzigen Tiefziehschritt erfolgen, oder sie kann mehrstufig erfolgen (
Für das Beschneiden kann, wie in
Durch den Kaltumformprozess und das Beschneiden (Prozessschritte II und III) wird aus der Platine 3 ein endkonturnah beschnittener Bauteil-Rohling 17 hergestellt der sowohl in Bezug auf seine dreidimensionale Form als auch in Bezug auf seine Randkontur 12' nur wenig von der gewünschten Form des Bauteils 1 abweicht. Die abgeschnittenen Randbereiche 11 werden in der Schneidvorrichtung 15 abgeführt; der Bauteil-Rohling 17 (
In einer besonders vorteilhaften Alternative sind die Prozessschritte II und III in einer einzigen Bearbeitungsstation integriert, in der das Umformen und Schneiden vollautomatisch vorgenommen wird. Die Entnahme des Bauteil-Rohlings 17 aus der Bearbeitungsstation kann automatisiert erfolgen oder es kann eine manuelle Entnahme und Abstapelung der Bauteil-Rohlinge 17 erfolgen.In a particularly advantageous alternative, the process steps II and III are integrated in a single processing station, in which the forming and cutting is carried out fully automatically. The removal of the component blank 17 from the processing station can be automated or there may be a manual removal and stacking of the
In dem folgenden Prozessschritt IV (
Die unbeschichteten Schnittstellen der Randkontur 12' der beschnittenen Bauteil-Rohlinge 17 stellen nur einen sehr geringen Flächenanteil des Bauteil-Rohlings 17 dar, so dass eine Haftung einer später aufgebrachten Schicht praktisch nicht beeinflusst wird. Ein geeignetes Schutzgas zur Inertisierung ist z.B. Kohlendioxid oder Stickstoff.The uncoated interfaces of the edge contour 12 'of the trimmed
Der erhitzte beschnittene Bauteil-Rohling 17 wird dann mit Hilfe eines Manipulators 22 in ein Warmumform-Werkzeug 23 eingelegt, in dem die dreidimensionale Gestalt und die Randkontur 12' des beschnittenen Bauteil-Rohlings 17 auf ihr gewünschtes Maß gebracht werden. Da der beschnittene Bauteil-Rohling 17 bereits endkonturnahe Maße aufweist, ist während der Warmumformung nur noch eine geringe Formanpassung notwendig. Im Warmumform-Werkzeug 23 wird der beschnittene Bauteil-Rohling 17 fertig geformt und schnell abgekühlt, wodurch ein feinkörniges martensitisches oder bainitisches Werkstoffgefüge eingestellt wird. Dieser Schritt entspricht einer Härtung des Bauteil-Rohlings 18 und ermöglicht eine gezielte Einstellung der Werkstofffestigkeit. Einzelheiten eines solchen Härtungsprozesses sind z.B. in der
Um eine schnelle Abschreckung des Bauteil-Rohlings 18 im Zuge der Warmumformung zu erreichen, kann der Bauteil-Rohling 18 in einem gekühlten Warmumform-Werkzeug 23 abgeschreckt werden. Da die Oberfläche durch die Schicht 33 der Vorbeschichtung nicht verzundert, kann eine anschließende Reinigung entfallen.In order to achieve a rapid quenching of the component blank 18 in the course of hot forming, the component blank 18 can be quenched in a cooled hot forming tool 23. Since the surface is not scaled by the
Da kein Laserschneiden des gehärteten Bauteil-Rohlings 18 erfolgen muss, sind die Taktzeiten im Fertigungsverfahren vorteilhaft kurz. Im Verfahrensablauf ist nunmehr das Abkühlen des Bauteil-Rohlings 18 ein möglicher Engpass. Um diesen zu entschärfen, können lufthärtende oder wasserhärtende Werkstoffe für die Bauteile 1 eingesetzt werden. Der Bauteil-Rohling 18 braucht dann nur soweit abzukühlen, bis eine ausreichende Warmfestigkeit, Steifigkeit und damit verbundene Maßhaltigkeit des Bauteil-Rohlings 18 erreicht ist. Dann kann der Bauteil-Rohling 18 aus dem Werkzeug 23 entnommen werden, so dass der weitere Wärmebehandlungsvorgang an der Luft oder in Wasser außerhalb des Werkzeugs 23 erfolgt, das dann nach einigen Sekunden sehr schnell wieder zur Aufnahme weiterer Bauteil-Rohlinge 17 zur Verfügung steht.Since laser cutting of the hardened component blank 18 does not have to take place, the cycle times in the production method are advantageously short. In the process, now the cooling of the component blank 18 is a possible bottleneck. To defuse this, air-hardening or water-hardening materials for the components 1 can be used. The component blank 18 then only needs to cool down until sufficient heat resistance, rigidity and the associated Dimensional accuracy of the component blank 18 is reached. Then, the component blank 18 can be removed from the tool 23, so that the further heat treatment process takes place in the air or in water outside of the tool 23, which then very quickly after a few seconds again for receiving
In einem weiteren Prozessschritt V (
In Abhängigkeit der Zusammensetzung des Pulvers, der Zeit und der Temperatur stellt sich auf den Bauteil-Rohlingen 18 eine gleichmäßige Schichtdicke ein, die beliebig zwischen einigen µm und über 100 µm, bevorzugt zwischen 5 µm und 120 µm, eingestellt werden kann. Die Schicht 34 ist schweißbar und ergibt eine Zugfestigkeit, die für ein Bauteil 1 aus BTR 165 mehr als 1300 MPa betragen kann. Bei dem thermischen Diffusionsverfahren fallen praktisch keine Rückstände oder Emissionen in die Umwelt an.Depending on the composition of the powder, the time and the temperature, a uniform layer thickness arises on the
Das Beschichtungsverfahren wird mit einem Passivierungsvorgang in einer angrenzenden Passivierungsstation 35 abgeschlossen, bei dem die Trommeln 31 aus der Beschichtungsanlage 30 ausgeschleust, in einer Kühlstation 36 gekühlt, in einer Reinigungsstation 37 mit Ultraschall von Rückständen des Beschichtungspulvers befreit und in einer Temperstation 38 bei einer Temperatur von etwa 200°C für etwa 1 h getempert werden, wobei die Schicht 34 passiviert wird. Gegebenenfalls können auch geeignete Passivierungszusätze zugegeben werden. Dann können die fertigen korrosionsgeschützten Bauteile 1 aus der Trommel 31 entnommen werden.The coating process is concluded with a passivation process in an
In einer alternativen Ausgestaltung (Prozessschritt V',
Dann wird der gehärtete Bauteil-Rohling 10' an eine Schneidvorrichtung 15' übergeben (
Das pressgehärtete, beschichtete Bauteil 1 ist insbesondere als Karosseriebauteil im Fahrzeugbau geeignet, welche in großen Stückzahlen hergestellt werden. Das erfindungsgemäße Verfahren ermöglicht eine vorteilhafte Prozessführung mit kurzen Taktzeiten, alle Prozessschritte haben Industrialisierungspotential. Trotz Verwendung eines vorbeschichteten Werkstoffs ist ein Einsatz einer konventionellen Vor-Umformung möglich. Durch das nachträgliche Aufbringen eines zusätzlichen Korrosionsschutzes wird ein konventionelles Umformen und Beschneiden auch bei hochfesten Werkstoffen möglich, so dass - bei Verwendung des Herstellungsverfahrens gemäß
Claims (7)
- Method for the production of press-hardened components, more particularly press-hardened components of the body of an automobile, consisting of a semi-finished product (2) made of non-hardened sheet steel adapted for hot working,
characterized in that
the following method steps are executed- using a cold working method, especially a drawing method, to form a component blank (10) from the semi-finished product (2) pre-coated with a first layer (33),- trimming the edge of the component blank (10) to an edge contour (12') that approximately corresponds to the component (1) to be produced;- heating the trimmed component blank (17) and press-hardening the same in a hot-working tool (23);- coating the press-hardened component blank (18) with a second, anticorrosion coating (34) in a coating step. - Method for the production of press-hardened components, in particular a car body component, from a semi-finished product (2) made of non-hardened sheet steel adapted for hot working,
characterized in that
the following method steps are executed- heating the blank (2) pre-coated with a first layer (33) and press-hardening the same in a hot-working tool (23);- trimming the edge of the press-hardened component blank (10') thus formed to a contour corresponding to the edge contour (12) of the component (1) to be produced;- coating the press-hardened component blank (18') with a second, anticorrosion coating (34) in a coating step. - Method of claim 1 or 2,
characterized in that
the second coating (34) is applied onto the press-hardened component blank (18, 18') by means of a galvanizing process. - Method of claim 1 or 2,
characterized in that
the second coating (34) is applied onto the press-hardened component blank (18, 18') by means of a thermal diffusion process. - Method of at least one of the preceding claims,
characterized in that
the second coating (34) is deposited both onto the pre-coating (33) and on uncoated parts of the component blank (18, 18'). - Method of at least one of the preceding claims,
characterized in that
after the coating step, residuals from the coating step are cleaned from the coated component blank (18, 18'). - Method of at least one of the preceding claims,
characterized in that
the coated component blank (18, 18') is tempered after the coating step.
Applications Claiming Priority (2)
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DE2003133166 DE10333166A1 (en) | 2003-07-22 | 2003-07-22 | Press-hardened component and method for producing a press-hardened component |
PCT/EP2004/008087 WO2005009642A1 (en) | 2003-07-22 | 2004-07-20 | Press-hardened component and method for the production of a press-hardened component |
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EP1646459A1 EP1646459A1 (en) | 2006-04-19 |
EP1646459B1 true EP1646459B1 (en) | 2010-05-05 |
EP1646459B2 EP1646459B2 (en) | 2019-01-02 |
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US (1) | US8127449B2 (en) |
EP (1) | EP1646459B2 (en) |
JP (1) | JP2006529002A (en) |
DE (2) | DE10333166A1 (en) |
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DE3828045C1 (en) † | 1988-08-18 | 1989-12-07 | Hoesch Stahl Ag, 4600 Dortmund, De | Method and apparatus for applying an anti-corrosive layer to the cut edges of a metal sheet |
DE4307563C2 (en) * | 1992-03-12 | 1994-09-22 | Bayerische Motoren Werke Ag | Method for manufacturing a sheet metal structural part which partially has a multiple sheet metal structure, and sheet metal structural part produced by the method |
DE19807823A1 (en) * | 1998-02-26 | 1999-09-09 | Fraunhofer Ges Forschung | Process for the production of a corrosion-protective coating and layer system for substrates made of light metal |
EP0964078A1 (en) * | 1998-06-12 | 1999-12-15 | Enamels and Ceramic Coatings International C.V. | Enamelling of zinc or zinc-alloy precoated steel surfaces |
FR2807447B1 (en) † | 2000-04-07 | 2002-10-11 | Usinor | METHOD FOR MAKING A PART WITH VERY HIGH MECHANICAL CHARACTERISTICS, SHAPED BY STAMPING, FROM A STRIP OF LAMINATED AND IN PARTICULAR HOT ROLLED AND COATED STEEL SHEET |
DE10049660B4 (en) * | 2000-10-07 | 2005-02-24 | Daimlerchrysler Ag | Method for producing locally reinforced sheet-metal formed parts |
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DE10135647C1 (en) * | 2001-07-21 | 2002-07-25 | Daimler Chrysler Ag | Corrosion-protected sheet deformation process, for structural components of vehicles, involves wetting contact region with inorganic non-metallic sealing mass before hot deformation |
DE10149221C1 (en) * | 2001-10-05 | 2002-08-08 | Benteler Automobiltechnik Gmbh | Process for producing a hardened sheet metal profile |
US7998289B2 (en) * | 2002-09-13 | 2011-08-16 | Daimler Ag | Press-hardened part and method for the production thereof |
-
2003
- 2003-07-22 DE DE2003133166 patent/DE10333166A1/en not_active Withdrawn
-
2004
- 2004-07-20 DE DE200450011133 patent/DE502004011133D1/en active Active
- 2004-07-20 WO PCT/EP2004/008087 patent/WO2005009642A1/en active Application Filing
- 2004-07-20 US US10/565,037 patent/US8127449B2/en not_active Expired - Fee Related
- 2004-07-20 JP JP2006520770A patent/JP2006529002A/en active Pending
- 2004-07-20 EP EP04741163.2A patent/EP1646459B2/en not_active Expired - Fee Related
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2006
- 2006-01-20 ZA ZA200600594A patent/ZA200600594B/en unknown
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WO2018078484A1 (en) | 2016-10-26 | 2018-05-03 | Thermission Ag | Method for applying a layer structure by thermodiffusion to a metallic or intermetallic surface |
Also Published As
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WO2005009642A1 (en) | 2005-02-03 |
ZA200600594B (en) | 2010-01-27 |
EP1646459A1 (en) | 2006-04-19 |
JP2006529002A (en) | 2006-12-28 |
US8127449B2 (en) | 2012-03-06 |
EP1646459B2 (en) | 2019-01-02 |
DE502004011133D1 (en) | 2010-06-17 |
US20070175040A1 (en) | 2007-08-02 |
DE10333166A1 (en) | 2005-02-10 |
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